,scann$ by ,*>les ,kell] ) ,omni,page ,pr(essional ,,ocr s(tw>e ,,tb is a triple bond4 4 is a dott$ 7coord9at$7 bond4 ,emphasis italics h a 99 m>k4 footnotes mov$ to ,e,o,paragraphs b ,,n r5umb]$4 7,!y are numb]$ a or b :5 two pages ( notes are toge!r47 ,comm5ts & guess$ at *>act]s 9 braces ne$ /ripp$_/fix$4 ,greek lett]s are encod$ 9 gr brackets1 & ! lett]s are bas$ on ,adobe's ,symbol font4 ,,organic ,,syn!ses ,,an ,,annual ,,publication ,,( ,,satisfactory ,,me?ods ,,= ,,! ,,prep>ation ,,( ,,organic ,,*emicals ,,editorial ,,bo>d ,,james ,,bryant ,,conant1 ,editor-9-,*ief ,,hans ,,?a*] ,,cl>ke ,,rog] ,,adams ,,oliv] ,,kamm ,,contributors ,g4 ,h4 ,,coleman ,j1 ,c4 ,,hessl] ,e4 ,p4 ,,kohl] ,c4 ,s4 ,,m>vel ,w4 ,a4 ,,noyes ,g4 ,r4 ,,rob]tson ,e4 ,b4 ,,vliet ,f4 ,c4 ,,:itmore ,,vol4 ,,ii4 ,caveat3 ,"s numb]s did n ,,ocr correctly & may n h be5 correct$ dur+ ! pro(+6 ,*eck ! #aida pr9t edition be=e try+ ^!6 ,,introduction ,,to ,,! ,,s]ies ,,! publication ( ?is s]ies ( pamphlets has be5 und]tak5 to make available 9 a p]man5t =m complete detail$ directions = ! prep>ation ( v>i\s organic *emical reag5ts4 ,9 ann\nc+ ?is purpose x may be well to m5tion at ! outset "s ( ! difficulties 9 ! way ( ! rese>* *emi/1 :i* x is hop$ ?is s]ies w be able to ov]come4 ,! co/ ( *emicals is prohibitive to ! majority ( *emi/s2 ?is 0 true be=e ! w> :5 ,kahlbaum's complete supply 0 available1 & to-day ) our dep5d5ce on dome/ic /ocks1 ?is co/ has increas$4 ,! delay 9 obta9+ *emicals1 especially f abroad1 ev5 if ! exp5se ne$ n be consid]$1 is an important factor4 ,^! difficulties h !re=e ?r[n ! rese>* *emi/ on 8 own res\rces4 ,! prep>ation ( mat]ials = rese>*1 always "t consum+ & annoy+1 is made increas+ly s by ! inexactness ( ! publi%$ in=mation :i* s (t5 omits ess5tial details4 ,because ( ?is1 mu* ne$less exp]im5tation is necess>y 9 ord] to obta9 ! results giv5 9 ! publi%$ reports4 ,z ! additional in=mation ?us acquir$ is seldom publi%$1 duplication ( su* exp]im5ts occurs aga9 & aga91-- a wa/e ( "t & mat]ial4 ,x is hop$ ^! difficulties may be rem$i$ by ! publication ( ?is s]ies ( pamphlets4 ,9 o!r words1 ! au?ors hope to make ?is a cle>+ h\se = ! ex*ange ( in=mation z to me?ods ( prep>ation ( "s ( ! mo/ ne$$ organic *emical reag5ts4 ,on acc\nt ( ! impossibility ( obta9+ ! less common organic *emicals 9 ! ,unit$ ,/ates dur+ ! pa/ few ye>s1 univ]sity laboratories h _h no option b to prep>e _! own supplies4 ,at ! ,univ]sity ( ,ill9ois1 = in/ance1 a special /udy has be5 made ( ?is field1 & me?ods = ! production ( v>i\s sub/ances h be5 inve/igat$4 ,z a result1 reliable me?ods & directions h be5 develop$ = produc+ ! mat]ials 9 "o-half to five p\nd lots4 ,su* "w z ,ill9ois has done is n[ be+ giv5 an ev5 m ext5sive scope at ! ,rese>* ,laboratory ( ! ,ea/man ,kodak ,company4 ,x is felt t ! results f ^! v>i\s laboratories %\ld be available to all *emi/s & x is hop$ t !y ev5tually w be completely incorporat$ 9 ^! pamphlets4 ,! organic *emicals h]e9 discuss$ h be5 q arbitr>ily *os51 be+ ^? :i* h be5 ne$$ 9 v>i\s rese>* laboratories 9 ! la/ ye>s & = :i* ! directions happ5 n[ to be ready = publication4 ,! me?ods are 9 only a few cases new ones2 !y are 9 g5]al ! mo/ satisfactory to be f\nd 9 ! lit]ature4 ,only su* details h be5 add$ z w enable a man ) a reasonable am\nt ( exp]i5ce 9 organic *emi/ry to duplicate ! results )\t difficulty4 ,to be absolutely sure t ea* set ( directions c be repeat$1 e exp]im5t has be5 c>ri$ out 9 at lea/ two laboratories4 ,only aft] exact duplication ( ! results 9 bo? laboratories are ! directions consid]$ ready = publication4 ,! names ( ! *emi/s :o h /udi$ ! v>i\s exp]im5ts are giv5 s t fur!r in=mation conc]n+ any obscure po9t c be obta9$ if any "q arises 9 us+ ^! directions4 ,& f9ally1 9 describ+ ! exp]im5ts1 special att5tion has be5 giv5 to ! explanation ( :y x is necess>y to foll[ ! directions c>efully1 & :at w happ5 if ^! directions are n foll[$4 ,al?\gh ! ma9 object 9 ?is s]ies is to give ! mo/ conv5i5t laboratory me?ods = prep>+ v>i\s sub/ances 9 "o-half to five p\nd lots1 an attempt has also be5 made to h ^! processes z f> z possible adaptable to l>ge scale developm5t4 ,= example1 extractions h be5 avoid$ :]ev] possible1 *eap solv5ts h be5 sub-/itut$ = exp5sive ones1 & me*anical agitation1 a proc$ure extremely important 9 ! success ( _m comm]cial processes1 has usually be5 specifi$4 ,! app>atus us$ is always c>efully describ$ & :]ev] necess>y an illu/ration is giv54 ,accompany+ ea* prep>ation !re w be f\nd a bibliography conta9+ ref]5ces to all ! me?ods = ! production ( ! sub/ance describ$ 9 ! lit]ature4 ,?is is giv5 9 ord] to aid any future inve/igator :o may wi% to /udy or improve ! me?ods ( prep>ation4 ,x is n claim$ t ! me?ods are1 9 e case1 completely p]fect1 b only t ! yields are v satisfactory & all[ ! production ( ! sub/ances at a reasonable co/4 ,x is hop$ !re=e t ! pamphlets w b5efit n only ! sci5tific rese>* man ( ! univ]sity1 b also ! te*nical *emi/ :o desires to develop ! prep>ation ( "o ( ^! sub/ances to a l>ge scale process ( manufacture4 ,! editors tru/ also t ?is "w may be us$ to advantage z a prep>ation manual 9 int]m$iate or advanc$ c\rses 9 organic *emi/ry 9 univ]sity laboratories1 & t x w aid small colleges 9 ! production ( necess>y reag5ts :i* !y are (t5 f9ancially unable to pur*ase4 ,! pamphlets are to be edit$ by ! foll[+ committee3 ,rog] ,adams1 ,univ]sity ( ,ill9ois1 ,urbana1 ,ill9ois2 ,j4 ,b4 ,conant1 ,h>v>d ,univ]sity1 ,cambridge1 ,massa*usetts2 ,h4 ,t4 ,cl>ke1 ,ea/man ,kodak ,company1 ,ro*e/]1 ,new ,york2 ,oliv] ,kamm1 ,p>ke1 ,davis ,company1 ,detroit1 ,mi*igan2 ea* to act = "o ye> z editor-9-*ief & ! o!r ?ree to assi/ him z associate editors4 ,a new numb] ( ! s]ies w appe> annually1 & e five ye>s ! data w be re>rang$1 revis$1 correct$1 & !n publi%$ 9 book =m4 ,! numb] ( prep>ations to be complet$ ye>ly is n fix$4 ,!re w be1 x is c]ta91 ab\t tw5ty2 & x is hop$1 z ! int]e/ is /imulat$ 9 ?is "w1 t ?is numb] may increase consid]ably4 ,! editors especially desire to solicit contributions f o!r *emi/s1 n only 9 ?is c\ntry b abroad4 ,:5ev] a comp\nd is ?or\ghly & ext5sively /udi$ 9 connection ) "s rese>*1 x is hop$ t complete directions = its prep>ation w be assembl$ & s5t to ! editor4 ,he w !n h !m *eck$ & publi%$ 9 a subsequ5t numb]4 ,directions = ! prep>ation ( sub/ances already on ! m>ket are ne$$ to make ?is "w complete & w be gladly accept$4 ,x w1 ( c\rse1 be recogniz$ t an occasional mi/ake or omission w inevitably be f\nd 9 su* a pamphlet z ?is :i* conta9s s _m ref]5ces & =mulae4 ,! committee on publication w !re=e deem x a favor if !y are notifi$ :5 any su* error is discov]$4 ,x is hop$ also t if any *emi/ kn[s a bett] me?od = ! prep>ation ( any ( ! comp\nds consid]$1 or if anyone discov]s any improvem5ts 9 ! me?ods1 he w furni% ! au?ors ) su* in=mation4 ,any po9ts :i* may arise 9 reg>d to ! v>i\s prep>ations w be gladly discuss$4 ,9 conclusion1 ! editors are ready to d all !y c to make ?is4 "w successful1 & welcome sugge/ions ( any k9d4 ,!y feel t ! success ( ! s]ies w und\bt$ly dep5d ^u ! coop]ation ( o!rs1 & z its success promises to be important to rese>* *emi/s1 ! editors urge all int]e/$ to assi/4 ,,! ,,editors ,,table ,,( ,,cont5ts ,,page ,i4 ,,b5zalacetoph5one4444444444444444444444 44444#a ,,ii4 ,,b5zyl ,,b5zoate44444444444444444444444444444#e ,,iii4 ,,b5zyl ,,cyanide44444444444444444444444444444#i ,,iv4 a1 g-,,di*loroacetone44444444444444#ac ,v4 p-,,dime?ylam9ob5zaldehyde44444444444444 4444#ag ,,vi4 ,,e?yl ,,oxalate4444444444444444444444444444444 #bc ,,vii4 ,,e?yl ,,ph5ylacetate444444444444444444444444#b g ,,viii4 ,,glyc]ol a1 g-,,di*lorohydr94444#bi ,,ix4 ,,glyc]ol a-,,mono*lororydr9444444444444#cc ,x4 ,,hydraz9e ,,sulfate4444444444444444444444444444#cg ,,xi4 ,,mesityl5e44444444444444444444444444444 44444#da ,,xii4 ,,me?yl ,,r$444444444444444444444444444444444#dg ,,xiii4 p-,,nitrob5zoic ,,acid44444444444444444444444#ec ,,xiv4 p-,,nitrob5zyl ,,cyai,,de4444444444444444444444#eg ,,xv4 p-,,nitroph5ylacetic ,,acid44444444444444444444#ei ,,xvi4 ,,nitroso-b-,,naph?ol4444444444444444444 4#fa ,,xvii4 ,,ph5ylacetic ,,acid4444444444444444444444444#fc ,,xviii4 ,,ph5ylacetyl5e4444444444444444444444444 4#fg ,,xix4 ,,ph5ylhydraz9e4444444444444444444444444 444#ga ,,xx4 ,,ph?alimide4444444444444444444444444444 44444#ge ,,xxi4 ,,qu9ol9e4444444444444444444444444444444 444#gi ,,xxii4 ,,qu9one44444444444444444444444444444444 444#he ,,xxiii4 ,,sodium p-,,tolu5esulf9ate4444444444444444#hi ,,xxiv4 #a1c1e-,,tr9trob5z5e44444444444444444444 44#ic ,,xxv4 #b1d1f-,,tr9trob5zoic ,,acid444444444444444444#ie ,,index444444444444444444444444444444444 4444#ii ,,organic ,,syn!ses ,i ,,b5zalacetoph5one ,c#f;,h#e;,,*o ,c#f;,h#e;,,co*#c 7,na,o,h7-- ,c#f;,h#e;,,*,,*coc#f;,h#e ,h#b,o ,prep>$ by ,e4 ,p4 ,,kohl] & ,e4 ,m4 ,,*adwell4 ,*eck$ by ,h4 ,t4 ,,cl>ke & ,r4 ,p4 ,,leavitt4 #a4 ,proc$ure ,a ,,solution ( #bah g4 ( sodium hydroxide 9 #aifj g4 ( wat] & #ajjj g4 ( #ie p] c5t alcohol are introduc$ into a #eejj-;cc4 bottle :i* is loosely cov]$ ) a p]=at$ disk ( c>dbo>d1 suppli$ ) an effective /irr]1 & support$ 9 a l>g] vessel s z to p]mit cool+ ) crack$ ice4 ,into ! alkal9e solution1 #ebj g4 ( pure acetoph5one is p\r$1 ! bottle is rapidly surr\nd$ ) crack$ ice1 & ! /irr] />t$2 #dfj g4 ( b5zaldehyde 7,u4 ,s4 ,p47 are !n add$ at once4 ,! temp]ature ( ! mixture %\ld n be bel[ #ae'j & x %\ld n be all[$ to rise above #cj'j dur+ ! reaction4 ,if x t5ds to d s1 ! /irr+ is n suffici5tly vigor\s4 ,x is advantage\s1 ?\gh n ess5tial1 to inoculate ! mixture ) a little p[d]$ b5zalacetoph5one aft] /irr+ = half an h\r4 ,aft] two to ?ree h\rs1 ! mixture becomes s ?ick t ! /irr+ is no long] effective4 ,! /irr] is !n remov$ & ! mixture left to itself 9 an ice-box = ab\t t5 h\rs4 ,! mixture n[ is a ?ick pa/e compos$ ( small %ot-l gra9s susp5d$ 9 an almo/ colorless liquid4 ,x is cool$ 9 a freez+ mixture & !n ei!r c5trifug$ or filt]$ on a l>ge ,bu*n] funnel1 wa%$ ) wat] until ! wa%+s are neutral to litmus1 & f9ally wa%$ ) #bjj cc4 ( alcohol1 :i* has previ\sly be5 cool$ to #j'j4 ,aft] ?or\gh dry+ 9 ! air1 ! crude product weighs ab\t #hhj g4 7yield #ig p] c5t ( ! !oretical am\nt7 & melts at #ej-ed'j4 ,x is suffici5tly pure = mo/ purposes b t5aci\sly holds traces ( wat]4 ,x is mo/ readily purifi$ by recry/allization f f\r to f\r & a half times its weight ( #ie p] c5t alcohol4 ,eight hundr$ & eighty grams ( crude product give #ggj g4 7#he p] c5t ( ! !oretical am\nt7 ( light-yell[ mat]ial 7m4 p4 #ee-eg'j7 & #dj-ej g4 t require recry/allization4 #b4 ,notes ,! acetoph5one %\ld be z pure z possible 7m4 p4 #bj'j74 ,comm]cial acetoph5one conta9s v>iable quantities ( impurities :i* r$uce ! yield4 ,by di/ill+ comm]cial acetoph5one ) ! help ( a good /ill-head 7pref]ably "u dim9i%$ pressure7 & us+ only ! fraction :i* boils at #bja-bjb'j 7#gf-gg'j_/aj mm47 great] quantities ( b5zalacetoph5one c be obta9$ ?an by us+ ! entire sample4 ,comm]cial b5zaldehyde c be us$ 9 place ( ! pur] product1 b ! am\nt us$ mu/ be increas$ to make up = ! impurities :i* are pres5t4 ,if ! temp]ature is too l[1 or ! /irr+ too sl[1 ! product sep>ates z an oil1 :i* lat] solidifies 9 l>ge lumps4 ,if ! temp]ature is all[$ to rise above #cj'j1 second>y reactions dim9i% bo? ! yield & ! purity ( ! product4 ,! mo/ favorable temp]ature is #be'j4 ,9 recry/alliz+ b5zalacetoph5one1 ! alcohol %\ld be saturat$ at #ej'j4 ,if ! solution is saturat$ above ?is temp]ature1 ! b5zalacetoph5one t5ds to sep>ate z an oil4 ,! solution %\ld be all[$ to cool gradually1 & %\ld f9ally be *ill$ 9 a freez+ mixture4 #c4 ,o!r ,me?ods ( ,prep>ation ,! me?ods = produc+ b5zalacetoph5one are3 ! action ( acids on a mixture ( b5zaldehyde & acetoph5one or on a solution ( ^! sub/ances 9 glacial acetic acid2#a ! cond5sation ( b5zaldehyde & acetoph5one ) a #cj p] c5t solution ( sodium me?ylate at l[ temp]atures2#b ! action ( sodium hydroxide on an alcoholic solution ( b5zaldehyde & acetoph5one4#c ,! me?ods bas$ on ! use ( acids z cond5s+ ag5ts 7 n consid]$1 because ,clais51 :o devis$ !m1 ab&on$ !m aft] he f\nd t alkal9e cond5s+ ag5ts gave bett] results4 ,! prelim9>y exp]im5ts %[$ t cond5sation ) sodium me?ylate takes a long "t & gives a product :i* x is difficult to h&le 9 l>ge quantities4 ,! me?od devis$ by ,ko/anecki & ,rossba*#c has !re=e be5 develop$4 #a ,b]4 #ad1 #bdfc 7#ahha74 #b ,b]4 #bj1 #feg 7#ahhg74 #c ,b]4 #bi1 #adib 7#ahif74 ,,ii ,,b5zyl ,,b5zoate #b ,c#f;,h#e;,,*o ,c#f;,h#e;,,*#b,o,na-- ,c#f;,h#e;,,co#b;,,*#b;,c#f;,h#e ,c#f;,h#e;,,*#b,o,na ,prep>$ by ,o4 ,,kamm & ,w4 ,f4 ,,kamm4 ,*eck$ by ,,rog] ,,adams & ,r4 ,l4 ,,j5k9s4 #a4 ,proc$ure ,,?ree grams ( metallic sodium are dissolv$ by w>m+ = half an h\r 9 #gj g4 ( pure b5zyl alcohol 7see notes71 & aft] ! mixture has cool$ to room temp]ature ! solution is add$ gradually1 ) ?or\gh mix+1 to #ded g4 ( c4 p4 b5zaldehyde 7:i* mu/ conta9 ,,less ?an #a p] c5t ( b5zoic acid74 ,! reaction mixture has a t5d5cy to become w>m1 b ! temp]ature %\ld be kept slightly bel[ #ej-fj'j by cool+1 if necess>y4 ,a pa/y gelat9\s mass results4 ,aft] ab\t half an h\r ! temp]ature ( ! mixture no long] rises2 x is !n w>m$ on ! wat] ba? = ab\t "o or two h\rs1 ) occasional %ak+4 ,! cool$ reaction product is treat$ ) #bjj cc4 ( wat]1 ! lay] ( oil sep>at$1 wa%$ once ) a second portion ( wat]1 & subject$ to di/illation 9 vacuo4 ,! fir/ fraction ( ! di/illate conta9s b5zyl alcohol toge!r ) un*ang$ aldehyde1 z well z a small quantity ( wat]4 ,! temp]ature !n rises rapidly to ! boil+-po9t ( b5zyl b5zoate1 :5 ! receiv]s are *ang$4 ,! product boils at #ahd-ahe'j_/ae mm41 & analysis by saponification %[s x to consi/ ( #ii p] c5t e/]4 ,a yield ( #daj-dbj g4 is obta9$1 :i* corresponds to #ij-ic p] c5t ( ! !oretical am\nt4 ,?is b5zyl b5zoate sup]cools readily1 b aft] solidify+ melts )9 "o degree ( ! highe/ record$ value 7#ai4d'j7 & !re=e ne$ n be refractionat$1 unless mat]ial ( exceptional grade is requir$4 #b4 ,notes ,9 ! pres5ce ( sodium b5zylate two molecules ( b5zaldehyde react ) ! alcoholate to =m an addition product4 ,:5 ! reaction mixture is ov]heat$ an important side reaction may occur1 z foll[s3 _/ ,,o*#b;,c#f;,h#e ,c#f;,h#e;,c -- ,,o*#b;,c#f;,h#e -- ,c#f;,h#e;,,co#b,na ,c#f;,h#e;,,*#b,,o*#b;,c#f;,h#e ,o,na ,dib5zyl e!r no d\bt =ms ! *ief impurity 9 b5zyl b5zoate4 ,s9ce ! boil+-po9t ( ! =m] lies ne> t ( ! e/]1 x is n remov$ dur+ ! process ( purification by di/illation4 ,! causes ( v>iations 9 yield by ! use ( ! old] me?ods c n[ be expla9$4 ,:5 b5zaldehyde is add$ ,,to ,,! ,,alcoholate1 & especially :5 ! latt] is /ill w>m1 local ov]heat+ results2 9 fact1 ! temp]ature may rise f> above #ajj'j ) ! result t b5zyl e!r is =m$4 ,simultane\sly1 ! sodium b5zylate is conv]t$ into sodium b5zoate1 :i* is ( no value = induc+ ! desir$ reaction1 & consequ5tly v little b5zyl b5zoate is obta9$4 ,! same side reactions expla9 ! failure ( ?is exp]im5t :5 ! b5zyl alcohol us$ 9 prep>+ ! cataly/ 7sodium b5zylate7 is contam9at$ ) b5zaldehyde4 ,! b5zyl alcohol us$ 9 ?is prep>ation mu/ be free f impurities1 especially aldehyde4 ,"o cc4 dissolv$ 9 #ej cc4 ( wat] & treat$ ) a fre%ly prep>$ cle> solution ( ph5ylhydraz9e acetate %\ld give no appreciable precipitate4 ,if x is n pure1 x mu/ fir/ be treat$ ) alkali z describ$ bel[4 ,! b5zaldehyde %\ld be titrat$ 9 ord] to det]m9e its acidity4 ,if x is f\nd to conta9 suffici5t b5zoic acid to react ) a consid]able proportion ( ! sodium alcoholate1 a poor yield ( e/] w be obta9$4 ,less ?an #a p] c5t ( b5zoic acid w n int]f]e s]i\sly ) ! yields obta9$1 b ! pres5ce ( l>g] quantities ( acid w be f\nd to be detrim5tal & mu/ be remov$ by wa%+ ! b5zaldehyde ) a sodium c>bonate solution & r$i/ill+ ) ! precautions necess>y to prev5t too free an access ( air to ! di/illate4 ,! ord] ( mix+ ! reag5ts & ! temp]ature ( ! +r$i5ts at ! "t ( mix+ are ! mo/ important factors 9 ! exp]im5t4 ,! temp]ature at :i* ! reaction mixture is ma9ta9$ aft] mix+1 provid$ t x is held bel[ #ajj'j1 is less important f ! /&po9t ( purity4 ,! reaction mixture is n treat$ ) acetic acid1 z usually recomm5d$1 = ! reason t su* a proc$ure yields a f9al product contam9at$ ) b5zoic acid1 unless an alkal9e wa% is appli$ subsequ5tly4 ,! recov]$ b5zyl alcohol c be us$ = ! prep>ation ( a second lot ( b5zyl b5zoate only aft] x has be5 boil$ ) /rong sodium hydroxide to remove all traces ( b5zaldehyde4 #c4 ,o!r ,me?ods ( ,prep>ation ,b5zyl b5zoate has be5 id5tifi$ 9 c]ta9 natural plant products4#a ,9 ! laboratory x has be5 prep>$ by ! action ( 7a7 b5zoyl *loride ^u b5zyl alcohol1#b 7b7 b5zyl *loride ^u sodium b5zoate1 & 7c7 alcoholates ^u b5zaldehyde4#c ,rec5tly1 ,gomb]g & ,bu*l]#d h %[n t reaction 7b7 may be conduct$ ev5 ) aque\s solutions ( sodium b5zoate4 #a ,ann4 #aeb1 #aca 7#ahfi74 #b ,gmel9's ,h&bu* d] ,organ4 ,*em4 #c1 #dj4 #c ,b]4 #bj1 #fdi 7#ahhg74 ,cf4 also ,j4 ,*em4 ,soc4 #ge1 #aaee 7#ahii74 #d ,j4 ,am ,*em4 ,soc4 #db1 #bjei 7#aibj74 ,! ,clais5 me?od 7c7 furni%es ! mo/ conv5i5t & practical proc$ure = ! prep>ation ( ?is e/]4 ,! mat]ials are *eap1 ! exp]im5tal proc$ure simple1 & ! product obta9$ is free f objectionable traces ( b5zyl *loride4 ,un=tunately ! me?od has be5 f\nd to be extremely erratic 9 reg>d to yield 7#aj-ie p] c5t71 z well z 9 reg>d to purity ( ! product 7#hg-ig p] c5t e/]74#a ,z a result ( ! pres5t /udy1#b causes = v>iations are fully acc\nt$ = & ! proc$ure has be5 conv]t$ into a satisfactory me?od ( prep>ation4 #a ,c4 ,a4 #ad1 #cejj 7#aibj74 #b ,j4 ,am4 ,ph>m4 ,assoc4 #aa1 #eii 7#aibb74 ,,iii ,,b5zyl ,,cyanide ,c#f;,h#e;,,*#b;,cl ,na,c,n-- ,c#f;,h#e;,,*#b;,,cn ,na,cl ,prep>$ by ,,rog] ,,adams & ,a4 ,f4 ,,?al ,*eck$ by ,o4 ,,kamm & ,a4 ,o4 ,,mat!ws4 #a4 ,proc$ure ,,9 a #e-l4 r\nd-bottom flask1 fitt$ ) a /opp] hold+ a reflux cond5s] & sep>atory funnel1 are plac$ #ejj g4 ( p[d]$ sodium cyanide 7#if-ih p] c5t pure7 & #dej cc4 ( wat]4 ,! mixture is w>m$ on a wat] ba? 9 ord] to dissolve mo/ ( ! sodium cyanide1 & !n #a kg4 ( b5zyl *loride 7b4 p4 #agj-ahj'j7 mix$ ) #a kg4 ( alcohol is run 9 ?r\gh ! sep>atory funnel 9 ! c\rse ( "o-half to ?ree-qu>t]s ( an h\r4 ,! mixture is !n heat$ ) a reflux cond5s] on ! /eam ba? = f\r h\rs1 cool$ & filt]$ ) suction to remove mo/ ( ! sodium *loride4 ,x is well to wa% ! filt]$ salt ) a small portion ( alcohol 9 ord] to remove any b5zyl cyanide :i* may h be5 me*anically held4 ,! flask is n[ fitt$ ) a cond5s]1 & z mu* alcohol z possible is di/ill$ (f on ! /eam ba?4 ,! residual liquid is cool$1 filt]$ if necess>y1 & ! lay] ( b5zyl cyanide sep>at$4 ,?is crude b5zyl cyanide is n[ plac$ 9 a ,clais5 di/ill+ flask & di/ill$ 9 vacuo1 ! wat] & alcohol com+ ov] fir/1 & f9ally ! cyanide4 ,x is advantage\s to use a fractionat+ column or1 bett] /ill1 a ,clais5 flask ) a modifi$ side-arm#a 7,vol4 ,i1 p4 #dj1 ,fig4 #c7 :i* gives ! same effect z a fractionat+ column4 ,! mat]ial is collect$ f #ace-adj'j_/ch mm4 7#aae-abj'j_/aj mm474 ,! yield is #gdj-hcj g4 7#hj-ij p] c5t ( ! !oretical am\nt74 #a ,j4 ,am4 ,*em4 ,soc4 #ci1 #bgah 7#aiag74 #b4 ,notes ,! quality ( ! b5zyl *loride m>k$ly affects ! yield ( pure b5zyl cyanide4 ,if a poor te*nical grade is us$1 ! yields w n be m ?an #fj-ge p] c5t ( ! !oretical1 :]eas consi/5t results ( ab\t #he p] c5t or m 7 always obta9$ :5 a product 0 us$ t boil$ ov] #aj'j4 ,! te*nical b5zyl *loride at h& yield$ on di/illation ab\t #h p] c5t ( high-boil+ mat]ial2 a te*nical grade f ano!r s\rce 0 ( unusual purity & boil$ ov] a #b'j range = ! mo/ "p4 ,x is advisable to di/il (f ! la/ portion ( alcohol & wat] 9 vacuo & also to di/il ! b5zyl cyanide 9 vacuo1 s9ce "u ord9>y pressures a :ite solid inv>iably sep>ates dur+ ! di/illation4 ,"o me?od ( purify+ ! b5zyl cyanide is to /eam di/il x aft] ! alcohol has be5 fir/ di/ill$ f ! reaction mixture4 ,at ord9>y pressures1 ?is /eam di/illation is v sl[ &1 ) an ord9>y cond5s]1 requires eighte5 to tw5ty h\rs 9 ord] to remove all ( ! volatile product f a run ( #ejj g4 ( b5zyl *loride4 ,! di/illate sep>ates into two lay]s2 ! b5zyl cyanide lay] is remov$ & di/ill$4 ,! product obta9$ 9 ?is way is v pure & conta9s no t>ry mat]ial1 &1 aft] ! excess ( b5zyl *loride has be5 remov$1 boils practically con/ant4 ,?is /eam di/illation is h>dly advisable 9 ! laboratory4 ,! b5zyl cyanide1 prep>$ accord+ to ! proc$ure z outl9$1 is collect$ ov] a #e'j range4 ,x v>ies 9 appe>ance f a colorless to a /raw-color$ liquid & (t5 develops appreciable color ^u /&+4 ,= a product ( special purity1 x %\ld be r$i/ill$ "u dim9i%$ pressure & collect$ ov] a #a-b'j range4 ,= mo/ purposes1 su* z ! prep>ation ( ph5ylacetic acid or e/]1 ! fraction boil+ #ace-adj'j_/ch mm4 is p]fectly satisfactory4 #c4 ,o!r ,me?ods ( ,prep>ation ,b5zyl cyanide occurs naturally 9 c]ta9 oils4#a ,! only feasible me?od ( prep>+ x t has be5 describ$ 9 ! lit]ature is ! "o 9 :i* alcoholic potassium cyanide & b5zyl *loride#b are employ$4 ,! *eap] sodium cyanide is j z satisfactory z ! potassium cyanide & !re=e is ! be/ mat]ial to use4 ,gomb]g has rec5tly prep>$ b5zyl cyanide f b5zyl *loride & an aque\s solution ( sodium cyanide4#c #a ,b]4 #g1 #eai1 #abic 7#ahgd72 #cb1 #bccg 7#ahii7 #b ,ann4 #if1 #bdg 7#ahee72 ,b]4 #c1 #aih 7#ahgj72 #ad1 #afde 7#ahha72 #ai1 #aiej 7#ahhf74 #c ,j4 ,am4 ,*em4 ,soc4 #db1 #bjei 7#aibj74 ,,iv a1 g-,,di*loroacetone ,,*#b;,cl,c,h,o,h,c,h#b;,cl ,o7,na#b;,cr#b,o#g ,h#b,,s#d7-- ,,*#b;,cl,c,o,c,h#b;,cl ,h#b,o ,prep>$ by ,j4 ,b4 ,,conant & ,o4 ,r4 ,,quayle4 ,*eck$ by ,a4 ,w4 ,,dox1 ,l4 ,,yod]1 & ,o4 ,,kamm4 #a4 ,proc$ure ,,9 a #b-l4 flask are plac$ #cge g4 ( comm]cial sodium di*romate1 #bbe cc4 ( wat]1 & #cjj g4 ( di*lorohydr9 7b4 p4 #fh-ge'j_/ad mm474 ,! flask is set 9 a wat] ba? & equipp$ ) a !rmomet] & me*anical /irr]4 ,! cont5ts are vigor\sly /irr$1 & #dej g4 ( sulfuric acid1 dilut$ ) #aae g4 ( wat]1 are introduc$ dur+ ! c\rse ( sev5 to eight h\rs4 ,x is conv5i5t to add ! acid at t5-m9ute int]vals4 ,! temp]ature is kept betwe5 #bj'j & #be'j dur+ ! entire reaction2 ?is is accompli%$ by add+ a little ice to ! wat] ba? f "t to "t4 ,! /irr+ is cont9u$ = sixte5 to sev5te5 h\rs aft] all ! acid has be5 add$2 z !re is v little heat evolv$ dur+ ?is "p ( ! reaction1 ! wat] ba? may be all[$ to come to room temp]ature4 ,suffici5t wat] is n[ add$ to ! mixture to dissolve ! pa/y *romium salts 7#cjj-hjj cc474 ,! mass ( cry/als is !n rapidly filt]$ on a ,bu*n] funnel & suck$ z dry z possible4 ,! cry/als are !n transf]r$ to a small laboratory c5trifuge & c5trifug$ = sev]al m9utes4 ,! cry/als are wa%$ 9 ! c5trifuge ) ab\t #ae-be cc4 ( ice wat]1 !n ) #aj-ae cc4 ( cold petroleum e!r1 & f9ally c5trifug$ till z dry z possible4 ,! crude di*loroacetone is dri$ 9 a vacuum desiccator ov] sulfuric acid ov]night ,x weighs ab\t #bbj g4 ,! crude product is be/ purifi$ by di/illation f a #bej-;cc4 di/ill+ flask fitt$ ) an air cond5s]4 ,a v small fraction 7#aj-ae g47 ( l[-boil+ mat]ial is obta9$1 & ! di*loroacetone 7#agj-age'j7 is !n collect$4 ,x solidifies 9 ! receiv] to a :ite cry/all9e mass :i* weighs #bjj-bbj g4 7#fe-gj p] c5t ( ! !oretical am\nt74 ,a few grams m may be obta9$ by *ill+ ! l[-boil+ fraction & filt]+ (f ! wat]4 #b4 ,notes ,great caution %\ld be ex]cis$ 9 work+ ) di*loroacetone1 z x is extremely la*rymatory & bli/]s ! sk94 ,9 transf]r+ ! cry/als f ! reaction flask to ! ,bu*n] funnel x is necess>y to use a c]ta9 am\nt ( wat] to dissolve ! pa/y *romium salts :i* are o!rwise q impossible to filt]4 ,! am\nt necess>y v>ies greatly 9 diff]5t runs1 accord+ to ! mann] 9 :i* ! *romium salts sep>ate4 ,! am\nt ( ?is wat] is kept l[ 9 ord] to dissolve z little ( ! product z possible4 ,nev]!less1 #aj-ae g4 ( di*loroacetone are ?us dissolv$2 ?is mat]ial1 toge!r ) a little un*ang$ di*lorohydr91 may be recov]$ by a long proc$ure involv+ extraction ) e!r & sodium bisulfite4 ,?is is n pr(itable1 h[ev]4 ,x is n necess>y to wa% ! cry/als 9 ! c5trifuge until !y are :ite4 ,a small am\nt ( *romic salt w n int]f]e ) ! subsequ5t purification4 ,comm]cial sodium di*romate is hygroscopic & conta9s v>y+ am\nts ( wat]4 ,! #cge g4 requir$ 9 ^! directions are equival5t to #cai g4 ( anhydr\s mat]ial4 ,! total "t requir$ = ! oxidation is tw5ty-f\r h\rs4 ,x is conv5i5t to />t ! reaction 9 ! morn+4 ,9 ?is way ! la/ "p ( ! reaction1 :i* requires no att5tion1 w be accompli%$ dur+ ! night4 ,! regulation ( ! temp]ature is necess>y1 z ! reaction proce$s v sl[ly bel[ #bj'j2 on ! o!r h&1 ! di*loroacetone itself is oxidiz$ at a some:at high] temp]ature ?an #be'j4 #c4 ,o!r ,me?ods ( ,prep>ation ,! prep>ation ( di*loroacetone by ! foll[+ me?ods is describ$ 9 ! lit]ature3 ! direct *lor9ation ( acetone2#a ! oxidation ( di*lorohydr92#b ! action ( silv] *loride on diiodoacetone2#c ! action ( di*loroprop5e 7,,*#b;,cl-,c,cl,,*#b7 & hypo*lor\s acid2#d ! action ( hydro*loric acid on e?oxymono*loroacetoacetic e/]2#e & ! hydrolytic cleavage ( di*loroacetoacetic e/]4#f #a ,jahresb4 #ahei1 #cde2 #ahga1 #eca2 ,j4 prakt4 ,*em4 7#b7d1 #eb 7#ahga72 ,b]4 #g1 #dfg 7#ahgd72 #h1 #accj1 #adch 7#ahge72 #bf1 #eih 7#ahic72 #db1 #cbcc 7#aiji72 ,ann4 #bgi1 #cae 7#ahid7 #b ,b]4 #f1 #abaj 7#ahgc72 #ac1 #agjf 7#ahhj72 #db1 #cbcc 7#aiji72 ,ann4 #bjh1 #cee 7#ahha72 #bfi1 #df 7#ahib72 ,ann4 *im4 phys4 7#f7 #i1 #ade 7#ahhf72 ,bull4 soc4 *im4 7#b7 #cf1 #ai 7#ahha74 #c ,ann4 #aib1 #ic 7#ahgh74 #d ,compt4 r5d4 #id1 #adbh 7#ahhb74 #e ,ann4 #bfi1 #ah 7#ahib74 #f ,b]4 #dc1 #cecc 7#aiaj74 ,v p-,,dime?ylam9ob5zaldehyde 7,,*#c7b,,nc#f;,h#e ,,hno#b-- 7,,*#c7b,,nc#f;,h#d,,no ,h#b,o 7,,*#c7b,,nc#f;,h#d,,no #b;,,h*o #b;,c#f;,h#e,n7,,*#c7b -- 7,,*#c7b,,nc#f;,h#d,n ,,*c#f;,h#d,n7,,*#c7b #b;,h#b7 7,,*#c7b,,nc#f;,h#d;,,*o 7,,*#c7b,,nc#f;,h#d,n ,,*c#f;,h#d,n7,,*#c7b ,,h*o--7 ,,*#c7b,,nc#f;,h#d,n ,,*#b 7,,*#c7b,,nc#f;,h#d;,,*o ,prep>$ by ,,rog] ,,adams & ,g4 ,h4 ,,coleman4 ,*eck$ by ,h4 ,t4 ,,cl>ke & ,w4 ,w4 ,,h>tman4 #a4 ,proc$ure ,,9 a #c-l4 r\nd-bottom flask fitt$ ) a me*anical /irr] #aej g4 ( te*nical dime?ylanil9e are dissolv$ 9 #gej cc4 ( dilut$ hydro*loric acid 7#a "p conc5trat$ acid to #a "p wat]74 ,?is solution is n[ cool$ to #j'j & a solution 7previ\sly cool$ to #j'j7 ( #ij g4 ( te*nical sodium nitrite 9 #aej cc4 ( wat] is add$ ?r\gh a sep>atory funnel4 ,dur+ ! addition ( ! nitrite solution1 me*anical /irr+ %\ld be employ$ & ! flask cool$ well ) ice & salt4 ,! addition is made at su* a rate 7?irty to =ty m9utes = ! entire addition7 t ! temp]ature does n rise above #e'j4 ,! precipitate ( nitroso dime?ylanil9e hydro*loride is filt]$ (f ) suction1 !n wa%$ ) ab\t #cjj cc4 ( dilut$ hydro*loric acid 7#a3a74 ,9 a #b-l4 beak]1 #ahj g4 ( te*nical dime?ylanil9e1 #abe cc4 ( =maldehyde 7te*nical #dj p] c5t71 & #cjj cc4 ( conc5trat$ hydro*loric acid are mix$ & heat$ = t5 m9utes on a /eam ba?4 ,! mixture is n[ plac$ 9 a hood & ! nitroso dime?ylanil9e add$ all at once1 or z rapidly z possible4 ,! beak] is !n cov]$ ) a wat* glass4 ,a vigor\s reaction soon occurs & is complete 9 ab\t five m9utes4 ,! result+ solution is transf]r$ to a #e-l4 flask & dilut$ to #d l42 /irr+ is />t$1 & a #be p] c5t solution ( sodium hydroxide is add$ until ! r$ color disappe>s 7ab\t #fej cc4 are requir$74 ,! yell[ b5zylid5e comp\nd sep>ates1 is filt]$ ) suction & wa%$ ) wat]4 ,! moi/ precipitate is transf]r$ to a #d-l4 glass j>1 cov]$ ) #ajjj cc4 ( #ej p] c5t acetic acid & #bej cc4 ( =maldehyde1 & /irr$ until tw5ty m9utes aft] ! b5zylid5e comp\nd has gone into solution4 ,:ile ! mixture is be+ /irr$ vigor\sly to prev5t lump+ ( ! precipitate1 #djj cc4 ( wat] & #bjj g4 ( crack$ ice are add$ dur+ ! c\rse ( five m9utes4 ,! dime?ylam9ob5zaldehyde g5]ally sep>ates gradually 9 fifte5 to tw5ty m9utes1 b 9 "s cases does n4 ,if ! precipitate does n =m1 ! solution is plac$ 9 a refrig]ator = a few h\rs or ov]night4 ,! mixture is filt]$ ) suction & wa%$ at lea/ t5 times ) #cjj cc4 ( wat]4 ,! precipitate is suck$ z dry z possible = fifte5 to ?irty m9utes4 ,! slightly moi/ aldehyde is di/ill$ "u dim9i%$ pressure f an oil ba?1 by means ( a #a-l4 ,clais5 flask4 ,a small am\nt ( wat] comes ov] fir/1 !n ! !rmomet] rises rapidly to ! boil+ po9t ( ! aldehyde 7#ahj'j_/bb mm474 ,9 *ang+ receiv]s betwe5 ! wat] fraction & ! aldehyde1 c>e %\ld be tak5 to keep ! side-arm ( ! di/ill+ flask w>m2 o!rwise1 on />t+ ! di/illation aga91 ! aldehyde w solidify 9 ! side-arm & cause tr\ble4 ,x is advisable n to collect ! v la/ portion ( ! di/illate ) ! ma9 portion1 z ! =m] is frequ5tly q r$4 ,?is is be/ add$ to crude mat]ial f ano!r run4 ,! ma9 di/illate is dissolv$ 9 #ajj cc4 ( alcohol 9 a #b-l4 beak]1 !n #ajjj cc4 ( wat] are gradually add$ ) vigor\s me*anical /irr+ to prev5t lump+4 ,! aldehyde sep>ates1 & is filt]$ ) suction4 ,! product1 :5 dry1 weighs #abe-acj g4 7#ef-ei p] c5t ( ! !oretical am\nt71 & melts at #gc'j4 ,! aldehyde prep>$ 9 ?is way is 9 ! =m ( small granul> cry/als1 :i* v>y 9 diff]5t runs f a fle% color to a lemon yell[4 ,= practically all purposes1 ?is slightly color$ product is entirely satisfactory & is ess5tially pure1 z c be judg$ by ! melt+ po9t4 ,= reag5t purposes x is desirable to remove ! color completely1 p>ticul>ly s9ce ! product obta9$ z j describ$ has a t5d5cy to take on a r$di% t+e on exposure to light4 ,fur!r purification c be accompli%$ by dissolv+ ! aldehyde 7x dissolves sl[ly7 9 dilute hydro*loric acid 7#a "p ( conc5trat$ acid1 sp4 gr4 #a4ai1 to #f p>ts ( wat]71 #abe g4 ( aldehyde requir+ #gjj cc4 ( ! acid4 ,! solution is plac$ 9 a j> & dilut$ ) half its volume ( wat]1 & dilute sodium hydroxide solution 7#ae-bj p] c5t7 is add$ sl[ly ) me*anical /irr+4 ,at ! beg9n+1 ! aldehyde comes d[n slightly color$4 ,aft] ab\t #aj to #cj g4 are precipitat$1 h[ev]1 ! product appe>s :ite2 ?is po9t c be readily se54 ,! fir/ precipitate is filt]$ (f & add$ to ! next run ( crude mat]ial1 or fractionally precipitat$ aga9 f hydro*loric acid4 ,! re/ ( ! aldehyde is n[ precipitat$ by means ( m sodium hydroxide solution1 & comes d[n almo/ :ite4 ,at ! v end ( ! neutralization1 p>ticul>ly if ! orig9al product 0 q yell[1 ! la/ #d to #e g4 ( aldehyde %\ld be precipitat$ sep>ately1 z !y are incl9$ to be slightly color$4 ,if too mu* alkali is add$ t[>ds ! end ( ! neutralization1 a br[n color appe>s1 b ! addition ( a little hydro*loric acid w de/roy ?is color4 ,! ma9 portion ( ! precipitate is filt]$ & dri$2 x weighs #ie-ajj g41 m4 p4 #gc'j4 ,! succe$+ runs yield #aae-abh g4 ( f9i%$ product1 on acc\nt ( ! extra crude mat]ial obta9$ f ! di/illation & reprecipitation ( ! previ\s run4 #b4 ,notes ,! aldehyde t is obta9$ )\t reprecipitation gradually takes on a p9ki% t+e on exposure to light4 ,aft] ! reprecipitation1 h[ev]1 ?is *>act]i/ic disappe>s4 ,?or\gh wa%+ ( ! crude aldehyde is p>ticul>ly desirable1 z x removes a r$di% impurity :i* t5ds to di/il ov] & color ! product lemon yell[ or sometimes ev5 br[ni% yell[4 ,:5 su* a br[ni% product is obta9$1 x is q necess>y to make a second precipitation1 z well z to obs]ve ! directions m5tion$ 9 ! purification ( ! crude aldehyde1 namely1 to precipitate ! fir/ few grams & ! la/ few grams ( ! aldehyde sep>ately4 ,! precaution ( reject+ ! fir/ & la/ portions ( ! precipitate is unnecess>y 9 ! reprecipitation4 ,9 ! reprecipitation ( a deeply color$ product1 ! portion ( aldehyde at ! end may be ev5 purpli% 9 color & p>ticul> c>e mu/ be tak5 to keep ?is sep>ate4 ,vigor\s me*anical /irr+ mu/ be employ$ dur+ ! precipitation ( ! crude aldehyde1 z o!rwise l>ge lumps are =m$ :i* make wa%+ difficult4 ,a previ\s inve/igator has m5tion$ t ! crude product mu/ be dri$ be=e di/ill+4 ,?is1 h[ev]1 is unnecess>y4 ,if ! aldehyde is dri$ be=e di/ill+1 x is possible to use a #ejj-;cc4 di/ill+ flask in/ead ( a #a-l "o4 ,9 purify+ ! aldehyde by dissolv+ 9 acid & reprecipitat+1 x is ess5tial n to use /rong] acid ?an t specifi$ 7#a3f71 z /rong] acid causes a deep5+ ( ! color ( ! solution4 ,if ! conc5trat$ acid1 :i* is to be dilut$ & us$ 9 ?is proc$ure1 does n h a sp4 gr4 ( #a4ai1 x w be necess>y to add ! equival5t am\nt ( weak] acid 9 ord] to dissolve ! p-dime?ylam9ob5zaldehyde4 ,9 purify+ ! aldehyde1 sodium c>bonate may be us$ 9 place ( sodium hydroxide = precipitation1 b x causes mu* foam+4 ,:5 ! app>atus = di/ill+1 etc41 is all set up1 a run su* z describ$ above requires ab\t five to six h\rs = completion4 #c4 ,o!r ,me?ods ( ,prep>ation p-,dime?ylam9ob5zaldehyde has be5 made by ! cond5sation ( *loral ) dime?ylanil9e1 & subsequ5t hydrolysis2#a by ! hydrolysis ( tetrame?yldiam9ob5zhydrol ) acetic acid2#b by ! cond5sation ( dime?ylanil9e1 =maldehyde & m-sulfo-p-tolyl hydroxylam9e foll[$ by hydrolysis2#c by ! electrolytic r$uction ( a mixture ( sodium nitrob5z5e sulfonate1 dime?ylanil9e & =maldehyde1 & subsequ5t hydrolysis2#d by ! r$uction ( a mixture ( dime?ylanil9e1 =maldehyde & sodium nitrob5z5e sulfonate ) iron & hydro*loric acid1 foll[$ by hydrolysis2#e by ! cond5sation ( alloxan ) dime?ylanil9e foll[$ by hydrolysis2#f by ! cond5sation ( dime?ylanil9e1 =maldehyde & sodium p-toluid9e sulfonate 9 ! pres5ce ( hydro*loric acid & potassium di*romate foll[$ by hydrolysis4#g ,! mo/ satisfactory me?od1 h[ev]1 is ! cond5sation ( dime?ylanil9e1 =maldehyde & nitroso dime?yanil9e1 foll[$ by hydrolysis1#h a me?od :i* 0 fir/ describ$ by ,e4 ,noelt+ & lat] p]fect$ 9 detail by ,l4 ,baumann4 #a ,b]4 #ah1 #aeai 7#ahhe72 #ai1 #cff 7#ahhf72 ,d4 ,r4 ,p4 #fa1 #eea2 ,frdl4 #c1 #aji 7#ahib74 #b ,b]4 #bg1 #ccag 7#ahid74 #c ,d4 ,r4 ,p4 #ajc1egh2 ,frdl4 #e1 #aja 7#ahii74 #d ,d4 ,r4 ,p4 #aje1ajc2 ,frdl4 #e1 #ajg 7#ahii74 #e ,d4 ,r4 ,p4 #aje1aje2 ,frdl4 #e1 #aji 7#ahii74 #f ,d4 ,r4 ,p4 #ajh1jhf2 ,frdl4 #e1 #aag 7#ahii74 #g ,d4 ,r4 ,p4 #aah1efg2 ,frdl4 #f1 #acc 7#aija74 #h ,b]4 #cg1 #heh 7#aijd72 ,j4 ,biol4 ,*em4 #da1 #adf 7#aibj74 ,,vi ,,e?yl ,,oxalate 7,,co#b;,h7#b #b ,c#b;,h#e,,oh-- 7,,co#b;,c#b;,h#e7b #b;,h#b,o ,prep>$ by ,h4 ,t4 ,,cl>ke & ,,anne ,w4 ,,davis4 ,*eck$ by ,,rog] ,,adams & ,w4 ,b4 ,,burnett4 #a4 ,proc$ure ,,9 a #e-l4 flask are plac$ #a kg4 ( cry/alliz$ 7hydrat$7 oxalic acid1 #a4ff kg4 ( #ie p] c5t e?yl alcohol1 & #a4cc kg4 ( c>bon tetra*loride4 ,! flask is !n fitt$ ) a fractionat+ column1 ,i met] long1 to :i* is atta*$ a cond5s] & an automatic sep>ator s arrang$ t ! light] liquid fl[s (f to a receiv] 7,fig4 #a74 ,! heavi] liquid fl[s ?r\gh a t[] ( anhydr\s potassium c>bonate1 & !n returns to ! reaction flask4 ,! bottom ( ! t[] is connect$ ) a small sep>atory funnel ?r\gh :i* any potassium c>bonate solution1 :i* fl[s f ! solid 9 ! t[]1 may be )drawn f "t to "t4 ,! mixture 9 ! flask is sl[ly di/ill$4 ,z soon z ab\t #ejj cc4 ( ! light] liquid has collect$1 x is plac$ 9 a fractionat+ app>atus & di/ill$1 ! mat]ial :i* boils up to #gi'j be+ collect$ sep>ately4 ,?is fraction1 :i* consi/s pr9cipally ( alcohol1 ) a little c>bon tetra*loride & moi/ure1 is dri$ ) potassium c>bonate & return$ to ! reaction mixture4 ,! high] fractions are r$i/ill$4 ,! above process is cont9u$ until ! di/illate no long] sep>ates into two phases 7ab\t tw5ty-sev5 h\rs74 ,! liquid 9 ! flask is !n di/ill$ ) ! use ( a column until ! temp]ature ( ! vapor rea*es #he'j2 ! residue is !n di/ill$ "u r$uc$ pressure1 & ! fraction :i* boils at #ajf-ajg_/be mm4 is collect$4 ,! yield is #ibj-ifj g4 ( a colorless liquid 7#hj-hd p] c5t ( ! !oretical am\nt74 #b4 ,notes ,wat]1 e?yl alcohol & c>bon tetra*loride =m a t]n>y mixture boil+ at ab\t #fa'j4 ,?is vapor mixture1 on cond5sation1 sep>ates into two phases2 ! heavi] liquid consi/s ( c>bon tetra*loride & alcohol ) only small am\nts ( wat]2 ! light] liquid consi/s ( approximately #fe p] c5t alcohol1 #be p] c5t wat] & #aj p] c5t c>bon tetra*loride4 ,by tak+ advantage ( ?is fact1 x is possible to conduct ! e/]ification at a temp]ature s l[ t ! e?yl hydrog5 oxalate fir/ =m$ does n decompose into e?yl =mate & o!r products1 z is ! case :5 ! cu/om>y me?ods ( e/]ification are employ$4 ,! reaction may be c>ri$ out some:at m exp$iti\sly if ! oxalic acid be dehydrat$ indep5d5tly be=e x is mix$ ) ! alcohol2 inde$1 x is also possible to remove ! bulk ( ! wat] f ! alcohol itself by a simil> me?od1 be=e mix+ x ) ! oxalic acid4 ,h[ev]1 s9ce wat] is =m$ dur+ ! e/]ification1 little is ga9$ by ?is proc$ure4 ,x is n absolutely necess>y to remove ! la/ traces ( wat] f ! alcohol-c>bon tetra*loride lay] by means ( potassium c>bonate be=e return+ x to ! reaction mixture2 ?is process is1 h[ev]1 s simple & requires s little att5tion t !re is no d\bt t x is ( mat]ial aid 9 cutt+ d[n ! "t ( op]ation4 ,! advantages ( us+ cry/alliz$ oxalic acid & comm]cial #ie p] c5t alcohol1 in/ead ( ! anhydr\s reag5ts1 are obvi\s4 ,:5 te*nical oxalic acid is us$1 ! yields are usually small] by #e to #aj p] c5t4 ,! app>atus %[n 9 ,fig4 #a may be some:at m simply con/ruct$ by us+ rubb] connections 9 sev]al places1 ?us elim9at+ a c]ta9 am\nt ( glass bl[+1 & mak+ a m flexible piece ( app>atus4 ,! side-arm ( ! sep>ator may be made ) two rubb] connections1-- "o above & "o bel[ ! tube lead+ to ! potassium c>bonate tube4 ,! long return tube to ! flask may be con/ruct$ ) a rubb] jo9t v ne> ! c>bonate tube & "o ne> ! flask4 #c4 ,o!r ,me?ods ( ,prep>ation ,e?yl oxalate has be5 prep>$ 9 poor yields by ! foll[+ me?ods3 by di/ill+ a mixture ( anhydr\s oxalic acid & absolute alcohol2#a by heat+ a mixture ( anhydr\s oxalic acid & #ig p] c5t alcohol "u a reflux cond5s] & fractionat+ ! result+ mixture2#b by di/ill+ a mixture ( anhydr\s oxalic acid & absolute alcohol1 ! vapor ( absolute alcohol be+ pass$ simultane\sly into ! mixture2#c by all[+ a saturat$ solution ( oxalic acid 9 alcohol to /& = a long "t at #dj-ej'j4d ,a good yield has be5 obta9$ by ,ans*utz#e by a me?od involv+ saturation ( a mixture ( cry/alliz$ oxalic acid & alcohol ) hydrog5 *loride1 removal ( ! alcohol & wat] by di/illation "u r$uc$ pressure1 & repetition ( ! treatm5t ) ! alcohol & hydrog5 *loride1 ! process be+ c>ri$ out sev]al times4 #a ,jahresb4 #ahfa1 #eih4 #b ,j prakt4 ,*em4 7#b71 #cd1 #ejj 7#ahhf74 #c ,monat%4 #ag1 #fad 7#ahif74 #d ,ann4 #fe1 #cej 7#ahdh74 #e ,b]4 #af1 #bdad 7#ahhc71 ,,vii ,,e?yl ,,ph5ylacetate ,c#f;,h#e;,,*#b;,,cn ,c#b;,h#e,,oh ,h#b,,s#d ,h#b,o-- ,c#f;,h#e;,,*#b;,,co#b;,c#b;,h#e ,,nh#d;,,hso#d ,prep>$ by ,,rog] ,,adams & ,a4 ,f4 ,,?al4 ,*eck$ by ,,oliv] ,,kamm4 #a4 ,proc$ure ,,9 a #c-l4 r\nd-bottom flask1 fitt$ ) an effici5t reflux cond5s]1 are mix$ #gej g4 ( #ie p] c5t alcohol1 #gej g4 ( conc5trat$ sulfuric acid & #dej g4 ( b5zyl cyanide4 ,! mixture1 :i* soon sep>ates into two lay]s1 is heat$ to boil+ ov] a l[ flame1 = six to sev5 h\rs1 cool$ & p\r$ into #b l4 ( wat]1 & ! upp] lay] is sep>at$4 ,?is is wa%$ ) a little #aj p] c5t sodium c>bonate solution to remove small am\nts ( ph5ylacetic acid :i* may h be5 =m$1 & !n di/ill$ 9 vacuo4 ,a small am\nt ( wat] goes ov] fir/ & !n a pure product boil+ #acb-ach'j_/cb mm4 7#abj-abe'j_/ag-ah mm474 ,! yield v>ies 9 g5]al betwe5 #ebe & #eej g4 7#hc-hg p] c5t ( ! !oretical am\nt74 #b4 ,notes ,! b5zyl cyanide c be mo/ conv5i5tly prep>$ accord+ to ! directions 9 prep>ation ,,iii 7p4 #i72 ! product :i* boils ov] a #e'j range %\ld be us$4 ,9 wa%+ ! lay] ( e?yl ph5ylacetate ) sodium c>bonate x is sometimes advisable to add a c]ta9 am\nt ( sodium *loride s t ! e/] w sep>ate m readily4 ,! product obta9$ is wat]-cle> & practically colorless4 ,al?\gh ! product is collect$ ov] a #e'j range1 mo/ ( ! liquid is f\nd to boil ov] a #a'j range1 if di/ill$ sl[ly )\t sup]heat+4 ,! boil+ po9t ( e?yl ph5ylacetate is ne> t ( b5zyl cyanide4 ,h[ev]1 a ,kjeldahl analysis ( ! product %[s t only a trace ( nitrog5 comp\nds is pres5t4 #c4 ,o!r ,me?ods ( ,prep>ation ,e?yl ph5ylacetate may be prep>$ by ! treatm5t ( b5zyl cyanide ) alcohol & hydro*loric acid gas4#a ,x is mu* m conv5i5t 9 ! laboratory1 h[ev]1 to use sulfuric acid 9 place ( hydro*loric acid2 9 fact1 ! yields obta9$ are bett] ?an ^? record$ 9 ! lit]ature4 ,?is e/] may also be made by ! e/]ification ( ph5ylacetic acid ) hydro*loric acid & alcohol2#b or ) alcohol & sulfuric acid2#c ! foll[+ less important me?ods ( prep>ation may be m5tion$2 ! action ( b5zyl magnesium *loride ^u e?yl *loroc>bonate1#d & ! action ( copp] on a mixture ( bromob5z5e & e?yl *loroacetate at #ahj'j4e #a ,b]4 #bj1 #eib 7#ahhg72 ,ann4 #bif1 #cfa 7#ahig7 #b ,b]4 #b1 #bjh 7#ahfi74 #c ,ann4 #bif1 #b1 footnote 7#ahig72 ,compt4 r5d4 #aeb1 #ahee 7#aiaa74 #d ,b]4 #cf1 #cjhh 7#aijc74 #e ,b]4 #b1 #gch 7#ahfi74 ,,viii ,,glyc]ol a1 g-,,di*lorohydr9 ,c#c;,h#e7,,oh7#c #b;,h,cl-- ,,*#b;,cl,c,h,o,h,c,h#b;,cl #b;,h#b,o ,prep>$ by ,j4 ,b4 ,,conant & ,o4 ,r4 ,,quayle4 ,*eck$ by ,o4 ,,kamm & ,a4 ,o4 ,,mat!ws4 #a4 ,proc$ure ,,"o kilo ( #ij p] c5t glyc]ol 7sp4 gr4 #a4bdc7 & #bj g4 ( acetic acid are plac$ 9 a weigh$ #b-l4 flask :i* is imm]s$ 9 an oil ba? heat$ to #ajj-aaj'j4 ,! flask is fitt$ ) a two-hole /opp]1 :i* c>ries a long tube rea*+ to ! bottom ( ! flask & a %ort exit tube4 ,! =m] is connect$ to a hydrog5 *loride g5]ator1 ! latt] to a cat*-bottle & "s sy/em = absorb+ any excess ( hydrog5 *loride4 ,a /ream ( dry hydrog5 *loride is pass$ into ! mixture4 ,! absorption ( gas is v rapid at ! />t1 b gradually falls (f t[>ds ! end ( ! reaction2 ! /ream ( hydrog5 *loride %\ld be regulat$ accord+ly4 ,! flask is remov$ f "t to "t & weigh$2 :5 ! absorption ( gas practically ceases1 ! increase 9 weight w be ab\t #hge g4 7#be p] c5t m ?an ! !oretical am\nt74 ,! product is n[ cool$1 plac$ 9 a #d-l4 beak]1 & treat$ ) solid sodium c>bonate until j alkal9e to litmus4 ,wat] is add$ f "t to "t1 to facilitate ! reaction ) ! sodium c>bonate & to prev5t ! sep>ation ( salt2 ab\t #ejj cc4 are requir$4 ,! mixture is transf]r$ to a sep>atory funnel & ! aque\s lay] sep>at$4 ,! crude di*lorohydr91 :i* weighs #abej g41 is di/ill$ 9 vacuo4 ,! fir/ fraction boil+ bel[ #fh'j_/ad mm4 weighs #bbe g41 & consi/s ( wat] & "s di*lorohydr92 ! di*lorohydr9 is collect$ betwe5 #fh-ge'j_/ad mm41 & weighs ab\t #gge g4 ,! wat] is sep>at$ f ! fir/ fraction1 :i* is !n r$i/ill$ & yields #ajj g4 ( di*lorohydr94 ,a /ill fur!r am\nt ( mat]ial 7#dj-de g47 may be obta9$ by extract+ ) b5z5e1 ! aque\s lay] obta9$ 9 ! neutralization process4 ,?is is1 h[ev]1 h>dly pr(itable4 ,! neutralization & di/illation w require ab\t f\r h\rs4 ,! #hge g4 ( di*lorohydr9 ?us obta9$ boils ov] a #g'j range2 ?is is #gj p] c5t ( ! !oretical am\nt4 ,r$i/illation yields #gjj-gbj g4 boil+ #gj-gc'j_/ad mm4 7#eg p] c5t ( ! !oretical am\nt74 #b4 ,notes ,! mo/ conv5i5t hydrog5 *loride g5]ator is t describ$ by ,swe5ey4#a ,conc5trat$ hydro*loric acid is introduc$ into conc5trat$ sulfuric acid1 by means ( a dropp+ funnel & a capill>y tube lead+ to ! bottom ( ! sulfuric acid conta9]4 ,x is conv5i5t to use a #c-l4 bottle = ?is conta9] & a #a-l4 funnel to conta9 ! hydro*loric acid4 ,! gas is dri$ by pass+ ?r\gh a wa%-bottle conta9+ conc5trat$ sulfuric acid4 ,an empty cat*-flask %\ld be connect$ betwe5 ! g5]ator & ! absorption flask 9 case any glyc]ol t5ds to suck back at ! />t ( ! reaction4 ,ab\t #f kg4 ( conc5trat$ hydro*loric acid & #aj kg4 ( conc5trat$ sulfuric acid are requir$ 9 "o run4 ,! g5]at+ flask w h to be re*>g$ e six h\rs2 x %\ld be half fill$ ) sulfuric acid4 ,aside f ?is1 ! app>atus ne$s no att5tion4 ,! oil ba? c be conv5i5tly heat$ on an electric hot plate4 ,! di*lorohydr9 boil+ ov] a #g'j range is suffici5tly pure = mo/ purposes4 ,x conta9s v little1 if any1 isom]ic di*lorohydr91 s9ce on oxidation x gives di*loroacetone 9 good yields4 #c4 ,o!r ,me?ods ( ,prep>ation ,! foll[+ me?ods ( prep>+ di*lorohydr9 are describ$ 9 ! lit]ature3 ! action ( gase\s hydrog5 *loride on glyc]ol2#a;b ! action ( gase\s hydrog5 *loride on glyc]ol mix$ ) an equal volume ( acetic acid2#b ! action ( hydrog5 *loride gas on glyc]ol conta9+ #a-b p] c5t ( "s organic acid1 z acetic1 z a cataly/2#c ! action ( aque\s solution ( hydro*loric acid on glyc]ol conta9+ acetic acid z a cataly/2#d ! action ( sulfur mono*loride on glyc]ol4#e ,! previ\s "w1 describ$ 9 ! lit]ature1 indicat$ t ! be/ yields 7 obta9$ by ! treatm5t ( glyc]ol conta9+ #a-b p] c5t ( acetic acid z a cataly/ by gase\s hydrog5 *loride4 ,!re=e ?is me?od 0 employ$4 #a;a ,j4 ,am4 ,*em4 ,soc4 #ci1 #bahg 7#aiag7 #a;b ,ann4 #hh1 #caa 7#ahec72 ,ann4 *im4 phys4 7#c7 #da1 #big 7#ahed72 7#f71 #bb1 #dcg 7#ahia72 ,bull4 soc4 *im4 7#b71 #dh1 #bcg 7#ahhg72 ,z4 physik4 ,*em4 #ib1 #gag 7#aiah72 #ic1 #ei 7#aiai72 #id1 #fia 7#aibj72 ,d4 ,r ,p4 #bfc1ajf2 #bgb1ccg2 ,frdl4 #aa1 #cc 7#aiab74 #b ,ann4 ,spl4 #a1 #b;,i#h 7#ahfa72 ,ann4 *im4 phys4 7#c7 #fj1 #ah 7#ahfj74 #c ,d4 ,r4 ,p4 #aig1cjh2 ,frdl4 #i1 #cc 7#aijh74 #d ,d4 ,r4 ,p4 #aig1cji2 ,frdl4 #i1 #cc 7#aijc74 #e ,ann4 #abb1 #gc 7#ahfb72 #afh1 #dc 7#ahgc72 ,b]4 #e1 #ced 7#ahgb72 ,ann4 *im4 phys4 7#f7 #bb1 #dcg 7#ahia74 ,,ix ,,glyc]ol a-,,mono*lorohydr9 ,c#c;,h#e7,,oh7#c ,h,cl-- ,,*#b;,cl,c,h,o,h,c,h#b,,oh ,h#b,o ,prep>$ by ,j4 ,b4 ,,conant & ,o4 ,r4 ,,quayle4 ,*eck$ by ,o4 ,,kamm & ,a4 ,o4 ,,mat!ws4 #a4 ,proc$ure ,,five ,,hundr$ grams ( glyc]ol 7#ij p] c5t7 & #aj g4 ( glacial acetic acid are mix$ 9 a weigh$ #a-l4 flask1 :i* is plac$ 9 an oil ba? heat$ to #aje-aaj'j4 ,a rapid /ream ( dry hydrog5 *loride is introduc$ into ! mixture4 ,! flask is remov$ f ! ba? f "t to "t & reweigh$4 ,at ! end ( ab\t f\r h\rs ! flask w h ga9$ #aij g4 9 weight4 ,! reaction is !n complete4 ,! product is di/ill$ "u dim9i%$ pressure4 ,bel[ #aad'j_/ad mm41 #bbj-bej g4 di/il2 ?is portion is mo/ly wat]4 ,! mono*lorohydr9 is collect$ betwe5 #aad-abj'j_/ad mm42 x weighs #cfj g41 :i* is #ff p] c5t ( ! !oretical am\nt4 ,ab\t #bj g4 m may be obta9$ by neutraliz+ ! fir/ fraction & sep>at+ ! aque\s lay]4 #b4 ,notes ,! same app>atus is employ$ z 9 ! prep>ation ( di*lorohydr9 7prep>ation ,,viii1 p4 #bi74 ,! portion boil+ #abj-acj'j_/ad mm4 only am\nts to #ae-cj g41 %[+ t v little ( ! b-comp\nd is =m$4 ,?is is fur!r %[n by ! fact t ! di*lorohydr9 =m$ by cont9u$ action ( hydrog5 *loride "u ! same conditions conta9s v little1 if any1 a1 b di*loride4 ,two kilograms ( conc5trat$ sulfuric acid & #gej g4 ( conc5trat$ hydro*loric acid are suffici5t to produce ! necess>y am\nt ( hydrog5 *loride4 ,a light /raw-color$ f9al product is obta9$ 9 "s cases4 ,an alt]native proc$ure :i* is sl[] & gives slightly l[] yields1 b does n require a hydrog5 *loride g5]ator1 is z foll[s3 ,?ree hundr$ grams ( glyc]ol1 #fjj cc4 ( hydro*loric acid 7sp4 gr4 #a4ai7 & #ae g4 ( glacial acetic acid are heat$ "u a reflux cond5s] = t5 h\rs1 9 a #b-l4 flask4 ,! boil+ %\ld be v g5tle 9 ! e>ly /age ( ! reaction1 z consid]able hydro*loric acid vapor is evolv$4 ,z ! reaction progresses1 & ! evolution ( acid vapors dim9i%es1 ! mixture is m /rongly heat$4 ,! reaction products are di/ill$ "u ord9>y pressure until ! temp]ature ( ! liquid has rea*$ #adj'j 7!rmomet] bulb imm]s$ 9 ! liquid74 ,! residual products are di/ill$ "u dim9i%$ pressure1 & ! foll[+ fractions obta9$4 7#a7 ,up to #aae'j_/aa mm42 7#b7 #aae-aag'j_/ #aa mm42 7#c7 #aag-agj'j_/aa mm4 7#a7 is mo/ly aque\s hydro*loric acid2 7#b7 is ! mono*lorohydr92 & 7#c7 is glyc]ol4 ,! second portion is r$i/ill$ & ! portion boil+ at #aae-aah'j_/aa mm4 or #acc-acf'j_/bj mm4 is collect$4 ,! yield is #aij-bje g41 #ec-eg p] c5t ( ! !oretical am\nt4 #c4 ,o!r ,me?ods ( ,prep>ation ,! foll[+ me?ods ( prep>+ mono*lorohydr9 are describ$ 9 ! lit]ature3 action on glyc]ol ( gase\s hydrog5 *loride2#a action ( gase\s hydrog5 *loride on glyc]ol mix$ ) an equal volume ( acetic acid2#b action ( aque\s hydro*loric acid on glyc]ol#c alone or ) an organic acid 7#a-b p] c5t71 su* z acetic1 z a cataly/2#d gase\s hydrog5 *loride ) an organic acid1 z acetic1 z a cataly/2#a;b gase\s hydrog5 *loride ) ! e/] ( an organic or inorganic acid z a cataly/2#b;b ! action ( sulfur mono*loride on glyc]ol4#c;b #a ,ann4 #hh1 #caa 7#ahec72 ,ann4 *im4 phys4 7#c7 #da1 #big 7#ahcd72 ,v4 ,r4 ,p4 #bed1gji2 #bfi1feg2 ,frdl4 #aa1 #ca 7#aiab74 #b ,ann4 *im4 phys4 7#c7 #fj1 #ah 7#ahfj74 #c ,d4 ,r4 ,p4 #ahj1ffh2 ,frdl4 #h1 #bg 7#aijg72 ,j4 ,am4 ,*em4 ,soc4 #db1 #bjif 7#aibj74 #d ,d4 ,r4 ,p4 #aig1cji2 ,frdl4 #i1 #cd 7#aijh74 #a;b ,d4 ,r4 ,p4 #aig1cjh2 ,frdl4 #i1 #cc 7#aijh74 #b;b ,d4 ,r4 ,p4 ,anm4 #bc1eaj2 #af1egi2 ,frdl4 #i1 #cf 7#aijh74 #c;b ,d4 ,r4 ,p4 #bja1bcj2 ,frdl4 #i1 #ce 7#aijh74 ,x ,,hydraz9e ,,sulfate #b ,,nh#c ,na,o,cl-- ,,nh#b,,nh#b ,h#b,o ,na,cl ,prep>$ by ,,rog] ,,adams & ,b4 ,k4 ,,br[n4 ,*eck$ by ,j4 ,b4 ,,conant & ,w4 ,l4 ,,hanaway4 #a4 ,proc$ure ,a ,,normal solution ( sodium hypo*lorite is prep>$ z foll[s3 9 a #e-l4 r\nd-bottom flask are plac$ #ahjj g4 ( sodium hydroxide solution 7#cjj g4 ( sodium hydroxide to #aejj g4 ( wat]7 & #aejj g4 ( ice4 ,*lor9e gas is !n pass$ into ! solution until x has ga9$ 9 weight approximately #bac g4 ,dur+ ?is addition1 ! solution mu/ be kept ?or\ghly cool$ ) ice1 9 ord] t *lorates w n be =m$4 ,aft] all ! *lor9e has be5 pass$ 91 x is necess>y to be c]ta9 t ! mixture is slightly alkal9e1 s9ce any excess ( free *lor9e 9 ! solution prev5ts ! =mation ( hydraz9e4 ,9 a #ad-;in* evaporat+ di% are plac$ #aejj cc4 ( c4 p4 ammonia wat] 7sp4 gr4 #j4ij71 #ijj cc4 ( di/ill$ wat]1 #cge cc4 ( #aj p] c5t gelat9e solution1 & #abjj cc4 ( ! normal sodium hypo*lorite solution prep>$ z above4 ,?is mixture is heat$ z rapidly z possible & boil$ d[n until "o-?ird ( ! orig9al volume is left4 ,?is solution is !n cool$ ?or\ghly ) ice & filt]$ ) suction1 fir/ ?r\gh two lay]s ( t[el+ & !n ?r\gh "o ?ickness ( ord9>y filt] pap] ov] clo?1 9 ord] to remove f9ely divid$ solid impurities4 ,! solution is !n plac$ 9 a precipitat+ j>1 & cool$ d[n ?or\ghly 7#j'j7 ) ice & salt2 #aj cc4 ( conc5trat$ sulfuric acid = ea* #ajj cc4 ( solution are gradually add$ ) con/ant /irr+4 ,a precipitate ( hydraz9e sulfate 7,,nh#b,,nh#b4;,h#b,,s#d7 =ms4 ,! mixture is all[$ to /& 9 ! cold = a few h\rs 9 ord] to complete ! precipitation1 & is !n filt]$ by suction 9 ! usual way & wa%$ ) cold alcohol4 ,! yield v>ies f #ec g4 to #eh g4 p] #aejj cc4 ( ammonia wat] 7#cd-cg p] c5t ( ! !oretical am\nt74 ,! product is p]fectly :ite & cry/all9e1 & satisfactory = almo/ any purpose4 ,if an absolutely pure product is desir$1 x mu/ be recry/alliz$ f wat]4 ,= e #ba g4 ( crude product1 #ajj g4 ( boil+ wat] are us$4 ,if ! crude hydraz9e is br[n1 x is advisable to use a little bone-black4 ,aft] ! mixture has be5 filt]$ & cool$ to #j'j1 #ai g4 ( pure :ite cry/als are obta9$4 #b4 ,notes ,9 ! prep>ation ( ! sodium hypo*lorite solution x is q necess>y t ! mixture be kept cold & be alkal9e to r$ litmus pap] at ! end ( ! reaction1 if good yields ( hydraz9e are to be obta9$4 ,s9ce iron is an anti-catalyz]1 x is necesss>ysic to use di/ill$ wat] ?r\gh\t ! process4 ,z a viscoliz]1 a sub/ance su* z />*1 glyc]ol1 glue or gelat9e may be us$2 ! la/1 h[ev]1 gives by f> ! mo/ satisfactory results4 ,9 ord] to obta9 a pure :ite hydraz9e sulfate z ! fir/ precipitate1 x is necess>y to cool ! hydraz9e solution ?or\ghly & filt] x twice be=e ! sulfuric acid is add$4 ,moreov]1 ! sulfuric acid mu/ be add$ sl[ly & ) /irr+4 ,if ^! conditions are n foll[$1 mat]ial conta9+ br[n p>ticles results4 ,! "m liquor obta9$ f ! cry/alliz$ hydraz9e sulfate conta9s a small am\nt ( hydraz9e4 ,if #bjj g4 ( copp] sulfate are dissolv$ 9 wat] & add$ to #aj l4 ( ! filtrates f ! above processes1 a light-blue cry/all9e precipitate ( ! d\ble salt ( copp] sulfate & hydraz9e sulfate w be =m$ aft] t5 h\rs4 ,?is salt1 :5 susp5d$ 9 t5 times its weight ( di/ill$ wat] & treat$ ) hydrog5 sulfide1 decomposes into copp] sulfide & hydraz9e sulfate4 ,aft] ! copp] salt has be5 filt]$ (f1 ! solution is conc5trat$ until ! hydraz9e sulfate cry/allizes4 ,! yield ( product is small1 s t x is h>dly advisable to und]take ?is recov]y 9 ! laboratory4 ,x is possible = "o man1 simultane\sly evaporat+ six di%es ( ! hydraz9e mixture1 to turn out f #bj to #be runs 9 n9e h\rs4 ,! "t = ! evaporation ( a solution1 su* z is m5tion$ 9 ! exp]im5tal "p1 ) a f\r-flame ,buns5 burn]1 is two to ?ree h\rs2 if ! evaporation is c>ri$ out m sl[ly ?an ?is1 ! yield ( product is di/9ctly dim9i%$4 #c4 ,o!r ,me?ods ( ,prep>ation ,hydraz9e salts h be5 prep>$ by ! action ( hypo*lorites on ammonia#a or urea2#b by ! hydrolysis ( salts ( sulfohydrazime?yl5e disulfonic acid2#c by ! hydrolysis ( triazoacetic acid2#d by ! r$uction ( diazoacetic e/]2#e by ! r$uction ( nitroguanid9e foll[$ by hydrolysis2#f by ! r$uction ( ! nitroso d]ivatives ( hexame?yl5e tetram9e2#g by ! r$uction ( nitrates or nitrites ) z9c 9 neutral solution2#h by ! action ( sodium bisulfite on hyponitr\s acid foll[$ by r$uction2#a;b by ! r$uction ( ,k#b,,s#c,n#b,o#b2b;b by ! action ( ammonia on di*lor\rea2#c;b by ! r$uction ( nitrosop>aldim92#d;b by ! action ( copp] sulfate on ammonia at high temp]atures2#e;b by ! r$uction ( me?yl5e diisonitrosoam9e2#f;b by ! hydrolysis ( ! addition product ( diazoacetic e/] & fum>ic or c9namic e/]s4#g;b #a ,d4 ,r4 ,p4 #aib1ghc2 ,*em4 ,z5tr4 #aijh 7,i71 #dbg2 ,*em4 ,ztg4 #ca1 #ibf 7#aijg72 ,d4 ,r4 ,p4 #aih1cjg2 ,*em4 ,z5tr4 #aijh 7,i71 #aieg2 ,eng4 ,pat4 #bb1ieg2 ,c4 ,a4 #b1 #aiii 7#aijh72 ,u4 ,s4 ,pat4 #iaj1heh2 ,c4 ,a4 #c1 #ajfe 7#aiji72 ,fr5* ,pat4 #chb1ceg2 ,c4 ,a4 #c1 #bceh 7#aiji72 ,b]4 #dj1 #dehh 7#aijg72 ,laboratory ,manual ( ,inorganic ,prep>ations1 by ,a4 ,b4 ,lamb1 ,h>v>d ,univ]sity1 ,cambridge1 ,mass4 #b ,j4 ,russ4 ,phys4 ,*em4 ,soc4 #cg1 #a 7#aije72 ,*em4 ,z5tr4 #aije 7,i7 #abbg2 ,d4 ,r4 ,p4 #afd1gee2 ,frdl4 #h1 #ec 7#aije72 ,fr5* ,pat4 #cbi1dcj2 ,j4 ,soc4 ,*em4 ,ind4 #bb1 #ajfc 7#aijc72 ,*em4 ,z5tr4 #aije 7,i7 #abbg4 #c ,d4 ,r4 ,p4 #gi1hhe2 ,frdl4 #d1 #bf 7#ahie72 ,b]4 #bh1 #bcha 7#ahie74 #d ,b]4 #bj1 #afcb 7#ahhg72 ,*em4 ,news #ee1 #bhh 7#ahhg72 ,d4 ,r4 ,p4 #dg1fjj2 ,frdl4 #b1 #eed 7#ahhi72 ,j4 prakt4 ,*em4 7#b7 #ci1 #bg 7#ahhi74 #e ,b]4 #bg1 #gge 7#ahid72 #bh1 #ahdh 7#ahie72 ,d4 ,r4 ,p4 #eh1gea2 ,frdl4 #c1 #af 7#ahia72 ,d4 ,r4 ,p4 #hg1aca2 ,frdl4 #d1 #bh 7#ahif74 #f ,ann4 #bgj1 #ca 7#ahib72 ,d4 ,r4 ,p4 #ei1bda2 ,frdl4 #c1 #af 7#ahia72 ,eng4 ,pat4 #f1ghf2 ,j4 ,soc4 ,*em4 ,ind4 #aa1 #cgj 7#ahib74 #g ,d4 ,r4 ,p4 #hj1dff2 ,frdl4 #d1 #bg 7#ahie72 ,ann4 #bhh1 #bcb 7#ahie74 #h ,eng4 ,pat4 #aa1 #baf2 ,j4 ,soc4 ,*em4 ,ind4 #ad1 #eie 7#ahie74 #a;b ,b]4 #cc1 #baae 7#aijj72 ,ann4 #bhh1 #cja 7#ahie74 #b;b ,b]4 #bg1 #cdih 7#ahid74 #c;b ,j4 ,*em4 ,soc4 #ie1 #bce 7#aiji72 ,*em4 ,news #ih1 #aff 7#aijh74 #d;b ,b]4 #bc1 #geb 7#ahij74 #e;b ,*em4 ,news #ff1 #bbc 7#ahib74 #f;b ,b]4 #bg1 #cbib 7#ahid72 #g;b ,b]4 #ba1 #bfcg 7#ahhh74 ,,xi ,,mesityl5e #c ,,*#c;,,co*#c 7,h#b,,s#d7-- ,c#f;,h#c7;,,*#c7c #c;,h#b,o ,prep>$ by ,,rog] ,,adams & ,r4 ,w4 ,,huff]d4 ,*eck$ by ,h4 ,t4 ,,cl>ke & ,w4 ,w4 ,,h>tman4 #a4 ,proc$ure ,,9 a #ab-l4 r\nd-bottom flask1 arrang$ s t ! cont5ts c be me*anically /irr$1 are plac$ #dfjj g4 7#egej cc47 ( te*nical acetone4 ,! flask is !n well cool$ ) an ice-&-salt mixture1 until ! temp]ature ( ! acetone is betwe5 #j'j & #e'j4 ,/irr+ is />t$1 & #dafj cc4 ( comm]cial conc5trat$ sulfuric acid is run 9 at su* a rate t ! temp]ature ( ! mixture nev] rises above ab\t #aj'j4 ,?is addition is accompli%$ 9 ab\t five to t5 h\rs4 ,! /irr+ is cont9u$ = ?ree to f\r h\rs long]1 :ile ! flask /ill rema9s imm]s$ 9 ! orig9al freez+ mixture to :i* no fur!r am\nt ( ice is add$4 ,! mixture is !n all[$ to /& at room temp]ature = eighte5 to tw5ty-f\r h\rs4 ,a #e-l4 r\nd-bottom flask is fitt$ ) a rubb] /opp] or a cork /opp] coat$ ) pit*1 c>ry+ two glass tubes1 "o ( :i* 7= ! entrance ( /eam7 rea*es to ! bottom ( ! flask1 :ile ! o!r ext5ds into ! op5 end ( a cond5s] set = d[nw>d di/illation4 ,! /opp] %\ld be wir$ into ! flask4 ,! glass deliv]y tube into ! cond5s] %\ld n be less ?an a #ab-mm4 bore1 & ! cond5s] %\ld consi/ ( two #abj-;cm4 wat]-cool$ cond5s]s atta*$ end to end4 ,to ! end ( ! cond5s+ sy/em1 an adapt] is atta*$1 ! small end ( :i* is at lea/ #h mm4 9 bore & is fitt$ tightly into a /opp] 9 a #b-l4 suction flask4 ,to ! side-arm ( ! suction flask is atta*$ a tube lead+ to an exhau/ fan1 9 ord] to c>ry away ! gases :i* are evolv$ dur+ ! subsequ5t di/illation4 ,9 ! #e-l4 flask are plac$ ab\t #b l4 ( ! sulfuric acid-acetone reaction mixture1 & ! flask is !n heat$ ) a free flame & %ak5 occasionally4 ,a reaction />ts at ! end ( ab\t fifte5 or tw5ty m9utes1 z %[n by ! evolution ( gas 7*iefly sulfur dioxide71 & is all[$ to run = ab\t ?ree m9utes4 ,at ! end ( ?is "t1 a curr5t ( /eam is pass$ 9 & cont9u$ = ab\t ?ree m9utes4 ,dur+ ?is p]iod a l>ge proportion ( ! mesityl5e di/ils & %\ld be kept sep>ate f ! subsequ5t di/illate4 ,! /eam di/illation is cont9u$ at su* a rate t ab\t #hjj cc4 di/ils 9 tw5ty-five to ?irty m9utes & is collect$ z a second di/illate4 ,at ! end ( ?is "t1 ! di/illation is /opp$1 ! wat] p\r$ (f f ! di/ill+ flask & ! t>ry mat]ial empti$ out :ile hot into wa/e j>s4 ,! total am\nt ( orig9al reaction mixture requires five di/illations simil> to ! "o j describ$4 ,! fir/ di/illates f ea* ( ! five di/illations are mix$1 & ! lay] ( mesityl5e is sep>at$ f ! wat]4 ,?is is %ak5 ) sodium hydroxide solution until no m odor ( sulfur dioxide is noticeable1 !n wa%$ twice ) wat] & di/ill$4 ,! fir/ portion ( ! di/illate consi/s ( a small am\nt ( wat] & mesityl5e & is add$ to ! comb9$ second di/illates4 ,! fraction :i* di/ils up to #baj'j is sav$4 ,! second di/illates are comb9$1 wa%$ 9 ! same way z ! fir/ & !n di/ill$2 ! fraction :i* di/ils up to #baj'j is comb9$ ) ! correspond+ fraction f ! fir/ di/illates4 ,^! comb9$ fractions 7:i* boil up to #baj'j7 & #ae g4 ( sodium are plac$ 9 a #b-l4 di/ill+ flask1 ! side-arm ( :i* is clos$ ) a rubb] tube & p9*cock & :i* is fitt$ ) a reflux cond5s]4 ,! mixture is heat$ j bel[ ! boil+ po9t = ab\t ?ree h\rs1 dur+ :i* "t ! impurities are attack$ by ! molt5 sodium1 & a gelat9\s1 r$di% mass =ms4 ,! reflux cond5s] is n[ remov$ & "o set = d[nw>d di/illation is atta*$ to ! side-arm4 ,! mixture is di/ill$ & ab\t two-?irds ( ! liquid remov$ 9 ?is way4 ,! residue is cool$1 ! liquid p\r$ (f f solid mat]ial & di/ill$ up to #baj'j4 ,! di/illates f ! sodium treatm5t are n[ fractionat$ ) a good column 7at lea/ #cj cm4 long71 & ! portion :i* boils at #afc-afg'j is collect$4 ,! yield ( ?is fraction v>ies 9 diff]5t runs f #dcj to #dgj g4 7#ac-ae p] c5t ( ! !oretical am\nt71 b v (t5 w be z high z #ejj g41 & has rea*$1 9 c]ta9 exp]im5ts1 #fjj g4 ,an alt]native me?od = ! purification ( ! crude mat]ial has be5 employ$ by ,cl>ke & ,h>tman1 & yields a slightly high]-grade product ?an ! sodium me?od4 ,x is z foll[s3 ,! comb9$ di/illates are treat$ ) an equal volume ( conc5trat$ sulfuric acid & ! solution w>m$ on a wat] ba? = an h\r1 "u a reflux cond5s]1 ) occasional %ak+ or1 bett]1 ) me*anical /irr+4 ,^u cool+1 mesityl5e sulfonic acid cry/allizes & ! unsulfonat$ mat]ial rema9s z an oil on ! surface4 ,! mixture is filt]$ ?r\gh flannel or a filtrose plate1 & ! cry/als are wa%$ ) #fj-gj p] c5t sulfuric acid4 ,! oily lay] is aga9 w>m$ ) sulfuric acid1 z be=e4 ,! acid & oily filtrates f ! two sulfuric acid treatm5ts are /eam di/ill$1 & ! di/illate comb9$ ) ! next bat* ( mat]ial4 ,! cry/als are mix$ ) #b l4 ( #ae p] c5t hydro*loric acid & heat$ "u a reflux cond5s] = two to ?ree h\rs4 ,! reaction mixture is n[ /eam di/ill$1 ! mesityl5e sep>at$1 dri$ ov] calcium *loride & fractionat$2 ! portion :i* boils at #afc-afg'j is collect$4 #b4 ,notes ,! cool+ ( ! reaction flask mu/ be v effici5t1 a #aj-ae cm4 blanket ( a ?or\gh mixture ( ice & salt be+ us$4 ,if ?is precaution is n employ$1 ! "t = ! addition ( ! sulfuric acid is greatly increas$1 provid$ ! temp]ature ( ! reaction mixture is /ill kept )9 ! limits m5tion$4 ,if a cork is us$ = ! /eam di/illation ( ! reaction mixture ( acetone & sulfuric acid1 x %\ld be coat$ well ) pit* & wir$ into ! flask4 ,?is is necess>y because ! vapors ( ! reaction mixture attack an ord9>y cork v badly1 & s(t5 x s mu* t x is necess>y to rewire x to prev5t x f slipp+ out4 ,a rubb] /opp] is satisfactory & may be us$ 9 sev]al runs4 ,! evolution ( gas is s vigor\s t x is n possible to di/il m ?an #b l4 ( ! orig9al reaction mixture at "o "t 9 ! app>atus describ$4 ,! connections on ! app>atus1 9 :i* ! mesityl5e is obta9$ f ! crude reaction mixture1 %\ld be tight1 s9ce ! fumes evolv$ dur+ ! heat+ are v irritat+4 ,! product :i* di/ils dur+ ! initial heat+ & ! ?ree m9utes ( /eam di/illation is ma9ly satisfactory mat]ial2 ! re/ ( ! /eam di/illation yields only a small am\nt ( pure product4 ,! two portions ( ! di/illate are1 !re=e1 kept sep>ate1 s9ce ! second di/illate always conta9s a consid]able am\nt ( high-boil+ product :i* t5ds to cause emulsification ( ! alkali 9 ! purification4 ,no recov]y ( acetone is made4 ,! me*anism ( ! reaction is und\bt$ly z foll[s3 :5 ! sulfuric acid & acetone are 9 contact = long p]iods ( "t1 sev]al molecules ( ! acetone cond5se to =m aldol cond5sation products4 ,^! d n break d[n into mesityl5e until ! temp]ature is rais$ 9 ! second "p ( ! exp]im5t4 ,:ile ! orig9al reaction mixture is /&+1 ! temp]ature gradually rises to #dj'j or #ej'j 9 ! c\rse ( six to t5 h\rs1 & !n gradually cools (f aga94 ,x is probable t at ! end ( ?is "t 7:5 ! flask has cool$ aga97 ! reaction mixture c\ld be di/ill$ ) ne>ly z good a yield z is obta9$ aft] /&+ eighte5 to tw5ty-f\r h\rs4 ,! wide v>iation 9 yields :i* are m5tion$ 9 ! exp]im5tal "p is probably due to a slight *ange 9 ! grade ( ! *emicals :i* are us$ 9 ?is prep>ation4 #c4 ,o!r ,me?ods ( ,prep>ation ,! *eape/ & mo/ conv5i5t me?od by :i* mesityl5e may be prep>$ is by ! action ( a dehydrat+ ag5t ^u acetone2 ! ag5t mo/ commonly us$ is sulfuric acid4#a ,x has be5 %[n also t phosphoric acid w conv]t acetone to mesityl5e4#b ,a numb] ( o!r me?ods h also be5 us$ = ! prep>ation ( mesityl5e3 ! action ( sulfuric acid on me?yl acetyl5e2#c ! action ( sulfuric acid on mesityl oxide & phorone2#d ! action ( alum9iumsic7briti%7 *loride on me?yl *loride & b5z5e2#e ! action ( m9]al acids ^u mesitoyl or b5zoyl mesityl5e2#f ! action ( phosphoric acid ^u diaceto-mesityl5e2#g ! treatm5t ( me?yl5e-#c-;dime?yl-#a1 #e-;cyclo-hex5e-#a ) brom9e & !n ) alcoholic pota%4#h #a ,ann4 #ada1 #aca 7#ahfg72 #adg1 #dc 7#ahfh72 #bgh1 #baj 7#ahic72 ,bud4 soc4 *im4 7#b7 #dj1 #bfg 7#ahhc72 ,j4 prakt4 ,*em4 7#a7 #ae1 #abi 7#ahch72 ,am4 ,*em4 ,j4 #ae1 #bef 7#ahic72 #bj1 #hjg 7#ahih74 #b ,j ,*em4 ,soc4 #ii1 #abea 7#aiaa74 #c ,b]4 #h1 #ag 7#ahge74 #d ,b]4 #g1 #aafi 7#ahgd72 #aj1 #heh 7#ahgg74 #e ,b]4 #ab1 #cbi 7#ahgi72 ,ann4 *im4 phys4 7#f7 #a1 #dfa 7#ahhd74 #f ,b]4 #cb1 #aiaj 7#ahii74 #g ,b]4 #cb1 #aefc 7#ahii74 #h ,b]4 #dc1 #cjic 7#aiaj74 ,,xii ,,me?yl ,,r$ 7o7,,ho#b;,,cc#f;,h#ds,,nh#b ,,hno#b ,h,cl--7 o7,,ho#b;,,cc#f;,h#d,n#b;,cl ,h#b,o 7o7 ,,ho#b;,,cc#f;,h#d,n#b;,cl ,c#f;,h#e,n7,,*#c7b--7 o7,,ho#b;,,cc#f;,h#d,n ,,nc#f;,h#d,n7,,*#c7b ,h,cl ,prep>$ by ,h4 ,t4 ,,cl>ke & ,w4 ,r4 ,,kirn]4 ,*eck$ by ,,rog] ,,adams & ,j4 ,b4 ,,davis4 #a4 ,proc$ure ,,te*nical an?ranilic acid 7g5]ally ab\t #ie p] c5t pure7 7#fhe g47 is dissolv$ 9 #a4e l4 ( wat] & #ejj cc4 ( conc5trat$ hydro*loric acid 7sp4 gr4 #a4ag71 by heat+4 ,! insoluble d>k impurity pres5t 9 small am\nts is filt]$ (f1 & ! filtrate is transf]r$ to a #aj-l4 crock & *ill$ ) /irr+4 ,x is !n mix$ ) a mu% ( #b4e kg4 ( ice & #gej cc4 ( conc5trat$ hydro*loric acid4 ,! crock is cool$ ext]nally ) ice1 & ! cont5ts /irr$ cont9u\sly4 ,:5 ! temp]ature rea*es ab\t #c'j1 a filt]$ solution ( #cfj g4 ( sodium nitrite 9 #gjj cc4 ( wat] is dropp$ 9 sl[ly1 ?r\gh a long capill>y tube rea*+ bel[ ! surface ( ! liquid1 until a fa9t b p]man5t reaction to />* potassium iodide pap] is obta9$2 ! temp]ature is kept betwe5 #c'j & #e'j4 ,?is op]ation requires all b ab\t #cj cc4 ( ! nitrite solution & occupies "o & a half to two h\rs4 ,to ! solution ( ! diazonium salt are n[ add$ #hdh g4 ( dime?ylanil9e2 ?is may be done rapidly1 z ! temp]ature does n rise appreciably4 ,/irr+ is cont9u$ = "o h\r1 ! temp]ature be+ kept at #e'j ,five hundr$ cc4 ( a filt]$ solution ( #fhj g4 ( cry/alliz$ sodium acetate dilut$ to #abjj cc4 are !n add$1 & ! /irr+ cont9u$ = f\r h\rs4 ,if a foamy solid rises to ! surface dur+ ?is "t & refuses to become incorporat$ by ! /irr]1 a few drops ( e?yl acetate may be add$ to r$uce ! foam4 ,! mixture is all[$ to /& ov]night 9 an ice ba? :i* is well insulat$ by sev]al ?icknesses ( burlap2 ! temp]ature mu/ be kept bel[ #g'j to get a good yield ( product4 ,! rema9d] ( ! sodium acetate solution is !n add$ ) /irr+1 & aft] ! mixture has be5 /irr$ = an additional p]iod ( "o to ?ree h\rs1 ! temp]ature is all[$ to rise sl[ly to #bj-be'j 9 ! c\rse ( tw5ty-f\r h\rs4 ,j en\gh sodium hydroxide solution is !n add$1 ) /irr+1 to cause ! mixture to h a di/9ct odor ( dime?ylanil9e 7ab\t #bdj cc4 ( a #dj p] c5t solution are g5]ally requir$71 & ! mixture is all[$ to /& = =ty-eight h\rs or long] at room temp]ature 7#bj-be'j74 ,! solid is !n filt]$ (f1 wa%$ fir/ ) wat]1 !n ) #djj cc4 ( #aj p] c5t acetic acid 7to remove ! dime?ylanil9e7 & f9ally ) di/ill$ wat]4 ,! la/ filtrate is g5]ally pale p9k4 ,! solid is suck$ z dry z possible1 spread out on a tray 9 ord] to all[ mo/ ( ! wat] to evaporate 7fifte5 to tw5ty h\rs7 & !n susp5d$ 9 #d l4 ( me?yl alcohol 9 a #ab-l4 flask4 ,?is mixture is /irr$ on ! /eam ba? "u a reflux cond5s] = "o to two h\rs1 all[$ to cool sl[ly1 & !n *ill$ 9 an ice ba? & filt]$4 ,! solid product is wa%$ ) a second #d l4 ( cold me?yl alcohol4 ,aft] be+ dri$ 9 air1 ! product v>ies 9 weight f #hbj to #hgj g4 ,! product is extract$ ) boil+ tolu5e 9 ! foll[+ mann]3 #aej g4 are plac$ 9 a flut$ filt] pap] ( #bi cm4 diamet] 9 a #be-;cm4 glass funnel :i* passes ?r\gh ! cork ( a #b-l4 flat-bottom conical flask conta9+ #abej cc4 ( tolu5e 7,fig4 #b74 ,! flask is heat$ on an electric /ove1 & a #ab-l4 r\nd-bottom flask is plac$ on ! funnel to act z a cond5s]1 cold wat] be+ run ?r\gh ! flask4 ,! tolu5e is boil$ until ! cond5s$ liquid runs ?r\gh almo/ colorless 7?is requires f f\r to t5 h\rs74 ,! heat+ is !n discont9u$1 &1 z soon z ! liquid ceases to boil1 ! flask is remov$ to a ba? conta9+ wat] at #ij-ajj'j2 ! level ( ! wat] %\ld be slightly above ! level ( ! liquid 9 ! flask4 ,?is arrangem5t p]mits ! temp]ature to fall sl[ly s t l>ge cry/als are obta9$4 ,9 ! meantime a second conical flask conta9+ #abej cc4 ( tolu5e is atta*$ to ! funnel1 & a new *>ge ( #aej g4 ( crude me?yl r$ is plac$ 9 ! pap]4 ,:5 extraction is complete x is f\nd t a c]ta9 am\nt ( black amorph\s insoluble matt] rema9s on ! filt]2 ?is is disc>d$4 ,! cry/als ( me?yl r$ are filt]$ (f & wa%$ ) a little tolu5e4 ,! weight ( pure mat]ial is #gee-hje g4 ,! "m liquors are conc5trat$ to "o-f\r? ( _! volume1 & ! cry/als :i* sep>ate on cool+ are recry/alliz$ f fre% tolu5e4 ,! recov]$ tolu5e c1 ( c\rse1 be employ$ aga94 ,! total yield ( pure me?yl r$ is #gij--hdj g4 ,x melts at #aha-ahb'j4 ,! wat]y "m liquors f ! crude me?yl r$ are r5d]$ alkal9e ) sodium hydroxide & di/ill$ until no m dime?ylanil9e passes ov]4 ,9 ?is way #bej to #djj g4 ( moi/ dime?ylanil9e are recov]$4 #b4 ,notes ,! am\nt ( hydro*loric acid indicat$ mu/ n be r$uc$2 o!rwise1 diazoam9o comp\nds are =m$4 ,x is ess5tial to keep ! temp]ature l[ :ile unreact$ diazob5zoic acid rema9s 9 solution1 9 ord] to avoid decomposition4 ,if ?is precaution is n tak51 ! yields are consid]ably dim9i%$1 ?r\gh ! =mation ( t>ry by-products4 ,! use ( a capill>y tube = ! addition ( sodium nitrite prev5ts loss ( nitr\s acid by local reaction at ! surface ( ! acid solution4 ,! tube %\ld n be tightly connect$ to ! dropp+ funnel1 b %\ld be s arrang$ t air is suck$ ?r\gh ) e drop4 ,9 ?is way1 ! entrance ( ! acid liquor into ! capill>y is prev5t$4 ,! =mation ( ! azo comp\nd takes place sl[ly on ! addition ( ! dime?ylanil9e1 b ! spe$ ( ! reaction is greatly increas$ :5 ! hydrog5 ion conc5tration is l[]$ by ! addition ( ! sodium acetate4 ,x is nev]!less necess>y to all[ ! reaction mixture to /& a long "t2 if ! product be filt]$ (f aft] only tw5ty-f\r h\rs1 a fur!r quantity ( dye w sep>ate f ! filtrate on /&+4 ,! hydro*loride ( me?yl r$ is only sp>+ly soluble 9 cold wat]1 & is apt to sep>ate 9 blue ne$les if ! acidity is n suffici5tly r$uc$4 ,! alcoholic filtrate1 obta9$ on dige/+ & wa%+ ! crude me?yl r$1 conta9s a m soluble r$ by-product :i* gives a br[ni%-yell[ solution 9 alkali4 ,! me?yl alcohol may be recov]$ ) v little loss by di/illation2 x is1 h[ev]1 impracticable to attempt to recov] any me?yl r$ f ! residue1 ow+ to ! t>ry nature ( ! by-product4 ,! proportion ( ?is by-product is greatly increas$ if ! temp]ature ( ! mixture is all[$ to rise too soon aft] ! addition ( ! sodium acetate4 ,me?yl r$ is describ$ z cry/alliz+ 9 ne$les f glacial acetic acid2 on recry/allization f tolu5e x sep>ates 9 plates4 ,:5 ! me?yl r$ is cry/alliz$ f tolu5e1 x sometimes sep>ates 9 ! =m ( bright-r$ lumps1 probably on acc\nt ( too rapid cry/allization4 ,"u ^! conditions x is advisable to cry/allize aga91 us+ a some:at l>g] am\nt ( tolu5e4 ,x is advisable to titrate ! crude an?ranilic acid ) /&>d alkali & ph5olph?ale9 be=e />t+ ! exp]im5t4 ,9 *eck+ ^! directions1 an #hj p] c5t an?ranilic acid 0 us$2 x gave a correspond+ly l[] yield ( me?yl r$ 7#fej-gjj g474 ,! yield ( me?yl r$ is ab\t #fe to #gj p] c5t bas$ on ! dime?ylanil9e actually us$ up1 b only #eh-fc p] c5t bas$ on ! an?ranilic acid actually pres5t 9 ! te*nical an?ranilic acid employ$4 #c4 ,o!r ,me?ods ( ,prep>ation ,me?yl r$ 0 fir/ prep>$#a by diazotization ( an?ranilic acid 9 alcoholic solution1 ! product be+ all[$ to react ) dime?ylanil9e 9 ! same solv5t4 ,x has be5 /at$#b t ?is process does n "w satisfactorily & yields a diff]5t product1 ( br[ni%-r$ color4 ,! prep>ation ( me?yl r$ 9 aque\s solution has be5 describ$ by two work]s1 "o ( :om#c gives b few details & claims a ne>ly quantitative yield2 ! o!r#d gives full] details & /ates ! yield to be #dc4a p] c5t ( ! !ory4 ,! recry/allization ( me?yl r$ f tolu5e is /at$#e to yield a product melt+ at #ahc'j4 #a ,b]4 #da1 #cije 7#aijh74 #b ,*em4 ,z5tr4 #aiaj1 7#a71 #ifj2 #aiaj1 7#aa71 #aefa4 #c ,j4 ,*em4 ,soc4 #ig1 #bdhe 7#aiaj74 #d ,c4 ,a4 #ad1 #cdjf 7#aibj7 #e ,j4 ,*em4 ,soc4 #ii1 #accd 7#aiaa74 ,,xiii p-,,nitrob5zoic ,,acid 7p7,,no#b;,c#f;,h#d;,,*#cs #c,o7,na#b;,cr#b,o#g ,h#b,,s#d7-- 7p7,,no#b;,c#f;,h#d;,,co#b;,h #c;,h#b,o ,prep>$ by ,o4 ,,kamm & ,a4 ,o4 ,,mat!ws4 ,*eck$ by ,h4 ,t4 ,,cl>ke & ,w4 ,w4 ,,h>tman4 #a4 ,proc$ure ,,9 a #e-l4 r\nd-bottom flask1 fitt$ ) a me*anical /irr]1 are plac$ #fhj g4 ( sodium di*romate1 #aejj cc4 ( wat]1 & #bcj g4 ( p-nitrotolu5e4 ,/irr+ is />t$1 & #agjj g4 ( conc5trat$ sulfuric acid are all[$ to fl[ 9 dur+ ab\t ?irty m9utes4 ,! heat ( dilution ( ! sulfuric acid w cause ! nitrotolu5e to melt1 & rapid oxidation w soon take place4 ,! la/ half ( ! sulfuric acid mu/ be add$ gradually1 9 ord] to prev5t too viol5t a reaction4 ,s9ce a small am\nt ( nitrotolu5e is volatiliz$1 x is advisable to c>ry on ?is "w "u a hood4 ,aft] ! sulfuric acid has be5 add$ & ! spontane\s heat+ ( ! reaction mixture has subsid$1 ! mixture is heat$ to g5tle boil+ = ab\t half an h\r4 ,aft] ! reaction mixture has cool$1 #b l4 ( wat] are add$1 ! cool$ solution is filt]$ ?r\gh a clo? filt]1 & ! product wa%$ ) ab\t #a l4 ( wat]4 ,9 ord] to remove ! *romium salts z completely z possible1 ! crude nitrob5zoic acid is w>m$ on ! wat] ba? & agitat$ ) #a l4 ( dilute 7#e p] c5t7 sulfuric acid solution4 ,aft] cool+1 ! product is aga9 filt]$4 ,x is !n dissolv$ 9 #e p] c5t sodium hydroxide solution1 filt]$ f any *romium hydroxide rema9+1 & also f un*ang$ nitrotolu5e4 ,! filtrate1 :i* %\ld be light yell[ or gre5i% 9 color1 is acidifi$ ) dilute sulfuric acid1 ) /irr+4 ,x is usually pref]able to run ! alkal9e solution into ! dilute sulfuric acid1 r ?an to use ! rev]se proc$ure1 = ! precipitation ( ! nitro acid4 ,! precipitat$ product is filt]$ ) suction1 wa%$ ?or\ghly1 & dri$4 ,! product %\ld possess only a light-lemon color4 ,! yield %\ld be #bcj-bdj g4 7#hj-he p] c5t ( ! !oretical am\nt74 ,= a product ( special purity1 cry/allization f b5z5e is advisable4 ,= mo/ purposes1 h[ev]1 ! nitrob5zoic acid may be us$ )\t cry/allization1 s9ce its melt+ po9t is f\nd to be )9 #b'j ( ! correct value ( #bch'j4 #b4 ,notes ,! above proc$ure diff]s f t record$ 9 ! lit]ature1 ma9ly 9 ! use ( a fairly l>ge excess ( sulfuric acid4 ,?is %ort5s ! reaction "t f =ty h\rs to ab\t "o h\r1 :i* is especially conv5i5t 9 ! prep>ation ( ! acid on a laboratory scale4 ,because ( ! use ( ?is l>ge excess ( sulfuric acid1 ! reaction is apt to be r viol5t if ! directions giv5 are n c>efully foll[$4 ,! oxidation %\ld be c>ri$ out "u a hood4 ,small am\nts ( nitrotolu5e are lo/ by volatilization1 b ?is loss is n s]i\s1 z c be se5 f ! yield ( product obta9$4 ,t5 or #bj g4 ( un*ang$ nitrotolu5e c be recov]$ f ! reaction mixture by /eam di/illation1 b ! value ( ! by-product w\ld n pay = ! "t sp5t 9 recov]y4 ,! wa%+ ( ! crude reaction product ) dilute sulfuric acid is advisable1 if good mat]ial is to be obta9$4 ,if an effici5t c5trifuge is available = use at ?is /age ( ! op]ation1 ?is sep>ate wa%+ may prove to be less ess5tial4 ,:5 a sp>+ly soluble organic acid is precipitat$ f fairly conc5trat$ solution1 ! precipitate is liable to c>ry d[n ) x "s ( ! salt ( ! organic acid4 ,addition ( ! salt solution to ! m9]al acid1 ) /irr+1 avoids ?is difficulty4 #c4 ,o!r ,me?ods ( ,prep>ation ,! nitration ( b5zoic acid produces only v small yields ( ! p-nitro product4#a ,! only practical me?od = ! prep>ation consi/s 9 ! oxidation ( p-nitrotolu5e1 al?\gh = ?is purpose v>i\s oxidiz+ ag5ts are us$4 ,9 addition to nitrotolu5e1 p-nitrob5zyl alcohol1 p-nitroc9namic acid & simil> comp\nds may be oxidiz$1 b _! co/ is prohibitive 9 comp>ison ) t ( ! *eap] nitro hydroc>bon4 p-,nitrotolu5e may be oxidiz$ by means ( /rong nitric acid1#b *romic acid mixture1#c or p]manganates4#d ,electrolytic oxidation#e has also be5 propos$4 ,! proc$ure giv5 above involves ! use ( *romic acid mixture1 b1 ow+ to a *ange 9 ! conc5tration ( sulfuric acid1 ! "t ( reaction is greatly %ort5$ & ! prep>ation is ?us consid]ably improv$4 #a ,b]4 #h1 #ebh1 #ecf 7#ahge7 #b ,ann4 #abg1 #acg 7#ahfc72 #abh1 #beg 7#ahfc7 #c ,ann4 #aci1 #cce 7#ahff74 #d ,j4 ,am4 ,*em4 ,soc4 #da1 #aege 7#aiai74 #e ,r4 ,p4 #aag1 #abi2 ,frdl4 #f1 #aab4 ,,xiv p-,,nitrob5zyl ,,cyanide ,c#f;,h#e;,,*#b;,,cn ,,hno#c-- 7p7,,no#b;,c#f;,h#d;,,*#b;,,cn ,h#b,o ,prep>$ by ,g4 ,r4 ,,rob]tson4 ,*eck$ by ,,rog] ,,adams & ,h4 ,o4 ,,calv]y4 #a4 ,proc$ure ,,9 a #b-l4 r\nd-bottom flask1 fitt$ ) a /opp] hold+ a dropp+ funnel & a me*anical /irr]1 is plac$ a mixture ( #bge cc4 ( conc5trat$ nitric acid 7sp4 gr4 #a4db7 & #bge cc4 ( conc5trat$ sulfuric acid 7sp4 gr4 #a4hd74 ,?is is cool$ to #aj'j 9 a freez+ mixture1 & #ajj g4 ( b5zyl cyanide 7free f alcohol & wat]7 are run 9 sl[ly1 at su* a rate t ! temp]ature rema9s at ab\t #aj'j & does n exce$ #bj'j4 ,aft] all ! b5zyl cyanide has be5 add$ 7ab\t "o h\r71 ! ice ba? is remov$1 ! mixture is /irr$ = an h\r & !n p\r$ on to #abjj g4 ( cru%$ ice4 ,a pa/y mass sl[ly sep>ates2 m ?an half ( ?is mass is p-nitrob5zyl cyanide1 ! o!r con/itu5ts be+ o-nitrob5zyl cyanide1 & a v>iable am\nt ( an oil :i* resi/s hydrolysis2 app>5tly no d9itro comp\nds are =m$4 ,! mass is filt]$ on a porcela9 funnel ) suction1 press$ well to remove z mu* oil z possible1 & dissolv$ 9 #ejj cc4 ( boil+ alcohol 7#ie p] c5t74 ,on cool+1 p-nitrob5zyl cyanide cry/allizes2 ! "m liquor1 on di/illation1 gives an impure alcohol :i* c be us$ = ! next run4 ,recry/allization f #eej cc4 ( #hj p] c5t alcohol 7sp4 gr4 #j4hf to #j4hg7 yields #gj to #ge g4 7#ej-ed p] c5t7 ( a product :i* melts at #aae-aaf'j4 ,?is product is satisfactory = mo/ purposes1 & incid5tally = ! prep>ation ( p-nitroph5ylacetic acid4 ,occasionally x mu/ be free ev5 f traces ( ! or?o comp\nd1 & 9 ?is case %\ld be cry/alliz$ aga9 f #hj p] c5t alcohol2 x !n melts at #aaf-aag'j4 #b4 ,notes ,fum+ nitric acid may be us$ 9 nitrat+ b5zyl cyanide1 b ! me?od "h describ$ is *eap]4 ,! yield ( #gj g4 is obta9$ f b5zyl cyanide1 :i* boils ov] a #e'j range prep>$ z describ$ 9 prep>ation ,,iii 7p4 #i74 ,v pure b5zyl cyanide w give a slightly high] yield1 :ile comm]cial grades may give only #ej g4 ( p-nitrob5zyl cyanide & mu* oil4 ,! reaction has be5 also c>ri$ out ) #ejj g4 ( b5zyl cyanide4 ,"u ^! conditions a #e-l4 flask 0 us$1 & x requir$ two & a half h\rs to add ! b5zyl cyanide4 ,! yield ( product 0 #cbe to #cgj g4 #c4 ,o!r ,me?ods ( ,prep>ation ,nitrob5zyl cyanide has hi!rto be5 prep>$ by ! action ( fum+ nitric acid#a on b5zyl cyanide4 #a ,b]4 #ag1 #eje 7#ahhd72 #cc1 #agj 7#aijj72 ,j4 ,biol4 ,*em4 #ci1 #ehe 7#aiai72 ,j4 ,am4 ,*em4 ,soc4 #dc1 #ahj 7#aiba74 ,,xv p-,,nitroph5ylacetic ,,acid 7p7,,no#b;,c#f;,h#d;,,cn ,h#b,,s#d #b;,h#b,o-- 7p7,,no#b;,c#f;,h#d;,,*#b;,,co#b;,h ,,nh#d;,,hso#d ,prep>$ by ,g4 ,r4 ,,rob]tson4 ,*eck$ by ,,rog] ,,adams & ,h4 ,o4 ,,calv]y4 #a4 ,proc$ure ,,9 a #a-l4 r\nd-bottom flask are plac$ #ajj g4 ( p-nitrob5zyl cyanide4 ,a solution ( #cjj cc4 ( conc5trat$ sulfuric acid 7sp4 gr4 #a4hd7 9 #bhj cc4 ( wat] is prep>$1 & two-?irds ( ?is solution is p\r$ on to ! p-nitrob5zyl cyanide4 ,! mixture is %ak5 well1 until ! solid is all moi/5$ ) ! acid4 ,any solid mat]ial /ick+ to ! walls ( ! vessel is n[ wa%$ d[n into ! liquid ) ! rema9d] ( ! acid1 ! flask is atta*$ to a reflux cond5s]1 !n set1 )\t %ak+1 ov] a #aj-;cm4 hole 9 a l>ge %eet ( asbe/os bo>d :i* re/s on a tripod1 & heat$ until ! mixture boils4 ,! boil+ is cont9u$ = fifte5 m9utes4 ,! reaction mixture1 :i* becomes r d>k1 is dilut$ ) an equal volume ( cold wat] & cool$ to #j'j or bel[4 ,! solution is filt]$1 ! precipitate is wa%$ sev]al times ) ice wat] & !n dissolv$ 9 #afjj cc4 ( boil+ wat]4 7,a few grams ( animal *>coal are add$ 9 dissolv+ ! precipitate1 if a te*nical p-nitrob5zyl cyanide has be5 us$47 ,?is solution is filt]$ z rapidly z possible ?r\gh a l>ge fold$ filt]1 pref]ably ) a /eam funnel4 ,9 spite ( all precautions1 h[ev]1 "s solid usually sep>ates on ! filt]4 ,?is mu/ be r$issolv$ 9 a m9imum quantity ( boil+ wat]1 & ?is solution !n filt]$ into ! ma9 solution4 ,! p-nitroph5ylacetic acid sep>ates 9 long1 pale-yell[ ne$les1 :i* melt at #aea-aeb'j4 ,! yield is #ajc to #ajf g4 7#ib- #c p] c5t ( ! !oretical am\nt74 #b4 ,notes ,if ! flask is n protect$ ) an asbe/os bo>d or ! equival5t1 decomposition occurs :]e ! sub/ance is sup]-heat$ on ! side walls ( ! flask4 ,if cry/als ( ! cyanide are all[$ to rema9 on ! upp] walls ( ! flask1 !y are n easily wa%$ d[n & s are n hydrolyz$4 ,! solubility curve ( p-nitroph5ylacetic acid is v /eep at temp]atures ne> #ajj'j1 s t ! filt]+ ( ! boil+ solution %\ld be rapid4 ,if a good grade ( cyanide be us$1 x is n necess>y to add bone-black 9 ord] to obta9 ! acid 9 a pure /ate4 ,9 mak+ exp]im5ts ) #ejj g4 ( p-nitrob5zyl cyanide1 x 0 f\nd t ! "t = hydrolysis 0 ab\t ! same z :5 small] am\nts 7 us$4 #c4 ,o!r ,me?ods ( ,prep>ation p-,nitroph5ylacetic acid has be5 =m$ by ! nitration ( ph5ylacetic acid2#a by ! hydrolysis ( its e/]#b or its amid1#c & by ! hydrolysis ( its nitrile ) hydro*loric acid4#d #a ,b]4 #db1 #ceif 7#aiji74 #b ,b]4 #ab1 #agfe 7#ahgi74 #c ,b]4 #ad1 #bcdb 7#ahha74 #d ,b]4 #ae1 #hcd 7#ahhb74 ,,xvi ,,nitroso-b-,,naph?ol ,c#aj;,h#g,,oh7b7 ,,hno#b-- ,c#aj;,h#f7,,oh7,,no7#a1b7 ,h#b,o ,prep>$ by ,c4 ,s4 ,,m>vel & ,p4 ,k4 ,,port]4 ,*eck$ by ,h4 ,t4 ,,cl>ke & ,w4 ,w4 ,,h>tman4 #a4 ,proc$ure ,,9 a #ab-l4 r\nd-bottom flask fitt$ ) a me*anical /irr] are plac$ #ejj g4 ( te*nical b-naph?ol dissolv$ 9 a w>m solution ( #adj g4 ( sodium hydroxide 9 #f l4 ( wat]4 ,! solution is cool$ to #j'j 9 an ice-&-salt ba?1 & #bej g4 ( p[d]$ te*nical sodium nitrite is add$4 ,/irr+ is />t$ & #aajj g4 ( sulfuric acid 7sp4 gr4 #a4cb7 are add$ f a dropp+ funnel1 at su* a rate t ! :ole is add$ 9 "o to "o & a half h\rs1 ! temp]ature be+ kept at #j'j4 ,dur+ ! reaction cru%$ ice is add$ f "t to "t to ma9ta9 ! temp]ature at #j'j2 ab\t #a kg4 is usually us$4 ,aft] all ( ! sulfuric acid has be5 add$1 ! solution %\ld react acid to ,congo pap]4 ,! mixture is /irr$ "o h\r long] at ! l[ temp]ature & !n ! nitroso-b-naph?ol1 :i* has gradually sep>at$ out dur+ ! reaction1 is filt]$ ) suction & wa%$ ?or\ghly ) wat]4 ,! product is at fir/ light yell[ 9 color1 b aft] ?ree to f\r days x gradually *anges to a d>k br[n4 ,! moi/ure cont5t seems to h "s effect on ! color4 ,aft] ! product has be5 air-dri$ = ab\t f\r days1 ! yield is ab\t #ffe g42 x melts at #ig'j4 ,a sample ( ?is p>tially dri$ product1 on dry+ 9 vacuo ov] sulfuric acid = tw5ty h\rs1 loses ab\t #aj p] c5t ( its weight & ! melt+ po9t is #ajf'j4 ,by long] dry+ "u ord9>y conditions1 ! melt+ po9t ( #ajf'j is rea*$4 ,! total yield ( dry product is ab\t #eie g4 7#ii p] c5t ( ! !oretical am\nt74 ,?is product is satisfactory = all purposes4 ,x may be obta9$ 9 a cry/all9e condition1 h[ev]1 by recry/alliz+ f hot ligro9 7sp4 gr4 #j4ga-j4gb74 ,ab\t #b g4 ( nitroso-b-naph?ol w dissolve 9 #ae cc4 ( boil+ ligro94 ,! product is n v soluble 9 cold ligro91 s t ne>ly all is recov]$4 #b4 ,notes ,x is v necess>y to keep ! temp]ature ne> #j'j :ile add+ ! sulfuric acid1 or a t>ry product w be obta9$4 ,vigor\s /irr+ & ! addition ( ! sulfuric acid at ! prop] rate are ess5tial = a good product4 ,a l>ge vessel is ne$$ = ! reaction1 z ! nitroso-b-naph?ol sep>ates 9 a f9ely divid$ condition & !re is "s t5d5cy to foam4 ,! f9al air-dri$ product is pure except = its moi/ure cont5t1 z is %[n by ! fact t on dry+ 9 vacuo x has a v good melt+ po9t4 ,a sample ( ,kahlbaum's nitroso-b-naph?ol melt$ at #aja--aje4 #c4 ,o!r ,me?ods ( ,prep>ation ,nitroso-b-naph?ol has be5 made by ! action ( hydroxylam9e hydro*loride on b-naph?o-qu9one-*lorimide2#a by ! action ( sulfuric acid ^u a solution ( potassium or sodium nitrite & ! sodium salt ( b-naph?ol2#b by ! action ( sodium nitrite ^u an alcoholic solution ( z9c *loride & b-naph?ol2#c by ! action ( sodium nitrite ^u b-naph?ol susp5d$ 9 z9c sulfate solution2#d by ! action ( nitr\s acid on b-d9aph?ol me?ane2#e & by ! action ( nitrosyl sulfate ^u ! sodium salt ( b-naph?ol4#f #a ,b]4 #bg1 #bda 7#ahid74 #b ,b]4 #h1 #ajbf 7#ahge72 #bg1 #cjgf 7#ahid72 ,j4 ,*em4 ,soc4 #de1 #bie 7#ahhd74 #c ,b]4 #ah1 #gje 7#ahhe74 #d ,d4 ,r4 ,p4 #be1dfi2 ,frdl4 #a1 #cce 7#ahhc74 #e ,b]4 #cc1 #hjf 7#aijj74 #f ,j ,*em4 ,soc4 #cb1 #dg 7#ahgg72 ,ann4 #ahi1 #adf 7#ahgg74 ,,xvii ,,ph5ylacetic ,,acid ,c#f;,h#e;,,*#b;,,cn #b;,h#b,o ,h#b,,s#d-- ,c#f;,h#e;,,*#b;,,co#b;,h ,,nh#d;,,hso#d ,prep>$ by ,,rog] ,,adams & ,a4 ,f4 ,,?al4 ,*eck$ by ,o4 ,,kamm & ,a4 ,o4 ,,mat!ws4 #a4 ,proc$ure ,,9 a #e-l4 r\nd-bottom flask1 fitt$ ) a me*anical /irr] & reflux cond5s]1 are mix$ #aaej cc4 ( wat]1 #hdj cc4 ( comm]cial sulfuric acid & #gjj g4 ( b5zyl cyanide 7prep>ation ,,iii1 p4 #i74 ,! mixture is heat$ "u a reflux cond5s] & /irr$ = ?ree h\rs1 cool$ slightly & !n p\r$ into #b l4 ( cold wat]4 ,! mixture %\ld be /irr$ s t a solid cake is n =m$2 ! ph5ylacetic acid is !n filt]$ (f4 ,?is crude mat]ial %\ld be melt$ "u wat] & wa%$ by decantation sev]al times ) hot wat]4 ,^! wa%+s1 on cool+1 deposit a small am\nt ( ph5ylacetic acid :i* is filt]$ (f & add$ to ! ma9 portion ( mat]ial4 ,! la/ ( ! hot wat] is p\r$ (f f ! mat]ial :ile x is /ill molt5 & x is !n transf]r$ to a #b-l4 ,clais5 di/ill+ flask & di/ill$ 9 vacuo4 ,a small am\nt ( wat] comes ov] fir/ & is reject$2 ab\t #bj cc41 conta9+ an appreciable am\nt ( b5zyl cyanide1 !n di/ils4 ,?is fraction is us$ 9 ! next run4 ,! di/illate boil+ #agf-ahi'j_/ej mm4 is collect$ sep>ately & solidifies on /&+4 ,x is practically pure ph5ylacetic acid1 m4 p4 #gf-gf4e'j2 x am\nts to #fcj g4 7#gg4e p] c5t ( ! !oretical am\nt74 ,z ! fraction :i* is return$ to ! second run ( mat]ial conta9s a consid]able portion ( ph5ylacetic acid1 ! yield actually am\nts to at lea/ #hj p] c5t4 ,= ! prep>ation ( small quantities ( ph5ylacetic acid1 x is conv5i5t to use ! modifi$ me?od giv5 9 ! ,notes4 #b4 ,notes ,! /&>d directions = ! prep>ation ( ph5ylacetic acid specify t ! b5zyl cyanide is to be treat$ ) dilute sulfuric acid prep>$ by add+ ?ree volumes ( sulfuric acid to two volumes ( wat]4 ,!re action1 h[ev]1 goes s vigor\sly t x is always necess>y to h a trap = collect+ ! b5zyl cyanide :i* is bl[n out ( ! app>atus4 ,! use ( ! m dilute acid1 z describ$ 9 ! above directions1 is m satisfactory4 ,! ph5ylacetic acid may also be made by boil+ "u a reflux cond5s] = eight to fifte5 h\rs1 )\t a /irr]1 b ?is me?od is n ne>ly s satisfactory z t describ$ 9 ! proc$ure4 ,:5 only small quantities ( ! acid are requir$1 ! foll[+ modifi$ proc$ure is ( value4 ,"o hundr$ grams ( b5zyl cyanide are add$ to a mixture conta9+ #ajj cc4 ( wat]1 #ajj cc4 ( conc5trat$ sulfuric acid1 & #ajj cc4 ( glacial acetic acid4 ,aft] ?is has be5 heat$ = =ty-five m9utes "u a reflux cond5s]1 ! hydrolysis is practically complete4 ,! reaction mixture is !n p\r$ into wat]1 & ! ph5ylacetic acid isolat$ 9 ! usual mann]4 ,! odor ( ph5ylacetic acid is disagreeable & p]si/5t4 #c4 ,o!r ,me?ods ( ,prep>ation ,! /&>d me?od ( prep>ation ( ph5ylacetic acid is by ! hydrolysis ( b5zyl cyanide ) ei!r alkali#a;a or acid4#b;a ,! acid hydrolysis runs by f> ! m smoo?ly & s 0 ! only "o /udi$4 ,!re are num]\s o!r ways 9 :i* ph5ylacetic acid has be5 =m$1 b none ( !m is ( practical importance = its prep>ation4 ,^! me?ods include ! foll[+3 ! action ( wat] on ph5yl ket5e2#c;a ! hydrolysis & subsequ5t oxidation ( ! product betwe5 b5zaldehyde & hippuric acid2#a ! r$uction ( m&elic acid2#b ! r$uction ( b5zoyl=mic acid ) hydriodic acid & phosphorus2#c ! hydrolysis ( b5zyl glyoxalidone2#d ! fusion ( atropic acid ) potassium hydroxide2#e ! action ( alcoholic pota% ^u *loroph5ylacetyl5e2#f ! action ( b5zoyl p]oxide ^u ph5ylacetyl5e2#g ! alkal9e hydrolysis ( triph5ylphlorogluc9ol2#h ! action ( ammonium sulfide ^u acetoph5one2#i ! heat+ ( ph5ylmalonic acid2#aj ! hydrolysis ( ph5ylacetoacetic e/]2#aa ! action ( hydriodic acid ^u m&elonitrile4#ab #a;a ,ann4 #if1 #bdg 7#ahee72 ,b]4 #ad1 #afde 7#ahha72 ,compt4 r5d4 #aea1 #bcf 7#aiaj74 #b;a ,b]4 #ai1 #aiej 7#ahhf74 #c;a ,b]4 #dd1 #ecg 7#aiaa74 #a ,ann4 #cgj1 #cga 7#aiji7;a #b ,*em4 7#b7 #a1 #ddc 7#ahfe72 ,b]4 #ad1 #bci 7#ahha74 #c ,b]4 #aj1 #hdg 7#ahgg7 #d ,j4 prakt4 ,*em4 7#b7 #hb1 #eb1 #eh 7#aiaj74 #e ,ann4 #adh1 #bdb 7#ahfh74 #f ,ann4 #cjh1 #cah 7#ahii74 #g ,j4 ,russ4 ,phys4 ,*em4 ,soc4 #db1 #achg 7#aiaj72 ,*em4 ,z5tr4 #aiaa 7,i7 #abgi4 #h ,ann4 #cgh1 #bfc 7#aiaa74 #i ,b]4 #ba1 #ecd 7#ahhh72 ,j4 prakt4 ,*em4 7#b7 #ha1 #chd 7#aiaj74 #aj ,b]4 #bg1 7#ahid74 #aa ,b]4 #ca1 #cafc 7#ahih7 #ab ,inaugural ,diss]tation ( ,a4 ,kohl] 7#aiji71 ,univ4 ( ,b]n4 ,,xviii ,,ph5ylacetyl5e ,c#f;,h#e;,,*,c,h,br ,,koh-- ,c#f;,h#e;,,ctb* ,k,br ,h#b,o ,prep>$ by ,,john ,c4 ,,hessl]4 ,*eck$ by ,j4 ,b4 ,,conant & ,e4 ,r4 ,,b>rett4 #a4 ,proc$ure ,,9 a #ejj-;cc4 ,pyrex di/ill+ flask are plac$ #aej g4 ( potassium hydroxide4 ,! m\? ( ! flask is provid$ ) a "o-hole /opp] hold+ a dropp+ funnel2 ! side tube ( ! flask is connect$ ) a cond5s] set = d[nw>d di/illation4 ,! b-bromo/yr5e 7#ajj g47 is plac$ 9 ! dropp+ funnel4 ,! di/ill+ flask is gradually heat$ 9 an oil ba? until ! temp]ature ( ! ba? is #bjj'j1 & ! bromo/yr5e is !n dropp$ 9 ^u ! molt5 potassium hydroxide1 at ! rate ( some:at less ?an a drop a second4 ,s9ce ! boil+ po9t ( ph5ylacetyl5e is #adb-adc'j1 & t ( bromo/yr5e is #bah-bbj'j1 ! ph5ylacetyl5e di/ils away f ! un*ang$ bromo/yr5e4 ,:ile ! bromo/yr5e is be+ dropp$ 91 ! temp]ature ( ! oil ba? is rais$ v gradually to #bae-bbj'j1 & is kept at ?is temp]ature until all ! bromo/yr5e has be5 add$4 ,f9ally ! temp]ature is rais$ to #bcj'j1 & is held !re until no m di/illate comes ov]4 ,! di/illate is colorless2 x consi/s ( two lay]s1 ! l[] "o be+ wat]4 ,! upp] lay] is sep>at$ & dri$ ) solid potassium hydroxide4 ,x is !n di/ill$4 ,! yield ( ! di/ill$ ph5ylacetyl5e1 boil+ at #adb-add'j1 is #cg g4 7#fg p] c5t ( ! !oretical am\nt74 #b4 ,notes ,t[>d ! end ( ! reaction1 a cru/ ( potassium bromide may t5d to cov] ! melt$ potassium hydroxide4 ,"o c break ! cru/ by %ak+ ! di/ill+ flask g5tly1 or by us+ a glass rod ins]t$ ?r\gh a second hole 9 ! /opp] hold+ ! dropp+ funnel4 ,x is conv5i5t to h su* a rod or /irr] pass+ ?r\gh a m]cury seal 9 ! /opp] ( ! flask4 ,an occasional turn ( ?is /irr] breaks ! cru/ & facilitates ! op]ation4 ,me*anical /irr+ %\ld n be employ$1 z x r$uces ! yield trem5d\sly4 ,app>5tly ?is is because x facilitates ! solution ( bromo/yr5e 9 ! t>ry by-products & ?us causes x to polym]ize in/ead ( react+ ) ! potassium hydroxide4 ,a s+le ,pyrex flask c be us$ = only ?ree or f\r runs4 ,! flask %\ld be empti$ :ile /ill v hot4 ,! yield ( mat]ial c be some:at increas$ by work+ ) small lots 7#be g4 ( bromo/yr5e74 ,! use ( /eel or copp] vessels 9 place ( a glass flask seems to dim9i% ! yield slightly4 #c4 ,o!r ,me?ods ( ,prep>ation ,ph5ylacetyl5e has be5 prep>$ by ! elim9ation ( c>bon dioxide f ph5ylpropiolic acid by means ( ph5ol#a or anil9e#b or by heat+ ) b>ium hydroxide2#c f /yr5e dibromide1 by heat+ ) potassium hydroxide 9 alcohol2#d by heat+ b-bromo or *loro /yr5e ) sodium e?ylate or potassium hydroxide 9 alcohol2#e by pass+ ! vapors ( a-di*loroe?ylb5z5e ov] hot soda lime2#f by ! action ( alcoholic potassium hydroxide on dib5zal-acetone tetra-bromide2#a;b by ! action ( aque\s potassium hydroxide on ph5yl prop>gylaldehyde2#b;b by ! action ( molt5 potassium hydroxide on b-bromo-/yr5e4#c;b #a ,b]4 #bj1 #cjha 7#ahhg74 #b ,rec4 trav4 *im4 #af1 #aeg 7#ahif74 #c ,arm4 #bba1 #gj 7#ahhc74 #d ,ann4 #aed1 #aee 7#ahgj72 #bce1 #ac 7#ahhf72 ,bull4 soc4 *im4 #ce1 #ee 7#ahha72 7#c7 #be1 #cji 7#aija74 #e ,ann4 #cjh1 #bfe 7#ahii72 #cdb1 #bbj 7#aije74 #f ,jahresb4 #ahgf1 #cjh2 ,gazz4 *im4 ital4 #bb 7#b71 #fg 7#ahib72 ,bull4 soc4 *im4 7#c7 #be1 #cji 7#aija74 #a;b ,b]4 #ci1 #dadf 7#aijj74 #b;b ,b]4 #ca1 #ajbc 7#ahih74 #c;b ,j4 ,am4 ,*em4 ,soc4 #dd1 #dbe 7#aibb74 ,,xix ,,ph5ylhydraz9e ,c#f;,h#e,,nh#b4;,h,cl ,na,n,o#b ,h,cl-- ,c#f;,h#e,n#b;,cl ,na,cl #b;,h#b,o ,c#f;,h#e,n#b;,cl #d;,h7,na#b,,s#c7-- ,c#f;,h#e,,nhnh#b4;,h,cl ,prep>$ by ,g4 ,h4 ,,coleman4 ,*eck$ by ,j4 ,b4 ,,conant & ,h4 ,r4 ,,?ompson4 #a4 ,proc$ure ,,9 a #ab-l4 r\nd-bottom flask1 fitt$ ) a me*anical /irr]1 are plac$ #ajde cc4 ( conc5trat$ comm]cial hydro*loric acid 7sp4 gr4 #a4ach74 ,! flask is surr\nd$ ) a freez+ mixture ( ice & salt1 & :5 ! cont5ts are at #j'j1 /irr+ is />t$ & #ejj g4 ( crack$ ice are add$2 !n #cgb g4 ( anil9e1 also cool$ to #j'j1 are run 9 dur+ five m9utes4 ,! mixture is treat$ ) #ejj g4 m ( crack$ ice1 & a cold solution 7#j'j7 ( #bij g4 ( te*nical sodium nitrite dissolv$ 9 #fjj cc4 ( wat] are all[$ to run 9 sl[ly 7tw5ty to ?irty m9utes7 f a dropp+ funnel1 ! end ( :i* is drawn to a small tip1 & rea*es ne>ly to ! bottom ( ! flask4 ,dur+ ?is addition1 ! /irr] is op]at$ r vigor\sly1 & ! temp]ature is kept z ne> #j'j z possible by ! frequ5t addition ( crack$ ice 7ab\t #a kg74 ,9 ! meantime1 a sodium sulfite solution is prep>$ by dissolv+ #hij g4 ( sodium hydroxide1 ( ab\t #ij p] c5t purity1 9 ab\t #a l4 ( wat] & !n dilut+ to #f l4 ,a few drops ( ph5olph?ale9 solution are add$ & sulfur dioxide pass$ 91 fir/ until an acid reaction is indicat$ & !n = two or ?ree m9utes long]4 ,dur+ ! addition ( ! sulfur dioxide1 ! solution is cool$ ) runn+ wat]4 ,on acc\nt ( ! /rong alkal9e solution1 ! orig9al color produc$ by ! ph5olph?ale9 is v fa9t1 b ?is sl[ly increases until x becomes deep j be=e ! acid po9t is rea*$4 ,x is be/ to remove a small sample ( ! liquid f "t to "t1 dilute ) ?ree or f\r volumes ( wat] & add a drop m ( ph5olph?ale94 ,! sodium sulfite solution is plac$ 9 a #ab-l4 flask & cool$ to ab\t #e'j4 ,approximately #ejj g4 ( crack$ ice are add$1 & !n1 ) me*anical /irr+1 ! diazonium salt solution is run 9 z rapidly z possible4 ,! mixture becomes a bright orange-r$4 ,! flask is n[ w>m$ to ab\t #bj'j on a /eam ba?1 until ! solid sodium sulfite1 :i* has sep>at$ :ile cool+1 r$issolves4 ,! total am\nt ( liquid is n[ ab\t #aj l4 ,"o-half ( ?is is p\r$ into ano!r #ab-l4 flask1 & bo? halves are w>m$ on ! /eam ba? to #fj-gj'j1 until ! color becomes q d>k 7?irty to sixty m9utes74 ,suffici5t hydro*loric acid 7#cjj-djj cc47 is n[ add$ to ea* flask to make ! solutions acid to litmus4 ,! heat+ is cont9u$ & ! color gradually becomes light] until1 aft] f\r to six h\rs1 ! solutions h become ne>ly colorless2 !y may be heat$ ov]night1 if desir$4 ,to ! hot solutions are n[ add$ ab\t "o-?ird ( _! volume ( conc5trat$ hydro*loric acid 7#b l4 to ea* portion7 & ! mixtures cool$1 fir/ 9 runn+ wat]1 !n 9 a freez+ mixture1 to #j'j4 ,! ph5ylhydraz9e hydro*loride precipitates 9 ! =m ( slightly yell[i% or p9ki% cry/als :i* may be filt]$ (f & dri$4 ,! free base is lib]at$ by add+ to ! ph5ylhydraz9e hydro*loride #a l4 ( a #be p] c5t solution ( sodium hydroxide4 ,! ph5ylhydraz9e sep>ates & is tak5 up ) b5z5e 7two #cjj-;cc4 portions74 ,! comb9$ extractions are well dri$ ) #bjj g4 ( solid sodium hydroxide1 p\r$ (f1 & di/ill$4 ,mo/ ( ! b5z5e may be di/ill$ "u ord9>y pressure1 & ! rema9d]1 & any l[-boil+ impurities1 "u dim9i%$ pressure4 ,! pure ph5ylhydraz9e boils at #acg-ach'j_/ah mm41 & is obta9$ z a pale-yell[ liquid4 ,x c be cry/alliz$ on cool+ 9 an ice ba?2 ! cry/als melt at #bcj4 ,! crude ph5ylhydraz9e f two lots ( anil9e 7#gdd g47 is be/ di/ill$ at "o "t & gives #fie-gbe g4 ( pure product 7#hj-hd p] c5t ( ! !oretical am\nt74 #b4 ,notes ,if ! sodium sulfite solution conta9s an excess ( alkali1 a black t> t5ds to =m :5 ! solution is w>m$1 & v little ph5ylhydraz9e is obta9$4 ,great c>e mu/ be tak5 9 det]m9+ ! end po9t 9 ! neutralization ( ! sodium hydroxide by ! sulfur dioxide4 ,if ! sodium sulfite-diazonium salt mixture is acidifi$ be=e w>m+ or be=e becom+ d>k1 ! r$ color ( ! solution does n disappe> on heat+1 & ! precipitat$ ph5ylhydraz9e hydro*loride obta9$ is color$ r$4 ,! b5z5e solution ( ph5ylhydraz9e %\ld be well dri$ be=e di/ill+1 s9ce ! pres5ce ( moi/ure causes an increas$ am\nt ( foam+ to take place j aft] ! b5z5e has di/ill$ (f4 ,:5 ! di/illation is c>ri$ out c>efully1 practically no ph5ylhydraz9e di/ils ) ! b5z5e or o!r l[-boil+ impurities4 ,9 ord] to obta9 ! maximum yield1 x is necess>y to cool ! hydro*loric acid solution ( ! ph5ylhydraz9e hydro*loride f #bj'j to #j'j1 be=e filtration4 ,f #e to #aj p] c5t ( product sep>ates betwe5 ^! two temp]atures4 ,:5 ?is is done1 no m ph5ylhydraz9e hydro*loride is obta9$ by conc5tration ( ! "m liquor4 ,an increase 9 ! am\nt ( hydro*loric acid above #b l4 = ! precipitation ( ! hydro*loride produces no increase 9 yield ( product4 ,mo/ publi%$ directions = ! prep>ation ( ph5ylhydraz9e specify ! use ( z9c du/ & acetic acid foll[+ ! r$uction ) sodium sulfite4 ,no improvem5t 9 ! quality or quantity ( ! product 0 obta9$ by us+ z9c & acetic acid4 ,x is be/ to use fre%ly prep>$ sodium sulfite = ! r$uction1 s9ce ! comm]cial quality is poor & gives a l[] yield ( ph5ylhydraz9e4 ,a cyl9d] ( liquid sulfur dioxide %\ld1 ( c\rse1 be available4 ,! rapid addition ( ! diazonium salt solution to ! sodium sulfite seems to be advantage\s4 ,pure ph5ylhydraz9e dissolves 9 dilute acetic acid to yield a p]fectly cle> solution4 ,! ph5ylhydraz9e hydro*loride may be purifi$ by cry/alliz+ f wat]4 ,a #fjj-;cc4 portion ( wat] is us$ = #ajj g4 ( crude hydro*loride1 & ! solution boil$ a %ort "t ) a few grams ( animal *>coal4 ,aft] filt]+1 #bjj cc4 ( conc5trat$ hydro*loric acid are add$1 & ! mixture cool$ to #j'j4 ,pure :ite cry/als 9 a yield ( #he-ij g4 are obta9$4 ,rubb] gloves %\ld be worn :5 work+ ) l>ge quantities ( ph5ylhydraz9e1 s9ce ! product may cause s]i\s injury to ! sk94 ,! vapors ( ph5ylhydraz9e %\ld n be inhal$4 #c4 ,o!r ,me?ods ( ,prep>ation ,ph5ylhydraz9e has be5 prep>$ by ! r$uction ( b5z5e diazonium salts ) sulfites2#a by ! r$uction ( b5z5e diazonium *loride ) /ann\s *loride2#b by ! r$uction ( b5z5e diazonium hydrate ) z9c or sulfur dioxide2#c by ! r$uction ( sodium b5z5e diazotate ) sodium /annite2#d by ! r$uction ( diazoam9o b5z5e2#e by ! r$uction ( nitrosoph5yl hydroxylam9e or its me?yl e!r2#f & by ! action ( hydraz9e hydrate on ph5ol4#g #a ,ann4 #aij1 #gi 7#chgh72 ,b]4 #bj1 #bdfc1 7#ahhg74 #b ,b]4 #af1 #bigf 7#ahhc72 #ag1 #egb1 footnote 7#ahhd74 #c ,b]4 #ca1 #cdf 7#ahih74 #d ,b]4 #cf1 #haf 7#aijc74 #e ,b]4 #ca1 #ehb 7#ahih74 #f ,ann4 #aij1 #gg 7#ahgh74 #g ,b]4 #ca1 #biaj 7#ahih74 ,! mo/ feasible me?od consi/s 9 ! r$uction ( diazonium salts ) sodium sulfite4 ,al?\gh ?is me?od is giv5 9 sev]al laboratory manuals1 ! results 7 n f\nd entirely satisfactory4 ,! pres5t directions provide = a l5g?y b ess5tial heat+ ( ! diazonium-sulfite mixture1 omit ! useless z9c du/ r$uction1 & supply exact details = prep>ation on a fairly l>ge laboratory scale4 ,,xx ,,ph?alimide ,,co ,,co ,c#f;,h#d ,o ,,nh#d,,oh-- ,c#f;,h#d ,,nh #b;,h#b,o ,,co ,,co ,,co ,,co #b;,c#fs,hs#d ,o 7,,nh#d7b;,,co#c-- #b;,c#f;,h#d ,,nh ,,co#b #c;,h#b,o ,,co ,,co ,prep>$ by ,w4 ,a4 ,,noyes & ,p4 ,k4 ,,port]4 ,*eck$ by ,h4 ,t4 ,,cl>ke & ,j4 ,h4 ,,bi%op4 #a4 ,proc$ure ,,9 a #e-l4 r\nd-bottom flask 7,pyrex7 is plac$ a mixture ( #ejj g4 ( ph?alic anhydride & #djj g4 ( #bh p] c5t ammonium hydroxide4 ,! flask is fitt$ ) an air cond5s] n less ?an #aj mm4 9 diamet] & is !n sl[ly heat$ ) a free flame until ! mixture is 9 a /ate ( quiet fusion at a temp]ature ( ab\t #cjj'j4 ,x requires ab\t "o h\r be=e all ! wat] has gone & ab\t "o & a half to two h\rs be=e ! temp]ature ( ! reaction mixture rea*es #cjj'j & ! mixture is a homog5e\s melt4 ,x is advisable1 dur+ ! heat+1 to %ake ! flask occasionally2 "s mat]ial sublimes into ! cond5s] & mu/ be pu%$ d[n ) a glass rod4 ,! hot reaction mixture is n[ p\r$ out into a crock1 cov]$ ) a pap] to prev5t loss by sublimation1 & all[$ to cool4 ,! product is practically pure )\t fur!r treatm5t1 & melts at #bcb-bce'j4 ,! yield is #dgj-dhj g4 7#id-ie p] c5t ( ! !oretical am\nt74 ,ph?alimide may also be made by us+ #ejj g4 ( ph?alic anhydride & #ejj g4 ( ammonium c>bonate :i* has be5 previ\sly gr\nd 9 a mort>4 ,! subsequ5t proc$ure is ! same z :5 aque\s ammonia is us$4 ,frequ5t %ak+ is necess>y1 & ! sublim$ mat]ial mu/ be occasionally pu%$ back into ! reaction flask4 ,ab\t two h\rs are requir$ = completion4 #b4 ,notes ,sev]al small] runs ( #be g4 ( ph?alic anhydride gave ! same p]c5tage yield4 ,ph?alimide may be recry/alliz$ f wat]1 b only ab\t #d g4 ( ph?alimide w dissolve 9 a lit] ( boil+ wat]4 ,x may also be cry/alliz$ f alcohol1 9 :i* solv5t x dissolves to ! ext5t ( five p>ts 9 a hundr$ at boil+ temp]ature4 ,on a l>ge scale1 x w\ld be advisable to collect ! small am\nt ( ammonia giv5 (f dur+ ! reaction4 ,if desir$1 ! product obta9$ by p\r+ ! reaction mass into ! crock may be treat$ ) hot wat] to s(t5 ! cake1 brok5 up ) a glass rod1 transf]r$ to a flask & boil$ ) wat] = a few m9utes4 ,?is treatm5t1 h[ev]1 is q unnecess>y2 = all practical purposes1 ! crude cake1 z x is obta9$1 may be gr\nd up & us$ directly4 #c4 ,o!r ,me?ods ( ,prep>ation ,ph?alimide has be5 =m$ by heat+ ammonium ph?alate2#a by heat+ acid ammonium ph?alate2#b by pass+ dry ammonia ov] heat$ ph?alic anhydride2#c by treat+ ph?alyl *loride ) dry ammonia2#d by heat+ ph?alamide2#e by heat+ ph?alic anhydride ) ammonium ?iocyanate2#f by heat+ ph?alic anhydride ) urea2#g by heat+ ph?alic anhydride ) ammonium c>bonate2#a;b by heat+ ph?alic acid ) nitriles2#b;b by fus+ o-cyanob5zoic acid2#c;b & by ! action ( pota% on o-cyanob5zaldehyde4#d;b #a ,jahresb4 #ahfh1 #edi2 ,ann4 #ai1 #dg 7#ahcf72 #da1 #aaj 7#ahdb72 #db1 #bbj 7#ahdb72 #bje1 #cjj 7#ahhj72 #bae1 #aha 7#ahhb74 #b ,jahresb4 #ahdg-ahdh1 #eij4 #c ,am4 ,*em4 ,j4 #c1 #bi 7#ahha74 #d ,am4 ,*em4 ,j4 #c1 #bh 7#ahha74 #e ,b]4 #ci1 #bbgh 7#aijf74 #f ,b]4 #ai1 #acih 7#ahhf71 #g ,b]4 #aj1 #aaff 7#ahgg72 ,am4 ,*em4 ,j4 #ah1 #ccc 7#ahif72 ,j4 ,am4 ,*em4 ,soc4 #cb1 #aaf 7#aiaj72 ,z4 angew4 ,*em4 #cb1 ,i1 #cja 7#aiai74 #a;b ,j4 ,am4 ,*em4 ,soc4 #db1 #abhb 7#aibj74 #b;b ,j ,am4 ,*em4 ,soc4 #ah1 #fhj 7#ahif72 #bj1 #fed 7#ahih74 #c;b ,rec4 trav4 *im4 7,i7 #aa1 #ic 7#ahib74 #d;b ,b]4 #cj1 #afih 7#ahig74 ,( ^!1 ! fir/ ?ree are ! only ones :i* ne$ be consid]$ z me?ods = ! prep>ation ( ph?alimide4 ,x 0 f\nd t ! ?ird 0 by no means easy to br+ ab\t3 dry ph?alic anhydride is app>5tly only sup]ficially affect$ by ! dry ammonia1 & x 0 difficult to introduce suffici5t heat into ! loose mass ( cry/als to cause ! reaction to />t4 ,,xxi ,,qu9ol9e _/ _/ ,c#c;,h#e7,,oh7#c ,c#f;,h#e,,nh#b #d,o7,c#f;,h#e,,no#b7-- #d;,h#b,o _/ n_/ ,prep>$ by ,h4 ,t4 ,,cl>ke & ,,anne ,w4 ,,davis4 ,*eck$ by ,,rog] ,,adams & ,a4 ,w4 ,,sloan4 #a4 ,proc$ure ,,9 a #e-l4 r\nd-bottom flask1 fitt$ ) an effici5t reflux cond5s] ( wide bore1 are plac$1 9 ! foll[+ ord]1 #hj g4 ( p[d]$ cry/all9e f]r\s sulfate1 #hfe g4 ( glyc]ol 7c4 p471 #bah g4 ( anil9e1 #agj g4 ( nitrob5z5e1 & #djj cc4 ( conc5trat$ sulfuric acid 7sp4 gr4 #a4hd74 ,! cont5ts ( ! flask are well mix$ & ! mixture heat$ g5tly ov] a free flame4 ,z soon z ! liquid beg9s to boil1 ! flame is remov$1 s9ce ! heat evolv$ by ! reaction is suffici5t to keep ! mixture boil+ = "o-half to "o h\r4 ,if ! reaction proce$s too viol5tly at ! beg9n+1 ! reflux cond5s] may be assi/$ by plac+ a wet t[el ov] ! upp] "p ( ! flask4 ,:5 ! boil+ has ceas$ ! heat is aga9 appli$ & ! mixture boil$ = five h\rs4 ,x is !n all[$ to cool to ab\t #ajj'j & transf]r$ to a #ab-l4 flask2 ! #e-l4 flask is r9s$ out ) a small quantity-( wat]4 ,! #ab-l4 flask is !n connect$ ) ! /eam-di/illation app>atus %[n 9 ,fig4 #c1 a #ab-l4 flask be+ us$ z a receiv]2 /eam is pass$ 9 7)\t ext]nal heat7 until #aejj cc4 h di/ill$ 7t5 to ?irty m9utes74 ,?is removes all ! un*ang$ nitrob5z5e 7#aj-bj cc474 ,! curr5t ( /eam is !n int]rupt$1 ! receiv] is *ang$1 & #aejj g4 ( #dj p] c5t sodium hydroxide solution are add$ cauti\sly ?r\gh ! /eam inlet4 ,! heat ( neutralization is suffici5t to cause ! liquids to boil & ?us become ?or\ghly mix$4 ,/eam is !n pass$ 9 z rapidly z possible until all ! qu9ol9e has di/ill$4 ,9 ?is process1 #f-h l4 ( di/illate are collect$ 7two & a half to ?ree & a half h\rs are requir$1 unless a v effici5t cond5s+ app>atus is us$1 "u :i* conditions ! di/illation may be complete 9 "o-half to "o & a half h\rs74 ,! di/illate is all[$ to cool1 & ! crude qu9ol9e sep>at$4 ,! aque\s lay] ( ! di/illate is aga9 di/ill$ ) /eam until all ! qu9ol9e has be5 volatiliz$ & collect$ 9 ab\t #c l4 ( di/illate4 ,^! #c l4 ( di/illate are !n mix$ ) ! fir/ yield ( qu9ol9e & #bhj g4 7#aej cc47 ( conc5trat$ sulfuric acid are add$4 ,! solution is cool$ to #j-e'j1 & a saturat$ solution ( sodium nitrite add$ until a di/9ct excess ( nitr\s acid is pres5t 7z %[n ei!r by />*-potassium iodide pap] or by ! odor74 ,?is g5]ally requires #ej to #gj g4 ( sodium nitrite4 ,! mixture is !n w>m$ on a /eam ba? = an h\r1 or until active evolution ( gas ceases1 & is !n di/ill$ ) /eam until all ! volatile mat]ial has be5 expell$ 7#da4 ( di/illate w result7 ,! receiv] is !n *ang$ & ! mixture 9 ! di/illation flask is neutraliz$1 z be=e1 ) #gjj g4 ( #dj p] c5t sodium hydroxide solution4 ,! qu9ol9e is di/ill$ exactly z describ$ above1 ! aque\s portions ( ! di/illate be+ di/ill$ ) /eam until all ! qu9ol9e has be5 isolat$4 ,! crude product is !n di/ill$ "u r$uc$ pressure1 & ! fraction :i* boils at #aaj-aad'j_/ad mm4 is collect$4 ,! =]uns are sep>at$ f any wat] :i* may be pres5t1 dri$ ) a little solid alkali1 & r$i/ill$4 ,! total yield is #bee-bge g4 7#hd-ia p] c5t ( ! !oretical am\nt bas$ on ! anil9e tak574 #b4 ,notes ,al?\gh ^! directions h be5 us$ _m times ) results exactly z describ$1 9 a few cases ! yields h dropp$ to #fj-fe p] c5t )\t any app>5t reason4 ,at pres5t no explanation c be giv5 = ?is4 ,9 ! ,skraup syn!sis ( qu9ol9e ! pr9cipal difficulty has always be5 ! viol5ce ) :i* ! reaction g5]ally takes place2 x occasionally proce$s relatively smoo?ly1 b 9 ! majority ( cases gets beyond control1 ) consequ5t loss ( mat]ial ?r\gh ! cond5s]4 ,by ! addition ( f]r\s sulfate1 :i* und\bt$ly functions z an oxyg5 c>ri]1 ! reaction is ext5d$ ov] a long] p]iod ( "t4 ,x is ?us possible to "w ) mu* l>g] quantities ( mat]ial :5 f]r\s sulfate is employ$4 ,x is important t ! mat]ials %\ld be add$ 9 ! correct ord]2 %\ld ! sulfuric acid be add$ be=e ! f]r\s sulfate1 ! reaction may />t at once4 ,x is also important to mix ! mat]ials well be=e apply+ heat2 ! anil9e sulfate %\ld h dissolv$ almo/ completely & ! f]r\s sulfate %\ld be di/ribut$ ?r\gh\t ! solution4 ,to avoid dang] ( ov]heat+1 x is well to apply ! flame away f ! c5t] ( ! flask :]e any solids w\ld be liable to congregate4 ,9 ! app>atus = /eam di/illation1 ! great] portion ( ! cond5sation is effect$ by ! /ream ( wat] pass+ ov] ! receiv]4 ,x is1 !re=e1 necess>y t ! /ream pass+ ?r\gh ! cond5s] %\ld be suffici5tly rapid to cause x to =m a uni=m film ov] ! receiv+ flask4 ,a #ab-l4 flask is ev5 m effici5t z a cond5s] ?an ! #e-l4 flask4 ,x is important t ! tube ?r\gh :i* ! vapors leave ! di/illation flask %\ld be nei!r too %ort nor1 especially1 too n>r[4 ,:]e ! ext]nal diamet] ( ! /eam inlet tube is #e-h mm41 ! int]nal diamet] ( ?is /eam head %\ld be n less ?an #bh mm4 ,7 x less1 ! curr5t ( /eam pass+ ?r\gh x w\ld be s rapid z to prev5t small quantities ( liquid f return+ to ! flask1 & ^! w\ld be driv5 ov] into ! receiv]4 ,mu* "t c be sav$ by ! use ( ! /eam di/illation app>atus describ$1 especially :5 l>ge quantities h to be h&l$4 ,! above directions avoid ! use ( extraction me?ods1 :i* n only consume m "t b may lead to appreciable losses ( mat]ial4 ,if ! d[nw>d cond5s] is ( iron1 ! app>atus is ev5 m effici5t & ! "t = ! /eam di/illation is halv$4 ,! p]c5tage yields h be5 bas$ on ! am\nt ( anil9e tak54 ,x w\ld probably be m legitimate to base ! calculation on ! am\nts ( anil9e tak5 & ( nitrob5z5e n recov]$1 s9ce und\bt$ly ! latt] is r$uc$ to anil9e dur+ ! c\rse ( ! reaction4 ,if ?is be done1 ! yield is f\nd to be only #ee to #fj p] c5t ( ! calculat$ am\nt4 ,9 a numb] ( exp]im5ts1 ! glyc]ol us$ conta9$ an appreciable am\nt ( wat]4 ,"u ^! conditions1 ! yield ( product is mu* l[]4 ,dynamite glyc]ol conta9+ less ?an half a p] c5t ( wat] is be/ employ$2 ,u4 ,s4 ,p4 glyc]ol conta9s #e p] c5t ( wat] & usually gives l[] yields4 #c4 ,o!r ,me?ods ( ,prep>ation ,qu9ol9e has be5 produc$ by pass+ ! vapor ( allylanil9e ov] r$-hot lead oxide2#a;a by heat+ acrylid5eanil9e1 or bett]1 a mixture ( anil9e1 glyc]ol & sulfuric acid2#b;a by heat+ anil9e ) glyc]ol & sulfuric acid1 us+ nitrob5z5e z an oxidiz+ ag5t2#a by treat+ a mixture ( glyoxal & o-toluid9e ) alkali2#b by treat+ a solution ( o-am9ob5zaldehyde ) acetaldehyde & alkali2#c by heat+ me?ylacetanilide ) z9c *loride2#d by heat+ am9oazob5z5e ) glyc]ol & sulfuric acid2#e by heat+ a mixture ( anil9e1 glyc]ol & sulfuric acid ) ars5ic acid4#f #a;a ,b]4 #ab1 #dec 7#ahgi74 #b;a ,b]4 #ac1 #iaa 7#ahhj72 ,monat%4 #a1 #caf 7#ahhj74 #a ,monat%4 #b1 #ada 7#ahha72 ,j4 prakt4 ,*em4 7#b7 #di1 #edi 7#ahid71 #b ,monat%4 #ae1 #bgg 7#ahid74 #c ,b]4 #ae1 #begd 7#ahhb72 #af1 #ahcc 7#ahhc74 #d ,b]4 #bc1 #aijc 7#ahij74 #e ,b]4 #bd1 #bfbc 7#ahia7 #f ,b]4 #bi1 #gjd 7#ahif7 ,( ! above me?ods1 ! only ones :i* ne$ be consid]$ are ^? 9 :i* a mixture ( anil9e1 glyc]ol & sulfuric acid is heat$ ) an oxidiz+ ag5t4 ,) ! use ( nitrob5z5e1 ! reaction1 accord+ to ! orig9al me?od1 takes place ) extreme viol5ce4 ,! me?od above describ$ is ! mo/ satisfactory = ! prep>ation ( qu9ol9e itself1 b = ! prep>ation ( homologues ( qu9ol9e1 ! use ( ars5ic acid is pref]able1 s9ce ! yields are some:at great]4 ,s9ce ! "w 0 c>ri$ out1 a me?od has be5 publi%$#g 9 :i* anil9e1 glyc]ol & sulfuric acid are treat$ ) f]ric oxide4 ,by ?is me?od ,adams & ,p>ks 7 unable to obta9 yields comp>able ) ^? result+ f ! above directions4 #g ,*em4 ,news #aba1 #bje 7#aibj74 ,,xxii ,,qu9one 7#a7;,,hoc#f;,h#d,,oh7#d7 ,o7,na#b;,cr#b,o#g ,h#b,,s#d7-- ,o,c#f;,h#d,o ,h#b,o ,prep>$ by ,e4 ,b4 ,,vliet4 ,*eck$ by ,,rog] ,,adams & ,e4 ,e4 ,,dreg]4 #a4 ,proc$ure ,,9 a #b4e-l4 beak]1 #ajj g4 ( hydroqu9one are dissolv$ 9 #bjjj cc4 ( wat] heat$ to ab\t #ej'j4 ,aft] ! solid is completely dissolv$1 ! solution is cool$ to #bj'j1 #ajj g4 ( conc5trat$ sulfuric acid are sl[ly p\r$ 91 & ! mixture is aga9 cool$ to #bj'j4 ,a conc5trat$ solution ( te*nical sodium di*romate is prep>$ by dissolv+ #adj g4 9 #fe cc4 ( wat]4 ,?is solution is !n add$ gradually to ! hydroqu9one solution1 ) ! use ( a me*anical /irr] 7see notes71 ! mixture be+ cool$ s t ! temp]ature nev] rises above #cj'j4 ,at fir/ a gre5i%-black precipitate =ms1 b ^u fur!r addition ( ! sodium di*romate solution1 ! color *anges to yell[i% gre54 ,z soon z ?is color rema9s p]man5t 7a slight excess ( sodium di*romate does no h>m7 ! reaction is complete4 ,?is requires ab\t "o-half to ?ree-qu>t]s ( an h\r2 #ij to #aaj cc4 ( sodium di*romate solution is necess>y4 ,! mixture is !n cool$ to ab\t #aj'j & filt]$ ) suction4 ,z mu* wat] z possible is press$ out ( ! cry/als4 ,! filtrate is extract$ twice1 #aej cc4 ( b5z5e be+ us$ = ea* extraction4 ,! precipitate ( qu9one is transf]r$ to a #a-l4 beak]1 & #ejj cc4 ( b5z5e1 includ+ ! #cjj cc4 us$ to extract ! filtrate1 are add$1 ,! mixture is n[ heat$ ) /irr+ on a /eam-ba?1 & z soon z mo/ ( ! qu9one has dissolv$ ! b5z5e lay] is decant$ into ano!r beak]4 ,x is dri$ :ile hot by /irr+ a %ort "t ) a little calcium *loride1 & !n filt]$ ?r\gh an ord9>y funnel into a #a-l4 di/ill+ flask be=e x cools4 ,!re is a c]ta9 am\nt ( qu9one :i* does n g into ! #ejj cc4 ( b5z5e1 s t ! residue is extract$ a second "t ) ab\t #ajj cc4 ( b5z5e1 :i* is dri$ & filt]$ ) ! fir/ extract4 ,dur+ ^! extractions1 ! b5z5e %\ld n be at ! boil+ po9t1 z ?is w cause a consid]able volatilization ( ! qu9one4 ,! di/ill+ flask is n[ atta*$ to a cond5s] set = d[nw>d di/illation1 & ! b5z5e is di/ill$4 ,z soon z ! qu9one />ts to sep>ate1 ! residue 9 ! flask is transf]r$ to a beak] & cool$ 9 an ice ba?4 ,! precipitate is filt]$ (f ) suction & ! product spread out = a %ort "t to dry4 ,! product is yell[ 9 color & weighs #ge to #hj g4 7#gf-ha p] c5t ( ! !oretical am\nt74 ,mat]ial made 9 ?is way w hold its yell[ color ov] long p]iods ( "t1 provid$ x is protect$ f light4 ,! b5z5e di/illate is yell[ & conta9s "s qu9one4 ,?is1 z well z ! b5z5e f ! f9al filtration ( ! qu9one cry/als1 may be us$ 9 a subsequ5t run & ?us raises ! yield ( ! subsequ5t runs to ab\t #he-ij g4 7#he-ij p] c5t ( ! !oretical am\nt74 #b4 ,notes ,z ! mixture becomes ?ick dur+ ! oxidation1 x is v necess>y to use a /irr] :i* w keep ! :ole mass agitat$ by rea*+ to ! sides & bottom ( ! beak]4 ,if impure hydroqu9one is us$1 a black1 /icky precipitate w usually appe> aft] ! addition ( ! sulfuric acid to ! hydroqu9one solution4 ,?is %\ld be remov$1 be=e ! oxidation is />t$1 by filtration )\t suction ?r\gh a flut$ filt]4 ,:5 te*nical sodium di*romate is us$1 ! solution %\ld be filt]$ ) suction1 be=e x is add$ to ! hydroqu9one1 9 ord] to remove any insoluble impurities4 ,9 ! laboratory x is conv5i5t to make sev]al small runs ( ! size indicat$1 z f> z ! oxidation is conc]n$2 b ! b5z5e extractions c be comb9$4 ,x is also possible to obta9 good yields ( qu9one 9 ! foll[+ mann]3 #aejj cc4 ( wat]1 #dfe g4 ( conc5trat$ sulfuric acid & #cjj g4 ( hydroqu9one are mix$ 9 a #c-l4 beak]4 ,! mixture is cool$ to #j'j1 & #ccj g4 ( sodium di*romate are add$ 9 p[d]$ =m1 ! temp]ature be+ kept bel[ #e'j at all times4 ,?is proc$ure requires a long] "t & mu* m c>e 9 ! control ( conditions ?an ! me?od describ$ above4 #c4 ,o!r ,me?ods ( ,prep>ation ,qu9one may be prep>$ by ! oxidation ( anil9e ) di*romate or manganese dioxide & sulfuric acid4#a ,?is is a m feasible comm]cial me?od ?an ! "o giv54 ,h[ev]1 ! oxidation ( hydroqu9one is m rapid & conv5i5t &1 h5ce is m desirable = use 9 ! laboratory4 ,v>i\s mat]ials h be5 oxidiz$ by *emical means to give qu9one3 !y are qu9ic-acid1#b hydroqu9one1#c b5zid9e1#d p-ph5yl5$iam9e1#e sulfanilic acid1#f p-ph5olsulfonic acid1#g arbut91#h anil9e black1#i & ! leaves ( v>i\s plants4#aj ,qu9one is also =m$ by sev]al o!r me?ods3 by ! f]m5tation ( fre% grass2#aa by ! action ( iod9e on ! lead salt ( hydroqu9one2#a;b by ! decomposition ( ! comp\nd1 ,c#f;,h#d4b;,cr,o#b;,cl ) wat]2#b;b by ! action ( sulfuric acid on ph5ol blue2#c;b by ! electro*emical oxidation ( anil9e1#d;b hydroqu9one#e;b or b5z5e2#f;b by ! catalytic oxidation ( b5z5e4#g;b #a ,jahresb4 #ahfc1 #dae2 ,b]4 #aj1 #aicd1 #bjje 7#ahgg72 #af1 #fhg 7#ahhc72 #ai1 #adfh 7#ahhf72 #bj1 #bbhc 7#ahhg72 #ca1 #aebd 7#ahih72 ,ann4 #bjj1 #bdj 7#ahhj72 #bae1 #abg 7#ahhb74 #b ,ann4 #bg1 #bfh 7#ahch74 #c ,ann4 #ea1 #aeb 7#ahdd7 j ,am4 ,*em4 ,j4 #ad1 #eee 7#ahib74 #d ,jahresb4 #ahfc1 #dae4 #e ,jahresb4 #ahfc1 #dbb4 #f ,ann4 #aei1 #g 7#ahga72 ,b]4 #h1 #gfj 7#ahge74 #g ,b]4 #h1 #gfj 7#ahge74 #h ,ann4 #ajg1 #bcc 7#aheh74 #i ,b]4 #aj1 #aicd 7#ahgg72 #cd1 #abhe 7#aija74 #aj ,ann4 #hi1 #bdg 7#ahed72 ,b]4 #cd1 #aafb 7#aija74 #aa ,b]4 #cj1 #ahgj 7#ahig74 #a;b ,b]4 #ca1 #adeh 7#ahih72 ,am4 ,*em4 ,j4 #bf1 #bj 7#aija74 #b;b ,ann4 *im4 phys4 7#e7 #bb1 #bgj 7#ahha74 #c;b ,b]4 #ah1 #biae 7#ahhe72 #ba1 #hhi 7#ahhh74 #d;b ,d4 ,r4 ,p4 #aji1jab2 ,frdl4 #e1 #ffd 7#aijj72 ,d4 ,r4 ,p4 #aag1abi2 ,frdl4 #f1 #aab 7#aija72 ,j4 ,soc4 ,dy]s & ,col\ri/s1 #cf1 #ach 7#aibj74 #e;b ,d4 ,r ,p4 #aag1abi2 ,frdl4 #f1 #aab 7#aija74 #f;b ,d4 ,r4 ,p4 #aag1bea2 ,frdl4 #f1 #aji 7#aija72 ,u4 ,s4 ,pat4 #a1cbb1ehj 7#aiai72 ,c4 ,a4 #ad1 #bhg 7#aibj72 ,rev4 produits *im4 #ba1 #bai 7#aiah72 #ba1 #bhh 7#aiah74 #g;b ,u4 ,s4 ,pat4 #a1cah1fca 7#aiai72 ,c4 ,a4 #ad1 #gj 7#aibj74 ,,xxiii ,,sodium p-,,tolu5esulf9ate #b;,,*#c;,c#f;,h#d,,s#b;,cl #c,zn-- 7,,*#c;,c#f;,h#d,,s#b7b,zn ,zn,cl#b 7,,*#c;,c#f;,h#d,,s#b7b,zn ,na#b;,,co#c-- #b;,,*#c;,c#f;,h#d,,s#b,na ,zn,c,o#c ,prep>$ by ,,frank ,c4 ,,:itmore & ,,francis ,h4 ,,hamilton ,*eck$ by ,j4 ,b4 ,,conant & ,,paul ,,all51 ,,jr4 #a4 ,proc$ure ,,five ,,hundr$ grams ( te*nical p-tolu5esulfonyl *loride are gr\nd 9 a mort> to break up all lumps4 ,?ree lit]s ( wat] are plac$ 9 a #ab-l4 crock provid$ ) a l>ge brass /irr] & a tube = pass+ /eam directly into ! liquid4 ,dry /eam is pass$ into ! wat] until ! temp]ature rea*es #gj'j4 ,! /eam is !n %ut (f & #djj g4 ( z9c du/ 7#ij to #ajj p] c5t pure7 is add$4 ,! sulfonyl *loride is !n add$ 9 small portions by means ( a porcela9 spoon4 ,! addition takes ab\t t5 m9utes4 ,! temp]ature rises to ab\t #hj'j4 ,/irr+ is cont9u$ = t5 m9utes aft] ! la/ ( ! *loride has be5 add$4 ,/eam is !n pass$ into ! mixture until ! temp]ature rea*es #ij'j4 ,if x is heat$ any hott]1 bump+ takes place4 ,! /eam is %ut (f1 & #bej cc4 ( #ab ,n4 sodium hydroxide solution is add$4 ,f9ely p[d]$ sodium c>bonate is !n add$ 9 #ej-;g4 portions until ! mixture is /rongly alkal9e4 ,! mixture fro?s consid]ably1 b ?is causes no tr\ble unless too small a crock is us$4 ,! /irr] is loos5$ & ! crock is remov$4 ,! mixture is filt]$ by suction 9 a l>ge funnel4 ,! filtrate has a volume ( ab\t #d4e l4 ,! cake ( un*ang$ z9c du/ & z9c comp\nds is transf]r$ to a #c-l4 batt]y j> & plac$ "u ! /irr]1 & ! latt] is clamp$ 9 place4 ,wat] 7#gej cc47 is add$1 ! /irr] is />t$1 & /eam is pass$ 9 until ! mixture />ts to fro? too viol5tly4 ,! /eam is !n %ut (f1 b ! /irr+ is cont9u$ = t5 m9utes4 ,! mixture is filt]$ & ! filtrate is add$ to ! ma9 solution 9 a l>ge evaporat+ di%4 ,! liquid is evaporat$ ov] a l>ge burn] to a volume ( ab\t #a l41 or until a consid]able cru/ =ms ar\nd ! edges4 ,! mixture is !n cool$4 ,l>ge1 flat1 transp>5t cry/als sep>ate4 ,! ?or\ghly cool$ mixture is filt]$ by suction1 & ! cry/als are air-dri$ until effloresc5ce j />ts4 ,!y are !n bottl$4 ,! product is ,,*#c;,c#f;,h#d,,s#b,na4#b;,h#b,o4 ,yield #cfj g4 7#fd p] c5t ( ! !oretical am\nt74 ,c>eful acidification ( ! "m liquor ) dilute hydro*loric acid yields #ae g4 ( ! free sulf9ic acid4 #b4 ,notes ,! free sulf9ic acid may be prep>$ by dissolv+ ! sodium salt 9 cold wat] & c>efully acidify+ ! solution ) hydro*loric acid4 ,an excess ( ! latt] mu/ be avoid$1 z x dissolves ! acid to a c]ta9 ext5t4 ,! sulf9ic acid is difficult to dry )\t p>tial conv]sion into ! sulfonic acid4 #c4 ,o!r ,me?ods ( ,prep>ation ,tolu5esulf9ic acid & its salts h be5 prep>$ by ?ree g5]al me?ods3 7#a7 ,! r$uction ( ! sulfonyl *loride4 ,! reag5ts :i* h be5 us$ = ?is are sodium amalgam1#a z9c du/ 9 alcohol or wat]1#b sodium sulfite1#c sodium sulfide1#d potassium hydrosulfide#e 7! ?io acid be+ fir/ =m$7 & sodium ars5ite4#f 7#b7 ,f tolu5e by ! ,fri$el & ,crafts reaction1 us+ ei!r sulfur dioxide & hydrog5 *loride#g or sulfuryl *loride4#h 7#c7 ,f p-toluid9e by diazotization & subsequ5t treatm5t ) sulfur dioxide & f9ely divid$ copp]4#a;b ,! comp\nd has also be5 obta9$ 9 c]ta9 reactions :i*1 h[ev]1 w\ld n be suitable = prep>ative "w2 ?us x is =m$ by hydrolysis & r$uction ( c]ta9 ?io d]ivatives#b;b prep>$ f ! acid itself & also by ! decomposition ( ditolylsulfonme?ylam9e4#c;b #a ,ann4 #adb1 #ic 7#ahfg74 #b ,b]4 #i1 #aehf 7#ahgf74 #c ,b]4 #c1 #ife 7#ahgj74 #d ,d4 ,r4 ,p4 #bbd1jai2 ,*em4 ,z5tr4 #aiaj1 7,,ii71 #eac4 #e ,b]4 #db1 #chba 7#aiji74 #f ,b]4 #da1 #ccea 7#aijh72 ,b]4 #db1 #dhj 7#aiji74 #g ,b]4 #da1 #ccah 7#aijh72 ,j4 ,*em4 ,soc4 #ic1 #ged 7#aijh74 #h ,rec4 trav4 *im4 7#b7 #cj1 #cha 7#aiaa74 #a;b ,b]4 #cb1 #aada 7#ahii72 ,j4 ,*em4 ,soc4 #ie1 #cdd 7#aiji74 #b;b ,b]4 #ae1 #acj 7#ahhb72 #bj1 #bjhh 7#ahhg72 #da1 #ccea 7#aijh74 #c;b ,j4 prakt4 ,*em4 7#b7 #fc1 #agj 7#aija74 ,,xxiv #a1c1e-,,tr9itrob5z5e ,c#f;,h#b7,,no#b7c;,,co#b;,h-- ,c#f;,h#c7,,no#b7c ,,co#b ,prep>$ by ,h4 ,t4 ,,cl>ke & ,w4 ,w4 ,,h>tman4 ,*eck$ by ,j4 ,b4 ,,conant & ,j4 ,j4 ,,toohy4 #a4 ,proc$ure ,,! crude tr9itrob5zoic acid obta9$ by oxidation ( #cfj g4 ( tr9itrotolu5e 7prep4 ,,xxv1 p4 #ie7 is mix$ ) #b l4 ( wat] at #ce'j 9 a #e-l4 flask provid$ ) a /irr]4 ,fifte5 p] c5t sodium hydroxide solution is add$1 ) cont9u\s /irr+1 until a ,,fa9t r$ color is j produc$4 7,see ,notes47 ,! color is !n imm$iately dis*>g$ by means ( "o or two drops ( acetic acid1 & ! liquid is filt]$ f un*ang$ tr9ibrotolu5e4 ,! filtrate is transf]r$ to a #e-l4 flask1 & #gj cc4 ( glacial acetic acid are add$4 ,! mixture is !n g5tly heat$1 ) cont9u\s /irr+1 :5 tr9itrob5z5e sep>ates 9 cry/all9e condition1 & floats on ! surface ( ! liquid z a fro?y lay]4 ,aft] ab\t "o & a half h\rs ! evolution ( gas ceases2 at ?is po9t ! cry/als beg9 to /ir into ! solution4 ,! heat+ & /irr+ is cont9u$ = ?ree-qu>t]s ( an h\r1 :5 ! mixture is all[$ to cool1 & ! cry/als filt]$ (f4 ,a sample ( ! filtrate %\ld be te/$ = undecompos$ tr9itrob5zoic acid3 if a precipitate is produc$ by ! addition ( sulfuric acid ! process mu/ be cont9u$4 ,aft] recry/allization f glacial acetic acid1 ! product melts at #aba-abb'j4 ,! yield is #ade-aee g4 7#dc to #df p] c5t ( ! !oretical am\nt calculat$ f ! tr9itrotolu5e74 #b4 ,notes ,dur+ ! solution ( ! tr9itrob5zoic acid1 ! temp]ature %\ld n be bel[ #ce'j1 ow+ to ! slight solubility ( tr9itrob5zoic acid 9 cold wat]4 ,! heat ( neutralization raises ! temp]ature to #de-ee'j1 b ! latt] temp]ature %\ld n be exce$$1 s9ce any tr9itrob5z5e =m$ at ?is po9t w\ld lat] be remov$ ) ! unreact$ tr9itrotolu5e4 ,c>e mu/ be tak5 t no m alkali is add$ ?an is j suffici5t to produce ! fa9t r$ color4 ,if an excess ( alkali is add$ x produces a p]man5t color1 :i* is n remov$ by acid & colors ! f9al product4 ,:5 once ! evolution ( c>bon dioxide sets 91 ! flame mu/ be cut d[n s z to avoid ! =mation ( a ?ick lay] ( fro? :i* might foam ov]4 #c4 ,o!r ,me?ods ( ,prep>ation #a1c1e-,tr9itrob5z5e c be prep>$ by heat+ m-d9itrob5z5e ) nitric acid & sulfuric acid to #abj'j2a by heat+ #b1d1f-tr9itrotolu5e ) fum+ nitric acid 9 a seal$ tube at #ahj'j = ?ree h\rs2#b by heat+ #b1d1f-tr9itrob5zoic acid or its sodium salt ) wat]1 alcohol1 dilute sodium c>bonate or o!r suitable solv5t4#c #a ,b]4 #i1 #djb 7#ahgf72 ,ann4 #bae1 #cdd 7#ahhb74 #b ,b]4 #af1 #aeif 7#ahhc74 #c ,d4 ,r4 ,p4 #gg1cec2 ,frdl4 #d1 #cd 7#ahid74 ,,xxv #b1 #d1 #f-,,tr9itrob5zoic ,,acid ,c#f;,h#b7,,no#b7c;,,*#c #c,o7,na#b;,cr#b,o#g ,h#b,,s#d7-- ,c#f;,h#b7,,no#b7c;,,co#b;,h ,h#b,o ,prep>$ by ,h4 ,t4 ,,cl>ke & ,w4 ,w4 ,,h>tman4 ,*eck$ by ,j4 ,b4 ,,conant & ,j4 ,j4 ,,toohy4 #a4 ,proc$ure ,to #cfjj g4 ( conc5trat$ sulfuric acid1 9 a #e-l4 flask plac$ 9 an empty wat] ba?1 are add$ #cfj g4 ( te*nical tr9itrotolu5e1 :ile ! mixture is /irr$ me*anically4 ,sodium di*romate 7,na#b;,cr#b,o#g #b;,h#b,o7 is n[ add$ 9 small quantities 7,,precaution3 see ,notes71 ) con/ant /irr+1 until ! temp]ature ( ! mixture rea*es #dj'j2 ! empty wat] ba? is n[ fill$ ) cold wat] & ! addition ( sodium di*romate cont9u$ at su* a rate t ! temp]ature rema9s at #de-ee'j4 ,9 all #edj g4 ( sodium di*romate are add$1 ! addition tak+ "o to two h\rs4 ,:5 all has be5 add$1 ! mixture1 :i* has n[ become v ?ick1 is /irr$ = two h\rs at #de-ee'j1 & p\r$ into a crock conta9+ #d kg4 ( cru%$ ice4 ,! insoluble tr9itrob5zoic acid is filt]$ (f1 & c>efully wa%$ ) cold wat] until free f *romium salts4 ,on dry+ x weighs #cbj-cdj g4 ,! product is n[ mix$ ) #b l4 ( di/ill$ wat] at #ce'j 9 a #e-l4 flask provid$ ) a /irr]1 & #ae p] c5t sodium hydroxide solution is dropp$ 9 ) cont9u\s /irr+ until a ,,fa9t r$ color is j produc$4 ,%\ld ?is disappe>1 x is re/or$ by ! addition ( a few drops m4 ,:5 x has p]si/$ = five m9utes1 ! color is dis*>g$ by ! addition ( a few drops ( acetic acid1 & ! insoluble unattack$ tr9itrotolu5e filt]$ (f & wa%$ ) a little wat]4 ,! tr9itrob5zoic acid is precipitat$ f ! filtrate by ! addition ( a slight excess ( #ej p] c5t sulfuric acid4 ,! solution is *ill$1 & ! acid filt]$ & wa%$ free f salts ) ice wat]4 ,:5 dri$ 9 air x weighs #bcj-bhj g4 7#eg to #fi p] c5t ( ! !oretical am\nt74 #b4 ,notes ,! "m liquors & wa%+s lose c>bon dioxide on boil+1 & ! insoluble tr9itrob5z5e sep>ates see prep>ation ,,xxiv72 aft] filt]+1 wa%+1 & dry+1 x weighs #ae-bj g4 7#d to #f p] c5t ( ! !oretical am\nt74 ,x is ess5tial t ! /irr+ %\ld be mo/ effici5t1 s t :5 ! mixture becomes ?ick ! di*romate w be ev5ly di/ribut$ ?r\gh\t ! liquid1 z rapidly z x is add$4 ,if ! /irr+ is n effici5t1 local reactions ( extreme viol5ce 79 c]ta9 cases lead+ to conflagration7 w occur4 ,an iron /irr] may be employ$ 9 ! oxidation reaction1 b n 9 ! purification4 ,te*nical sodium di*romate g5]ally conta9s a c]ta9 am\nt ( *lorides1 & ! *lor9e lib]at$ f ^! t5ds to cause a tr\blesome foam t[>ds ! end1 ( ! reaction4 ,only a v effici5t /irr]1 :i* draws d[n ! surface ( ! liquid1 is able to combat ?is difficulty4 ,! am\nt ( solid sodium di*romate giv5 is = ! dry cry/all9e comp\nd conta9+ two molecules ( wat] ( cry/allization4 ,great c>e %\ld be tak5 9 dissolv+ ! crude acid 9 ! alkali4 ,if an excess ( alkali p]si/s = any l5g? ( "t1 a p]man5t color is produc$ :i* w discolor ! f9al product4 ,! acid is fairly soluble 9 cold wat] & %\ld be wa%$ ) c>e4 #c4 ,o!r ,me?ods ( ,prep>ation #b1d1f-,tr9itrob5zoic acid has be5 prep>$ by heat+ tr9itrotolu5e ) fum+ acid 9 a seal$ tube to #ajj'j1 = two weeks1#a;a ! oxidation be+ only p>tial4 ,x c also be prep>$ by heat+ tr9itrotolu5e "u a reflux cond5s]1 ) a mixture ( #e p>ts ( conc5trat$ nitric acid & #aj p>ts ( conc5trat$ sulfuric acid2#a ?is me?od is1 h[ev]1 unsuitable 9 ! laboratory ow+ to ! difficulty ( devis+ suitable app>atus4 ,ano!r me?od is to dissolve tr9itrotolu5e 9 nitric acid &1 to ?is solution 7at #ie'j71 to add potassium *lorate at su* a rate t ! temp]ature does n fall2#b ?is me?od has be5 f\nd to be difficult to control on a laboratory scale4 #a;a ,b]4 #c1 #bbc 7#ahgj7 #a ,d4 ,r4 ,p4 #gg1eei2 ,frdl4 #d1 #cd 7#ahid7 #b ,d4 ,r4 ,p4 #bbf1bbe2 ,frdl4 #aj1 #afg 7#aiaj74 ,! me?od describ$ above is a modification ( a pat5t$ process1#c 9 :i* tr9itrotolu5e susp5d$ 9 sulfuric acid is treat$ ) *romic anhydride4 #c ,d4 ,r4 ,p4 #abg1cbe2 ,frdl4 #f1 #adh 7#aija74 ,,index ,a ,acetic acid1 #ah1 #cc1 #fd ,acetone1 #da ,acetoph5one1 #a ,ammonium c>bonate1 #ge ,ammonium hydroxide1 #cg1 #ge ,anil9e1 #ga1 #gi ,an?ranilic acid1 #dg ,b ,b5zalacetoph5one1 #a ,b5zaldehyde1 #a1 #e ,b5zoic acid1 #e ,b5zyl alcohol1 #e ,b5zyl b5zoate1 #f ,b5zyl *loride #i ,b5zyl cyanide1 #i-aa1 #bg1 #eg1 #fc ,bromo/yr5e1 #fg ,c ,c>bon tetra*loride1 #bc ,*lor9e1 #cg ,copp] sulfate1 #ch ,d ,dib5zyl e!r1 #f a1 g-,di*loroacetone1 #ac-ae ,dime?ylam9ob5zaldehyde1 #ag-ba ,dime?ylanil9e1 #ag1 #dg ,e ,e?yl alcohol1 #bc1 #bg ,e?yl oxalate1 #bc-bf ,e?yl ph5ylacetate1 #bg-bh ,f ,f]r\s sulfate1 #gi ,=maldehyde1 #ag ,g ,gelat9e solution1 #cg ,glyc]ol1 #bi1 #cc1 #gi ,glyc]ol a1 g-di*lorohydr91 #bi-ca ,glyc]ol a-mono*lorohydr91 #cc-ce ,h ,hydraz9e sulfate1 #cg #dj ,hydro*loric acid1 #ag1 #cj1 #cd1 #dg1 #ga ,hydroqu9one1 #he ,m ,mesityl5e1 #da-de ,me?yl r$1 #dg-fa ,n ,naph?ol1 #fa ,nitric acid1 #eg ,nitrob5z5e1 #gi p-,nitrob5zoic acid1 #fc-ff p-,nitrob5zyl cyanide1 #fg-eh1 #ei p-,nitroph5ylacetic acid1 #fidj ,nitrosodime?ylanil9e hydro*loride1 #ag ,nitroso-1#c-naph?ol1 #fa-fb ,nitrotolu5e1 #ec ,o ,oxalic acid1 #bc ,p ,ph5ylacetic acid1 #aj1 #fc-fe ,ph5ylacetyl5e1 #fg-fi ,ph5ylhydraz9e1 #ga-gd ,ph?alic anhydride1 #ge ,ph?alimide1 #ggh ,potassium hydroxide1 #fg ,q ,qu9ol9e1 #gi #hc ,qu9one1 #hf #hh ,s ,sodium acetate1 #dh ,sodium b5zylate1 #f ,sodium cyanide1 #i ,sodium di*romate1 #ac1 #ec1 #he1 #ie ,sodium hydroxide1 #a1 #cg1 #fa1 #ic ,sodium hypo*lorite1 #cg ,sodium1 metallic1 #e1 #db ,sodium nitrite1 #ag1 #dg1 #fa1 #ga1 #hj ,sodium sulfite1 #ga ,sodium p-tolu5e sulf9ate1--#ia ,sulfur dioxide1 #ga ,sulfuric acid1 #ac1 #bg1 #cj4 #cd1 #cg1 #da1 #dc1 #ec1 #eg1 #ei1 #fc1 #gi1 #he1 #ie ,t ,tolu5e1 #dh ,tolu5esulfonyl *loride1 #hi ,i1 #c1 s-,tr9itrob5z5e1 #ic-- #id1 #if #b1 #d1 #f-,tr9itrob5zoic acid1 #ic1 #if #ig #b1 #d1 #f-,tr9itrotolu5e1 #ic1 #ie ,z9c du/1 #hi