,,bo/on ,,univ]sity ,,graduate ,,s*ool ,,!sis ,,meta ,,tolu5e ,,sulphonic ,,acid & ,,relat$ ,,comp\nds ,submitt$ by ,*>les ,francis ,hit*cock ,all5 7,a4,b41 ,bo/on ,univ]sity1 #aiai7 ,9 p>tial fulfilm5t ( requirem5ts = ! degree ( ,ma/] ( ,arts #aibj ,,table ,,( ,,cont5ts4 ,,meta ,,tolu5e ,,sulphonic ,,acid & ,,relat$ ,,comp\nds ,,!oretical ,,discussion ,,sulphonation ,,( ,,or?o ,,toluid9e ,,sulphonation ,,( ,,p>a ,,toluid9e ,,diazotization ,,( ,,or?o ,,toluid9e ,,sulphonic ,,acid4 ,,physical ,,prop]ties ,,( ,,! ,,diazo ,,comp\nd ,,decomposition ,,( ,,! ,,diazo ,,comp\nd ,a ,,/udy ,,( ,,! ,,solution ,,obta9$ ,,by ,,! ,,decomposition ,,( ,,! ,,diazo ,,comp\nd ,,conclusion ,,bibliography ,,meta ,,tolu5e ,,sulphonic ,,acid & ,,relat$ ,,comp\nds ,!oretically tolu5e %\ld yield ?ree isom]ic mono sulphonic acids1 9 :i* ! ent]+ sulphonic acid gr\p occupies ! positions or?o1 meta1 or p>a to ! me?yl gr\p4 ,! action ( sulphuric acid on tolu5e 0 fir/ inve/igat$ by ,jaworsky1 7,zts*r4 ,*em4 #a1bgb71 :o describ$ "o tolu5e sulphonic acid z ! result+ comp\nd4 ,9 #ahfi ,engelh>dt & ,lats*9(f 7,ibid4 #fag71 heat$ tolu5e ) sulphuric acid & made & /udi$ ! potassium salt ( ! result+ acid4 ,!y obta9$ two =ms1 & id5tifi$ !m by fusion ) cau/ic pota% :i* conv]t$ !m into ! or?o & p>a cresols1 %[+ t sulphonation _h tak5 place 9 ! positions or?o & p>a to ! me?yl gr\p4 ,b>? 7,ann4 *em4 7,liebig7 #aeb1ia71 work+ simil>ly b fus+ "u diff]5t conditions :i* also caus$ oxidation ( ! me?yl gr\p to a c>boxyl gr\p obta9$ p>a hydroxy b5zoic acid & salicylic acid 7or?o hydroxy b5zoic acid47 ,?is also prov$ t ! sulphonic acid gr\p _h ent]$ 9 ! or?o & p>a positions4 ,anna ,wolk[ 7,zts*r4 ,*em 7#ahgj7 #cba71 confirm$ ?is "w b ascrib$ ! meta position to ! sulphonic acid t pass$ into salicylic acid4 ,%e also made two acid *lorides & amides & record$ _! melt+ po9ts4 ,fittig & ,ramsay 7,ann4 *em4 7,liebig7 #afh1bdb7 /udi$ ?is result ( ,anna ,wolk[1 & to det]m9e & settle ! con/itutions ( ! sulphonic acids1 c>efully prep>$ & purifi$ _! sulphonic acids2 !y prov$ def9itely t no meta acid 0 =m$1 & t ! products 7 only ! or?o & p>a tolu5e sulphonic acids4 ,hubn] & ,po/ 7,ann4 *em4 7,liebig7 #afi1dg7 work$ on pure p>a brom tolu5e1 & obta9$ two p>a brom tolu5e mono-sulphonic acids1 "o ( :i* !y prov$ to be ! or?o acid by removal ( ! brom9e by metallic sodium1 & oxidation to salicylic acid4 ,by exclusion !y decid$ t ! o!r acid mu/ be "o conta9+ ! sulphonic acid gr\p 9 meta position to ! me?yl gr\p4 ,f4,c4,g4 ,mll] 7same z ,hubn] & ,po/7 made ! b>ium salt ( or?o brom tolu5e sulphonic acid1 & !n remov$ ! brom9e by treatm5t ) sodium amalgam4 ,! excess ( alkali 0 remov$ by sulphuric acid1 ! sodium sulphate remov$ by evaporation & cry/allization1 & ! residue dri$4 ,on treatm5t ) phosphorus p5ta*loride an oily tolu5e sulphon*loride 0 obta9$2 ?is 0 decompos$ by heat+ ) wat]1 ! hydro*loric acid remov$ by repeat$ evaporations1 & ! syrup ?us obta9$ evaporat$ to a cry/all9e condition4 ,sev]al salts 7 made & /udi$4 ,8 amide melt$ at #ij-ia4 ,because ?is acid diff]$ 9 prop]ties f ! two previ\sly m5tion$1 ,mll] consid]$ x to be ! meta tolu5e sulphonic acid4 ,ab\t ?is "t ,f4 ,g]vor 7,ann4 *em4 7,liebig7 #afi1chc71 made or?o diazo tolu5e sulphonic acid by subject+ or?o toluid9e sulphonic acid to nitr\s fumes4 ,?is 0 decompos$ ) alcohol "u pressure1 & a sodium salt ( ! acid obta9$2 ?is 0 conv]t$ into ! *loride & an amide :i* melt$ at #adh1 diff]+ 9 ?is & o!r prop]ties f ! amides ( ! or?o & p>a tolu5e sulphonic acids previ\sly kn[n4 ,9 #ahgd ,pe*mann 7,ibid41 #agc1aie7 obta9$ a quantity ( p>a toluid9e meta sulphonic acid by heat+ p>a toluid9e ) sulphuric acid1 & cry/alliz+ out ! p>a toluid9e or?o sulphonic acid & disulphonic acids1 leav+ ! meta acid 9 solution because ( its great] solubility4 ,! diazo comp\nd 0 made by treatm5t ( ! acid 9 alcoholic susp5sion ) nitr\s fumes1 & decompos$ ) alcohol "u pressure4 ,v>i\s salts ( ! result+ sulphonic acid 7 made & /udi$1 also ! *loride & amide :i* melt$ some:]e bel[ #ajj4 ,9 #ahge ,pagel 7,ann4 *em4 7,liebig7 #agf1big7 work+ on or?o toluid9e sulphonic acid1 made a tolu5e sulphonic acid :i* resembl$ ,mull]'s4 ,8 amide melt$ at #ajd4 ,9 #ahgg ,beckurts 7,b]4d4*e4 ,ges4 #aj1 #idc71 seek+ = a good me?od ( obta9+ pure or?o tolu5e sulphonic acid1 heat$ tolu5e & sulphuric acid 9 ! ord9>y way1 & made ! potassium salts ( ! result+ acids4 ,by treatm5t ) phosphorus p5ta*loride he obta9$ ! acid *lorides :i* he sep>at$ by cool+ to -#ae1 & filt]+ (f ! solid p>a comp\nd4 ,! rema9+ liquid 0 trans=m$ into an amide & purifi$ by fractional cry/allization4 ,two comp\nds 7 obta9$ ) %>p melt+ po9ts ( #aec & #ajd4 ,f ?is "w he conclud$ t ! sulphonation ( tolu5e yield$ all ! ?ree possible acids4 ,fahlb]g 7,am4 ,*em4 ,j4 #a1 #agj71 d\bt$ ,beckurts' /atem5t1 because al?\gh 8 acid %[$ diff]5t prop]ties he neglect$ to prove its con/itution by conv]t+ x into ! hydroxy b5zoic acid4 ,he !re=e repeat$ ,beckurts' "w1 & id5tifi$ ! amide melt+ at #aed z com+ f or?o tolu5e sulphonic acid1 by conv]sion into salicylic acid4 ,! o!r amide ) a %>p1 con/ant melt+ po9t ( #ajh 0 oxidiz$1 & ! products sep>at$ & id5tifi$ z p>a sulpham9e b5zoic acid1 anhydro or?o sulpham9e b5zoic acid1 & acid potassium or?o sulphob5zoate4 ,^! 7 ! products "o w\ld expect f an oxidation ( a mixture ( ! or?o & p>a tolu5e sulphonamides4 ,fur!r pro( t 8 acid 0 a mixture 0 obta9$ by mix+ am\nts ( pure or?o & p>a tolu5e sulphonic acids1 & by repeat$ cry/allizations a =m 0 obta9$ :i* melt$ at #ajh4 ,f4,h4,s4 ,mull] 7,b]4 d4 *em4 ,ges4 #ac1 #acdh71 m5tion$ ! =mation ( meta tolu5e sulphonic acid by ! action ( sulphur\s acid ^u ! correspond+ diazo comp\nd1 b gave no details except ! melt+ po9ts ( 8 amide1 anilide1 & toluide4 ,claesson & ,wall9 9 #ahgi 7,ibid4 p4 #ahdh71 claim$ t !y _h obta9$ meta tolu5e sulphonic acid by ! action ( *lorsulphonic acid ^u tolu5e4 ,!y us$ v l>ge quantities ( mat]ials4 ,!y obta9$ ?ree acids1 & id5tifi$ !m z ! or?o & p>a1 & call$ ! ?ird ! meta acid1 despite ! fact t !y _h k ( ,fahlb]g's "w4 ,! next /ep 0 und]tak5 by ,r4 ,otto 7,ibid1 #ac1 #abib71 at ! reque/ ( ,beckurts4 ,he exam9$ "s ( ! latt]'s suppos$ meta tolu5e sulphonamide1 & f\nd x to be a mixture ( ! amides ( ! or?o & p>a acids4 ,nevile & ,w9!r 7,ibid4 #ac1 #aidj71 :ile inve/igat+ ! =mation ( am9o sulphonic acids1 obta9$ a tolu5e sulphonic acid by heat+ or?o diazo tolu5e sulphonic acid ) alcohol "u pressure1 & also by r$uc+ brom tolu5e sulphonic acid ) sodium amalgam4 ,x 0 conv]t$ into ! *loride & amide1--! latt] melt+ at #ajf4e-ajg4e4 ,9 #ahhf1 ,val9 7,ibid4 #bieb71 conv9c$ by ! "w ( ,otto t ,fahlb]g's views 7 correct1 & t he & ,klason _h n obta9$ meta tolu5e sulphonic acid1 aga9 attack$ ! problem2 an acid 0 made & salts describ$4 ,9 #ahia1 ,metcalf 7,am4 ,*e4 ,j4 #ae1cja7 7,diss]tation1 #ahib71 prov$ t decomposition ( p>a diazo tolu5e meta sulphonic acid ) e?yl alcohol "u pressure result$ 9 ! =mation ( p>a e?oxy meta tolu5e sulphonic acid 9 f> great] quantity4 ,consequ5tly ! tolu5e meta sulphonic acid c\ld n h be5 obta9$ by ei!r ,pe*mann or ,val94 ,griff91 7,diss]tation1 #ahie71 prep>$ :at he ?\ght 0 a solution ( ! meta tolu5e sulphonic acid f ! amide1 & made & /udi$ sev]al salts z well z ! anilide & toluide4 ,h[ev] he did n inve/igate 8 solution to f9d out :at x conta9$1 b w5t ahead on ! assumption t he _h a solution ( ?is acid4 ,x is on ! basis ( 8 lack ( inve/igation t ,i am work+4 ,! d]ivatives ( p>a tolu5e sulphonic acid h be5 made & /udi$ by ,newell1 7,diss]tation1 #ahie71 & are be+ inve/igat$ fur!r4 ,he prep>$ p>a tolyl ph5yl sulphone by ! ,fri$al-,crafts reaction1 p>a ph5yl sulphone b5zoic acid by oxidation ( ! sulphone ) *romic acid1 its salts1 *loride1 amide1 & anilide1 & p>a b5zoyl diph5yl sulphone f ! acid by ! ,fri$al-,crafts reaction1 & /udi$ _! reactions & prop]ties4 ,! analog\s d]ivatives ( or?o tolu5e sulphonic acid 7 made & /udi$ by ,cant]1 7,diss]tation1 #aijj74 ,he prep>$ or?o tolyl ph5yl sulphone by ! ,fri$al-,crafts reaction1 or?o ph5yl sulphone b5zoic acid by oxidation ( ! sulphone by potassium p]manganate1 its *loride1 amide1 & anilide1 & or?o b5zoyl diph5yl sulphone f ! acid by ! ,fri$al-,crafts reaction4 ,! analog\s d]ivatives ( ! meta tolu5e sulphonic acid ) "o or two exceptions h n be5 made or /udi$1 nor has ! acid itself be5 prep>$ 9 a =m :i* c\ld be recogniz$4 ,! foll[+ d]ivatives ( meta tolu5e sulphonic acid h be5 made & /udi$2 ! amide by ,mll]1 ,pe*mann1 ,pagel1 ,beckurts1 ,f4,h4,s4 ,mull]1 ,nevile & ,w9!r1 ,*ase ,palm]1 ,klason1 ,val91 ,noyes & ,walk]1 ,metcalf1 & ,griff92 meta sulpham9e b5zoic acid by ,limpri*t & ,usl>1 & ,griff92 meta tolu5e sulphon anilide & toluide by ,mull] & ,wies+]1 7,b]4 d4 *em4 ,ges1 #ab1acdh71 & by ,griff92 ! latt] also made & /udi$ sev]al metallic salts4 ,! lit]ature on ! or?o & p>a tolu5e sulphonic acids & _! d]ivatives is volum9\s1 & cov]s a great _m d]ivatives :i* h be5 ?or\ghly /udi$ & ^: /ructure has be5 det]m9$4 ,! lit]ature on meta tolu5e sulphonic acid is v meagre1 comp>atively1 & all t c\ld be f\nd is m5tion$ 9 ?is pap]4 ,?is w\ld seem to indicate t inve/igators h avoid$ ?is s]ies1 & app>5tly ! reason is due to ! difficulties enc\nt]$ 9 isolat+ ! free acid4 ,,!oretical ,,discussion ,! object ( ?is pap] is to prep>e a solution ( meta tolu5e sulphonic acid1 z probably obta9$ by ,griff91 by ! mo/ promis+ ( ! inve/igat$ me?ods & to f9d an acceptable "o = isolat+ ! acid 9 ! solid /ate4 ,aft] a solution is obta9$ simil> to t f\nd by ,griff91 7loc4 cit471 ! int5tion is to remove z mu* wat] z possible by di/illation "u dim9i%$ pressure & !n to precipitate ! acid by ! me?od ( ,ka/le1 7,am]4 ,*em4 ,j41 ,vol4 #dd1 page #dhc71 namely saturate ! rema9+ solution ) gase\s hydro*loric acid4 ,x is hop$ t 9 ?is way ! solid acid may be obta9$ :i* c !n be /udi$4 ,z has be5 prov$ by previ\s exp]im5t]s & discuss$ above1 no direct me?od ( sulphonat+ tolu5e w give any ( ! meta sulphonic acid4 ,!re=e to get a comp\nd conta9+ a me?yl gr\p ) a sulphonic acid gr\p 9 ! position meta to x "s comp\nd ) ^! already 9 t position & conta9+ "s o!r gr\p :i* c be replac$ by hydrog5 might be us$1 i4e4 a disub/itut$ tolu5e4 ,! two gr\ps :i* c be readily replac$ by hydrog5 are ! am9o gr\p & brom9e1 ! =m] by ! diazo reaction & ! latt] by treatm5t ) metallic sodium2 ! easi] ( ! two to prep>e & replace is ! am9o gr\p & ?is is ! "o made use ( 9 ?is syn!sis4 ,?is replacem5t has be5 widely /udi$ 7,am]4 ,*em4 ,j41 by ,palm] #h1 #bdc2 ,orndorff #i1 #chg2 ,graham #aa1 #cai2 ,da%iell #ae1 #abd2 ,metcalf #ae1 #cja2 ,p>ks #ae1 #cbj2 ,%ob] #ae1 #cgi2 ,beeson #af1 #bdd2 & ,diss]tations by ,weida1 ,cam]on1 & ,*amb]la91 all #ahid471 & ! v>i\s conditions affect+ x det]m9$4 ,! =ego+ inve/igators decompos$ _! diazo comp\nds ) alcohols sometimes us+ c]ta9 sub/ances to cause ! alkoxy or hydrog5 reactions to take place4 ,lat] inve/igators 7,bu*ka1 ,b]i*te #bc1 #afbh1 ,/4 ,von ,niemant[ski1 ,ibid41 #cd1 #ccbe 7#aija71 ,ullman & ,bieleck1 ,ibid41 #cd1 #bagd1 & ,bigel[1 ,j4 ,am]4 ,*em4 ,soc41 ,vol4 #da1 #aeff71 h %[n t ?is decomposition is greatly increas$ by ! pres5ce ( copp] p[d]4 ,z ! fir/ me?od has be5 m ext5sively /udi$ x 0 adopt$ 9 ?is case4 ,! action ( me?yl1 e?yl1 & n-propyl alcohols on diazo comp\nds has be5 well /udi$ by ! above au?ors1 & x has be5 %[n t ! fir/ two at ord9>y pressures give ! alkoxy reaction ei!r 9 :ole or 9 "p2 n-propyl alcohol gives ! hydrog5 reaction only4 ,also ! fir/ two give ! hydrog5 reaction 9 ! pres5ce ( z9c du/ or sodium c>bonate1 b 9 ^! cases =m salts ( ! acid4 ,on acc\nt ( its r>ity n-propyl alcohol 0 n us$1 b n-butyl alcohol :i* is available 9 l>ge quantities & 9 a pure condition 0 employ$4 ,rec5t advances 9 f]m5tation z appli$ to organic *emi/ry h made ?is sub/ance easily obta9able z a byproduct 9 ! production ( acetone :i* 0 ne$$ 9 l>ge am\nts dur+ ! late w>4 ,its use 0 f\nd to be successful2 x boils at #aag & s c be easily di/ill$ (f aft] decomposition has be5 effect$ )\t a great increase 9 temp]ature above ! boil+ po9t ( wat]1 :i* increase ,griff9 7loc4 cit47 %[$ to cause c>bonization4 ,= ?is reason i-amyl alcohol al?\gh available 0 n consid]$1--also high] alcohols because ( ?is fact & because ( _! r>ity4 ,( ! f\r am9o tolu5e sulphonic acids !oretically possible 9 :i* ! sulphonic acid gr\p is 9 ! meta position 9 ref]5ce to ! me?yl gr\p only two are commonly kn[n1 ,no4 #a1 & ,no4 #b4 ,,*#c ,,*#c ,,*#c ,,*#c _/ _/ _/ _/ _/ _/ _/ _/ _/ ,,nh#b _/ _/ ,,nh#b _/ ,,hso#c _/ _/ ,,hso#c _/ ,,nh#b _/ ,,hso#c _/ _/ _/ _/ _/ _/ _/ _/ ,,nh#b ,me?ods ( prep>+ ,no4 #a & ,no4 #b 7 f\nd b )\t details1 s a me?od _h to be work$ out to obta9 !m easily & 9 good yield4 ,aft] a little exp]im5t+ ,no4 #a1 or or?o toluid9e sulphonic acid 0 readily obta9$ 9 good yield & 9 a fairly pure condition4 ,no4 #b1 or p>a toluid9e meta sulphonic acid 0 obta9$ 9 only a t5 p] c5t yield & by means ( a mu* m difficult me?od ( proc$ure4 ,! prep>ation ( ?is acid 0 und]tak5 fir/ & consum$ a long "t2 ,griff9 did 8 "w />t+ ) ?is acid & ,i hop$ to get z f> z he did e>li]4 ,x 0 !n available 9 ! m>ket z 0 ! or?o toluid9e sulphonic acid1 b n[ nei!r are available4 ,! me?ods employ$ by e>li] inve/igators :5 !y wi%$ to isolate _! diazo comp\nds 0 to susp5d ! sub/ance to be diazotiz$ 9 alcohol1 & !n pass 9 nitr\s fumes g5]at$ by dropp+ conc5trat$ nitric acid onto ars5i\s oxide4 ,! diazo comp\nd f or?o toluid9e sulphonic acid is s ne>ly insoluble 9 wat] t x 0 f\nd possible to diazotize x 9 wat] susp5sion1 & g5]ate ! nitr\s fumes 9 ! solution itself by add+ a solution ( sodium nitrite to ! wat] susp5sion conta9+ hydro*loric acid4 ,aft] a %ort "t ! diazo comp\nd sep>ates out & c be filt]$ (f1 wa%$ & dri$4 ,x is a v /able sub/ance z comp>$ ) o!r diazo comp\nds4 ,?is me?od 0 work$ out1 !re be+ no m5tion ( x 9 ! lit]ature4 ,,sulphonation ,,( ,,or?o ,,toluid9e ,( ! possible sulphonic acids ( or?o toluid9e ! comm]cial product ( =m] days 0 ! "o 9 :i* ! sulphonic acid gr\p 0 9 ! p>a position to ! am9o gr\p1 & meta to ! me?yl gr\p2 ?us ?is acid c\ld f9d use 9 prep>+ ! tolu5e meta sulphonic acid if a me?od ( replac+ ! am9o gr\p by hydrog5 c\ld be f\nd4 ,?is acid is n n[ on ! m>ket 9 ,am]ica because ( its limit$ use 9 dye/uffs4 ,x is m5tion$ 9 ,s*ultz & ,julius1 78,f>be/(f ,tabell501 #ahid ,edition1 ,trans4 by ,f4 ,c4 ,gre571 ,ca91 78,! ,manufacture ( ,int]m$iate ,products = ,dyes07 & ,nevile & ,w9!r1 7,b]4 d4 *em4 ,ges4 #ac1 #aidj471 :i* latt] give a me?od ( prep>ation :i* 0 us$ indu/rially1--! bak+ ( or?o toluid9e sulphate4 ,_! description is r indef9ite b aft] a few prelim9>y trials a suitable me?od 0 f\nd4 ,i w describe all ! exp]im5ts attempt$1 & include ! "o f9ally adopt$4 ,! or?o toluid9e us$ 0 78,practical407 obta9$ f ,ea/man ,kodak ,co4 ,exp]im5t #a4 ,or?o toluid9e 0 susp5d$ 9 wat] & conc4 sulphuric acid add$ ) vigor\s /irr+ until all ! am9e _h dissolv$4 ,! solution 0 heat$ to boil+ until ! sulphate _h dissolv$1 & !n cool$ & ! cry/als ?us obta9$ filt]$ (f & dri$4 ,?is 0 !n p[d]$ & gr\nd ) "s p[d]$ oxalic acid4 ,^! mixtures ) & )\t oxalic acid 7 !n bak$ until a sample 0 completely soluble 9 sodium hydroxide4 ,! mass _h become a deep grayi% purple4 ,x dissolv$ 9 wat] to give a deep r$ solution4 ,no?+ satisfactory 0 obta9$ f any ( ^! bakes1 ! =mation ( a r$ dye/uff z m5tion$ by ,nevile & ,w9!r seem+ to be =m$ 9 a great quantity & v easily4 ,h5ce ?is me?od 0 disc>d$4 ,exp]im5t #b4 ,9 ?is case an excess ( sulphuric acid 0 us$4 ,aft] ! oxalic acid _h all be5 decompos$ or driv5 (f ! mass turn$ black & became v pit*y4 ,no?+ c\ld be done ) x s x 0 ?r[n away4 ,exp]im5t #c4 ,9 ?is case an excess ( or?o toluid9e 0 us$4 ,! r$ dye/uff 0 =m$ 9 great am\nt & v easily4 ,! temp]ature 0 kept bel[ #aie to lose none ( ! toluid9e :i* boil$ at #aii4 ,exp]im5t #d4 ,?is me?od gave ! be/ results & is ! "o employ$ 9 ! prep>ation ( all ! mat]ial us$ 9 ! !sis4 ,equal weights ( or?o toluid9e & sulphuric acid 7#ajj;gms4 ( ea* 7 us$2 #ajj;gms4 ( or?o toluid9e is #ajh;cc41 & #ajj;gms4 ( sulphuric acid 7s4 g4 #a4hd7 are #ef;cc471 7 mix$ & bak$ at #aij-aie until a sample w\ld dissolve 9 t5 p] c5t sodium hydroxide solution to give a cle> solution2 ?is took "o & a half h\rs4 ,! mixture at fir/ melts 9 ! solution ( ! sulphate & sulphuric acid =m$ by ! heat ( comb9ation2 z heat+ is cont9u$ x gradually becomes solid & f9ally v h>d2 x has become gray 9 color4 ,:5 x is p]fectly dry a te/ is made to see if x dissolves 9 sodium hydroxide giv+ a cle> solution4 ,if s1 sulphonation is complete4 ,by us+ an ov5 ) a glass door ! reaction mixture c be wat*$ & ! completion ( ! bak+ obs]v$4 ,h[ev] ! te/ = complete solubility %\ld always be made4 ,! addition ( p[d]$ oxalic acid to ! reaction mixture did n seem to be ( advantage1 because no visible reaction comm5c$ until ?is _h be5 driv5 (f or decompos$4 ,x is usually add$ 9 produc+ sulphonic acids by bak+ ! sulphates ( ! am9es to increase ! porosity ( ! mass & ?us facilitate removal ( ! product4 ,h[ev] "h ! only effect seem$ to be to ret>d ! reaction1 z ! product 0 ! sane h>d grayi% mass z )\t ! acid1 & x 0 j z difficult to dig x out4 ,x took an h\r long] to complete ! reaction ) ! addition ( ! oxalic acid4 ,! be/ results 7 obta9$ :5 ! temp]ature ( ! ov5 0 kept at #aic1 al?\gh five degrees v>iation did n appreciably affect ! product4 ,a l[] temp]ature gives little or no action1 :ile a high] "o drives (f ! or?o toluid9e & also seems to favor ! =mation ( ! r$ dye/uff4 ,z /at$ above1 complete sulphonation is %[n by ! solubility ( ! acid 9 t5 p] c5t sodium hydroxide solution4 ,if any un*ang$ am9e is pres5t z sulphate ! solution w become milky due to lib]ation ( ! insoluble am9e4 ,on boil+ a solution ( ! acid a slight hydrolysis takes place s t ! smell ( or?o toluid9e is pres5t1 yet ! solution is always p]fectly cle>4 ,! product or 8bake0 appe>s z a h>d grayi% mass1 slightly por\s4 ,x is dug out1 pulv]iz$1 boil$ up 9 a l>ge evaporat+ di%1 conta9+ wat] & a little 7#aj;cc47 hydro*loric acid1 ) animal *>coal & filt]$4 ,! solution %\ld be almo/ colorless4 ,! effect ( ! slight am\nt ( hydro*loric acid 0 accid5tal2 ! fir/ solutions 7 always a deep r$ color due to "s ( ! r$ dye/uff seem+ to be pres5t1 & ! long] ! solution 0 boil$ ! r$d] x got4 ,a little acid seems to prev5t ?is entirely4 ,! solution is evaporat$ on a wat] ba? until a scum has =m$ on ! surface :5 x is all[$ to cool & cry/allize4 ,x cry/allizes 9 small almo/ :ite ne$les1 :i* appe> to fill ! entire liquid2 ?is is deceptive z on filt]+ ! bulk is consid]ably r$uc$4 ,!y fall to a p[d] :5 !y are dry4 ,if !y are color$ r$ or p9k !y are wa%$ :ile /ill on ! filt] ) wat]2 alcohol does n remove ?is color4 ,! acid z =m$ has no melt+ po9t1 b *>s & decomposes on heat+4 ,a sample 0 te/$ = nitrog5 & sulphur ) v good positive results4 ,on fusion ) cau/ic soda & acidification ( ! product a positive reaction 0 obta9$ on ! addition ( brom9e wat] z is cu/om>y ) ph5ols4 ,x 0 id5tifi$ z id5tical ) ! acid ( ,nevile & ,w9!r 7loc4 cit47 by conv]sion ?ru ! diazo comp\nd into d9itro or?o cresol1 melt+ at #he4h z describ$ "u ! description ( ! diazo comp\nd4 ,,sulphonation ,,( ,,p>a ,,toluid9e ,metcalf1 7loc4 cit471 gives a me?od = ! prep>ation ( ! sulphonic acids ( p>a toluid9e1 & /ates t bo? ! possible acids are =m$1 ) ! meta position 7ref]r$ to ! me?yl gr\p7 9 good yield4 ,s*ultz & ,julius1 78,f>be/(f ,tabell501 #ahid ,edition1 ,trans1 by ,f4 ,c4 ,gre571 & ,nevile & ,w9!r1 7loc4 cit471 say t ! sulphonation ( p>a toluid9e gives a mixture ( ! sulphonic acids1 ) ! or?o 7ref]r$ to ! me?yl gr\p7 sulphonic acid 9 a mu* great] yield4 ,z ! sulphonation ( p>a nitro tolu5e gives 7,diss]tation1 ,r4 ,s4 ,norris1 ,,bpl4 #eigf4aji7 a n9ety-five p] c5t yield ( ! or?o sulphonic acid1 x w\ld seem z ?\gh ! am9o comp\nd %\ld give a l>ge yield ( ! acid 7sulphonic acid gr\p or?o to ! me?yl gr\p17 & su* 0 f\nd to be ! case4 ,i foll[$ ,metcalf's directions z foll[s3 9 an app>atus fitt$ ) an automatic /irr] & a !rmomet] ,i plac$ #bjj grams 7#aaj;cc47 ( tw5ty p] c5t fum+ sulphuric acid4 ,i !n sl[ly add$ ) rapid /irr+ #ajj;grams ( p[d]$ p>a toluid9e :i* 0 obta9$ f ! ,newport ,*emical ,works4 ,! addition took ?irte5 m9utes4 ,! initial temp]ature ( ! solution 0 #ah;,c4 ,! maximum 0 obta9$ :5 ab\t half ! toluid9e _h be5 add$ & 0 #adh;,c4 ,! f9al temp]ature 0 #acj;,c4 ,aft] addition 0 complete ,i /irr$ = five m9utes1 & !n sl[ly heat$ ! mixture to #ahj;,c4 & kept x !re = an h\r4 ,sulphonation 0 !n complete4 ,i !n p\r$ x into an equal volume ( cold wat] 7#bbj;cc47 9 an evaporat+ di% & all[$ x to /& ov] night4 ,! next day ! di% seem$ fill$ ) grayi% cry/als2 ^! 7 filt]$ (f4 ,! solution 0 all[$ to /& = f\r weeks ) no results4 7,metcalf says t ! disulphonic acid sep>at$ 9 ?ree weeks f 8 solution47 ,i dissolv$ ! crude acid obta9$ z above 9 t5 lit]s ( wat] 7,metcalf's directions7 & precipitat$ ! excess ( sulphuric acid ) b>ium hydroxide1 & !n filt]$ ! solution4 ,x 0 a cle> br[ni% color4 ,i !n evaporat$ to #ajj;cc4 ,a smell ( p>a toluid9e 0 always pres5t 9 ! vapor indicat+ a probable hydrolysis ( ! acid4 7,nevile & ,w9!r 7loc4 cit47 say t ?is sulphonic acid c be hydrolyz$ by heat+ ) wat]71 ,a te/ aft] sulphonation & be=e evaporation %[$ a sample to be completely soluble 9 wat]1 & no cl\d9ess 0 produc$ :5 a sample 0 dissolv$ 9 sodium hydroxide1 z is ! case if a solution ( p>a toluid9e sulphate is dissolv$ 9 ! same reag5t4 ,:5 ! volume _h rea*$ #ajj;cc4 a light br[n cru/ _h =m$ on top ( ! liquid & on cool+ & filt]+ two products 7 obta9$2 a light br[n p[d]y sub/ance 9 l>g] am\nt 7#dg4e grams471 & a small am\nt ( h>d squ>e br[n cry/als4 ,on evaporat+ ! filtrate ne>ly to dryness m mat]ial sep>at$ :i* did n look l ei!r ( ! above sub/ances2 x weigh$ tw5ty grams4 ,?is has n be5 inve/igat$ z yet4 ,z ! br[ni% p[d]y sub/ance 0 mix$ ) ! flat cry/als produc$ above1 a me?od _h to be f\nd to sep>ate !m & purify ea*4 ,i scre5$ !m z mu* z possible ) good results4 ,i remov$ ! la/ ( ! f9e p[d] by dissolv+ x (f ) hot wat]4 ,metcalf said t !y c\ld be sep>at$ by _! diff]5ce 9 specific gravity 9 fifty p] c5t alcohol b ?is me?od 0 unsuccessful4 ,i boil$ up ! aque\s solution ( ! p[d]y sub/ance ) animal *>coal1 filt]$ & evaporat$ to cry/allization4 ,squ>e1 flat1 :ite cry/als 7 obta9$ id5tical 9 all b color ) ^? m5tion$ above4 ,!y are soluble ) difficulty 9 cold wat]1 readily 9 hot1 & insoluble 9 alcohol4 ,9 ^! prop]ties & 9 appe>ance !y comp>e to ! or?o sulphonic acid ( p>a toluid9e z made & describ$ by ,p>ks1 7,diss]tation1 #ahib74 ,metcalf & ,nevile & ,w9!r say t ! meta sulphonic acid ( p>a toluid9e =ms ne$les1 b ,i obta9$ no?+ t c\ld 9 any way be call$ ne$les4 ,?is sulphonic acid _h no melt+ po9t1 b *>r$ & decompos$4 ,a te/ = elem5ts %[$ nitrog5 & sulphur to be pres5t4 ,! aque\s solution _h a /rong acid reaction to litmus4 ,9 ord] to see if ?is might be ! desir$ acid ,i tri$ to prep>e an acid *loride ) phosphorus p5ta*loride 9 ! usual way1 & !n int5d$ to conv]t x into ! amide & get a melt+ po9t = id5tification4 ,i us$ equal weights ( ! acid & phosphorus p5ta*loride4 ,i gr\nd !m toge!r at ord9>y temp]ature 9 a mort>3 no result4 ,i heat$ x on a wat] ba?3 no result4 ,i heat$ x on a gauze ov] a flame3 no result except decomposition & c>bonization4 ,h[ev] ,i p\r$ wat] into ! mixture & decompos$ ! excess ( phosphorus p5ta*loride1 & filt]$4 ,a gummy br[ni% mass rema9$ :i* 0 insoluble 9 all reag5ts tri$1 7me?yl & e?yl alcohol1 b5z9e1 petroleum e!r1 7#dj-fj71 wat]1 c>bon tetra*loride1 dilute hydro*loric acid1 acetone1 & acetic acid47 ,e?yl e!r extract$ a v small am\nt1 j en\gh to color x yell[1 & leave a yell[ color on porcela9 on evaporation1 b n en\gh to make a /udy ( ! prop]ties4 ,on %ak+ up ) conc5trat$ ammonia ! mass became v f9ely divid$1 b no solution appe>$ to take place2 on filt]+ & evaporat+ to dryness !re 0 no residue4 ,! mat]ial m5tion$ above z be+ ! f9al product f ! sulphonation ( p>a toluid9e1 obta9$ 9 a yield ( tw5ty grams or t5 p] c5t yield & !n un9ve/igat$1 has s9ce be5 id5tifi$ z ! acid ,i 0 look+ =1 or p>a toluid9e meta sulphonic acid4 ,a small am\nt 0 cool$ & diazotiz$ 9 ! usual mann]2 ! diazo comp\nd seem$ to be insoluble 9 ! am\nt ( wat] us$1 = a :ite cry/all9e ne$le-l precipitate appe>$4 ,?is 0 decompos$ by boil+ ) dilute nitric acid 7,nevile & ,w9!r1 loc4 cit471 & on cool+ small tufts ( yell[ ne$les sep>at$4 ,^! 7 filt]$ (f & dri$1 !n recry/alliz$ f alcohol4 ,! be/ portions ( ^! 7 !n recry/alliz$ f e!r & ! melt+ po9t det]m9$4 ,!y melt$ at #gi4e-gi4h 7uncorr474 ,nevile & ,w9!r gave #gi-hj1 %[+ t !y did n purify _! comp\nd4 ,! product is d9itro p>a cresol1 or #c-nitro1 #d-;hydroxy1 #e-nitro tolu5e4 ,,diazotization ,,( ,,or?o ,,toluid9e ,,sulphonic ,,acid4 ,nevile & ,w9!r 7loc4 cit471 /at$ t !y obta9$ a diazo comp\nd f _! or?o toluid9e sulphonic acid & describ$ a few prop]ties1 b gave no details ( manipulation1 s ,i made sev]al trials to det]m9e ! be/ acceptable me?od4 ,exp]im5t #a4 ,i susp5d$ "s or?o toluid9e sulphonic acid 9 d5atur$ alcohol1 & pass$ 9 a rapid curr5t ( nitr\s fumes1 g5]at$ by dropp+ conc5trat$ nitric acid into a saturat$ solution ( sodium nitrite1 = fifte5 m9utes4 ,! susp5sion became slightly w>m1 & r pa/y at ! end4 ,i all[$ x to /& a half h\r1 & at ! end ( t "t x _h become v ?ick & pa/y4 ,i !n filt]$ x (f by suction1 wa%$ ) e!r1 & dri$4 ,exp]im5t #b4 ,! proc$ure us$ 0 ! same z above us+ e?yl alcohol 9 place ( d5atur$ alcohol1 b = "s reason no diazotization appe>$ to take place4 ,! acid 0 filt]$ (f & us$ aga94 ,exp]im5t #c4 ,a saturat$ wat] solution ( ! acid 0 made by boil+ "s ( x up ) wat]1 cool+ & filt]+4 ,no precipitate appe>$ on pass+ 9 nitr\s fumes4 ,exp]im5t #d4 ,"s ( ! acid 0 dissolv$ 9 sodium c>bonate solution1 sodium nitrite solution add$1 & aft] cool+1 conc5trat$ hydro*loric acid add$ drop by drop4 ,nitr\s fumes 7 giv5 (f1 b no precipitate appe>$4 ,exp]im5t #e4 ,?is seems to be ! be/ me?od & ! "o employ$ h]eaft] 9 ! prep>ation ( all ! mat]ial subsequ5tly us$4 ,! solid or?o toluid9e sulphonic acid is susp5d$ 9 conc5trat$ hydro*loric acid & vigor\sly /irr$4 ,! solution becomes w>m & ! cry/als *ange 9 appe>ance1 probably due to ! =mation ( ! hydro*loride4 ,! mass is !n cool$ to #e1 & sodium nitrite solution add$ sl[ly ) /irr+4 ,imm$iate reaction takes place1 & ! mass becomes v pa/y z 9 ! fir/ exp]im5t4 ,aft] obta9+ a reaction ) />* iodide pap] ! mixture 0 all[$ to /& a half h\r1 !n filt]$ by suction1 wa%$ ) e!r & dri$4 ,9 appe>ance x 0 id5tical ) ! diazo comp\nd obta9$ 9 exp]im5t #a1 & c be kept 9 ! same way4 ,t x 0 a diazo comp\nd 0 %[n z foll[s3 ,x 0 spott$ on a piece ( filt] pap] ) an alkal9e solution ( ,h acid--a r$ coloration indicates ! =mation ( a r$ azo dye/uff4 ,"s ( ! diazo comp\nd 0 boil$ ) dilute nitric acid z describ$ by ,nevile & ,w9!r1 & a yell[i% precipitate ( ne$les obta9$1 :i* on recry/allization f d5atur$ alcohol gave light yell[ ne$les ( d9itro or?o cresol1 7#c-;hydroxy #c1e-;d9itro tolu5e71 melt+ at #hc4e-hd uncorr4 7,nevile & ,w9!r gave #he = ! pure sub/ance47 ,?is d9itro comp\nd 0 obta9$ 9 ne>ly quantitative yield indicat+ t ! diazo comp\nd 0 presumably pure4 ,,physical ,,prop]ties ,,( ,,! ,,diazo ,,comp\nd ,x is almo/ insoluble 9 wat]1 & is insoluble 9 d5atur$ alcohol & e!r4 ,x is a :ite solid :i* c be dri$ & kept )\t app>5t decomposition2 x gradually turns p9k :5 expos$ to ! light = sev]al days1 s is kept 9 a br[n bottle if n requir$ = imm$iate use4 ,x does n explode :5 /ruck ) a hamm]1 b deflagrates viol5tly if a flame is br\ght ne> or if heat$ on porcela94 ,,decomposition ,,( ,,! ,,diazo ,,comp\nd 7#a7 ,) n-,butyl alcohol 9 ! pres5ce ( sodium c>bonate4 ,a portion ( ! dry diazo comp\nd 0 plac$ 9 a flask connect$ ) a reflux cond5s]1 & solid sodium c>bonate & n-butyl alcohol add$4 ,no reaction took place at ord9>y temp]ature s heat 0 appli$4 ,decomposition />t$ at #fe & evolution ( hydrog5 proce$$ ev5ly & smoo?ly until all ! diazo comp\nd _h disappe>$4 ,! alcohol1 at fir/ colorless1 became an orange & f9ally a br[n color4 ,! solution 0 !n reflux$ an h\r to ensure complete decomposition ( ! diazo comp\nd4 ,! smell ( an aldehyde 0 evid5t indicat+ t ! hydrog5 reaction 0 tak+ place2 ! solution 0 te/$ ) ,s*iff's reag5t & ) ammoniacal silv] nitrate ) di/9ct positive results 9 bo? cases1 %[+ aldehyde 0 pres5t4 ,! alcoholic solution 0 filt]$ f ! sodium c>bonate rema9+1 & ! alcohol di/ill$ (f on an oil ba?4 ,a yell[i%-orange por\s solid 0 left 9 su* a small am\nt t no d]ivatives c\ld be made & /udi$4 ,x 0 free f ! diazo comp\nd1 %[n by its giv+ no color ) an alkal9e solution ( ,h acid4 7#b7 ,) n-,butyl ,alcohol alone4 ,! previ\s exp]im5t %[$ t n-butyl alcohol w\ld decompose ! diazo comp\nd 9 ! pres5ce ( sodium c>bonate & replace ! am9o gr\p by hydrog51 s ?is "t a decomposition ) ! alcohol alone 0 tri$4 ,decomposition took place ev5ly & smoo?ly z be=e at ! same temp]ature1 & ! solution became a cle> br[ni%-orange4 ,aldehyde 0 giv5 (f & te/$ = z be=e ) positive results4 ,! alcohol 0 remov$ by di/illation & a ?ick br[ni% syrupy liquid 0 left4 ,?is 0 easily soluble 9 wat]1 s 0 dissolv$1 filt]$1 & ! solution us$ 9 ! foll[+ exp]im5ts4 ,at ?is po9t x is simil> 9 e way to ! solution obta9$ by ,griff9 7loc4 cit47 f ! diazo comp\nd ( p>a toluid9e meta sulphonic acid4 ,subsequ5t prep>ations ( ?is syrup 7 made 9 ! above way ) simil> results 9 e case4 ,! only precaution to be obs]v$ is t no "p ( ! flask conta9+ ! reaction mixture be all[$ to become too hot z ! diazo comp\nd is !n decompos$ viol5tly leav+ a grayi% a%4 ,a ,,/udy ,,( ,,! ,,solution ,,obta9$ ,,by ,,! ,,decomposition ,,( ,,! ,,diazo ,,comp\nd ,! syrup :i* rema9$ aft] di/ill+ (f ! n-butyl alcohol 0 a ?ick br[n visc\s fluid 9 all cases4 ,x has an acid reaction & is completely soluble 9 wat]4 ,on te/+ x %[$ ! pres5ce ( sulphur 9 quantity & ! abs5ce ( nitrog54 ,"s 0 dissolv$ 9 wat]1 filt]$1 & evaporat$ on ! wat] ba?4 ,aft] its volume _h be5 consid]ably r$uc$ x turn$ a v d>k br[n1 !n blacki%1 & smell$ v t>ry4 ,x did n cry/allize at all1 f9ally becom+ v black4 ,to a drop on a wat* glass1 a drop & !n an excess ( conc5trat$ hydro*loric acid 0 add$ b ) no app>5t result4 ,ano!r portion ( ! syrup 0 dissolv$ 9 wat]1 boil$ ) purifi$ animal *>coal1 & filt]$4 ,! filtrate 0 colorless4 ,x 0 !n evaporat$ on ! wat] ba? & solidifi$ completely4 ,"s ( ?is solid 0 ignit$ & a :ite a% 0 left2 _h x be5 a sulphonic acid !re w\ld h be5 no residue4 ,a qualitative analysis ( ! a% 0 made & mu* phosphate & calcium f\nd pres5t2 !re=e ?is solid 0 presum$ to be a mixture ( calcium phosphate f ! animal *>coal & p]haps ! calcium salt ( ! sulphonic acid4 ,?is %[$ t animal *>coal c\ld n be us$ = purposes ( purification4 8,activat$ *>coal0 has be5 advocat$ = decoloriz+ solutions z well z = absorb+ toxic gases2 ! au?or _h become acqua9t$ ) ?is mat]ial :ile 9 ! ,*emical ,w>f>e ,s]vice1 & _h obta9$ small samples ( 8,dorsite0 & 8,c>bonite04 ,"s ( ?is 0 p[d]$ & ! br[n solution boil$ ) x until mo/ ( ! color 0 remov$4 ,! solution 0 !n filt]$ & evaporat$ on ! wat] ba?2 a :ite cry/all9e solid 0 aga9 left4 ,inve/igation ( ! activat$ *>coal %[$ t conc5trat$ acids extract$ "s sub/ance :i* 0 ?r[n d[n 9 a floccul5t :ite precipitate on mak+ alkal9e ) ammonia4 ,!re=e ano!r sample ( ! activat$ *>coal 0 boil$ ) conc5trat$ nitric acid1 filt]$1 & ! *>coal wa%$ free f acid2 ?is sample did n decolorize well4 ,a sample ( a specially prep>$ *>coal = decoloriz+ purposes manufactur$ by ! ,b>neby-,*5ey ,co4 0 obta9$ & tri$1 b 0 unsuccessful2 ! color 0 n remov$4 ,infusorial e>?1 kiesel guhr1 & 8,sil-o-cel0 7 also tri$ unsuccessfully2 ,full]s ,e>? made a v cle> solution b no color 0 remov$4 ,"s ( ! br[n visc\s solution 0 dissolv$ 9 wat]1 ! solution filt]$ & evaporat$ to a con/ant volume 7e/imat$ :5 no m vapor c\ld be se5 to cond5se7 "u dim9i%$ pressure 7wat] pump7 until x became m br[n4 ,x 0 !n all[$ to cool1 & dry hydro*loric acid gas pass$ 91 fir/ to expel all air or o!r vapor pres5t1 & !n "u pressure4 ,! solution became slightly w>m4 ,a few f9e cry/als =m$ on ! int]ior surface ( ! flask :]e "s ( ! solution _h spatt]$ dur+ di/illation1 :i* h[ev] 7 q indi/9ct & seem$ to be 9 ! c5t] ( a drop ( wat] or solution4 ,on all[+ ! flask to /& ov] night ! :ole ( ! solution seem$ to be fill$ ) cry/als4 ,!y 7 too indi/9ct to enable _! cry/all9e =m to be det]m9$ s an attempt 0 made to remove "s = exam9ation4 ,z soon z !y came into contact ) ! air !y disappe>$ & left a v visc\s solution1 indicat+ t !y are v hygroscopic4 ,a small am\nt 0 remov$ & plac$ 9 a di% 9 a vacuum desiccator :i* 0 evacuat$ & left = a mon?1 ) p]iodical exam9ations4 ,no solid appe>$ at any "t4 ,?is is z f> z ! inve/igation has be5 c>ri$ at ! pres5t "t1 ,april tw5ty-fif?1 b its /udy is be+ cont9u$4 ,,conclusion ,! results ( ?is inve/igation may be briefly summ>iz$ z foll[s3 7#a7 ,or?o toluid9e may be easily conv]t$ into its sulphonic acid 9 :i* ! sulphonic acid gr\p is 9 ! position meta to ! me?yl gr\p4 7#b7 ,p>a toluid9e is conv]t$ into a mixture ( two isom]ic sulphonic acids ( :i* ! "o ) ! sulphonic acid gr\p 9 ! position meta to ! me?yl gr\p is obta9$ 9 a t5 p] c5t yield4 7#c7 ,or?o toluid9e sulphonic acid may be easily diazotiz$ us+ sodium nitrite & conc5trat$ hydro*loric acid4 7#d7 ,! diazo comp\nd is v /able4 7#e7 ,! diazo comp\nd is easily decompos$ ) n-butyl alcohol1 ! hydrog5 reaction tak+ place4 ,,bibliography ,9 addition to ! ref]5ces made 9 ! !sis itself ! foll[+ au?orities h be5 consult$ = ! !oretical discussion3 ,beil/e91 ,f4 ,c41 8,h&bu* d] organis*5 ,*emie0 #ahhf-ahij4 ,voss1 ,hamburg4 ,victor von ,ri*t]1 8,organic ,*emi/ry0 ,trans4 #ahii-aijj4 ,p4 ,blaki/on's1 ,philadelphia1 ,pa4 ,b4,p4,l4 #cigd4afj ,mey] & ,jacobson1 8,lehrbu* d] organis*5 ,*emie0 #ahic4 ,veit ,co41 ,leipzig4 ,b4,p4,l4 #cigc4adc ,transcrib]'s ,note3 ,table ( cont5ts add$ by transcrib]4 ,obvi\s pr9t] errors correct$ sil5tly4 ,inconsi/5t spell+ & hyph5ation are z 9 ! orig9al4