The Sandmeyer Reaction (Nitrile) with P-Toluidin-Meta-Sulfonic Acid Citation Stewart, Earl Deloris (1925) The Sandmeyer Reaction (Nitrile) with P-Toluidin-Meta-Sulfonic Acid. Bachelor's thesis, California Institute of Technology. doi:10.7907/zwan-w729. https://resolver.caltech.edu/CaltechTHESIS:08082024-181856789 Abstract No abstract. Item Type: Thesis (Bachelor's thesis) Subject Keywords: (Chemistry) Degree Grantor: California Institute of Technology Division: Chemistry and Chemical Engineering Major Option: Chemistry Thesis Availability: Public (worldwide access) Research Advisor(s): Unknown, Unknown Thesis Committee: Unknown, Unknown Defense Date: 1 January 1925 Record Number: CaltechTHESIS:08082024-181856789 Persistent URL: https://resolver.caltech.edu/CaltechTHESIS:08082024-181856789 DOI: 10.7907/zwan-w729 Default Usage Policy: No commercial reproduction, distribution, display or performance rights in this work are provided. ID Code: 16622 Collection: CaltechTHESIS Deposited By: Benjamin Perez Deposited On: 09 Aug 2024 17:05 Last Modified: 09 Aug 2024 17:31 Thesis Files PDF - Final Version See Usage Policy. 6MB Repository Staff Only: item control page

T1:-LE s~rn:.JSY-.GR 11.1.!Jl.C'.i:I OlJ ( HI TE.ILE ) ViITH ;e_S: OLUI DHi- 1:::&TJL. SULFOl'IIC ACID Thes is by Earl D. ~tewart I n partial fulfillment of the requir ements for the degree of Bach elor of Science in Ch emistry California I nstitute of Tec'.n.r..ology Pasadena, California 1 )! 25 The ;.3 a n d.:-neyer React ion {r,i trile ) with .i?ara-toluid i nmeta- sulfo~ic acid ~h e ori g inal purpose of this work was to study compounds of the type, with a view to their use as i ndicat ors. The h omologous compounds prepared from benzene sulfonic acid are of course \Yell knovvn, being first .Prepared by Remsen and h i s pupil s vrh o gave them the name nsulfone.thaleinsn. The com_pou...nd, wh ose formula is g iven above, was pr epared by Lyman i n 1 094 { Am. Chem . J. 1 6 ,,5'1 3 et se q. '3 . :Ie call ed it 11 ph enol-Para-methyl-sulfon- :pthaleinn a na. noted t ha tnin alkaline carbonat e s, more r e adily than i n caustic alkalies, it dissolves to a red liquid muc h like an alkaline s olut ion of :phenol:pthalein n, (loc, ci t. p. _516). No fu:tther reference to t h e compound has been found in the li t eratur e. Lyma~1 pr epared this subs tanc e fr om sulfo-toluic acid, which he r>re:Par e a. according to the method desc ri bea. by Randall in 18 7·1 { Am. Ch . J. 13., 2.56 et se q. ) • 1landall :pre.Pared the acia. from meth- 2 yl saccharin~ which he obtained from the Badische A.nilin Soda Fabrik, the o~vners of the patent on the substance, (D.R.P. 48583). The process described is as follows, (B. 22,vol.3, Ref. 71 9) , CH3 - CH.3 ) Oso~t:/ a~o,N# C/1 .: ., cllj O so,_,/VI/ Co_,,,,.,, rt seemed likely that it might be bos r::i.r J.. low this procedure as far as the compound, O by hya_rolysis to form, oc H.::, • Inas- G~ as ex( loc. }1ad not ..:,;;,e:Pt in 60 <=IV been de- 0 • ocl{~ t o foland much ~# eN' seri bed .S D,3H C..D<>H the patent literature, cit.), it was thought desirable to attempt to isolate it. The firs t step, the sulfonation of p-toluidine, was first carried out,,. by von J:'echman ( A. 1 7 3, ·1 ') 5 etseq. ) • lii s methoo_ vras to use iUHiin6 sulfuric a~id, heating the sulfon2, ting mixture to 1 su 0 until so2 began to come off. 3 This method. was tried •with substantially the same results Cll.:3 as von Pecr...man describes. The two a cids H3 Q an d .SD.3H . vrere formed in about equal quar ti ties. D,.3 H ;illff_._-z- 11 ( The acids are differentiated by their crysL, a ine erties and .form, the ortho acid. being heavy rhombic crystals and the meta acid light, fluf'fy needles. See v • .2echman, lee.cit. 197, also :Letcalf, .Am, CJ.1.• J. 1.5, 303) Considerable residue without easily identifiable crystalline form rer.1ained and there was evid_ence of considerable charring. The yield. was very poor - less t han 20 7{> . Eeville and Wi nther also inves tic;ated.. the sulfonation of .P-'coluidine ( B. 13,1 947.}. Their method. seemed on the whole the most sat i sfc,.ctory and with some modif ications was used i n this work. The reaction was less violent a nd more easily controlled. Charring was practically eliminated., the acid vms lighter i n color and the ;irield was much i mproved - 3u - 3.5-;;s . Separation of the sulfonic acid by the use of barium hydroxide seemed most sat isfact ory although both lead. and calciuJn salts v.rere also tried. ihe lead salt of the s ulfonic acid refused to cryst allize out. only a sticky, oily liq_uid resulted.(For Ca see experimental i)art}. Since ..some tolui di ne s ulfat e is also ~, . pre s ent' the acia: cannot be crys tallized fro m the first solution, ~hile t h e alkali salts are all so soluble that they can be cr;i stallized only vri th ctifficul ty. 4 ( see h e t cal f loc. cit. ) r t ,.vas deci de d,at first, to carry out th e diazo- reaction i n alcoholic solution as described by I'-.:etcalf (loc. cit. 304 ) . A tri al showed ~ha t t h e me thod was slo~ unsatisfactory and rather wast eful of sodium nitrite. In subse~uent experiments the sulfonic acid was diazo t ised in aqueous solution very satisfactorily. The diazonium compound is quite soluble i n water at room temperature but i s onl y s li c;htly soluble i n wa ter at O - .5°. At t h e latter tempera t u.re it separa ted out as a pinkish whi t e, granular to flocculent precipita t e. The Sand.meyer r eaction wa s first a t tempted according to the method used for t h e formation of p- tolunitrile, given by E.ar ry Fisher. ( La bor a t ory :r:a nual of Organic Chemis t r y , :P, 187 ) . Da r k color ed .s olutions were t h e r esult, sh owing much tarry matter and gummy material on evaporation . No cry s t al lization of any value could be performed from any ·;J f these :Preliminarjr exper i men ts. may ex~::t::h t ,\: • f : : : / 66 ) S::oo th;~ tl:n:,·Q : y:ides iV= ;t/ ,,e fur th er showed t ha t !::..tV th e syn- form s ar e f ormed at low t e:r..Pera t u r es ( l)elow 5°) ana_ tlrn, t t hey g o over on standing to t h e an ti- f orms espe c ially at h i 0 h er tem.f)erat-ures. iie also showed t ha t t h e syn- forms decompo se on t he addi t- .5 ion of cop:per powder according to the equation, 0 0 Cl,Id. # ==-t¥ + #SN c;V (loc. cit.) Since the ordinary Sa:ndmeyer reaction gave such inconclusive results, the formation of Hantsch•s syn-d.iazo c;sranide was attempted. Theoretically the reaction However ho gas was ~iven off even on heating the solution. It woulcl seem probable that this is a case of steric hindrance and that the rate of formation of the syn- com.Pound at these low temperatures is very small. Hantsch worlced .Principally with sul:fanilic acid in his experiments and as far as I have been able to a_etermine, the reaction 'c1as not been carried 0\1t with a sulfonic acid. grou:p ortho to the amino grou.P. Since ll::;,ntsch 1 s method gave no useful results a method for making l}-tolunltrile given in Organic 3yntheses Vol IV P, 69 was used. This involved first forming a solution of HaCu( CH) 2 • J.!'our runs were made varying the co:1ditions as follows, 'i. Diazonium solution neutralized and ru.11 into 6 and diazonium salt suspension added at room temperature. 1:ixture heated to boiling. 3. Same as 2 except that the cyanide solution vms boiling when the diazo::1ium salt was added. Boiling continued for five hours. 4. Same as three exce1>t that evaporation vvas done in a more acid solution. The first method was not satisfactory. 1here was apparently little or no decomposition. The second method vms also unsatisfactory, but not for the same reason, The copper salts crystallized out along with the product and were difficult to remove. ·J:he t hird method yielded a considerable quantity of ~aper thin, dark red, hexagonal plates. These plates fused to a brown liquid on :platinum foil and finally charred, giving an odor resembling nitrobenz:ene, They became opaque and v1hi te 0 11 standing but retained their crystalline form. (iuali ta ti ve tests gave the followinG res;\Uts, N Present S present halogen= a trace. The halogen test was very faint and might easily have been due to NaCl occluded or dried on the surface of the crystals. The fourth method was essentially the same as the '/ third_ . .ii.. fresh i.iaCu( c.:_; ) 2 solution was made up and the s olution boiled a s before. i~re acid was added to :Precipitate the cop_ger salts than in ru.n No. 3. Consequently boiling to remove H2S and to evaporat e was done in a more acid solution. Concentration was carried further than in previous experiments and on cooling the dish became filled with long thin needles almo st forming a thin jelly. 6n filtering off and redi s solving and allowing them to recrystallize slowly from dilute solution the same thin h exagonal plates appeared as before. 'J:he se, ho~;rever, were li ghter in color ( nearl y colorless 7. On dry i ng they lo st ':ia t er and be came o_pag_ue. this J:)he- nomenon vras also n otic ed. on d. issolving them in \-vater by t h e aid of heat . They f irst seemed to lose water and then to dissolve. In cold \7at s r t he,y d. i ss olved vrith out be - coming opaque. An a nalysis f or nitrogen b;{ the Gunni ng-Arr1. old- Dy er modification of the Kjeldahl method gave the following results, I 6, '.) .5 c1" •'- r -' :, .n ~1- ( 1 '1' .) '- CN (4) 1 Calcul ated for /'-' "3 C6E. z- S03ria {3) 6.4;1' Deterni nat ion No. II was not r eliable since the mercury -=-- ---- - C - Safety Tube O- Nercur y Seal - Standard Hi! S04 G - Strong KOH H Gasometer e> - Separatory Funnel Reservoir F E,E - Safety Bottles used for Study of Sand me yer Reaction A - Reaction f(asK Apparatus ---11 - a 9 used a s a catalyst i n the oxida tion :process was n ot com.Pletely .PreciJ?i ta ted as HgS . Some of i t came dO"i'lil on add.;. ins water t o the oxia_a t ion liquid and when lTa,.-t!.. S was added a li ght br oi:,m ,Precipitate formed i nstead of a blaclc one. The :J:)resence of sodium i n ahundant q_uant i t y wa s pr c··red. b y t h e :potas s ium :py roanti:n on a t e test. ~ ~Toj- es, -.;;,ua.1.;. ._ i ta t ive Chemical Analysis >1 t h ea_. P. 1 28 ). 1:i:his analysis would. indicate that the hexac;onal pl at es were the soa_ium salt of the para - n i tr ile of meta-toluene sulfo:nic acid. The crystals are ,Probably triclinic al th ouzh it i s d.ifficul t to say d efi :ni tely.) s ince th e crystal measured h ad. ver;r low syrri.iuetrJ . r:easurement s of the face ~ngles are given on the following pag e. { '.i:he me as ur ements were 'by ~r. Li nus .iauli:ng of thi s l s,b ora t ory ) I n orcle r to d.iscover to what e:z:: te n t the r e action z oes to compl e t ion , a d e composition was carried out i n t}1e a :p_paratus shovvn i n t ':i e £' i 5ure. '.Che result of a nm usin g four teen _::;rams of the SiJ.lfonic acid. were as follows, :No m1 was g iven off. '.Chi s v1as tested. oy al1sorp t ion 3 iTI s tandard li2so 4 and back t i trat ing with standard J aGH. T>is would_ not g ive d.epend.a,ble results if t he arn.ou..r1t of JE1;,;v,ere v er;;r small. CornJ:eq_uently t h e acia_ was mad.e alkaline ,/ I 3' e-( I II _6 I ~ \......S" lo I A-I Face 5 broJ.cen ste:pwise \G /0 )-; /0 SectioB 8,3,1 ,6 8- 2$'1 Angle 4,5 2U t 4- 106° 4Cl 3- 326 57' 1- 26 11 6- 289 1- .5- 2 11 14 X 7- 318 28 141- 15 11 '- 97 2U .5,, 2 UU o- 140 X ') c...- 1- 6- 17 16 0 '' ' r , c...OC:. 7- 2; .!L.'1.gle 31 ~ 2.5 " 3 44 c.:: 39 54 42 Angle 6,7 5- 2/7 0 8 t 1- 46 X S e c ti on 5 , '1 , ~~ , 1 1 11 - 4- 1U6 8- 1 66 Angle 5,6 8 47 3/· iillgle 4,8 Section, 971 4 ')- 232°15 ! 4;; 1 j2 1 Yi 7,2 X 7- 1>3 31 2- 1 4U 47 x indicates a poor reflection. ~he difference between two successive readings is the angle between the corresponding faces. 11 a~c distilled, - with the same r ~sul.ts. The gas measu.rem ments we re not so conclusive as the absorption system used. was not com.i)letely absorptive nor were the connections compl e tely airtight. fhe data obtained were as follows, Air displaced by heating to boiling, _-----3 0G5 c.c • .A.ir a_isplaced luring ad.di tion of diazonium compound,-----155 0 . During the boiling ana_ refluxing a s teaa_y leak kept up so that the figures on the 0 ases evolved. are inconclusive beyond the point given above. '.i:he 6 as evolved c1uring the aa_di tion corresponds roughly to the theoretical. volume of nitrogen v,;hich shoul.6_ be given off d_v..ring the r eaction l<'or future work on this _point it might be sugg ested that a similar a~paratus be used but with a more efficie~ absorption Bottle and better gasometric appliances. tonclusion, ~'rom this work it may be concluc:_ecl that the Sandmeyer reaction on .P-toluid.ine-m-sulfonic 2,cid goes nearly to completion. From the manner in which the experiments were carried out it ·would seem likely that Fant sch 1 s c1.iazo cy anide was first formed but is at once transformed into the ni t rile with the loss of' N,, , these conditions C. being broucht about b:; heat and allcaline solution {see ~~antsch, B. I~ This work was carried out at the suggestion G,nd with the aid of ..::rofessor F .J. Lucas, to whom many thanks are d.ue :for ·whateve r success maJ Lave been attained in it. The aid. of r·r. Linus .t,auling, 1'lhO made the crystallog raphic measurements, is also much appreciated. :;_,:xperiment al J:.'a::r,t. _S ulfonci tion of £-toluidine One mol of H2 so/~(as cor. centrated sulfuric acidJ was placed in a 1.5 u;; c. c. flask equi.f:)_pea_ with a mechanicc:l Llt irre r and. a thermo~1et c r, and surrounded. by a cold water bath. 1 U7 g ms. of P-toluidin~ (one moll were me lted. and poured. Vf: ry slor;ly into the sulfuricacid, stirring all the while. The flask was coole d as often as necessar? to Pr Pv e nt the reaction from becoming too violent. When all the .P-toluid.ine had been ad.ded the wat e r batb. was removed ana. the flask heated. to a teml)era t ure Of '"'1 c. '' ,J o - ~ ,.: 3u.. o an d. lcep-c• t'nere a:u.r1.ng " • _,l,11.e ._, • d er re ma in of the re~ction. ( :naked. f lame was used in this ex- perime nt but an oil bath vrould. probabl~ work better es0 i)ecially as the reacting mass becomes rr; or e nearly solid). The heating was continued over a period of about two hours during vrhich time the content s of the flask became gray - e:: reen in color and expremely viscous, 1.·:hen they became too thick to stir the stirrer was removed and the lj heatinf; cautiously continued until the mass was nearly reaa_y to solidify in the :flask. The contents were then emptie d as complet el y as possible in to cracked ice { about 5uu c,c.). Th e portio ~ that solidified in the flask was -:Hashed out when cool, using t h e minimum quantity of water. The wh ole mix ture w2,s then s et aside jor twenty-four hours to cry stallize as com.i,Jletely as ~ possible. The r e sulting cry stal 1Y1.a s s was separated from t h e spe n t a ci~by suction. ( 'r he s.f)ent acid contains some sulfo n ic 2. cid ·wh ich may be removed} but the g_uanti ty is quite small a n d is h ardly worth the trouble and material to ootain it. In case considerable q_uantity of P-toluidine ·were sulfona t ,,a_ it mi i h t :pay to d.o so, in which caee t h e SQme procedure can be used as for the crystallized portion,) The crystals are dissolved. in 15uu c,c. of' water in a t hree liter flask and ·fr mol of Ba( OH) 2 added plus about 20 5G or enough to complet ely precipitat e the sulfuric acid remaining with the crystals, ( BaC03 may be used but the mixture requires boiling and i s somewhat troublesome on account of the gases evolved, Cao forms CaS64 vihich is soluble enough to r emain in solution and crystallize out willlh the sulfonic a cid.') ;.i:h e BaS0 4 is filtered off, the precipitat e wa sh ed twice by boiling with vrater and filtering a n d a dding the washings to the filtra t e. {.A_l'J.Y toluidine not r e acting can be recovered. by cListilling t lte Ba precipitate with steam. 1.J:his 14 affords a good check on the completeness of the reaction. About 20 gms of toluidine were r e ~overed in the run described.) 'l:he filtrate was now a li ght y ellow liquid and slightly alkaline in r eaction. Dilute I-L2so 4 was then added until a precipitate ce a sed to form ( a sligh t excess does no harm). The barium sulfate was filtered off as before and. t h e solution { now about thre e liters ') was e- vaporate d. to a.bout 8UU c.c. and_ set a s ide to crystallize. Ju'ter about twenty:.four hours the dish was filled with long nee d.les,light yellow i n color. 1:heir bulk is 1 d.e ceptive for they shrink tremendously on filt ering. Successive crops of crystals were taken off e ~ day until microscopic examination showed that other substances were crystallizing out in quantities comparable to that of the sulfonic acid. Recrystallizing gives a light er colored product. Yield, 6U - 65 gms of :p-toluidine-m-sulfonic acid, 33~,; of theo retical. ( If t he fi nal mother liquor is evaporated to dryness and saved and combined with similar residues from other runs, and re crystallized again considerable more sulfonic acid may be recovered.) freJ.1aration of' tpJJJere meta ... sulfonic acid Para-diazonium chloride!!. As the ~ara-toluidin-me ta-sulfonic acid was obtained it was a coarse crystalline powder . In the preliminary experiment, ten b1llS, of the acid were placed in a 6UU l;> c.c. oeaker surrounded by ice water. A mechanical stir. rer was provided and 1J u c.c. o:f water were added to the acid. 3.42 gms. of ari..hydrous sodiu."11 carbonate were ad- ded and the mi:-: ture stirred U..".ltil e:ff'ervescence had ceased and the acid had gone into solution. 4.75 gms o:f HCl (13 . c.c. of' 31 .5% acid.) were then ada_ed slowly • A thick yellow cream rs su.l ted. .i:h e whole obj act of this procedure is 1 to get the sulf'onic acid into as fine a state of subdivision as possible since it is only slightly soluble in i:va ter at ordinary temperatures. '~ The theoretical quantity of NaN0 2 was now added in the form of a dilute solution ( u.075 gms per c.c.) through a dropping funnel. Th e reaction was cons idered. complete when the reacting mixture gave a permanent blue color with starch and potassium iodide T.3. { Sinc e t h e re a ction goes slower toward the end, the mere production of a blue color does not necessarily mean the end of the reaction. The flow of sodium nitrite should. be stopped and. t h e reacting solution stirr ed. f or a minute or two a nd tested a gain. Gnly when the solution contains free nitrous acid should t h e reaction be consid.ered complete. Even then ther e mas be ij. f E:.W y eJ.1ow cry stals remaining in the bottom of the beaker.) EreParation of NaCu(C N)~ solution, l 1'ifty gms, of cus o 4 • 51-L>G ( 1 / 5 mol, were disL. olved. in 1 /J U c.c. of water and 13 gms of NaCl added. The solution was carried out in a 60CJ c.c. beaker by heatir..g ·1 b and stirring with a mec hanical stirrer. 11 gms. of NaHS03 and 7 gms. of Na OH were dissolved_ .d>n 1UU o.o. of water and added slowly to the boiling copper solution. When entirely added and the supernatant liquid was of a very light blue color ( if not more NaHS0 3 s hould be added) t he h eating and stirring were stop.Ped and the CuCl was washed by decan tation or by suction a nd washing on t h e filter. :ihen the wash water appeared clear t h e cuprous chloride 1 was mixea with about 2uu c.c. water and 26 gms. of 76 - 98% NaCN dissolved in 1 UU c.c. of water were added. The copp er goes into solution with the evolution of heat. Some Cu{vE)2 may ap:f) ear in the solution but may be filtered off. The filteri ng s houl d be don e into a tare d bottle so that the solution may be weighed out for the Sandmeyer Reaction. { Thi!.s is e s sen tially the same method. as is given in Or ganic Sy ntheses Vol. III :p. 33 and Vol. IV 'the Sand.meyer Reaction, (nitrile') The theoretical quan tity of l:,TaCu( Cl'Ij 2 ( one mol of Cu to on e mol of diazonium com.POUJ.1.d') vms plac ed in a three liter flask equipped with a mec hanical stirrer. 6. 8. gms. of anhydrous sodium c arbonat e v:as added { :aS"ufficient to neutralize t he H61 i n the d. iazoniu.r:J. chloride) a nd t h e solution boiled. Vi11.e11. the boiling commenced the diazonium compound was run in from a s e.Paratory funnel at a rate suf ficient to i n trQduce the whole in about fifteen mi nutes. .rhe cy ani de solution was kep t boiling during the 1 I •/ time of a d.di tion o:f the diazonium compou11d 0 The stirring vms stopped when the addition was complete and the dark red liquid reflu..~ed for five hours. V'l11en the solution had cooled dilute HCl was added e.arefully until :precipitation had ceased ( if too much acid is added the J?reci.Pita te tlissolvesj. HCNjs evolved during the addition of the acid, The :Precipitate of CuCl was filtered off and H2S :passed into the filtrate until it ·was saturated. The solution was now heated to boiling to remove H2 S and. the CuS :precipitated was filtered off. The filtrat e was evaporated u...~til a portion of it crystallized o~ cooli ng and the n set aside to crystallize. rl'he first cro.P of crystals was removed and washed once by sucking a s dry as possible, removing t he suction, moistening the cry stals for an instant and reapply ing the suction at once, 1he crystals ar e so soluble that any other treatment dissolves them almo s t irunediately. The mother liq_uor and vrashin;-s were set aside to crystallize by evaporation. The first crop were dissolved in water ana. r ecrys tallized, The cry stals s eparated as trans ~are nt, rose colore d , hexagonal pl a tes. Th e crystals can be grovm l ar g er by slovsr cry s t ~dlization in a dee:p a.ish. Some cHfficul t y is involved h owever as the solution shows a remarka~ tend ency to creep ove r the sides of the dish. Sandmeyer Reaction with gas absorption. The reaction was carried out as given before but in the modified apparatus shown in the figure on pag e8 The gases evolved bubbled first through .3 N sulfuric acid and then through strong KOH solution to absorb the CO2 given off and were fi nally collected in a gasometer. The R/30 1n1 3 4 v:as titrated with stand.ar HaOH and the amount of formed was ccdcula tea_. r.rhis wa s checkea_ by making t h e acid alkaline and distilling as in the Kj ela_ahl method. The N~C. was calculated from the volwne of water removed from the gasometer. Su...rronary 1. The sulfonation and diazotization of p-toluidine has been described.. 2. The Sandmeyer (nitrile) reaction on P-toluidine-~sulfonic acid has been studied and a method sugge sted for its further study~