148 R,EADE : ~BROMOPHENYLTRIMETHYLAMMONIWM PERHALIDES.

X I X . p -B rom o p h e n y Z Ir ime t h y lunwns ?a iaun Perh u 1 ides . By THOMAS HAROLD READE.

THE study of the phenyltrimethylammonium perhalides investigated by McCombie and Reade (T., 1923,123, 141) has been extended to the p-bromophenyltrimethylammonium series in this communication and to the p-iodophenyltrimethylammonium series (Reade and Sim , following paper). The result of degrading perhalides by acetone has yielded analogous quaternary ammonium salts in all three series. For example :

Perhnlide Product Part removed (empirical formula). isolated. by acetone.

(a)* QmC1,I -+ QmC1 + ICl ( b ) QmC1,Br -+ QmBr + C1, ( c ) QmClBrI -+ QmBr + ICl (d)* QmBr,I + QmBr + IBr

where Qm = NPhMe, or, when marked with asterisk, (p)C,H,Br.NMe, or ( p)CGH,I.NMe,.

In view of the marked electronegative nature of chlorine? reactions ( b ) and ( c ) are noteworthy, since the quaternary salt isolated was the bromide, not the chloride.

The table on p. 149 summarises the results of submitting p-bromo- phenyltrimethylammonium halides and perhalides to the further action of the halogens.

The points of difference between this series and the unsub- stituted phenyltrimethylammonium perhalides were :

(1) That QmBrI, yielded QmBr in the p-bromo-series when treated with acetone, whereas itls analogue in t'he unsubstituted phenyl series was not attacked.

(2) That well-defined, double perhalides have been obtained in several reactions ; for example, (QmC1,I + QmClBrI) resulted from

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Form

atio

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p-C

,H,B

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p-bromophenyltrimethylammonium.

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150 READE : rJ-BROMOPHEN3%TRIMET3TUMXO~ITJM PERHBLIDES.

the action of bromine on QmCl,I, gave identical analytical figures after crystallisation from ethyl alcohol or acetic acid, and yielded a mixture of QmC1 and QmBr on degradation by acetone.

No exception to the statement that chlorine replaces the N-halogen in iodides and periodides, that it replaces N-bromine only when iodine is also present, and that it replaces added halogens in per- bromides (giving QmBr,Cl,) has been encountered. But bromine and iodine replace N-chlorine to an a'ppreciable extent, and iodine replaces N-bromine in one instance. Consequently, the generalis- ations for the replacement of halogen atoms in the phenyltrimethyl- ammonium perhalides, although useful as a guide, are not rigidly applicable to this series of perhalides.

E X P E R I M E N T A L . IdentiJicution.-Owing to the rapidity with which decomposition

takes place at the temperature of fusion, the melting point is of little value as a criterion of purity of these perhalides.

Analysis .-Mixed halogens have been estimated by Carius's method, and also by a method described by Reade and Sim (following paper) whereby the ionisable halogens only are estimated, the p-bromine atom not being attacked.

Degradation.-(a) Ethyl malonate and (6) acetone have been used exactly as described by McCombie and Reade (loc. cit .).

p-Brmophenyltrimethylammonium Methyl Xulphate, C 6H,Br*NMe3*S 0,Me.

-p-Bromodimethylaniline (100 grams), diluted with COO C.C. of benzene, was heated for five hours under reff ux with 49 c .c. of methyl sulphate. After cooling, the product, part crystalline and part oil, was separated, heated under reflux with 200 C.C. of dry acetone, and cooled. The solid thus obtained was twice recrystallised from alcohol and ether, yielding white crystals, m. p. 208" with decom- position, which were readily soluble in methyl or ethyl alcohol and sparingly soluble in benzene, xylene, chloroform, or ether (Found : SO, = 29-55; C = 36-3; H = 4.8. C,H,Br*NMe,*SO,Me requires SO, = 29.45 ; C = 36-8 ; H = 4.9 per cent.).

When treated with bromine in hydrobroniic acid solution, it gnre an orange perbromide, C,H,Br*NMe,Br,. p-Bromophenyltrimethylammonium perbromide, C,H,Br*NMe3Br3,

was prepared by heating 24 grams of p-bromodimethylaniline, 8 grams of methyl sulphate, and 30 C.C. of pure methyl alcohol under reflux for six hours. The methyl alcohol was then distilled, the residue digested with water, and 32 grams of potassium bromide, 23 grams of bromine, and 10 C.C. of glacial acetic acid were added, whereby 34 grams of the perbromide were precipitated, which

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READE : ~BROMOPHENYLTRIMETHYLAMMONJTM PERHALIDES. 151

crystallised from acetic acid in orange-red leaflets, m. p. 175" with decomposition (Found : Br = 70.4. C,H,Br*NMe,Br, requires Br = 70.3 per cent.).

This perbromide yielded the bromide C6H4Br*NMe3Br when warmed with acetone.

Iodine in acetic acid gave C,H,Br*NIVIe,Br,IBr (Found : Br = 29-8; I = 28.8.

Chlorine in acetic acid gave C6H4Br-NMe,Br,C1,, pale lemon- yellow plates melting a t 158" with decomposition after crystal- lisation from acetic acid. p-Bromophenyltrimethylammonium bromide, C,H,Br*NMe,Br, is

formed when the corresponding iodide is shaken with excess of silver bromide. It is best prepared, however, by shaking the per- bromide C,H,Br*NMeBr, with five times its weight of dry acetone; the bromide is precipitated after a few minutes, the yield being 85 per cent. of the theoretical. It forms white crystals from alcohol, which darken at 200" and melt at 210". The compound is insoluble in chloroform or acetone, easily soluble in acetic acid or alcohol, and very easily soluble in hot water (Found : C = 36.6; H = 4.4; Br = 54.?. C,H,Br*NMe,Br requires C = 36.6; H = 4.4; Br = 54-24 per cent .) .

The action of halogens in acetic acid on this bromide was as follows : chlorine gave the bromodichloride, C,H,Br*NMe3Br,C1,, m. p. 158" ; bromine gave the perbromide, C,H,Br*NMe,Br,, m. p. 172"; and iodine gave the bromodi-iodide, C,H,Br*NMe,BrI,, m. p. 172".

Calc., Br = 31.8; I = 25.3 per cent.).

Iodine monochloride gave the bromo-iodochloride, C ,H,Br*NMe,Br ,ICl,

m. p. 181", whilst iodine monobromide gave the bromo-iodobromide, C,H,Br*NMe,Br,IBr, melting a t 185" with decomposition.

Action of Halogens on p-Bromophenyltrimethylctmmonium Iodide.- Chlorine in glacial acetic acid a t 60" gave p-bromophenyltrimethyl- ammonium chloride iodotrichloride, C6H4Br*N&kC1,1C1,, m. p. 187". Bromine under similar conditions gave p - bromophenyltrimethyl- ammonium bmmo-iodobromide, orange plates, m. p. 185".

Iodine (1 mol.) in alcohol, or in acetic acid, gave the tri-iodide C6H4Br*PJn/Ie3,13, coppery plates, m. p. 172" ; whilst iodine (2 mols.) gave brownish-black, shining leaflets which were recrystallisable from acetic acid without change, but gave the tri-iodide only when crystallised from alcohol (the thiosulphate titration value for the brownish-black leaflets was 1 per cent. below that required for the aggregate C,H,Br*NMe,I,I, + C,H,Br*N&k,~,I,). p-BromophenyltrimethyEammonium Tri-iodide, c6H4Br*me313.-

Equimolecular quantities of iodine and C,H4Br*NRrle31 were mixed in methylated spirit a t 70", and the solution was allowed to cool,

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152 READE : ~)-BROMOPHENYLTR~ETHYLAMMONmM: PERILBLfDES.

when brown, coppery plates, melting with deccmFosition a t 172", crystallised. The yield was 80 per cent. of the theoretical (Found : I' = 63.9. C6H4Br*NMe313 requires I' = 63.9 per cent.).

The crystals are very easily solublc in acetone, and easily soluble in hot alcohol or in hot acetic acid, horn which they crystallise on cooling.

Action of Halogens.-Chlorine in acetic acid gave c 6H *me,CI , Ic1,

(Found : 0.1862 gave by the Carius method 0.3531 of silver halides, which gave 0.3369 of AgCl. Calc., 0-3840 of silver haIides, giving 0.3320 of AgCl).

Bromine (2 mok.) in acetic acid gave C,H,Br*~e,Br,IRr, orange plates, m. p. 185O.

p-Br~phenyltrimethylammonium Chloride lodotrichbride, C,H4Br*~e,C1,1C1,.

-This substance can be prepared by the action of chlorine on an acetic acid solution of any of the following perhalides :

C,H4Br.~e3Br,ICI, c ,H,Br*me,Br, IB r, c ,H4Br *NMe3C1, ICI, c ,H4Br*me3Br, I,, C6H4Br*NMe313. It was prepared by the chlorination of- 16 grams of p-bromophenyltrimethylammonium iodide in 1 litre of hot glacial acetic acid, the yield being 17 grams. It crystallised from acetic acid in canary-yellow needles; m. p. 186-189" with decom- position (Found: 0.3046 gave 0.6199 of mixed silver halides, which yielded after chlorination the ratio silver halideslAgC1 = 1.15. C,H4Br*NMe3C1,1CI, requires 0.6270 of mixed halides and the ratio 1.16).

Degradation by dry acetone at 25" yielded the chloride,

Calc., C1' = 14.16 per cent.). c6H4Br *NMe,CI

(Found : C1' = 14.1, 13.9. Degradation by ethyl malonate at 60" in a vacuum gave the crude

dichloroiodide in 90 per cent. yield (Found : 0.1530 gave 0-2702 of silver halides, which yielded after chlorination the ratio silver halides/AgCl = 1.22. C6H,Br*~fe,C1,1C1 requires 0.2635 of silver halides and the ratio 1.237).

Attempts to purify the crude product by crystallisation from ethyl alcohol proved abortive, a series of perhalides being obtained which contained less chlorine the longer the period of treatment.

Very rapid crystallisation from alcohol gave yellow crystals approximating in composition to the formula C,H4Br*NMe,Cl,ICI (Found : 0.2333 gave 0.3875 of mixed silver halides, which yielded after chlorination the ratio mixed halides/AgCl = 1-27. Calc., 0.4010 of mixed halides and the ratio 1.24).

The substance was heated with alcohol for ten minutes; red

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READE : ~BROMOPHENYLTRIMETHYLAMMONIUM PERHALIDES. 153

needles were obtained on cooling, the yield being 45 per cent. (Found : C = 23.5; H = 2.8; 0.1000 gave 0.1626,0.1639 of mixed silver halides, which aEter chlorination gave the ratio mixed halides / AgCl = 1-34. C6H4Br*N&fe,C1,1C1 + C,H4Br*me3C1,1, requires C = 23-5; H = 2-83 per cent.; mixed halides 0.1645 and ratio 1-32).

If heating in alcohol was continued for two hours, coppery plates of c6H4&'*N&Ie313 crystallised on cooling, whilst the mother-liquor, on addition of ether, yielded a precipitate of C,H4Br*NlHe3C1, which was converted into its double salt with mercuric chloride (Found : C1' L- 19-9. C,H4Br*NMe3Cl,HgCI, requires Cl' = 2 0 4 per cent.).

Chlorine and bromine in acetic acid were without action on C,H4Br*NMe,C1,IC1, ; iodine, however, gave C6H4Br*NMe,C1,1C1 (Found : C1= 18.7 ; I = 26.5. Calc., C1= 17.2 ; I = 30.7 per cent.).

~-Bromo~henyltrimet~ylamnaonium Chloride Ioclochloride, C6H4Br*NMe3C1,1C1.

-Chlorine was passed into an acetic acid solution of p-bromo- phenyltrimethylammonium iodide a t 70" until the colour of the solution was a clear claret-red ; the product crystallised, on cooling, in bright yellow needles, m. p. 177" with decomposition (The m. p. of a specimen which had been kept in the light for one month was 165"). The substance is easily soluble in hot ethyl alcohol, methyl alcohol, or acetic acid (Found : 0.1000 and 0.1000 gave 0.1261 and 0.1267, respectively, of AgCl + Agl. C,H4Br*NMeC1,1C1 rcquires 0.1264 of AgCl -k AgI).

Degradation.-Acetone a t 25" gave a red solution and precipitated C6H,Br*NMe3C1 (free from iodide), which was converted into its double salt with mercuric chloride for analysis (Found : C1' = 20.17. C6H4Br*A~e3C1,HgC1, requires C1' = 20.42 per cent.).

Action of Halogens.-Chlorine gave C6H4Br*NMe,Cl,IC13 ; iodine gave traces of periodides with much unchanged dichloroiodide ; bromine gave a golden-yellow double perhalide,

C,H,Br*NMe,Cl,ICI + C6H4Br*NMe,Br,IC1, recrystallisable from acetic acid or ethyl alcohol (Found : 0-PO00 of material crystallised from acetic acid gave 0.1248 of ionisable silver halides, which after chlorination gave the ratio silver halideslAgC1 = 1.261. 0.1000 of material crystallised from alcohol gave 0.1249 of silver halides, and the ratio 1.260. C,H,Br*NMe,Cl,ICl +- C,H,Br*NMe,Br,ICl requires 0.1250 of silver halides and the ratio 1.263).

This double perhalide gave a mixture of the quaternary chloride and bromide when treated wit,h acetone (Bound: Br' == 19.7; C1' = 3-6. Calc. for C6H4Br*NMe3Br, Br' = 27.1; and for C6H4Br*NMe3Cl, c1' = 13.1 per cent.).

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154 READE : $?-BROMOPHENYLTRIMETHYLAMMONIUM PERHALIDES.

p-Bromophenyltrimethylammoniurn Chloride, C6H4Br*NMe3Cl.- This substance, prepared by the action of dry acetone on

C,H,BrmNMe3C1,1C1, forms hygroscopic, white crystals, very easily soluble in water, easily soluble in hot ethyl alcohol, sparingly soluble in boiling acetone, and slightly soluble in cold acetone, benzene, or ether. It darkens a t 191" and melts with decomposition a t 199". With aqueous potassium iodide, C,H4Br*N&1e,I is precipitated.

Action of Halogens in Acetic Acid.-Chlorine was without action. Bromine gave C,H,Br*NMe,Br, in 80 per cent. yield (Found : C1' = 1.2; Br' = 49.6.

Iodine gave chocolate-coloured crystals, green in thin layers, melting a t 172 ", consisting of C,H,Br*NMe,I, + C,H4Br*NMe,I,, whilst iodine monochloride remained in the solution (Found : I = 69.

Iodine monobromide (1 mol.) in cold acetic acid gave an immediate precipitate of C6H4Br*NMe,Br,IC1, melting a t 177", which on treatment with acetone yielded chiefly the bromide (Found : Br' = 24; C1' = 2. Calc. for C,H,Br*N&Ie3Br, Br' = 27.1 per cent .) .

Calc., Er' = 52-7 per cent.).

Calc., I = 70.3 per cent.).

Iodine monochloride (1 mol.) gave pale yellow crystals of C,H,Br*NMe3Cl,ICl

(Found : 0.0724 gave 0.1254 of ionisable silver halides. Calc., 0.1245). p-Bromophenyltrimethylammonium Bromide Iodobromide,

C,H,Br*me,Br, IBr . -Eight grams of bromine were added to 16 grams of p-bromophenyl- trimethylammonium iodide in 1 litre of glacial acetic acid a t 80". Orange, laminated plates crystallised on cooling. These began to darken a t 170" and melted with decomposition a t 189". Yield 13i grams. The mother-liquor was used for a second preparation and yielded 20 grams [Found : Br (total) = 45.2 ; Br (ionisable) = 30-3 ; I = 27.7. C,H,Br.NMe,Br,IBr requires total Br = 47.7; ionisable Br = 31.9; I = 25-3 per cent.].

The constitution was inferred from its yielding (a) the bromide C,H,Br*NMe,Br when treated with acetone, and ( b ) a pink colour in dilute acetic acid solution when treated wiOh aqueous starch solution.

Action of Halogens in Acetic i4cid.-Chlorine gave yellow crystals of C,H,Br*NMe3C1,1CI,, m. p. 185" ; bromine was without action ; whilst iodine gave a red, double perhalide, C,H,Br*NMe,Br,IBr + C,H4Br*NMe3Br,12, m. p. 185" with decomposition, crystallisable from alcohol or acetic acid (Pound : I = 36-8; Er' = 22-3. Calc., I = 36.3 ; Br' = 22.8 per cent.).

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READE : ~BROMOPHENYLTRIMETHYLAMMONIUM PERHALIDES. 1 5 5

p - Bromophenyltrimeth ylammonium bromide d i- iodide, C,H,Br*NMe,Br , I,,

was prepared by mixing hot acetic acid solutions containing equi- molecular quantities of iodine and C,H,Br*me,Br. The reddish- brown crystals, after two crystallisations from acetic acid, melted at 172" with decomposition (Pound: 0.1917 gave 0.2960 of mixed silver halides, C,H,Br=Nnle,Br,T, requires 0.2952 of silver halides).

Its constitution mas inferred from its giving (a) in dilute acetic a,cid solution an intense blue colour with starch, and ( b ) 10 per cent. of the bromide C,H,Br*NMe,Br after twenty-four hours' treatment wit8h acetone at 18".

Action of Halogens in Acetic Acid.-Chlorine gave yellow needles of C,H,Br*NMe,CI,ICI,, m. p. 186"; bromine gave orange plates of C,H,Br*NMe,Br,IBr, m. p. 189"; iodine gave a mixture of the tri-iodide, C,H,Br*NMe,I,, and unchanged bromide di-iodide.

p- Brornophenyltrimethylammonium Bromide Iodochloride, C,H,Br*NMe,Br,ICl.

-Equimolecular quantities of iodine monochloride and

were dissolved separately in hot acetic acid and the solutions mixed. Sandy, yellow crystals, which darken at 165" and melt a t 178-179" with decomposition, separated on cooling (Found : 0.2026 gave 0.3344 of mixed silver halides, which after chlorination gave the ratio total silver halides/AgCl = 1.30. C,H,Br*NMe3Br,ICI requires 0.3340 of mixed halides and the ratio 1.31). It was also formed by adding iodine monobromide to C,H,&-NMe,CI in acetic acid.

Degradation by acetone yielded the bromide, with traces only of the chloride (Found : for the crude, dried product, Er' = 24.2; C1' = 1.4.

c ,H,Br*NMe,Br

Calc. for C6H,Br-NMe,Br, Br' = 27.1 per cent.). Action of Halogens in Acetic Acid.-Chlorine gave

C,H4Br*N&!fe3C1,IC~,, m. p. 186". Bromine gave a mixture of C6H4Br-NMe3Br,IBr and C6H,Br*NMe,Br,IC1 (Found : 0.1477 gave 0.1810 of ionisable mixed silver halides, which after chlorination yielded the ratio mixed silver halidesIAgC1 = 1-39. C,H,Br*NMe,Br,IBr requires 0-1796 of silver halides and the ratio 1.42. C,H,Br*NMe,Br,ICl requires 0.1828 of silver halides and the ratio 1.32).

Iodine gave red needles, m. p. 182', of a double perhalide, crystal- lisable from alcohol or acetic acid (Found : 0.1000 of material crystallised from acetic acid gave 0.1216 of ionisable silver halides, which yielded after chlorination the ratio silver halides/AgCl -;= 1.38. Found : in material crystallised from alcohol, 0.1000 and 0.1000 gave 0-1223 and 0-1212 of silver halides and the ratio 1.38 and 1.39,

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156 READE : ~BROMOPHENYLTRINETHYLABIMONIUM PERHALIDES.

respectively. C,H,Br*NMe3Br,I, + c6H4Br*me,Br,Ic1 requires 0.1219 of silver halides and the ratio 1-42).

Degradation by acetone gave C6H4Br*mk3Br. p-Bronzophenyltrimethylammonium bromide dichloride,

c ,H4Br*~e3Br,C1,, was precipitated when p - bromophenyltrimethylammonium bromide in acetic acid a t 60" was added to acetic acid saturated with chlorine a t 18". Recrystallised from acetic acid heated to 75" only, it formed greenish-yellow crystals which lose chlorine readily and melt a t 158" with rapid decomposition (Pound : C1 = 17.6; Br = 46.1. C,H,Br*NMe,Br,CI, requires CI = 19.4 ; Br = 43.7 per cent.).

Degradation by acetone gave C,H4Br-NMe3Br (Found : Br' = 27.4.

Action of Halogens irL Acetic Acid.-Chlorine or bromine was without action. Iodine (4 mol.), however, gave C,H4Br*me3Br,IC1, m. p. 178", which gave C,H,Br*NMe,Br when degraded by acetone.

Calc., Br' = 27.1 per cent.).

Summary.

The reactions between p-bromophenyltrimethylammonium halides and molecular halogen, yielding perhalides, are described.

The reaction, Perhalide + acetone -+ quaternary ammonium salt +halogenated acetone has been utilised to classify these perhalides, and has given results analogous to those obtained by McCombie and Reade (Zoc. ci t . ) for phenyltrimethylammonium perhalides, thus affording support t o the view that this reaction is of service in determining the constitution of perhalides.

The results of treating p-bromophenyltrimethylammonium perhalides with molecular halogen are included in Table I, and indicate that the mobility of the halogen atoms in perhalides is in many cases greater than that which would be inferred from the generalisations given by McCombie and Reade (Zoc. cit.). The following statement, however, is applicable to both series ; chlorine invariably replaces the N-halogen in the quaternary ammonium iodide, or in periodidcs. It replaces N-bromine only when iodine is also present, but replaces " added bromine " in QmBr,Br2, giving &mBr,CI,, wherc N-halogen and " added bromine " are used in the sense defined by McCombie and Reade.

MARISCHAL COLLEGE, UNIVERSITY OF ABEXDEEN. [Received, August 20th, 1923.1

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