MERCURY MERCAPTIDE NITRIDES ETC. 261 XXVII -Mercury Mercaptide Nitrites and theb Reaction with the Alliyl Iodides. Part 1V. Chain Compounds of Sulphur (continued). By PRAFULLA CHANDRA RAY and PRAFULLA CHANDRA GUEIA. IN this investigation the reactions of several actual and potential mercaptans some of them cyclic have been studied. It was ex-pected that in these the molecules being of a more complex nature, the radicle especially -SHgNO, would far more readily part com-pany with the parent substance and lead an independent existence as the compound 3(SHgN02),Hg0 (T. 1917 11’1 101). The result has proved to be just the reverse. 5-Thiol-2-thio-3-phenyl-2 3-dihydro-1 3 4-thiodiazole, >C*SH rPh*N c 8--s yields with mercuric nitrite the corresponding mercaptide nitrite (compare T.1916 109 131), RSH + Hg(NO,),= RS*HgNO,+ HNO,. Mercuric nitrite and phenyl mercapt”an furnish a compound, Ph,S,Hg evidently a mercaptide and sometimes another oxy-salt, (3PhS,HgO),. It is only in exceptional cases (see p. 264) that the expected mercaptide nitrite PhS-HgNO, is obtained and then only in an impure form. The reaction appears to proceed in the following stages: PhSH + Hg(NO,) = PhS*HgN02+ HNO,. The nitrous acid thus liberated oxidises another pair of molecules of phenyl mereaptIan to diphenyl disulphide and the latter then forms with mercuric nitrite the compound, PhS*SPh N203 PhS*SPh /\ -+ /\ 0;NHk &02 Hg-0 Two molecules of this compound combine with a molecule of diphenyl disulphide giving rise to the compound, PhSaSPh 2 /\ ,Ph,S,.Hg-0 3-Phenyl-5-methyl-2-thiohydantoin gives the mercaptide nitrite, VOL. cxv. 262 R.kY AND GUHA MERCURY MERCAPTIDE NITRITES Pot e ti tial Mercaptans. The interaction of mercuric nitrite and the aryl substituted thiocarbamides thiosemicarbazides thiocarbazides etc. ? follows the ordinary course but no detachment of the organic radicle takes place. Thus with phenylt,hiocarbamide w-B have N 11 Ph* C( NH2):S Hg(h’oF N1IPh.C (:N H)*S*HgNO + N H Ph* C (1 N H) S( HgN O,)<tg. AttenGon may also here be directed to the interesting analogous case of potassium phenyldithiocarbazinate which combines in itself t,he function of a real and of a potential mercaptnn thus: n’HPh*NH*CS,K so$ NHPh*N:C(SH)*SK + N H Ph*N :C( S*RgNO,)* S(HgNO,)<p.The sulphur atom belonging t o the potential mercaptan alone beconies qu adrivalen t,. Migration of Alkyl Badicles. When thimarbanilide methyl ether is treated with mercuric nitrite the methyl group migrates to the neighbouring nitrogen atom hydrogen taking it,s place thus: NHPh*C(:NPh)-SMe H%o$ NMePh*C(:NPh)*SH+ NMePh*C( :NPh) *S*HgNO,* That the reactions described above are of wide application is borne out by the behaviour of 5-methylthiol-2-thio-3-phenyl-2 3-dihydro-1 3 4-thiodiazole which wiih mercuric nitrite gives the compound, yPhoNMe>(J( HgNO,)*S*HgNO,. cs-s Reaction with the Allcyl Zodides Formation of Mono- Di- and Tm’-sulph~’~m COTIZPOU~S. The reaction follows the general course with this material differ-ence that tFie complex radicle being overweighted can no longer retain its entity but the less stable part of it is usually ruptured.Of special significance from this point of view is the rupture of t.he ring of the heterocyclic mercaptide nitrites. When the mercaptide nitrite of 5-thiol-2-thio-3-phenyl-2 3-dihydro-l 3 4 AND THEIR REACTION WITH THE ALKYL IODIDES. PART IV. 263 thiodiazole is digested with an alkyl iodide the product (I) is obtained and by further action of the alkyl iodide the phenyl HgI R y g 1 YgI i i f 1 - t i I I R*NPhaN:CR*S-- SR NK,-N:CR*S--dK NR,*NR*ClZ,*S--SR , (1.1 (11.) (111.) group is displaced by the alkyl group and the compound (11) is formed. Finally two more alkyl groups are attached with the production of the compound (111). By the action of methyl iodide two compounds corresponding with stages (I) and (111) have been isolated whereas in the case of ethyl iodide only one compound has been obtained,.which corre-sponds with stage (11). When 2-thie3-phenyl-2 3-dihydro-1 3 4-thiodiazole disulphide dissolved in carbon disulphide was heated under reflux with ethyl and mercuric iodides not only was there no rupture of the thio-diazole rings but one of the tertiary nitrogen atoms became quaternary by combining with a molecule of ethyl iodide and the following compound, HgI Et I 1 was obtained. The action of alkyl iodides on phenyl mercaptide nitrite follows the usual course and yields compounds of the general formula PhRS,,HgI,,RI. An interesting monosulphoniuni compound has been obtained from the mercaptide nitrite' of thiocarbanilide.The reaction prob-ably takes place as shown below : N€€Ph*C( :NPh)*S(HgNO,)<p CEt,I*SEtI*HgI. The interaction of mercaptide nitrites of thiocarbanilide alkyl ethers and alkyl iodide t,akes place as follows : NlflPh- C( :NPh)*S*HgNO R'I, BgI R' HgI R' I I I NRPh*C(:NPh)*S-S*C(:NPh)*NRPh + R'*b-SR . i i i 264 RAY AND QUHA MERCURY MERCAPTIDE NITRIDES EXPERIMENTAL. 1iLteraction of the Potassium Salt of 5-Thiot-2-thio-3-phemyl-2 3-dihydro-1 3 4-thiodi‘azole and Mercuric Nitrite Formation of the cor?*espo?zding Nercaptide Nitrite rPh*’ >C*SHgN 0,. c s--s The mercury salt was obtained sometimes anhydrous but often combined with three five or eight molecules of water the degree of hydration evidently depending on the dilution of the reacting substances.They all evolved nitrous fumes when treated with hydrochloric acid : 0.2724 gave 0.1187 Hg. Hg=43-59. 0.1100 , 0.0810 CO and 0.0187 H,O. @=20*08; H=1.89. 0.1420 , 10.2 C.C. N a t 25O and 760 mm. N=8*10. C8HH,0,N3S,Hg requires Hg= 42.46 ; C = 20.38 ; H = 1.06 ; N =. 8.93 per cent . The above with 3&O: Found Hg = 38-05 ; @= 18.28 ; H = 3.29 ; N = 8.30 ; S = 18.56. Calc. Hg = 38.09 ; C = 18.29 ; H = 2.1 ; N = 8.00 ; S = 18.29 per The compound with 5H20 : Found Hg=35.75; C-16.92; H=3.20. Calc. Hg= 35-65 ; C = 17.12 ; H = 2-67 per cent. The compound with 8H20 : Found Hg=32.10; C=15.10; H=3*56; N=6.16; S=15.08. Cab. Hg = 32.52 ; C = 15.63 ; H = 3-41 ; N = 6.83 ; S = 15.61 per cent. cent.Mercuric Nitrite and Phemyt Mercaptam. Three different compounds have been isolated in this case. When an alcoholic solution of phenyl mercaptan is added slowly t o an excess of mercuric nitrite solution the reaction t’akes t.he ordinary course and the mercaptide nitrite PhS*HgN02 is mainly formed. It is a dull yellow light granular powder and is a trim nit8rite. When however the mercaptan is rapidly added in excess, the whole of the mixture assumes a dirty yellow colour and nitrous fumes are evolved. On keeping a white granular powder is obtained which when crystallised from hot benzene until quite pure melts sharply a t 146O. Under slightly varying conditions an oxy-compound (SPhS,HgO), is formed. As is evident i t is not easy t o control the reaction so as to give one product to the ex AND THEIR REACTION WITH THE ALKYL IODIDES.PART IV. 265 clusion of the others. The mercaptide nitrite is always found t o be admixed with t'he other products of this reaction. The mercaptide nitrite gave different results of analysis on different occasions depending on the proportion of the cornpowid, Ph,S,Hg admixed with it; generally however the values were found t o be intermediate between those required for the pxre inaterial and the compound Ph,S,Hg. The compound Ph,S,Hg melting a t 146O gave the following results : 0.1942 gave 0.0864 Hg and 0.3134 BaSO,. Hg=44*48; 0.0964 gave 0.116 CO and 0.0230 H20, S = 22.16. C=32.17; H=2.7. C,,13,,S3Hg requires Hg = 44.44 ; S = 21.30 ; C = 32.00 ; H= 2.30 per cen t4. The campound (3PhS,HgO), gave the following results : 0-4016 gave 0.1506 Hg.Hg=37-50. 0.4333 , 0.5620 BaSO,. S=17*82. 0.1230 , 0.1886 (20,. C=41.81. C,,H,O,S,Hg requires Hg= 38.02 ; S = 18.25 ; C = 41-07 per cent. The above two compounds were proved t o be non-nitrogenous by combustion analysis. Mercuric Nitrite mi3 3-Phe?a?/l-5-met7~?/1-2-thioh~~~~ri toin : FO-NPh CHMe*N >C*S*HgNO,,ZH,O. Formation of the Compound, The compotund was greenish-grey : 0.1981 gave 0.0954 IIgS and 0.1110 BaSO,. Hg=41*61; S = 7.69. -0.1774 gave 0-1586 CO and 0.0582 H,O. 0.2836 , 20.8 C.C. N a t 30° and 760 mm. N=8*10. C=34.38; H-3-65. C,,€I,,O,N,SHg requires Hg = 41.07 ; S = 6.57 ; C = 24-64 ; H= 2.67 ; N=8.63 per cent. P o t e PL t ia 1 .iW e r c a p t a n s. Mercuric Nitriie and Phemylthiocadarnide F o ~ m l i o n of the Compound NHPh*C( NH).S( HgNO,)<p.This was deep yellow: 0.3512 gave 0.2350 Hg and 0.1227 BaSO,. 0.2015 , 11.4 C . C . N a t 26O and 760 mm. N=6*40. Rg=66*9; S=4.S. C7H70,N,SHg2 requires Hg= 65.25 ; S = 5-22 ; N = 6.85 per cent 266 RAY AND QUHA MERCURY MERCAPTIDE NITRIDES Mercuric Nitrite and s-Diphenylthiocarbamide Formation of the Compound NHPh*C( :NPh)*S(HgNO,)<zg . This was a brownish-yellow granular powder : 0.3422 gave 0.1970 Hg and 0.1069 BaSO,. Hg=57-57; S=4.64. 0.39?0 , 0-1141 CO and 0.0244 H,O. C=22*27; H=1*94, C,,H,,O,N,SHg requires Hg = 58-07 ; S = 4.64 ; C = 22.64 ; H = 1.60 per cent. The product gencr-ally obtained conforms t o the formula The above compound is only rarely formed.Hg[NPh*C( :NPh)*S-HgNO,] : 0,1555 gave 0.0947 HgS and 0.0741 BaSO,. Hg=52.51; 0.2275 gave 0.1367 HgS and 0.0992 BaSO,. Hg=51*80; S = 6.55. s = 5.99. C,,H,,O,N,S,Hg requires Hg = 52-43 ; S = 5.59 per cent. Mercuric Nitrite and Thiosemicarbazide Fomnatton of the Compound H g [N (NH,) C( N H ) S HgNO,] . An aqueous solution of the thioi-compound was useld. The pro-0.2715 gave 0.1870 HgS and 0.1362 BaSO,. Hg=68*87; 0.1032 gave 11-8 C.C. N a t 32O and 760 mm. duct was a dull yellow granular powder: S= 6.89. N=12*60. C,H,O,N,S,Hg requires Hg = 68.96 ; S= 7.36 ; N = 12-87 per cent. Mercuric Nitrite amd Diphe.lz~lthiosemicarbcczide Formtion of the Compmd Hg[N(NHPh)*C( :NPh)*S*HgN02},. This is an mange-yellow granular powder : 0-1797 gave 0.0925 Hg.Hg=51.48. 0.2577 , 0.2498 CO and 0,0523 H,O. C=26*21; H=2*25. 0-1380 , 11.7 C.C. N a t 32" and 760 mm. N=9*38. C,,H,,0,N,S,Hg3 requires Hg = 51.11 ; C = 28.57 ; H = 1.87 ; N=9-54 per cent AND THEIR REACTION WITH THE ALKYL IODIDES. P A ~ T IV. 267 Mercuric Nitrite and Diphenylthiocarbaside Formation of the Compmnd Hg[N(NHPh)*C(:N*NHPh)*S*HgNO&. This is a pink granular powder: 0.1667 gave 0-0965 HgS and 0-0607 BaSO,. Hg=49*91; 0.1463 gave 0.1404 CO and 0.0327 H,O. 0.1167 , 11.7 C.C. N a t 30° and 760 mm. N=ll-26. S = 5.00. C=26.14; H=2*48. C2,H,,0,Nl,S,Hg3 requires Hg=49*83 ; S =5.31; C = 25.91 ; H=1*82; N=11*62 per cent. Mercuric Nitrite a,nd Phenylkydrasine Phenyldithiocarb aziriat e : Formation of the Compound, N H Ph h' c ( SHg N 0,) S( HgNO,) < y .This is a blackish-violet granular powder : 0.1971 gave 0.1549 HgS and 0.1031 BaSO,. Hg=67*71; 0.1651 gave 8.5 C.C. N at 27O and 760 mm. S = 7.18. N=5.89. C7H60,N4SzHg3 requires Hg = 67-40 ; S = 7- 19 ; N = 6.30 ; CT = 9.44 per cent. The same compound is formed by the interaction ,of mercuric nitrite and potassium phenyldithiocarbazinate. (Found Hg = 67-97; C=9.24; H=0*98; N=5*88 per cent.) Mercuric Nitrite and Thiocarbanilide Methyl Ether Formation of the Compound NMePh*C(:NPh)*S*HgNO,. This is an orange-yellow granular powder : 0.2301 gave 0.1038 Hg. Hg=39*86. 0.2377 , 0.3027 CO and 0.0738 H,O. @=34-70; H=3*45. 0.2863 , 22.6 C.C. N a t 29O and 760 mm. N=8.99. C,,H,,O,N,SHg requires Hg = 40.90 ; C = 34-50 ; H = 2-67 ; N= 8.86 per cent.Mercuric Nitrite and Thiocarbanilide Ethyl Ether Formatiore of the Compound NEtPh*C( :NPh)*S*HgNO,. The substance is an orange-yellow granular powder : 0-3730 gave 0.1478 Hg and 0.1874 BaSO,. 0.1232 , 9.4 C.C. N a t 32O and 760 mm. N=8.43. Hg=39*63; S=6*91. C,SH,,0,N3SHg requires Hg = 39.92 ; S = 6.39 ; N = 8-38 per cent 26s RAY AND OUHA MERCURY MERCAPTIDE NITRITES ilfercrcric Nitrite and 5-ilf ethylthiol-2-thio-3-phenyl-2 S-dihydro-1 3 4-thiodiazole Formation. of the Conzpound rPh*NMi>C( CS- IJgzu'O,).S* HgNO, 8H,O. A clear solution of the thio-compound in chloroform was vigorously agitated with mercuric nitrite solution for nearly half an hour when an emulsion was formed which after being allowed to remain overnight gave a cream-coloured granular mass : 0.1984 gave 0.1055 HgS and 0.1384 BaSO,.Hg=45.85; 0.1879 gave 0.0884 CO and 0.0296 H,O. 0.1603 ) 10.2 C.C. N a t 30° and 760 mm. N=7.03. S = 9.58. C=12*83; H=1-75. C,H,,O,,N,S,Hg requires Hg= 45-67 ; S = 10.96 ; C = 12.33 ; H=O*91; N=6-39 per cent,. Mercztric Nitrite and 2-Thio-3-phenyl-2 3-dd~gdro-1 3 4-thio-diazole Disulphide Formation of the Cornyoii?zd, NPh*N Yg-? N.7P-l bs--sSC'~-~'CQs-cY NO HgNO, 0.2940 gave 0.1288 Hg. Hg=43*80. 0.1190 ) 9-00 C.C. N a t 30° and 760 mm. N=8*35. (compare T. 1916 109 133): C16H,,0,N6S,Hg requires Hg= 41.75 ; N = 8-77 per cent. R c a c t i o n w i t h the A l k y l I o d i d e s . lnt eraction of t h e Mercapt ide iVitrit e of 5-Thiol-2- t hio-3-phenyl-2 ; 3-&hydro-1 3 4-thiodiazole and Methyl Iodide Formation of the Compound, HgI Me 1 1 I NMe,*NNe*CMeBoS--Sble i I The method of procedure is exactly the same as in the inter-action of simple mercury mercaptide nitrites and the alkyl iodides.After heating with methyl iodide under reflux a portion was left undissolved which when purified by washing several times with acetone melted sharply a t 1 2 7 O . The portion soluble in acetone was purified by precipitation with ether and melted a t 107O AND TEEIR RBACTION WITH THE ALKYL IODIDES. PART xv. 269 0.3129 gave 0.0811 Hg. Hg=25*92. 0.4107 , 0.1066 H g and 0.3718 AgI. Hg=25.96; I=48.72. 0.0844 , 0.0363 CO and 0.0237 H,O. C=11*73; H=2.45. @,H,,N,I,S,Hg requires Hg= 25-32 ; I = 48-23 ; C= 12.15 ; H = 2.66 per cent. The compound insoluble in acetone has the formula HgI Me I I NMePh*N:CMe*S-SMe .f i 0.1867 gave 0.0449 Hg 0.1527 AgI and 0.0870 BaSO,. 0.1070 gave 0.0590 CO and 0.0734 H20. 0.1227 , 4.2 C.C. N a t 35O and 760 mm. N=3.7. Hg= 25.96 ; I = 48.93 ; S = 6-40. C=15-06; I'I=1.39. C,,H,7N,I,S,Hg requires Hg = 24.33 ; I =46.35 ; S = 7-79 ; C=16*06; H=2.87; N=3*4 per cent. Tr~teraction of the above Mercaptide i'CT'itrite and Ethyl Iodide : Formution of the Compound, HgI Et NEt2*N:CEt*S-dEt. I i f (m. p. 73-74O). 0.2316 gave 0-0572 Hg 0.1960 AgI and 0.0972 BaS04. 0.2564 gave 0-0611 Hg. Hg=23-83. 0.1278 , 0.0703 CO and 0.0296 H20. C=15*41; H=2-58. 0.2470 , 7.8 C.C. N a t 3 1 O and 760 mm. N=3*50. C,,H,N,I,S,Hg requires Hg=24.09; I=45*90; S:=7*72; C=15-90 j H=3.07; N=3.57 per cent.Hg =24*69 ; I= 45.74; S=5.77.* PJhenyl Mercaptide Nitrite and Methyl Iodide Formation of the Compound PhMeS,,HgI,,MeI. The pure substance was obtained by repeated crystallisation, 0.4616 gave 0-1252 H g and 0.4353 AgI. Hg=27.12; 1=50.96. 0.1131 , 0.0551 (20,. C=13*29. C,H,,13S2Hg requires Hg=26*6; 1=50*66; C=12.77 per cent. * See footnote p. 271. and was a dull yellow crystalline powder melting a t 90°: M 270 RAY AND GIUHA MERCURY MEROAPTIDE NITRITES Pltenyl Mercaptide Nitrite and Ethyl Zodide Formation of the Compound PhEtS,,HgI,,EtI (m. p. 59O). 0-2994 gave 0.0774 Hg and 0.2673 AgI. Hg=25*85; 1=48*24. 0.1302 , 0.0740 CO and 0.0282 H,O. C=15.5; H=1.86. C,oH,,13S2Hg requires Hg=25.64; 1=48*84; C=15.39; H=1*92 per cent. Interaction of the Compound Ph,S,Hg and MetJiyl Iodide : I €'h Pli I I I Formatiolz of the Compowzd C€T,*S-S-S*CH , I I I HgI I I The product was an oil which on stirring crystallised.It was washed several times with acetone when the colour changed to yellowish-white. It was insoluble in acetone and melted a t 11 1-1 1 2 O : 0.3150 gave 0.0615 Hg 0.2915 AgI and 0.2007 BaSO,. Hg= 19.53; I= 50.00; S = 8.75. 0-1410 gave 0.0902 CO and 0.0390 H,O. C=17*41; H=3.07. C,,H,,I,S,Hg requires Hg= 20.24 ; I= 51.42 ; S = 9.71 ; C= 17-00 ; H=1*62 per cent. It will be noticed that whenever a sulphonium compound con-tains phenyl groups it becomes insoluble in acetone. Mercaptide Nitrite of Thiocarbanilide and Ethyl Zodide : Formation of tlbe Compound CE t,I* SEtI- HgI . I n this case deep purple needle-shaped crystals were obtained 0.3083 gave 0.0890 Hg 0.2920 AgI and 0.1042 BaSO,.0.1214 gave 0.0552 CO and 0.0232 H,O. which were soluble in acetone: Hg=28*73; I= 51.113; 5-4-64. C=12.04; H=2.12. C,H,,13SHg requires Hg=28.09; I=53.51; S=4-49; C=11.80; H=2-11 per cent. Mercaptide Nitrite of Thiocarbmilide Methyl Ether and Methyl Zodide Formatiom of the Cornpmmd Me,E&,HgIz,MeI. The mercaptide nitrite was heated under reflux with methyl It was obtained pure by fractional precipitation from a iodide AND THEIR REACTION WITH THE ALKYL IODIDES. PART IV. 271 concentrated solution the process five or six which melted a t 160-in acetone by adding ether and repeating times when a fairly good crop was obtained -162' : 0.3290 gave 0.0791 Hg and 0.3281 AgI.Hg=29.51; 1=53-89. 0.1150 , 0.0221 CO and 0.0218 H,O. C=5.24; H=2*11, C3H91,S,Hg requires Hg=28*98; 1=55*21; C=5*22; H=1.30 per cent. Memaptide Nitrite of Thiocarbanilide Ethyl Ether and Ethyl Iodide Formation of the Compound Et+S,,HgI,,EtI. The procedure was almost the same as in the previous instance. On concentrating the acetone solution a portion crystallised out, which was purified by repeated fractional crystlallisation ; when pure it melted sharply a t 1 1 1 O : Hg=27*57; 1=51*46. 0.3127 gave 0.0862 Hg and 0.0978 AgI. 0.0861 , 0-0327 CO and 0.0255 H,O. C=10*37; H=3.29. C,H,,I,S2Hg requires Hg = 27.33 ; I = 52.05 ; C = 10.37 ; H = 3-29 per cent. 2-Thio-3-phenyl-2 3-&hydro-1 3 4-thiodiazde Disulphide Mercuric Iodide und E'thyl Zodide Formatioit of the Compound, HgI Et T I 0.3127 gave 0*0512 Hg 0.2366 AgI and 0.3026 BaSO,. 0.1574 gave 0.1066 CO,. C=18.47. C,,H2,N414S6Hg requires Hg- 16.45 ; I = 41.75 ; S = 15.75 ; C = 19.74 per cent. Hg=16*38; I=40*89; S=13*29.* CHEMICAL LABORATORY, COLLEUE OIP SOIENCE, UNIVERSITY OF CALCUTTA. [Received November 8th 1917.) * Owing to the tedious process involved in analysis the values for sulphur and iodine are sometimes too low (compare T. 1916 109 135)