J. ALDENMURRAY AND F. B. DAINS
144
Summary The preparation of 3,3”3”,3”’-tetranitro-, 3,3”3’”3’’’-tetraamino- and 3,3’,3”,3’”-tetra-
[CONTRIBUTIONFROM
THE
Vol. 56
(acetylamino) -tetraphenyldiarsyl has been described. ANN ARBOR,RIICH.
DEPARTMENT O F CHEMISTRY, UfiIVERSITY
RECEIVED A V ~ ~ X J3, S T1933
O F KANSAb]
The Action of Amines on the Esters of Carboxy Substituted Ureas, Thioureas and Guanidines. I11 BY J. ALDENMURRAYAXD F. B. DAINS This is a continuation of the study of the action of amines on carbonyldiurethan and allophanic ester] together with their sulfur analogs and on the ethyl esters of guanidinecarboxylic acids. These latter can be regarded as derivatives of allophanic ester or carbonyldiurethan in which the carbonyl oxygen is replaced by S, CHBS,NH or “2. The experimental results have shown that with the sulfur derivatives the S or CHIS was the first point of attack, while with the guanidinecarboxylic esters, as in carbonyldiurethan, the carbethoxy groups were first affected. In some cases ring closure occurred to form heterocyclic compounds. Experimental 1. Urea Derivatives Methyl and Ethyl Amines and Allophanic Ester.-On long :standing the ester went into solution in the amines (33y0) and from the residues, on evaporation, were isolated 1-methylbiuret (m. p. 175”) and 1-ethylbiuret (ni. p. 159”) in 60% yields.* Benzylamine and Allophanic Ester.-7-Benzylallophanic ester3 (I), CeHsCH2NHCONHCOOC2H5, was the main product when the components were heated a t 135” for three hours. Heated a t 150” for five hours, 1,5-dibenzylbiuet (11), HK(CONHCH2C6HJ2, (m, p. 169”) resulted, while a t 200” the biuret dissociated to give cyanuric acid and s-dibenzylurea (m. p . 169’).4 Phenyl Isocyanate and Allophanic Ester.-The ester and isocyanate were heated a t 125” for five hours.5 The residue consisted of unchanged ester, carbanilide, and the addition product 1-phenyl-5-carbethoxybiuret ( m . p. 173 I) , 6 Phenylhydrazine and r-Phenylallophanic Ester.-This mixtiire, when heated a t 130” for five hours, gave aniline and i-phenylurazole (m. p . 263”).‘ (1) (a) Dains Greider, and Kidwell, THIS J O U R N A L , 41, 1004 1919): (bj Doins and XVertheim, ibid. 43, 2303 (1920). ( 2 ) Hofmann, Rer , 4, 265 (1871); Biltz and Jeltsch, ibid., 56, 1919 \IW:?j. ( 3 ) Preparecl. for comparison, i n SOY, yield by heating benzylnrea :md ethyl chloroformate on t h e steam-bath for a n hour. ( 4 ) .4 m i x t u r e of the biuret and urea melted about 150’. 1 5 ) 1 ukrd ; r i i r l Daini, ‘ h i s J O U R N A L , 51, 2221 (1929). 01) Ref I.,. p 1007 ( T I Ref l h . 11 2308.
Methyl and Ethyl Amines and Carbony1diurethan.-The diurethan dissolved immediately in an excess of 33% ethylamine solution, but in a few minutes a deposit of allophanic ester appeared.* On two weeks standing this dissolved and the solution was found to contain 1-ethylbiuret and traces of an oil, the ethyl ester of ethylcarbamic acid.g With methylamine, the diurethan gave, in thirty-six hours, 1-methylbiuret. Benzylamine and Carbony1diurethan.-In water solution on standing, and a t 115” without water, the reactants formed allophanic ester and ethyl benzylcarbamate (In.p . 49’),In results due to simple aminolysis. A t 135”, the products were ammonia, allophanic ester and ethyl ybenzylallophanate (I) ; a t 160 O , 1,5-dibenzylbiuret (11) ; and a t 200” s-dibenzylurea. Hydrazine and Carbonyldiurethan-On standing in alcoholic solution, allophanic ester alone. was isolated. Phenylhydrazine and Carbony1diurethan.-When molar quantities were heated a t 115 or 140”, 1-phenylurazole was the main product,‘ but a t 160’ iminodicarboxylic acid diphenylhydrazide ( 111), H N ( CONHNHC6Hb)z, was formed. It is soluble in sodium hydroxide. 2. Thiourea Derivatives Thioallophanic Ester, H2NCSNHCOOC2Hj.11--The cster was hydrolyzed to thiourea by aqueous ammonia and alkyl amines, and by alcoholic potassium hydroxide. Heated at 160” for an hour with aniline or o-toluidine, it yielded the s-diary1 oxygen ureas. Efforts to methylate the ester were fruitless. Amines and the Methyl Ether of Thiocarbonyldiurethan, CH3SC(NCOOCzHj)NHC00CzHj.’Z-The primary amines react with the methyl thioether in alcoholic solution with the loss of mercaptan and the formation of substituted guanidines. The yields were very satisfactory. Thus, methylamine gave y-methyl-p-dicarbethoxyguanidine (IV), CH~NHC(~’COOC~H~)NHCOOCZH;. Analogous results were obtained with ethylaniine (V), ethanolamine (VI), benzylamine (VII), aniline (T‘III), o-toluidine ( I X ) , phenylhydrazine (X), o-aminophenol (XI), p aminobenzoic acid ( X I I ) , anthranilic acid (XIII), and methyl anthranilate (XIV). ( 8 ) Ref. l a , p. 1007. (4) Basterfield, Woods and [Thelen. 1 H I S J O U R N A L , 49, 2848 (192i \ . 110) Hantzsch. R z r , 31, IS0 (1898) (11) Doran, J . C‘heiri . Y o ( . . 69, 3 2 5 , 3:il, :33li (1896): Dinon arid Taylor, t b z d . , 93, lj!lii (190B): r)ixon a n d Kennedy, ibid , 117, XO (1920). (12) Olin a n d Dains, ’Tixis J O U R N A L , 52, 3320 (1930).
A
Jan., 1 9 N
Z ON CXRBOXY ~ ~SUBSTITUTED ~ ~ NITROGEN ~ COMPOUNDS ~
Glycine and the Methyl Ether of Thiocarbonyldiurethan. Dicarbethoxyguanidineacetic Acid (XV), HOOCCH2NHC(SCOOCrHj)NHCC)OCnHj.- ~ - T h ccomponents were refltiscd in vrnter--alcohol solution. The compound was so\ul,lc in hot water. V:hcn boiled in alcoholic potassium for ) twcnty minutes, it gave potassiuiii hydroxide (,..i:& I,icai-ltonate ant1 t h i potassiuin salt of monocarbethoxyguanidineacrtic acid. Tlw Free acid (XVI) was practically in:;oiiil)le c s c q t in acid5 and bases. On hydro1 p i ? of XT: with dilute hydrochloric acid carbonyldiuretlian and glycine were formed. The ethyl ester of dicarbethoxyguanidineacetic acid (X1-11) w a s .‘oriiied when an alcohol-water solution of the thio inethyl ether and ethyl aniinoacetate stood for six weeks. Heterocyclic Compounds
TABLE I Yield,
%
Compound -, -Benzylallophanic e b ter ( C 1 1 H ~ h ~ 2 0 4 1.5-Dihenzylhiuret (CifiHiiK3Oz) Iminoilicarboxylic acid diphenylhydrazide (CiaHisNiO?)
S O
I 11 111
145
y.p . , c.
..
103
12.44
12 61
..
169
14 82
14 64
..
291
24.67
24.55
19.33 15 18
19.14 18.33
17 06 14?,:3 15 05 14 33 19 05
16 88 14.40 15 17 14 37 19 05
14 23
14.18
1 3 00
13 94
1:) 00
12.92
12.49 16 09
12.49 16.16
2 1 22 14.92 24 ‘28 34,fB 4.07 32.56 34 38 4 68 20.48 ;5K.31 5 . -11 16 \I2
32.17 14.50 24 25 :34 92 3.76 32.65 34.85 4.38 20.43 58 55 5 31 14 03
5ii li7 4 :Ti
,5!5 3:: 4 76
s.54
8 43
?i 44
27 50
19.34
19.31
18.!19
19.22
25.45
25.50
23.91
23.84
R a.0-Dicarbethoxyguanidines Methyl (CsHisXaO~) IV ( 2 5 ) 70 il V Ethyl (CgHijN30d 75 (Oil) 8-Hydroxgethyl vI (CgHiiNiOa) 80 98 VI1 Benzyl ( C M H ~ ~ S J O I ) ( 5 5 ) 89 (Oil) VI11 Phenyl ( C ~ H I ~ N ~ O ~ I 70 il IX o - m y i ( c ~ ~ H ~ ~ P ~ . , o ~ 90 ~) 75 ( 5 5 ) 8 5 192 X Anilino (CirHisNaOl) Hydroxylamine and the Methyl Ether of Thiocarbonyl o-Hydroxyphenyl XI 50 135 diurethan. Tetrahydro-3-carbethoxyimino-5-oxy-1,2,3,4(CiaHiiNaOfi) 1 2 3 4 6 XI1 p-Carboxypheny l oxdiazole (XvrIIj, OSHC!SC03C,H,)SHCO.- ---Hy60 198 (c141~17~306) L. . _ _ _ ~ ~ _ _ ___ _ J XI11 o-Carboxyphenyl 45 174 (ClnHi7TaOs) drosylainiiie ant1 tlir eitcr, on standing in alcohol o-Carbomethoxyphen) I solution, evolved mercaptan and gave the o~diazole,’~ XIV 40 67 (C15~~isN306) which mas vtry soluble in acids or bases. Xv Acetic acid ( C O H I J X ~ O ~ ) 40 210 Hydrazine and the Methyl Ether of Thiocarbonyldi- XT.1 Acetic (8-Carbethoxy) 65 Chars (C6HxN304) 250-275 urethan. Tetrahydro-3-carbethoxyimino-5-oxy-l,2,4-tri1 2 :I 4 5 x\11 Ethylaceto (CiiHisN.,Od 30 56 azole (XIX), SHN?-IC:NC03C?F-I:~)hH~O.--Thchydra- X Y I I I ‘Ietrahy dro-3-carhethoxy- 45 226 iniino-5-oxy-1,2,4-0~c H diazole (CsHiXaOa) zine was allowed to react with the thioether in alcohol soluTetrahydro-3-carbeth60 Over 335 tion or the t n i ~ i u r eheated gently until the evolution of mer- X I X c oxyimino-5-oxy-1,2,4solucaptan ceased. ‘l‘hc precipitate, which was about triazole (CsHsSaOa) H tile in water, was readily soluble in ammonia or weak bases. X X Z-Carbethoxyimino-2,307 320 (dec ) o-Phenylenediamine and the Methyl Ether of Thiodihydrobenzimidazole C 11 (Ci oH1iN.102) carbonyldiurethan. 2 Carbethoxyimino 2,3 dihydroXXI 9-Carbethoxgimino-4(13) S5 163 oxy-1.2.3,4-tetrahyc benzimidazole (XXi C,HIhH$( NCOOC2Hi)&H.---11Iolar ~. rlroqiiinazoline 11 (CIIHII?\IJO’) quantitie? wvtrc heated in alcohol solution. The diKiXXII 0.o’-Dicarbomethoxy~:ultlysoluble iniidazc~!eis c1 weak base, being precipitated carbanilide iCi;HisXnOd 30 144 iroiii its solation in g l z i c l l acetic acid hy water. X X I I I Hexahydro-l-phenyl-2,6dioxy-d-imino-s-triAnthranilic Acid Derivatives 30 Over339 azine (CgH&4O?) 2-Carbethoxyimino-4-oxy-112,3,4tetrahydroquinazoline XXID rr-Methyl-a;, -dicarbethoxyguanidine 1 2 3 4 (C8Hi&304) 07 85 (XXI), CsHaNHC(hiCOOCzH5jNHC0, was formed in small L___~~__~~_~____-J xxv Carhethouydicarboxanilidoguanidine yield when the guanidine ester (XIV) was heated carefully. (CiaHisNsOi) 40 151 (dec.) I t was also formed, in good yield, when either of the X X V l Hexahydro-l-phenyl-2guanidine esti!rs (XIX) or (SIT) was boiled for fifteen thio-4-imino-6-oxy-striazine (CgHsNiOS) (50) 90 180 (dec.) minutes in an alcoholic solution of an equivalent quantity of potassium hydroside. The mixture was poured into XXVII l-Phen)-l-2-methylthio4-imino-fi-oxy-1,4,5.6water and acidified and thc precipitate recrystallized from tetrah~,dro-s-triazine 1 alcohol. (C!oHioS1OS) 40 247 y
lY0
-
-
-
5yo
’-Dicarbomethoxycarbanilide (XXII), CO( IL”C6H4COOCH3)p, was formed when the methyl thioether and methyl anthranilate wcrc heated a t 140’ for three hours. I t was identical with a qxcimen synthesized from phosgene and methyl anthranilate. Amines a n i Thiocarbonyldiurethan, SC(NHCGOC2H3):.I2--Tn co.itradiction to carbonyldiurethan, in which group’; arc the points of attad
