[1]United States Patent Office 3@317@529 3,317,529 N-HALOMETHYL S-TRIAZINES Michael Thomas Beachem, Somerset, and John Christian Oppelt, Manville, N.J., assignors to American Cyana. 5 mid Company, Stamford, -Conn., a corporation of Maine No Drawing. Filed July 7, 1964, Ser. No. 380,947 12 Claims. (Cl. 260-249.6) This invention relates to a new class of compgunds and 10 to processes for their preparation. -More particularly, it relates to N-halomethyl s-triazines and their process of preparation and still more particularly s-triazines of the formulas set forth hereinbelow. R 15 1 u Yi NI "'M Y 11 I / - N-C CN \ 20 Y2 N CHZ-X A c c kl25 y N y@ y@ N N y NI-C C N NC C-N X-C@2 \N":@" \Y2 Y2/ \N:@' \.CHr-X (II) 30 wherein X is chlorine or bromine; R is hydrogen, alkyl, aralkyl, aryl, or /y8 N Y4 35 A is a @divalent hydrocarlyon radical (polymethylene or phenylene); Y, YI, Y2, Y3 and Y4 are lower alkyll -CH20R, or -CH2X; R, is alkyl or alkene; and the R and A radicals may be substituted by inert substitu- 40 ents such as cyano, halogen, etc. T'he compounds of this invention are prepared by reacting an s-triazine of Formulas III and IV with certain acid halides such as acid chlorides or acid brornides in accordance with the following equations: 45 R I c yi N N y \ 11 @- / + acid balide @ compounds of 50 N-U \ N \ Formula I Y( N CHz-ORi (III) A 55 y N Yi Yi N N y \ 11 I / \ 11 I / / N-0 C-N \ N-0 C-N Rio-CH2 N Y2 y@ \N \CH2--ORI 60 acid _ coomp=ds of r + halide rm II (IV) In Formulas III and IV above, R is hydrogen, alkyl, aralkyl, aryl or 65 Y3 N Y4 . 0 Y, YI, Y2, Y3 and Y4 are lower alkyl, -CH2-X or I -CH,ORI; A is a divalent hydrocarbon ra-dical; R, is Patented May 2, 1967 2 alkyl or alkenyl; and X is chlorine or bromine. The acid balide may be an acid bromide or acid chloride. -It will be observed from the formulas set forth above that the striazines of Formulas 1, 1-1, III and IV are Nsubstituted derivatives of guanamines and melamine. The s-triazines of Formulas IH and IV are N-alkoxymethyl derivatives of 2,4-diamino-s-triazines (guanamines) and of 2,4,6- triamino-s-triazines (melamines), resper,tively. The non-nuclear (i.e., amido) nitrogens of the s-triazinp-s must be completely substituted by alkoxymethyl or lower alkyl groups. The striazines must be free of all active hydrogens Suitable melamine derivatives @of Formulas III and IV employable in the process of this inventign include N,NN',N',N",N"-hexakis(meth-oxymethyl) -2,4,6- triamino-s-triazine, N',N',N"-triinethyl-N,N',N"-tris(methoxymethyl)-2,4,6- triamino-s-triazine, N,N,N',N"-tetramethyl-N',N"-bis-(methoxymethyl)- 2,4,6-triamino-s-triazine, N,N,N',N"-tetrametbyl-N',N"-bis(octyloxymethyl)- N,N,N',N',N",N"-hexakis (allyloxymethyl) -2,4,6- triamino-s-triazine, NN,N',N"-tetramethyl-N',N"-bis (octadecyloxymet@hyl) 2,4,6-t-riamino-s-triazine, and the like. Examples of suitable guanamine derivatives which may be employed in the process of this invention -are the following: N,N,N',N'-tetrakis(methoxymethyl)-2,4-diamino-striazine, N,N,N',N'-tetrakis(methoxymethyl)-2,4-diamino-6- methyl-s-triazine, NIN,N,N'-tetrakis(methoxymethyl)-2,4-diamino-6- ethyl-s-triazine, N,N,N',N'-tetrakis(methoxymethyl)-2,4-diamino-6- octyl-s-triazine, N,N,N',N'-tetrakis(methoxyniethyl)-2,4-diamino-6- heptadecyl-s-triazine, N,N,N',N'-tetrakis(methoxymethyl)-2,4-diamino-6- phenyl-s-triazine, 2,2'-hexamethylenebis(N,N,N',N'-tetrakis[methoxy-methyl ] -4,6-diamino-s-triazine), N,NiN',N'-tetrakis (butoxymethyl) -2,4-diamino-striazine, and the like. The acid halides which may be employed in the process of this invention are chlorides and bromides. They include thionyl chloride, thionyl bromide, phosgene, phosphorous pentachloride, phosphorous pentabromide, various acyl halides such as acetyl chloride, acetyl bromide, -decanoyl brdmide, succinyl chloride, and alkyl halosul'fites, as for example methylchlorosulfite (CH,O-SO-Cl) and the like. In general, acid halides may be defined as halogen compounds of the formula D-X where X is bromine or chlorine and D is 0 0 0 0 11- 11- 11- 11 R2-C , X-S , X-C , R20-sor X4P-, and R2 is alkyl or aryl. The preferred acid halides are phosgene and thionyl chloride and, of these, phosgene is preferred for reasons as will become apparent hereinafter. The amount of acid halide employed in the process depends upon the number of halogen atoms in the acid halide and the properties of the by-pr@oducts formed in
[2]3,317,529 3 the reaction. Thus, the amount depends upon the number of available halogen atoms present in the acid halide. It also depends upon the desired number of halogen atoms to be introduced into the molecule. In the case of the mono-halogen acid halides, one mole is required for each 5 chloromethyl -roup to be formed. In the case of phosgene and ph@osphorous pentahalide, there is only one available halogen, and therefore one mole of acid halide is required for each halomethyl group to be formed. The by-product from phosgene is 10 which does not react further with a -CH20R, group, but decomposes to give RIX and carbon dioxide. The byproducts of phosphorous pentahalideare POX3 and CH3X 15 and further reaction does not take place. The byproduct from the reaction with thionyl cworide, on the other hand, is 0 11 20 RiO-S-cl which then partially decomposes to form sulfur dioxide and RiCl and partially reacts further with another -CH20R, group to form -CH2---X. Because of the properties of the by-products, phosgene 25 in most cases is preferred over thionyl chloride. Methyl chloroformate, the by-product of phosgene, is stable and can therefore be recovered. Since methyl chloroformate is stable, and therefore exactly one chlorine atom of phosgene is available for the reaction with compounds of the 30 Formulas III @and IV above, the amount of phosgene to be employed is readily calculated. In distinction, the by@product resulting from the use of thionyl chloride is methyl chlorosulfite, which is unstable. Although a portion of the methyl chlorosulfite 35 Will Teact with the compounds of Formulas I and II, the remainder decomposes. The amount that reacts and the amount that decomposes -depends upon the reaction con,ditions and are difficult to predict. Thus, there is a problem in determining how much thionyl compound should be 40 employed. A further disadvantage is that it is difficult to remove the last of the by@product sulfur dioxide from the reaction product. The,by-products from the reaetion with acyl halide and alkyl halosulfites are esters of carboxylic acids and Sul45 furous acid, respectively. The reactionof the compounds of Formulas III and IV with the acid halide or halogen compound D-X may be ,carried out with -or without a solvent, though a solvent is preferred in that the reaction is more readily controlled. 50 Suitable solvents include benzene, toluene, xylene, chlorobenzene, chloroform and the like. In carryingout the reaction, the acid halide or halogen compound may be added to the Tnolten s-triazine of Formulas III and IV or to a solution of the,s-triazine at a t;5 temperature of from between 0 and 100, C. and normally the reaction mixture is heated at the final stages of reaction to a temperature of from between 40' and 120' C ' until the reaction is essentially complete. The by-products and solvents, if used, may then be removed by dis- 60 tillation, preferably in vacuo. The residue is the product. While normally the reaction is carried out at atmospheric pressure, it may be carried out at subatmospheric or superatmospheric pressure -and may be carried out in ,a batch or continuous manner. 65 The N-halomethyl s-triazines of this invention are useful as fiber reartive agents and provide means of achieving a number of special effects on fibrous substrates, as for example @textile materials. In particular, when the compounds contain two -or more chloromethyl groups 70 they serve as cross4inking reactants imparting crease resistance and shrinkage control to such substrates as cellulosic and proteinaccous textile materials. - Moreover, the halornethyl @s-triazines of this invention have all been found to possess @antifungal activity against Trichophyton 75 4 meittagrophytes, Mici-ospoi,uiii gypseum, and Chaetomium globsumi species of fungi. In @order that the present invention may be more fully understood, the following examples are given primarily by way of illustration. No specific details or enumerations contained therein should be construed as limitations on the present invention except insofar as they appear in the appended claims. All parts and percentages are by weight unless otherwise specifically designated. EXAMPLE 1 N-chloramethyl-N,N',N',N",N"-pentakis(methoxymethyl)-2,4,6-triamino-s-ti-iazine N(CH20CH3)2 I c N N CH20CII3 11 I (CH30CH2)2N-C C-NI N CH2Cl To a solution of 60 parts (0.154 mole) of N,N,N',N', N",N"-hexakis(methoxymethyl)- 2,4,6-triamino-s-triazine in about 90 parts of chloroform is added a solution of 18.3 parts (0.154 mole) of thionyl chloride in about 45 parts of chloroform while extemally cooling with ice. The reaction mixture is then warmed to between 40' and 50' C. while distilling,off sulfur dioxide and methyl chloride. The remainder of the volatile materials are removed by distillation in vacuo. The residual oil (about 60 parts) comprises the product. EXAMPLE 2 NIN'-bis(chloromethyl)-NN',N",N"-tetrakis(methoxymethyl) -2,4,6-triamino-s-triazine N(CH20CH3)2 C CII30CH2 N N C1120CH3 \ 11 N-C @-NI CiCH2 N CH2CI The general procedure of Example 1 is followed, using 19.5 parts of N,N,N',N',N",N"- hexakis(methoxymethyl) 2,4,6-triamino-s-triazine, 6.0 partsof thionyl chloride and about 40 parts of benzene as solvent. After removal of the volatile materials, the product is obtained as an oil which clrystallizes on standiiig. EXAMPLE 3 1V,N',N"-fris(chloromethyl)-N,N',N"-ti-is(niethoxymethyl)-2,4,6-triamino-s-triazine CHsOCII2 CH2cl \N CH30CH2 N N CH20CH3 \ 11 I / N-C C-N cic@, \N;,-- \CH201 To 39.0 parts (0.1 mole) of N,N,N',N',N",N"hexakis(methoxymethyl) - 2,4,6 - triamino - s - triazine is added a solution of 47.1 parts (0.6 mole) of acetyl chloride in about 20 parts of benzene. After a heating period, the reaction mixture is distilled in vacuo to remove the volatile materials. (Analysis of the distillate indicates that three methoxy groups have been replaced by chlorine.) EXAMPLE 4 N-chloromethyl-N,N',N',N",N"-pentakis(inethoxymethyl)-2,4,6-ti-iamino-s-triazitle N(CH20CHB)2 N N CH20CH3 (CII30CH2)2N-C C-N \ N \ CH201
[3]5 To a solution of 19.5 parts (0.05 mole) of N,N,N', N',N",N" - hexakis(methoxymethyl) - 2,4,6 - triaminos-triazine in about 50 par-ts of benzene there is added at a temperature between O' and 5' C. 5.0 parts (0.05 mole) of phosgene,over about 30 minutes. The reaction mixture is then slowly heated to the reflux point and held at reflux for three hours. After removal of the benzene by distillation in vacuo, the desired product is recove-red. EXAMPLE 5 N,N',N"-tris(chloromethyl)-N,N',N"-ti-is(methoxymethyl)-2,4,6-ti-iamino-s-ti-iazine CH30CH2 CH2CI N CH30CH2 N N CH20CH3 \ 11 / N-C -N \ cic@@ \N CH2CI To 20 parts (0.051 mole) of molten N,N,N',N',N", N" ,-hexakis(methoxymethyl-2,4,6- triamino-s-triazine at a temperature between 80 and 90' C. there is added over 30 minutes 20 parts (0.204 mole) of phosgene. After removal of the volatile materials, including methyl chloroformate, by distilaltion in 'vacuo, the product is -obtained as a residue analyzing for three atoms of chlorine per mole of s-triazine. EXAMPLE 6 N-broinomethyl-N,N',N'N",N"-pentakis(ethoxymetlzyl)-2,4,6-triamino-s-triazine N(CH2OC2lI5)2 N N CH2Oc2]l5 11 I / (C2II50CY2)2N-C C-N \ N CH2Br To a solution of 4.75 parts (0.01 mole) of N,N,N', N",N"-hexakis (ethoxymethyl)- 2,4,6-triamono-s-triazine in about 3 parts of toluene at ab,out 80' C. is added a solution of 1.23 parts (0.01 mole) of acetyl bromide in about 2 par-ts of toluene. Ethyl acetate is evolved. The remaining volatile materials are removed by distillation in vacuo leaving a crystalline residue. This is the desired product. Calculated for Cl9H37BrNr,05: N, 16.5. Found: N, 16.4. EY.AMPLE 7 N,N',N"-tris(chloromethyl)-N,N',N"-trimethyl-2,4,6- triamino-s-triazine C'R3 CH201 NI CH3 N Zt@z N CH3 \ 11 I / X-C C-N i@@ CiCII2 N cH2cl To a warm solution of 3.0 parts (0.01 mole) Of N,N',N" - trimethyl - N,N1,N" - ,tris(methoxymethyl) 2,4,,6-triamino-s-triazine in about 10 parts of benzene is added a solution of 3.57 parts (0.03 mole) of thionyl chloride in about 10 parts of benzene. The reaction mixture is heated for a short time while sulfur dioxide and methyl chloride are evolved, and the volatile materials are then removed bydistillation in vacuo. A crystahine product is obtained. Calculated for C9H5Cl3N6: C, 34.5; N, 26.8. Found: C, 34.5; N, 26.9. 3,317,529 6 EXAMPLE 8 N,N'-bis(chloromethyl)-NN',N",N"-tetramethyl-2,4,6t riamino-s-triazine 5 N (C H3)2 C CH3 N N CH3 \ 11 I/ NC C N 10 clo @2 N @:- , \ CH2CI To a warm solution of 2.7 parts (0.01 mole) of N,N, N',N"-tetrainethyl-N',N"- bis(methoxymethyl)-2,4,6triamino-s-triazine in about 5 parts of benzene there is added a solution of 3.@ parts (0.0277 mole) of thionyl 15 chloride in about 5 parts of benzene. After the reaction mixture has refluxed for about 30 minutes, the volatile materials are removed bydistillation in vacuo. The residue solidifies on standing and is the desired product. Calculated for CgHIGC12N6: N, 29.69. Found: 20 N, 29.32. EYAMPLE 9 N,N'-his(chlaromethyl)-NN1,N",N"-tetramethyl-2,4,6t riamino-s-triazine 25 N(CH3)2 CH3 N N CH3 \ 11 I / NC C-N 30 CIC @2 \N5 @' \CH 2CI To a solution of 2.06 parts (0.0044 mole) of N,N,N' ,N'@-tetramethyl-N',N"-bis (octyloxymethyl) -2,4,6triamin-o-s-triazine in about 10 parts of benzene there is 35 added 1.19 parts (0.01 mole) of thionyl chloride. After refluxing for a short time to expel sulfur dioxide, the reaction mixture is distwed in vacuo to remove benzene and octyl chloride, The crystalline residue is the desired product according to the infrared spectrum when com40 pared with the product of Example 8. EX AMPLE 10 IV N,N1,Nl-tetrakis(chlaromethyl) -2,4-diami no-s-triazine H 45 C N (ClC H2)2N-C C-N(CH2CI)2 50 To a solution of 50 parts (0.42 mole) of thionyl chloride in about 25 parts of benzene is added a solution of . 28.7 parts (0.1 mole) of NN,N',N'-tetrakis(methoxymet hyl)-2,4-diamino-s-triazine in about 15 parts of benzen e. The reaction mixture is heated while sulfur dioxide 55 and methyl chloride are evolved. The remaining volatile materials are removed by vacuum distillation. The residue is the desired product. EXAMPLE 11 NN@-bis(chloiomethyl)-NN'-bis(methoxymethyl)-2,4- diamino-6-ethyl-s-triazine C2H 4 1 C 65 CH 30CH2 N N CE1 20CHS NC C-N CIC @2 \N \cn2 cl To a solution of 6.30 parts (0.02 mole) of - N,N,N',N'- 70 tetrakis(methoxymethyl)-2,4,-diamino-6-ethyl-s-triazine in about 10 parts of benzene there is added a solution of 12.0 parts (0. I mole) of thionyl chloride in IO parts of benzene while heating the reaction mixture. After removal of the volatile materials by distillation in vacuo, the residue 75 solidifies. This is the desired product.
[4]3,317,529 7 EXAMPLE 12 1V,N'-bis(bromomethyl)-N,N'-bis(methoxymethyl)-2,4d iaiiiitzo-6-pheityl-s-ti-iaziiie 5 CH30CH2 N N CIE120 CH3 11 I / 1'4-C C-N \ 5@@, 10 BrCH2 N CH2Br To a solution of 18.17 parts (0.05 mole) of N,N,N',N'- tetrakis(methoxymethyl) - 2,4 - diamino - 6 - pbenyl - striazine in about 20 parts of toluene at 80' C. there is 15 added a solution of 7.37 parts (0.06 mole) of acetyl bromide in about 5 parts of toluene. The byproduct, methyl acetate, and toluene are removed by distillation, The residue on trituration witb ether yields the product as 20 a solid. EXAMPLE 13 N,N,N',N'-teti-akis(bi-omoi,nethyl)-2,4-dianiino-6- phenyl-s-ty-lazitie 25 c6H5 u N N 11 I 3o (BrCH2)2N-C C-N(CH2Br)2 To a solution of 9.08 parts (0.025 mole) of N,N,N',N'- tetrakis(methoxymetbyl) - 2,4 - diamino - 6 - phenyl - s- 35 triazine in about 175 parts of benzene there is added a solution of 16.0 parts (0.12 mole) of acetyl bromide in about 25 parts of benzene. The reaction mixture is heated at the reflux temperature for about one hour. After removal of a portion of the solvent by distillation, 40 the residue is cooled, and the product is separated by filtration. Calculated for C13Hl3Br4N,5: C, 28.1; H, 2.33; Br, 57.1; N, 12.5. Found: C, 28.1; H, 2.70; Br, 57.3; N, 13.0. 45 EXAMPLE 14 2,2'-octamethyleizebis[N,N'-bis(chloromethyl)-N,N'- bis(methoxymethyl)-4,6-diamino-s-triazitie] 50 CH30CH2 CH2CI CH30CH2 CH2CI N CHaOCI-I2 N N N N CH20CH3 55 \ ii 11 / N-C C-(CH2)8--- C C-N \ @@ \ 5@, CICH2 N N CH2CI To a solution of 3.2 parts (0.005 mole) of 2,2'-octa- (o methylenebis[N,N,N',N' - tetrakis(methoxymethyl) - 4, 6-diamino-s-triazine] in about 5 parts of benzene there is added a solution of 6.0 parts (0.05 mole) of thionyi chloride in about 5 parts of benzene. The reaction mixture is beated for about 30 minutes and the volatile mate- 65 rials are removed by distillation in vacuo. The residual oil solidifies on standing to give the desired product. Calculated for C26H44Cl4NIO04: C, 44.4; H, 6.3; N, 19.9, Found: C, 44.4; H, 6.4; Np 1.9.9, 8 We
