2,716,134 United States Patent Office Patented Aug. 23, 1955 2 series of new tetrasubstituted diamines. Other objects will become apparent hereinafter. 2,716,134 In accordance with our invention, glycol disulfonates having the general formulas: N,N',N',N'-TETRASUBSTITUTED DIAM NES 5 Delbert D. Reynolds and Thomas T. M. Laakso, Roch ester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application April 19, 1950, wherein in represents a positive integer as previously Serial No. 156,934 defined and R1 represents an alkyl group containing from 1 to 4 carbon atoms or an aryl group, are heated with a 7 Claims. (CI. 260-570.5) secondary amine having the general formula: 5 YH This invention relates to N,N,N',N'-tetrasubstituted / diamines and to a process for their preparation. R. Various methods have been proposed heretofore for the preparation of tetraSubstituted diamines. For example, wherein each R can be the same or different groups as Freund et al., in Berichte der Deutsch. Chem., vol. 30, previously mentioned, distilling off the excess amine, if page 1385 (1897), proposed the preparation of N,N,N',N'- 20 desired, after the reaction is completed, adding an excess tetramethyl ethylene diamine by heating ethylene bromide of an aqueous alkali metal hydroxide (e. g. sodium, with dimethylamine in a closed tube at 100 C., while potassium or lithium hydroxide), separating the oil layer Knorr et al., ibid, vol. 39, page 1428 (1906), proposed which thereupon forms and recovering the tetrasubsti the preparation of N,N,N',N'-tetramethyl trimethylene tuted diamine by fractional distillation of the oil layer. diamine by heating trimethylene bromide with alcoholic 25 Advantageously the water layer can be extracted with a dimethylamine at 150° C. More recently, Gilman and water-insoluble solvent such as benzene, diethyl ether, Pickens, in J. Amer. Chem. Soc., vol. 47, pages 245-54 etc. in which case, the oil layer and the extract are com (1925), have described the preparation of N,N,N',N'- bined and dried over a dehydrating agent such as sodium tetraethyl ethylene diamine by boiling a mixture of hydroxide pellets, anhydrous potassium carbonate, etc., B-chloroethylbenzene sulfonate and diethylamine. How 30 and then fractionally distilled. For maximum yields, it is ever, the prior art processes have given relatively low essential that the reactants be thoroughly dried and reacted yields and the intermediates for preparing tetrasubstituted under strictly anhydrous conditions. Advantageously, an diamines with longer carbon chains are not readily avail inert solvent Such as dry benzene, 1,4-dioxane, toluene or able. Xylene is employed as the reaction medium where the 35 reactants are not readily compatible with one another. We have now found that tetrasubstituted diamines hav The amount of the secondary amine employed in the ing the general formulas: reaction can be varied widely from 4 to 25 mol weights R of the amine to each mol weight of the glycol disulfonate, but for the most efficient operation from 15 to 20 mol 40 weights of the amine are used for each mol weight of the glycol disulfonate. The excess of the amine can be R recovered and used in Succeeding runs or recycled in Y-C-Hi-O-O-Hi-N, continuous operation. The temperature of the reaction / N can vary from 50 to 150° C., but preferably it is con R R ducted at the temperature corresponding to the refluxing and or boiling temperature of the amine or of the inert sol C-C2 CI-CI vent medium or their mixtures. The caustic alkali em N / N-(CH2)-N Y. ployed to neutralize the reaction mixture, after the reac N / / tion has been completed, can be varied from just enough CH-CH2 CH-CH 50 caustic alkali to neutralize all of the acid groups released wherein in represents a positive integer of from 2 to 6, in the reaction and to free the tetrasubstituted amine from each R can be the same or different members selected its salts, that is, from 2 to 15 mol weights of the caustic from the group consisting of an alkyl group containing alkali to each mol weight of the glycol disulfonate, but from 1 to 18 carbon atoms (e. g. methyl, ethyl, isopropyl, preferably from 5 to 10 mol weights of the caustic alkali propyl, n-butyl, isobutyl, sec. butyl, tert, butyl, etc. 55 to each mol weight of the glycol disulfonate. Advanta groups), a cycloalkyl group containing from 5 to 6 geously, an aqueous solution of the caustic alkali is em carbon atoms (e. g. cyclopentyl or cyclohexyl groups), ployed. Where an inert solvent is employed as the reac an aryl group (e.g. phenyl, p-tolyl, o-tolyl, etc.) or an tion medium, the total concentration of reactants can aralkyl group (e.g. benzyl, phenylethyl, etc. groups) and vary within any practical limits, it being possible to operate X represents -CH2- or O, can be prepared in a con 60 at concentrations which contain as low as 10% and as venient and economic was by reacting a glycol disulfonate high as 75% of reactants. with a secondary amine and separating the tetrasubsti Suitable secondary amines which can be employed in tuted diamine which forms. The above-defined diamines the practice of our invention are dialkylamines such as are useful as intermediates in the preparation of other dimethylamine, diethylamine, diisopropylamine, di-n- organic compounds, for example, in the preparation of 65 propylamine, di-n-butylamine, dihexylamine, didodecyla quaternized polymeric sulfonates which are applicable as mine, distearylamine, etc., mixed dialkylamines such as mordants in certain photographic color processes. They methylethylamine, methyl propylamine, methylisopro are also valuable in the preparation of various insec pylamine, methyl n-butylamine, ethyl propylamine, ethyl ticides and as pharmaceutical chemicals. n-butylamine, methyl dodecylamine, etc., diarylamines It is, accordingly, an object of the invention to provide 70 such as diphenylamine, di-p-tolylamine, etc., diaralkyla a convenient and economic way for obtaining tetra mines such as dibenzylamine, di-ethylphenylamine, etc. substituted diamines. Another object is to provide a and dicycloalkylamines such as dicyclophentylamine, di 2,716,134 3 4 cyclohexylamine, etc. Suitable glycol disulfonates can be residual oil having a boiling point of 89/31.5 mm. The prepared by condensing the appropriate sulfonyl chloride yield of product was 40 g. equivalent to 79.5% of theory. with the alkylene glycol or with diethylene glycol as illustrated hereinafter. Among such suitable glycol di ANALYSIS sulfonates are 1,2-di(methanesulfonoxy) ethane, 1,2-di (ethanesulfonoxy) ethane, 1,3-di(methanesulfonoxy) Found CalcuE. propane, 1,4-di- (methanesulfonoxy)butane, 1,5 - di (methanesulfonoxy)-pentane, 2,5-di(methanesulfonoxy) Percent Percent 70.3 70,0 hexane, 1,2-di(benzenesulfonoxy) ethane, 1,3-di(benzene 4.1 3.7 sulfonoxy) propane, 1,4-di(benzenesulfonoxy) butane, 16.7 16.7 1,2-di(p-toluenesulfonoxy) ethane, 1,3-di(p-toluenesul fonoxy) propane, 1,4-di(p-toluenesulfonoxy) butane, Example 2.-N,N,N',N'-tetraisopropyl trimethylene 6,6'-dicbenzene sulfonoxy)- diethyl ether, etc. diamine The following examples will serve further to illustrate 606 g. (6 mol) of diisopropylamine and 115 g. (0.32 mannerthe tetrasubstituted of preparing diaminesthe same. of the invention and the 15 mol) of anhydrous 1,3-di(benzenesulfonoxy) propane o were placed in a 2-liter flask equipped with a calcium PREPARATION OF GLYCOL DISULFONATES chloride-vent tube, a variable take-off still head and a A number of glycol disulfonate intermediates were receiver, and the mixture refused for 20 hours. Most prepared by dissolving 1 mol of the desired anhydrous 20 of the amine (excess) was distilled off, 56 g. of potas glycol in 3’to 5 volumes of anhydrous pyridine and 2 sium hydroxide dissolved in 300 cc. of water was added mols of the appropriate sulfonyl chloride were added to and the mixture warmed until all of the solids went this well-stirred solution at such a rate as to keep the into solution. 300 cc. of benzene were then added, and temperature between 5 and 15 C. After the reaction the benzene layer which separated was dried oyer 40 g. was completed, the reaction mixture was stirred into 25 of potassium hydroxide pellets and distilled through a threetalline times product its volumewhich ofseparated finely crushedwas washed ice. Thewith crys- ice "actionatingN,N,N',N-teraisopropyl column. There trimethylene were obtained diamine, 60 equiva. g of water and then dried. It was purified by recrystalliza- ent to 85.7% of theory, having a boiling point of tion from ethanol. The following table shows a number 83/0.25 mm. of glycol disulfonates prepared by the above-described 30 ANALYSIS method. Other glycol disulfonates can be prepared in similar manner by selecting the desired sulfonyl chlo- Found le: ride. In the table, the first column shows the glycol which lated is reacted with the appropriate sulfonyl chloride to give the glycol disulfonate corresponding thereto and shown in 35 C. Perg, Pereg 5 the second column, while the other columns show the fIII.I.I.I.I.I.I.I.I. i3.3 i46 melting points, analyses and yields of the respective sul- 1.5 1.5 fonate derivatives. TABLE - Analysis Glycol Sulfonate Derivative M.P., C. i. Caled Found Ethylene glycol------ 1,2-Di-(benzenesulfonoxy) ethane------------ 48-50 { C, 49.24. 49.44.2 647 . S, 18.6 18.3 Propane-1,3-diol.----- 1,3-Di-(p-toluenesulfonoxy) propane--------- 92-93 {i,C, 53.25.2 52.95.2 69. 4. - - - - - S, 16.8 . 16.5 Butane-1,4-diol-------- 1,4-Di-p-toluenesulfonoxy)butane----------- 81-82 sC, 54.35.5 - 54.35.5 67.0 S, 16.1.