The analogy between dialkylmonoamine-carbon disulfide and the homologous N ,N'-dialkyldiamine-carbon disulfide reactions was discussed in Part I. We will show that a parallelism also is found between the dialkylmonoamine-formaldehyde-carbon disulfide and the N , N'-dialkyldiamine-formaldehyde-carbon disulfide reactions. These have been summarized in Chart I ; as in Part I, the compounds with related structures have the same number with the "A" series representing the cyclic types.Dialkylamine-aldehyde-carbon disulfide products have been patented (1, 2,3) as accelerators for the vulcanization of rubber, although the patents contain no suggestion of molecular structures of the reaction products.Three methods are available for the synthesis of amine-aldehyde-carbon disulfide accelerators. For example, we have found that the compound obtained from methylene-bis-piperidine (I, R and R' = cyclopentamethylene) and carbon disulfide is identical with the compound prepared by Levi (4) from piperidinium N ,N-cyclopentamethylenedithiocarbamate (111, R and R' = cyclopentamethylene) and formaldehyde. Furthermore, we have prepared the same compound from the dithiocarbamate (111) and piperidinomethanol. This would indicate that the order of addition of formaldehyde and carbon disulfide to the amine does not affect the nature of the final product.The third method, which involves the use of an alkylaminomethanol, also makes possible the synthesis of the same type of compound in which the N and N' alkyl groups are dissimilar. The reaction of piperidinomethanol with morpholinium W , N-oxadiethylenedithiocarbamate and with dicyclohexylammonium N , N-dicyclohexyldithiocarbamate resulted in products having dissimilar N , N'alkyl substituents. These also were found to have activity in accelerating the vulcanization of rubber. The structure of the above compounds, which result from the three methods of preparation just described, has not been clearly elucidated. Levi proposed an electrovalent, salt type of structure for his product, namely, methylenepiperidinium N , N-cyclopentamethylenedithiocarbamate (11-alternate, R and R' = cyclopentamethylene) . However, there is also the possibility that the methylene group can act as a purely covalent link between the dithiocarbamic acid and m i n e radicaIs thereby forming a dithioester, N' ,N'-dialkylaminomethyl N , Ndialkyldithiocarbamate (11). In fact similar compounds have been patented by Presented before the Division of Organic Chemistry a t the 110th meeting of the American Chemical Society, Chicago, Ill., Sept., 1946.
952CARBON DISULFIDE WITH MONO-AND DI-AMINES. 11