Substitution reactions of 13 kinds of compounds having a substituent on m-or p-position of benzene ring of 2, 4-bis (anilino)-6-chloro-S-triazine with benzylamine in tetrahydrofuran solvent have been investigated. The measurements of the Reactionrates indicated that these reactions agreed well with be'simple second-oder kinetics and were represented to SN 2 process.As to the reactivity of these derivatives, it was found that the relation between the reaction velocity and the substituent in benzene ring followed the Hammett's rule well when the triazinylamino group was considered as a side chain of both benzene rings. It was also clarified that the effectof substituent was mainly due to its polar effect.
The rate of the reactions between benzylamine and 2, 4-dichloro-(1) or 2-chloro-4-substituted-6-anilino-S-triaziazine derivatiltes (B) in tetrahydrofuran were estimated.In each case, the reaction was found to be a reactionof SN 2 process.A comparison of the rate constants was made on each of these derivatives and the deactivating effects of the substituents on the reactivity of chlorine atom were investigated, deactivating effects of substituentu were in the order -NH-nC4H9≈NHCH3≈-NHC2H5>-N(CH3)2>-NH2;morpholinyl>-NHC6H5>-0C2H5≈-OCH3. The results showed good agreements with heretofore known data but the effects of amino, mono-substituted amino and disubstituted amino groups howedno agreement with Thurstone' s data. Disc ussions were made on the relationship between the effects of substituents and the Hammett's rule.
Reactions betweens aromatic primary amines and 2-amino-4, 6-dichloro-S-triazinetype compounds (A) in tetrahydrofuran have been investigated. The reaetionr between (A) and p-toluidine showed good agreement with a simple second order eaction without accompanying auto-catalytic action.The reaction with aniline or p-chloroaniline was clearly an auto-catalytic reaction and the reaction rate increased with the progress of The reaction.In case of the auto-catalytic reactions, compounds with R=-NH2 or -NHCH3 showed far greater reactivities than the compound with R=-N(CH3)2. There was no induction period in the autocatalytic reaction. Also, auto-catalytic actions were observed on those of R=-N(CH3)2 and-NC6H5 CH3 without hydrogen on amino nitrogen atom. These self-catalytic actions were considered to be due to the activation of the central carbon atom by the addition of proton on the nitrogen atom of the heterocyclic ring.
Reaction of N-(1-chloroethyl) phthalimidej and thioglycolic acid at room temperature caused dehydrochlorination and gave N-(1-carboxymethylmercaptoethy1) phthalimide with good yield. This substance can be esterified easily with alcohols in the presence of sulfuric acid as a catalyst. An addition reaction of thioglycolic acid to N-vinylphthalimide in the presence of sulfuric acid catalyst was followed by Markownikoff's rule and formed an α-addition product, N-(1-carboxymethylmercaptoethyl) phthalimide. Similarly, methyl and ethyl thioglycolate gave additive products.
Ctalytic reduction of dithiodiglycolic acid was carried out with molybdenum sulfide catalyst at high pressure.The reaction was started at around 100°C with an initial pressure of hydrogen at 50 atm and gave thioglycolic acid as a main product.The maximum yield was 64.3% at 130°C but it was mixed with unreacted sample.Reduction to acetic acid was accompanied with an increase of temperature and nearly all was converted into acetic acid at 180°C.Comparison of the resul with that of general disulfides indicated that the cleavage of S-S bond of dithiodiglycolic acid was proceeded at low temperature and the mercapto group of thioglycolic acid formed also showed a tendency of cleavage to acetic acid the yield of thioglycolic acid was low for this reason. Comparison of result oi similar reduction of β-dithiodipropionic acid indicated that a characteristic reductive reaction of dithiodiglycolic acid was assumed to the effect of carboxy, group in α-position against the sulfur atom.