The catalytic addition reaction of maleic or fumaric acid diester to castor fatty acid methyl ester by flow method was investigated. It was found that the addition of dimethyl and diethyl esters of maleic or fumaric acid to the castor fatty ester are easily carried out by continuously passing over a synthetic silica-alumina catalyst. The fumarate adduct was confirmed to be formed by the Diels-Alder addition of the fumarate to the conjugated octadecadienoate produced by the dehydration of methyl ricinoleate, main component of the castor fatty ester. On the other hand, the addition products of the maleate to the castor fatty ester were known to be mainly consisted of two compounds (adduct I and II) at produced ratio of ca. 1 : 4. The adduct I was confirmed to be formed by the Diels-Alder addition of the maleate to the conjugated octadecadienoate, and adduct II was noticed to have a structure produced with the Diels-Alder addition of maleic anhdride to the octadecadienoate. We discussed about the reasons for the formation of adduct II from addduct I observed only at the addition reaction of the maleate and for no compound such as adduct II produced at the addition reaction of the fumarate.
Hydrogen-deuterium exchange of 4-methylpyridine (1b) has been studied by using fatty acid RCO2H (R=C1C10) as a catalyst in D2O at 120°C. The reaction mixture is homogeneous in the case of R=C1C3, and heterogeneous with R=C4C10. The conversion (or contents) -time curves show typical stepwise reactions (d0→d1→d2→d3). The rate increases with the increase in the concentration of the acids. The conversion decreases and increases, respectively, in the cases of R=C5C10 and R=C1C3 with increasing the concentration of the substrates. The mode of the valeric acid catalyzed reaction (R=C4) is an intermediate between the two groups above. The reactivity is in the order of 2-methylpyridine (1a) < (1b) in the case of R=C1C6, but, (1a) > (1b) with R=C7C10. From the above observations, a possible mechanism involving protonation and rate-determining attack of free base or carboxylate ion is proposed and discussed by assuming an ion pair model.
On the influence of alkyl and carboxymethyl groups on the building performance of chelating-type polycarboxylic acids were studied. The following ether polycarboxylates were prepared by the reaction of the corresponding alcohols with ethyl diazoacetate or some other reagents, and their building performances were compared with those of sodium tripolyphosphate (STPP) and disodium oxydiacetate (ODA-Na) in a detergent system formulating alkylbenzenesulfonate (LAS) : Sodium t-butoxyacetic acid (TBA-Na), disodium 4, 5-dimethyl-3, 6-dioxaoctanedioate (BGDA-Na), disodium 4, 4-dimethyl-3, 6-dioxaoctanedioate (IBGDA-Na), disodium 4, 4, 5, 5-tetramethyl-3, 6-dioxaoctanedioate (PDA-Na), disodium 4, 5-diethyl-3, 6-dioxaoctanedioate (HGDA-Na), disodium 4, 8-dimethyl-3, 6, 9-trioxaundecanedioate (DPGDA-Na), disodium 4, 7-dimethyl-3, 6, 9-trioxaundecanedioate (IDPGDA-Na), disodium 3, 6, 9-trioxaundecanedioate (DEGDA-Na), disodium 5, 5-dimethyl-3, 7-dioxanonanedioate (NPGDA-Na), trisodium 4-methyl-5-carboxylatomethoxy-3, 7-dioxanonanedioate (MGTA-Na), tetrasodium 5, 6-bis (carboxy-latomethoxy) -3, 8-dioxadecanedioate (ETTeA-Na), tetrasodium 5, 5-bis (carboxylatomethoxymethyl) -3, 7-dioxanonanedioate (PETTeA-Na), and hexasodium 5, 6, 7, 8-tetrakis (carboxylatomethoxy) -3, 10-dioxadodecanedioate (SHA-Na). The detergency were tested on naturally soiled cotton patches and the detergency powers were evaluated by the Scheffe's method. From the results summarized in Fig.-1, it is evident that the ether polycarboxylates containing methyl groups show the building performance much superior to that of the corresponding ether carboxylates without methyl groups. The building performance of disodium 4, 4, 5, 5-tetramethyl-3, 6-dioxaoc-tanedioate (PDA-Na) was similar to that of STPP. On the building performance of the ether polycarboxylic acids methyl groups were most effective when the methyl groups were introduced to the carbon bonding carboxymethoxyl groups. The introduction of carboxymethoxyl groups to such places was also effective, but its effect was less than that of methyl group.
The influence of the physico-chemical properties of the aqueous solution of a series of chelating-type polycarboxylates containing methyl groups or ethyl groups on detergencies have been studied, and compared with those of corresponding compounds without methyl or ethyl groups as well as STPP. The correlation between building performance and molecular structure has been discussed. The detergency were tested on naturally soiled cotton patches and the detergency powers were evaluated by Scheffe's method in a detergent system formulating alkylbensenesulfonate (LAS). Measurements were made on the surface tension, the critical micelle concentration, and the emulsifying capacity of the builder solution with DBS. The buffering and dispersing capacities for carbon black and manganese dioxide in the aqueous builder solution, and the chelate stability constants of the builders with alkaline earth metals were determined. From the results summarized in Fig, -2Fig.-4 and Table-2Table-3, it is evident that the introduction of methyl groups to ether polycarboxylates made their detergency powers and the dispersing capacities for manganese dioxide much superior to those of corresponding compounds without methyl group, but methyl groups did not affect the chelate stability considerably. And the washing performances of the builders were not correlated well with logKca values when they had the high stability values. The effects of the methyl groups to the detergency, dispersing capacity for manganese dioxide, and chelating power were largest, when the methyl groups were bound to the carbon binding the carboxymethoxyl groups. It seems that the ether polycarboxylate builders with logKca (logKca>3), show better washing performance when the appropriate substituents such as methyl groups are introduced to appropriate places in the compounds.
A study was made on preparation of amphoteric surfactants by the reaction of 1- (2-hydroxyethyl) -2-undecyl-2-imidazoline (1) with ethyl acrylate. Imidazolines are easily hydrolyzed with water, especially in the presence of a base, to afford amidoamines. After (1) was hydrolyzed, the reaction mixture was allowed to react with ethyl acrylate and then saponified. Only sodium salts of N- [N'- (2-carboxyethyl) -N'- (2-hydroxyethyl) aminoethyl] laurylamide (4) was obtained. However, when the reaction of (1) with ethylacrylate was carried out in the presence of water, followed by saponification, ring cleavage of (1) occurred at 2, 3 position, different from hydrolysis of (1) where the cleavage occurred at 1, 2 position, to give sodium salts of N- [N'- (2-carboxyethyl) ami-noethyl] -N- (2-hydroxyethyl) laurylamide (5) and N- [N', N'-bis (2-carboxyethyl) aminoethyl] -N- (2-hydroxyethyl) laurylamide (6) as main products. In case of the reaction of (1) with ethyl acrylate under unhydrous condition, 1- (ethylcarboxyethoxyethyl) -2-undecyl-2-imidazoline (7) was obtained as a major product, however, the reaction was rather slow, and gave sodium salt of N- [N'- (carboxyethoxyethyl) aminoethyl] laurylamide (8) and N- [N'- (2-hydroxyethyl) aminoethyl] -laurylamide (2) by saponification. By the reaction of (7) with ethyl acrylate in the presence of water, followed by saponification, sodium salt of N- [N'- (carboxyethoxyethyl) -N'- (2-carboxyethyl) aminoethyl] laurylamide (9) was obtained.
The addition reactions of 2-nonyl-2-imidazoline with ethylene oxide in benzene were carried out at 60140°C in an autoclave. The reaction proceeded easily at low temperature and stepwise giving 1 : 1, 1 : 2 and higher adducts. As the amount of ethylene oxide increased, the rate of the reaction increased even at low temperature. The aqueous solution of products showed surface active, good foaming and emulsifying properties for xylene,
Thermal and aluminium chloride catalytic addition for the reaction of d-Limonene with methyl acrylate gave a mixture of methyl 5- (4-methyl-3-cyclohexen-1-yl) -5-hexenoate (2) and methyl 5- (4-methyl-3-cyclohexen-1-yliden) hexanoate (3) in the yield of 23%. From the reaction of methylmagnesium iodide and the compound (2), 2-methyl-6- (4-methyl-3-cyclohexen 1-yl) -6-hepten 2-ol (4) was obtained. By the dehydration of the compound (4) with potassium bisulfate, a mixture of β-bisabolene and its isomers was obtained.