Dodecanonitrile in xylene as a solvent and in the presence of sulfur was reduced with molybdenum sulfide catalyst at an initial pressure of hydrogen 100 atmospheres. The reaction was started at around 150°C and yielded 70-5% dodecylmercaptan at 200-50°C. The reaction below 200°C left much of unreacted raw material, besides showing much yield of didodecyl disulfide as a by-product, while the reaction above 250°C was accompanied with the cleavage to dodecane and the yield of mercaptan was low. The results of reaction by using varied amount of sulfur indicated that the yield of mercaptan was increased with an increase of sulfur and it reached a constant value at the molar ratio of 1.5. The formation of amine was only a small amount in all cases. The result indicated that the route of reaction is the formation of thioamide from hydrogen sulfide, produced from reduction of sulfur, and the sample, and the mercaptan is presumed to be formed from its reduction.
Conditions for obtaining p-thiocresol by the catalytic reduction of p-toluenesulfonyl chloride with molybdenum sulfide catalyst and with pressure have been investigated. Catalytic reduction by use of cyclohexane as a solvent with an initial pressure at 100 atmospheres showed the reaction at around 100°C and yielded di-p-tolyl disulfide as a main product and a small amount of p-thiocresol. However, the reaction was accompanied with hydrolysis of sample to give p-toluenesulfonic acid as a by-product and the yield of reduction product was below 50% for this reason. In order to prevent this hydrolysis, the reaction was proceeded with an addition of alumina (Al2O3), magnesium oxide (MgO) or calcium oxide (CaO) and these were found to be fairly effective. This enabled to give an increase in yield of reduction product, gave p-thiocresol as a main product at 160-200°C. The yield of p-thiocresol was 79% with the addition of CaO and the effects of these additives were in order of CaO > MgO > Al2O3.
The reaction of N-nitrso-p-nitroacetanilide with anisole at room temperature yielded 2-methoxy-4′-nitrobiphenyl, 3-methoxy-4′-nitrobiphenyl and 4-methoxy-4′-nitrobiphenyl in a molar ratio of 11.8: 1: 2.2. From the result of a competitive run in a mixture of anisole and benzene, the partial rate factors of the ortho, meta and para positions of anisole towards the p-nitrophenyl radical are calculated to be 4.9, 0.4 and 1.7 respectively, the reactivity of one position of benzene being taken as unity. Similar partial rate factors (o:m: p=3.3: 0.4: 1.6) for anisole were obtained from the result of an experiment at 94°C using p-nitrobenzoyl peroxide as a p-nitrophenyl radical source. The decomposition of anisoyl peroxide in a mixture of nitrobenzene and benzene at 92-5°C yielded 4-methoxybiphenyl, 4-methoxy-2′-nitrobiphenyl, 4-methoxy-3′-nitrobiphenyl and 4-methoxy-4′-nitrobiphenyl, from whose molar ratio the partial rate factors of the ortho, meta and para positions of nitrobenzene towards the p-methoxyphenyl radical were found to be 4.6, 0.2 and 6.2 respectively.
The determination, by means of isotope dilution analysis, of the molar ratio of p-chlorobiphenyl-36Cl, 4-chloro-2′-nitrobiphenyl-36Cl, 4-chloro-3′-nitrobiphenyl-36Cl, 4-chloro-4′-nitrobiphenyl-36Cl, 4-chloro-2′-methoxybiphenyl-36Cl, 4-chloro-3′-methoxybiphenyl-36Cl and 4-chloro-4′-methoxybiphenyl-36Cl formed through the reaction of N-nitroso-p-chloroacetanilide-36Cl in an equimolar mixture of nitrobenzene, anisole and benzene, is described. From the results, the partial rate factors of the ortho, meta and para, positions for the homolytic p-chlorophenylation were found to be 4.35, 0.61 and 6.18 for nitrobenzene and 3.93, 0.94 and 1.54 for anisole, respectively, the reactivity of the one position of benzene being taken as unity.
The determination of the molar ratio of p-chlorobiphenyl-36Cl, 4-chloro-2′-methylbiphenyl-36Cl, 4-chloro-3′-methylbiphenyl-36Cl and 4-chloro-4′-methylbiphenyl-36C1 formed through the reaction of N-nitroso-p-chloroacetanilide-36Cl in an equimolar mixture of toluene and benzene is described. From the results, the partial rate factors of the ortho, meta and para positions of toluene for the homolytic p-chlorophenylation were found to be 2.97, 1.07 and 1.32, respectively. Partial rate factors for chlorobenzene, 2.70, 0.86 and 1.33 were obtained from the results of experiments in a mixture of chlorobenzene and benzene. From the sequence of the relative reactivities of meta positions of aromatic compounds, it is suggested that the p-chlorophenyl radical has electrophilic character.
The determination, by means of isotope dilution analysis, of the molar ratio of p-methoxybiphenyl-14C, 4-methoxy-2′-nitrobiphenyl-14C, 4-methoxy-3′-nitrobiphenyl-14C, 4-methoxy-4′-nitrobiphenyl-14C, 2-chloro-4′-methoxybiphenyl-14C, 3-chloro-4′-methoxybiphenyl-14C and 4-chloro-4′-methoxybiphenyl-14C formed through the reaction of N-nitrosoacet-P-anisidide-(phenyl-14C) in an equimolar mixture of nitrobenzene, chlorobenzene and benzene, is described. From the results, the partial rate factors of the ortho, meta and para positions for the homolytic p-methoxyphenylation were found to be 6.45, 1.19 and 8.36 for nitrobenzene and 3.08, 1.82 and 1.74 for chlorobenzene, respectively, the reactivity of the one position of benzene being taken as unity.
This report describes on the synthesis of methyl α-chloroacrylate and its reaction process has been clarified. A standard method of its analysis has been formulated and various factors for increasing the yield have been investigated. The maximum yield was obtained by the reaction for 4-5hrs. and the best temperature was at 90-110°C. Using of 3-4moles of sulfuric acid against trichloroethylene was found to be suitable. The velocity of adding dropwise of formalin-methanol and methanol was regulated to 5g/min. for the former and that of the latter was made slowly and heating for a short time in the later period for smooth progress of the reaction. For separation of objective product, it was necessary to keep the temperature of content above 110°C before staring of steam distillation and the desirable temperature of distillation was around160°C. By use of the same procedure for preparation of methyl ct-chloroacrylate, syntheses of various esters of aliphatic alcohols and polyhydric alcohols have been made. The results indicated that the esterification of aliphatic alcohol was proceeded nearly in the same way as in the case of methanol but the higher in the carbon number of aliphatic alcohol, easier was the reaction. The reaction of polyhydric alcohols was found to be difficult but that of cyclohexanol was proceeded well.