Through a series of experimental studies hitherto done, it has been found that in the reactions of the various organic compounds with sodium hydrosulfide in liquid ammonia, nucleophilic substitution, oxidation-reduction and addition reactions take place.
In this paper, the reactions of aromatic carbonyl compounds with sodium hydrosulfide in the presence of ammonium chloride is discussed.
The reaction of benzaldehyde (1) with sodium hydrosulfide and ammonium chloride was carried out in liquid ammonia, and thiobenzamide and benzyl disulfide were obtained. Sodium hydrosulfide and ammonium chloride were let to react with the following aromatic carbonyl compounds in liquid ammonia; 4-anisaldehyde (2), 4-dimethylamino (3) and 4-hydroxybenzaldehyde (4), benzophenone (5), benzil (6) and benzoin (7).
1) In the reactions of (2) and (3), the corresponding thiobenzamide and benzyl disulfide were obtained.
2) In the reaction of (4), 4-hydroxythiobenzamide, 4, 4'-dihydroxybenzyl sulfide and 4-hydroxy benzamidine·2H₂O were formed.
3) In the reaction of (5), dibenzhydryldisulfide was the main product.
4) In the reactions of (6) and (7), condensation products and reduction products were formed.

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The economical synthesis of alkyl terpenyl maleate (ATM) was investigated, for they are expected to be valuable as intermediates for anionic, cationic, amphoteric or nonionic surfactants of succinate type.
The alkyl maleic monoesters were prepared at first by the reaction of maleic anhydride (1mol) with various fatty alcohols (1mol) at 105°C for four hours.
Then, to these monoesters, camphene (1.2mol) was added in the presence of cation exchange resin as catalyst, the amount of which was 5% by weight of camphene. The temperature was kept at 65°C for ten hours further more.
ATM was obtained in 75% over all yield.
Terpenyl groups of ATM were confirmed mainly to exist as isobornyl and as minor constituents, as camphenilyl, l-β-fenchyl, n-bornyl or epi-isobornyl.
It has been found that cation exchange resin can stand repeated use over again, and terpenyl groups of ATM were found to be much more stable than alkyl groups in alkaline condition.

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The effects of solvents on the hydrogenation of benzene and pyridine have been studied with nickel catalysts supported by active carbon, alumina, and silica. In the case of benzene, the effects of solvents were almost independent of the nature of the carriers. The reaction proceeded most rapidly when benezene was hydrogenated in hydrocarbons or without solvents. The reaction was retarded by the solvents having oxygen atoms. In the case of pyridine, the effects of solvents were much different from those observed in the case of benzene. Many of the solvents having oxygen atoms accelerated the reaction. The extent of acceleration varied a little with the nature of supports. Methanol and water were exceptions; in the case of nickel-active carbon catalyst, the accelerating effects were hardly noticed, but in the cases of nickel-alumina and nickel-silica, the solvents strongly retarded the reaction.

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The authors have previously reported that prenyl halides dimerized by the action of the Lewis acids to give compounds having the lavandulyl skeletons. In the present paper 1-chloro-2-methyl-4-acetoxybutene-2 (1) was dimerized by the action of boron trifluoride-etherate to give the lavandulyl derivative (2), but by zinc chloride to give the other products.

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[in Japanese]

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