Improved methods for the preparation of carbamoyl-O-methylisourea (CMI) and N-carbamoyl compounds of cyanamide derivertives using CMI were investigated.
The reaction of cyanourea copper salt with methanol gave CMI copper complex, which was converted by treatment with H₂S to CMI in good yield.
1-Thioallophanic acid O-methyl ester was obtained by the reaction of CMI with H₂S in aqueous solution at room temperature.
CMI was hydrolyzed or decomposed in acidic or alkaline medium to biuret, methylallophanate and cyanourea.
CMI salt reacted with methylamine to give methylguanylurea salt in good yield, but no reaction occurred with aniline.
Carbamoylmelamine was obtained by the reaction of CMI with biguanide at room temperature, and cyanoguanylurea was obtained with cyanamide in good yield in the same manner.

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Phthaloylation of melamine (M) with phthalic anhydride (PA) and/or o-carbomethoxybenzoic anhydride (CBA) was studied.
N-Phthaloylmelamine (1) was prepared from M and PA by fusion at temperatures near 200°C or by refluxing in nitrobenzene. N, N'-Diphthaloylmelamine (2) and N, N', N''-triphthaloylmelamine (3) were obtained by the reaction of (1) and PA in nitrobenzene for a long period of time.
(1) was obtained from M and CBA in dioxane through the intermediate, N-o-carbomethoxymelamine (4). The reaction of M with CBA at 153200°C gave (2) and (3).

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Hydration was studied for myrcene (1) or isoprene (2) with halogenated acetic acid under following conditions ; the equimolar mixtures of (1) or (2) and halogenated acetic acid (monochloro-, dichloro- or trichloroacetic acid) was stirred in flask with or without dichloroethane, benzene, n-hexane or water.
(1) yielded the following six alcohols : linallol (3), myrcenol (5), 3, 7-dimethyl-1, 3-octadiene-7-ol (6), β-terpineol (7), α-terpineol (8), geraniol (9); two unidentified compounds were also found in small amounts.
Conversion is 81% under the best conditions. The content of (5) plus (9) in the hydration products is 51% under the best conditions.
(2) yielded the following three alcohols : (7), (8), (9); two unidentified compounds were also found in small amounts.
(8) is the main product (68%) from the monoterpene alcohols when the hydration is carried out in the presence of a solvent.
When dichloroacetic acid was used as a telogen in the absence of a solvent, the content of (9) in the monoterpene alcohols was 53%.

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[in Japanese]

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