Hydrogenation of 2-methyl-4-amino-5-cyanopyrimidine with nickel catalyst results in the formation of a primary amine, 2-methyl-4-amino-5-aminomethylpyrimidine, with a by-product, not of a secondary amine, but of c, c′-di-(2-methyl-4-aminopyrimidyl)-methylalmethylimide-(5), (I), a compound not reduced as yet, which possesses a strong resistance against reduction, especially in alcoholic solvent than in water and it can be reduced to a secondary amine by itself. (I) can be synthesized from 2-methyl-4-aminopyrimidyl-aldehyde-(5), (II), and 2-methyl-4-amino-5-aminomethylpyrimidine, or vice versa. (II) can be reduced to 2-methyl-4-amino-5-hydroxymethylpyrimidine catalytically with Ni or Pd-coal, or by Al-amalgam method.
Several kinds of 1, 1-dimethyl-4-acyl-cyclohexane dione-3, 5 were synthesized as tricarbonylmethane type compounds, in which the acyl radicals were the cinnamoyl, furfurylidene-acetyl, 4, 5-methylene-dioxy-cinnamoyl, 4-hydroxy-5-methoxycinnamoyl, 4, 5-dimethoxy-6-carboxycinnamoyl and cinnamoyl-ideneacetyl radicals and those of dehydracetic acid, 3-acetyl-4-hydroxycoumarine and 3-benzoyl-4-hydroxycoumarine. Antibacterial actions of these compounds against Staphylococcus aureus Terashima and avian type Mycobacterium tuberculosis in vitro were tested and it was found that the antibacterial action increased when one of the 3 carbonyl radicals in the compound was conjugated to a double bond and when this conjugated system increased. However, of the compounds synthesized, the antibacterial action was found to be lower in 1, 1-dimethyl-4-acyl-cyclohexane dione-3, 5 in which the acyl radical contained a furan nucleus instead of benzene and in those with benzenue nucleus possessing several substituents compared with that without the substituents.
p-Acetylaminomethyl-benzenesulfonamide was prepared from acetylbenzylamine by sulfonation with chlorosulfonic acid and amination. From the mother liquor of the above compound, m-acetylaminomethyl-benzenesulfonamide was obtained in 5:1 ratio. On the other hand, m-aminomethyl-benzenesulfonamide hydrochloride was obtained by the reduction of m-cyanobenzenesulfonamide and was found to coincide with the compound obtained by the saponification of the above-mentioned m-acetyl compound with HCI. o-Aminomethyl-benzenesulfonamide was obtained by the oxidation of o-toluenesulfonamide to the aldehyde and by subsequent reduction of its oxime.
Reaction of ethoxymethylene-acetoacetic ester and acetopyruvic ester with guanidine carbonate gives 2-amino-4-methyl-5-carbethoxy-pyrimidine, m.p. 220°, and 2-amino-4-methyl-6-carbethoxypyrimidine, m.p. 151°, respectively. Reaction of these β-diketones with acetosulfanilyl-guanidine gives 2-sulfanilamido-4-methylpyrimidine derivatives as shown in Table I. Their carboxy derivatives give acetosulfamerazine by heating. Reaction of diacetoacetic ester with guanidine carbonate gives 2-amino-4-methylpyrimidone, acetic acid and alcohol. o-Acetylacetoacetic ester and acetoacetic ester both give the same product. Reaction of diacetoacetic ester and acetosulfanilyl-guanidine gives 2-acetosulfanilamido-4-methyl-5-acetopyrimidone, decompn. 266°, EtOH and H2O. By the same reaction, O-acetylacetoacetic ester gives a compound of unknown structure, decompn. 258°. Addition of K2CO3 as a conversion catalyst to C-acetyl-acetoacetic ester also gives a substance with decompn. 266°.
1) Diphenyl sulfide compounds difficult to be oxidized can easily be oxidized to diphenyl sulfone compounds by CrO3 in HNO3 solution. 2) Several kinds of diphenyl sulfone compounds were synthesized and their effective action were examined.
By fusion of 1mol. of p-acetaminobenzene sulfochloride with 2mol. each of 2-aminopyridine-5-carboxylic ester, 2-aminothiazole-4-carboxylic ester, 2-aminothiazole-5-carboxylic ester and 2-aminopyrimidine, the corresponding p-acetaminobenzenesulfonamide compounds are obtaind. Hydrolyses of these comounds give corresponding sulfanilamides.
The authors succeeded in isolating venomous substance from scorpion (Buthus Martensii Karsch) by obtaining its pure picrate and then by changing it into a hydrochloride. The substance which was isolated affects respiration and its physiological symptoms coincide with those appearing in literature. However, the substance is much more poisonous than the other venoms extracted from scorpion. The substance extracted by the authors resembles crotoxin and neurotoxin, snake venoms reported by Slotta and Michael, respectively, from chemical and pharmacological standpoint, with the exception that it contains more sulfur and its physiological actions are temporary. The substance herewith reported is being designated as “buthotoxin” which is assumed to crotoxin and neurotoxin, differing in that the content of sulfur is larger and in its combination.
Calculated amount of Cl2 was passed into the CHCl3 solution of 2, 4-dihydroxy-5-alkyl-benzaldehydes and 2, 4-dihydroxy-3-chloro-5-alkyl-benzaldehydes were synthesized. All the monochloro compounds obtained were virtually tasteless and possessed practically no irritating actions.
Antiseptic tests against soy sauce were carried out with ethyl-, n-propyl-, n-butyl-, n-amyl-, iso-amyl-, n-hexyl- and n-heptyl-resorcinols. As a result it was found that the antiseptic power against soy sauce and anthelmintic property against Ascaris lumbricoides Linnaeus always went in parallel.
Syntheses of following compounds are described. These compounds were tested for their antihistaminic activities and it was found that their activities were very weak compared to benadryl, especially in those compounds in which no aromatic substituents are present in N. Compounds obtained were: N-(β-diethylaminoethyl)-α-pyrrolidone; N-(β-dimethylaminoethyl)-α-pyrrolidone; N-(β-dimethylaminoethyl)-α-pyridone, -α-piperidone, -piperidine; N-(β-dimethylaminoethyl)-phthalimidine; N-(β-dimethylaminoethyl)-α-quinolone, -3, 4-dihydroquinolone-(2), -tetrahydroquinoline; 6, 7-methylenedioxy-3-methyl-2-(β-dimethylaminoethyl)-3, 4-dihydroisoquinolone-(1); 6, 7-methylenedioxy-3-methyl-2-(β-dimethylaminoethyl)-1, 2, 3, 4-tetrahydroisoquinoline.
Hoffmann's exhaustive methylation was carried out on N-(β-dimethylaminoethyl)-α-pyridone (I), -α-quinnolone (II), -phthalimidine (III), -α-piperidone (IV), -α-pyrrolidone (V), phenylacetic acid-(β-dimethylaminoethylmethylamide) (VI), -(β-dimethylaminoethylamide) (VII) and benzoie acid-(β-dimethylaminoethylamide) (VIII). It was found that compounds in which the H-atom attached to C-atom in β-position is easily liberated as a proton undergo olefin decomposition to give N-vinyl compounds, as in (I) and (II) where N-vinyl-α-pyridone and -α-quinolone, respectively, are formed. Other compounds such as (IV), (V) and (VI) undergo alcoholic decomposition. (III) is an intermediate of these two, while (VII) and (VIII) give some products which are assumed to be due to N-vinyl compound formed by olefin decomposition. The ease or difficulty in liberation of H at β-C as a proton depends on the effect of the lactam ring or acid amide radical, becoming easier as these tend to negative effect. The author has made some explanations of these decomposition reactions from electronic theory.
Nine kinds of N1-derivatives of p-aminomethylbenzenesulfonamide were synthesized by the condensation of p-phthaliminomethylbenzene sulfochloride and phenylamine with subsequent liberation of phthalyl radical. Antibacterial action of these compounds are far inferior than that of p-aminomethylbenzenesulfonamide.