The Acidity of Nitroguanylhydrazones

Henry, Ronald A.; Vries, J extern de; Boschan, Robert H.

doi:10.1021/ja01626a068

Cited by 7 publications

(3 citation statements)

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“…Reaction of N G with other secondary amines resulted in denitrosation (6). In the reaction of N G with azide ion the methylnitrosamino group is eliminated and 5-nitroaminotetrazole is formed by cyclization of the intermediate nitrogiianylazide (7). The reaction between MNTS and piperidine results in transfer of the nitroso group to form N-nitrosopiperidine without the formation of any diazomethane (4).…”

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confidence: 99%

Reactions of cysteine with N-methyl-N-nitroso-p-toluenesulfonamide and N-methyl-N′-nitro-N-nitrosoguanidine

Schulz¹,

McCalla²

1969

Can. J. Chem.

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The reaction between cysteine and N-methyl-N-nitroso-p-toluenesulfonamide affords almost quantitative yields of cystine and N-methyl-p-toluenesuIfonaniide. A mechanism based on the intermediacy of the S-nitroso derivative of cysteine and the intermediate formation of nitric oxide is proposed. Nitrous oxide is shown to be a final product. In the reaction of cysteine with N-methyl-N'-nitro-N-nitrosoguanidine a substantial yield of 2-nitramino-4-carboxyl-thiazoline is obtained. Cystine, N-methyl-N'-nitroguanidine and S-methylcysteine are formed in lesser amounts. The major product arises from nucleophilic attack on the iniino carbon of N-methyl-N'-nitro-N-nitrosoguanidine. Concomitant elimination of the methylnitrosamino group accounts for the methylating ability of the system. Canadian Journal of Chemistry, 47, 2021 (1969) Previous work in this laboratory has shown that deoxyribonucleic acid (DNA) becomes methylated when it is allowed to react in vitro with either N-methyl-N'-nitro-N-nitrosoguanidine (NG) or with N-methyl-N-nitroso-p-toluenesulfonamide (MNTS) (1). Addition of cysteine to the reaction mixture was found to increase methylation by N G but to decrease dramatically methylation by MNTS, results which are of considerable interest in view of biological studies showing that cysteine has a protective action against certain types of alkylating agents (2).Both N G and MNTS are well-established sources of diazomethane in their reactions with aqueous base (3,4). For the reactions of N G and MNTS with nucleophilic reagents other than oxygen nucleophiles, a variety of products are reported. McKay and Wright (5) demonstrated that primary alkyl or aryl amines react with N G with the elimination of the methylnitrosamino group and the formation of N-substituted nitroguanidines. The only secondary amine to react with N G to give a Ndisubstituted-Nf-nitroguanidine is dimethylamine. Reaction of N G with other secondary amines resulted in denitrosation (6). In the reaction of N G with azide ion the methylnitrosamino group is eliminated and 5-nitroaminotetrazole is formed by cyclization of the intermediate nitrogiianylazide (7). The reaction between MNTS and piperidine results in transfer of the nitroso group to form N-nitrosopiperidine without the formation of any diazomethane (4). Low yields of diphenylnitrosamine are reported to result from reaction of MNTS with diphenylamine (8).Thus, while the existing literature pointed to the fact that the N-methyl-N-nitroso compounds under consideration exhibit two centers susceptible to nucleophilic attack, resulting in loss of the methylnitrosamino group and the nitroso function respectively, no information was available on their reactions with mercaptans. We report here data that provide a reasonable explanation for the difference in the behavior of N G and MNTS in the presence of cysteine. Results and Discussion Reactions of Cysteitze rvith M N T SThe reactions of cysteine with MNTS were carried out at room temperature in aqueous 25 % ethanol at pH 7 in an atmosphere of nit...

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confidence: 99%

Reactions of cysteine with N-methyl-N-nitroso-p-toluenesulfonamide and N-methyl-N′-nitro-N-nitrosoguanidine

Schulz¹,

McCalla²

1969

Can. J. Chem.

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“…Upon treatment of II with the corresponding alkyl or aryl halide at room temperature, a solid powder was obtained after recrystallization. On the basis of the spectral and analytical data, it was found that in the product, the alkyl or aryl groups were connected to the secondary amine (−NH−) rather than the less sterically hindered primary amine (−NH 2 ) . A simple calculation was used to determine the heat of anion formation.…”

Section: Resultsmentioning

confidence: 99%

N′-Nitro-2-hydrocarbylidenehydrazinecarboximidamides: Design, Synthesis, Crystal Structure, Insecticidal Activity, and Structure–Activity Relationships

Zhou

et al. 2012

J. Agric. Food Chem.

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A novel series of acyclic imine-substituted nitenpyram analogues were designed and synthesized from nitroaminoguanidine, and their structures were confirmed using X-ray diffraction crystallography. Preliminary bioassays showed that the target molecules exhibited good activities against aphids in laboratory (Myzus persicae Sulzer) and field trials (M. persicae Sulzer and Brevicoryne brassicae Linnaeus). Comparative molecular field analysis and comparative molecular similarity indices analysis were employed to develop a three-dimensional quantitative structure-activity relationship model that describes the insecticidal activity of 21 neonicotinoid derivatives. Simple synthesis, low cost, and good insecticidal activity have made this series of compounds become very promising candidates for future commercial pesticides.

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“…Bacarella, Grunwald, Marshall, and Purlee (5) determined the pK" values of formic, acetic, propionic, and benzoic acids and for V-methyl-and V,V-dimethylnnilinium ions in methanol-water containing from 0 to 95% methanol. Henry, De Vries, and Bosch an (87) spectrophotometrically determined the acid dissociation constant, pKa, of the follow- Martin (160) observed that peracids are stronger than the parent acid by about 3.5 pK" units; hydroperoxides behave as very weak acids with pK" values of 11.6 to 12.8. The acid strength of a peroxide is greater when the peroxide is linked to a primary rather than to a secondary carbon.…”

Section: Strengths Of Acids and Basesmentioning

confidence: 99%