Substituent Effects on Nitrosation of 1,3-Diarylureas with Nitrosyl Chloride, Dinitrogen Trioxide, and Dinitrogen Tetroxide

スポンサーリンク

概要

• 論文の詳細を見る

• Twenty-eight para-substituted and eleven ortho-substituted 1,3-diarylureas were prepared.Their proton nuclear magnetic resonance (^1H-NMR) spectra were measured to evaluate the acidity of the ureido protons in the para-substituted ureas, and to estimate the conformations of ortho-substituted molecules. The chemical shifts and acidities of two ureido protons were additively controlled by the two para-substituents in the 1,3-diarylureas. The sixteen para-substitued diarylureas were nitrosated with gaseous nitrosating reagents (dinitrogen trioxide, dinitrogen tetroxide or nitroxyl chloride) to give unstable isomeric mixtures of 1,3-diaryl-1-nitrosoureas [R^1-C_6H_4-N(NO)-CO-NH-C_6H_4-R^2] and 1,3-diaryl-3-nitrosoureas [R^1-C_6H_4-NH-CO-N(NO)-C_6H_4-R^2]. The isomer ratio of each nitrosated urea was correlated with the difference between the chemical shifts (d[NH]) of the two ureido protons in the ^1H-NMR spectrum of the starting urea. When d[NH] was below 0.25 ppm (with NOCl) or 0.45 ppm (with N_2O_3), good linearity was obtained (r(NOCl)=0.943,n=11; r(N_2O_3)=0.869,n=15). When d[NH] was over 0.25 ppm (NOCl) or 0.45 ppm (N_2O_3), the 1-nitrosated isomer [R^1-C_6H_4-N(NO)-CO-NH-C_6H_4-R^2] was the sole product. These principles ould not be extended to dinitrogen tetroxide.Thirteen para-substituted diarylureas gave 1- or 3-nitrosated ureido derivatives as sole products and only four gave nitrosated isomeric mixtures.The ^1H-NMR spectra of 5 types of ortho-substituted 1,3-diarylureas were measured for comformational analysis. Their conformations seem to be different from those of para-substituted diarylureas. Eleven ortho-substituted 1,3-diarylureas were nitrosated with nitrosyl chloride and dinitrogen tetroxide. In many cases, the nitroso group was predominantly introduced at the ureido nitrogen, which is less hindered sterically, and isomeric mixtures of 1- and 3-nitrosated ureas were obtained.

• 公益社団法人日本薬学会の論文
• 1986-05-25

著者

• 宮原 誠

  National Institute of Hygienic Sciences, University of Tokyo

• 宮原 誠

  National Institute Of Hygienic Sciences

関連論文

• Degradation of 1,3-Diaryl-1-nitrosoureas in Aqueous Solutions and in Organic Solvents(Organic,Chemical)
• Expanded Coagulating Cleanup Procedures for Simultaneous Gas Chromatographic Determination of Organoposphorus Pesticides in Crops and Fruits
• A Cyclization of 1,2-Bisureido Compounds with Sodium Nitrite
• Nitrosation of 1-Phenyl-3-(pyridylmethyl)ureas and the Reactivity of Two Nitrosated Isomers
• Reactions of 1-Nitroso-1-phenyl-3-(4-pyridylmethyl)ureas
• Cyclization of (2-Hydroxyethyl) urea Derivatives to Give 3-Nitroso-2-oxazolidinones under Usual Nitrosation Conditions
• Action Mechanism of Anti-AH13 Activity of 1,3-Diaryl-1-nitrosoureas and Related Compounds
• Nitrosation of 1,3-Diarylureas with Nitrosyl Chloride, Dinitrogen Trioxide and Dinitrogen Tetroxide in Dimethylformamide
• Antitumor Activity of 2-Acylamino-1,3,4-thiadiazoles and Related Compounds
• Thermal Decomposition of 1,3-Diaryl-1-nitrosoureas in Benzene
• Antitumor Activity of 3-Nitroso-2-oxazolidones
• Substituent Effects on Nitrosation of 1,3-Diarylureas with Nitrosyl Chloride, Dinitrogen Trioxide, and Dinitrogen Tetroxide
• コ-ヒ-豆及び穀類中のオクラトキシンAの迅速分析法
• 4-(N,N-dimethylaminosulhonyl)-7-fluoro-2,1,3-benzoxadiazole(DBD-F)を用いたプレカラムHPLC法によるとうもろこし中のフモニシンB1,B2の定量〔英文〕

もっと見る 閉じる

スポンサーリンク