ChemInform Abstract: OPEN-CHAIN NITROGEN COMPOUNDS. PART II. PREPARATION, CHARACTERIZATION, AND DEGRADATION OF 1(3)-ARYL-3(1)-METHYLTRIAZENES, THE EFFECT OF SUBSTITUENTS ON THE REACTION OF DIAZONIUM SALTS WITH METHYLAMINE

1977 ◽  
Vol 8 (37) ◽  
pp. no-no
Author(s):  
T. P. AHERN ◽  
H. FONG ◽  
K. VAUGHAN
Keyword(s):  
Diazonium Salts ◽  
Nitrogen Compounds ◽  
Open Chain ◽  
Effect Of Substituents

Open-chain nitrogen compounds. Part II. Preparation, characterization, and degradation of 1(3)-Aryl-3(1)-methyltriazenes; the effect of substituents on the reaction of diazonium salts with methylamine

1977 ◽  
Vol 55 (10) ◽  
pp. 1701-1709 ◽  
Author(s):  
T. Patrick Ahern ◽  
Handrick Fong ◽  
Keith Vaughan
Keyword(s):  
Degradation Products ◽  
Diazonium Salt ◽  
Diazonium Salts ◽  
Nitrogen Compounds ◽  
Open Chain ◽  
Effect Of Substituents ◽  
Electron Withdrawing Group

Treatment of the diazonium salts, X•C6H4N2+, with aqueous methylamine affords good yields of the monomethyltriazenes, X•C6H4•N=N•NHMe, when the substituent is a strongly electron-withdrawing group (X = o-, m-, and p-NO2; o-, m-, and p-CO2R; p-CN and p-COCH3). Preparation of the triazene from the p-bromobenzene diazonium salt was accompanied by formation of a pentaazadiene. Monomethyltriazenes were not obtained when diazonium salts containing other substituents (X = H, p-CH3, o-CF3, p-Cl, p-F, p-NMe2, p-OH, p-OCH3, p-Ph, p-NHCOCH3) were treated with methylamine. In these cases the products were either pentaazadiene, or 1,3-diaryltriazenes or unstable materials. The monomethyltriazenes vary considerably in stability and give rise to a number of different degradation products, which were either diaryltriazenes or 3-alkyl-1,3-diaryltriazenes or simply arylamines. 1(3)-(p-Nitrophenyl)-3(1)-methyltriazene was found to be a moderately effective methylating agent.

Open-chain nitrogen compounds. Part III. The formation of triazenes in the reaction of diazonium salts with α-aminoacetonitrile and related α-substituted alky lamines

1977 ◽  
Vol 55 (21) ◽  
pp. 3751-3754 ◽  
Author(s):  
Theresa A. Daniels ◽  
Shiraz Sidi ◽  
Keith Vaughan
Keyword(s):  
Aqueous Solution ◽  
Diazonium Salt ◽  
Diazonium Salts ◽  
Nitrogen Compounds ◽  
Open Chain ◽  
Diazonium Ion ◽  
Methylene Group

Several triazenes of type Ar•N==N•NH•CH2Y, where Y is electron withdrawing, have been prepared by reaction of the diazonium salts X•C6H4N2+ (X = H, p-NO2, p-CO2Me, p-COPh, and o-COPh) with the α-substituted alkylamines NH2CH2Y (Y = CN, CO2Et, COPh, and CH(OCH3)2) in aqueous solution, without prior isolation of the diazonium salt. In all cases, the diazonium ion attacks at the NH2 moiety exclusively and the methylene group in NH2CH2Y shows no tendency to compete for the diazonium ion.

Open chain nitrogen compounds. Part XIII. 1-Aryl-3-arylthiomethyl-3-methyltriazenes and 3-(arylazo)-1,3-thiazolidines

1988 ◽  
Vol 66 (10) ◽  
pp. 2487-2491 ◽  
Author(s):  
Keith Vaughan ◽  
Hartford W. Manning ◽  
Marcus P. Merrin ◽  
Donald L. Hooper
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Active Metabolite ◽  
Aqueous Acetone ◽  
Rotational Isomerism ◽  
Nitrogen Compounds ◽  
Open Chain ◽  
New Class ◽  
Nuclear Magnetic Resonance Spectra ◽  
Show Evidence

Reaction of 3-acetoxymethyl-1-aryl-3-methyltriazenes with sodium thiophenolate or thiocresolate in anhydrous dimethylformamide affords a new series of 3-arylthiomethyltriazenes (2), Ar-S-CH2-NMe-N=N-Ar′. These triazenes are remarkably labile in aqueous buffer and may be good pro-drugs for the active metabolite of the antitumour dimethyltriazenes. The reaction of arenediazonium fluoroborates with 1,3-thiazolidine in aqueous acetone affords a new series of N-arylazo-1,3-thiazolidines (4); the arylazothiazolidines represent a new class of triazene in which the N3 nitrogen is incorporated into a heterocyclic unit, in this case a 1,3-thiazolidine. Nuclear magnetic resonance spectra of the arylazothiazolidines show evidence for rotational isomerism of the exocyclic N2—N3 bond in the triazene moiety.

Open chain nitrogen compounds. Part X. Thermolysis of α-diazoacetanilides in methanol: a convenient synthesis of α-methoxyacetanilides from ethyl N-(arylazo)glycinate

1986 ◽  
Vol 64 (4) ◽  
pp. 799-802
Author(s):  
Kumudini U. K. Gamage Nicholas ◽  
Keith Vaughan
Keyword(s):  
Tertiary Amine ◽  
Methanol Solution ◽  
Small Scale ◽  
Nitrogen Compounds ◽  
Rare Type ◽  
Open Chain ◽  
Amide Derivative ◽  
Convenient Synthesis ◽  
Synthetic Equivalent ◽  
Electron Withdrawing Group

α-Diazoacetanilides (4), which are readily available from the open-chain triazenes (2), undergo thermolysis in methanol solution to afford the α-methoxyacetanilides (5), an apparently rare type of ether/amide derivative. The methanolic thermolysis is inhibited by the presence of a tertiary amine in the solvent, suggesting that a carbocation, rather than a carbene, intermediate is involved in the conversion of the diazo-amide to the methyl ether. This hypothesis is supported by the retardation of the reaction in the presence of an electron-withdrawing group in the para position of the anilide. The conversion 4 → 5 was also observed, on a small scale, under photolytic conditions. It is suggested that the α-diazoacetanilide represents a useful synthetic equivalent for the synthon ArNHCOCH2+.

1008. Infrared spectra of open-chain boron–nitrogen compounds

1960 ◽  
Vol 0 (0) ◽  
pp. 5239-5246 ◽  
Author(s):  
D. W. Aubrey ◽  
M. F. Lappert ◽  
H. Pyszora
Keyword(s):  
Infrared Spectra ◽  
Nitrogen Compounds ◽  
Open Chain ◽  
Boron Nitrogen

Open-chain nitrogen compounds. Part XII. Methanolysis of 3-alkyl-3,4-dihydro-1,2,3-benzotriazin-4-ols: evidence for ring-chain tautomerism with the cytotoxic monoalkyltriazenes

1987 ◽  
Vol 65 (2) ◽  
pp. 292-297 ◽  
Author(s):  
Ronald J. Lafrance ◽  
Hartford W. Manning ◽  
Keith Vaughan
Keyword(s):  
In Vitro Cytotoxicity ◽  
Nitrogen Compounds ◽  
Open Chain ◽  
Chemical Behaviour ◽  
Anti Tumor Activity

A series of 4-hydroxy-3,4-dihydro-1,2,3-benzotriazines ("triazinols"), potential pro-drugs for the cytotoxic monoalkyltriazenes, have been investigated for anti-tumor activity and have been found to have marginal activity against the TLX5 tumor. The in vivo anti-tumor activity correlates with previously observed in vitro cytotoxicity of the compounds. The chemical behaviour of the triazinols is consistent with carbinolamine [Formula: see text] triazene ring-chain tautomerism in solution. The triazinols undergo methanolysis to give a series of new 4-methoxytriazines; the rate of methanolysis is primarily dependent on the substituent at C-4 of the triazinol. Those triazinols that undergo methanolysis rapidly are also more active biologically, suggesting that cytotoxicity and anti-tumor activity derive from the insitu generation of the open chain triazene.

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