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 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.

Regioselective Arylation of 1,3-Dimethyllumazine and Its 5-Oxide by Diazonium Salts

Pteridines ◽  
1997 ◽  
Vol 8 (3) ◽  
pp. 188-194 ◽  
Author(s):  
Takashi Sugimoto ◽  
Chihiro Seo ◽  
Shizuaki Murata ◽  
Wolfgang Pfleiderer
Keyword(s):  
Aqueous Solution ◽  
Molecular Orbital ◽  
Alkaline Solution ◽  
Diazonium Salt ◽  
New Method ◽  
Diazonium Salts ◽  
Molecular Orbital Calculations ◽  
Aqueous Alkaline Solution ◽  
Aryl Group ◽  
Benzene Diazonium

Summary A new method to introduce an aryl group directly into the pteridine nucleus by the action of arene diazonium salt in an aqueous alkaline solution is described. 1,3-Dimethyllumazine and benzene diazonium chloride reacts in an aqueous solution at pH 8-9 to give 7 -phenyl-1 ,3-dimethyllumazine together with a little of 6-phenyi-1 ,3-dimethyllumazine. The analogous reactions of 1,3-dimethyllumazine with 4-methyl-, 4-methm.),-, 4-chloro-, and 3-chlorobenzene diazonium chlorides give the corresponding 7-aryl-1,3-dimethyllumazines as major products together with a little of 6-aryl-1,3-dimethyllumazines. Reactions of 1,3-dimethyllumazine 5-oxide with arene diazonium salts under the same conditions exclusively afford the corresponding 6-aryl-1,3-dimethyllumazine 5-oxides which are easily converted to 6-aryl-1,3-dimethyllumazine by the action of tributylphosphine. Mechanisms concerning regioselectivities are investigated by using molecular orbital calculations.

Open-chain nitrogen compounds. Part VI. The formation of bis(1-aryl-3- methyltriazen-3-ylmethyl) methylamines in the reaction of diazonium ions with mixtures of formaldehyde and methylamine

1984 ◽  
Vol 62 (4) ◽  
pp. 749-754 ◽  
Author(s):  
Hartford W. Manning ◽  
Chantal M. Hemens ◽  
Ronald J. LaFrance ◽  
York Tang ◽  
Keith Vaughan
Keyword(s):  
Diazonium Salts ◽  
Mechanism Of Formation ◽  
Open Chain ◽  
Cyclic Trimer ◽  
Anti Tumour Activity ◽  
Diazonium Ions ◽  
Diazonium Ion ◽  
A Minor ◽  
Identical Product ◽  
Tumour Activity

The synthesis of a series of N,N-bis(1-aryl-3-methyltriazen-3-ylmethyl) methylamines from coupling diazonium salts with mixtures of methylamine and formaldehyde is described. These novel bis-triazenes, or heptazanonadienes, have significant anti-tumour activity against the TLX5 lymphoma in mouse. The mechanism of formation of these triazenes is discussed with reference to the implication to the presumed equilibria taking place in the methylamine/formaldehyde solution. The formation of the bis-triazene is usually accompanied by the formation of a 3-hydroxymethyitriazene, and it has been shown that the hydroxymethyltriazene can be transformed into the bis-triazene. The proportions of the two products are strongly influenced by the relative amounts of methylamine and formaldehyde. Coupling the p-bromobenzenediazonium salt to a 1:1 methylamine/formaldehyde mixture affords mainly the bis-triazene, whereas a 1:50 mixture gives almost totally the hydroxymethyl triazene. These results suggest that the two triazenes arise from diazonium coupling to different species in the amine/formaldehyde mixture; this hypothesis is supported by the formation of identical product mixtures from coupling the diazonium ion with (a) a 1:1 MeNH2/CH2O mixture, and (b) the cyclic trimer of the carbinolamine MeNHCH2OH, and by the identification of a minor product from the reaction of p-chlorobenzenediazonium fluoroborate with MeNH2/CH2O as bis(1-p-chlorophenyl-3-methyltriazen-3-yl) methane.

Open-chain nitrogen compounds. Part V. Hydroxymethyltriazenes: synthesis of some new alkyl homologues of the anti-tumour 3-methyl-3-hydroxymethyltriazenes and preparation of the derived acetoxymethyl-, benzoyloxymethyl-, and methoxymethyltriazenes

1984 ◽  
Vol 62 (4) ◽  
pp. 741-748 ◽  
Author(s):  
Chantal M. Hemens ◽  
Hartford W. Manning ◽  
Keith Vaughan ◽  
Ronald J. LaFrance ◽  
York Tang
Keyword(s):  
Benzoyl Chloride ◽  
Diazonium Salt ◽  
Nitrogen Compounds ◽  
Ortho Position ◽  
The Novel ◽  
Ethanolic Solution ◽  
Ether Linkage ◽  
Open Chain ◽  
Diazonium Ions ◽  
Derivatives Of

The synthesis of some new 1-aryl-3-alkyl-3-hydroxymethyltriazenes is described. The method of coupling a diazonium salt with an alkylamine/formaldehyde mixture has been extended to (a) some diazonium ions with para substituents other than—M groups, (b) those with substituents in the ortho position, and (c) to homologous alkylamines (e.g. ethylamine, propylamine, etc.). Hydroxymethyltriazenes can also be prepared by the reaction of a 1-aryl-3-methyltriazene with formaldehyde. Several new derivatives of the hydroxymethyl function have been prepared. Reaction with acetic anhydride or benzoyl chloride in pyridine affords respectively the acetoxymethyl- and benzoyloxymethyl-triazenes; the acetates and benzoates react readily with methanol to give the novel methoxymethyltriazenes. This is the first report of a series of dialkyltriazenes with an ether linkage in the α position. An ether of this type has also been obtained directly from the diazonium fluoroborate salt by coupling with a mixture of benzylamine and formaldehyde in ethanolic solution.

scholarly journals INFLUENCE OF CHEMICAL STRUCTURE ON THE RATE OF AZO COUPLING AND ITS SIGNIFICANCE IN HISTOCHEMICAL METHODOLOGY

1959 ◽  
Vol 7 (1) ◽  
pp. 50-65 ◽  
Author(s):  
MARVIN M. NACHLAS ◽  
THEODORE P. GOLDSTEIN ◽  
DAVID H. ROSENBLATT ◽  
MARVIN KIRSCH ◽  
ARNOLD M. SELIGMAN
Keyword(s):  
Aromatic Amines ◽  
Diazonium Salt ◽  
Tissue Sections ◽  
Coupling Techniques ◽  
Diazonium Ions ◽  
Coupling Rate ◽  
Diazonium Ion ◽  
Hydroxy Compounds ◽  
Positive Groups ◽  
Electro Negativity

Reliability of enzymatic localization in tissue sections by the simultaneous coupling techniques is dependent to a great extent upon the speed of coupling. Therefore, the influence on coupling rate of the structure of the diazonium ion and of the coupling component was studied. Electro-negative groups in the diazonium ion increase the rate of coupling, while the same groups in the coupling component decrease the rate. Electro-positive groups in the coupling component accelerate coupling, but slow it when present in the diazonium ion. The relation of coupling rate and electro-negativity of the substituents in the diazonium ion follows Hammett's equation (8). Although the relations is linear on coupling with aromatic hydroxy compounds, it is not so with aromatic amines. The most active diazonium ions showed no increase in coupling rate with aromatic amines. This suggests that for those enzymes hydrolyzing an ester link, increase of coupling rate might be accomplished by modifying the structure of either the coupling component used in the substrate or the diazonium salt. However, for enzymes splitting amide linkages, the only possibility of improving the localization is by modifying the structure of the coupling component.

Reactions of 2-(benzimidazol-2-yl)acetonitrile and its N-ethoxycarbonyl derivative with some azol-3-diazonium salts

1984 ◽  
Vol 49 (1) ◽  
pp. 275-279 ◽  
Author(s):  
Jan Slouka ◽  
Vojtěch Bekárek
Keyword(s):  
Diazonium Salt ◽  
Ethyl Chloroformate ◽  
Diazonium Salts

Coupling of 2-(1-ethoxycarbonyl-benzimidazol-2-yl)acetonitrile (II) with 5-methylpyrazol-3-diazonium (IIIa) or indazol-3-diazonium salt (IIIb) does not give the corresponding derivatives VIIa, VIIb of pyrazolo[3,2-c]-1,2,4-triazine but, instead, gives the corresponding 2-(3-azolyl)-1-oxo-1,2-dihydro-1,2,4-triazino-[4,5-a]benzimidazole-4-carbonitriles VIIIa, VIIIb. Coupling of 2-(benzimidazol-2-yl)acetonitrile (I) with the diazonium salt IIIa gives 7-amino-6-(benzimidazol-2-yl)-2-methylpyrazolo[3,2-c]-1,2,4-triazine (VIa) which, on reaction with ethyl chloroformate, undergoes cyclization to 2-methyl-12,13-dihydropyrazolo[3",2":3',4']-1,2,4-triazino[5',6':6,5]-pyrimido[3,4-a]benzimidazol-12-one (IXa). The compound VIa and 1-amino-2-(benzimidazol-2-yl)-1,2,4-triazono[4,3-b]indazole (VIb) are also formed by recyclization of the compounds VIIIa and VIIIb, respectively, in boiling aqueous pyridine.

Molecular Grafting on Si(111) Surfaces: An Electrochemical Approach

1996 ◽  
Vol 451 ◽  
Author(s):  
C. Henry de Villeneuve ◽  
J. Pinson ◽  
F. Ozanam ◽  
J. N. Chazalviel ◽  
P. Allongue
Keyword(s):  
Aqueous Solution ◽  
Electrochemical Method ◽  
Organic Molecules ◽  
Diazonium Salts ◽  
Molecular Films ◽  
Electrochemical Approach ◽  
The Stability ◽  
Structural Characterizations ◽  
Direct Attachment

ABSTRACTThis works addresses the question of the direct attachment of organic molecules on Si(111) by an electrochemical method. Anodic grafting of -OR group is demonstrated by in-situ STM and the LDOS characterized. The grafting of aryl groups, by reduction of aryl diazonium salts in aqueous solution, is also described. This approach leads to well ordered and close-packed thin molecular films with various functionality. Different chemical and structural characterizations conclude to a Si-C binding, between the Si surface and aryl groups. The stability of films is also investigated.

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