- A weakly basic amine diazonium salt preparation method, and its preparation tertiary amine weakly basic amine azo dye method
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The invention relates to a preparation method for weak-base arylamine diazonium salt and a method for preparing tertiary amine weak-base arylamine azo dye by the weak-base arylamine diazonium salt, and belongs to the technical field of clean production of the dye. The preparation method comprises the following steps of adding naphthalenesulfonic acid and alkyl nitrite to weak-base arylamine solution in sequence, reacting for 20min to 60min at 0 DEG C to 25 DEG C, and performing solid-liquid separation to obtain weak-base arylamine diazonium salt solid; solvent for dissolving weak-base arylamine is tetrahydrofuran, 1,4-dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether or ethyl acetate. The preparation method for the weak-base arylamine diazonium salt and the method for preparing the tertiary amine weak-base arylamine azo dye by the weak-base arylamine diazonium salt, disclosed by the invention, have the beneficial effects that no sulfuric acid is used in a process of preparing the weak-base arylamine diazonium salt and the tertiary amine weak-base arylamine azo dye, therefore the environment is protected.
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Paragraph 0031; 0032; 0033; 0034
(2017/08/16)
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- Stable diazonium salts of weakly basic amines—Convenient reagents for synthesis of disperse azo dyes
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A new synthetic strategy for industrially important deep-shade disperse azo dyes was presented in this study. The key procedure is to prepare stable solid diazonium salts of weakly basic amines in the absence of concentrated sulfuric acid. Diazotization by tert-butyl nitrite in ethyl acetate was allowed to proceed in the presence of equivalent 1,5-naphthalenedisulfonic acid as stabilizer of diazonium salts and donor of hydrogen ion for the reaction. The separated solid diazonium salts exhibited good thermal stability. The corresponding disperse azo dyes were subsequently synthesized through the azo-coupling of the prepared solid diazonium salts with a range of aromatic tertiary amines. The azo dyes were produced in short reaction time, excellent yields, mild reaction conditions, simple experimental procedure and low energy consumption.
- Qiu, Jinjing,Tang, Bingtao,Ju, Benzhi,Xu, Yuanji,Zhang, Shufen
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- Cyanide Substitution in Aryl Halides by Copper(I) Complexes Derived from Formamide and from Formaldehyde Oxime
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The copper complexes , and derived from formamide, and and derived from formaldehyde oxime (formaldoxime) react with 2'-acetamido-6-bromo-4'-diethylamino-2,4-dinitroazobenzene, ArBr, to form the corresponding aryl cyanide, ArCN, and the products ArH and Ar2 of reductive substitution and biaryl coupling.Copper(I) bromide complexes are also formed.Kinetic studies of these reactions in acetonitrile solution show that the cyanation reactions are equal concentration, second-order processes in each case.The effect of a radial scavenger on the reaction suggests the involvement of radicals in the formation of Ar2, but not in the formation of ArCN.A mechanism involving concerted nucleophilic substitution within the co-ordination sphere of copper(I) is proposed.
- Connor, Joseph A.,Gibson, Danuta,Price, Raymond
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p. 619 - 622
(2007/10/02)
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- The Copper-promoted Reaction of o-Halogenodiarylazo-compounds with Nucleophiles. Part 3. The Copper-promoted Reaction of o-Bromodiarylazo-compounds with Carboxylate Ions. A Novel Method for the Preparation of o-Hydroxydiarylazo-compounds
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o-Bromo-o'-acetylaminodiarylazo-compounds react with potassium acetate in the presence of copper(II) acetate in dipolar aprotic solvents to give the copper(II) complex of the corresponding o-hydroxy-o'-acetylaminodiarylazo-compounds in good yield.The reaction proceeds via the intermediate o-acetoxy-o'-acetylaminodiarylazo-compound which undergoes facile, in situ, copper-promoted hydrolysis.When the diarylazo-compound contains two o-bromine atoms only one is replaced, with a single exception.
- Price, Raymond,Yates, John E.
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p. 1775 - 1782
(2007/10/02)
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- Phosphonation of Aryl Halides by Copper(I) Complexes of Trialkyl Phosphites
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The copper complexes 2> (1; R=Me or Et), (bpy)> (2; R=Me or Et) (bpy is 2,2'-bipyridine), and 2> react with certain 2-halogenoazobenzene compounds, ArX, at room temperature to form the corresponding dialkyl arylphosphonates, ArP(O)(OR)2, and the products, ArH and Ar2, of reductive substitution and biaryl coupling.The ester, MeCO2R, and a copper(I) halide complex (e.g. >) are also formed.Kinetic studies of the reactions of some of these copper complexes with 2'-acetamido-6-bromo-4'-diethylamino-2,4-dinitroazobenzene in alcohol solution show that the phosphonation reactions are equal concentration second-order processes in each case.The effects of a radical scavenger and of light on the reaction suggest the involvement of radicals in the formation of ArH and Ar2, but not in the formation of ArP(O)(OR)2.The effects of different substituents in ArX, of changes in solvent, and of various additives on these reactions are investigated.A mechanism involving concerted nucleophilic substitution within the coordination sphere of copper(I) is proposed.
- Connor, Joseph A.,Dubowski, Danuta,Jones, Anthony,Price, Raymond
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p. 1143 - 1148
(2007/10/02)
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- Copper(II) Ethanoate-assisted Phosphonation of Aryl Halides
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A mixed valence trinuclear copper complex 2> is formed in the reaction between a 2-halogenoaryl azo compound and a trialkyl phosphite in the presence of copper(II) ethanoate which gives the corresponding 2-(dialkylphosphonato)aryl azo compound.
- Connor, Joseph A.,Jones, Anthony C.,Price, Raymomd
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p. 137 - 138
(2007/10/02)
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- Process for the manufacture of aromatic nitriles
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Process for the manufacture of aromatic nitriles by reacting an aromatic halogen compound with formaldoxime in the presence of a copper catalyst and an acid-binding agent, preferably a tertiary amine. Particularly applicable to replacement of halogen ortho to the azo linkage of an azo dyestuff by cyano.
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