Ueber eine directe Bildungsweise aromatischer Amine aus den Kohlenwasserstoffen

Graebe, C.

doi:10.1002/cber.19010340276

Cited by 15 publications

(2 citation statements)

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“…Direct onestep amination is known, however it proceeds only in low yield [1,2], since in many cases the initial aromatic compound is used as solvent. Hydroxylamine [3,4], alkylhydroxylamines [5], hydroxylamine O-sulfonic acid [6], and hydrazoic acid [7] in the presence of a Lewis acids are used as aminating reagents. More recently Olah has used hydrazoic acid [8] and trimethylsilyl azide [9] in the presence of a superacid for these purposes.…”

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confidence: 99%

Synthesis and special features of the structure of 6(7)-aminoperimidine derivatives

Аксенов

Lyakhovnenko

Karaivanov

et al. 2010

Chem Heterocycl Comp

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A method of synthesizing 6(7)-aminoperimidines has been developed based on the electrophilic amination of perimidines with sodium azide in PPA. The corresponding amides were synthesized by acylation and were also obtained by the Schmidt reaction from 6(7)-acetyl(or benzoyl)perimidines. A special feature of the structure of the 2-substituted amines and amides is the presence of annular tautomerism slow in NMR time.Aromatic amines serve as important synthetic building blocks. The standard method of synthesizing them is sequential nitration and then reduction of the nitro compound formed at the first stage [1]. Direct onestep amination is known, however it proceeds only in low yield [1,2], since in many cases the initial aromatic compound is used as solvent. Hydroxylamine [3,4], alkylhydroxylamines [5], hydroxylamine O-sulfonic acid [6], and hydrazoic acid [7] in the presence of a Lewis acids are used as aminating reagents. More recently Olah has used hydrazoic acid [8] and trimethylsilyl azide [9] in the presence of a superacid for these purposes. The latter system is the most efficient, the yield was ~90% calculated on azide, but as a result of using a large excess of aromatic compound the degree of conversion of the latter does not exceed 10%.In the present work we propose a method of aminating perimidines based on a new reactant system, sodium azide -PPA (for preliminary communication see [10]).We have proposed that the PPA azide 1 will be formed as a result of the reaction of sodium azide with PPA, which may be protonated both at the nitrogen atom a and also b with the formation of two tautomeric cations 2. As the result of azocoupling of the latter with perimidines 3a-c the intermediates 4a-c will be formed, the hydrolysis of which leads to a mixture of tautomers of amines 5a-c and 6a-c.

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confidence: 99%

Synthesis and special features of the structure of 6(7)-aminoperimidine derivatives

Аксенов

Lyakhovnenko

Karaivanov

et al. 2010

Chem Heterocycl Comp

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“…However, attempts have been made with reagents such as hydroxyl ammonium salts, [566][567][568][569][570][571] hydroxylamine-O-sulfonic acid, 572,573 hydrazoic acid, [574][575][576] and organic azides, [577][578][579][580] mostly under Lewis acid-catalyzed conditions (and also with thermal initiation [581][582][583][584][585][586][587] or photolysis 588,589 ). However, attempts have been made with reagents such as hydroxyl ammonium salts, [566][567][568][569][570][571] hydroxylamine-O-sulfonic acid, 572,573 hydrazoic acid, [574][575][576] and organic azides, [577][578][579][580] mostly under Lewis acid-catalyzed conditions (and also with thermal initiation [581][582][583][584][585][586][587] or photolysis 588,589 ).…”

Section: Aminationmentioning

confidence: 99%

Superacid‐Catalyzed Reactions

Oláh¹,

Prakash²,

Molnár³

et al. 2008

Superacid Chemistry

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Friedel‐Crafts Reactions

Oláh

Reddy

Prakash

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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After the initial discovery by Friedel and his American associate, James Mason Crafts, that anhydrous aluminum chloride could be used as a condensing agent in a general synthetic method for furnishing an infinite number of hydrocarbons. They extended their discoveries of the catalytic effect of aluminum chloride in a variety of organic reactions: (1) reactions of alkyl and acyl halides and unsaturated compounds with aromatic and aliphatic hydrocarbons; (2) reactions of acid anhydrides with aromatic hydrocarbons; (3) reactions of oxygen, sulfur, sulfur dioxide, carbon dioxide, and phosgene with aromatic hydrocarbons; (4) cracking of aliphatic and aromatic hydrocarbons; and (5) polymerization of unsaturated hydrocarbons. The diversity of reactions is astounding. Many important industrial processes such as the production of high octane gasoline, ethylbenzene (eventually leading to polystyrene), synthetic rubber, plastics, and detergent alkylates are based on Friedel‐Crafts chemistry. Friedel‐Crafts‐type reactions are generally considered to be any substitution, isomerization, elimination, cracking, polymerization, or addition reaction that takes place under the catalytic effect of Lewis acid‐type acidic halides (with or without cocatalysts) or Brønsted acids. Friedel‐Crafts reactions can be divided into two general categories: alkylations and acylations. Within these two broad areas there is considerable diversity. Friedel‐Crafts catalysts are electron acceptors, ie, Lewis acids. Catalysts include acid halides (Lewis acids), metal alkyls and alkoxides, protic acids (Brønsted Acids), acidic oxides and sulfides (acidic chalcogenides), acidic cation‐exchange resins, and superacids (Brønsted superacids, super Lewis acids, Brønsted‐Lewis superacids, solid superacids, and superacidic zeolites).

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Ueber eine directe Bildungsweise aromatischer Amine aus den Kohlenwasserstoffen

Cited by 15 publications

References 0 publications

Synthesis and special features of the structure of 6(7)-aminoperimidine derivatives

Synthesis and special features of the structure of 6(7)-aminoperimidine derivatives

Superacid‐Catalyzed Reactions

Friedel‐Crafts Reactions

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