The use of [2,3] sigmatropic rearrangements for the specific ortho-substitution of polycyclic aromatic amines. The methylation of naphthylamines and the synthesis of 1H-benz[g]indoles and 3H-benz[e]indoles

Gassman, Paul G.; Schenk, William N.

doi:10.1021/jo00440a008

Cited by 27 publications

(2 citation statements)

References 14 publications

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“…It is possible that the high vibrationally excited states of the ground state participate in the C−N bond cleavage observed in the irradiation of 1a with the long-wavelength light. However, it appears that this possibility can be excluded, because the thermolysis of 1a in o -dichlorobenzene at 150 °C afforded 2-methyl-3 H -benz[ e ]indole ( 10 ) (Scheme ). No trace amounts of the products obtained in the long-wavelength irradiation of 1a were detected in its thermolysis even in the presence of O 2 .…”

Section: Resultsmentioning

confidence: 99%

Photochemistry of 2-(1-Naphthyl)-2H-azirines in Matrixes and in Solutions: Wavelength-Dependent C−C and C−N Bond Cleavage of the Azirine Ring

Inui

Murata

2005

J. Am. Chem. Soc.

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The photochemistry of 3-methyl-2-(1-naphthyl)-2H-azirine (1a) was investigated by the direct observation of reactive intermediates in matrixes at 10 K and by the characterization of reaction products in solutions. As already reported, the photolysis of the azirine 1a with the short-wavelength light (>300 nm) caused the C-C bond cleavage of the 2H-azirine ring to produce the nitrile ylide 2. However, the products derived from the C-N bond cleavage were exclusively obtained in the irradiation of 1a with the long-wavelength light (366 nm) both in matrixes and in solutions. When 1a was irradiated in the presence of O(2) with the long-wavelength light, acetonitrile oxide (6) was produced through the capture of the biradical 4 generated by the C-N bond cleavage of 1a with O(2). An introduction of a nitro group into the naphthyl ring of 1a resulted in an acceleration of the decomposition in the long-wavelength irradiation and an extension of the wavelength region where the products derived from the C-N bond cleavage were selectively obtained. On the basis of molecular orbital calculations with the INDO/S method, the reason for the wavelength-dependent selective C-C and C-N bond cleavage of the azirine ring of 1a is discussed.

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Section: Resultsmentioning

confidence: 99%

Photochemistry of 2-(1-Naphthyl)-2H-azirines in Matrixes and in Solutions: Wavelength-Dependent C−C and C−N Bond Cleavage of the Azirine Ring

Inui

Murata

2005

J. Am. Chem. Soc.

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“…Alternative methods of reduction have also been used: sodium dithionite, 21 iron in acetic acid, 22 stannous chloride, 22 and titanium trichloride. 23 This method has been applied to the preparation of polycyclic indoles 12,24 and azaindoles 24,25,26 as well.…”

Section: Discussionmentioning

confidence: 99%

Indoles from 2‐Methylnitrobenzenes by Condensation with Formamide Acetals Followed by Reduction: 4‐Benzyloxyindole

Batcho

Leimgruber

2003

Organic Syntheses

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Indoles from 2‐Methylnitrobenzenes by Condensation with Formamide Acetals Followed by Reduction: 4‐Benzyloxyindole intermediate: 6‐benzyloxy‐2‐nitrotoluene intermediate: (E)‐6‐benzyloxy‐2‐nitro‐β‐pyrrolidinostyrene and (E)‐6‐benzyloxy‐β‐dimethylamino‐2‐nitrostyrene product: 4‐benzyloxyindole intermediate: pyrrolidine enamine, mp 108–110° (MeOH), and N,N‐dimethylenamine

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ortho‐Alkylation of Anilines: Ethyl 4‐Amino‐3‐Methylbenzoate

Gassman

Gruetzmacher

2003

Organic Syntheses

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ortho ‐Alkylation of anilines: ethyl 4‐amino‐3‐methylbenzoate reactant: 16.50 g. (0.1000 mole) of ethyl 4‐aminobenzoate (Benzocaine, ) intermediate: ethyl 4‐amino‐3‐(methylthiomethyl)benzoate product: ethyl 4‐amino‐3‐methylbenzoate

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The use of [2,3] sigmatropic rearrangements for the specific ortho-substitution of polycyclic aromatic amines. The methylation of naphthylamines and the synthesis of 1H-benz[g]indoles and 3H-benz[e]indoles

Cited by 27 publications

References 14 publications

Photochemistry of 2-(1-Naphthyl)-2H-azirines in Matrixes and in Solutions: Wavelength-Dependent C−C and C−N Bond Cleavage of the Azirine Ring

Photochemistry of 2-(1-Naphthyl)-2H-azirines in Matrixes and in Solutions: Wavelength-Dependent C−C and C−N Bond Cleavage of the Azirine Ring

Indoles from 2‐Methylnitrobenzenes by Condensation with Formamide Acetals Followed by Reduction: 4‐Benzyloxyindole

ortho‐Alkylation of Anilines: Ethyl 4‐Amino‐3‐Methylbenzoate

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