Photolysis of (arylmethyl)triphenylphosphonium salts. Substituent, counterion, and solvent effects on reaction products

Imrie, Christopher; Modro, Tomasz A.; Rohwer, Egmont Richard; Wagener, Carl

doi:10.1021/jo00073a023

Cited by 40 publications

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“…The obtained residue was fractionally distilled and the desired product was purified as convenient. The following ethers were prepared by Method B: 1-(methoxymethyl)-4-methylbenzene (1d, 10.88 g, 80% from the corresponding alcohol and Me 2 SO 4 ), [59] 1-methoxy-3-(methoxymethyl)benzene (1p, 12.77 g, 84% from the corresponding alcohol and Me 2 SO 4 ), [66] (hexyloxymethyl)benzene (1aa, 10.56 g, 55% from hexanol and phenylmethyl bromide), [67] [(cyclopentyloxy)methyl]benzene (1cc, 15.14 g, 86% from cyclopentanol and phenylmethyl bromide), [68] and (1-methoxyethyl)benzene (1ee, 12.92 g, 95% from 1-phenylethanol and Me 2 SO 4 ). [69] …”

Section: General Procedures For the Synthesis Of Some Ethers (Methods B)mentioning

confidence: 99%

“…[54] Benzyl methyl ethers were almost exclusively prepared by the classical Williamson synthesis, by treatment of an MeOH solution of the appropriate halide (100.0 mmol in 100 mL) with MeONa in MeOH (200 mmol in 100 mL), by a described procedure (Method A). [55] 1-(Methoxymethyl)-3-methylbenzene (1c, 11.02 g, 81% from the chloride), [56] 1-(1,1-dimethylethyl)-4-(methoxymethyl)benzene (1e, 14.60 g, 82% from the bromide), [57] 1-chloro-2-(methoxymethyl)benzene (1f, 11.70 g, 75% from the chloride), [58] 1-chloro-3-(methoxymethyl)benzene (1g, 12.48 g, 80% from the chloride), [58] 1-chloro-4-(methoxymethyl)benzene (1h, 12.17 g, 78% from the chloride), [59] 1,3-dichloro-4-(methoxymethyl)benzene (1j, 17.57 g, 92% from the chloride), [60] 1-(methoxymethyl)-2-nitrobenzene (1k, 12.53 g, 75% from the iodide), [61] 1-(methoxymethyl)-3-nitrobenzene (1m, 13.03 g, 78% from the iodide), [62] 1-(methoxymethyl)-4-nitrobenzene (1n, 12.69 g, 76% from the iodide), [62] and diphenylmethyl methyl ether (1hh, 17.62 g, 89% from the chloride) [63] were prepared by Method A. [(1,1-Dimethylethoxy)methyl]benzene [64] (1dd, 7.22 g, 44%) was prepared in a similar way, from benzyl bromide and potassium tert-butoxide.…”

Section: Synthesis Of Intermediates and Substratesmentioning

confidence: 99%

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Oxidation of Benzylic Alcohols and Ethers to Carbonyl Derivatives by Nitric Acid in Dichloromethane

Strazzolini

Runcio

2003

Eur J Org Chem

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Nitric acid in dichloromethane may be successfully employed for the oxidation of benzylic alcohols and ethers to the corresponding carbonyl compounds. The proposed method proved to be of general applicability, affording very good yields of aldehydes and ketones and showing interesting chemoselectivity in many instances, allowing competitive aromatic nitration to be avoided, as well as − in the case of aldehydes − any further oxidation to carboxylic acids. The reaction probably proceeds by a radical mechanism, the active species in the oxidation process being NO2. Competitive formation of nitro esters was observed in some cases, whereas poor results were obtained with allylic and non‐benzylic substrates. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Section: General Procedures For the Synthesis Of Some Ethers (Methods B)mentioning

confidence: 99%

Section: Synthesis Of Intermediates and Substratesmentioning

confidence: 99%

Oxidation of Benzylic Alcohols and Ethers to Carbonyl Derivatives by Nitric Acid in Dichloromethane

Strazzolini

Runcio

2003

Eur J Org Chem

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“…The following ethers were prepared by Method B: 1-(methoxymethyl)-4-methylbenzene (1d, 10.88 g, 80% from the corresponding alcohol and Me 2 SO 4 ), [59] 1-methoxy-3-(methoxymethyl)benzene (1p, 12.77 g, 84% from the corresponding alcohol and Me 2 SO 4 ), [66] (hexyloxymethyl)benzene (1aa, 10.56 g, 55% from hexanol and phenylmethyl bromide), [67] [(cyclopentyloxy)methyl]benzene (1cc, 15.14 g, 86% from cyclopentanol and phenylmethyl bromide), [68] and (1-methoxyethyl)benzene (1ee, 12.92 g, 95% from 1-phenylethanol and Me 2 SO 4 ). [69] 1-(Methoxymethyl)-3-phenoxybenzene (1q): Yield: 19.69 g (92%, Method B, from the corresponding alcohol and Me 2 SO 4 ); colourless liquid, b.p.…”

Section: General Procedures For the Synthesis Of Some Ethers (Methods B)mentioning

confidence: 99%

“…[49] (3-Nitrophenyl)methyl Nitrate (9): Yield: 2.97 g (75%, Method A); yellowish solid, m.p. [55] 1-(Methoxymethyl)-3-methylbenzene (1c, 11.02 g, 81% from the chloride), [56] 1-(1,1-dimethylethyl)-4-(methoxymethyl)benzene (1e, 14.60 g, 82% from the bromide), [57] 1-chloro-2-(methoxymethyl)benzene (1f, 11.70 g, 75% from the chloride), [58] 1-chloro-3-(methoxymethyl)benzene (1g, 12.48 g, 80% from the chloride), [58] 1-chloro-4-(methoxymethyl)benzene (1h, 12.17 g, 78% from the chloride), [59] 1,3-dichloro-4-(methoxymethyl)benzene (1j, 17.57 g, 92% from the chloride), [60] 1-(methoxymethyl)-2-nitrobenzene (1k, 12.53 g, 75% from the iodide), [61] 1-(methoxymethyl)-3-nitrobenzene (1m, 13.03 g, 78% from the iodide), [62] 1-(methoxymethyl)-4nitrobenzene (1n, 12.69 g, 76% from the iodide), [62] and diphenylmethyl methyl ether (1hh, 17.62 g, 89% from the chloride) [63] were prepared by Method A. 1 (25, 9.71 g, 73%), [50] 2-chloro-2-methylpropyl nitrate (52, 6.42 g, 38%), [51] 1-phenylethyl nitrate (17,11.36 g, 68%), [52] 1,2-diphenylethyl nitrate (18, 10.2 g, 42%), [37] and 2-(nitrooxy)-1,2-diphenylethanone (19, 16.45 g, 64%) [53] were prepared by treatment of CH 2 Cl 2 solutions of the corresponding alco-hols (100.0 mmol in 5.0 mL) with a mixture of HNO 3 (200.0 mmol) and H 2 SO 4 (100.0 mmol), by a reported procedure (Method B).…”

Section: Synthesis Of Intermediates and Substratesmentioning

confidence: 99%

Oxidation of Benzylic Alcohols and Ethers to Carbonyl Derivatives by Nitric Acid in Dichloromethane.

Strazzolini

Runcio

2003

ChemInform

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“…Esta nova rota sintética utilizada [49][50][51] Uma grande vantagem encontrada durante a síntese deste substrato foram os dados referentes à suas propriedades físicas (tabela 13).…”

Section: V8 Rota Alternativa Para a Síntese De Aril-éteres Substituunclassified

Mn(III)porfirinas sintéticas como modelos químicos do Citocromo P-450: a O-desalquilação oxidativa de aril éteres substituídos como modelos de drogas por iodosilbenzeno

Neto¹,

Alberto²

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DedicoAos meus pais, Profa. Dra. Yassuko Iamamoto,Exemplo de verdadeira mestre e cientista, que se destaca no meio universitário pela sua constante preocupação na formação de seus alunos. Agradeço por seu precioso tempo dedicado a minha formação, durante o período que estive em seu laboratório. Sinto-me honrado e feliz pelas oportunidades de aprendizado e constantes discussões científicas que me foram proporcionadas por ela. As palavras são poucas para expressar minha profunda gratidão. Muito obrigado..... AGRADECIMENTOSA Profa. Dra. Yassuko Iamamoto pelas discussões, conselhos e livrearbítrio durante os últimos anos.Ao Prof. Dr. John Lindsay Smith, pelas discussões científicas na realização deste trabalho.A minha irmã Daniela, pela cumplicidade e por ser a única pessoa que sabe como me irritar! Aos meus familiares pelo apoio, incentivo, confiança e amor. Muito obrigado por vocês existirem na minha vida, amo todos vocês.A Dani Dani, pelo companheirismo, estando presente nos bons e maus momentos, sempre atenciosa, compreensiva e me socorrendo sempre que preciso. Muito obrigado. Te amo! Aos meus grandes amigos de longa data do Ensino Médio, Luis Ricardo, Paulo Eduardo, Paulo Domingues, Nunes, Tatu, Leno, Teresa, Amendoim, Aboma, Bleise, Puff, Maria Luiza, Junior, Carolina.Aos meus queridos amigos Deza, Miguel, Ricardo, Leonardo, Nara, Daniela Garçon, Daniele, Tatiana pelo carinho e companheirismo dedicados em todos os anos de convivência em Ribeirão Preto. We initially studied the catalytic oxidation of methyl benzyl ether. All the reactions catalyzed by the various MnPs were selective, and benzaldehyde was the product common to all oxidations. The best reaction condition was catalyst/oxidant/substrate molar ration = 1:50:1224. As for the reactions with the substituted substrates, the catalytic oxidation of p-methoxybenzyl methyl ether by PhIO was not as selective as the ones of methyl benzyl ether, clearlyshowing that the methoxy group affects the reactivity of the original aryl ether.Nevertheless, p-methoxybenzaldehyde was still the main product, being the conversion to p-methoxybenzylic alcohol observed in minor amount. With the substrate p-nitrobenzyl methyl ether, the effect of the electronwithdrawing substituent in the para-position of the aromatic ring could be observed in the final product distribution once again, and total selectivity toward the formation of p-nitrobenzaldehyde to the detriment of p-nitrobenzoic alcohol was observed.In relation to the two last substrates of the proposed series, the methyl p-methylbenzyl and methyl p-chlorobenzyl ethers, the reactions accomplished with p-chlorobenzyl methyl ether were not as selective as the ones carried out with methyl p-nitrobenzyl ether, showing that the chloro group increased the reactivity of the chloro-ether in relation to the ether with the original nitrosubstituent. Even so, p-chlorobenzaldehyde was the main product, being the conversion to the p-chlorobenzylic alcohol observed in smaller amount.Concerning the oxidation reactions of p-methylbenzy...

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Photolysis of (arylmethyl)triphenylphosphonium salts. Substituent, counterion, and solvent effects on reaction products

Cited by 40 publications

References 0 publications

Oxidation of Benzylic Alcohols and Ethers to Carbonyl Derivatives by Nitric Acid in Dichloromethane

Oxidation of Benzylic Alcohols and Ethers to Carbonyl Derivatives by Nitric Acid in Dichloromethane

Oxidation of Benzylic Alcohols and Ethers to Carbonyl Derivatives by Nitric Acid in Dichloromethane.

Mn(III)porfirinas sintéticas como modelos químicos do Citocromo P-450: a O-desalquilação oxidativa de aril éteres substituídos como modelos de drogas por iodosilbenzeno

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