The Photoanilide Rearrangement

Elad, D.; Rao, Durvasula V.; Stenberg, Virgil I.

doi:10.1021/jo01020a536

“…benzanilide have been previously reported (1,2), although product analyses were only made after For personal use only.…”

Section: Ch3-(and!j--443mentioning

confidence: 99%

“…In the presence of dissolved oxygen, aniline and o-toluidine are probably destroyed by the attack of peroxy radicals generated from the solvent after benzoyl or anilino radical attack (14). Previous work has indicated that the prolonged photolysis of 1 with a full mercury arc in N2-saturated ethanol gave only low yields of the 2-and 4-aminobenzophenones (-14% of each based on the amount of 1 consumed), together with a trace amount of aniline and a higher yield of benzoic acid (27% of 1 consumed) for a 32% loss of 1 (1). This earlier work can be reconciled with our data if trace amounts of 0, were present in the previous workers' system, so that C6H,C0 interception by 0, to give benzoic acid as a final product could have occurred, together with extensive secondary photolysis of the aminobenzophenones.…”

Section: Vol 53 1975mentioning

confidence: 99%

The Photolyses of Fully Aromatic Amides

Carlsson¹,

Gan²,

Wiles³

1975

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The 254 nm photolyses of ethanol solutions of four fully aromatic amides were followed by liquid chromatography and u.v. spectroscopy, and quantum yields for the major products calculated. The photolysis of benzanilide was examined in detail at various wavelengths and in several solvents, both in the presence and absence of oxygen. Quantum yields for 2- and 4-aminobenzophenones and products from free radical precursors decreased with increasing solvent polarity and with increasing incident wavelength of irradiation. Oxygen had no affect on aminobenzophenone formation but produced benzoic acid from free radical fragments which escaped the solvent cage. The results are tentatively interpreted in terms of an energy dependent radiationless conversion to a reactive 1π*-carbonyl which then cleaves the N—C bond to give caged free radicals, rather than by a concerted, nonradical rearrangement.

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“…

Two years ago, Woodward and Hoffmann presented an ingenious theory in an attempt to interpret the stereochemical cours of the so-called "electrocyclic" and "sigmatropic" transformations.1) They suggested1b) that the photo-Claisen rearrangement reported to give a para-rearrangernent product2) would serve as an example of the [3,5] sigmatropic transformation.Another example of the photo-Claisen rearrangement had previously been reported to give only a pararearrangement product.3)Although this interpretation of the photo-Claisen rearrangement was highly attractive, the following facts seemed to us conflicting enough to warrant a thorough reinvestigation of the photo-rearrangement of allyl phenyl ethers:(1) An eight-membered cyclic transition state these systems seems sterically impossible.(3) Several related systems, phenyl esters,4) acyl anilides,5) phenoxyacetic acid,6) and ethyl phenyl carbonate,7) have been reported to rearrange photochemically to ortho-and para-rearrangement products.The recent publication of a communication8) dealing with an investigation closely related to ours prompts us to publish our own results.

ExperimentalMaterials. The allyl phenyl ethers for the photoreaction were purified by rectification until no appreciable impurity was observed by glc.

Reaction Procedure.

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mentioning

confidence: 99%

“…Two years ago, Woodward and Hoffmann presented an ingenious theory in an attempt to interpret the stereochemical cours of the so-called "electrocyclic" and "sigmatropic" transformations.1) They suggested1b) that the photo-Claisen rearrangement reported to give a para-rearrangernent product2) would serve as an example of the [3,5] sigmatropic transformation.…”

mentioning

confidence: 99%

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Photo-Claisen Rearrangement. The Photochemical Rearrangement of Allyl Phenyl Ethers

Koga¹,

Kikuchi²,

Koga³

1968

Bulletin of the Chemical Society of Japan

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Two years ago, Woodward and Hoffmann presented an ingenious theory in an attempt to interpret the stereochemical cours of the so-called "electrocyclic" and "sigmatropic" transformations.1) They suggested1b) that the photo-Claisen rearrangement reported to give a para-rearrangernent product2) would serve as an example of the [3,5] sigmatropic transformation.Another example of the photo-Claisen rearrangement had previously been reported to give only a pararearrangement product.3)Although this interpretation of the photo-Claisen rearrangement was highly attractive, the following facts seemed to us conflicting enough to warrant a thorough reinvestigation of the photo-rearrangement of allyl phenyl ethers:(1) An eight-membered cyclic transition state these systems seems sterically impossible.(3) Several related systems, phenyl esters,4) acyl anilides,5) phenoxyacetic acid,6) and ethyl phenyl carbonate,7) have been reported to rearrange photochemically to ortho-and para-rearrangement products.The recent publication of a communication8) dealing with an investigation closely related to ours prompts us to publish our own results. ExperimentalMaterials. The allyl phenyl ethers for the photoreaction were purified by rectification until no appreciable impurity was observed by glc.Reaction Procedure. A 5% solution of a sample in isopropyl alcohol was irradiated with an immersiontype 10W low-pressure mercury lamp (Ricoh Kagaku Sangyo Co., UVL300Q) under a nitrogen atmosphere. After irradiation, most of the solvent was removed under reduced pressure, and the residual mixture was analyzed by glc.Identification of Products. o-and p-Allylphenols, 2-allyl-3,5-dimethylphenol, trans-o-and -p-but-2-enylphenols, and o-and p-(1-methyl-prop-2-enyl)phenols were identified by a comparison of their retention times with those of authentic sample. 4-Allyl-3,5-dimethylphenol was isolated from the reaction mixture by means of preparative glc and was identified spectrometrically. Two unknown peaks in the gas chromatogram of the reaction mixture from traps-but-2-cnyl phenyl ether were tentatively assigned to cis-o-and -p-but-2-enylphenols on the basis of their having been formed by the irradiation of their trans-isomers.Analyses. The samples were analyzed by the use of a Hitachi K-23 gas chromatograph. A 1-meter Celite-545 (60-80mesh) column with 33% Silicon KF-54 was used. The results in the table are given as the percentage ratio of the peak area. Results and DiscussionAs shown in the table, all the compounds rearranged to give ortho-and para-rearrangement products in addition to the parent phenols of the starting ethers. Some unidentified products were also present. trans-But-2-enyl phenyl ether was shown to give o-and p-but-2-enyl and o-and p-(1-methylprop-2-enyl)phenols.The results are consistent with those of Schmid2) and clearly indicate that the rearrangement does not proceed *1 A preliminary account of this investigation has been presented at

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