The Hydration and Cyclization of some Divinylacetylenes

Hennion, G. F.; Davis, Richard A.

doi:10.1021/jo50002a017

Cited by 8 publications

(5 citation statements)

References 4 publications

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“…Ozonization of 4,5,5-trimethyl-2-cyclopenten-l-one followed by oxidation with nitric acid gave trimethylsuccinic acid (238). Similarly, the corresponding succinic acid derivatives were obtained in good yields from other substituted cyclopentenones (308), and isophorone, a cyclohexenone, may be cleaved to a,«-dimethylsuccinic acid (231).…”

Section: Comparable Results Have Also Been Obtained With the Substitu...mentioning

confidence: 92%

Syntheses Of Alkylated Alkanedioic Acids

Diaper¹,

KUKSIS²

1959

Chem. Rev.

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example of such a synthesis is the conversion of 2-pentenal, through a Reformatsky condensation with ethyl -bromopropionate and oxalation of the unsaturated product, eventually to 2,6-dimethylsuberic acid (401).It has been shown that formates and oxalates may function as carbonyl components in a Reformatsky synthesis. Ethyl -bromoisobutyrate reacts with ethyl oxalate (569) and with ethyl formate (82), giving hydroxy esters which could be converted to 2,2-dimethylsuccinic and 2,2,4,4-tetramethyIglutaric acids, respectively.The application of the Reformatsky reaction to nitriles (154) leads to the formation of ketones in a manner comparable with the Grignard reaction and is a convenient method for the synthesis of /3-keto esters.By varying the nature of the carbonyl compounds and the halo esters employed, many alkylated dicarboxylic acids have been prepared with the help of this reaction, yet the possible products may be of only a few types. Branching is confined to the a-and ß-positions at one or both ends of the chain, and while the -position may bear one, two, or no alkyl groups, the /3-position cannot bear more than one side chain.Theoretically, in all of the above cases the ester groups of the final products may be converted into aldehyde or keto groups through the acyl chlorides and dialkyl metals (142).A repetition of the Reformatsky process would lengthen the chain with or without further branching at the new points of junction of carbon chains (629).

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Section: Comparable Results Have Also Been Obtained With the Substitu...mentioning

confidence: 92%

Syntheses Of Alkylated Alkanedioic Acids

Diaper¹,

KUKSIS²

1959

Chem. Rev.

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“…showed it to be 3,4-dichloro-23-dimethyl-2,4-hexadiene (6) and not the corresponding 1,3-dichloro compound as earlier considered (8).4 Treatment of 6 with hot 85% sulfuric acid gave 7.…”

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confidence: 86%

“…de l'acide polyphosphorique chaud, suivie par un piCgeage avec de l'eau, conduit aux produits suivants : l'hydroxy-2 dimethyl-2,5 hexkne-4 one-3 (3), la trimithyl-2,4,4 cyclopentkne-2 one-1 (7), la trimethyl-3,5,5 cyclopentkne-2 one-1 (8), le tetrahydro tCtramCthy1-3,4,5,5 furannediol-2,3 (11), le dihydro-2,5 trimethyl-3,5,5 mCthyl6ne-2 furanne (17) There have been many investigations of the reactions of organic compounds with strong acids (3,4). Several of these have concerned substrates with saturated or unsaturated carbony1 functions.…”

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confidence: 99%

Keto ethers. IV. Products formed on reaction of dihydro-2,2,5,5-tetramethyl-3(2H)-furanone with strong acids

Yates¹,

Burke²

1987

Can. J. Chem.

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Can. J. Chem. 65, 1695Chem. 65, (1987. Reaction of tetrahydro-2,2,5,5-tetramethyl-3(2H)-furanone (1) with 96 or ca. 100% sulfuric acid or hot polyphosphoric acid followed by aqueous quenching gave the following products: 2-hydroxy-2,5-dimethyl-4-hexen-3-one (3), 2,4,4-trimethyl-2-cyclopenten-1-one (7), 3,5,5-trimethyl-2-cyclopenten-1-one (8), tetrahydro-3,4,5,5-tetramethylfuran-2,3-diol ( l l ) , 2,5-dihydro-3,5,5-trimethyl-2-methylenefuran (17) and its dimer 20, 2,5-dihydro-2,3,5,5-tetramethyl-2-furanol (IS), 4-hydroxy-2,4-dimethyl-2-pentenoic acid y-lactone (22), 2,3,5-trimethyl-2-cyclopenten-1-one (23), and tetramethylfuran (25). In 96% sulfuric acid the products arise by ring opening, ring opening followed by reclosure to carbocyclic products, methyl migration from C-2 to C-3 to give rearranged furan derivatives, and oxidation. Inca. 100% sulfuric acid or hot polyphosphoric acid further methyl migrations can occur to give 23 and 25.PETER YATES et PATRICK MICHAEL BURKE. Can. J. Chem. 65, 1695Chem. 65, (1987.La reaction de la tetrahydro tCtramCthyl-2,2,5,5 2H-furannone-3 (1) avec de I'acide sufurique a 96 ou t i environ 100% ou avec de l'acide polyphosphorique chaud, suivie par un piCgeage avec de l'eau, conduit aux produits suivants : l'hydroxy-2 dimethyl-2,5 hexkne-4 one-3 (3), la trimithyl-2,4,4 cyclopentkne-2 one-1 (7), la trimethyl-3,5,5 cyclopentkne-2 one-1 (8), le tetrahydro tCtramCthy1-3,4,5,5 furannediol-2,3 (11), le dihydro-2,5 trimethyl-3,5,5 mCthyl6ne-2 furanne (17) There have been many investigations of the reactions of organic compounds with strong acids (3, 4). Several of these have concerned substrates with saturated or unsaturated carbony1 functions. Less attention has been paid to carbonyl compounds containing other functional groups. We report on an investigation of the variety of reactions undergone by the keto ether 1 in strongly acidic media.3 We describe here the isolation and determination of the structures of the products formed in such reactions and plan, in a subsequent publication, to discuss the formation of these products in terms of the site(s) of protonation of 1 and the nature of the cationic intermediates.Compound 1 is readily available from the ynediol 2 (6). Reactions in strongly acidic media followed by aqueous quenching gave mixtures of products whose composition was dependent on both the nature of the medium and the time of reaction. These products were isolated by standard procedures and identified by their spectra (Tables 1 and 2) and by comparison in most cases with independently synthesized samples.Vapor phase chromatographic (vpc) analyses of product mixtures from 96% sulfuric acid showed that one compound was formed rapidly and that the amount of this product reached a maximum after 2 h and then fell to zero after several days. This compound was shown to be 3 by comparison with an authentic

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“…The above crude dichloro compound (162 g) was cyclised with 850/0 sulphuric acid as described by Henni.on and Davis [2] except that the product was removed after the reaction by steam distillation at 200 mm. 3-0xo-2, 2, 4-trimethylcyclopentanecarboxylic acid (IX, R =C0 2 ll) a.…”

Section: 4 4-trimethylcyclopent-2-enone (V)mentioning

confidence: 99%

“…The preparation of 2,2, 4-trimethylcyclopent-2-enone (V), a possible starting material, has been described by Rennion and Davis [2] and by Nazarov and Bukhmutskaya [3]. The former group of workers showed that the dienyne (III), on treatment with aqueous hydrochloric acid in the presence of cuprous and ammonium chlorides, gave a dihydrochloride, formulated by them as having structure (VI).…”

Section: Mementioning

confidence: 99%