1006. Some addition reactions of β-pinene derivatives

Hartshorn, MP; Wallis, A. F. A.

doi:10.1039/jr9640005254

Cited by 35 publications

(29 citation statements)

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“…Chemicals were of reagent-grade quality and were obtained commercially. Pinocarvone was prepared using procedure reported previously [35]. 4-Methylthiazole, benzothiazole and 2-acetylthiazole were purchased from Aldrich and used as received.…”

Section: General Methodsmentioning

confidence: 99%

New chiral bidentate ligands containing thiazolyl and pyridyl donors for copper-catalyzed asymmetric allylic oxidation of cyclohexene

Teng

Tsang

Yeung

et al. 2006

Journal of Organometallic Chemistry

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Section: General Methodsmentioning

confidence: 99%

New chiral bidentate ligands containing thiazolyl and pyridyl donors for copper-catalyzed asymmetric allylic oxidation of cyclohexene

Teng

Tsang

Yeung

et al. 2006

Journal of Organometallic Chemistry

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“…Finally, the products which result from oxidative attack on the double bond were found to be pinocamphone (2), pinocarveol (12), campholenaldehyde (13), and pinol (14). All of these are the products from initial attack on the C-2 position of a-pinene followed by rearrangements.…”

Section: Traduit Par Le Journal]mentioning

confidence: 99%

“…The rearrangement of oxides to the corresponding ketones with Lewis acids is a common preparative procedure (12). Acid-catalyzed opening of the epoxide also readily leads to pinocarveol (12) (13). The treatments of a-pinene oxide with zinc bromide (14) or p-toluenesulfonic acid (15) are both known to give campholenaldehyde (13) along with other products including p-cymene (7).…”

Section: Traduit Par Le Journal]mentioning

confidence: 99%

The Chromyl Chloride Oxidation of α-Pinene

Bachelor¹,

Cheriyan²

1972

Can. J. Chem.

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The oxidation of α-pinene with chromyl chloride has been investigated and 11 compounds amounting to 81% of the total reaction have been isolated and identified. Besides a small amount of recovered α-pinene these compounds have been found to be products of acid-catalyzed rearrangement (bornyl chloride, borneol, and limonene); products of allylic oxidation (myrtenal, myrtenol, and verbenone); and products of oxidative addition–rearrangement (pinocamphone, pinocarveol, campholenaldehyde, and pinol). In addition, p-cymene was isolated which may arise from several oxidation sequences. The isolation of optically active pinol suggests that at least part of the oxidation of α-pinene is initiated by attack of the chromyl chloride on the same side of the double bond as the dimethyl substituted bridge. An attack by a positive chromium atom on the double bond is ruled out by a deuteration study.

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“…Therefore, their spectral characteristics were taken as the mixture. Spectral data for the 6-endo-isomer are known because it was obtained earlier via isomerization of 3-endo-bromocamphor and oxidation of 6-endo-Br-isoborneol, which was prepared via the reaction of cis-pinocarveol and HBr [13,14]. Bromination of 2, which was prepared beforehand via 1,4-conjugate reduction of verbenone, using CuBr 2 produced an even more complicated product mixture than that of 1.…”

mentioning

confidence: 99%

Several Monoterpenoid Bromination Products

et al. 2014

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Keywords: terpenoids, bromination, mono-and dibromo-derivatives, Meldrum's acid dibromide, oxidative brominating system.D-Dicarbonyl compounds have recently become interesting for broader application in organic synthesis because of their high reactivity. They are used to prepare aliphatic, aromatic, and heterocyclic low-and high-molecular-weight products with an array of valuable properties. Thus, several heterocyclic compounds such as imidazoles, quinoxalines, and pyrazines, i.e., a unique class of chiral N,N-coordinated ligands that are widely used in asymmetric synthesis [1,2], in addition to quinoline derivatives that usually exhibit various biological and pharmacological activities [3,4] were synthesized from terpene D-diketones.Oxidation of the corresponding D-bromoketones is one method for synthesizing D-diketones. The oxidation of 3-endo-bromocamphors by O 2 or air in aprotic polar solvents in the presence of NaI or KI to form camphoroquinone in high yield is well known [5,6]. In a similar manner, the cyclic D-diketones 1,2-cyclooctanedione and 1,2-cyclododecanedione were synthesized in 65-71% yield from D-bromoketones [7]. It was recently shown that biotransformation of D-bromo-and D,Dc-dibromoketones formed highly selectively D-hydroxyketones and diketones, respectively [8].The goal of the present work was to synthesize secondary D-bromoketones from isopinocamphone (1), cis-verbanone (2), and menthone (3) for possible further transformation into the corresponding D-diketones. The brominating reagents were Br 2 , CuBr 2 , Meldrum's acid dibromide, and the oxidative-brominating system Ce(III)-LiBr-H 2 O 2 .Attempted monobromination of isopinocamphone by Br 2 in AcOH (ketone-Br 2 mole ratio 1:1) formed mainly dibromoderivative 4 and monobromo-derivative 5 in yields of 48 and 12%, respectively, according to GC. Furthermore, the reaction products included pinocamphone (15%) and an insignificant (~2%) amount of 6. 2D,4D-Dibromopinanone-3 (4) was isolated by column chromatography over silica gel as a crystalline product. Br O Br + Br O + O Br 4 5 6 OH O a 7 1 b c 5 + 4 1 + + O Br d 9 Br O 8 Mixture of compounds a. Br 2 ; b. CuBr 2 ; c. Meldrum's acid dibromide; d. Ce(NO 3 ) 3 -LiBr-H 2 O 2

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1006. Some addition reactions of β-pinene derivatives

Cited by 35 publications

References 0 publications

New chiral bidentate ligands containing thiazolyl and pyridyl donors for copper-catalyzed asymmetric allylic oxidation of cyclohexene

New chiral bidentate ligands containing thiazolyl and pyridyl donors for copper-catalyzed asymmetric allylic oxidation of cyclohexene

The Chromyl Chloride Oxidation of α-Pinene

Several Monoterpenoid Bromination Products

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