The reaction of hypochlorous acid with olefins. A convenient synthesis of allylic chlorides

Hegde, Shridhar G.; Vogel, Martin K.; Saddler, J. C.; HRINYO, T.; Rockwell, Ned; HAYNES, R.; Oliver, M. M.; Wolinsky, Joseph

doi:10.1016/s0040-4039(00)71427-4

Cited by 69 publications

(18 citation statements)

References 17 publications

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“…[12][13][14][15][16] This investigation shows clearly the role of MoCl 5 /NaOCl system in the activation and orientation of the reaction toward the desired product.…”

Section: Resultsmentioning

confidence: 98%

“…15 CeCl 3 or InCl 3 combined with NaOCl have been reported as efficient systems for allylic chlorination of terminal olefins. [12][13][14][15][16] In line with our continuous interest in the functionalization of natural terpenic olefins, [5][6][7] we report here the result of our investigation on the allylic chlorination using a combination of sodium hypochlorite and molybdenum pentachloride.…”

Section: Introductionmentioning

confidence: 99%

“…[8][9][10][11] Chloride compounds can be prepared directly by bubbling molecular chlorine, but the difficulty of handling chlorine gas limits this procedure. 12 Other authors have shown a convenient method for this transformation using solid CO 2 and calcium hypochlorite 13,14 or a combination of Vilsmeier reagent and H 2 O 2 . 15 However, this procedure is limited to non acid-sensitive substrates.…”

Section: Introductionmentioning

confidence: 99%

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Allylic chlorination of terpenic olefins using a combination of MoCl5 and NaOCl

Boualy¹,

Firdoussi²,

Ali³

et al. 2011

J. Braz. Chem. Soc.

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MoCl 5 é usado como eficiente agente na cloração alílica de olefinas terpênicas na presença de NaOCl como doador de cloro. Vários terpenóides são convertidos aos cloretos de alila correspondentes em moderados a bons rendimentos em condições reacionais brandas e otimizadas. Diferentes precursores de molibdênio são estudados. Dentre eles, MoO 3 fornece bom rendimento, mas depois de um tempo de reação maior.MoCl 5 is applied as efficient agent in allylic chlorination of terpenic olefins in the presence of NaOCl as chlorine donor. Various terpenes are converted to the corresponding allylic chlorides in moderate to good yield under mild and optimized reaction conditions. Different molybdenum precursors are also studied. Among them, MoO 3 gives good yield, but after a longer reaction time.

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“…[12][13][14][15][16] This investigation shows clearly the role of MoCl 5 /NaOCl system in the activation and orientation of the reaction toward the desired product.…”

Section: Resultsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Allylic chlorination of terpenic olefins using a combination of MoCl5 and NaOCl

Boualy¹,

Firdoussi²,

Ali³

et al. 2011

J. Braz. Chem. Soc.

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“…The Wolinsky reaction of 4 (using a two-phase solvent system and hypochlorous acid) yielded the chlorohydrin 5 as the major product, but the chloride 6 could be isolated from the mixture by distillation in about 25% yield. Believing that the favouring of the chlorohydrin was because of the increased water solubility of the esters over the hydrocarbons used by Wolinsky [4], we attempted to lower the solubility in the aqueous phase by adding salt, but there was a negligible effect on the yield of 6. Treatment of 6 with tiglic acid and sodium ethoxide in ethanol at reflux gave slow conversion to the ester 3 (R' = tiglyl, R2 = (CH&CHCO).…”

Section: Discussionmentioning

confidence: 99%

The Occurrence of Some Novel Diesters in Roman Camomile Oil

Thomas

1981

Helvetica Chimica Acta

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SummaryThree diols, 2-methylidene-l , 3-propanediol, 2-methyl-l , 3-propanediol and 1,3-butanediol, esterified on one hydroxyl group with isobutyric acid and on the other with angelic acid'), have been isolated from Anthemis nobilis oil (Roman camomile) and synthesized. The presence of homologous esters is very probable.In previous publications [ 11 [ 2 ] , we presented some of our results on the analysis of the oil of Roman camomile (Anthemis nobilis). We now describe the isolation and synthesis of three diesters 1-3 (R' = angelyl'), R2 = (CH3),CHCO), and suggest that other similar esters are present, notably the homologue 1, with R' = angelyl and R2= CH3CH2CH(CH3)C0. These esters contribute to the odour of the oil.Work-up of the oil was described in the foregoing publication [2], and the diesters now described occurred in the fraction which was slightly more polar than the one containing the unsaturated ketones discussed there. All these compounds have approximately the same volatility, and 1-3 (R' = angelyl, R2= (CH3)2CHCO) were eluted in that order from a Carbowax gas chromatography (GC.) column.Clearly 1 and 2 are chiral (when R' and R2 are different in the case of 2), and sufficient of 1 (R' = angelyl, R2= (CH&CHCO) was available to show that the natural product was laevorotatory. The identification of all the esters was by 'H-NMR. and i i i , r \ \ spectrometn (MS.; see exper. part). In the 360-MHz-'H-NMR. spectrum of 3 (R' = angelyl, R2= (CH,),CHCO) a doublet at 1.27 ppm was observed indicating the presence of an impurity. This doublet is at the same position as that of the methyl group in the butanediol part of 1 (R'= angelyl, R2= (CH&CHCO). In this impurity there appeared to be another methyl group giving rise to a triplet at 0.90, and we suggest that the presence of the homologue 1 (R'=angelyl,

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“…A feasible procedure for this purpose was reported by Wolinsky and co-workers, using solid CO 2 and calcium hypochlorite. 14,15 As an alternative, Li and co-workers employed a combination of the Vilsmeier reagent and H 2 O 2 in the synthesis of eudesmane acids, but the presence of POCl 3 excludes the use of acid-sensitive substrates. 16 Recently, Massanet and co-workers, described the preparation of allylic chlorides by reaction of terminal olefins with sodium hypochlorite in the presence of cerium trichloride heptahydrate as an ene-type reaction.…”

Section: Introductionmentioning

confidence: 99%

InCl3/NaClO: A reagent for allylic chlorination of terminal olefins

Pisoni¹,

Gamba²,

Fonseca³

et al. 2006

J. Braz. Chem. Soc.

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Tricloreto de índio na presença de hipoclorito de sódio promove a cloração alílica de olefinas terminais em meio bifásico (diclorometano/água) com bons rendimentos. Para estabelecer um procedimento geral, escolheu-se a carvona como composto modelo e otimizou-se a estequiometria, temperatura, e tempo de conversão para o respectivo cloreto alílico. Tratando-se β-pineno com tricloreto de índio/hipoclorito de sódio obteve-se seletivamente o cloreto perílico, um precursor importante para a obtenção de derivados de limoneno oxigenados no carbono C-7.Indium trichloride promotes the chlorination of terminal olefins in the presence of sodium hypochlorite with good results. Carvone was chosen as a model compound to examine some of the general features of this reaction, such as stoichiometry, temperature, reaction time and product conversion. Treatment of β-pinene with sodium hypochlorite in the presence of indium trichloride resulted in a facile rearrangement to selectively yield perillyl chloride, which is an important precursor for C-7 oxygenated limonenes.

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The reaction of hypochlorous acid with olefins. A convenient synthesis of allylic chlorides

Cited by 69 publications

References 17 publications

Allylic chlorination of terpenic olefins using a combination of MoCl5 and NaOCl

Allylic chlorination of terpenic olefins using a combination of MoCl5 and NaOCl

The Occurrence of Some Novel Diesters in Roman Camomile Oil

InCl3/NaClO: A reagent for allylic chlorination of terminal olefins

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