Conversion of 2,3-Butylene Glycol to 1,3-Butadiene by Pyrolysis of Diacetate

Morell, Sam; Geller, H. H.; Lathrop, Elbert C.

doi:10.1021/ie50429a024

Cited by 16 publications

(8 citation statements)

References 8 publications

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“…Crowder and Elrn (4) found that p)-rolysis of both hydroxyacyloxy and diacyloxy stearic acid as well as the epoxy compo~~ncl yielded varying amounts of the conjugated diene. This is in agreement with others (14).…”

Section: Introductionsupporting

confidence: 94%

Hydroxylation and Epoxidation of Rapeseed Oil Derivatives With Subsequent Pyrolysis and Ammonolysis

Mageli¹,

Patteson²,

Spencer³

1953

Can. J. Chem.

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A method was developed to follow the hydroxylation of rapeseed oil and erucic acid derivatives with peracetic acid. Peracetic acid prepared insitu was found to be equally as effective as the preformed acid in hydroxylation of methyl erucate. Among the compounds synthesized were ethyl 13,14-dihydroxybehenate, methyl 13,14-oxidoerucate, ethyl 13,14-diacetoxybehenate, and methyl 13,14(14,13)-hydroxyacetoxybehenate which were subsequently pyrolyzed at approximately 300 °C with p-toluenesulphonic acid as catalyst. The first compound yielded mainly the corresponding ketone with a small amount of the oxido derivative, the chief product of the second compound was also the ketone with some unsaturated material, the third compound yielded 43% of the diene, while the last one yielded 60%. Ammonolysis of the oxido compound or the bromohydrin to yield the corresponding aminohydroxy derivative under pressure with liquid ammonia and ammonium bromide was unsuccessful. A new compound oxidoerucamide, m.p.101.5°, was synthesized.

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Section: Introductionsupporting

confidence: 94%

Hydroxylation and Epoxidation of Rapeseed Oil Derivatives With Subsequent Pyrolysis and Ammonolysis

Mageli¹,

Patteson²,

Spencer³

1953

Can. J. Chem.

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“…Thus, a diester of 2,3-BDO, synthesized by an esterification process, can lead to 1,3-BDE with really good yields (about 90%) by pyrolysis without any catalyst. The esterification using a homogeneous catalyst was studied in 1945 under the Synthetic Rubber Program (SRP). − In this work, the esterification reaction between 2,3-BDO and acetic acid (AA) is discussed using a heterogeneous catalyst.…”

Section: Introductionmentioning

confidence: 99%

Kinetics Modeling of the Heterogeneously Catalyzed Esterification of 2,3-Butanediol with Acetic Acid

Richard

Denis

Jacquin

2016

Ind. Eng. Chem. Res.

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Esterification of 2,3-butanediol using a homogeneous catalyst was studied in 1945 under the Synthetic Rubber Program. The aim of this paper is to show that this reaction can be carried out with a heterogeneous catalyst, which presents many advantages such as the possibility of separation and recycling. The kinetic behavior of heterogeneous esterification of 2,3-butanediol with acetic acid over an ion-exchange resin Amberlyst 36 was investigated in a batch reactor. The experiments were conducted with different amounts of catalyst (from 1.1% to 4.4%, relatively to the initial molar quantity of 2,3-butanediol), with molar ratios of reactants (acetic acid to 2,3-butanediol) varying from 2 to 12, and at temperatures from 50 to 110 °C. Our experimental system was able to acquire kinetic data, even during the first minutes of the reaction. A simple model based on reliable hypotheses was built and the experimental data were used to determine all the kinetic and thermodynamic constants of the reaction. A single set of parameters is able to represent correctly the evolution of all different species present during the esterification reaction in function of time.

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“…. B.p [64][65] . v,,,(film)/cm-* 3349 (OH) and 2246( C g ) ; G(CDC1,) 4.46 (1 H, dq, J 1.7 and 6.5, CHOH), 2.52 (1 H, d septet, J 1.7 and 6.8, CHMe,), 2.20 (1 H, s, OH), 1.37(3 H, d, J6.5, MeCHOH), and 1.11 (6 H, d, J6.8, Me,CH); m/z 111 (2%, M -H), 97 (100, M -Me) and 69 (92, M -C3H7) (Found M + -H, 11 1.0808.…”

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confidence: 99%

A regioselective and stereospecific synthesis of allylsilanes from secondary allylic alcohol derivatives

Fleming¹,

Higgins²,

Thomas³

1992

J. Chem. Soc., Perkin Trans. 1

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Primary and secondary allylic acetates and bentoates react with the dimethyl (pheny1)silyl -cuprate reagent to give allylsilanes, provided that the THF in which the cuprate is prepared is diluted with ether before addition of the allylic ester. The reaction is reasonably regioselective in some cases: (i) when the allylic system is more-substituted at one end than the other, as in the reactions 4-5 and 9 --+ 10; (ii) when the steric hindrance at one end is neopentyl-like, as in the reactions 15 -+ 16;and (iii) when the disubstituted double bond has the 2 configuration, as in the reactions Z-19-+ E-21 or, better, because the silyl group is becoming attached to the less-sterically hindered end of the allylic system, Z-20-+ 2-22. The regioselectivity is better if a phenyl carbamate is used in place of the ester, and a three-step protocol assembling the mixed cuprate on the leaving group is used, as in the reactions 23 -+ 24 and E-or 2-29 + E-21, or, best of all, because the silyl group is again becoming attached to the less-sterically hindered end of the allylic system, E-or 2-30-E-22. This sequence works well t o move the silyl group onto the more substituted end of an ally1 system, but only when the move is from a secondary allylic carbamate t o a tertiary allylsilane, as in the reaction 38 + 39. Allyl(trimethyl)silanes can be made using alkyl-or aryl-cuprates on trimethylsilyl-containing allylic esters and carbamates, as in the reactions 40 -+ 41, and 43 + 44. The reaction of the silylcuprate with allylic esters and the three-step sequence with the allylic carbamates are stereochemically complementary, the former being stereospecifically anti and the latter stereospecifically syn. Homochiral allylsilanes can be made by these methods with high levels of stereospecificity, as shown by the synthesis of the allylsilanes 54,58 and 59.Allylsilanes undergo electrophilic substitution reactions regiospecifically in the SE2' sense,' and stereospecifically in an anti sense, as shown, principally, by the work of Wetter,' Es~henmoser,~ Kumada? Kitching and ourselves.6 To take full advantage of the highly stereospecific and regiospecific reactions of allylsilanes, and anticipating a need to test whether the osmylation, epoxidation, Simmons-Smith r e a~t i o n ,~ hydroboration * and protodesilylation ' of allylsilanes, reported in the three preceding papers to this one, might be similarly well controlled, we sought new ways of making allylsilanes. There are, of course, many ways of making allylsilanes," but it was imperative that the new routes should be both regiocontrolled and stereocontrolled, for which there were no general methods. In this paper and that following, we describe two such routes, the first using allylic alcohols as substrates, and the second using diastereoselective aldol reactions followed by stereospecific decarboxylative eliminations. ' We have reported some of the present work using allylic alcohol derivatives in two preliminary communications. 'We had already established13 a simple synthesis of allylsilan...

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Conversion of 2,3-Butylene Glycol to 1,3-Butadiene by Pyrolysis of Diacetate

Cited by 16 publications

References 8 publications

Hydroxylation and Epoxidation of Rapeseed Oil Derivatives With Subsequent Pyrolysis and Ammonolysis

Hydroxylation and Epoxidation of Rapeseed Oil Derivatives With Subsequent Pyrolysis and Ammonolysis

Kinetics Modeling of the Heterogeneously Catalyzed Esterification of 2,3-Butanediol with Acetic Acid

A regioselective and stereospecific synthesis of allylsilanes from secondary allylic alcohol derivatives

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