Acylation reaction of hydroxyl group

a technology of acylation reaction and hydroxyl group, which is applied in the preparation of carboxylic acid nitrile, carboxylic acid amides, organic chemistry, etc., can solve the problem of not being able to say that the production method has high economic efficiency, and achieve the effect of efficient production

Inactive Publication Date: 2013-07-25
TAKASAGO INTERNATIONAL CORPORATION
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

This approach enables the selective acylation of hydroxyl groups, producing ester compounds with high efficiency and compatibility for various functional groups, improving economic efficiency and sustainability while avoiding environmental hazards associated with traditional catalysts.

Problems solved by technology

That is to say, in order to obtain an acylated form (ester form) of a hydroxyl group, multiple processes are required for protecting a competing nucleophilic functional group in advance, and then performing esterification and deprotection, and therefore, this cannot be said to be a production method with high economic efficiency.

Method used

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  • Acylation reaction of hydroxyl group
  • Acylation reaction of hydroxyl group
  • Acylation reaction of hydroxyl group

Examples

Experimental program
Comparison scheme
Effect test

example 1

Selective Acylation of 6-aminohexan-1-ol

[0094]In an argon atmosphere, a mixture of methyl benzoate (3.0 mmol), 6-aminohexan-1-ol (3.6 mmol), Zn4(OCOCF3)6O (1.25 mol % in terms of the mole number of zinc atoms; in the following Examples, the amount will be similarly expressed in terms of the mole number of zinc atoms) and diisopropyl ether (5.0 ml) was heated to reflux for 18 hours, and as a result, 6-aminohexyl benzoate having an acylated hydroxyl group was obtained at a yield of 82% (the yield is based on the carboxylic acid ester. The same applies in the following). The yield of 6-benzoylaminohexyl benzoate in which an amino group and a hydroxyl group were both acylated, was 18%.

[0095]6-Aminohexyl benzoate:

[0096]Pale yellow oil:

[0097]1H-NMR (CDCl3, 35° C.) δ

[0098]1.4-1.5 (m, 4H, methylene),

[0099]1.59 (tt, J=7.5, 6.9 Hz, 2H, methylene),

[0100]1.77 (tt, J=7.5, 6.9 Hz, 2H, methylene),

[0101]2.81 (t, J=7.5 Hz, 2H, NHCH2), 3.90 (bs, 2H, NH2),

[0102]4.30 (t, J=6.6 Hz, 2H, OCH2), 7.4-7.6 (m...

example 2

Selective Acylation of 8-aminooctan-1-ol

[0104]In an argon atmosphere, a mixture of methyl benzoate (3.0 mmol), 8-aminooctan-1-ol (3.6 mmol), Zn4(OCOCF3)6O (1.25 mol % in terms of mole number) and diisopropyl ether (5.0 ml) was heated to reflux for 20 hours, and as a result, 8-aminooctyl benzoate was obtained at a yield of 90%. The yield of 8-benzoylaminooctyl benzoate was 7%.

[0105]8-Aminooctyl benzoate:

[0106]Pale yellow crystal: m.p. 60-62° C.

[0107]1H-NMR (CDCl3, 35° C.) δ

[0108]1.3-1.5 (m, 10H, methylene),

[0109]1.76 (tt, J=6.9, 6.9 Hz, 2H, OCH2CH2), 2.10 (bs, 2H, NH2),

[0110]2.68 (t, J=6.9 Hz, 2H, NH2CH2),

[0111]4.31 (t, J=6.9 Hz, 2H, OCH2), 7.4-7.6 (m, 3H, Ph),

[0112]8.0-8.1 (m, 2H, Ph)

example 3

Selective Acylation of 10-aminodecan-1-ol

[0113]In an argon atmosphere, a mixture of methyl benzoate (3.0 mmol), 10-aminodecan-1-ol (3.6 mmol), Zn4(OCOCF3)6O (1.25 mol % in terms of mole number) and diisopropyl ether (5.0 ml) was heated to reflux for 20 hours, and as a result, 10-aminodecyl benzoate was obtained at a yield of 90%. The yield of 10-benzoylaminodecyl benzoate was 7%.

[0114]10-Aminodecyl benzoate:

[0115]Pale yellow crystal: m.p. 68-70° C.

[0116]1H-NMR (CDCl3, 35° C.) δ

[0117]1.3-1.5 (m, 16H, methylene, NH2),

[0118]1.76 (tt, J=6.6, 6.6 Hz, 2H, OCH2CH2),

[0119]2.67 (t, J=6.6 Hz, 2H, NH2CH2).

[0120]4.31 (t, J=6.6 Hz, 2H, OCH2), 7.4-7.5 (m, 3H, Ph),

[0121]8.0-8.1 (m, 2H, Ph)

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Abstract

Disclosed is a selective ester production process of an alcoholic hydroxyl group, which proceeds under chemically mild conditions, while having adequate environmental suitability, operability and economical efficiency. Specifically disclosed is a process for producing an ester compound, which is characterized in that an alcohol and a carboxylic acid ester compound are reacted in the presence of a compound containing zinc element, thereby selectively acylating a hydroxyl group of the alcohol.

Description

TECHNICAL FIELD[0001]The present invention provides a process for producing an ester compound by performing a transesterification reaction in the presence of a catalyst containing zinc element.BACKGROUND ART[0002]Ester compounds are abundantly found in nature, as well as in medicines, agrochemicals, perfumes, functional materials and the like. In the syntheses of these materials, reactions between corresponding alcohols and carboxylic acids, carboxylic acid chlorides, carboxylic acid anhydrides and the like, or trans-esterification reactions making use of ester compounds are widely used. A series of methods play an important role not only for the purpose of producing ester compounds, but also as a method for protecting a hydroxyl group or a carboxyl group.[0003]A method of using an ester compound derived from a low boiling point alcohol as an acylating agent (transesterification reaction) can be said to be a technique excellent in operability and economic efficiency from the aspect ...

Claims

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Application Information

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Patent Type & AuthorityApplications(United States)
IPC IPC(8): C07D213/55C07C67/08C07D211/34
CPCC07C67/03C07D213/55C07C231/02C07C253/30C07C2101/14C07C2102/08C07C2102/10C07D295/195C07C213/06C07D211/34C07C67/08C07C69/618C07C69/24C07C69/612C07C69/76C07C69/78C07C219/14C07C219/18C07C219/22C07C233/69C07C233/73C07C255/57C07C2601/14C07C2602/08C07C2602/10
InventorMASHIMA, KAZUSHIOHSHIMA, TAKASHIIWASAKI, TAKANORISAYO, NOBORU
OwnerTAKASAGO INTERNATIONAL CORPORATION