Manufacturing method of optical activity alcohol

An optically active, polar solvent technology, applied in the field of preparation of optically active alcohols, can solve the problems of low yield or enantiomeric excess, difficulty in preparing optically active alcohols, etc.

Inactive Publication Date: 2007-03-07
KANTO CHEM CO INC +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] However, using the catalyst disclosed in Japanese Patent Laid-Open No. 2003-104993, although an optically active alcohol can be obtained from a ketone compound in the absence of a base, the yield or enantiomeric excess is low due to the reaction substrate.
In addition, the organic base triethylamine in Japanese Patent Laid-Open No. 11-322649 is necessary, so it is difficult to prepare optically active alcohols from reaction substrates that are unstable in bases such as acetylenone.

Method used

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  • Manufacturing method of optical activity alcohol
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  • Manufacturing method of optical activity alcohol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0070] An example of synthesizing (S)-4-phenyl-3-butyn-2-ol by hydrogenation reaction of 4-phenyl-3-butyn-2-one will be described below. A ruthenium complex RuCl[(S,S)-Tsdpen] (p-cymene) (1.6 mg, 0.0025 mmol) was charged in a 50 mL stainless steel autoclave, and replaced with argon. Add 4-phenyl-3-butyn-2-one (0.291 mL, 2 mmol), methanol (5 mL), pressurize with hydrogen, and perform 5 displacements. Add hydrogen to 50 atmospheres to start the reaction. After stirring for 11 hours at 30°C, the reaction pressure was returned to normal pressure. From the 1 HNMR and HPLC analysis show that (S)-4-phenyl-3-butyn-2-alcohol of 90%ee is generated with a yield of 63%. The nomenclature of the ruthenium complex here starts from the left with metal atom, An anionic group, a diamine ligand, and an aromatic hydrocarbon ligand are arranged in order (refer to the following formula (4)).

[0071] Formula (4)

[0072]

Embodiment 2-10

[0076] Except for changing the catalyst and hydrogen pressure used, the reaction was carried out under the same conditions as in Example 1 to synthesize (S)-4-phenyl-3-butyn-2-ol. The results are shown in Table 1.

[0077] Table 1

[0078]

[0079] Example

[0080] Conditions: chiral ruthenium catalyst 0.0025mmol, CH 3 OH5ml, S / C=800, temperature 30°C, time 11 hours, [ketone]=0.4M, dmb: 1,4-dimethylbenzene, teb: 1,3,5-triethylbenzene, durene: 1 , 2,4,5-tetramethylbenzene, pmb: pentamethylbenzene, hmb: hexamethylbenzene.

Embodiment 11-19

[0082] Except changing the concentration of the substrate and the reaction temperature, and using additives, the reaction was carried out under the same conditions as in Example 1 to synthesize (S)-4-phenyl-3-butyn-2-ol. The results are shown in Table 2.

[0083] Table 2

[0084]

[0085] Example

[0086] Condition: CH 3 [Kone] in OH=0.4M, RuCl[(S,S)-Tsdpen](p-cymene) 0.0025mmol, S / C=800, H 2 50atm, time 11 hours, solvent 5ml, a [ketone] = 0.1M, b [ketone] = 1.0M.

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Abstract

A ruthenium complex RuCl[(S,S)-Tsdpen](p-cymene) represented by a formula below and a ketone compound are placed in a polar solvent, and the resulting mixture is mixed under pressurized hydrogen to hydrogenate the ketone compound and to thereby produce an optically active alcohol:

Description

technical field [0001] The invention relates to a preparation method of an optically active alcohol using a ruthenium metal complex or the like as a catalyst. Background technique [0002] Previously, various methods for preparing optically active alcohols using metal complexes as catalysts have been disclosed. In particular, the synthesis of optically active alcohols from carbonyl compounds using asymmetric metal complexes as catalysts is being intensively studied. [0003] For example, Japanese Patent Laid-Open No. 2003-104993 discloses many examples, such as using diphosphine such as BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) as a catalyst. Tetrahydroborate salts of asymmetric ruthenium metal complexes of compound and diamine compound coordinated on ruthenium, hydrogenation of various ketone compounds in 2-propanol without adding base under pressurized hydrogen to prepare optically active alcohols. Specifically, the corresponding optically active alcohols are p...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C29/145C07C33/30C07C33/46C07C31/20C07C35/32C07C39/11C07C43/23C07D311/22C07D495/04C07B53/00B01J31/22B01J31/18B01J31/24C07C311/18
CPCB01J31/182C07B2200/07B01J2231/643C07D311/22B01J31/2452C07C311/18C07C29/145B01J2531/821C07C2602/08C07C2602/10C07C2602/12C07C31/20C07C31/205C07C31/207C07C31/36C07C31/38C07C33/042C07C33/26C07C33/28C07C33/46C07C35/23C07C35/32C07C35/36C07C35/52C07B53/00
Inventor 野依良治大熊毅堤邦彦内海典之村田邦彦
Owner KANTO CHEM CO INC
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