A kind of synthetic method of cis-1,4-cyclohexanediol

A synthesis method and compound technology, applied in the directions of organic chemistry methods, chemical instruments and methods, formation/introduction of hydroxyl groups, etc., can solve the problems of unsuitable promotion and rare raw materials, and achieve the effects of short steps, convenient purification and simple operation.

Active Publication Date: 2021-02-26
PHARMABLOCK SCIENCES (NANJING) INC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0014] But the content of cis-1,4-cyclohexanediol is only 17%, and the raw material is rare, so this method is not suitable for popularization

Method used

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  • A kind of synthetic method of cis-1,4-cyclohexanediol
  • A kind of synthetic method of cis-1,4-cyclohexanediol
  • A kind of synthetic method of cis-1,4-cyclohexanediol

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035]

[0036] 1. Preparation of Compound III-1 from Compound II-1

[0037] Dissolve raw material II-1 (148.0g, 0.641mol, 1.0eq.) in methanol (1.2L), add KBH in batches at -15°C 4 (68.8g, 1.28mol, 2.0eq.), after the addition was complete, the reaction was maintained at this temperature for 4 hours.

[0038] Add 1.5 L of saturated ammonium chloride solution dropwise to the reaction mixture, stir until no bubbles are generated, add ethyl acetate for extraction, combine the organic phases for column chromatography (petroleum ether: ethyl acetate is 10:2), and remove under reduced pressure After solvent, white solid III-1 (68.5g, 0.30mol) yield: 46.1%; and white solid IV-1 (45.7g, 0.197mol) were obtained, yield: 30.8%. 1 H NMR (400M Hz, DMSO-d 6 )δ(ppm)7.24-7.27(m,5H),4.65(m,1H),3.75(s,2H),3.58(br,1H),1.57-1.54(m,4H),1.44-1.40(m, 4H).

[0039] 2. Preparation of Compound I from Compound III-1

[0040] Dissolve III-1 (68.5g, 0.30mol, 1.0eq.) in 90% aqueous methanol (0.8L), ...

Embodiment 2

[0042]

[0043] 1. Preparation of Compound III-2 from Compound II-2

[0044] The material II-2 (156.0g, 0.788mol, 1.0eq.) was dissolved in ethanol (1.5L), and NaBH was added in batches at 10°C 4 (53.7g, 1.42mol, 1.8eq.), after the addition was complete, the reaction was maintained at this temperature for 1.5 hours.

[0045] Add 2.0L of saturated sodium chloride solution dropwise to the reaction mixture, stir until no bubbles are generated, add ethyl acetate for extraction, combine the organic phases for column chromatography (petroleum ether:ethyl acetate:ethanol is 20:3:1), After removing the solvent under reduced pressure, white solid III-2 (75.8 g, 0.381 mol) yield: 48.3%; and white solid IV-2 (41.7 g, 0.209 mol) were obtained, yield: 26.6%. 1 H NMR (400M Hz, DMSO-d 6 )δ (ppm) 4.61 (m, 1H), 4.29-4.28 (d, 1H), 1.57-1.54 (m, 4H), 1.44-1.40 (m, 4H), 1.27 (s, 9H).

[0046] 2. Preparation of Compound I from Compound III-2

[0047]Dissolve III-2 (75.8g, 0.381mol, 1.0eq.) i...

Embodiment 3

[0049]

[0050] 1. Preparation of Compound III-3 from Compound II-3

[0051] Material II-3 (176.5g, 1.13mol, 1.0eq.) was dissolved in methanol (2.5L), and LiBH was added in batches at -10°C 4 (36.9g, 1.70mol, 1.5eq.), after the addition was complete, the reaction was maintained at this temperature for 3.5 hours.

[0052] Add 3.0L saturated sodium chloride solution dropwise to the reaction mixture, stir until no bubbles are generated, add ethyl acetate for extraction, combine the organic phases for column chromatography (petroleum ether: methylene chloride 5:1), remove under reduced pressure After solvent, white solid III-3 (82.7g, 0.526mol) yield: 46.6%; and white solid IV-3 (45.0g, 0.286mol) were obtained, yield: 25.3%. 1 H NMR (400M Hz, DMSO-d 6 )δ (ppm) 4.59 (m, 1H), 4.29-4.28 (d, 1H), 2.02 (s, 3H), 1.57-1.54 (m, 4H), 1.44-1.40 (m, 4H).

[0053] 2. Preparation of Compound I from Compound III-3

[0054] Dissolve III-3 (82.7g, 0.526mol, 1.0eq.) in 90% aqueous methanol ...

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Abstract

The invention discloses a method for synthesizing cis-1,4-cyclohexanediol, which belongs to the field of organic chemical synthesis. The method uses 4-(hydrocarbyl acyloxy)cyclohexanone as a raw material, and only undergoes reduction and hydrolysis. cis-1,4-cyclohexanediol can be easily synthesized. The method can ensure high selectivity of the reaction, and the obtained product yield is high, and is suitable for large-scale production.

Description

technical field [0001] The invention relates to the field of organic chemical synthesis, in particular to a synthesis method of cis-1,4-cyclohexanediol. Background technique [0002] Recent discoveries have been made in the synthesis of bromodomain inhibitors, 11β-hydroxysteroid dehydrogenase type 1 protein inhibitors, star polymers for live-cell imaging, substituted azine insecticides, and kinase inhibitors. , Among the raw materials for polymers, cis-1,4-cyclohexanediol is indispensable. Therefore, research work on the synthesis of cis-1,4-cyclohexanediol is increasing. [0003] Regarding the synthesis of cis-1,4-cyclohexanediol, the following literature reports are currently available: [0004] Dana A. etc. reported the method of hydrogenation synthesis of 1,4-cyclohexanediol isomers with cyclohexanedione under the effect of Shvo-ruthenium catalyst in Tetrahedron Letters 55 (2014) 128~132, their Studies have shown that the ΔR of these two isomers of 1,4-cyclohexanediol...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C35/14C07C29/09C07C27/02
CPCC07B41/02C07B57/00C07B2200/07C07C29/095C07C67/29C07C67/56C07C201/12C07C201/16C07C35/14C07C69/614C07C69/28C07C69/16C07C69/78C07C69/76C07C69/92C07C69/738C07C69/612C07C205/57
Inventor 朱春瑞刘文博李辉揭元萍
Owner PHARMABLOCK SCIENCES (NANJING) INC
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