Synthesis of geranyl geraniol

A technology of geranylgeraniol and its synthesis method, which is applied in chemical instruments and methods, preparation of hydroxyl compounds, preparation of organic compounds, etc., and can solve problems such as lack of practical application value

Inactive Publication Date: 2005-09-14
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Dangerous and expensive reagents such as n-butyllithium, potassium hydride, triphenylarsenic-palladium complex, dihydroxyboromethane and diisobutylaluminum hydride are used in the reaction, so there is no practical application value

Method used

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  • Synthesis of geranyl geraniol
  • Synthesis of geranyl geraniol
  • Synthesis of geranyl geraniol

Examples

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preparation example Construction

[0027] The preparation of 9-sulfone-geranylgeraniol is obtained by condensation of trans-8-bromoacetic acid geranyl ester and geranyl sulfone under alkaline conditions. In this step, the α-H of the sulfone group in geranyl sulfone is taken away under strong alkaline conditions to form a carbanion, and then undergoes a nucleophilic substitution reaction with geranyl bromoacetate to generate the product 9-sulfone Geranylgeraniol.

[0028] The synthesis method proposed by Kikumasa Sato et al. uses n-butyllithium as a strong basic reagent in a mixed solvent of dimethylamide and hexamethylphosphoric triamide, and the reaction temperature is -78°C. Since n-butyllithium and hexamethylphosphoric triamide are very expensive, the present invention uses potassium tert-butoxide as a condensing agent in dimethylamide to carry out the condensation reaction at -20-0°C. Wherein the molar ratio of potassium tert-butoxide to geranyl sulfone is 1-2:1.

[0029] The sulfone group in the condensa...

Embodiment 2

[0047] 1) Using geranyl acetate as a raw material, first in the solvent dichloromethane, use selenium dioxide-tert-butyl hydroperoxide binary oxidant at 0°C to selectively allyle the trans-methyl group of geranyl acetate Oxidation at the trans-allyl position to obtain a mixed oxidation product of trans-allyl carbonylation and hydroxylation; and then reduction with sodium borohydride in methanol at 0°C to obtain a single oxidation product, trans-geranyl 8-hydroxyacetate;

[0048] 2) Trans-geranyl 8-hydroxyacetate is reacted with phosphorus tribromide in anhydrous ether in the presence of pyridine at -15°C to obtain trans-geranyl 8-bromoacetate;

[0049] 3) Then in N,N-dimethylformamide, in the presence of potassium tert-butoxide, geranyl sulfone and trans-8-bromoacetic acid geranyl ester were condensed at -20°C to obtain 9-sulfone base aromatic Phyllogeraniol;

[0050] 4) 9-Sulfone-geranylgeraniol At -78°C, the sulfone group was removed using a lithium-methylamine reducing age...

Embodiment 3

[0052] 1) Using geranyl acetate as a raw material, first in the solvent dichloromethane, use selenium dioxide-tert-butyl hydroperoxide binary oxidant at 25°C to selectively allyle the trans-methyl group of geranyl acetate Oxidation at the trans-allyl position to obtain a mixed oxidation product of trans-allyl carbonylation and hydroxylation; then reduce it with sodium borohydride in methanol at 10°C to obtain a single oxidation product, trans-geranyl 8-hydroxyacetate;

[0053] 2) Trans-geranyl 8-hydroxyacetate is reacted with phosphorus tribromide in anhydrous ether in the presence of pyridine at -10°C to obtain trans-geranyl 8-bromoacetate;

[0054] 3) Then in N,N-dimethylformamide, in the presence of potassium tert-butoxide, geranyl sulfone and trans-8-bromoacetic acid geranyl ester were condensed at 0°C to obtain 9-sulfone-geranyl Geraniol;

[0055] 4) 9-Sulfone-geranylgeraniol At -60°C, the sulfone group was removed using a lithium-methylamine reducing agent to obtain the...

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Abstract

A process for synthesizing geranylgeraniol includes such steps as selectively oxidizing (E)-methyl of geranyl acetate by SeO2-tert-butyl hydrogen peroxide in dichloromethane to obtain mixed oxide, reducting by sodium borohydride in emthanol to obtain 8-geranyl hydroxy acetate, reacting on phosphorus tribromide in anhydrous ether under existance of pyridine to obtain trans-8-geranyl bromoacetate, condensation reacting on geranyl sulfone in N,N-dimethyl methylamide under existance of tert-butanol potassium to obtain 9-sulfogeranyl geraniol, and reducting by lithium in methylamine.

Description

technical field [0001] The invention relates to a method for synthesizing geranylgeraniol. Background technique [0002] Geranyl geraniol (all-trans-Geranylgeraniol, 3, 7, 11, 15-tetramethylhexadeca-2E, 6E, 10E, 14-tetraenol) is a straight-chain diterpenoid, and its molecular structure is: [0003] [0004] Geranylgeraniol itself has a wide range of physiological activities, such as anti-virus, anti-virus and anti-tumor, etc., and has therapeutic effects on many diseases, such as ulcers, neurasthenia, skin aging, thrombosis, atherosclerosis and immune deficiency, etc. (U.S. Patent No. 20030092144). [0005] Geranylgeraniol is a biosynthetic precursor for a variety of biochemically important products, such as terpenoids, carotene, steroids, cholesterol, and paclitaxel (Taxol  )Wait. [0006] Geranylgeraniol is also an important organic synthesis intermediate of various drugs, such as coenzyme Q n (I), vitamin K (II and III) series compounds, ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C29/00C07C33/02
Inventor 唐飞宇陈志荣
Owner ZHEJIANG UNIV
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