Method for synthesizing (E,E) Geranyl linalool

Abstract

This invention relates to synthetic method of a ( E, E) - geranyl linalool. The invention takes (E) - nerolidol as raw material. The hydroxyl is shield by dihydropyrane, gain ( E) - nerolidol tetrahydropyrane aether; selenium dioxide and teri-butyl hydroperoxide selectively oxidize the anti-form methyl of ( E) - nerolidol tetrahydropyrane aether to gain anti-form allyl position hydroxylated oxidative product ( E, E) - 12 - hydroxy nerolidol tetrahydropyrane aether, transit halogenating reaction to gain ( E, E) - 12 - halogeno- nerolidol tetrahydropyrane aether, then take reaction with isopropyl methyl ketone that is selectively divested one proton by diisopropyl amido lithium, generate ( 6E, 10E) - 2, 6, 10, 14 - tetramethyl - 14 - ( tetrahydropyrane - 2 - oxygen) -16 - 6, 10, 15 - triene - 3 - ketone, use sodium borohydride to reduce to gain ( 6E, 10E) - 2, 6, 10, 14 - tetramethyl - 14 - ( tetrahydropyrane - 2 - oxygen) -16 - 6, 10, 15 - triene - 3 - alcohol, takes reaction with sulfonyl chloride or sulphonic acid ester with alkali presence to gain ( 6E, 10E) - 2, 6, 10, 14 - tetramethyl - 14 - ( tetrahydropyrane - 2 oxygen) -16 - 6, 10, 15 - triene - 3 - alcoholic sulphonic acid ester, then divide sulphonic acid ester group under base catalysis to gain ( E, E) - geranyl linalool tetrahydropyrane aether, and by deprotection to gain ( E, E) - geranyl linalool. ˕For the configuration of ( E) - nerolidol 3 position tertiary carbon is not influenced in the course of reaction, if use ( E) - nerolidol that has optical activity as raw material, should gain optical active ( E, E) - geranyl linalool. ((E, E)-geranyl linalool can replace Teprenone and such type medicament intermediate, natural product intermediate, insect pheromone and spice etc.

Description

technical field [0001] The invention relates to a synthesis method of (E, E)-geranyl linalool. Background technique [0002] (E,E)-Geranyllinalool ((E,E)-Geranyllinalool, (6E,10E)-3,7,11,15-Tetramethyl-hexadeca-1,6,10,14-tetraen-3-ol ) is a straight-chain diterpenoid, and its molecular structural formula is: [0003] [0004] (E,E)-Geranyllinalool is an important intermediate of chain diterpenoids and natural products, a bioactive compound and a fragrance-fixing component of spices. [0005] (E, E)-geranyllinalool reacts with methyl acetoacetate under the catalysis of aluminum isopropoxide to obtain the gastric mucosal protective agent teprenone, which will be the most convenient synthesis method for teprenone. Geranyl linalool undergoes a one-step rearrangement to obtain geranyl nerolidol. (E, E)-geranyllinalool can also be used as insect pheromone and insect natural insecticide. It is also a fragrance-fixing component of high-end fragrances. Therefore, (E, E)-geran...

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Problems solved by technology

[0011] Recently, Svatos synthesized (3R)- and (3S)-geranyllinalool from geranyl bromide and L-configuration or D-configuration citramalic acid through 7 steps, but the method used a large amount of cuprous cyanide , dicyclopentenyl zirconium chloride, butyl lithium, 2-thiophene lithium, borane and other flammable, explosive and highly toxic dangerous goods, lacking practical application value (Coll.Czech.Chem.Commun.2002 , 67(1):83-90)

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