Dissertation
Dissertation > Medicine, health > Chinese Medicine > Of Pharmacy > Pharmacology

The Study of Chemical Synthesis for Crocins

Author ZhangJunGuo
Tutor ZhangHong
School Sichuan Normal University
Course Environmental Science
Keywords chemical synthesis Wittig-Horner reaction crocetin-dimeathyleste crocetin crocins
CLC R285
Type Master's thesis
Year 2009
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In this paper we describe an efficient seven-step synthesis of crocetin, which is the key intermediate for the synthesis of several carotenoids and other polyene natural, such as crocins.The synthesis stars by treatment of E-1, 4-dibrom-2-butene and triethylphosphit, according to Wittig-Horner reaction, to give the E-butene- (2)-diphosphon acid- (1,4)-tetraethylester , as a fleet tan oil with a 95% yield. E-butene- (2)-diphosphon acid- (1,4)-tetraethylester was submitted to next reaction processing with pyruvic aldehyde dimethyl acetal under nitrogen ,then added NaH to give the 2,7-Dimethyl- octatrien-(2,4,6)-dial, as a fleet yellow solid with a 71.12% yield.Another synthesis was performed by treatment of 1 equiv of trans-2, 3, -dimethylacrylic acid, 1 equiv of NBS and small amount of dibenzoyl peroxide to give trans-2-methyl-4-bromocrotonic acid with 90%. trans-2-methyl-4- bromocrotonic acid was reacted with excess methanol and thionyl chloride for 16 h to give methyl trans-2-methyl-4-bromocrotonate (methyl E-γ-bromotiglate) in 73.23% yield.The synthesis was carried on by treatment of methyl trans-2-methyl- 4-bromocrotonate (methyl E-γ-bromotiglate) and triethylphosphit, according to Wittig-Horner reaction, to give the methyl O,O-diethyl-γ- phosphonotiglate , as a fleet tan oil with a 94% yield. methyl O,O-diethyl-γ- phosphonotiglate was submitted to next reaction processing with 2,7-Dimethyl- octatrien-(2,4,6)-dial at 0℃under nitrogen, then added NaH to give the crocetin-dimeathylester, as a red solid with a 60.20% yield.A solution of crocetin-dimeathylester in methanol and THF[V∶V=2:3] was added to alkalic hydrolysis , at 50℃for 1h. The solid was removed by filtration and then was acidulated to give the crocetin in 91.2% yield; A solution of crocetin and N,N-Carbonyldiimidazole in DMSO at room temperature for 1h-2h to give crocetin-imidazole, as a red solid with a 95.8% yield. Crocetin-imidazole was submitted to next reaction processing with saccharides under nitrogen in a suspension of NaH of pyridine to give crocins , as a red solid with a 70.8% yield.The structure of crocetin-dimeathylester, crocetin, crocetin-imidazole and crocins were affirmed by 1HNMR spectra, 13CNMR spectra, UV and FT-IR spectroscopy. Therefore, the designing route of synthesis is feasible.

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