5（Z），14（Z）-二十碳二烯-1-醇的合成研究
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摘要
本文概述了环氧-二十碳三烯酸(EETs)及其结构类似物14, 15-环氧-5(Z)-二十碳二烯酸(14,15-EE-5-ZE)的研究近况,对14,15-EE-5-ZE的全合成进行了探讨,设计了14,15-EE-5-ZE的前体化合物5(Z), 14(Z)-二十碳二烯-1-醇的一条新合成路线,并对其合成进行了详细的研究。
以1,8-辛二醇为原料,与40%氢溴酸进行单溴代反应,得到8-溴-1-辛醇,在对甲苯磺酸吡啶盐(PPTs)的催化下与2,3-二氢吡喃反应,保护分子中的羟基,再与1-庚炔进行偶联,以P-2镍为催化剂立体选择性催化加氢,酸性条件下脱末端的2,3-二氢吡喃对羟基的保护,使用氯铬酸吡啶盐(PCC)将醇氧化成醛(a)。再以1,5-戊二醇为原料,三溴化磷使之单溴代,得到5-溴-1-戊醇,在对甲苯磺酸吡啶盐(PPTs)的催化下与2,3-二氢吡喃反应保护其另一端的羟基,与三苯基膦反应生成季磷盐(b)。(a)与(b)在强碱正丁基锂的作用下进行Wittig反应,然后脱去末端的2,3-二氢吡喃保护基,得到5(Z), 14(Z)-二十碳二烯醇。反应总收率为3.4%。
本文在合成方面所做的工作:系统研究了对称二醇的单溴代反应反应时间、反应温度、溶剂用量、反应物摩尔比等因素对产率的影响。末端炔与溴代物的偶联反应条件的优化,初步探讨了反应机理。顺式加氢催化剂P-2镍制备方法的改进。其他反应条件的探索及讨论。实验过程中应用薄层层析的方法摸索产品的分离条件,利用硅胶柱层析提纯产品,并通过红外光谱、核磁共振碳谱及质谱验证了产品结构。实验表明,这一合成路线具有反应条件温和,立体选择性较高的特点,合成路线是可行的。
In this paper, we overviewed the epoxyeicosatrienoic acid(EETs) and its analogue-14, 15-epoxyeicosa-5(Z)-enoic acid(14,15-EE-5-ZE) recent status. The total synthesis of 14, 15-EE-5-ZE was primarily explored. A new stereoselective synthesis route of the key intermediate -(5Z,14Z)-gadoleyl-1-ol was designed and researched.
In this work , 1,8-octodiol, the starting material, reacted with 40% hydrobromic acid to produce 8-bromooctan-1-ol, with the catalytic action of PPTs, its hydroxyl group was protected by 2,3-dihydropyran. Then it coupled with 1-heptaalkyne, by means of P-2 nickel as catalyst, stereoselectivity catalysis hydrogenated, with the catalytic action of acid to take off extremital 2, 3-dihydropyran which protected hydroxy group, then used PCC to oxidize alcohol into corresponding aldehyde(a). 1,5-Pentanediol reacted with phosphorus tribromide to make it mono-bromination, under the catalytic action of PPTs it reacted with 2,3-dihydropyran to protect another hydroxy group, then to react with triphosphine, produced quarterphossal(b). (a) with (b) under strong base butyl Lithium, Wittig reaction was carried out, after cast off extremital 2,3-dihydropyran which protected hydroxy group, then 5(Z),14(Z)-gadoleyl-1-ol was obtained. Total yield was 3.4%.
The main work we did on synthesis: We studied bromination reaction influence factor in detail, such as reaction time、reaction temperature、solvent dosage、reagent mole ratio, and optimized the reaction condition, discussed reaction mechanism rudimentally. We optimized reaction condition and discussed the mechanism of 1-heptaalkyne coupled with mono-bromide. We improved on the technique of preparation P-2 nickel catalyst. We explored and discussed the reaction condition of other reactions. During experiment we applied thin-layer chromatography to grope the separating condition of product, utilized silica gel column chromatography to separate and purify product, and applied infrared spectrum, 13C NMR, mass spectrum to testify product structure.
Result indicated this route of synthesis possess mild reaction conditions, a higher stereoselectivity. Synthetic route was feasible.
以1,8-辛二醇为原料,与40%氢溴酸进行单溴代反应,得到8-溴-1-辛醇,在对甲苯磺酸吡啶盐(PPTs)的催化下与2,3-二氢吡喃反应,保护分子中的羟基,再与1-庚炔进行偶联,以P-2镍为催化剂立体选择性催化加氢,酸性条件下脱末端的2,3-二氢吡喃对羟基的保护,使用氯铬酸吡啶盐(PCC)将醇氧化成醛(a)。再以1,5-戊二醇为原料,三溴化磷使之单溴代,得到5-溴-1-戊醇,在对甲苯磺酸吡啶盐(PPTs)的催化下与2,3-二氢吡喃反应保护其另一端的羟基,与三苯基膦反应生成季磷盐(b)。(a)与(b)在强碱正丁基锂的作用下进行Wittig反应,然后脱去末端的2,3-二氢吡喃保护基,得到5(Z), 14(Z)-二十碳二烯醇。反应总收率为3.4%。
本文在合成方面所做的工作:系统研究了对称二醇的单溴代反应反应时间、反应温度、溶剂用量、反应物摩尔比等因素对产率的影响。末端炔与溴代物的偶联反应条件的优化,初步探讨了反应机理。顺式加氢催化剂P-2镍制备方法的改进。其他反应条件的探索及讨论。实验过程中应用薄层层析的方法摸索产品的分离条件,利用硅胶柱层析提纯产品,并通过红外光谱、核磁共振碳谱及质谱验证了产品结构。实验表明,这一合成路线具有反应条件温和,立体选择性较高的特点,合成路线是可行的。
In this paper, we overviewed the epoxyeicosatrienoic acid(EETs) and its analogue-14, 15-epoxyeicosa-5(Z)-enoic acid(14,15-EE-5-ZE) recent status. The total synthesis of 14, 15-EE-5-ZE was primarily explored. A new stereoselective synthesis route of the key intermediate -(5Z,14Z)-gadoleyl-1-ol was designed and researched.
In this work , 1,8-octodiol, the starting material, reacted with 40% hydrobromic acid to produce 8-bromooctan-1-ol, with the catalytic action of PPTs, its hydroxyl group was protected by 2,3-dihydropyran. Then it coupled with 1-heptaalkyne, by means of P-2 nickel as catalyst, stereoselectivity catalysis hydrogenated, with the catalytic action of acid to take off extremital 2, 3-dihydropyran which protected hydroxy group, then used PCC to oxidize alcohol into corresponding aldehyde(a). 1,5-Pentanediol reacted with phosphorus tribromide to make it mono-bromination, under the catalytic action of PPTs it reacted with 2,3-dihydropyran to protect another hydroxy group, then to react with triphosphine, produced quarterphossal(b). (a) with (b) under strong base butyl Lithium, Wittig reaction was carried out, after cast off extremital 2,3-dihydropyran which protected hydroxy group, then 5(Z),14(Z)-gadoleyl-1-ol was obtained. Total yield was 3.4%.
The main work we did on synthesis: We studied bromination reaction influence factor in detail, such as reaction time、reaction temperature、solvent dosage、reagent mole ratio, and optimized the reaction condition, discussed reaction mechanism rudimentally. We optimized reaction condition and discussed the mechanism of 1-heptaalkyne coupled with mono-bromide. We improved on the technique of preparation P-2 nickel catalyst. We explored and discussed the reaction condition of other reactions. During experiment we applied thin-layer chromatography to grope the separating condition of product, utilized silica gel column chromatography to separate and purify product, and applied infrared spectrum, 13C NMR, mass spectrum to testify product structure.
Result indicated this route of synthesis possess mild reaction conditions, a higher stereoselectivity. Synthetic route was feasible.
引文
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[2] Rosolowsky M, Campbell WB, Role of PGI2 and epoxyeicosatrienoic acids in relaxation of bovine coronary arteries to arachidonic acid[J]. Am. J. Physiol, 1993, 264: 327~335
[3] Fukao M, Hattori Y, Kanno M, et al., Evidence against a role of cytochrome P450 -derived arachidonic acid metabolites in endothelium-dependent hyperpolarization by acetylcholine in rat isolated mesenteric artery[J]. Br. J. Pharmacol, 1997, 120: 439~446
[4] Campbell WB, Gebremedhin D, Pratt PF, et al., Identification of epoxyeicosatrienoic acids as endothelium-derived hyperpolarizing factor[J]. Circ. Res., 1996, 78: 415~423
[5] Proctor KG, Falck JR, Capdevila J, et al., Intestinal vasodilation by epoxyeicosatrienoic acids: Arachidonic acid metabolites produced by a cytochrome P450 monooxygenase[J]. Circ. Res., 1987, 60: 50~59
[6] Feletou M, Vanhoutte PW, Endothelium-derived hyperpolarization factor[J]. Clin. Exp. Pharmacol Physiol, 1996, 23(12): 1082~1090
[7] Adeagbo ASO, Varying extracellular k+: a functional approach to separating EDHF- and EDNO- related mechanisms in perfused rat mesenteric arterial bed[J]. Cardiovasc Pharmacol, 1993, 21: 423~429
[8] Carroll MA, Schwartzman M, Capdevila J, et al., Vasoactivity of arachidonic acid epoxides [J]. Eur. J. Pharmacol, 1987, 138: 281~283
[9] Gebremedhin D, Ma YH, Falck JR, et al., Mechanism of action of cerebral epoxyeicosatrienoic acids on cerebral arterial smooth muscle [J]. Am. J. Physiol, 1992, 263: 519~525
[10] Fulton D, Mcgiff JC, Quilley J, Pharmacological evaluation of an epoxide as the hyperpolarizing factor mediating the nitric oxide independent vasodilator effect of bradykinin in the rat heart [J]. J. Pharmacol Exp. Ther., 1998, 287: 497~503
[11] Oltman CL, Weintraub NL, VanRollins M, et al., Epoxyeicosatrienoic acids and dihydroxyeicosatrienoic acids are potent vasodilators in the canine coronary microcirculation[J]. Circ. Res., 1998, 83: 932~939
[12] Hayabuohi Y, Nakaya Y, Matsuoka S, et al., Endothelium-derived hyperpolarizing factor activates Ca2+ activated K+ channel in porcine coronary artery smooth muscle cells[J]. J. Cardiovasc Pharmacol, 1998, 32: 642~649
[13] Hoebel BG, Graier WF, 11,12-epoxyeicosatrienoic acid stimulates tyrosine kinase activity in porcine aortic endothelial cells[J]. Eur. J. Pharmacol, 1998, 346(1): 115~ 117
[14] Hu S, Kim H, Activation of K+ channel in vascular smooth muscles by cytochrome P450 metabolites of arachidonic acid[J]. Eur. J. Pharmacol, 1993, 230(2): 215~221
[15] Xiao YF, Huang L, Morgan JP, Cytochrome P450: A novel system modulating Ca2+ channels and contraction in mammalian heart cells[J]. J. Physiol, 1998, 508: 777~792
[16] Chen JK, Falck JR, Reddy KM, et al., Epoxyeicosatrienoic acids and their sulfonmide derivatives stimulate tyrosine phosphorylation and induce mitogensis in renal epithelial cells[J]. J. Bio. Chem., 1998, 273(44): 29254~29261
[17] Lane CJ, Yang H, Muller BJ, et al., Disparate effects of 11,12-epoxyeicosatrienoic acid and arachidonic acid in perfused and ischemic myocardium[J] . J. Biophy, 1998, 74(1): 161~161
[18] Price A, Shi Q, Morris D, et al., Marked inhibition of tumor growth in a malignant glioma tumor model by a novel synthetic matrix metalloproteinase inhibitor AG3340[J]. Clin. Cancer Res., 1999, 5(4): 845~854
[19] Hanahan D, Folkman J, patterns and emerging mechanisms of the angiogernic switch during tumorigenesis[J]. Cell, 1996, 85(3): 353~364
[20] Folkman J, Tumor angiogenesis: therapentic implications[J]. N. Engl. J. Med., 1971,285(21): 1182~1186
[21] Folkman J, What is the evidence that tumors are angiogenesis dependent?[J]. Nat. J. Cancer Inst., 1990, 82(1): 4~6
[22] Folkman J, Fight cancer by attacking its blood supply[J]. Sei. Am., 1996, 275(3): 150~154
[23] J. R. Falck, U. Murali Krishna, Y. Krishna Reddy, et al., Comparison of vasodilatory properties of 14,15-EET analogs: structural requirements for dilation[J]. A. J. P. Heart 2003, 284: 337~349
[24] Gauthier KM, Deeter C, Krishna UM, et al., 14,15-Epoxyeicosa-5(Z)-enoic acid: a selective epoxy eicosatrienoic acid antagonist that inhibits endothelium-dependent hyperpolarization and relaxation in coronary arteries[J]. Circ. Res., 2002, 90(9): 1028~1036
[25] 克莱夫 A. 亨里克著,昆虫信息素的合成[M]. 科学出版社,1979
[26] Roelof W L, Comeau A, Hill A, et al., The synthesis of inset sex pheromones[J]. Science, 1971(174): 297~302
[27] Descoins C, Henrick C A, Steroselective synthesis of a sex attractant of the cold ling moth[J]. Tetrahedron letters, 1972(30): 2999~3002
[28] Clive A H, The synthesis of inset sex pheromones[J]. Tetrahedron, 1977(33): 1845~1889
[29] Schlosser M, Topics in Stereochemistry[M]. New York: Wiley-Interscience, 1970, 366~390
[30] D.D.佩林著,时雨译,实验室化学药品的提纯方法[M], 化学工业出版社,1987,第二版
[31] 李述文,范如霖 编译, 《实用有机化学手册》[M],上海科学技术出版社,1981
[32] D. S. Shriver, The Manipulation of Air-sensitive Compounds[M]. Mc. Graw-Hill, New York, 1970
[33] 范如霖, 《有机合成特殊技术》[M],上海交大出版社,1987
[34] 藤有为,庭玉华,冯留贵等, 简法合成 ω-溴代醇-1[J]. 有机化学, 1988(3): 275~277
[35] 李在国,有机中间体制备[M]. 北京:化学工业出版社,2001,274
[36] 赵之中,周瑾编译, 有机化学中的保护基团[M]. 北京:科学出版社,1986
[37] Vogel, Authur Israel, Vogel’s Textbook of Practical Organic Chemistry[M]. London: Longman Scientific & Technical; New York: Wiley, 1989
[38] Pierre P, Roumestant M L, Jacques G. New sythesis of 3,7-dimethyl-pentadecan-2-yl acetate sex pheromone of the pine sawfly neodiprion lecontei[J]. J. Org. Chem., 1978, 43(5): 1001
[39] 姜麟忠, 催化氢化在有机合成中的应用[M], 北京:化学工业出版社,1987
[40] Brown H C, Bhat K S, Enantiomeric (Z)- and (E)-crotyldiisopinocampheylboranes, synthesis in high optical of all four possible stereoisomers of β-methylhomoallyl alcohols[J]. J. Am. Chem. Soc., 1986, 108: 293~294
[41] Core E J, Suggs J W, Oxidation of alcohols effected by pyridinium chlorochromate [J]. Tetrahedron letters, 1975, 16(31): 2647~2650
[42] Core E J, Schmidt G. Useful procedures for the oxidation of alcohols involving pyridinium dichromate in aprotic media [J]. Tetrahedron letters, 1979, 20(5): 399
[43] Agarwal S, Tiwari H P, Sharma J P, Pyridinium chlorochromoate: an improved method for its synthesis and use of anhydrous acetic acid as catalyst for oxidization reactions[J]. Tetrahedron, 1990, 46(21): 4417~4420
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