艾维激素的全合成研究
|
摘要
艾维激素(简称AVG),中文商品名为保鲜灵,化学名称是氨基乙氧基乙烯基甘氨酸,结构式如下：
其作为天然氨基酸的衍生物,是一种极为重要的植物生长调节剂,有关它在果实的增收以及农产品保鲜等方面的应用的报道已经屡见不鲜。
目前市面上销售的艾维激素主要是从国外进口,且价格非常昂贵。除此之外,艾维激素主要通过生物提取获得,关于其化学合成却鲜有报道。因此找到一种化学合成艾维激素的方法且将其应用到农业生产当中就显得尤为重要。
本文首先通过验证比较目前已经报道的几种艾维激素的合成方法,在此基础之上,以L-蛋氨酸为起始原料设计了三条艾维激素合成路线,并最终找到一种全新合成艾维激素的方法。
本文的创新点在于找到了一种全新合成艾维激素的方法,且整条路线的原料便宜易得,实验操作也比较简单。
(S)-trans-2-amino-4-(2-aminoethoxy)-3-butenoic acid hydrochloride (Abbreviation: AVG), chinese brand name is baoxianling, structural formula:
As a kind of natural amino acid derivatives, it is an extremely important plant growth regulator, which also has been frequent reported about its application in respect of the fruits of increase product, and agricultural preservation.
AVG on the market is mainly imported from abroad, and the price is very expensive. In addition, AVG is obtained primarily through biological extraction, and little literatures have been reported on its chemical synthesis. Therefore, it is particularly important to find a chemical method of synthesis of AVG and its application to agricultural production.
Firstly, the thesis has verified and compared several AVG synthesis methods which have been reported, on this basis, three AVG synthesis routes were designed using L-methionine as a starting material, and eventually the thesis finds a new synthesis method of AVG.
The innovation of this thesis is to find a new method of AVG synthesis, and the entire route of the raw materials are cheap and easy to get, relatively simple experimental operation.
其作为天然氨基酸的衍生物,是一种极为重要的植物生长调节剂,有关它在果实的增收以及农产品保鲜等方面的应用的报道已经屡见不鲜。
目前市面上销售的艾维激素主要是从国外进口,且价格非常昂贵。除此之外,艾维激素主要通过生物提取获得,关于其化学合成却鲜有报道。因此找到一种化学合成艾维激素的方法且将其应用到农业生产当中就显得尤为重要。
本文首先通过验证比较目前已经报道的几种艾维激素的合成方法,在此基础之上,以L-蛋氨酸为起始原料设计了三条艾维激素合成路线,并最终找到一种全新合成艾维激素的方法。
本文的创新点在于找到了一种全新合成艾维激素的方法,且整条路线的原料便宜易得,实验操作也比较简单。
(S)-trans-2-amino-4-(2-aminoethoxy)-3-butenoic acid hydrochloride (Abbreviation: AVG), chinese brand name is baoxianling, structural formula:
As a kind of natural amino acid derivatives, it is an extremely important plant growth regulator, which also has been frequent reported about its application in respect of the fruits of increase product, and agricultural preservation.
AVG on the market is mainly imported from abroad, and the price is very expensive. In addition, AVG is obtained primarily through biological extraction, and little literatures have been reported on its chemical synthesis. Therefore, it is particularly important to find a chemical method of synthesis of AVG and its application to agricultural production.
Firstly, the thesis has verified and compared several AVG synthesis methods which have been reported, on this basis, three AVG synthesis routes were designed using L-methionine as a starting material, and eventually the thesis finds a new synthesis method of AVG.
The innovation of this thesis is to find a new method of AVG synthesis, and the entire route of the raw materials are cheap and easy to get, relatively simple experimental operation.
引文
[1]David Pruess, David Pruess, US3751459,1973.
[2]Finch Charles.W, EP0874545A1,1998.
[3]胡建芳,贺海洋.AVG(2-aminoethoxyvinylglycine)处理对‘巨峰’葡萄坐果的影响.中国农业大学学报,2001,6(1),7-11.
[4]胡建芳,贺海洋,廖康等.氨基乙氧基乙烯甘氨酸(AVG)处理对‘巨峰’葡萄胚珠和种子发育的影响.园艺学报,2001,28(5),445-447.
[5]萧韵琴.采前喷AVG对苹果贮妞寿命和品质的影响.中国果实,1993,2,18-23.
[6]李富军,张新华,王相友.AVG对肥城桃采收品质和采后乙烯合成的影响.农业机械学报,2002,37(2),76-79.
[7]李富军,翟衡,杨洪强等.12MCP和AVG对肥城桃果实采后衰老的影响[J].果树学报,2004,21(3),272-274.
[8]汤日圣,王红,童红玉.混用4PU30、Pix和AVG提高棉花成铃的效果及机理.江苏农业学报,2001,17(3),158-162.
[9]邢虎成,秦占军,佘玮等.两种乙烯抑制剂对苎麻(Boehmeria nivea(L.) Gaud)性别及植物学性状的影响.中国麻业科学,2007,29(2),71-73.
[10]焦健,李朝周,黄高宝.乙烯产生抑制剂对高温胁迫下蚕豆幼苗叶片的保护作用.植物生态学报,2006,30(3),465-471.
[11]Hyeung-geun Park, Dong-Hwa Kim, Mi-Sook Yoo, et al. Practical regioselective synthetic method for (E)-enol ether. Tetrahedron Letters.2000,41,4579-4582.
[12]Sylvain Ponthieux, Francis Outurquin, Claude Paulmier. Preparation of Silyl Enol Ethers Derived from a-Phenylseleno aldehydes and cx-Phenylseleno ketones. Tetrahedron. 1995,51(35),9564-9580.
[13]Annick.Rohrer, Ruben.Ocampo, HenryJ.Callot. Synthesis of meso-13C and 15N Labelled Octaethylporphyrin and Optimisation of the "Symmetrical" Route to Oct-aalkylporphyrins. Synthesis. 1994, 9,923-925.
[14]Alan F. Thomas, Michel Ozainne. Addition of a functionalized isoprene unit to an allyl alcohol. Part Ⅱ. Reactions with furylmethanol and thienylmethanol and synthesis of torreyal and dendrolasin. J. Chem. Soc. C. 1970,2,220-224.
[15]Daums. M, Voquang.L, Legoffic F. New Non-Proteogenic Aminoacids Bearing an-Enol Aryl-Ether Moiety. Terrahedron.1992,48(12),2313-2384.
[16]Scannell, J. P, Pruess, D. L, et al. J. Antibiot. 1972,25,122-127. b) Sahm, U.; Kn-obloch, G; Wagner, F. J. Antibiot. 1973,26,389-390. c) Miles, E. W. Enzyme-Act. Irreversible Inhibitors. Proc. Int.Symp. 1978, 73-85.
[17]David B. Berkowitz, Bradley D. Charette, Kannan R. Karukurichi, et al. a-Vinylic-amino acids:occurrence, asymmetric synthesis, and biochemical mechanisms. Tetrahedron, Asymmetry.2006,17,869-882.
[18]Owens, L. D; Thompson, J. F; Pitcher, R. G; Williams, T. J. Chem. Soc, Chem. Commun.1972,714. b) Yasuta, T.; Okazaki, S.; Mitsui, H.; Yuhashi, K.-L; Ezura,H.; Minamisawa, K. Appl. Environ. Microbiol.2001,67,4999-5009. c) Giovanelli, J.; Owens, L. D.; Mudd, S. H. Biochim. Biophys.Acta.1971,227,671-684.
[19]Dennis D. Keith, Roxana Yang. Synthesis of DL-2-Amino -42-(aminoethoxy)-trans-but-3-enoic Acid. J. Org. Chem.1978,43,19.
[20]黄成美,南京理工大学硕士毕业论文,南京,2009.
[21]Martinez, Rodolfo A, US2009/25906,2009.
[22]Sato, Kazuhiko. Preparation of 3,5-bis-(β-d-glycopyranosyl)-1,2,4-thiadiazoles from C-(β-d-glycopyranosyl)thioformamides. Tetrahedron.2001,57(13),2469 2476.
[23]Kiumars Bahrami, Mohammad M. Khodaei, Mehdi Sheikh Arabi. TAPC-Promoted Oxidation of Sulfides and Deoxygenation of Sulfoxides. J. Org. Chem.2010,75 (18),6208-6213.
[24]Satoh, Tsuyoshi; Kondo, Atsushi; Musashi, Jun. Generation of magnesium carbeno ids from 1-chloroalkyl phenyl sulfoxides with a Grignard reagent and applications to alkylation and olefin synthesis. Tetrahedron.2004, 60(25), 5453-5460.
[25]David B. Berkowitz. a-Vinylic amino acids:occurrence, asymmetric synthesis, and biochemical mechanisms. Tetrahedron:Asymmetry.2006,17,869-882.
[26]Lumbroso, Alexandre. An efficient and scalable synthesis of N-(benzyloxy-carbonyl)-and N-(methyloxycarbonyl)-(S)-vinylglycinol. Tetrahedron Letters. 2010, 51 (24),3226-3228.
[27]Truong, Thien Van; Rapoport, Henry. Chirospecific synthesis of the tetrahydro-imidazodiazepinol aglycon of pentostatin and its analogs. J. Org. Chem.1993,58 (22),6090-6096.
[28]Santiago Rodriguez. Diastereoselective synthesis of γ-hydroxy α, β-epoxy-esters and their conversion into (3-hydroxy a-sulfenyl y-butyrolactones. Tetrahedron.2006, 62(48),11112-11123.
[29]Fowler Joseph C, US650934,1900.
[30]Mansour Haddad, Marc Larcheveque. A Straight Route Towards Glyceric Chirons. Synthetic Communications. 2003,33(5), 687-692.
[31]Hirai Kenji, Ono Ryuta, JP9227535A,1996.
[32]Hatakeyama, Susumi. Efficient enantiospecific synthesis of key A-ring synthons for the preparation of 1.alpha.,25-dihydroxyvitamin D3 using a chro miu m (Ⅱ)-mediated reaction. J. Org. Chem.1989,54 (15),3515-3517.
[33]Canet, Jean-Louis; Fadel, Antoine; Salauen, Jacques. Asymmetric construction of quaternary carbons from chiral malonates:selective and versatile total syntheses of the enantiomers of alpha and beta cuparenones from a common optically active precursor. J. Org. Chem.1992,57 (12),3463-3473.
[34]Lubell William, Jamieson Andrew, WO2010105367,2009.
[35]Patrick.Meffre, Philippe.Durand, Francois.Le Goffic. Straightforward Synthesis of Optically Pure Methyl (S)-2-Phthalimido-4-oxobutanoate and Some of Its Acetal and Thioacetal Derivatives. Synthesis. 1995,9,1111-1114.
[36]Wenkert, E. Oxycyclopropanes in organochemical synthesis. Total syntheses of (+-.)-.alpha.-cuparenone and (.+-.)-.beta.-vetivone. J. Am. Chem. Soc. 1978,100(4), 1267-1273.
[37]Martin A. Berliner, Katherine Belecki. Simple, Rapid Procedure for the Synthes is of Chloromethyl Methyl Ether and Other Chloro Alkyl Ethers. J. Org. Chem.2005, 70,9618-9621.
[38]Yoshihiro Yamauchi, Yoshihiro Miyake, Yoshiaki Nishibayashi. Rutheniu m-Cat alyzed Oxypropargylation of Alkenes. Organometallics.2009,28 (1),48-50.
[39]Robert A. Mosey. Synthesis of tert-Alkyl Amino Hydroxy Carboxylic Esters via an Intermolecular Ene-Type Reaction of Oxazolones and Enol Ethers. Org. Lett.2008, 10(5),825-828.
[40]Aqeel Ahmed, Patrick H. Dussault. Stereoselective allylation of chiral mono-peroxya cetals. Tetradedron.2005,61,4657-4670.
[41]Dehmlow, Eckehard Volker; Westerheide, Ralf. A New Simple Route to N,O-Prote-cted (S)-2-Amino-4-oxobutyric Acid. Synthesis.1993,12,1225-1226.
[42]Robert J. Jones, Henry Rapoport. Enantiospecific synthesis of an aziridino-benzazocinone, an advanced intermediate containing the core nucleus of FR900482 and FK973. J. Org. Chem.1990,55 (4),1144-1146.
[43]Fukuchi. Journal of the Chemical Society, Perkin Transactions 1:Organic and Bio-Organic Chemistry (1972-1999).1992,9,1149-1158.
[2]Finch Charles.W, EP0874545A1,1998.
[3]胡建芳,贺海洋.AVG(2-aminoethoxyvinylglycine)处理对‘巨峰’葡萄坐果的影响.中国农业大学学报,2001,6(1),7-11.
[4]胡建芳,贺海洋,廖康等.氨基乙氧基乙烯甘氨酸(AVG)处理对‘巨峰’葡萄胚珠和种子发育的影响.园艺学报,2001,28(5),445-447.
[5]萧韵琴.采前喷AVG对苹果贮妞寿命和品质的影响.中国果实,1993,2,18-23.
[6]李富军,张新华,王相友.AVG对肥城桃采收品质和采后乙烯合成的影响.农业机械学报,2002,37(2),76-79.
[7]李富军,翟衡,杨洪强等.12MCP和AVG对肥城桃果实采后衰老的影响[J].果树学报,2004,21(3),272-274.
[8]汤日圣,王红,童红玉.混用4PU30、Pix和AVG提高棉花成铃的效果及机理.江苏农业学报,2001,17(3),158-162.
[9]邢虎成,秦占军,佘玮等.两种乙烯抑制剂对苎麻(Boehmeria nivea(L.) Gaud)性别及植物学性状的影响.中国麻业科学,2007,29(2),71-73.
[10]焦健,李朝周,黄高宝.乙烯产生抑制剂对高温胁迫下蚕豆幼苗叶片的保护作用.植物生态学报,2006,30(3),465-471.
[11]Hyeung-geun Park, Dong-Hwa Kim, Mi-Sook Yoo, et al. Practical regioselective synthetic method for (E)-enol ether. Tetrahedron Letters.2000,41,4579-4582.
[12]Sylvain Ponthieux, Francis Outurquin, Claude Paulmier. Preparation of Silyl Enol Ethers Derived from a-Phenylseleno aldehydes and cx-Phenylseleno ketones. Tetrahedron. 1995,51(35),9564-9580.
[13]Annick.Rohrer, Ruben.Ocampo, HenryJ.Callot. Synthesis of meso-13C and 15N Labelled Octaethylporphyrin and Optimisation of the "Symmetrical" Route to Oct-aalkylporphyrins. Synthesis. 1994, 9,923-925.
[14]Alan F. Thomas, Michel Ozainne. Addition of a functionalized isoprene unit to an allyl alcohol. Part Ⅱ. Reactions with furylmethanol and thienylmethanol and synthesis of torreyal and dendrolasin. J. Chem. Soc. C. 1970,2,220-224.
[15]Daums. M, Voquang.L, Legoffic F. New Non-Proteogenic Aminoacids Bearing an-Enol Aryl-Ether Moiety. Terrahedron.1992,48(12),2313-2384.
[16]Scannell, J. P, Pruess, D. L, et al. J. Antibiot. 1972,25,122-127. b) Sahm, U.; Kn-obloch, G; Wagner, F. J. Antibiot. 1973,26,389-390. c) Miles, E. W. Enzyme-Act. Irreversible Inhibitors. Proc. Int.Symp. 1978, 73-85.
[17]David B. Berkowitz, Bradley D. Charette, Kannan R. Karukurichi, et al. a-Vinylic-amino acids:occurrence, asymmetric synthesis, and biochemical mechanisms. Tetrahedron, Asymmetry.2006,17,869-882.
[18]Owens, L. D; Thompson, J. F; Pitcher, R. G; Williams, T. J. Chem. Soc, Chem. Commun.1972,714. b) Yasuta, T.; Okazaki, S.; Mitsui, H.; Yuhashi, K.-L; Ezura,H.; Minamisawa, K. Appl. Environ. Microbiol.2001,67,4999-5009. c) Giovanelli, J.; Owens, L. D.; Mudd, S. H. Biochim. Biophys.Acta.1971,227,671-684.
[19]Dennis D. Keith, Roxana Yang. Synthesis of DL-2-Amino -42-(aminoethoxy)-trans-but-3-enoic Acid. J. Org. Chem.1978,43,19.
[20]黄成美,南京理工大学硕士毕业论文,南京,2009.
[21]Martinez, Rodolfo A, US2009/25906,2009.
[22]Sato, Kazuhiko. Preparation of 3,5-bis-(β-d-glycopyranosyl)-1,2,4-thiadiazoles from C-(β-d-glycopyranosyl)thioformamides. Tetrahedron.2001,57(13),2469 2476.
[23]Kiumars Bahrami, Mohammad M. Khodaei, Mehdi Sheikh Arabi. TAPC-Promoted Oxidation of Sulfides and Deoxygenation of Sulfoxides. J. Org. Chem.2010,75 (18),6208-6213.
[24]Satoh, Tsuyoshi; Kondo, Atsushi; Musashi, Jun. Generation of magnesium carbeno ids from 1-chloroalkyl phenyl sulfoxides with a Grignard reagent and applications to alkylation and olefin synthesis. Tetrahedron.2004, 60(25), 5453-5460.
[25]David B. Berkowitz. a-Vinylic amino acids:occurrence, asymmetric synthesis, and biochemical mechanisms. Tetrahedron:Asymmetry.2006,17,869-882.
[26]Lumbroso, Alexandre. An efficient and scalable synthesis of N-(benzyloxy-carbonyl)-and N-(methyloxycarbonyl)-(S)-vinylglycinol. Tetrahedron Letters. 2010, 51 (24),3226-3228.
[27]Truong, Thien Van; Rapoport, Henry. Chirospecific synthesis of the tetrahydro-imidazodiazepinol aglycon of pentostatin and its analogs. J. Org. Chem.1993,58 (22),6090-6096.
[28]Santiago Rodriguez. Diastereoselective synthesis of γ-hydroxy α, β-epoxy-esters and their conversion into (3-hydroxy a-sulfenyl y-butyrolactones. Tetrahedron.2006, 62(48),11112-11123.
[29]Fowler Joseph C, US650934,1900.
[30]Mansour Haddad, Marc Larcheveque. A Straight Route Towards Glyceric Chirons. Synthetic Communications. 2003,33(5), 687-692.
[31]Hirai Kenji, Ono Ryuta, JP9227535A,1996.
[32]Hatakeyama, Susumi. Efficient enantiospecific synthesis of key A-ring synthons for the preparation of 1.alpha.,25-dihydroxyvitamin D3 using a chro miu m (Ⅱ)-mediated reaction. J. Org. Chem.1989,54 (15),3515-3517.
[33]Canet, Jean-Louis; Fadel, Antoine; Salauen, Jacques. Asymmetric construction of quaternary carbons from chiral malonates:selective and versatile total syntheses of the enantiomers of alpha and beta cuparenones from a common optically active precursor. J. Org. Chem.1992,57 (12),3463-3473.
[34]Lubell William, Jamieson Andrew, WO2010105367,2009.
[35]Patrick.Meffre, Philippe.Durand, Francois.Le Goffic. Straightforward Synthesis of Optically Pure Methyl (S)-2-Phthalimido-4-oxobutanoate and Some of Its Acetal and Thioacetal Derivatives. Synthesis. 1995,9,1111-1114.
[36]Wenkert, E. Oxycyclopropanes in organochemical synthesis. Total syntheses of (+-.)-.alpha.-cuparenone and (.+-.)-.beta.-vetivone. J. Am. Chem. Soc. 1978,100(4), 1267-1273.
[37]Martin A. Berliner, Katherine Belecki. Simple, Rapid Procedure for the Synthes is of Chloromethyl Methyl Ether and Other Chloro Alkyl Ethers. J. Org. Chem.2005, 70,9618-9621.
[38]Yoshihiro Yamauchi, Yoshihiro Miyake, Yoshiaki Nishibayashi. Rutheniu m-Cat alyzed Oxypropargylation of Alkenes. Organometallics.2009,28 (1),48-50.
[39]Robert A. Mosey. Synthesis of tert-Alkyl Amino Hydroxy Carboxylic Esters via an Intermolecular Ene-Type Reaction of Oxazolones and Enol Ethers. Org. Lett.2008, 10(5),825-828.
[40]Aqeel Ahmed, Patrick H. Dussault. Stereoselective allylation of chiral mono-peroxya cetals. Tetradedron.2005,61,4657-4670.
[41]Dehmlow, Eckehard Volker; Westerheide, Ralf. A New Simple Route to N,O-Prote-cted (S)-2-Amino-4-oxobutyric Acid. Synthesis.1993,12,1225-1226.
[42]Robert J. Jones, Henry Rapoport. Enantiospecific synthesis of an aziridino-benzazocinone, an advanced intermediate containing the core nucleus of FR900482 and FK973. J. Org. Chem.1990,55 (4),1144-1146.
[43]Fukuchi. Journal of the Chemical Society, Perkin Transactions 1:Organic and Bio-Organic Chemistry (1972-1999).1992,9,1149-1158.