CN102614923A - 一种手性双膦配体-铱复合纳米催化剂及其在不对称氢化合成(s)-异丙甲草胺中的应用 - Google Patents
一种手性双膦配体-铱复合纳米催化剂及其在不对称氢化合成(s)-异丙甲草胺中的应用 Download PDFInfo
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Abstract
本发明涉及一种手性双膦配体-铱复合纳米催化剂及其用途。这些催化剂是由手性双膦配体-铱复合催化剂与纳米材料复合在一起制得,用此催化剂催化2-甲基-6-乙基-N-亚甲基苯胺(EMA-亚胺)氢化反应可得到(S)-N-(1-甲氧基-2-丙基)-2-甲基-6-乙基苯胺((S)-NAA),对映体过量值(ee)可达到85%,将(S)-NAA与氯乙酰氯进行酰化反应获得ee值84.5%的(S)-异丙甲草胺,该催化剂可重复使用5次以上。
Description
技术领域
本发明属于手性农药的生产技术领域。本发明提供的手性双膦配体与铱--环辛二烯配合物([IrCl(cod)]2)与纳米载体作用得到的手性双膦配体-铱复合催化剂可应用于亚胺的不对称氢化反应,进而可用以用于手性除草剂(S-)异丙甲草胺的生产。
技术背景
异丙甲草胺(商品名:Dual)是由前汽巴-嘉基公司研制的广谱除草剂,对人、畜低毒,可用于玉米和其他多种旱田农作物防除一年生禾本科杂草及阔叶性杂草。研究发现异丙甲草胺具有四个立体异构体,一个手性轴和一个手性中心,且95%的除草活性存在于(1’S)-非对映异构体中,其立体结构式如下:
四种异构体中,(aR,1S)体以及(aS,1S)体为有效体,而(aS,1R)以及(aR,1R)为低效体(Byung T C等,Tetrahedron:Asymmetry.1992,3(3),337)。环境保护的压力要求减少低效体或无效体的直接排放,2002年,欧盟开始禁用混旋的异丙甲草胺,导致近年来(S)-异丙甲草胺((S)-metolachlor)的市场需求量显著增加。据调查显示,2002年异丙甲草胺年全球销售额达到4.36亿美元,其中(S)-异丙甲草胺销售额达到2.44亿美元,仅次于草甘膦,位居 第二。
据文献报道,有三种路线可用来合成(S)-异丙甲草胺:1、以手性乳酸酯为原料的手性合成子路线。在已公开的专利CN 101367746中,我们用价格低廉的L-乳酸酯为手性原料,通过五步反应获得了ee值为85%左右的(S)-异丙甲草胺,但该方法存在一定的局限:步骤较多,工业化生产的成本仍较高。2、拆分路线:用2-溴丙酸酯为原料,与2-甲基-6-乙基苯胺进行缩合得到N-(2-甲基-6-乙基苯基)丙氨酸酯,对其进行化学(US 5002606)或酶动力学拆分(Zhang Suoqin等,Can.J.Chem.2006,84,1058)后,进行还原、酰基化、甲基化等反应获得(S)-异丙甲草胺,拆分得到的无效异构体可以通过消旋化反复利用,其产品的ee值可达到90%以上。但该过程步骤仍然较长,反应过程不具原子经济性。3、亚胺不对称氢化路线:与混旋体异丙甲草胺的生产工艺的主要差别在于对N-(2/-甲基-6/-乙基苯基)-1-甲氧基丙酮亚胺(EMA-亚胺)的氢化时使用了手性催化剂。据报道下述手性双膦配体与Rh(I)、Ru、Ir等过渡金属形成的催化剂在亚胺不对称氢化领域取得较好的效果(参见如下结构式)(Kagan H B,et al.Journal of Organometallic Chemistry.1975,90(3),353;Oppolzer W,et al.Tetrahedron Letters 1990,31(29),4117;Blaser H U,et al.Advanced Synthesis Catalysis 2002,334(1),17;Colacot T J.Chemical Reviews 2003,103(8),3101;Ramon M C,et al.Tetrahedron:Asymmetry 2000,11(7),1469.):
Spindler等以Ir与手性双膦BDPP形成的[IrCl(cod)]2/BDPP为催化剂,实现 了(S)-异丙甲草胺的中间体的定向合成。随后他们对这一合成工艺又作出改进:将[IrCl(cod)]2,(R)-(S)-xyliphos,助催化剂碘化物和酸一起加入到反应器中(S/C=106),在323K,80bar下反应初始TOF值超过1.8×106h-1,时间仅需要4h,得到(S)-异丙甲草胺,ee值可达到80%。研究表明,助催化剂碘化物和酸的用量对手性控制有很重要的影响(WO 9521151;Blaser H U,et al.Advanced Synthesis Catalysis 2002,334(1),17)。
无疑,在合成(S)-异丙甲草胺的三种路线中,不对称氢化最具生产清洁性和原子经济性。本课题组于2010年申请了一项有关发明专利(CN 201010197924.7),主要是一类手性双膦配体与[IrCl(cod)]2、四丁基碘化铵、冰醋酸形成的原位催化剂是一类有效的亚胺氢化不对称催化剂,及其用于合成手性农药(S)-异丙甲草胺的合成,e.e.%可达85%。但是该方法的催化剂难以重复利用,使得其使用成本较高,为此,本申请在前述申请的基础上将该催化剂负载于纳米颗粒上,使得该催化剂可重复使用5次以上,而e.e.%基本不下降。
发明内容
本发明所涉及的一种手性双膦配体-铱复合纳米催化剂制备方法是,结构如通式如下的手性双膦配体I-铱复合催化剂溶解在溶剂中,加入纳米材料搅拌,旋蒸除去溶剂。
结构通式I
其中,R为甲基、乙基、丙基、异丙基、正丁基、仲丁基、叔丁基中的一种。
其中纳米材料为纳米二氧化硅,纳米二氧化钛。
其中溶剂为乙醚,乙酸乙酯,乙醇,氯仿和四氢呋喃。
将N-(2-甲基-6-乙基苯基)-1-甲氧基丙酮亚胺(EMA-亚胺)及权利要求1所述的复合纳米催化剂按照EMA-亚胺与复合催化剂II的摩尔比为105~106加入到压力釜中,在80~120公斤压力、30~130℃下进行氢化反应5~60小时,得到(S)-N-(1-甲氧基-2-丙基)-2-甲基-6-乙基苯胺((S)-NAA),其e.e.%最高可达到85%;将(S)-NAA与氯乙酰氯进行酰化反应得到(S)-异丙甲草胺,ee值可达到85%,该催化剂可重复使用5次以上,其收率和e.e.%基本不下降。
以下提供本发明的具体实施方式,可以说明本发明涉及的手性配体及催化剂的制备方法及其在(S)-异丙甲草胺的合成中的应用,但不对本发明的权利要求构成限制。
具体实施方式
实施例一 配体Ia(结构通式I,R=甲基)-铱复合纳米催化剂IIat的制备
手性双膦配体Ia(结构通式I,R=甲基)-铱复合催化剂溶解在乙醚中,加入20%纳米二氧化钛搅拌,旋蒸除去乙醚,即得配体Ia-铱复合纳米催化剂IIat。
实施例二 配体Ib(如结构通式I,R=叔丁基)-铱复合纳米催化剂IIbs的制备
手性双膦配体Ib(如结构通式I,R=叔丁基)-铱复合催化剂溶解在乙酸乙酯中,加入20%纳米二氧化硅搅拌,旋蒸除去乙酸乙酯,即得配体Ib-铱复合纳米催化剂IIbs。
实施例三 配体Ic(如结构通式I,R=乙基)-铱复合纳米催化剂IIct的制备
手性双膦配体Ic(如结构通式I,R=乙基)-铱复合催化剂溶解在氯仿中,加入20%纳米二氧化钛搅拌,旋蒸除去溶剂,即得配体Ic-铱复合纳米催化剂IIct。
实施例四 配体Ib(如结构通式I,R=叔丁基)-铱复合纳米催化剂IIbt的制备
手性双膦配体Ib(如结构通式I,R=叔丁基)-铱复合催化剂溶解在乙醇中,加入20%纳米二氧化钛搅拌,旋蒸除去溶剂,即得配体Ib-铱复合纳米催化剂IIbt。
实施例五 配体Id(如结构通式I,R=丁基)-铱复合纳米催化剂IIds的制备
手性双膦配体Id(如结构通式I,R=丁基)-铱复合催化剂溶解在四氢呋喃中,加入20%纳米二氧化硅搅拌,旋蒸除去四氢呋喃,即得配体Id-铱复合纳米催化剂IIds。
实施例六 复合催化剂IIat在EMA-亚胺的氢化反应中的催化应用
将将新蒸馏的EMA-亚胺(1mol)、冰醋酸(80mL)加入到500mL高压反应釜中。将催化剂IIat加入到反应釜中,气体交换后,调节压力至90公斤、温度50℃下进行氢化反应。气相色谱跟踪:10h,转化率达到98%。冷却后取出物料,减压蒸出冰醋酸,剩余物用二氯乙烷分散,加入5%氢氧化钠溶液(30mL)洗涤,水洗,脱去溶剂得到(S)-NAA,收率90%。气相色谱归一法分析含量:95%,用手性高效液相方法分析ee值:85%(柱型:Daicel Chiralcel-OD,流动相:正己烷/异丙醇:95∶5)。
实施例七 催化剂IIbs在EMA-亚胺的氢化反应中的催化应用
将新蒸馏的EMA-亚胺(1mol)、冰醋酸(40mL)加入到500mL高压反应釜中。将催化剂IIbs加入到反应釜中,气体交换后,调节压力至80公斤、温度80℃下进行氢化反应。气相色谱跟踪:15h后转化率达到98%。冷却后取出物料,减压蒸出冰醋酸,剩余物用二氯乙烷分散,加入5%氢氧化钠溶液(30mL)洗涤,水洗,脱去溶剂得到(S)-NAA,收率89%。用手性高效液相方法分析ee 值:80%(柱型:Daicel Chiralcel-OD,流动相:正己烷/异丙醇:95∶5)。
实施例八 催化剂IIbt催化EMA-亚胺的氢化反应
将新蒸馏的EMA-亚胺(1mol)、冰醋酸(100mL)加入到500mL高压反应釜中。将催化剂IIbt加入到反应釜中,气体交换后,调节压力至120公斤、温度40℃下进行氢化反应。气相色谱跟踪:26h后转化率达到98%。冷却后取出物料,减压蒸出冰醋酸,剩余物用二氯乙烷分散,加入5%氢氧化钠溶液中和至pH=7,有机层用水洗涤,无水硫酸钠干燥,脱去溶剂得到(S)-NAA,收率:91%。用手性高效液相方法分析产物的ee值为84.5%(柱型:Daicel Chiralcel-OD,流动相:正己烷/异丙醇:97∶3)。
实施例九 催化剂IIds催化EMA-亚胺氢化反应
将新蒸馏的EMA-亚胺(1mol)、冰醋酸(100mL)加入到500mL高压反应釜中。将催化剂IIds加入到反应釜中,气体交换后,调节压力至100公斤、温度115℃,气相色谱跟踪:6h,EMA-亚胺转化率达到80%,15h后转化率达到98%。冷却后取出物料,减压蒸出冰醋酸,剩余物用二氯乙烷分散,用5%氢氧化钠溶液中和至pH=7,有机层用水洗涤,无水硫酸钠干燥,脱去溶剂得到(S)-NAA,收率88%。用手性高效液相方法分析产物的ee值为80%(柱型:Daicel Chiralcel-OD,流动相:正己烷/异丙醇:97∶3)。
实施例十~十五 催化剂IIat重复使用催化EMA-亚胺的氢化反应
按照实施例一的操作,将回收得到的催化剂IIat重复应用,结果如表1所示。
表1 催化剂IIat重复应用情况
序号 | 重复次数 | 收率% | ee值% | 催化剂回收率 |
实施例十 | 2 | 90 | 85 | 98 |
实施例十一 | 3 | 90 | 84.7 | 98 |
实施例十二 | 4 | 88 | 84.5 | 97 |
实施例十三 | 5 | 88 | 84.2 | 97 |
实施例十四 | 6 | 83 | 84 | 96 |
实施例十五 | 7 | 83 | 83 | 93 |
Claims (4)
2.如权利要求1所述的手性双膦配体-铱复合纳米催化剂的制备方法,其特征在于:纳米材料为纳米二氧化硅,纳米二氧化钛。
3.如权利要求1所述的手性双膦配体-铱复合纳米催化剂的制备方法,其特征在于:溶剂为乙醚,乙酸乙酯,乙醇,氯仿和四氢呋喃。
4.如权利要求1所述的手性双膦配体-铱复合纳米催化剂在亚胺不对称氢化反应合成手性农药(S)-异丙甲草胺中的应用,其特征在于:将N-(2-甲基-6-乙基苯基)-1-甲氧基丙酮亚胺(EMA-亚胺)及权利要求1所述的复合纳米催化剂按照EMA-亚胺与复合催化剂II的摩尔比为105~106加入到压力釜中,在80~120公斤压力、30~130℃下进行氢化反应5~60小时,得到(S)-N-(1-甲氧基-2-丙基)-2-甲基-6-乙基苯胺(S)-NAA,其e.e.%最高可达到85%;将(S)-NAA与氯乙酰氯进行酰化反应得到(S)-异丙甲草胺,e.e.%可达到85%,该催化剂可重复使用5次以上,其收率和e.e.%基本不下降。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105523947A (zh) * | 2016-01-19 | 2016-04-27 | 江苏长青农化南通有限公司 | 精异丙甲草胺连续化不对称氢化反应工艺 |
PT108303A (pt) * | 2015-03-20 | 2016-09-20 | Sapec Agro S A | Processo de produção de (s)-metolacloro |
CN106866730A (zh) * | 2015-12-14 | 2017-06-20 | 中国科学院大连化学物理研究所 | 一种钯催化亚胺膦酸酯不对称氢化合成手性胺基膦酸酯的方法 |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101028604A (zh) * | 2006-03-01 | 2007-09-05 | 中国科学院大连化学物理研究所 | 一种多相手性金属催化剂及其制备方法 |
CN101857612A (zh) * | 2010-06-11 | 2010-10-13 | 南京工业大学 | 一类手性双膦配体及其铱复合催化剂、制备方法及在不对称氢化合成(s)-异丙甲草胺中的应用 |
-
2012
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101028604A (zh) * | 2006-03-01 | 2007-09-05 | 中国科学院大连化学物理研究所 | 一种多相手性金属催化剂及其制备方法 |
CN101857612A (zh) * | 2010-06-11 | 2010-10-13 | 南京工业大学 | 一类手性双膦配体及其铱复合催化剂、制备方法及在不对称氢化合成(s)-异丙甲草胺中的应用 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PT108303A (pt) * | 2015-03-20 | 2016-09-20 | Sapec Agro S A | Processo de produção de (s)-metolacloro |
CN106866730A (zh) * | 2015-12-14 | 2017-06-20 | 中国科学院大连化学物理研究所 | 一种钯催化亚胺膦酸酯不对称氢化合成手性胺基膦酸酯的方法 |
CN105523947A (zh) * | 2016-01-19 | 2016-04-27 | 江苏长青农化南通有限公司 | 精异丙甲草胺连续化不对称氢化反应工艺 |
CN111138310A (zh) * | 2019-12-23 | 2020-05-12 | 江苏长青农化股份有限公司 | (s)-异丙甲草胺的制备方法以及制备过程中使用的催化剂 |
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