CN1802341A - 制备工业化学品的方法 - Google Patents
制备工业化学品的方法 Download PDFInfo
- Publication number
- CN1802341A CN1802341A CNA2004800021727A CN200480002172A CN1802341A CN 1802341 A CN1802341 A CN 1802341A CN A2004800021727 A CNA2004800021727 A CN A2004800021727A CN 200480002172 A CN200480002172 A CN 200480002172A CN 1802341 A CN1802341 A CN 1802341A
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- Prior art keywords
- acid
- derivative
- octene
- metathesis catalyst
- ester
- Prior art date
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Abstract
本发明公开了从可再生资源生产具有工业重要性的化学品的方法。“生物基”方法采用容易得到的可再生资源包括脂肪酸而不是采用矿物资源如煤炭和石油。在本发明方法的一个实施方案中,通过酶介导的异构化反应,然后通过与乙烯的易位反应,从亚油酸生产1-辛烯、以及9-癸烯酸酯和丁二烯。亚油酸可以分离自植物油如大豆油。
Description
相关申请的交叉引用
本申请要求于2003年1月13号提交的美国临时申请第60/439,959号的优先权,该文献被并入本文作为参考。
技术领域
本发明涉及制备工业有机化学品的方法,该方法的一个实施方案包括例如烯烃特别是脂肪酸或脂肪酸衍生物的酶介导异构化的不饱和位置的异构化与易位化学的结合。
背景技术
用于生产各种工业产品如涂料、溶剂、合成纤维和塑料的有机化学品,目前主要从石油基产品合成。另外,大部分的药物和精细化学品也从衍生自石油的有机化学品生产。实际上,美国每年生产的上亿吨以上的精细化学品,特别是中间化学品和日用化学品中,仅有十分之一的这些化合物品是基于生物而生产的,即,从可再生资源生产。Committee on Biobased Industrial Products,Biobased Industrial Products:Research and Commercialization Priorities,National Academies Press:Washington,DC,1999,pp.17,18。越来越需要用衍生自可再生资源的化学品替代衍生自石油的化学品。
不饱和化合物,如链烯(其在本文中也称作烯烃),是用于生产各种产品的特别重要的化学原料,包括聚乙烯、聚丙烯和聚丁烯聚合物。通过与各种不饱和化学品共聚,这些聚合物得以改性。例如,直链低密度聚乙烯(LLDPE)通过乙烯和1-辛烯共聚生产。已知用于从石油基资源生产1-辛烯的方法,如费-托法或SHOP型乙烯齐聚法,效率低下而且以统计学比例生成低聚产品的混合物。因此,生产了大量不需要的材料,因此,目前1-辛烯缺乏,由于1-辛烯的供应受到限制而约束了LLDPE的生产。
另一个与目前的方法有关的不利之处是,在煤炭和石油的提取和加工过程中,释放污染物,对环境和人体健康造成了巨大的潜在危害。因此,除了经济学影响之外,越来越多的对环境和健康的担忧提供了从可再生资源开发生物基产品来替代石油基产品的动力。
形成不饱和工业化学品的一个可能的方法是易位化学法。易位通常包括使两种不同的化合物通过互换两种分子之间的原子或原子的基团而反应。烯烃易位反应可以被认为是这样一种反应,其中烯烃中的碳-碳双键断开,并以统计学方式重新排列。链烯易位的例子在图解1中说明。
图解1
最近几年中,随着新的、明确的、耐官能团的易位催化剂的开发,已经将易位化学应用到高分子化学和络合物全合成中。例如参见Fürstner,A.Olefin Metathesis and Beyond.Angew.Chem.,Int.Ed.Engl.2000,39,3012-3043。
Newman等人的PCT申请第WO 02/076920(Newman)中公开了不饱和脂肪酸酯或者不饱和脂肪酸与短链烯烃的易位法。Newman公开了“在易位催化剂的存在下,将不饱和脂肪酸酯或者不饱和脂肪酸…与乙烯接触”,Newman,第5页,第22-24行。Newman陈述了在“与此有关的最优选实施方案中,不饱和脂肪酸是油酸;低级烯烃是乙烯;烯烃易位产品包括1-癸烯和9-癸烯酸”,Newman,第5页第32行到第6页第2行。然而,Newman未公开任何用于使脂肪酸或者脂肪酸衍生物异构化的方法,也未教导共轭亚油酸或其制备方法。纽曼也未公开生产1-辛烯的方法。
因此,考虑到上述原因,希望用于将可再生资源转化成工业化学品如1-辛烯的新方法。
发明内容
根据本文公开的该方法的实施方案,具有工业重要性的不饱和烃从可再生资源生产。在具体实施方案中,可再生资源是脂肪酸或者脂肪酸衍生物。具有至少一个不饱和位置的脂肪酸可容易地得自植物油,包括但不限于大豆、蓖麻子、脱水蓖麻子、玉米、黄瓜、罂粟种子、红花、亚麻子、油菜籽、诸葛菜(lesquerella)、亚麻子、葡萄子、向日葵、胡桃、南瓜、棉籽、白芒花、芥菜籽、花生、紫苏、tall、桐树和芝麻油。在某些实施方案中,加工油如吹制油是脂肪酸的来源。尽管植物油是实施本发明方法的实施方案的优选资源,但是也可使用得自动物脂肪的脂肪酸,包括但不限于猪油和鱼油,例如沙丁鱼油和鲱鱼油等等。如上所述,在某些实施方案中,所需的脂肪酸或者脂肪酸前体从实际发现的植物或动物生产。然而,特定的脂肪酸或者脂肪酸前体有利地得自基因改性有机物,如基因改性植物。这些基因改性有机物经设计用于以生物合成的方式生产所需脂肪酸或者脂肪酸前体,或用于生产大量的这些化合物。
公开的本发明方法的一个实施方案包括提供不饱和化合物,如共轭亚油酸(例如Δ9,11-十八碳二烯酸),使该化合物与易位催化剂接触,生产所需的低级烯烃。或者,公开的实施方案包括提供不饱和化合物,例如脂肪酸或者脂肪酸衍生物,使脂肪酸或者脂肪酸衍生物中的不饱和位置异构化,生产异构化的脂肪酸或者脂肪酸衍生物,然后使该异构化的脂肪酸或者脂肪酸酯与低级烯烃或炔在易位催化剂的存在下接触。如本文所用的,“低级”通常是指具有至多20个碳原子、通常具有1个-约10个碳原子的化合物。对于易位反应,在提供至少一种不饱和产品,该不饱和产品是链烯、炔、或二者都是的条件下进行接触步骤。通常,在该实施方案中,经受易位反应的不饱和脂肪酸衍生物是二烯;然而,也可以使用单不饱和脂肪酸以及具有至少两个不饱和位置的脂肪酸。在该方法的一个方面中,单不饱和脂肪酸从多不饱和脂肪酸生产。
在有或没有随后的酯化作用或者酯交换的条件下,可通过脂肪酸或者脂肪酸酯的异构化生产异构化的脂肪酸或者脂肪酸酯。异构化可以通过生化技术或者化学技术催化。例如,可使用异构酶如亚油酸异构酶将亚油酸的顺式9,顺式12异构体异构化为顺式9,反式11异构体。该异构化方法是立体有择的,然而,可使用非立体有择方法,因为顺反异构体两者都适用于易位。例如,可替代的方法使用了化学异构化催化剂,如酸性或者碱性催化剂,可用于使在分子中的一个位置处具有不饱和位置的不饱和脂肪酸或者脂肪酸衍生物异构化,变成在分子中的不同位置处具有不饱和位置的不饱和脂肪酸或者脂肪酸衍生物。金属或者有机金属催化剂也可用于不饱和脂肪酸或者脂肪酸衍生物的异构化。例如,已知镍催化剂催化脂肪酸衍生物中不饱和位置的位置异构化。同样地,原料化合物或者产品例如脂肪酸或者脂肪酸衍生物的酯化作用、酯交换、还原、氧化和/或其它改性可通过生化技术或者化学技术催化。例如,脂肪酸或者脂肪酸衍生物在异构化之前或之后可以通过脂肪酶、酯酶、还原酶或者其他酶改性。
在特别公开的实施方案中,该方法涉及了使用亚油酸异构酶将亚油酸或者亚油酸衍生物转化成顺式9,反式11异构体,然后顺式9,反式11异构体在乙烯的存在下经受易位反应条件。所得易位反应生成了工业上有用的产品,包括1,3-丁二烯,1-辛烯和9-癸烯酸或其衍生物。特定的衍生物包括9-癸烯酸酯,如9-癸烯酸低级烷基酯。
在该方法的另一个实施方案中,在固定化反应器中使用了酶例如异构酶,使易位反应底物可被连续地生产。在具体实施方案中,亚油酸异构酶与固相支持体结合,固定化酶反应器使用经过分离的结合亚油酸异构酶构建。
在公开的本发明方法的另一个实施方案中,使用了固定化易位催化剂。易位催化剂的固定能够得到要用于易位法的流动条件并可帮助催化剂再循环。
附图说明
图1是转化率-时间(小时)曲线,说明了在各种易位催化剂的存在下通过乙烯醇分解从Δ9,11-十八碳二烯酸向9-癸烯酸甲酯转化的时程。
图2是转化率-时间(小时)曲线,说明了在各种易位催化剂的存在下通过乙烯醇分解从Δ9,11-十八碳二烯酸向1-辛烯转化的时程。
发明详述
根据公开的本发明方法的实施方案,工业化学品可从可再生资源生产,农作物可用作用于生产这些工业化学品的化学原料。尽管本发明的方法不局限于使用脂肪酸作为用于生产工业化学品的前体,特别公开的本发明方法的实施方案使用了可得自可再生资源的脂肪酸和脂肪酸衍生物。如本文所用,术语“脂肪酸”泛指任何通过水解从脂肪,特别是那些在动植物油中发现的脂肪得来的羧酸。代表性地,然而并非必要地,脂肪酸是具有约3到约20个碳原子的直链烃。也可以理解,某些化合物等价于脂肪酸,例如,脂肪酸及其相应的盐和酯可容易地互换。通常,在本发明方法中使用的酯衍生物是低级烷基酯,所述低级烷基包括但不限于甲基、乙基、丙基、异丙基、丁基、叔丁基、仲丁基、异丁基等。另外,包括来源于脂肪酸或理论上来源于脂肪酸的任何化合物或者化合物的一部分的脂肪酸衍生物,包括但不限于酯化、脱水、还原和氧化的脂肪酸衍生物。例如,脂肪酸可以在羧化物或者在不饱和位置被还原,得到可用于根据本发明的方法生产工业化学品的脂肪酸衍生物。
根据公开的本发明方法的实施方案,前体脂肪酸是经过分离的。脂肪酸可经过改性得到脂肪酸衍生物。然后通过至少一种易位反应,脂肪酸衍生物转化为一种或多种工业化学品。在该方法的某些方面,脂肪酸直接经受易位条件而无任何化学改性。这种直接易位法的产品可选择性地经过化学改性,生产出所需衍生物。后面将进一步描述本发明方法的各个步骤的实施方案。
I.可再生资源
用于工业化学品的生物基生产的原材料包括油,如植物油和动物脂肪。目前只有少数具有工业重要性的化学品可通过这些原材料与链烯或者炔的直接易位生产。为了解决这一问题,本发明方法的实施方案提供了在易位之前对这些原材料异构化,从这些原材料生产工业化学品的方法。例如,目前1-辛烯不足,但是不能直接通过任何常见的脂肪酸的易位获得1-辛烯。
根据本发明方法的特定实施方案,可通过异构化法和易位法的结合使用,从可再生资源生产1-辛烯。例如,亚油酸可异构化为共轭亚油酸(CLA)。CLA是指亚油酸的几个共轭异构体的通用术语。任何在9和11位具有烯(顺式或反式)的CLA可用于生产工业有用的化学品1-辛烯,丁二烯和9-癸烯酸。
历史上,已经通过在强碱性材料如氢氧化物的存在下加热亚油酸而生产共轭亚油酸。这一工序提供了具有共轭位置的异构体的混合物、以及顺式和反式双键的混合物。本发明方法的实施方案展示了酶促变换的选择性,其生产出在9和11位具有烯并基本上没有其它CLA异构体的CLA。
不饱和脂肪酸在本文中的命名根据它们的普通名称,***名称,或由碳数表示的简写名称,后面跟有任意双键的数目和位置,其从羧化物的碳开始数起。例如,具有普通名称亚油酸的结构8(图解2),具有十八个碳原子和两个双键,第一个双键在第九和第十个碳之间,第二个双键在第十二和第十三个碳之间。因此,亚油酸8***命名为Δ9,12-十八碳二烯酸,其中“十八”是指具有18个碳原子,“二烯”是指具有两个双键,Δ9,12是指链烯碳。“酸(oic)”是指该化合物是游离羧酸,而不是酯化羧酸。用于命名亚油酸8的简记体系为18:2Δ9,12,其中18是指碳数,2是指双键数,Δ9,12是指碳链上两个双键的位置。
对于图解2,在酶,即亚油酸异构酶的存在下,Δ9,12-十八碳二烯酸8异构化为Δ9,11-十八碳二烯酸10。在本发明方法的另一个实施方案中,单烯脂肪酸如具有C-11烯的11-十八碳烯酸异构体通过异构化反应、氢化反应、或通过这两种方法生产。例如,在该方法的一个方面中,具有C-11烯的二烯和另一种烯烃被选择地酶促还原,得到Δ11-十八碳烯酸。这种变换通过例如鲁门微生物实施,参见Kelly等人的J.Nutr.1998,128,881-885,起被并入本文作为参考。这种11-十八碳烯酸异构体也是用于通过易位生产1-辛烯的有用的中间体。
图解2
根据公开的本发明方法的实施方案,其使用酶来异构化不饱和位置,该酶可以是经过分离的酶或可作为全细胞制剂被使用。“分离的”是指经过部分纯化或基本上完全纯化的酶。分离酶可提高酶活性。经过分离的酶的例子包括粗提物、膜结合酶、可溶性酶、重组生产的酶、增溶酶等等。在特定实施方案中,酶可通过与脂质、蛋白质、人工膜或其组合被增溶或者稳定化。
在使用亚油酸异构酶的实施方案中,该酶可以是经过分离的,或以全细胞形式使用,根据Rosson等人在PCT公开第WO 99/32604中公开的方法。某些实施方案可以使用全细胞生产Δ9,11-十八碳二烯酸,根据Pariza和Yang在美国专利第6,060,304中公开的发酵方案。公开的PCT公开第WO 99/32604和美国专利第6,060,304被并入本文作为参考。
某些实施方案中,酶或具有酶的细胞可被固定化。例如,可通过选自基质截留、微囊法、吸附、和共价键合的技术固定酶。表达酶的细胞可通过使用双官能或多官能交联剂交联到表面上而固定,或可通过非共价相互作用,如蛋白质-配体相互作用结合到表面上。在这些实施方案中,可使用流动反应器进行异构化反应。
另一个变为化合物10的路线使用了Δ9-十八碳烯酸(未示出)并使用了Δ11-去饱和酶来生产化合物10。或者,另一个路线使用了饱和原材料,硬脂酸和Δ11-脱氢酶来生产Δ11-十八碳烯酸(未示出),其通常称作11-十八碳烯酸,这种路线同样可使用Δ9-去饱和酶来生产化合物10。Δ11-十八碳烯酸是用于生产1-辛烯的有用的中间体,并且该脂肪酸也可通过容易获得的Δ9,12-十八碳二烯酸异构化为Δ9,11-十八碳二烯酸,然后通过Δ9双键的选择性酶促还原而生产。
II.易位
根据本发明方法的实施方案,任何已知的或将来开发出的易位催化剂可以单独使用、或与一种或多种其它催化剂组合使用。用于该所公开的实施方案的典型的易位催化剂包括基于过渡金属例如钌的金属碳烯催化剂。示例性的钌基易位催化剂包括那些由结构12(通常称作Grubbs′s催化剂)的市售催化剂,结构14和16表示的催化剂。
下面所述的结构18-28代表了其它有用的钌基易位催化剂。使用催化剂12-28以及其它有关的易位催化剂的技术在PCT公开第WO99/26949、WO 00/71554、WO 02/14376和美国专利申请公开第2002/0177710中公开。这些专利公开文献被全文并入本文作为参考。
其它易位催化剂包括但不限于选自钼、锇、铬、铼、钨和钨碳烯复合物的金属碳烯复合物。术语“络合物”是指金属原子如过渡金属原子与至少一种与所述金属原子协同或结合的配体或络合剂。这种配体在可用于链烯、炔或者链烯易位的金属碳烯复合物中通常是路易斯碱。这种配体的典型实例包括膦、卤化物和稳定的碳烯。一些易位催化剂使用多种金属或者金属共催化剂。例如,德国专利公开第A1-282591(并入本文作为参考)公开了包括钨卤化物、四烷基锡化合物和有机铝化合物的催化剂。
固定化催化剂可用于易位法。例如参见Blechert等人的Synthesisand Application of a Permanently Immobilized Olefin MetathesisCatalyst,Angew.Chem.Int.Ed.Engl.,2000,39,3898-3901,并入本文作为参考。这种固定化酶可用于流水作业,该作业是本领域技术人员公开的。固定化酶可简化产品的纯化和催化剂的回收,方便催化剂的再循环。
用于生产工业化学品的易位法可在任何足够生产所需易位产品或者各种产品的条件下进行。例如,可选择化学计算法、大气、溶剂、温度与压力来生产所需产品并使不受欢迎的副产品最小化。易位法通常在惰性气氛下进行。同样地,如果提供的烯烃或者炔试剂是气体,则可使用惰性气体稀释剂。惰性气氛或者惰性气体稀释剂通常是惰性气体,是指气体不影响易位催化剂以基本上阻碍催化作用。例如,特定的惰性气体选自氦、氖、氩、氮及其组合。再某些实施方案中,使用了气态的低级不饱和试剂。在这种实施方案中,可以在有气体稀释剂或无气体稀释剂的条件下使用低级不饱和试剂。
同样地,如果使用了溶剂,则通常选择的溶剂相对于易位催化剂基本上是惰性的。例如,基本上为惰性的溶剂包括但不限于芳香族烃,例如苯、甲苯、二甲苯等等;卤化芳香族烃,例如氯苯和二氯苯;脂肪族溶剂,包括戊烷、己烷、庚烷、环己烷等等;氯化链烷,例如二氯甲烷、氯仿、二氯乙烷等等。
在某些实施方案中,将配体加入到易位反应混合物中。通常配体是可稳定催化剂从而增加催化剂周转率的分子。有时候,配体可改变反应选择性和产品分布。可用配体的例子包括路易斯碱配体,例如但不限于三烷基膦,例如,三环己基膦和三丁基膦;三芳基膦,如三苯基膦;二芳基烷基膦,如二苯基环己基膦;吡啶,例如2,6-二甲基吡啶,2,4,6-三甲基吡啶;以及其它的路易斯碱性配体,如氧化膦和phosphinite。
使用目前已知的催化剂,易位反应温度很大程度上是速率依赖性变量,其中选择温度来以可接受的生产率提供所需产品。所选温度通常大于约-40℃,通常大于约-20℃,更通常大于约0℃,最典型地大于约20℃。通常,易位反应温度通常小于约150℃,优选小于约120。因此,易位反应目前的优选温度范围为大于约20℃到约120℃。可使用更低的温度,例如,来使不希望有的杂质的产生最小化,或有利于特定的反应通路。使用温度控制反映速率和改变反应产物的例子在PCT公开第WO 02/094748(作为参考引入本文)中公开。
易位反应可在任何气体链烯、炔和/或稀释剂的压力下进行。总压力通常大于约30kPa,更通常大于约100kPa。通常,总压力小于约7,000kPa,更通常小于约3,000kPa。因此,易位反应的可能有用的压力范围为约100kPa到约3,000kPa之间的压力。
任何可用量的所选易位催化剂可被用于目前的方法中。如果催化剂具有比较高的周转率,则易位反应前体如不饱和脂肪酸或者脂肪酸衍生物对催化剂的摩尔比可高达约10,000,000比1,但通常小于约500,000比1。不饱和脂肪酸或者脂肪酸衍生物对催化剂的摩尔比典型地大于约5比1,优选大于约50比1,更优选大于约100比1。几个具体实施例使用了底物对催化剂的摩尔比为25比1。
III.工业化学品的生产
工业化学品通常源自于石油资源。使用目前的方法可从可再生资源,通过选择适当的不饱和的前体脂肪酸和适当的不饱和试剂生产所需的工业化学品。该过程的逆合成在图解3中说明。
图解3
对于图解3,结构36表示所需化合物,结构32和34表示向36转化的母体,具有结构32和34的化合物可通过易位反应转化为具有结构36的化合物。结构32可使用异构化反应从可再生资源30获得。
在优选实施方案中,生产出不止一个工业有用的产品。如图解4中逆合成路线中所说明的,可形成结构36和38的两种产品化合物。
或者,可生产出三种或多种产品。例如,根据本发明方法的实施方案,具有两个或更多不饱和位置的多不饱和脂肪酸生成两种或多种产品,参见以下的图解5。
图解3-5所示的本发明方法的实施方案特别用于生产那些不能直接通过易位反应从可容易获得的可再生资源获得的化学品。特别有价值的工业化学品类型包括α-烯烃。α-烯烃是末端链烯,并主要用作与第二烯烃生产聚烯烃的共聚单体。用于生产α-烯烃的特别有用的方法包括以乙烯作为原材料。例如,对于上述的图解3-5,R3是氢,化合物34是乙烯。
参考图解3-5,在图解3-5中公开的本发明方法通常使用烯烃试剂如结构34的化合物。然而,在具体的实施方案中,可使用炔烃试剂代替烯烃试剂。在这种实施方案中,通过链烯-炔烃(烯炔)易位形成1,3-二烯衍生物。烯烃或炔烃试剂与脂肪酸反应,产生至少一种所需的化学品。
在本发明方法的优选实施方案中,烯烃或炔烃为低级不饱和试剂,如低级烯烃或炔烃。在定义上,低级不饱和试剂具有至少一个碳碳双键或三键,或可具有多个碳碳双键或三键。低级烯烃可含有内部双键或三键、或末端双键或三键、或同时含有内部或末端双键或三键。双键可以被四、三、二、或单取代。用于低级不饱和试剂的适当的取代基包括但不限于脂肪族、芳香族、羟基、醚、酮、醛、和卤素官能团。优选地,脂肪族取代基为低级烷基取代基。优选的低级烯烃包括乙烯、丙烯、丁烯、丁二烯、戊烯、己烯、及其异构体。优选的低级炔烃包括乙炔和丙炔。
公开的本发明方法的实施方案的收率定义为相对于脂肪酸前体的摩尔百分数。代表性地,易位方法的至少一种不饱和产品的收率大于约35摩尔百分数,更代表性地大于约50摩尔百分数。
参考图解6,根据本发明方法的实施方案,从共轭亚油酸如亚油酸甲酯衍生物48开始,生产1-辛烯。可以如图解2中所示将亚油酸(18:2Δ9,12)异构化为共轭亚油酸异构体10(18:2Δ9,11)制备化合物48。10与甲醇的酯化得到48。然后在乙烯的存在下使共轭亚油酸甲酯衍生物48与易位催化剂接触,得到1-辛烯50、9-癸烯酸甲酯52和丁二烯54。或者,可无需先前的酯化,在易位反应中直接使用共轭亚油酸异构体10,生成50、54和9-癸烯酸(未表示)。
图解6
图解6中所示的三种产品50、52和54都是工业上有用的化学品。例如,1-辛烯50在工业上用作与乙烯共聚的单体生产LLDPE。9-癸烯酸甲酯52可用于生产壬二酸、癸醇、癸酸、氨基癸酸和其它工业上有用的化合物。这些化合物工业上用于生产尼龙和热固性树脂以及其它产品。丁二烯54工业上用于橡胶和胶乳橡胶生产中。
图解7说明通过区域选择性还原反应从亚油酸衍生物48(18:2Δ9,11)生产11-十八碳烯酸衍生物56(18:1Δ11)的选择性的实施方案。随后与乙烯的易位得到1-辛烯50和11-十二碳烯酸甲酯58。如图解6中所示,选择性实施方案使用了亚油酸异构体10代替了甲酯48。在这一实施方案中,生产了化合物56和58的相应的游离酸。
图解7
图解8说明适合于生产有用的工业化学品9-癸烯酸甲酯的公开的本发明方法的实施方案。在这一实施方案中,通过区域选择性酶促还原方法从亚油酸衍生物60(18:2Δ9,12)生产油酸衍生物62。随后与乙烯的易位得到1-癸烯64和9-癸烯酸甲酯66。与在本发明方法的其它实施例中一样,可直接使用化合物60的相应的脂肪酸得到9-癸烯酸。
图解8
实施例
提供以下实施例用于说明本公开的某些具体实施方案。可以理解,不限于这些所述具体特征的另外的实施方案与以下实施例是一致的。
实施例1
本实施例描述从亚油酸生产Δ9,11-共轭亚油酸10(CLA)的方法。本文中使用的细胞Lactobacillus reuteri PYR8(ATCC保藏号55739,1996年2月15日在American Type Culture Collection(ATCC)中保藏,10801 University Boulevard,Manassas,VA 20110,USA)在具有有限顶部空间的密闭容器中在MRS Lactobacillus Broth(BBL)中生长。大量的培养物在没有搅拌的2-L瓶中在37℃下生长(1-2%接种物)约36到约40小时,通过离心收获,用0.1M bis-tris、0.9%NaCl、pH6.0缓冲液洗涤一次,立即使用或在约-80℃下储存。
使Lactobacillus reuteri(或携带亚油酸异构酶基因的另一种生物体)的细胞在由40g/L酵母抽提物、20g/L Hy-soy和40g/L葡萄糖改性的AV培养基中生长到细胞密度为约3-4g/L的细胞干重。当细胞达到静止期时,将它们收获并以5到20g细胞干重/升的浓度再悬浮在破坏缓冲液中。优选在4℃到8℃之间的温度下进行生物转化,以保持最佳的酶活性。可将亚油酸作为例如纯度约99%的纯物质加入,或将其作为另一种油如豆油的组分加入,所述油具有约50%的亚油酸浓度。或者,可以将亚油酸溶解于共溶剂如丙二醇中。代表性地,通过将亚油酸以若干小份的较小量的亚油酸加入使其浓度为约0.5到4g/L。可以随着反应的进行在随后的步骤中加入细胞得到更高的CLA产品浓度。在这种条件下使用公开的亚油酸浓度,在约2到约8小时内亚油酸向CLA的转化率为80%到100%。
可以从如上所述生产的化合物10制备Δ9,11-十八碳二烯酸甲酯以及其它酯。在制备这种酯的一个方法中,在Dean-Stark条件下在1%硫酸的存在下用甲醇使化合物10酯化,得到相应的甲酯。在没有更多水放出之后,蒸馏过量的甲醇,留下Δ9,11-十八碳二烯酸甲酯。
实施例2
本实施例描述脂肪酸分析方法,测定亚油酸向Δ9,11-CLA的转化。从实施例1中所述的反应混合物中,加入0.5mL的5M NaCl后,从约1mL到约2.5mL含水样品中提出出脂肪酸。将样品在具有Teflon螺纹帽的玻璃螺纹管中与5mL的氯仿/甲醇的2∶1混合物振摇。分液,并取出约1到2mL的氯仿层。用Na2SO4干燥有机层并浓缩。通过采用由Chin等人,J.Food Composition,1992,5,185-192中所述方法改进的以下过程将浓缩的脂肪酸转化为相应的甲酯:将预热到60℃的约6mL的4%HCl甲醇溶液加入到含有脂肪酸样品的玻璃管中。用聚四氟乙烯螺纹帽密封管并在60℃的管式加热器中培养20分钟,冷却到室温并加入2mL的水和3mL的己烷。振摇后,分液,Na2SO4干燥,并通过气相色谱法分析。
实施例3
本实施例描述通过乙烯醇分解从Δ9,11-十八碳二烯酸甲酯生产工业化学品。在惰性气氛下的手套箱中,将实施例1生产的Δ9,11-十八碳二烯酸甲酯(2.95g;0.01mol)溶解于二氯甲烷中,制备100mL的0.1M原液。另外,还在二氯甲烷(1mL)中制备20(60mg,0.1mmol)的0.1M溶液。然后在装备有搅拌棒的Fisher-Porter瓶中进料共轭亚油酸甲酯溶液(25mL)。通过微型注射器加入催化剂20的溶液(100μL)并在瓶上安装装备有压力计和浸渍管的Fisher-Porter瓶该。将***密封并取出手套箱,连接于乙烯管道。然后用乙烯清洗容器(3次),增压到150psi(1034kPa)的乙烯并至于30℃的油浴中。通过在不同的反应时间通过浸渍管收集样品并通过加入三羟甲基膦的溶液促灭各个样品监测反应。然后在60℃加热样品至少1小时,用蒸馏水洗,用己烷萃取并通过气相色谱法(GC)分析。在反应过程中,可以通过GC观察到以下的乙烯醇分解产物:1-辛烯(C8,图解6,化合物50);1,3-癸二烯(C10);9-癸烯酸甲酯(图解6,化合物52);7-十四碳烯(C14);9,11-十二碳二烯酸甲酯(C12);和9-十八碳烯二酸-1,18-二甲酯(C18)。这些产物在反应混合物中的随时间的百分比(%)记录于表1中。
表1
时间(小时) | 50 | C10 | 52 | C12 | C14 | C18 | 48 | 杂质 |
0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 98.4 | 1.6 |
0.5 | 14.3 | 22.8 | 35.6 | 5.3 | 0.7 | 0.0 | 16.9 | 4.4 |
2.0 | 8.5 | 22.1 | 37.4 | 5.5 | 0.6 | 0.0 | 16.7 | 9.2 |
6.75 | 13.2 | 23.7 | 36.7 | 8.2 | NI | 0.0 | 16.2 | 2.0 |
17.45 | 13.4 | 21.6 | 35.2 | 7.4 | NI | 0.0 | 15.6 | 6.8 |
NI=未统计
实施例4
本实施例描述通过使用催化剂12的乙烯醇分解生产工业化学品。使用实施例2中所述的通用过程和条件,监测催化剂12催化的共轭亚油酸甲酯随时间的乙烯醇分解。反应混合物中乙烯醇分解产物随时间的百分比(%)记录于表2中。
表2
时间(小时) | 50 | C10 | 52 | C12 | C14 | C18 | 48 | 杂质 |
0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 98.4 | 1.6 |
0.5 | 12.9 | 20.2 | 32.1 | 7.4 | 0.7 | 0.0 | 19.1 | 7.6 |
2.0 | 17.6 | 21.5 | 42.2 | 6.8 | 0.4 | 0.0 | 7.3 | 4.2 |
6.75 | 17.8 | 23.2 | 43.7 | 6.9 | 0.5 | 0.0 | 5.9 | 2.0 |
17.45 | 19.2 | 20.2 | 43.9 | 5.5 | 0.6 | 0.0 | 6.3 | 4.3 |
实施例5
本实施例描述通过使用催化剂16的乙烯醇分解生产工业化学品。使用实施例2中所述的通用过程和条件,监测催化剂16催化的共轭亚油酸甲酯随时间的乙烯醇分解。反应混合物中乙烯醇分解产物随时间的百分比(%)记录于表3中。
表3
时间(小时) | 50 | C10 | 52 | C12 | C14 | C18 | 48 | 杂质 |
0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 98.4 | 1.6 |
0.5 | 11.2 | 20.9 | 29.1 | 8.3 | 0.0 | 0.0 | 27.8 | 2.7 |
2.0 | 16.6 | 23.2 | 39.4 | 7.7 | 0.0 | 0.0 | 9.6 | 3.5 |
7.0 | 17.2 | 23.6 | 42.6 | 7.4 | 0.0 | 0.0 | 7.2 | 2.0 |
17.50 | 15.6 | 22.5 | 41.6 | 7.0 | 0.0 | 0.0 | 6.8 | 6.5 |
实施例6
本实施例描述通过使用催化剂18的乙烯醇分解生产工业化学品。使用实施例2中所述的通用过程和条件,监测催化剂18催化的共轭亚油酸甲酯随时间的乙烯醇分解。反应混合物中乙烯醇分解产物随时间的百分比(%)记录于表4中。
表4
时间(小时) | 50 | C10 | 52 | C12 | C14 | C18 | 48 | 杂质 |
0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 98.4 | 1.6 |
0.5 | 4.3 | 18.6 | 22.7 | 6.4 | 0.0 | 0.0 | 44.8 | 3.2 |
2.0 | 9.0 | 23.5 | 29.8 | 7.3 | 0.0 | 0.0 | 26.8 | 3.6 |
7.0 | 7.3 | 23.6 | 30.6 | 7.9 | 0.0 | 0.0 | 29.4 | 1.2 |
17.50 | 5.1 | 23.4 | 30.0 | 7.7 | 0.0 | 0.0 | 28.0 | 5.8 |
实施例7
本实施例描述通过使用催化剂14的乙烯醇分解生产工业化学品。使用实施例3中所述的通用过程和条件,监测催化剂14催化的共轭亚油酸甲酯随时间的乙烯醇分解。反应混合物中乙烯醇分解产物随时间的百分比(%)记录于表5中。
表5
时间(小时) | 50 | C10 | 52 | C12 | C14 | C18 | 48 | 杂质 |
0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 98.4 | 1.6 |
0.5 | 0.4 | 0.7 | 2.0 | 0.5 | 0.7 | 5.8 | 59.7 | 30.2 |
2.0 | 1.7 | 1.5 | 4.4 | 0.8 | 0.7 | 5.8 | 55.2 | 29.9 |
7.0 | 2.4 | 1.6 | 4.7 | 0.9 | 1.0 | 5.9 | 54.5 | 29.0 |
17.50 | 1.6 | 1.6 | 5.0 | 1.5 | 0.7 | 5.4 | 53.0 | 31.2 |
实施例8
本实施例描述通过使用催化剂26的乙烯醇分解生产工业化学品。使用实施例3中所述的通用过程和条件,监测催化剂26催化的共轭亚油酸甲酯随时间的乙烯醇分解。反应混合物中乙烯醇分解产物随时间的百分比(%)记录于表6中。
表6
时间(小时) | 50 | C10 | 52 | C12 | C14 | C18 | 48 | 杂质 |
0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 98.4 | 1.6 |
0.5 | 2.5 | 3.2 | 7.4 | 2.0 | 0.0 | 2.0 | 48.4 | 34.5 |
2.0 | 5.0 | 5.0 | 10.6 | 1.1 | 0.0 | 2.8 | 49.1 | 26.4 |
6.75 | 5.9 | 5.3 | 10.0 | 1.5 | 0.0 | 3.5 | 47.1 | 26.7 |
17.45 | 5.6 | 4.4 | 10.4 | 1.2 | 0.0 | 3.9 | 48.7 | 25.8 |
实施例9
本实施例描述通过使用催化剂28的乙烯醇分解生产工业化学品。使用实施例3中所述的通用过程和条件,监测催化剂28催化的共轭亚油酸甲酯随时间的乙烯醇分解。反应混合物中乙烯醇分解产物随时间的百分比(%)记录于表7中。
表7
时间(小时) | 50 | C10 | 52 | C12 | C14 | C18 | 48 | 杂质 |
0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 98.4 | 1.6 |
0.5 | 7.4 | 8.6 | 18.8 | 3.3 | 1.0 | 0.0 | 50.3 | 10.6 |
2.0 | 8.8 | 9.2 | 19.7 | 4.6 | 1.0 | 1.1 | 51.0 | 4.6 |
6.75 | 9.0 | 9.5 | 19.4 | 4.8 | 0.0 | 1.7 | 49.4 | 6.2 |
17.45 | 10.2 | 8.6 | 18.6 | 4.0 | 0.0 | 1.3 | 49.5 | 7.8 |
实施例10
本实施例描述通过使用催化剂24的乙烯醇分解生产工业化学品。使用实施例3中所述的通用过程和条件,监测催化剂24催化的共轭亚油酸甲酯随时间的乙烯醇分解。反应混合物中乙烯醇分解产物随时间的百分比(%)记录于表8中。
表8
时间(小时) | 50 | C10 | 52 | C12 | C14 | C18 | 48 | 杂质 |
0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 98.4 | 1.6 |
0.5 | 0.6 | 1.0 | 2.6 | 1.0 | 1.3 | 6.8 | 51.2 | 35.5 |
2.0 | 0.6 | 1.0 | 2.7 | 0.8 | 1.3 | 6.8 | 50.2 | 36.6 |
7.0 | 0.9 | 1.0 | 2.5 | 0.6 | 1.4 | 7.0 | 52.2 | 34.4 |
17.50 | 0.0 | 1.0 | 2.9 | 0.9 | 1.0 | 6.5 | 50.4 | 37.3 |
实施例11
使用高压Parr反应器,除了乙烯压力增加到800psi(5517kPa)之外,以与实施例3-10中一样在室温(24℃)下进行Δ9,11-十八碳二烯酸甲酯(图解6,化合物48)的乙烯醇分解反应。如前所述分析样品。在使用不同催化剂的反应混合物中在2小时观察的乙烯醇分解产品的百分比(%)记录在表9中。
表9
时间(小时) | 50 | C10 | 52 | C12 | C14 | C18 | 48 | 杂质 |
601 | 5.4 | 16.6 | 19.3 | 7.1 | 0.0 | 0.0 | 49.1 | 2.5 |
823 | 5.9 | 18.4 | 20.9 | 7.9 | 0.0 | 0.0 | 41.1 | 5.8 |
712 | 4.8 | 6.6 | 8.2 | 3.6 | 0.1 | 2.8 | 60.2 | 13.8 |
933 | 1.2 | 2.1 | 2.6 | 0.7 | 0.2 | 3.0 | 67.9 | 22.5 |
对于本领域技术人员来说,显而易见,可对本发明的方法进行多种修改和变化而不脱离本发明的范围和精神实质。考虑本说明书和本文中公开的过程的实践,该方法的其它实施方案对于本领域技术人员来说是显而易见的。认为本发明的说明书和实施例只是示例性的,本发明的真实的范围和精神实质由以下权利要求表明。
Claims (29)
1.生产工业化学品的方法,其包括:
提供异构化前体;
使前体中不饱和位置异构化,生成异构化的衍生物;和
在易位催化剂的存在下使异构化的衍生物与不饱和化合物反应,生成至少一种所需的工业化学品。
2.权利要求1的方法,其中异构化前体是不饱和脂肪酸或脂肪酸衍生物。
3.权利要求2的方法,其中脂肪酸或脂肪酸衍生物是多不饱和脂肪酸。
4.权利要求1的方法,其中易位催化剂是钌基催化剂。
5.权利要求2的方法,其中使脂肪酸或脂肪酸衍生物异构化包括使脂肪酸或脂肪酸衍生物与酶接触。
6.权利要求1的方法,其中异构化生成共轭二烯衍生物。
7.权利要求6的方法,其中共轭二烯衍生物是共轭亚油酸。
8.权利要求7的方法,其中共轭亚油酸是18∶2 Δ9,11亚油酸。
9.权利要求1的方法,其中使异构化的衍生物反应生成至少一种选自丁二烯、1-辛烯、9-癸烯酸、其衍生物、及其组合的化合物。
10.权利要求2的方法,其中使脂肪酸或脂肪酸衍生物与不饱和化合物反应生成至少一种选自丁二烯、1-辛烯、9-癸烯酸、其衍生物、及其组合的化合物。
11.权利要求10的方法,其中使脂肪酸或脂肪酸衍生物与不饱和化合物反应生成1-辛烯。
12.生产1-辛烯的方法,其包括:
提供亚油酸或其衍生物;
使亚油酸或其衍生物中的不饱和位置酶促异构化,生成异构化的亚油酸或异构化的亚油酸低级酯;和
在乙烯的存在下使异构化的亚油酸或异构化的亚油酸低级酯与易位催化剂反应,从而生成1-辛烯。
13.权利要求12的方法,其中异构化的亚油酸为Δ9,11-十八碳二烯酸。
14.权利要求13的方法,其中在易位催化剂的存在下与乙烯反应之前将Δ9,11-十八碳二烯酸酯化,提供低级烷基酯。
15.权利要求12的方法,其中易位催化剂是钌基催化剂。
16.权利要求15的方法,其中易位催化剂为
17.权利要求12的方法,其中亚油酸衍生自大豆油。
18.生产1-辛烯的方法,其包括:
提供得自大豆油的亚油酸;
使亚油酸与亚油酸异构酶接触,生成Δ9,11-十八碳二烯酸;
使Δ9,11-十八碳二烯酸酯化,生成低级烷基酯;和
在乙烯的存在下使酯与易位催化剂接触,从而生成1-辛烯。
19.权利要求18的方法,其中在乙烯的存在下使酯与易位催化剂接触,生成9-癸烯酸酯。
20.权利要求18的方法,其中催化剂为钌烯催化剂。
22.生产1-辛烯的方法,其包括:
提供脂肪酸二烯或其酯;
将脂肪酸二烯或其酯转化为11-十八碳烯酸或其酯;和
在乙烯的存在下使11-十八碳烯酸或其酯与易位催化剂接触,从而生成1-辛烯。
23.生产1-辛烯的方法,其包括:
提供Δ9,11-十八碳二烯酸或其衍生物;和
在乙烯的存在下使Δ9,11-十八碳二烯酸或其衍生物与易位催化剂接触,从而生成1-辛烯。
24.权利要求23的方法,其中Δ9,11-十八碳二烯酸或其衍生物以Δ9,11-十八碳二烯酸的酯或盐的形式提供。
25.权利要求24的方法,其中提供包括提供十八碳二烯酸的低级烷基酯。
26.权利要求25的方法,其中酯为甲酯。
27.权利要求23的方法,其中该方法生成9-癸烯酸。
28.权利要求23的方法,其中易位催化剂是钌基催化剂。
29.权利要求23的方法,其中易位催化剂选自:
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-
2004
- 2004-01-13 CA CA002512815A patent/CA2512815A1/en not_active Abandoned
- 2004-01-13 US US10/542,167 patent/US7960599B2/en not_active Expired - Fee Related
- 2004-01-13 CN CNA2004800021727A patent/CN1802341A/zh active Pending
- 2004-01-13 BR BR0406756-8A patent/BRPI0406756A/pt not_active IP Right Cessation
- 2004-01-13 WO PCT/US2004/000841 patent/WO2004062763A2/en active Application Filing
- 2004-01-13 EP EP04701810A patent/EP1603857A4/en not_active Withdrawn
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103492357A (zh) * | 2011-04-20 | 2014-01-01 | 考格尼斯知识产权管理有限责任公司 | 制备不饱和化合物的方法 |
CN108485698A (zh) * | 2012-06-20 | 2018-09-04 | 埃莱万斯可再生能源科学股份有限公司 | 天然油易位组合物 |
CN104395277A (zh) * | 2012-06-26 | 2015-03-04 | 巴斯夫欧洲公司 | 制备不饱和化合物的方法 |
Also Published As
Publication number | Publication date |
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WO2004062763A2 (en) | 2004-07-29 |
EP1603857A2 (en) | 2005-12-14 |
EP1603857A4 (en) | 2006-05-17 |
WO2004062763A3 (en) | 2005-10-20 |
CA2512815A1 (en) | 2004-07-29 |
US7960599B2 (en) | 2011-06-14 |
US20070270621A1 (en) | 2007-11-22 |
BRPI0406756A (pt) | 2005-12-20 |
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