CN101522602B - 氢甲酰化方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000007037 hydroformylation reaction Methods 0.000 title description 21
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 33
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001273 butane Substances 0.000 claims abstract description 26
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010948 rhodium Substances 0.000 claims abstract description 23
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 22
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 23
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 abstract description 3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
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Abstract
本发明描述了生产4-羟基丁醛的方法。所述方法包括在溶剂和催化剂体系的存在下使烯丙醇与一氧化碳和氢气的混合物反应,所述催化剂体系包含铑络合物和2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二正烷基苯基)膦基]丁烷。与3-羟基-2-甲基丙醛相比,所述方法给出了4-羟基丁醛的高产率。
Description
发明领域
本发明涉及将烯丙醇氢甲酰化以生产4-羟基丁醛的方法。所述方法产生出乎意料地高的4-羟基丁醛:3-羟基-2-甲基丙醛(直链:支化)产物之比。
发明背景
烯丙醇的氢甲酰化是公知的和工业上实践的方法。参见,例如,美国专利号4,064,145、4,215,077、4,238,419、4,678,857和5,290,743。在氢甲酰化反应中,烯丙醇与CO/H2气体混合物在催化剂的存在下反应以生成4-羟基丁醛(HBA)。该HBA然后可以例如通过水萃取与催化剂分开,并加氢以生成1,4-丁二醇(BDO)。参见美国专利号5,504,261。
已经开发了各种催化剂体系用于该氢甲酰化反应,最特别的是与膦配体在一起的铑络合物(参见,例如,美国专利号4,064,145、4,238,419和4,567,305)。通常采用的膦配体是三取代的膦例如三苯基膦。氢甲酰化方法的一个缺点是除了想要的HBA直链产物外,还生成其它共产物或副产物。烯丙醇的氢甲酰化通常产生一些3-羟基-2-甲基丙醛(HMPA)支化共产物和C3副产物例如正丙醇和丙醛。尽管HMPA可以被加氢以产生有用的物质1,3-甲基丙二醇(MPD),但该MPD共产物降低了BDO的产率。C3副产物的生成有效地反映了该过程中的另一产率损失,这会对于过程经济性有严重的不利影响。
为了增加BDO产率,持续研究以改进氢甲酰化方法并降低不那么想要的共产物/副产物。美国专利号6,127,584公开了使用具有至少2个甲基的三烷基膦配体导致增加的HBA∶HMPA之比。还发现使用二膦配体改进了HBA∶HMPA之比。使用铑络合物催化剂和DI OP二膦配体来氢甲酰化烯丙醇在本领域中,特别是在日本Kokai号06-279345和06-279344和美国专利号4,306,087中是已知的。此外,美国专利号6,225,509公开了将CO在反应液体中的浓度维持在高于约4.5毫摩尔/升降低了在使用由铑络合物和配体例如D1OP组成的催化剂来氢甲酰化烯丙醇过程中生成不想要的C3共产物。
总之,需要用来氢甲酰化烯丙醇以生产4-羟基丁醛的新方法。特别有价值的方法将导致高的4-羟基丁醛(HBA)与3-羟基-2-甲基丙醛(HMPA)之比。
发明概述
本发明是一种方法,该方法包括在溶剂和催化剂体系的存在下使烯丙醇与一氧化碳和氢气反应以生产4-羟基丁醛。所述催化剂体系包含铑络合物和2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二正烷基苯基)膦基]丁烷。本发明令人惊讶地导致高的4-羟基丁醛产物与3-羟基-2-甲基丙醛之比。
发明详述
本发明的方法包括在溶剂和催化剂体系的存在下氢甲酰化烯丙醇。本发明的催化剂体系包含铑络合物和2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二正烷基苯基)膦基]丁烷。适宜的铑络合物含有与配体基团连接的铑。所述铑络合物在所述溶剂中是可溶的。对于与所述铑络合物连接的配体的选择没有特别的限制。例如,适宜的配体包括氢、羰基、取代的和未取代的环戊二烯基、2,4-链烷双酸根(2,4-alkanedionates)、三烷基或三芳基膦、二膦和它们的混合物。特别优选的配体包括羰基、乙酰丙酮化物(2,4-戊二酸根(2,4-pentanedionate))、三苯基膦和它们的混合物。优选的铑络合物的实例包括(乙酰丙酮)二羰基铑和三(三苯基膦)铑羰基氢化物。
本发明的催化剂体系也包含二膦配体2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二正烷基苯基)膦基]丁烷。2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二正烷基苯基)膦基]丁烷具有以下化学式:
其中R是正烷基。优选地,R是甲基、乙基或丙基。
所述二膦配体最优选是2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二甲基苯基)膦基]丁烷或2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二乙基苯基)膦基]丁烷。
所述2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二正烷基苯基)膦基]丁烷可以通过任何可能的方法来制备。例如,它可以通过2,2-二甲基-4,5-双[(甲苯磺酰氧基甲基)甲基]-1,3-二氧戊环与锂二(3,5-二正烷基苯基)-膦反应来制备。
所述2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二正烷基苯基)膦基]丁烷配体可以在用于氢甲酰化反应之前与所述铑络合物预先结合,或者它可以被单独加入。然而,优选所述2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二正烷基苯基)膦基]丁烷配体与所述铑络合物分开加入。
尽管并非必需,所述催化剂体系可以额外地包含单膦化合物。所述单膦化合物还可以是与所述铑络合物结合的任何膦配体。所述单膦化合物是可用以下化学式表示的三取代的膦:
其中R1是芳基或烷基。适宜的脂族R1基团包括甲基、乙基、正丁基、仲丁基、辛基和癸基。适宜的芳族R1基团包括苯基、甲苯基和萘基。R1基团可相同或不同,但优选相同。优选地,所述单膦是三取代的芳基膦。更优选地,所述单膦是三苯基膦或三甲苯基膦。三苯基膦是特别优选的。
本发明的方法也需要反应溶剂。一般的溶剂是能够溶解所述铑络合物和对于氢甲酰化步骤中产生的羟基醛不具有反应性的那些。适宜的溶剂包括在水中具有非常低或最小的溶解度的任何有机溶剂。优选的溶剂包括C5-C20脂族烃、C6-C20芳族烃、醇、醚和它们的混合物。特别优选的溶剂包括甲苯、环己烷、甲基叔丁基醚和它们的混合物。
用于所述氢甲酰化步骤的一般的反应条件是温和的以有利于生成直链4-羟基丁醛(HBA)而非支化的3-羟基-2-甲基丙醛(HMPA)反应产物。反应条件优选为约20-120℃和约20-600psig的压力,更优选为约45-85℃和30-400psig,和最优选为约50-80℃和40-300psig。CO∶H2摩尔比一般为约1∶1,尽管该比例可以相当大地变化。CO的分压一般为5-100psig。氢气的分压一般为40-200psig。在这些条件下进行该反应直至绝大多数烯丙醇(例如60-99.9%)已经反应,产物大部分是4-羟基丁醛,有一些是支化的反应产物。通常,1-4小时的反应时间是足够的。
优选地,烯丙醇在进料基础上的反应溶剂中的起始浓度为在所述溶剂中的约5-40wt%;更优选地,可以使用5-10wt%的更低的浓度。
优选地,这样实施烯丙醇的氢甲酰化以使得CO在液相中的浓度([CO]液)在氢甲酰化过程中维持在高于4毫摩尔/升(0.004M)。[CO]液的值在美国专利号6,225,509中有定义。优选地,液相氢气∶一氧化碳摩尔比为10∶1至约1∶2,更优选5∶1至约1∶2。
氢甲酰化步骤之后,优选通过在萃取溶剂中进行水萃取来将HBA产物与所述溶剂和催化剂体系分开。水萃取方法是本领域公知的,并且可以通过任何适宜的设备来实施,例如混合器-沉降器、填料萃取塔或板式萃取塔、旋转盘接触器,或送至沉降槽来将该混合物分离成水相和有机相。HBA和任何HMPA在水(含水)相中保持溶解,并与溶剂(有机)相分开。
所述4-羟基丁醛(和任何3-羟基-2-甲基丙醛)反应产物优选经过额外的在加氢催化剂的存在下对4-羟基丁醛进行加氢的步骤以产生1,4-丁二醇(BDO)。将氢气加入到用于该加氢的反应容器中。适宜的加氢催化剂包括任何VIII族金属,例如镍、钴、钌、铂和钯,以及铜、锌和铬和它们的混合物和合金。特别优选的是镍催化剂。最优选的是型镍和固定床镍催化剂。
所述加氢反应条件优选为约60-200℃和约200-1000psig的压力,更优选约80-140℃和300-1000psig。通常1-10小时的反应时间是适当的。在该加氢反应过程中,生成BDO和MPD,而高的直链与支化产物之比基本上保留,还有其它低级共产物/副产物。
以下实施例仅举例说明本发明。本领域技术人员将意识到在本发明的主旨和权利要求的范围内的许多变化。
实施例1:制备二膦配体
如下所述制备以下通式的二膦配体。
在氩气下将2,2-二甲基-4,5-双[(甲苯磺酰氧基甲基)甲基]-1,3-二氧戊环在干燥/脱气的THF中的溶液(1当量,1.73g,3.7×10-3摩尔的二氧戊环在50mL THF中)逐滴加入到适量的锂二芳基膦(见以上化学式)在干燥/脱气的THF中的溶液(2.3当量,在100mL THF)中。在回流下加热该混合物2小时,然后冷却,并在减压下除去溶剂。将剩余的固体重新溶解在二氯甲烷中,通过二氧化硅床过滤,并在减压下除去溶剂以得到2,3-O-异亚丙基-2,3-二羟基-1,4-双(二芳基膦基)丁烷。
二膦1A:2,3-O-亚异丙基-2,3-二羟基-1,4-双[双(3,5-二甲基苯基)膦基]丁烷。
二膦1B:2,3-O-亚异丙基-2,3-二羟基-1,4-双[双(3,5-二乙基苯基)膦基]。
对比性的二膦1C:2,3-O-亚异丙基-2,3-二羟基-1,4-双[双(苯基)膦基],称作DIOP。
对比性的二膦1D:2,3-O-亚异丙基-2,3-二羟基-1,4-双[双(4-甲基苯基)膦基]丁烷。
对比性的二膦1E:2,3-O-亚异丙基-2,3-二羟基-1,4-双[双(3,5-二甲基-4-甲氧基苯基)膦基]丁烷。
对比性的二膦1F:2,3-O-亚异丙基-2,3-二羟基-1,4-双[双(4-氯苯基)膦基]丁烷。
对比性的二膦1G:2,3-O-亚异丙基-2,3-二羟基-1,4-双[双(3,5-二(三氟甲基)苯基)膦基]丁烷。
对比性的二膦1H:2,3-O-亚异丙基-2,3-二羟基-1,4-双[双(3,5-二(叔丁基)苯基)膦基]丁烷。
对比性的二膦1I:2,3-O-亚异丙基-2,3-二羟基-1,4-双[双(2-萘次甲基)膦基]丁烷。
对比性的二膦1J:2,3-O-亚异丙基-2,3-二羟基-1,4-双[双(2,4,6-三甲基苯基)膦基]丁烷。
实施例2:使用二膦配体的氢甲酰化反应
根据以下程序使用二膦配体1A-1J来氢甲酰化烯丙醇:
将想要的二膦(2当量或8.6×10-5摩尔)在干燥脱气的甲苯(15g)中的溶液加入到位于100mL Parr高压釜中的[Rh(CO)2(acac)](1当量或4.3×10-5摩尔)中。用1∶1CO/H2混合物冲洗该溶液三次,然后用该CO/H2混合物加压至180psig。然后在搅拌下将该高压釜加热至65℃,注入烯丙醇(3.5mL),并用该CO/H2混合物将该高压釜加压至200psig。该高压釜保持在200psig的恒定压力下,并监测该反应的气体吸收。当没有进一步的气体吸收时,冷却该高压釜并卸压。用气相色谱分析所得到的溶液以确定该反应的产物。该反应产生HBA、HMPA和C3产物(正丙醇和丙醛)。
示于表1中的结果表明,本发明的2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二正烷基苯基)膦基]丁烷出乎意料地导致比任何其它对比的二膦配体显著更高的HBA∶HMPA(I∶b)之比。
表1:二膦对比
二膦 | 转化率(%) | HBA(%) | HMPA(%) | C3(%) | I∶b比例 |
1A | 99.66 | 89.83 | 9.41 | 0.21 | 9.54 |
1B | 99.36 | 89.24 | 9.41 | 0.25 | 9.48 |
1C* | 99.75 | 86.2 | 11.7 | 0.18 | 7.36 |
1D* | 99.98 | 86.51 | 11.27 | 0.19 | 7.68 |
1E* | 99.94 | 82.18 | 14.73 | 0.28 | 5.58 |
1F* | 99.68 | 77.64 | 21.55 | 0.36 | 3.60 |
1G* | 99.96 | 78.23 | 16.11 | 4.54 | 4.86 |
1H* | 95.68 | 84.36 | 10.96 | 0.23 | 7.70 |
1I* | 99.76 | 85.96 | 13.24 | 0.26 | 6.49 |
1J* | 6.33 | 2.15 | 0.53 | 3.43 | 4.05 |
*对比例
Claims (12)
1.生产4-羟基丁醛的方法,包括在溶剂和催化剂体系的存在下使烯丙醇与一氧化碳和氢气反应,所述催化剂体系包含铑络合物和2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二正烷基苯基)膦基]丁烷,所述2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二正烷基苯基)膦基]丁烷选自2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二甲基苯基)膦基]丁烷、2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二乙基苯基)膦基]丁烷和2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二正丙基苯基)膦基]丁烷。
2.权利要求1的方法,其中所述催化剂体系包含铑络合物和2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二甲基苯基)膦基]丁烷。
3.权利要求1的方法,其中所述催化剂体系包含铑络合物和2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二乙基苯基)膦基]丁烷。
4.权利要求1的方法,其中所述溶剂选自由C5-C20脂族烃、C6-C20芳族烃、醚、醇和它们的混合物组成的组。
5.权利要求1的方法,其中所述溶剂选自由甲苯、环己烷、甲基叔丁基醚和它们的混合物组成的组。
6.权利要求1的方法,其中所述铑络合物包含铑和配体,所述配体选自由氢、羰基、三烷基或三芳基膦、二膦、环戊二烯基、2,4-链烷双酸根和它们的混合物组成的组。
7.权利要求1的方法,其中所述反应在45℃-85℃范围内的温度下和30-400psig范围内的压力下进行。
8.权利要求1的方法,其中所述催化剂体系还包含单膦化合物。
9.权利要求8的方法,其中所述单膦化合物是三苯基膦。
10.权利要求1的方法,其中将一氧化碳在液相中的浓度维持在高于4毫摩尔/升。
11.权利要求1的方法,还包括在加氢催化剂的存在下加氢所述4-羟基丁醛以生成1,4-丁二醇。
12.权利要求11的方法,其中所述加氢催化剂是镍催化剂。
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