CN103562213A - 新的加氢甲酰化方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000007037 hydroformylation reaction Methods 0.000 title claims description 11
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000010948 rhodium Substances 0.000 claims abstract description 11
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002798 polar solvent Substances 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- -1 (triphen methoxymethyl) tetramethylene Chemical group 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- ZYKGKDHAOCCWCU-UHFFFAOYSA-N [2-(3,5-dimethylphenyl)-1-methylcyclobutyl]phosphane Chemical group C1(=CC(=CC(=C1)C)C)C1C(CC1)(C)P ZYKGKDHAOCCWCU-UHFFFAOYSA-N 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 238000000638 solvent extraction Methods 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract 2
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000007717 exclusion Effects 0.000 abstract 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N propionic aldehyde Natural products CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical class [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000007070 tosylation reaction Methods 0.000 description 1
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C07C45/50—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 by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
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- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5027—Polyphosphines
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- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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Abstract
本发明涉及一种用于产生4-羟基丁醛的方法，其特征在于将溶于极性溶剂的烯丙醇在一种催化体系的存在下与CO以及H2反应，该催化体系是由一种铑络合物和一种含有至少两个反式配位的1,3-二烷基苯-膦甲基基团的环丁烷配体形成，其中排除含有脂族、芳脂族或环脂族的膦作为配体的催化剂。其中R1是烷基，优选甲基、乙基或丙基，R2是H或烷氧基基团，R3和R4彼此独立地是H、CH2OR1、CH2O-芳烷基、CH2OH、CH2-[P(3,5-R1,R1-4-R2-苯基)2]或CH2O-(CH2-CH2-O)m-H，其中m是从1到1000的一个数字。
Description
本发明涉及一种将烯丙醇加氢甲酰化以产生4-羟基丁醛的方法。
发明背景
烯丙醇的加氢甲酰化已被公知并得以工业化应用（见例如USP4,064,145；USP4,215,077；USP4,238,419；USP4,678,857；USP5,290,743）。在这些过程中，烯丙醇与CO/H2气体混合物进行反应，生成4-羟基丁醛（HBA）。在通过蒸馏去除了不希望的副产品后，HBA以一种已知的方式氢化生成1,4-丁二醇（BDO）。
这种生产方式的一个缺点就是形成了不希望的副产物。具体地，和希望的直链产物一起，同时形成的还有同分异构的分支产物3-羟基-2-甲基丙醛（HMPA）和其他C3副产物（例如正丙醇和丙醛）。这对该方法的经济可行性有负面的影响。
本发明提供了一种用于产生4-羟基丁醛的方法，其特征在于，溶于极性溶剂的烯丙醇在催化体系的存在下与CO以及H2反应，该催化体系是由铑络合物和含有至少两个反式配位的1,3-二烷基苯-膦甲基基团的环丁烷配体形成，排除含有脂族、脂族或环脂族膦作为配体的催化剂。
发明详细说明
在本发明中用作配体的反式-l,2-(1,3-二烷基苯基膦甲基)环丁烷具有化学式[A]
在其中
R1为烷基，优选为甲基，乙基或丙基
R2是H或一个烷氧基基团，
R3和R4彼此独立地分别是H、CH2OR1、CH2O-芳烷基、CH2OH、CH2-[P(3,5-R1,R1-4-R2-苯基)2]或
CH2O-(CH2-CH2-O)m-H，其中m是从1到1000的一个数字。
优选[A]是全反式环丁烷衍生物。
本发明的另一个方面是具有化学式[A]的新颖的催化剂的用途，即允许根据本发明的方法的不同实施例。
通常，使用公知的催化剂的烯丙醇加氢甲酰化是在均相中进行。反应结束后，将HBA、HMPA和其他副产物通过用水萃取从催化剂中分离出来。
根据本发明的加氢甲酰化在极性溶剂中允许具有化学式[A]的亲脂性催化剂通过用疏水性溶剂萃取来进行分离，并且催化剂返回到第一过程阶段。
含有聚醚基团的具有化学式[A]的新颖的亲水性催化剂体系可以用在隔膜反应器中并因此允许过程产品在加氢甲酰化后不断地分离出来。
根据本发明的方法相对于迄今描述的用于产生HBA的过程的不同之处在于，排除含有化学式PR'3的配体的催化剂，其中R'是脂族、芳脂族或环脂族基。这种类型的催化剂将相当比例的所用的烯丙醇氢化以生成不希望的副产物（参见USP7,655,821Bl）。
与此相比，在根据本发明的方法中，代替含有环丁烷配体（其具有至少两个反式配位的1,3-二烷基苯基膦基-甲基基团）的催化剂，还有可能使用DIOP系列的二膦，例如2,3-O-异亚丙基-2,3-二羟基-1,4-双[双(3,5-二甲基苯膦基)]丁烷；（参见WO2010/132087）。
然而，优选的是环丁烷系列的催化剂，这些催化剂允许实现更有利的HBA:HMPA比例。
根据本发明的方法中所用的极性溶剂不与加氢甲酰化的产物反应。相比在公知的方法中所用的溶剂，（参见例如WO2010/132087），它们是以显著比例可溶于水的，并且有时还完全溶于水。
可以提及的极性溶剂是，例如乙醇、丙醇、正丁醇、异丁醇、1,4-丁二醇以及具有化学式CH3O-(-CH2-CH2-O)n-H其中分子量>2000的聚醚。
加氢甲酰化是在本身已知的反应条件下（在从20℃至120℃的温度范围内并且在2巴至20巴的压力范围内）发生。取决于已有设备，可以通过适合的预备实验来确定最优性能。
CO:H2的摩尔比为约1:1，但是取决于实施例也可以显著变化。
反应时间为0.5至4小时。反应开始时，基于溶剂或者溶剂混合物，丙烯醇浓度为5%至50%，优选为10%至25%。
HBA（以及HMPA）以本身已知的方式氢化来生成相应的二羟基化合物，并且粗产品的分馏生成所希望的处于纯的形式的1,4-丁二醇。Ni、Co、Ru、Pt、Pd、Cu、Zn以及Cr催化剂可以用于氢化。特别优选使用
Ni催化剂。氢化通常是在60℃至200℃的温度下并在15巴至70巴的压力范围内进行。
以下实例说明了根据本发明的方法：
实例1
制备在根据本发明的方法中所用的新颖的催化剂：
a)从已知的全反式1,2,3,4-(羟基-甲基)环丁烷制备一种新颖的中间体：
将88mg（0.5mmol）全反式1,2,3,4-(羟甲基)环丁烷溶于3ml无水吡啶中并且在0℃下在剧烈搅拌下加入251mg（0.9mmol）三苯基氯甲烷。将反应混合物保持在0℃下搅拌过夜。然后加入10ml水并用乙酸乙酯（3x5ml）萃取，之后用MgSO4干燥并在一个旋转式蒸发器里蒸干。
用色谱分析法（硅胶）分离粗产品。（洗脱液：乙酸乙酯:乙烷1:3→2:3→乙酸乙酯:甲醇95:5）。
得到的主产物是114mg（理论值的34%）全反式l,2-(羟甲基)-3,4-(三苯甲氧基甲基)环丁烷。
1H-NMR(500MHz,CDCl3):7.15-7.4(m,15H,Ar)；3.86(m,2H,H-6a,H-7a)：3.63(m,2H,H-6b,H-7b)；3.18(m,2H,H-5a,H-8a);2.98(m,2H,H-5b,H-8b);1.84(m,4H,H-1,H-2,H-3和H-4);13C-NMR(CDCl3):143.95;128.60;127.79:126,98,86.84;66.24;65.71:43.68;39.06。
b)以本身已知的方式，将此化合物甲苯磺酰化并且与LiP(3,5-甲苄基)2反应。
实例2
对应于根据本发明方法的加氢甲酰化：
在4ml干燥且脱气的叔丁基甲基醚中，16mmol全反式-l,2,3,4-(3,5-甲苄基膦甲基)环丁烷与[Rh(CO)2(乙酰丙酮)]（8mmol）在氩气下进行反应。
将得到的溶液在氩气下注射到高压釜中并用CO:H2为1:1的混合物冲洗。通过一个侧臂，然后加入1ml烯丙醇在15ml乙醇中的溶液并在40巴的压力下和120℃的温度下进行反应。这给出了比例为约14:1的HBA+HMPA（理论的97%）。
Claims (18)
1.一种用于产生4-羟基丁醛的方法，其特征在于将烯丙醇在极性溶剂中在一种催化体系的存在下与CO以及H2进行反应，该催化体系是由一种铑络合物和一种包含至少两个反式配位的1,3-二烷基苯基膦甲基基团的环丁烷配体形成，其中排除含有脂族、芳脂族或环脂族的膦作为配体的催化剂。
2.根据权利要求1所述的方法，其特征在于使用了由一种铑络合物和全反式-l,2,3,4-(3,5-甲苄基膦基-甲基)环丁烷形成的催化体系。
3.根据权利要求1所述的方法，其特征在于使用了由一种铑络合物和反式-l,2-(3,5-甲苄基膦基-甲基环丁烷形成的催化体系。
4.根据权利要求1所述的方法，其特征在于使用了由一种铑络合物和全反式-l,2,3-(3,5-甲苄基膦基-甲基)-4-(甲氧基甲基)环丁烷形成的催化体系。
5.根据权利要求1所述的方法，其特征在于使用了由一种铑络合物和全反式-l,2-(3,5-甲苄基膦基-甲基)-3,4-双(三苯甲氧基甲基)环丁烷形成的催化体系。
6.根据权利要求1所述的方法，其特征在于使用其中水可溶解至少2%重量份，优选>5%，的醇类作为极性溶剂。
7.根据权利要求1所述的方法，其特征在于使用水溶性的且分子量>2000的聚醚类作为极性溶剂。
8.权利要求2中所用的催化剂。
9.权利要求4中所用的催化剂。
10.权利要求5中所用的催化剂。
11.全反式-l,2-(羟甲基)-3,4-(三苯甲氧基甲基)环丁烷。
12.根据权利要求1所述的方法，其特征在于使用了由一种铑络合物和全反式-l,2,3-(3,5-甲苄基膦基-甲基)-4-(羟甲基)环丁烷形成的催化体系。
13.根据权利要求1所述的方法，其特征在于使用了由一种铑络合物和全反式-l,2,3-(3,5-甲苄基膦基-甲基)-4-CH2-(O-CH2-CH2-O)m-H形成的催化体系，其中m是从1到1000的一个数字。
14.根据权利要求13所述的方法，其特征在于加氢甲酰化是在隔膜反应器中发生。
15.根据权利要求1所述的方法，其特征在于所用的催化剂是，任选地在加水后，通过用疏水性溶剂萃取从该反应混合物中分离出来并且被重复使用。
16.根据权利要求1所述的方法，其特征在于使用了由一种铑络合物和全反式-l,2,3,4-(3,5-甲苄基膦基-甲基)环丁烷形成的催化体系。
17.权利要求16中所用的催化剂。
18.根据权利要求1所述的方法，其特征在于在权利要求16中所用的催化体系是，任选地在加水后，用疏水性溶剂分离出来并且被重复使用。
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| DE102011102666A DE102011102666A1 (de) | 2011-05-27 | 2011-05-27 | Neues Verfahren zur Hydroformylierung |
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| DE102011110621.2 | 2011-08-16 | ||
| PCT/EP2012/059841 WO2012163831A1 (en) | 2011-05-27 | 2012-05-25 | Novel hydroformylation process |
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| CN110975941A (zh) * | 2019-12-17 | 2020-04-10 | 万华化学集团股份有限公司 | 一种氢甲酰化反应催化剂组合物及丙烯氢甲酰化反应制备醛的方法 |
| CN112457165A (zh) * | 2019-09-06 | 2021-03-09 | 南京延长反应技术研究院有限公司 | 一种烯丙醇加氢制备1，4-丁二醇的强化系统及工艺 |
| CN113874382A (zh) * | 2019-05-31 | 2021-12-31 | 利安德化学技术有限公司 | 用于烯丙醇加氢甲酰化的高线性选择性配体 |
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| BR112013029852A2 (pt) | 2011-05-27 | 2016-12-20 | Umicore Ag & Co Kg | ligantes e sistemas catalisadores para processos de hidroformilação |
| ES2673115T3 (es) | 2015-12-16 | 2018-06-19 | Evonik Degussa Gmbh | Procedimiento para la carbonilación doble de alcoholes alílicos para dar los correspondientes diésteres |
| EP3530644B1 (en) | 2018-02-26 | 2022-11-02 | Lyondell Chemical Technology, L.P. | Improving rhenium catalysts for glycerin to allyl alcohol conversion |
| CN113061149B (zh) * | 2021-03-29 | 2022-04-22 | 万华化学集团股份有限公司 | 一种互配型配体和氢甲酰化催化剂、及二元醇的制备方法 |
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| US7655821B1 (en) * | 2008-11-25 | 2010-02-02 | Lyondell Chemical Technology, L.P. | Direct hydrocarbonylation process |
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| CN113874382A (zh) * | 2019-05-31 | 2021-12-31 | 利安德化学技术有限公司 | 用于烯丙醇加氢甲酰化的高线性选择性配体 |
| CN113874382B (zh) * | 2019-05-31 | 2022-09-02 | 利安德化学技术有限公司 | 用于烯丙醇加氢甲酰化的高线性选择性配体 |
| CN112457165A (zh) * | 2019-09-06 | 2021-03-09 | 南京延长反应技术研究院有限公司 | 一种烯丙醇加氢制备1，4-丁二醇的强化系统及工艺 |
| CN110975941A (zh) * | 2019-12-17 | 2020-04-10 | 万华化学集团股份有限公司 | 一种氢甲酰化反应催化剂组合物及丙烯氢甲酰化反应制备醛的方法 |
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| US20140114090A1 (en) | 2014-04-24 |
| EP2714700A1 (en) | 2014-04-09 |
| BR112013029852A2 (pt) | 2016-12-20 |
| EP2714699A1 (en) | 2014-04-09 |
| RU2013157751A (ru) | 2015-07-10 |
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| WO2012163831A1 (en) | 2012-12-06 |
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