CN87107325A - 烯烃羧酸衍生物的选择性制备法 - Google Patents
烯烃羧酸衍生物的选择性制备法 Download PDFInfo
- Publication number
- CN87107325A CN87107325A CN87107325.0A CN87107325A CN87107325A CN 87107325 A CN87107325 A CN 87107325A CN 87107325 A CN87107325 A CN 87107325A CN 87107325 A CN87107325 A CN 87107325A
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- CN
- China
- Prior art keywords
- acid
- diphenyl phosphine
- phosphine
- catalyst system
- palladium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- -1 alkene carboxylic acid derivatives Chemical class 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 61
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003446 ligand Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 12
- 230000006315 carbonylation Effects 0.000 claims abstract description 11
- 150000001993 dienes Chemical class 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 78
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 14
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 12
- QKLWAMMQKBOTCD-UHFFFAOYSA-N butane;diphenylphosphane Chemical compound CCCC.C=1C=CC=CC=1PC1=CC=CC=C1 QKLWAMMQKBOTCD-UHFFFAOYSA-N 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- FFFIRKXTFQCCKJ-UHFFFAOYSA-N 2,4,6-trimethylbenzoic acid Chemical compound CC1=CC(C)=C(C(O)=O)C(C)=C1 FFFIRKXTFQCCKJ-UHFFFAOYSA-N 0.000 claims description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 9
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000001118 alkylidene group Chemical group 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 125000001624 naphthyl group Chemical group 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- ONDPGJBEBGWAKI-UHFFFAOYSA-N diphenylphosphane;propane Chemical compound CCC.C=1C=CC=CC=1PC1=CC=CC=C1 ONDPGJBEBGWAKI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 5
- SAMCXPGNUAXAOO-UHFFFAOYSA-N diphenylphosphane;pentane Chemical compound CCCCC.C=1C=CC=CC=1PC1=CC=CC=C1 SAMCXPGNUAXAOO-UHFFFAOYSA-N 0.000 claims description 5
- 150000003003 phosphines Chemical class 0.000 claims description 5
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- 230000001846 repelling effect Effects 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- FSRXIRGQJIHEFB-UHFFFAOYSA-N diphenylphosphane;ethane Chemical compound CC.C=1C=CC=CC=1PC1=CC=CC=C1 FSRXIRGQJIHEFB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- ZDULHUHNYHJYKA-UHFFFAOYSA-N 2-propan-2-ylsulfonylpropane Chemical compound CC(C)S(=O)(=O)C(C)C ZDULHUHNYHJYKA-UHFFFAOYSA-N 0.000 claims description 2
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- DFSFLGZBVMBZTO-UHFFFAOYSA-N FC1(C(C(C(C=C1)(F)F)(F)F)(F)F)F.C1(=CC=CC=C1)PC1=CC=CC=C1 Chemical compound FC1(C(C(C(C=C1)(F)F)(F)F)(F)F)F.C1(=CC=CC=C1)PC1=CC=CC=C1 DFSFLGZBVMBZTO-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- ZUENHQDDMWOOQE-UHFFFAOYSA-N benzene;diphenylphosphane Chemical compound C1=CC=CC=C1.C=1C=CC=CC=1PC1=CC=CC=C1 ZUENHQDDMWOOQE-UHFFFAOYSA-N 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 150000002941 palladium compounds Chemical class 0.000 claims 2
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 150000003457 sulfones Chemical class 0.000 claims 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 claims 1
- 230000001131 transforming effect Effects 0.000 claims 1
- 150000007530 organic bases Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 23
- YIYBQIKDCADOSF-UHFFFAOYSA-N pent-2-enoic acid Chemical compound CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 description 19
- 238000002474 experimental method Methods 0.000 description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 9
- UIUWNILCHFBLEQ-NSCUHMNNSA-N trans-pent-3-enoic acid Chemical compound C\C=C\CC(O)=O UIUWNILCHFBLEQ-NSCUHMNNSA-N 0.000 description 8
- 239000000376 reactant Substances 0.000 description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 4
- UIUWNILCHFBLEQ-UHFFFAOYSA-N pent-3-enoic acid Chemical compound CC=CCC(O)=O UIUWNILCHFBLEQ-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
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- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
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- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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Abstract
在含羟基的化合物(如水、醇、酚或羧酸)存在下,在液相中进行共轭二烯烃选择羰基化的方法。其特征在于羰基化在特定的无含氮有机碱催化剂体系存在下进行,该催化剂体系可由下列分构成:
(a)钯的化合物和
(b)至少一种多齿有机磷配位体。
Description
本发明涉及通过共轭二烯烃的羰基化来制备烯烃羧酸衍生物的方法,尤其涉及由1,3-丁二烯和高级共轭二烯烃制备3-戊烯酸和高级同系物的方法。
烯属不饱和烃羰基化的方法可以专门从英国专利说明书No1,110,405和美国专利说明书No4,172,087和4,414,409知道。
英国专利说明书No1,110,405描述了二烯烃与一氧化碳和醇或酚在一定的催化剂的存在下制备酯的方法。此催化剂含有铂、钯和/或镍和/或
(a)溴和/或碘离子或
(b)能与催化剂中金属组分形成配位键合的配位体,该配位体可含氮、磷、砷或硫。优先被选择的是含三价磷的配位体。最好选择伯膦、仲膦或叔膦或亚磷酸烷基酯、亚磷酸芳基酯或亚磷酸环烷基酯。
虽然丁二烯转化作为一个实施方案提及,但在第2页97~103行清楚表明二烯烃类化合物作为初始化合物是可取的。它们中的双键可被2,3或4个单键所隔开。并且反应最好在酸化的反应介质(如在对甲苯磺酸存在下)中进行。
从有关的实施例中描述的3-戊烯酸酯的产率看,对精通工艺的人来说,很清楚上述的英国专利说明书没有对由1,3-丁二烯和高级共轭二烯烃选择性地制备3-戊烯酸酯和高级的同系物的方法提供任何暗示。
从美国专利说明书No4,172,087可知由含4至8个碳原子的脂族二烯烃原料同时制备不饱和羧酸和它们的酯的两类化合物的方法,其中:
(a)每2摩尔的参与反应的共轭脂族二烯烃与一个三组分混合物相混合,该三组分混合物的组成是:
(ⅰ)至少为催化剂量的钯催化剂,它的组成是一种或多种囟化钯与一种或多种含叔膦给体的一齿配位体相结合,或者一种或多种不含囟化物的钯盐与一种或多种含叔膦给体的多齿配位体相结合;
(ⅱ)至少一摩尔当量的含羟基的共反应剂,此类试剂是从水或含1至12个碳原子的脂族醇中选取,以及
(ⅲ)N-杂环胺碱,
(b)反应混合物用足够量的一氧化碳加压,一氧化碳用量应满足羰基化反应的化学计量;
(c)加热加压反应物,直到达到所期望的脂族羧酸衍生物大量生成为止,以及
(d)分离反应所得到的不饱和羧酸衍生物。
尽管提及1,3-丁二烯和共轭脂族二烯烃的转化问题,但是N-杂环碱的存在是必需考虑的主要先决条件。这些杂环碱可以是吡啶、烷基化吡啶、喹啉、二甲基吡啶、甲基吡啶、异喹啉、烷基化喹啉和烷基化异喹啉、吖啶和N-甲基-2-吡咯烷酮或N,N-二甲基苯胺、N,N-二乙基苯胺、N,N-二乙基甲苯胺、N,N-二丁基甲苯胺以及N,N-二甲基甲酰胺等。
尤其是从所描述的实施例涉及的3-戊烯酸酯的产率看,对于本领域熟练技术人员来说,显然上述的美国专利说明书No4,172,087的方法没有对由1,3-丁二烯和高级共轭二烯烃选择性地制备3-戊烯酸酯和高级的同系物的方法提供任何暗示。
由美国专利说明书No4,414,409可知采用羰基化的方法制备酸和酯,即在约50至约150℃温度下,在由有机膦配位体钯络合物和全氟磺酸组成的催化剂存在下,将烯属不饱和化合物、一氧化碳和羟基化合物转化为酸和酯。
另外如文中2栏26~29行和9栏27行中指出的,此法最适用于非共轭烃类的转化。
很清楚,上文所述的方法既不适用于共轭不饱和化合物的转化,似乎尤其不适用于选择性地制备3-戊烯酸或它的衍生物和高级同系物。而且上文所述的方法已索制了寻求改善选择性制备3-戊烯酸及其衍生物方法的熟练技术人员,而3-戊烯酸及其衍生物日益成为有机合成(如己二酸及其衍生物的重要原料。
更广地说,许多已知的方法存在着一定的缺点,如使用相当高浓度的相应的催化剂体系,使用象氢囟酸及其盐这样有腐蚀性的反应组分以及其它严酷的反应条件。这些条件迫使有关保证安全和设备寿命(腐蚀)所需的费用增加。
为此,本发明的目的是要提出一种改进的选择羰基化方法,将1,3-丁二烯和高级同系物转化成象3-戊烯酸或它的衍生物这样有价值的产品。
令人意外地目前已经发现一种改进的方法可适于象1,3-丁二烯、1,4-己二烯和2,4-庚二烯这样的共轭二烯的选择转化,该反应在液相中进行转化率有一定的提高。反应在特定的催化剂体系中进行不需要加N-杂环胺和/或囟化物。因而允许用价廉的钢材做反应器设备。
因此本发明涉及一个适用于共轭二烯烃选择羰基化的方法,反应在含羟基的化合物(如水、醇、酚或羧酸)存在下的液相中进行。反应使用特定的上无含氮有机碱的催化剂体系,该催化剂体系由下列组分组成:
(a)钯的化合物和
(b)至少一种多齿有机磷配位体。
具体地说,上述方法是在下列催化剂体系存在下进行,该催化剂体系由下列组分组成:
(a)钯的化合物和
(b)至少一种二齿膦衍生物配位体,其通式为
式中R1,R2,R3和R4是被一个或多个取代随意取代的烃基,R是至少有2个架桥碳原子的二价有机桥键基团。
更可取的是,基团R1和R3是随意取代的芳基,以苯基或萘基为最好,基团R2和R4是随意取代的1~20个碳原子的烷基、最好是2~6个碳原子的烷基、环烷基或芳基,基团R为含2~6个碳原子的亚烷基、亚苯基或环亚烷基。
上述的烃基本身可以被烷基或1~4个碳原子的烷氧基,最好是氟或氯这样的囟素所替代。
按照最佳实施方案,依据所选择的其它催化剂组份情况,可以加入催化剂量的质子酸(pka值>3),以便在丁二烯转化处于近似恒定的高选择性情况下增加戊烯酸酯产品的产量。例如象3-戊烯酸或它的衍生物的选择性可以百分数表示,其定义为:
(a)/(b) ×100
式中“a”是1,3-丁二烯转化成3-戊烯酸或它的衍生物的量,“b”是已转化的1,3-丁二烯的总量。
很明显实验发现以1,3-丁二烯转化成3-戊烯酸和它的衍生物为例的反应可得到很高的选择性,这是以在反应时同时有3,8-壬二烯酸或它的衍生物、4-乙烯基-1-环己烯和1,3,7-辛三烯生成为代价的。这在所熟悉的早期方法中也是同时生成的。
特别合适的磷配位体的例子如下:
1,2-二(二苯膦基)乙烷,
1,3-二(二苯膦基)丙烷,
1,4-二(二苯膦基)丁烷,
1,5-二(二苯膦基)戊烷,
1,6-二(二苯膦基)己烷,
1,2-双(二苯膦基)苯
1,2-双(二三氟甲基膦基)乙烷
1,3-双(二三氟甲基膦基)丙烷
1,3-双(三氟甲基苯基膦基)丙烷
1,2-双(二苯膦基)六氟环戊烯
1,2-双(二苯膦基)四氟环丁烯
1,2-双(二苯膦基)八氟环己烯
1,4-二苯基-1,4-二磷杂环己烷或它们的混合物。
使用1,4-二(二苯膦基)丁烷、1,3-二(二苯膦基)丙烷或1,5-二(二苯膦基)戊烷或它们的混合物可以得很好的结果。而且还发现,如果除了在上述的催化剂体系中必须存在的多齿,最好是二齿膦配位体以外,还存在一种或多种一齿膦配位体的话,则可得到一个相当好的转化结果。属于这些最后提到的特别好的一类化合物中含有如下通式所代表的基团:
式中R6是随意取代的芳基,最好是苯基或萘基,R7和R8各为随意取代的烷基、随意取代的环烷基或随意取代的芳基,或者式中R7和R8合起来是一个随意取代的亚烷基或磷杂环亚烷基。也可使用这些膦的混合物。最好这里每个烷基最多含20个碳原子,每个环烷基在环内最多含7个碳原子以及每个芳基在环内最多含18个碳原子。芳基可以是蒽基、萘基或苯基。根据式Ⅲ,若式中R6和R7各为一随意取代的苯基,则这类膦构成最理想的一类化合物。在这类膦中,若R8也是一随意取代的苯基,则可构成更理想的一类化合物。
可以加到催化剂体系的pka值>3的质子酸最好是苯甲酸或被一个或多个电子排斥基所取代的苯甲酸,如2,4,6-三甲基苯甲酸、对羟基苯甲酸和间羟基苯甲酸。
均相和多相钯催化剂组分都能用于本发明的选择性转化作用。然而均相催化剂体系更为可取。合适的均相催化剂组分的例子为钯的硝酸盐、硫酸盐或碳原子数不大于12的烷链羧酸盐。它们中间以乙酸钯(Ⅱ)为最好。然而一些钯的络合物,如乙酰丙酮酸钯、乙酸邻-甲苯膦钯或硫酸双三苯膦钯也能作催化剂使用。钯和离子交换剂(如含磺酸基团的离子交换剂)相键合可作为合适的多相催化剂组分的例子。钯的使用量没有一定的标准。若使用两价钯的化合物,对每摩尔共轭二烯烃(尤其是丁二烯),它的最合适的使用量在10-5至10-1克原子钯的范围内。
已经发现为了得到最好的结果,有机磷化物与钯的摩尔比对每克原子钯而言,膦不应大于10摩尔。如果膦对钯的摩尔比在2至5摩尔膦/每克原子钯之间,则可得到很高的选择性和很高的转化率(例如反应在5小时内150℃温度下丁二烯可100%转化)。已发现若加入pka值>3的质子酸,则它的用量应在6至10酸当量/每克原子钯范围内为最好。
专门的溶剂对于本发明的方法不是必不可少的,通常反应物或生成物中的某一组分过量都会形成一合适的液相。但是在某些情况下,也要求使用专门的溶剂。原则上讲,凡惰性溶剂都可在此法中使用。例如它们可以从下列化合物中选取:亚砜类和砜类化合物,如二甲基亚砜、二异丙基砜或四氢噻砜1,1-二氧化物(也叫环丁砜)、2-甲基-4-丁基环丁砜、3-甲基环丁砜;芳烃类,如苯、甲苯、二甲苯;酯类,如乙酸甲酯和丁内酯;酮类,如丙酮或甲基异丁基酮;醚类,如苯甲醚、二甘醇二甲醚、二苯醚和二异丙醚或它们的混合物。以使用二苯醚为最好。
本发明的方法能采用较温和的反应条件。已经发现反应温度在50至150℃,较特殊的在20至200℃范围内是十分合适的。
一氧化碳的初始压力可在一个宽的范围内变化,但一般低于至今所知的方法。压力值在25至65巴范围内为最宜。
在本发明的方法中,一氧化碳可以纯态使用,也可用惰性气体(如氮气、惰性气体或二氧化碳)稀释后使用。一般地说,不希望存在高于5%的氢气,因为在反应条件下这能引起在共轭二烯烃的氢化作用。
醇、酚、水或羧酸对共轭二烯烃(尤其是丁二烯)的摩尔比可在宽的限度内变化,一般它们的比值在0.1∶1至10∶1的范围内。
按照本发明方法的择优实施方案,可用醇作为含羟基的反应物。这种醇可以是脂肪醇、环脂族醇或芳香醇,如果需要,也可带一个或多个惰性取代基。最多为20个碳原子的醇都是合适的醇。一个或多个羟基可以存在,在这种情况下可能生成不同的产物。例如,多元醇,尤其是低糖类能与适当量的丁二烯反应生成单酯或多元酯。这些低糖类的例子有葡萄糖、果糖、甘露糖、半乳糖、蔗糖、阿洛糖、阿卓糖、塔罗糖、果洛糖、艾杜糖、核糖、阿拉伯糖、木糖、来苏糖、赤鲜糖或苏糖。因此醇的选择将仅由所希望得到的产物来定。链烷醇类(如甲醇、乙醇、丙醇或2,2-二羟甲基-1-丁醇)和含醚键的醇类(如三甘醇),它们都能给出有价值的产品。
按照本发明方法的其它实施方案,各种不同的羧酸可用作反应物。举例来说,这些羧酸可以是脂肪酸、环脂酸或芳香酸,它们也能带有惰性取代基。最多为25个碳原子的羧酸都是合适的酸。用作反应物的羧酸最好是链烷酸或链烯酸。作为合适的烷链羧酸的典型例子是甲酸、乙酸、丙酸、正丁酸、异丁酸、新戊酸、正戊酸、正己酸、辛酸、癸酸、月桂酸、十四烷酸、十六烷酸、十八烷酸、苯二甲酸和对苯二酸。链烯酸的例子有丙烯酸、丙炔酸、甲基丙烯酸、丁烯酸、异丁烯酸、油酸、顺式丁烯二酸、反式丁烯二酸、甲基顺式丁烯二酸和甲基反式丁烯二酸。
原则上讲本发明的方法中也可使用多元羧酸来进行。据此,依据所选择的反应条件,包括所用反应的摩尔比,可以得到所希望的各种不同的产物。如果依据本发明的方法,利用1,3-丁二烯转化成链烷酸,则能得到对称酐或混合酐。
本发明的方法最好使用弱酸,这种酸在18℃的水性介质中测得的pka值>3。
使用不能酯化或难以酯化的酸更为理想,否则它在反应过程中会发生损耗。
已经发现本发明的方法特别适用于连续过程,即可重复使用相应的催化剂体系,这就为本发明方法在工业规模上使用提供了很大的方便。
本发明也涉及在含羟基的化合物(如醇、酚、羧酸和水)存在下,进行共轭二烯烃选择性羰基化所用的实际上无含氮有机碱的催化剂体系,该催化剂体系的构成为:
(a)钯的化合物和
(b)至少一种二齿膦衍生物配位体,其通式为:
式中R1,R2,R3和R4是被一个或多个取代基随意取代的烃基,R是含有至少2个架桥碳原子的二价有机桥键基团。
(c)一齿膦衍生物配位体。
在本发明的催化剂体系中最好含有pka值>3的质子酸。
更可取的是,基团R1和R3为随意取代的芳基,最好是苯基或萘基,基团R2和R4是随意取代的1~20个碳原子的烷基,最好是含2~6个碳原子的烷基,环烷基或芳基。基团R表示含2~6个碳原子的亚烷基、亚苯基或环亚烷基。
本发明的催化剂体系中的特别合适的磷配位体的例子已在上文描述。
本发明的催化剂体系中存在的合适的一齿膦配位体可从下式中选择合适基团而得到:
式中R6是可任意取代的芳基并以苯基和萘基为最好,R7和R8各为随意取代的烷基、随意取代的环烷基或随意取代的芳基,或者这里R7和R8合在一起是一个随意取代的亚烷基或磷杂环亚烷基,或它们的混合物。
依据式Ⅱ,若R6、R7、R8各为随意取代的苯基的膦可形成一理想的催化剂配位体。
可以加到本发明的催化剂体系中的pka值>3的质子酸最好为苯甲酸或带有一个或多个电子排斥基的苯甲酸(如2,4,6-三甲基苯甲酸、对羟基苯甲酸和间羟基苯甲酸)。
本发明的最理想的催化剂体系由作为均相催化剂组分的乙酸钯构成。并且如果在这些催化剂体系中膦对钯的摩尔比在2至5摩尔/每克原子钯之间,则可得到很高的选择性和很高的转化率。
在本发明的催化剂体系中能加入的pka值>3的质子酸的比例最好应在6~10酸当量/每克原子钯范围内。
最理想催化剂体系包括附加溶剂。这种附加溶剂可从已在上文所述的亚砜和砜类化合物例子中选取。
本发明通过下述实施例进行说明。
实施例1
将15ml乙醇、40ml二苯醚、1毫摩尔醋酸钯和5毫摩尔1,4-二(二苯膦基)丁烷加入体积为300ml带磁搅拌的Hastello
高压釜(Hastelloy一词是注册商标)。抽空反应釜,然后加入8ml丁二烯和一氧化碳使初始一氧化碳压力为60bar.加热高压釜至155℃。反应5小时后,用气-液色谱分析高压釜中成份。实验得到丁二烯转化为戊烯酸酯的选择性为95%,戊烯酸酯的产率为30%(以丁二烯的初始量为基准计算)。
实施例2
使用实施例1所述的基本相类似的方法进行实验。实验中所用的催化剂体系是1毫摩尔乙酸钯和1.5毫摩尔的1,3-二(二苯膦基)丙烷。实验得到丁二烯转化为戊烯酸酯的选择性为92%,戊烯酸酯的产率为50%(以丁二烯的初始量为基准计算)。
实施例3
使用和实施例1所述的基本相类似的方法进行实验。实验中所用的催化剂体系是1毫摩尔乙酸钯、2毫摩尔的1,4-二(二苯膦基)丁烷和5毫摩尔三苯膦。得到丁二烯转化为戊烯酸酯的选择性为93%,戊烯酸酯产率为50%(以丁二烯的初始量为基准计算)。
实施例4
使用和实施例1所述的基本相类似的方法进行实验。实验所用的催化剂体系是1毫摩尔乙酸钯、4毫摩尔1,4-二(二苯膦基)丁烷和7.5毫摩尔2,4,6-三甲基苯甲酸。反应温度为150℃,反应时间为2.5小时。实验得到丁二烯转化为戊烯酸酯的选择性为96%,戊烯酸酯的产率为90%(以丁二烯的初始量为基准计算)。
实施例5
使用和实施例1中所述的基本相类似的方法进行实验。实验所用的催化剂体系是1毫摩尔乙酸钯、4毫摩尔1,4-二(二苯膦基)丁烷、4毫摩尔三苯膦和7.5毫摩尔2,4,6-三甲基苯甲酸。反应温度为150℃,反应时间为2.5小时。实验得到丁二烯转化为戊烯酸酯的选择性为91%,戊烯酸酯的产率为88%(以丁二烯的初始量为基准计算)。
实施例6
使用和实施例1所述的基本相类似的方法进行实验。实验所用的催化剂体系是1毫摩尔乙酸钯、4毫摩尔的1,4-二(二苯膦基)丁烷和7.5毫摩尔的2,4,6-三甲基苯甲酸。一氧化碳的初始压力为30巴。反应温度为150℃,反应时间为2.5小时。实验得到丁二烯转化为戊烯酸酯的选择性为90%,戊烯酸酯的产率为89%(以丁二烯初始量为基准计算)。
实施例7
使用和实施例1所述的基本相类似的方法进行实验。实验所用的催化剂体系是1毫摩尔乙酸钯、10毫摩尔三苯膦和7.5毫摩尔2,4,6-三甲基苯甲酸。反应温度为150℃,反应时间为2.5小时。实验得到丁二烯转化为戊烯酸酯的选择性为75%(还发现有15%的丁二烯已转化为壬二烯酸酯),戊烯酸酯的产率为55%(以丁二烯的初始量为基准计算)。
实施例8
使用和实施例1所述的基本相类似的方法进行实验。实验所用的催化剂体系是1毫摩尔乙酸钯和1.5毫摩尔1,2-二(二苯膦基)乙烷。实验得到丁二烯转化为戊烯酸酯的选择性为88%,戊烯酸酯的产率为40%(以丁二烯的初始量为基准计算)。
实施例9
使用和实施例1所述的基本相类似的方法进行实验。实验所用的催化剂体系是1毫摩尔乙酸钯和4毫摩尔1,2,4-二(二苯膦)丁烷和7.5毫摩尔2,4,6-三甲基苯甲酸。在10小时的反应过程中,以25毫摩尔乙醇和25毫摩尔丁二烯/小时的投料速度加入补充的乙醇和丁二烯。实验得到丁二烯转化为戊烯酸酯的选择性为90%,戊烯酸酯的产率为81%(以丁二烯的初始量为基准计算)。
Claims (24)
1、一种在含羟基的化合物(如水、醇、酚或羧酸)存在下,在液相中进行共轭二烯烃选择羰基化的方法。其特征在于羰基化作用在特定的无含氮有机碱的催化剂体系存在下进行。该催化剂体系可由下列组分构成:
(a)钯化合物和
(b)至少一种多齿有机磷配位体。
3、根据权利要求2的方法,其特征在于基团R1和R3是随意取代的芳基,最好是苯基或萘基,基团R2和R4表示随意取代的1~20个碳原子的烷基,最好是2~6个碳原子的烷基,环烷基或芳基,基团R是含2~6个碳原子的亚烷基、亚苯基或环亚烷基团。
4、根据权利要求2或3的方法,其特征在于烃基可以用烷基或1~4个碳原子的烷氧基和囟素所代替。
5、根据权利要求1至4的任一方法,其特征在于应加入催化剂用量的pka>3的质子酸。
6、根据权利要求5的方法,其特征在于作为质子酸使用的化合物为苯甲酸或用一个或多个电子排斥基团取代的苯甲酸,如2,4,6-三甲基苯甲酸、对羟基苯甲酸或间羟基苯甲酸。
7、根据权利要求1~6中任一方法,其特征在于下列化合物可用作磷配位体:
1,2-二(二苯膦基)乙烷,
1,3-二(二苯膦基)丙烷,
1,4-二(二苯膦基)丁烷,
1,5-二(二苯膦基)戊烷,
1,6-二(二苯膦基)己烷,
1,2-双(二苯膦基)苯,
1,2-双(二三氟甲基膦基)乙烷,
1,3-双(二三氟甲基膦基)丙烷,
1,3-双(三氟甲基苯基膦基)丙烷,
1,2-双(二苯膦基)六氟环戊烯,
1,2-双(二苯膦基)四氟环丁烯,
1,2-双(二苯膦基)八氟环己烯,
1,4-二苯基-1,4-二磷杂环己烷或它们的混合物。
8、根据权利要求1~7中任一方法,其特征在于可以使用1,4-二(二苯膦基)丁烷、1,3-二(二苯膦基)丙烷或1,5-二(二苯膦基)戊烷或它们的混合物。
9、根据权利要求1~8中的任一方法,其特征在于除了有二齿磷配位体外,还应有一个或多个一齿配位体存在。
11、根据权利要求10的方法,其特征在于使用磷配位体,式中R6、R7和R8表示随意取代的苯基。
12、根据权利要求1~11中的任一方法,其特征在于使用乙酸钯(Ⅱ)。
13、根据权利要求1~12中的任一方法,其特征在于每摩尔共轭二烯(最好是丁二烯)使用10-10克原子的钯。
14、根据权利要求1~13中任一方法,其特征在于膦与钯的摩尔比在2至5摩尔之间(每克原子钯)。
15、根据权利要求1~14中任一方法,其特征在于每克原子钯使用6~10酸当量的pka值>3的质子酸。
16、根据权利要求1~15中任一方法,其特征在于使用的附加溶剂选自亚砜类或砜类有机物,例如二甲基亚砜、二异丙基砜、四氢噻吩1,1-二氧化物(环丁砜)、2-甲基-4-丁基环丁砜、或3-甲基环丁砜;芳烃类,如苯,甲苯、二甲苯;酯类,如乙酸甲酯和丁内酯;酮类,如丙酮或甲基异丁基酮以及醚类,如苯甲醚、二甘醇二甲醚、二苯醚和二异丙醚或它们的混合物。
17、根据权利要求16的方法,其特征在于使用二苯醚。
18、根据权利要求1~17中任一方法,其特征在于每摩尔二烯使用醇、酚、水或羧酸的摩尔量在0.1至10之间。
19、根据权利要求1~18中任一方法,其特征在于转化1,3-丁二烯。
21、根据权利要求20的催化剂体系,其特征在于包含pka>3的质子酸。
22、根据权利要求21的催化剂体系,其特征在于其中包含苯甲酸或被一个或多个电子排斥基团取代的苯甲酸,例如2,4,6-三甲基苯甲酸、对羟基苯甲酸和间羟基苯甲酸。
23、根据权利要求20~22中的任一种催化剂体系,其特征在于二齿膦配位体由1,4-二(二苯膦基)丁烷、1,3-二(二苯膦基)丙烷或1,5-二(二苯膦基)戊烷组成。
24、根据权利要求20~23中的任一种催化剂体系,其特征在于包含附加溶剂。
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CN87107325A Expired - Fee Related CN1032351C (zh) | 1986-12-10 | 1987-12-08 | 烯烃羧酸衍生物的选择性制备法 |
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Country | Link |
---|---|
US (1) | US5028734A (zh) |
EP (1) | EP0273489B1 (zh) |
JP (1) | JP2867137B2 (zh) |
KR (2) | KR880007418A (zh) |
CN (1) | CN1032351C (zh) |
AT (1) | ATE65489T1 (zh) |
AU (1) | AU597451B2 (zh) |
CA (1) | CA1292475C (zh) |
DE (1) | DE3771686D1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1037962C (zh) * | 1992-06-29 | 1998-04-08 | 国际壳牌研究有限公司 | 链烷双酸衍生物的制备方法 |
CN1297562C (zh) * | 2001-10-02 | 2007-01-31 | 巴斯福股份公司 | 二膦 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9014724D0 (en) * | 1990-07-03 | 1990-08-22 | Shell Int Research | Process for the preparation of alpha,beta-olefinically unsaturated compounds |
US5026901A (en) * | 1990-03-29 | 1991-06-25 | E. I. Du Pont De Nemours And Company | Palladium catalyzed carboalkoxylation of butadiene |
US5350876A (en) * | 1992-06-29 | 1994-09-27 | Shell Oil Company | Carbonylation of conjugated dienes |
EP0577204B1 (en) * | 1992-06-29 | 1996-10-09 | Shell Internationale Researchmaatschappij B.V. | Preparation of alkanedioic derivatives |
EP0577205B1 (en) * | 1992-06-29 | 1997-10-08 | Shell Internationale Researchmaatschappij B.V. | Carbonylation of conjugated dienes |
US5254720A (en) * | 1992-12-28 | 1993-10-19 | Ethyl Corporation | Process for preparing aryl-substituted aliphatic carboxylic acids and their alkyl esters |
US5414109A (en) * | 1993-03-19 | 1995-05-09 | Shell Oil Company | Process for the carbonylation of acetylenically unsaturated compounds |
BE1007422A3 (nl) * | 1993-08-23 | 1995-06-13 | Dsm Nv | Werkwijze voor de bereiding van een mengsel van penteenzure alkylesters. |
US5315026A (en) * | 1993-09-29 | 1994-05-24 | Ethyl Corporation | Process for preparing aryl-substituted aliphatic carboxylic acids and their esters using cyclic phosphine catalysts |
US5495041A (en) * | 1995-02-22 | 1996-02-27 | Dsm N.W. | Process for the preparation of a pentenoate ester |
KR960031420A (ko) * | 1995-02-22 | 1996-09-17 | 미키엘 크램윈켈. | 부티디엔 또는 부타디엔 유도체의 카르보닐화 방법 |
US5886236A (en) * | 1997-04-15 | 1999-03-23 | Union Carbide Chemicals & Plastics Technology Corporation | Process for producing aldehyde acid salts |
US5925754A (en) * | 1997-04-15 | 1999-07-20 | Union Carbide Chemicals & Plastics Technology Corporation | Epsilon caprolactam compositions |
US5962680A (en) * | 1997-04-15 | 1999-10-05 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for producing epsilon caprolactams |
US6049005A (en) * | 1997-10-07 | 2000-04-11 | Dsm N.V. | Process to prepare a pentenoic acid anhydride |
US6010975A (en) * | 1998-06-19 | 2000-01-04 | Industrial Technology Research Institute | Catalyst composition for preparing 3-pentenoic ester from butadiene |
US5973174A (en) * | 1998-11-24 | 1999-10-26 | Shell Oil Company | Preparation of transition metal catalysts from phosphonium salts |
US6087533A (en) * | 1998-12-18 | 2000-07-11 | E I. Du Pont De Nemours And Company | Rhodium catalyzed carbonylation of an allylic butenol or butenyl ester to beta-gamma unsaturated anhydrides |
TW524801B (en) * | 1999-03-22 | 2003-03-21 | Shell Int Research | Process for the carbonylation of conjugated dienes |
CH694251A5 (de) * | 1999-07-14 | 2004-10-15 | Eprova Ag | Herstellung von Tetrahydropterin und Derivaten. |
EP1332124A1 (en) * | 2000-09-27 | 2003-08-06 | Dsm N.V. | Process for the carbonylation of a conjugated diene |
US6362354B1 (en) | 2000-11-17 | 2002-03-26 | E. I. Du Pont De Nemours And Company | Phosphonite ligands, catalyst compositions and hydroformylation process utilizing same |
US6437192B1 (en) | 2000-11-17 | 2002-08-20 | E. I. Du Pont De Nmeours And Company | Hydroformylation of conjugated dienes to alkenals using phosphonite ligands |
US20030105348A1 (en) * | 2001-11-19 | 2003-06-05 | Bunel Emilio E. | Process for making 5-cyanovaleric acid, adipic acid or dimethyl adipate |
AU2003303065A1 (en) * | 2002-12-17 | 2004-07-09 | Shell Internationale Research Maatschappij B.V. | Process for the hydroformylation of ethylenically unsaturated compounds in the presence of an acid and a mono tert-phosphine |
EP1572608B1 (en) | 2002-12-17 | 2008-07-02 | Shell Internationale Researchmaatschappij B.V. | Hydroformylation process for the conversion of an ethylenically unsaturated compound to an alcohol |
US20060235241A1 (en) * | 2003-05-22 | 2006-10-19 | Eit Drent | Process for the carbonylation of a conuugated diene |
US7265242B2 (en) | 2004-02-26 | 2007-09-04 | Shell Oil Company | Process for the carbonylation of ethylenically or acetylenically unsaturated compounds |
BRPI0507918A (pt) * | 2004-02-26 | 2007-07-10 | Shell Int Research | processo para a carbonilação de compostos insaturados, composição de catalisador, e, ligando de difosfina bidentado assimétrico |
JP4508722B2 (ja) * | 2004-05-14 | 2010-07-21 | 日本ゼオン株式会社 | 含フッ素リンイリド化合物及びその製造方法 |
CN115403465B (zh) * | 2022-05-20 | 2023-08-18 | 湖南工程学院 | 一种二氧化碳和烯烃合成有机羧酸酯的制备方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1249867B (de) * | 1964-12-19 | 1967-09-14 | Badische Anilin- &. Soda-Fabnk Aktiengesellschaft, Ludwigshaf en/Rhem | Verfahren zur Herstellung von Carbonsauren oder Carbonsaureestern |
GB1110405A (en) * | 1964-12-23 | 1968-04-18 | Ici Ltd | The production of esters |
US3530155A (en) * | 1968-02-06 | 1970-09-22 | Union Oil Co | Hydrocarboxylation of olefins |
US4243829A (en) * | 1976-10-04 | 1981-01-06 | Charles U. Pittman, Jr. | Production of 1,7-octadiene from butadiene |
US4124617A (en) * | 1977-06-28 | 1978-11-07 | Texaco Development Corporation | Process for preparing unsaturated aliphatic esters from aliphatic dienes |
US4172087A (en) * | 1978-02-13 | 1979-10-23 | Texaco Development Corporation | Process for preparing unsaturated aliphatic esters from aliphatic dienes |
GB2058074B (en) * | 1979-08-23 | 1983-10-12 | Secr Defence | Palladium complexes |
US4582817A (en) * | 1981-04-27 | 1986-04-15 | National Distillers And Chemical Corporation | Process for the preparation of alkyl nonadienoate esters |
US4414409A (en) * | 1981-12-21 | 1983-11-08 | E. I. Du Pont De Nemours & Company | Palladium sulfonate catalyst systems for carbonylation of olefins |
GB8501919D0 (en) * | 1985-01-25 | 1985-02-27 | Shell Int Research | Carbonylation of allenically unsaturated compounds |
GB8509641D0 (en) * | 1985-04-15 | 1985-05-22 | Shell Int Research | Carboxylic di-esters/acids |
KR880007427A (ko) | 1986-12-05 | 1988-08-27 | 오노 알버어스 | 공역 디엔의 카르보닐화 방법 및 이를 위한 촉매 시스템 |
-
1986
- 1986-12-08 KR KR860013964A patent/KR880007418A/ko unknown
-
1987
- 1987-11-23 CA CA000552454A patent/CA1292475C/en not_active Expired - Fee Related
- 1987-11-25 EP EP87202334A patent/EP0273489B1/en not_active Expired - Lifetime
- 1987-11-25 DE DE8787202334T patent/DE3771686D1/de not_active Expired - Fee Related
- 1987-11-25 AT AT87202334T patent/ATE65489T1/de active
- 1987-12-08 CN CN87107325A patent/CN1032351C/zh not_active Expired - Fee Related
- 1987-12-08 AU AU82201/87A patent/AU597451B2/en not_active Ceased
- 1987-12-08 KR KR1019870013964A patent/KR960001890B1/ko not_active IP Right Cessation
- 1987-12-08 JP JP62308829A patent/JP2867137B2/ja not_active Expired - Fee Related
-
1989
- 1989-01-27 US US07/303,596 patent/US5028734A/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1037962C (zh) * | 1992-06-29 | 1998-04-08 | 国际壳牌研究有限公司 | 链烷双酸衍生物的制备方法 |
CN1297562C (zh) * | 2001-10-02 | 2007-01-31 | 巴斯福股份公司 | 二膦 |
Also Published As
Publication number | Publication date |
---|---|
CA1292475C (en) | 1991-11-26 |
US5028734A (en) | 1991-07-02 |
ATE65489T1 (de) | 1991-08-15 |
KR960001890B1 (ko) | 1996-02-06 |
EP0273489A2 (en) | 1988-07-06 |
EP0273489B1 (en) | 1991-07-24 |
AU8220187A (en) | 1988-06-16 |
CN1032351C (zh) | 1996-07-24 |
EP0273489A3 (en) | 1988-07-20 |
AU597451B2 (en) | 1990-05-31 |
JPS63156745A (ja) | 1988-06-29 |
KR880007418A (ko) | 1988-08-27 |
DE3771686D1 (de) | 1991-08-29 |
JP2867137B2 (ja) | 1999-03-08 |
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