CN114085247A - 一种双齿膦型配体、氢甲酰化催化剂、及不饱和脂肪酸制备线性二元醇的方法 - Google Patents
一种双齿膦型配体、氢甲酰化催化剂、及不饱和脂肪酸制备线性二元醇的方法 Download PDFInfo
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- CN114085247A CN114085247A CN202111460185.0A CN202111460185A CN114085247A CN 114085247 A CN114085247 A CN 114085247A CN 202111460185 A CN202111460185 A CN 202111460185A CN 114085247 A CN114085247 A CN 114085247A
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- unsaturated fatty
- fatty acid
- hydroformylation
- acetylacetonate
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- 239000003446 ligand Substances 0.000 title claims abstract description 42
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 235000021122 unsaturated fatty acids Nutrition 0.000 title claims abstract description 22
- 150000004670 unsaturated fatty acids Chemical class 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 11
- -1 (4- (5-bromofuran-2-yl) phenyl) disubstituted phosphine Chemical class 0.000 claims description 9
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 9
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 9
- 150000003623 transition metal compounds Chemical class 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 8
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 claims description 8
- VLJNHYLEOZPXFW-UHFFFAOYSA-N pyrrolidine-2-carboxamide Chemical compound NC(=O)C1CCCN1 VLJNHYLEOZPXFW-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- BDDWSAASCFBVBK-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical group [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BDDWSAASCFBVBK-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- ATMPMEZIXCBUHT-UHFFFAOYSA-N cobalt;triphenylphosphane Chemical compound [Co].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ATMPMEZIXCBUHT-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- HWVKIRQMNIWOLT-UHFFFAOYSA-L cobalt(2+);octanoate Chemical compound [Co+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HWVKIRQMNIWOLT-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- HDKCVDHYIIKWFM-UHFFFAOYSA-K octanoate;rhodium(3+) Chemical compound [Rh+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HDKCVDHYIIKWFM-UHFFFAOYSA-K 0.000 claims description 2
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 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 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 3
- 229940043375 1,5-pentanediol Drugs 0.000 description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- JRTOLVNURLQVBB-UHFFFAOYSA-N 4-diphenylphosphanylaniline Chemical compound C1=CC(N)=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 JRTOLVNURLQVBB-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GNPXKHTZVDUNOY-UHFFFAOYSA-N oxomethylidenerhodium Chemical compound O=C=[Rh] GNPXKHTZVDUNOY-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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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
- C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
- C07F9/65586—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system at least one of the hetero rings does not contain nitrogen as ring hetero atom
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- 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
- 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
- B01J31/2409—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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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Abstract
本发明公开一种双齿膦型配体、氢甲酰化催化剂、及不饱和脂肪酸制备线性二元醇的方法。所述配体结构通式为
Description
技术领域
本发明涉及有机合成领域,具体涉及双齿膦配体和氢甲酰化催化剂,还涉及其在催化不饱和脂肪酸氢甲酰化制备线性二元醇中的应用。
背景技术
氢甲酰化是一种以烯烃为原料来制备多一个碳原子醛的合成方法,在工业化生产中有着巨大的应用,其下游的醇/酸也在有机合成中有着重要的应用。
线性二元醇如1,3-丙二醇、1,4-丁二醇等常用作于制备聚酯的不可替代单体,由于其制备方法单一,成本高,需求量大具有较高的利润。
将价格较低的不饱和脂肪酸配合成本较低的氢甲酰化方法制备二元醇是一种具有工业化前景的路线,专利CN105523891A提出了一种已混合金属为催化剂、SiO2/Al2O3为载体催化醋酸烯丙酯氢甲酰化、水解制备1,3-丙二醇的方法;专利US4072709提出了以均相铑为催化剂将乙酸乙烯酯氢甲酰化、水解制备1,3-丙二醇;但上述方法后期需经复杂工艺降低二元醇的中杂质含量,并且产率不高。
因此,需要一种经济、稳定地配体来制造线性二元醇的技术。
发明内容
为克服现有技术中存在的上述缺陷,本发明的目的是提供一种双齿膦型配体、氢甲酰化催化剂,所述配体稳定性好,具有高反应活性。
本发明的另一目的是提供一种所述配体在不饱和脂肪酸氢甲酰化制备线性二元醇中的应用,具有高反应活性和线性选择性。
为达到以上技术效果,本发明采用如下技术方案:
本发明提出的一种双齿膦型配体,其结构通式I如下:
其中R1、R2、R3、R4为C1-C10的烷烃基、芳香烃基,优选的为苯基、异戊基、噻吩基;R1、R2、R3、R4相同或不同,优选的为相同。
本发明所述配体的制备方法,包括以下步骤:
(3)M2与(4-(5-溴呋喃-2-基)苯基)二取代基膦反应生成配体。
配体的制备方程式示意如下:
本发明所述步骤(1)中,吡咯烷-2-甲酰胺的加入量为4-(二取代基膦)苯胺摩尔量的1.0-3.0倍,优选的为1.0-1.5倍。
本发明所述步骤(1)中,催化剂为三苯基膦乙酰丙酮羰基铑和/或乙酰丙酮钴,优选的为三苯基膦乙酰丙酮羰基铑。
本发明所述步骤(1)中,催化剂加入量为4-(二取代基膦)苯胺摩尔量的0.001-0.01倍,优选的为0.005-0.007倍。
本发明所述步骤(1),优选在溶剂的存在下进行,所述溶剂为苯、甲苯、氯苯中的一种或多种。
本发明所述步骤(1)中,反应温度为80-140℃,优选的为90-110℃,反应时间为1.0-5.0h,优选的为1.0-2.0h。
本发明所述步骤(2)中,NBS的加入量为4-(二取代基膦)苯胺摩尔量的1.0-3.0倍,优选的为1.2-1.5倍。
本发明所述步骤(2)种,反应温度为室温,反应时间为0.5-3.0h,优选的为0.5-1.0h。
本发明所述步骤(3)中,(4-(5-溴呋喃-2-基)苯基)二取代基膦的加入量为M2摩尔量的1.0-5.0倍,优选的为1.0-1.5倍。
本发明所述步骤(3),在催化剂的存在下进行,所述催化剂包括Mg粉、四甲基乙二胺和FeCl3。其中,Mg粉的加入量为M2摩尔量的1.0-2.0倍,优选的为1.2-1.5倍;四甲基乙二胺的加入量为M2摩尔量的1.0-2.0倍,优选的为1.2-1.5倍;FeCl3的加入量为M2摩尔量的0.01-0.1倍,优选的为0.05-0.08倍。
本发明所述步骤(3)中,反应温度为0-30℃,优选的为0-5℃;反应时间为1.0-10.0h,优选的为2.0-3.0h
本发明所述步骤(3),优选在溶剂的存在下进行,所述溶剂为四氢呋喃和/或二氯甲烷。
本发明所述的配体用于催化不饱和脂肪酸氢甲酰化制备线性二元醇。
一种氢甲酰化催化剂,包括:本发明所述配体和过渡金属化合物。
本发明所述的不饱和脂肪酸为C3-C15的不饱和脂肪酸,优选的为丙烯酸、丁烯酸、4-戊烯酸。
本发明所述的过渡金属化合物包括醋酸铑、辛酸铑、乙酰丙酮铑、乙酰丙酮羰基铑、二羰基乙酰丙酮铑、三苯基膦乙酰丙酮铑、醋酸钴、辛酸钴、乙酰丙酮钴、乙酰丙酮羰基钴、三苯基膦乙酰丙酮钴中的一种或多种,优选的为二羰基乙酰丙酮铑和/或三苯基膦乙酰丙酮钴。
一种不饱和脂肪酸氢甲酰化制备线性二元醇的方法,包括以下步骤:将本发明所述配体和过渡金属化合物、不饱和脂肪酸溶解于溶剂中,然后通入合成气至反应压力,升温至反应温度,反应一定时间得到产品。
本发明所述配体的加入量为过渡金属化合物摩尔量的30-100倍,优选的为50-80倍。
本发明所述的不饱和脂肪酸氢甲酰化制备线性二元醇的方法中,所述溶剂为四氢呋喃、二氯甲烷、苯、甲苯中的一种或多种,优选的为苯、甲苯。
本发明所述的不饱和脂肪酸氢甲酰化制备线性二元醇的方法中,溶剂的加入量为过渡金属化合物摩尔量的100-500倍,优选的为200-400倍。
本发明所述的不饱和脂肪酸氢甲酰化制备线性二元醇的方法中,过渡金属化合物的加入量为不饱和脂肪酸摩尔量的0.01-0.03倍,优选的为0.01-0.02倍。
本发明所述的氢甲酰化反应压力为1.0-10.0MPaG,优选的为1.0-6.0MpaG。
本发明所述的氢甲酰化反应的反应温度为80-200℃,优选的为90-120℃。
本发明所述的氢甲酰化反应的反应时间为1.0-5.0小时,优选的为2.0-3.0小时。
本发明的配体,其原理是利用酰胺基于吡咯烷中的NH与不饱和脂肪酸中的羰基氧形成氢键,呋喃中的O原子与羧基中的羟基氢形成氢键将不饱和脂肪酸束缚住,在反应后期由于高温使羧基中的羟基脱落;同时烯烃与金属-双齿膦配体配位由于苯环较大的空间位阻CO端基插入从而保证了反应选择性生成线性二醛,在低CO:H2比的环境下,线性二元醛加氢形成二元醇。
使用该配体得到线性二元醇,催化活性高、线性选择性好(选择性可以达95-98%),与金属有较强的鳌合能力,反应活性高。本发明制备线性二元醇的方法具有工艺简便、成本与能耗低、生产安全性好、所得产品质量高等多重优点,特别适用于大规模的工业化生产。
具体实施方式
以下结合具体实施例对本发明的技术方案做进一步详细说明。
本发明实施例和对比例中使用的试剂原料来源如下:
吡咯烷-2-甲酰胺、4-(二取代基膦)苯胺购自Sigma-Adrich公司;三氯化铁、四甲基乙二胺、丙烯酸、丁烯酸、4-戊烯酸、购自上海国药试剂有限公司。
其余试剂原料如无特别说明,均为市售产品。
以上试剂均购买后直接使用。
本发明实施例和对比例中使用的测试方法如下:
产物结构由元素分析仪器测定,仪器为德国Elementar公司Vario EL cube分析仪,核磁仪器为布鲁克AVANCE NEO 500M分析仪;色谱分析为Agilent7890B气相色谱仪:安捷伦DB-5色谱柱,进样口温度:220℃;检测器温度:250℃;H2流量:40/min;空气流量:360ml/min。柱箱升温程序为:初始温度20℃,升温速率为20℃/min,保持4min;100-250℃,升温速率15℃/min,保持10min。
以下结合具体实施例,对本发明作进一步说明。应理解,以下实施例仅用于说明本发明而非用于限定本发明的范围。
实施例1
(1)催化剂的制备
M2的制备:将4-(二苯基膦基)苯胺(277.3g,1mol)、吡咯烷-2-甲酰胺(114.2g,1.0mol)、三苯基膦乙酰丙酮羰基铑(2.46g,0.005mol)溶于甲苯中,温度升温至90℃,反应1.0小时,降温至室温后加入NBS(213.6g,1.2mol),室温反应0.5小时,得到M2(430.7g,0.95mol)。
元素分析:C:60.96;H:4.91;N:6.13;P:6.85;O:3.56;Br:17.59。
1H NMR(500MHz,Chloroform-d)δ9.18(s,1H),7.59(ddd,2H),7.39–7.26(m,12H),4.73(dt,1H),4.45(t,1H),3.91(dt,1H),2.16–2.05(m,2H),1.86(ddt,2H).
配体的制备:将M2(430.7g,0.95mol)、(4-(5-溴呋喃-2-基)苯基)二苯基膦(386.9g,0.95mol)、Mg粉(27.4g,1.14mol)、四甲基乙二胺(132.5g,1.14mol)、FeCl3(7.7g,0.047mol)加入到四氢呋喃中,冰浴下反应2.0小时,得到配体(630.7,0.9mol)。
元素分析:C:77.15;H:5.50;N:3.96;P:8.85;O:4.54。
1H NMR(500MHz,Chloroform-d)δ9.26(s,1H),7.76(td,2H),7.59(ddd,2H),7.37–7.26(m,24H),6.91(d,1H),6.41(d,1H),4.35(dt,1H),3.88(dt,1H),3.74(dd,1H),2.09–2.00(m,1H),1.85(dtd,1H),1.69(td,2H).
(2)丙烯酸氢甲酰化制备正丁醛
以丙烯酸:三苯基膦乙酰丙酮钴:配体摩尔比=1:0.01:0.5加入到反应釜中,在CO/H2摩尔比为1:3,压力为1MPa,温度90℃,反应1.0小时,转化率为99.0%;由气相色谱分析得到线性产物1,4-丁二醇,选择性为96.1%,1,3-二羟基丁烷选择性为0.25%。
实施例2
(1)催化剂的制备
M2的制备:将4-(二噻吩基膦基)苯胺(289.4g,1mol)、吡咯烷-2-甲酰胺(171.2g,1.5mol)、三苯基膦乙酰丙酮羰基铑(3.45g,0.007mol)溶于甲苯中,温度升温至90℃,反应1.0小时,降温至室温后加入NBS(267.0g,1.5mol),室温反应1.0小时,得到M2(446.7g,0.96mol)。
元素分析:C:49.08;H:3.95;N:6.05;P:6.68;O:3.48;S:13.79;Br:16.97。
1H NMR(500MHz,Chloroform-d)δ9.18(s,1H),7.63–7.55(m,2H),7.46(dd,2H),7.27–7.20(m,4H),7.09(ddd,2H),4.73(dt,1H),4.45(s,1H),3.91(dt,1H),2.16–2.05(m,2H),1.91–1.81(m,2H).
配体的制备:将M2(446.7g,0.96mol)、(4-(5-溴呋喃-2-基)苯基)二噻吩基膦(603.8g,1.44mol)、Mg粉(34.6g,1.44mol)、四甲基乙二胺(132.5g,1.14mol)、FeCl3(12.5g,0.05mol)加入到四氢呋喃中,冰浴下反应3.0小时,得到配体(666.1g,0.92mol)。
元素分析:C:61.32;H:4.20;N:3.88;P:8.54;O:4.42;S:17.64
1H NMR(500MHz,Chloroform-d)δ9.26(s,1H),7.79–7.72(m,2H),7.63–7.55(m,2H),7.46(dd,4H),7.28–7.20(m,8H),7.09(ddd,4H),6.91(d,1H),6.40(d,1H),4.38–4.32(m,1H),3.88(dt,1H),3.74(dd,1H),2.09–2.00(m,1H),1.85(dtd,1H),1.69(td,2H).
(2)丁烯酸氢甲酰化制备
以丁烯酸:Rh(acac)(CO)2:配体摩尔比=1:0.02:1.5加入到反应釜中,在CO/H2质量比为1:3,压力为5MPa,温度110℃,反应2.0小时,转化率为97.8%;由气相色谱分析得到线性产物1,5-戊二醇,选择性为96.0%,1,4-二羟基戊烷选择性为0.19%。
实施例3
(1)催化剂的制备
M2的制备:将4-(二异戊基膦基)苯胺(265.4g,1.0mol)、吡咯烷-2-甲酰胺(137.0g,1.2mol)、三苯基膦乙酰丙酮羰基铑(2.95g,0.006mol)溶于甲苯中,温度升温至110℃,反应1.5小时,降温至室温后加入NBS(231.3g,1.3mol),室温反应1.0小时,得到M2(423.7g,0.96mol)。
元素分析:C:57.18;H:7.80;N:6.35;P:7.01;O:3.61;Br:18.05。
1H NMR(500MHz,Chloroform-d)δ9.18(s,1H),7.50(tt,2H),7.34–7.28(m,2H),4.73(dt,1H),4.47–4.43(m,1H),3.91(dt,1H),2.29(dtd,4H),2.16–2.05(m,2H),1.91–1.81(m,2H),1.54–1.35(m,6H),0.80–0.70(m,12H).
配体的制备:将M2(423.7g,0.96mol)、(4-(5-溴呋喃-2-基)苯基)二异戊基膦(454.6g,1.15mol)、Mg粉(30.0g,1.25mol)、四甲基乙二胺(145.3g,1.25mol)、FeCl3(13.0g,0.08mol)加入到四氢呋喃中,冰浴下反应2.5小时,得到配体(609.2g,0.90mol)。
元素分析:C:72.77;H:9.25;N:4.18;P:9.12;O:4.68
1H NMR(500MHz,Chloroform-d)δ9.26(s,1H),7.68–7.60(m,2H),7.54–7.46(m,2H),7.41–7.35(m,2H),7.34–7.28(m,2H),6.91(d,1H),6.40(d,1H),4.38–4.32(m,1H),3.88(dt,1H),3.74(dd,1H),2.29(dtd,8H),2.09–2.00(m,1H),1.85(dtd,1H),1.69(td,2H),1.54–1.37(m,12H),0.80–0.70(m,24H).
(2)4-戊烯酸氢甲酰化制备
按4-戊烯酸:Rh(acac)(CO)2:配体摩尔比=1:0.015:0.9加入到反应釜中,在CO/H2质量比为1:3,压力为4.0MPa,温度110℃,反应2.5小时,转化率为98.2%;由气相色谱分析得到线性产物1,6-己二醇,选择性为95.9%,1,5-二羟基已烷选择性为0.39%。
对比例1
丁烯酸氢甲酰化制备
以丁烯酸:Rh(acac)(CO)2:中间体M2摩尔比=1:0.02:1.5加入到反应釜中,在CO/H2质量比为1:3,压力为5MPa,温度110℃,反应2.0小时,转化率为70.5%;由气相色谱分析得到线性产物1,5-戊二醇,选择性为15.4%,1,4-二羟基戊烷选择性为27.19%。
对比例2
丁烯酸氢甲酰化制备
以丁烯酸:Rh(acac)(CO)2:三苯基膦摩尔比=1:0.02:1.5加入到反应釜中,在CO/H2质量比为1:3,压力为5MPa,温度110℃,反应2.0小时,转化率为75.5%;由气相色谱分析得到线性产物1,5-戊二醇,选择性为68.2%,1,4-二羟基戊烷选择性为24.38%。
对比例3
4-戊烯酸氢甲酰化制备
按4-戊烯酸:Rh(acac)(CO)2:4-(二苯基膦)苯胺摩尔比=1:0.015:0.9加入到反应釜中,在CO/H2质量比为1:3,压力为4.0MPa,温度110℃,反应2.5小时,转化率为68.2%;由气相色谱分析得到线性产物1,6-己二醇,选择性为65.9%,1,5-二羟基己烷选择性为23.19%。
对比例4
按4-戊烯酸:Rh(acac)(CO)2:三苯基膦摩尔比=1:0.015:0.9加入到反应釜中,在CO/H2质量比为1:3,压力为4.0MPa,温度110℃,反应2.5小时,转化率为88.2%;由气相色谱分析得到线性产物1,6-己二醇,选择性为80.9%,1,5-二羟基己烷选择性为13.26%。
Claims (10)
3.根据权利要求2所述的配体,其特征在于,所述步骤(1)中,吡咯烷-2-甲酰胺的加入量为4-(二取代基膦)苯胺摩尔量的1.0-3.0倍,优选的为1.0-1.5倍。
4.根据权利要求2或3所述的配体,其特征在于,所述步骤(1)中,催化剂为三苯基膦乙酰丙酮羰基铑和/或乙酰丙酮钴。
5.根据权利要求2-4中任一项所述的配体,所述步骤(3),在催化剂的存在下进行,所述催化剂包括Mg粉、四甲基乙二胺和FeCl3。
6.根据权利要求5所述的配体,其特征在于,Mg粉的加入量为M2摩尔量的1.0-2.0倍,优选的为1.2-1.5倍;四甲基乙二胺的加入量为M2摩尔量的1.0-2.0倍,优选的为1.2-1.5倍;FeCl3的加入量为M2摩尔量的0.01-0.1倍,优选的为0.05-0.08倍。
7.一种氢甲酰化催化剂,包括权利要求1-6任一项所述的配体和过渡金属化合物,所述的过渡金属化合物包括醋酸铑、辛酸铑、乙酰丙酮铑、乙酰丙酮羰基铑、二羰基乙酰丙酮铑、三苯基膦乙酰丙酮铑、醋酸钴、辛酸钴、乙酰丙酮钴、乙酰丙酮羰基钴、三苯基膦乙酰丙酮钴中的一种或多种。
8.根据权利要求7所述的催化剂,其特征在于,所述配体的加入量为过渡金属化合物摩尔量的30-100倍,优选的为50-80倍。
9.一种不饱和脂肪酸氢甲酰化制备线性二元醇的方法,包括以下步骤:将权利要求7或8所述的氢甲酰化催化剂、不饱和脂肪酸溶解于溶剂中,进行氢甲酰化反应。
10.根据权利要求9所述的方法,其特征在于,所述的不饱和脂肪酸为C3-C15的不饱和脂肪酸,优选为丙烯酸、丁烯酸、4-戊烯酸。
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