CN115594716A - 一种用于催化烯烃氢甲酰化反应制备支链醛的配体及其制备方法和用途 - Google Patents
一种用于催化烯烃氢甲酰化反应制备支链醛的配体及其制备方法和用途 Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 42
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 18
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 4
- 238000002360 preparation method Methods 0.000 title claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 3
- 125000004076 pyridyl group Chemical group 0.000 claims abstract description 3
- 125000000168 pyrrolyl group Chemical group 0.000 claims abstract description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 3
- 125000000335 thiazolyl group Chemical group 0.000 claims abstract description 3
- 125000001544 thienyl group Chemical group 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 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 8
- 150000003017 phosphorus Chemical class 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003377 acid catalyst Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 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
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 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
- BDDWSAASCFBVBK-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical compound [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BDDWSAASCFBVBK-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- LKLLNYWECKEQIB-UHFFFAOYSA-N 1,3,5-triazinane Chemical compound C1NCNCN1 LKLLNYWECKEQIB-UHFFFAOYSA-N 0.000 claims 2
- HWVKIRQMNIWOLT-UHFFFAOYSA-L cobalt(2+);octanoate Chemical compound [Co+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HWVKIRQMNIWOLT-UHFFFAOYSA-L 0.000 claims 1
- 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 1
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 150000001299 aldehydes Chemical class 0.000 description 12
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical compound C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003623 transition metal compounds Chemical class 0.000 description 4
- UETDPXQCHSIJJU-UHFFFAOYSA-N (2-acetyloxy-3-methyl-4-oxobutyl) acetate Chemical compound O=CC(C)C(OC(C)=O)COC(C)=O UETDPXQCHSIJJU-UHFFFAOYSA-N 0.000 description 3
- MWWXARALRVYLAE-UHFFFAOYSA-N 2-acetyloxybut-3-enyl acetate Chemical compound CC(=O)OCC(C=C)OC(C)=O MWWXARALRVYLAE-UHFFFAOYSA-N 0.000 description 3
- JRPPVSMCCSLJPL-UHFFFAOYSA-N 7-methyloctanal Chemical compound CC(C)CCCCCC=O JRPPVSMCCSLJPL-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- BOHKXQAJUVXBDQ-UHFFFAOYSA-N 2,3-dimethylpentanal Chemical compound CCC(C)C(C)C=O BOHKXQAJUVXBDQ-UHFFFAOYSA-N 0.000 description 2
- NKBWMBRPILTCRD-UHFFFAOYSA-N 2-Methylheptanoic acid Chemical compound CCCCCC(C)C(O)=O NKBWMBRPILTCRD-UHFFFAOYSA-N 0.000 description 2
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical compound CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 230000009257 reactivity Effects 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
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 239000004439 Isononyl alcohol Substances 0.000 description 1
- WWZMZEIUOKBGFX-UHFFFAOYSA-N N1NNCCC1.N1CNCNC1 Chemical compound N1NNCCC1.N1CNCNC1 WWZMZEIUOKBGFX-UHFFFAOYSA-N 0.000 description 1
- UIKJRDSCEYGECG-UHFFFAOYSA-N Phenylmethyl 2-methylpropanoate Chemical compound CC(C)C(=O)OCC1=CC=CC=C1 UIKJRDSCEYGECG-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- YOTZYFSGUCFUKA-UHFFFAOYSA-N dimethylphosphine Chemical compound CPC YOTZYFSGUCFUKA-UHFFFAOYSA-N 0.000 description 1
- MTWCVKTUVWXLFS-UHFFFAOYSA-N dipropylphosphane Chemical compound CCCPCCC MTWCVKTUVWXLFS-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- FMKOJHQHASLBPH-UHFFFAOYSA-N isopropyl iodide Chemical compound CC(C)I FMKOJHQHASLBPH-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
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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
- 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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Abstract
Description
技术领域
本发明涉及一种N型三膦配体及其制备方法,还涉及其在烯烃氢甲酰化制备支链醛中的应用。
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醇的合成方法,在工业化生产中有着巨大的应用。目前羰基合成过程中主要的攻克方向为得到高产率的线性醛/醇,而支链醛通常作为副产,且产率较低。
支链醛衍生物在香精香料及生命科学行业有着广泛的应用,如异丁酸乙酯有草莓香味、异丁酸苄酯有着水果味香气在香氛中有着广泛的应用;而2-甲基庚酸有着奶酪的味道在食品添加剂中有着广泛的应用。
美国专利US3732287提出了一种以铑为催化剂催化3,4-二乙酰氧基-1-丁烯氢甲酰化制备支链醛1,2-二乙酰氧基-3-甲酰丁烷的方法,但该方法需要至少300atm的压力;中国专利CN104271545B提出了一种以烯烃为原料,碘化物作为催化剂、助剂的支链醛制备方法,但该方法需使用大量氢碘酸或遇热不稳定的2-碘丙烷,导致装置投资高、生产批次平行性差。
因此,急需一种经济、稳定地制造支链醛的技术。
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用于烯烃氢甲酰化反应中的配体,所述配体稳定性好,具有高反应活性。
本发明的另一个目的在于提供所述的配体的制备方法。
本发明的另一目的是提供一种所述配体在烯烃氢甲酰化制备支链醛中的应用,具有高反应活性和支链选择性。
本发明提出的一种N-P型配体,其结构通式I如下:
通式中:R1、R2为C1-C8烷基、芳基或取代芳基、噻吩基、吡咯基、噻唑基、咪唑基、吡啶基中的一种;R2与R1相同或不同,优选的为C1-C3直链烷基。
本发明述配体的制备方法:二取代磷与甲醛在酸催化剂的存在下加成生成中间体II;中间体II再与1,3,5-三嗪烷(六氢三嗪)反应生成配体I,如下式所示:
其中,甲醛的加入量为二取代磷摩尔量2.0-10.0倍,优选的为2.0-3.5倍。生成中间体II的反应在溶剂存在下进行,溶剂为甲醇、乙醇、乙腈、氯仿中的一种或多种,优选的为氯仿、甲醇。溶剂的加入量为甲醛摩尔量的1-4倍,优选的为2-3倍;所述的酸催化剂为盐酸、硫酸、醋酸的一种或多种,优选的为盐酸,加入量为二取代磷摩尔量的0.01-0.1倍,优选的为0.01-0.05倍。反应时间为0.5-5.0h,优选的为1.0-2.0h;反应温度为室温。
本发明所述配体的制备方法:六氢三嗪的加入量为二取代膦摩尔量的0.05-0.3倍,优选的为0.2-0.3倍。生成配体I的反应在溶剂存在下进行,溶剂为甲醇、乙醇、乙腈、氯仿中的一种或多种,优选的为氯仿和/或甲醇。溶剂的加入量为六氢三嗪摩尔量的10-30倍,优选的为10-15倍。反应温度为40-130℃,优选的为60-80℃;反应时间为1.0-10h,优选的为1.5-3.0h。
本发明所述的配体用于催化烯烃氢甲酰化制备支链醛。
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。
本发明所述的烯烃为C2-C10的单烯烃或二烯烃,优选的为丙烯、丁烯、丁二烯、戊烯、戊二烯、庚烯、辛烯。
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。
本发明中,将过渡金属化合物、配体溶解于溶剂中,随后通入烯烃至反应压力,升温至反应温度,反应一定时间得到产品;配体的加入量为金属催化剂摩尔量的20-80倍,优选的为30-50倍。
其中,过渡金属化合物的加入量为烯烃摩尔量的0.02-0.2倍,优选的为0.02-0.06倍;和/或,溶剂为四氢呋喃、二氯甲烷、苯、甲苯、氯仿、正己烷中的一种或多种,优选的为苯、甲苯。溶剂的加入量为催化剂摩尔量的100-500倍,优选的为200-400倍。
所述的氢甲酰化的反应压力为3.0-20.0MPaG,优选的为5.0-13.0MPaG;反应温度为80-200℃,优选的为90-130℃,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,其原理是利用六氢三嗪中的N原子的给电子能力增强了配体P的碱性,增强了金属-烷基中的β-氢消除的能力,使直链醛的产生降低;同时相邻两直链取代的烷基P配体降低了金属中心的空间位阻,使羰基插入更加容易,提高了反应速率。
使用该配体得到支链醇,大大降低了设备投资,催化活性高、支链选择性好(选择性可以达95~98%),与金属有较强的鳌合能力,反应活性高。本发明制备支链醛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:
六氢三嗪、二羰基乙酰丙酮铑、二取代膦、三苯基膦乙酰丙酮钴购自百灵威试剂公司;氯仿、甲醇、甲醛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,核磁分析仪器为美国Bruker AscendTM 500MHz。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
将二甲基膦(620.5g,10mol)溶于2L甲醇中,随后加入甲醛水溶液(其中甲醛20mol,600.6g),混合均匀后,逐滴加入盐酸水溶液(其中HCl 0.1mol,3.75g),反应1.5h,得到中间体,随后加入六氢三嗪(261.4g,3.0mol),升温至60℃,反应2h,得到配体(866.07g,2.8mol)。
元素分析:C:46.62;H:9.78;N:13.60;P:30.00
中间体核磁:1H NMR(500MHz):δ4.92(t,2H),2.40(dd,4H),2.02(d,6H)
配体核磁:1H NMR(500MHz):δ3.94(s,6H),2.40(d,6H),1.15(d,18H)
(2)丙烯氢甲酰化制备异丁醛
以摩尔比:丙烯:三苯基膦乙酰丙酮钴:配体M:甲苯=1:0.04:1.2:8加入到反应釜中,,在CO/H2摩尔比为1:1,压力为8MPa,温度95℃,反应3小时,转化率为99.3%;由气相色谱分析得到支链产物异丁醛,选择性为95.3%。
实施例2
(1)催化剂的制备
将二丙基膦(2363.2g,20mol)溶于5L甲醇中,随后加入甲醛水溶液(其中甲醛70mol,2102.1g),混合均匀后,逐滴加入盐酸水溶液(其中HCl 0.2mol,7.5g),反应1.0h,得到中间体,随后加入六氢三嗪(348.52g,4mol),升温至130℃,反应2h,得到配体1.815kg(3.8mol)。
元素分析:C:60.31;N:8.82;H:11.48;P:19.39。
中间体核磁:1H NMR(500MHz):δ4.92(t,2H),2.40(dd,4H),2.02(d,14H)
1H NMR(500MHz):δ3.94(s,6H),2.40(d,6H),1.15(d,42H)
(2)辛烯氢甲酰化制备异壬醇
以摩尔比:辛烯:Rh(acac)(CO)2:目标配体M:甲苯=1:0.06:3:24加入到反应釜中,在CO/H2质量比为2:1,压力为5MPa,温度110℃,反应2.0小时,转化率为97.9%;由气相色谱分析得到支链产物异壬醛,选择性为98.1%。
实施例3
(1)催化剂的制备
将二噻吩基膦(3964.8g,20mol)溶于7L甲醇中,随后加入甲醛水溶液(其中甲醛70mol,2102.1g),混合均匀后,逐滴加入盐酸水溶液(其中HCl 0.2mol,7.5g),反应2.0h,得到中间体,随后加入六氢三嗪(522.78g,6mol),升温至90℃,反应2.5h,得到配体3.99kg(5.7mol)。
元素分析:C:50.21;N:5.87;H:4.25;P:12.88;S:26.79。
1H NMR(500MHz):δ7.36(dd,6H),7.24(dt,6H),7.04(ddd,6H),3.97(s,6H),3.78(d,6H)
(2)辛烯氢甲酰化制备异壬醛
按摩尔比:辛烯:Rh(acac)(CO)2:目标配体M:甲苯=1:0.04:1.6:12加入到反应釜中,在CO/H2质量比为2:1,压力为6MPa,温度110℃,反应2.5小时,转化率为98.1%;由气相色谱分析得到支链产物异壬醛,选择性为96.1%。
实施例4
(1)催化剂的制备
将二吡咯基膦(3.28kg,20mol)溶于6L甲醇中,随后加入甲醛水溶液(其中甲醛60mol,1800g),混合均匀后,逐滴加入盐酸水溶液(其中HCl 0.2mol,7.5g),反应1.5h,得到中间体,随后加入六氢三嗪(435.65g,5mol),升温至60℃,反应2h,得到配体2.83kg(4.6mol)。
元素分析:C:58.51;N:20.44;H:5.87;P:15.18;。
1H NMR(500MHz):δ9.52(d,6H),6.99(ddd,6H),6.53(dt,6H),6.38(m,6H),3.98(s,6H),3.90(d,6H)。
(2)丁二烯氢甲酰化制备2,3-二甲基戊醛
按质量比正丁烯:Rh(acac)(CO)2:目标配体M:甲苯=1:0.05:2:15加入到反应釜中,在CO/H2质量比为2:1,压力为9MPa,反应温度100℃,反应2.0小时,转化率为97.3%;由气相色谱分析得到支链产物2,3-二甲基戊醛,选择性为97.3%。
实施例5
配体采用实施例1所制备配体。600份3,4-二乙酰氧基-1-丁烯与12份(C8H12RhCl)2、600份实施例1所制备配体加入到高压釜中,在摩尔比为CO/H2=1:1,压力为100个大气压力下反应2.0小时,反应温度100℃,最终得到1,2-二乙酰氧基-3-甲酰丁烷(收率97.6%)。
对比例1
600份3,4-二乙酰氧基-1-丁烯与12份(C8H12RhCl)2加入到高压釜中,在摩尔比CO/H2=1:1,压力为300个大气压力下反应14小时,反应温度100℃,最终得到1,2-二乙酰氧基-3-甲酰丁烷(收率70%)。
Claims (10)
3.根据权利要求2所述的制备方法,其特征在于,甲醛的加入量为二取代磷摩尔量的2.0-10.0倍,优选的为2.0-3.5倍;和/或,生成中间体II的反应在溶剂存在下进行,溶剂为甲醇、乙醇、乙腈、氯仿中的一种或多种,优选的为氯仿、甲醇。
4.根据权利要求3所述的制备方法,其特征在于,所述的酸催化剂为盐酸、硫酸、醋酸的一种或多种,优选的为盐酸,加入量为二取代磷摩尔量的0.01-0.1倍,优选的为0.01-0.05倍;和/或,反应时间为0.5-5.0h,优选的为1.0-2.0h;和/或,反应温度为室温。
5.根据权利要求2-4中任一项所述的制备方法,其特征在于,1,3,5-三嗪烷的加入量为二取代磷摩尔量的0.05-0.3倍,优选的为0.2-0.3倍;和/或,生成配体I的反应在溶剂存在下进行,溶剂为甲醇、乙醇、乙腈、氯仿中的一种或多种,优选的为氯仿、甲醇;和/或,反应温度为40-130℃,优选的为60-80℃;和/或,反应时间为1.0-10h,优选的为1.5-3.0h。
6.根据权利要求1所述的配体或权利要求2-5中任一项制备方法制得的配体在催化烯烃氢甲酰化反应制备支链醛的用途,所述的烯烃为C2-C10的单烯烃或二烯烃,优选的为丙烯、丁烯、丁二烯、戊烯、辛烯、戊二烯、庚烯。
7.根据权利要求6所述的用途,其特征在于,所述催化氢甲酰化反应的催化剂为醋酸铑、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。
8.根据权利要求7所述的用途,其特征在于,将催化剂、配体溶解于溶剂中,随后通入烯烃至反应压力,升温至反应温度,反应一定时间得到产品;配体的加入量为催化剂摩尔量的20-80倍,优选的为30-50倍。
9.根据权利要求8所述的用途,其特征在于,催化剂的加入量为烯烃摩尔量的0.02-0.2倍,优选的为0.02-0.06倍;和/或,溶剂为四氢呋喃、二氯甲烷、苯、甲苯、氯仿、正己烷中的一种或多种,优选的为苯、甲苯。
10.根据权利要求8或9所述的用途,其特征在于,所述的反应压力为3.0-20.0MPaG,优选的为5.0-13.0MPaG;反应温度为80-200℃,优选的为90-130℃,反应时间为1.0-5.0小时,优选的为2.0-3.0小时。
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