CN1131138A - 醛的制备方法 - Google Patents
醛的制备方法 Download PDFInfo
- Publication number
- CN1131138A CN1131138A CN95120188.3A CN95120188A CN1131138A CN 1131138 A CN1131138 A CN 1131138A CN 95120188 A CN95120188 A CN 95120188A CN 1131138 A CN1131138 A CN 1131138A
- Authority
- CN
- China
- Prior art keywords
- group
- compound
- acid ester
- phosphorous acid
- rhodium
- 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.)
- Pending
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- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims 3
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- -1 aldehyde compound Chemical class 0.000 claims abstract description 63
- 239000003446 ligand Substances 0.000 claims abstract description 42
- 239000010948 rhodium Substances 0.000 claims abstract description 30
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 24
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 13
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000000962 organic group Chemical group 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 125000004437 phosphorous atom Chemical group 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 125000001118 alkylidene group Chemical group 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- YIYBQIKDCADOSF-UHFFFAOYSA-N alpha-Butylen-alpha-carbonsaeure Natural products CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000003158 alcohol group Chemical group 0.000 claims description 4
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 3
- ISBHMJZRKAFTGE-UHFFFAOYSA-N pent-2-enenitrile Chemical compound CCC=CC#N ISBHMJZRKAFTGE-UHFFFAOYSA-N 0.000 claims description 2
- 230000026030 halogenation Effects 0.000 claims 2
- 238000005658 halogenation reaction Methods 0.000 claims 2
- 238000007037 hydroformylation reaction Methods 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 description 15
- 150000003254 radicals Chemical group 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
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- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000004702 methyl esters Chemical class 0.000 description 5
- 150000003284 rhodium compounds Chemical class 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- 239000000758 substrate Substances 0.000 description 4
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
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- 239000000460 chlorine Substances 0.000 description 3
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- IQZLUWLMQNGTIW-UHFFFAOYSA-N acetoveratrone Chemical compound COC1=CC=C(C(C)=O)C=C1OC IQZLUWLMQNGTIW-UHFFFAOYSA-N 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 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 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- ZFJMTDFOGDGPTF-UHFFFAOYSA-N phosphanium;chloride;hydrochloride Chemical compound P.Cl.Cl ZFJMTDFOGDGPTF-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
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- 239000011541 reaction mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- HITROERJXNWVOI-SOFGYWHQSA-N (5e)-octa-1,5-diene Chemical compound CC\C=C\CCC=C HITROERJXNWVOI-SOFGYWHQSA-N 0.000 description 1
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Abstract
借烯属不饱和有机化合物的加氢甲酰化作用制备一种醛的方法,其中使用的催化剂系统包括铑和一种亚磷酸酯二齿配位体,该亚磷酸酯二齿配位体是式(1)的化合物:
其中R1和R3分别是一种有机基团,可相同或不同,其中R2是四价有机基团。
Description
本发明涉及借助烯属不饱和有机化合物的加氢甲酰化作用来制备一种醛化合物的方法,其中使用的催化剂系统包括铑和一种亚磷酸酯二齿配位体。
加氢甲酰化是指在加氢甲酰化催化剂存在下烯属不饱和有机化合物与氢和一氧化碳反应。
例如EP-A-518241描述了其中催化剂系统包括铑和一种亚磷酸酯二齿配位体的制备醛类的加氢甲酰化方法。该专利申请中记载了通式为A-[-O-P(OR)(OR)]2的亚磷酸酯二齿配位体(A是二价有机基团,R是有机基团),其中例举叙述了1-辛烯的加氢甲酰化。
上述加氢甲酰化方法的缺点是大部分不饱和有机化合物被氢化成相应的饱和有机化合物,一种不需要的产物。
本发明的目的是提供一种加氢甲酰化方法,它与EP-A-518241所述方法相比具有较高的醛类选择性和较低的氢化程度。
达到本发明目的的亚磷酸酯二齿配位体是式(1)的化合物:其中R1和R3是相同或不同的有机基团,R2是四价有机基团。
当按本发明方法制备醛化合物时,发现比EP-A-518241所述方法对醛的选择性要高,不饱和起始化合物的氢化程度要低。
能用作本发明亚磷酸酯二齿配位体的一些化合物记载于US-A-5103035中,尤其是R2为四甲基甲烷基团,R1和R3为烷基取代的苯基的那些化合物。这些亚磷酸酯化合物在US-A-5103035中用作聚合物组合物的稳定剂,但US-A-5103035的说明书没有提出这些稳定剂化合物能有效地用作加氢甲酰化催化剂的一部分。
R1和R3可含有杂原子,如N,S,Si或Sn。R1和R3优选为相同或不同的烷基,环烷基,芳基,芳烷基或烷芳基基团,其中该基团含1-30个碳原子,可被有机或无机基团取代。R1和R3可能的基团的例子有:叔丁基、异丙基、环戊基、环己基、苯基、萘基、苄基、苯乙基、基、甲苯基和二甲苯基基团。优选的R1和R3是芳基,烷芳基或芳烷基基团,如苯基、苄基或萘基,更优选的R1和R3是芳基基团。
R1和R3可被取代,可能的取代基例子有:含1-12个碳原子的烷基、芳基、烷氧基基团,含1-12个碳原子的三甲基甲硅烷基基团和卤代基团,如氟、氯或溴基团。当R1和/或R3是取代的芳基或芳烷基基团时,R1和/或R3优选是邻位取代的。R1和/或R3优选被选自叔丁基、叔丙基、叔戊基或三甲基甲硅烷基的取代基邻位取代。
R4通常是含至少4个碳原子的四价有机基团,四价有机基团一般含少于35个碳原子。
优选R2是四价有机基团,该基团应柔韧到足以使配位体的两个磷原子与一个铑原子配位形成螯合物。所谓螯合物是指(基本上)亚磷酸酯二齿配位体的两个磷原子与一个铑原子/离子形成一配位键。所谓非螯合型配合物是指基本上只有亚磷酸酯二齿配位体两个磷原子之一个与一个铑原子或离子形成一配位键。桥连基团R2的选择将决定亚磷酸酯二齿配位体与铑是否形成螯合物。具有足够柔性的基团R2的配位体可与铑形成螯合物。式(2),(3)和(4)的配位体以及US-A-5103035所述的化合物不具有足以形成螯合物的柔性桥连基团。
业已发现,当具有这种柔性桥连基团R2的二齿配位体是催化剂系统的一部分时,加氢甲酰化反应的选择性进一步提高,特别是从末端不饱和有机化合物如α-链烯烃开始反应时更是如此。
两个磷原子之间的桥连基团R2优选应足够柔韧以使两个磷原子都与一个铑原子离子配位。人员可利用几种技术专业来确定配位体是否与金属配位成为螯合物。惯用技术是对铑配合物晶体作X-射线结晶学分析,或核磁共振(NMR)技术,如31P,13C和103Rh NMR。后一技术描述在R.H.Cabtree、John Wiley & Sons于1994年纽约所著的“过渡金属的有机金属化学”第10章中。
柔性桥连基团R2优选是含至少8个碳原子的四价有机基团,如芳基和烷基基团。四价有机基团的四个基位于这些位置,即该处亚磷酸酯二齿配位体的四个氧原子连接到桥连基团上。杂原子,如N,S和O可存在于有机基团R2上。柔性桥连基团R2的例子可以是烷四基基团,邻-亚芳基-(Q)n-邻-亚芳基基团,亚烷基-(Q)n-亚烷基基团或邻-亚芳基-(Q)n-亚烷基基团,其中n=0,1,2,3或4以及Q是亚芳基基团,-(CR4R5)-基团,其中R4和R5各代表氢或含1-12个碳原子的烷基基团,或者Q是-0-(其中n=1)。邻-亚芳基基团优选为邻-亚苯基基团。上述四价有机基团部分的亚烷基基团的例子可以是1,3-异丙烷二基(1,3-isopropanediyl)和1,4-异丁烷二基(1,4-isobutanediyl)。上述四价有机基团部分的邻-亚芳基基团的例子有邻-亚苯基和邻亚萘基,其中(Q)n基团可连接到式(5)-(7)中苯环上任何标有数字的位置:
四价烷四基基团(alkatetrayl group)R2一般具有8-15个碳原子,如可由下式(8)代表:其中R6代表至少含2个碳原子的亚烷基,优选的R6含2-7个碳原子,基团R6的例子可以是亚乙基、三亚甲基、二亚乙基-醚、四亚甲基、1,5-亚戊基和l,6-亚己基。
上述邻-亚芳基和亚烷基可被含1-12个碳原子的烷基基团、苯基、甲苯基、茴香基、或卤素基团,如氟、氯和溴取代。
具柔性桥连基团R2的亚磷酸酯二齿配位体的例子可以是由式(9)-(12)代表,其中MeO是甲氧基基团,“-C-C-C”基团表示饱和二价烷基基团。 式(1)的二齿配位亚磷酸酯化合物例如可按前述US-A-5103035中相同的方法制备。
式(1)的二齿配位亚磷酸酯化合物由下述原料制备:(a)有4个羟基基团的化合物(R2(OH)4),(b)亚磷化合物和(c)有1个羟基基团的化合物(或化合物的混合物)(R1OH和R3OH)。优选的磷化合物为卤化磷,如PCl3。二齿配位体优选这样制备:磷化合物原料与含4个羟基官能团的分子反应首先制备出烷基或芳基氯化亚磷。烷基或芳基氯化亚磷进一步与含一个醇官能团的化合物反应以获得所需配位体,如果需要,二齿配位亚磷酸酯化合物可经结晶或柱色谱进行纯化。
催化剂系统按公知的配合物形成方法,在适宜的溶剂中将适宜的铑化合物与亚磷酸酯二齿配位体混合而制备。适宜的铑化合物有铑的氢化物、卤化物、有机酸盐、无机酸盐、氧化物、羰基化合物和胺化合物。
适宜铑化合物的实例例如有:RhCl3,Rh(NO3)3,Rh(OAc)3,Rh2O3,Rh(acac)(CO)2,[Rh(OAc)(COD)]2,Rh4(CO)12,Rh6(CO)16,RhH(CO)(ph3P)3,[Rh(OAc)(CO)2]2和[RhCl(COD)]2(其中“acac”是乙酰丙酮化物基团;“Ac”是乙酰基团;“COD”是1,5-环辛二烯;及“ph”是苯基)。但值得注意的是铑化合物不限于上列化合物。
亚磷酸酯二齿配位体与催化剂系统中铑的摩尔比没有特别的限制,但最好加以选择使得在催化剂活性和选择性方面获得最佳效果。该比例一般是约1-100,优选是1-25(mol亚磷酸酯/mol金属)。
用于加氢甲酰化中的铑量没有特别的限制,但最好加以选择使得在催化剂活性和经济方面获得最佳效果。铑量一般是10ppm-1000ppm。
反应介质的选择并不关键,该反应介质可以是加氢甲酰化本身的反应混合物,如不饱和起始化合物、醛产物和/或副产物。如果使用溶剂,它可以为芳香溶剂、例如苯、甲苯、二甲苯、十二烷基苯;酮类,例如丙酮、二乙酮和甲乙酮;醚类,例如四氢呋喃和二口恶烷或酯类,例如乙酸乙酯和邻苯二甲酯二正辛酯。亦可使用混合溶剂。
只要用于制备醛化合物的烯属不饱和有机化合物分子中至少含一个烯键(C=C),该化合物就无需特别限制。烯属不饱和有机化合物通常有2-20个碳原子,它的例子可以是线性(末)端烯烃,如乙烯、丙烯、1-丁烯、1、3-丁二烯、1-戊烯、1-己烯、1-辛烯、1-壬稀、1癸烯、1-十四碳烯、1-十六碳烯、1-十八碳烯、1-二十碳烯和1-十二碳烯;支链(末)端烯烃,如异丁烯和2-甲基-1-丁烯;线性内烯烃,如顺式和反式-2-丁烯,顺式和反式-2-己烯,顺式和反式-3-己烯,顺式和反式-2-辛烯,及顺式和反式-3-辛烯;支链内烯烃,如2,3-二甲基-2-丁烯,2-甲基-2-丁烯和2-甲基-2-戊烯;端烯烃-内烯烃混合物,如丁烯二聚制备的辛烯,包括丙烯、正丁烯、异丁烯等低级链烯烃的链烯低聚异构体混合物(二聚物至四聚物);以及环脂族烯烃,如环戊烯、环己烯、1-甲基环己烯、环辛烯和苎烯。
含不饱和烃基的烃基所取代的烯属化合物例子包括含芳族取代基的烯属化合物,例如苯乙烯、α-甲基苯乙烯和烯丙基苯;以及二烯化合物,例如1,5-己二烯,1,7-辛二烯和降冰片二烯。
烯属不饱和有机化合物可被1个或多个含杂原子如氧、硫、氮和磷的官能团取代。这些取代的烯属不饱和有机化合物例子有乙烯基·甲基醚、油酸甲酯、烯丙醇、油醇、3-甲基-3-丁烯-1-醇、3-戊烯酸甲酯、4-戊烯酸甲酯、3-戊烯酸、4-戊烯酸、3-羟基-1,7-辛二烯、1-羟基-2,7-辛二烯、1-甲氧基-2,7-辛二烯、7-辛烯-1-醛、己-1-烯-4-醇、丙烯腈、丙烯酸酯,如丙烯酸甲酯、甲基丙烯酸酯如甲基丙烯酸甲酯、乙烯基乙酸酯和1-乙酸基-2,7-辛二烯。
优选的作用物是戊烯腈、戊烯酸和戊烯酸C1-C6烷基酯化合物,如3-戊烯腈、3戊烯酸、3-戊烯酸甲酯、3-戊烯酸乙酯和4-戊烯酸甲酯。由于这些化合物生成的醛化合物能有效地用来制备尼龙-6和尼龙-6.6,故这些化合物是优选的。
根据本发明进行加氢甲酰化的反应条件取决于具体的烯属不饱和有机化合物原料,其温度通常是室温至200℃,优选50-150°C,压力通常是(标准)大气压至20MPa,优选0.2-10MPa,更优选0.5-5MPa,该压力常为氢和一氧化碳分压之和。亦可有惰性气体存在。氢与一氧化碳的摩尔比一般是10∶1-1∶10,优选2∶1-1∶2。
加氢甲酰化反应系统的例子包括连续型、半连续型或间歇型操作,例如采用搅拌型罐式反应器或泡罩塔罐反应器。
本发明还涉及一种新的催化剂系统,它包括式(1)的亚磷酸酯二齿配位体和周期表的第八族金属。该催化剂系统能用作各种反应的均相催化剂。例如该催化剂系统能用作氢氰化、聚合、加氢甲酰化、异构化和羰基化的催化剂。已发现上述亚磷酸酯二齿配位体能有效地与第八族金属联合应用作为加氢甲酰化催化剂。当催化剂系统是用于加氢甲酰化时,优选的第八族金属是铑。合适的第八族金属例子有钻、钌、铑、钯、铂、锇和铱,第八族金属化合物的例子包括钌化合物如Ru3(CO)12、Ru(NO3)3、RuCl3(Ph3P)3和Ru(acac)3;钯化合物如PdCl2、Pd(OAc)2、Pd(acac)2、PdCl2(COD)和PdCl2(Ph3P)2;锇化合物如Os3(CO)12和OsCl3;铱化合物如Ir4(CO)12和IrSO4;铂化合物如K2PtCl4、PtCl2(PhCN)2和Na2PtCl6·6H2O;钻化合物如CoCl2、Co(NO3)2、Co(OAC)2和Co2(CO)8;以及上述铑化合物。
优选的催化剂系统包括式(1)的亚磷酸酯二齿配位体与铑的螯合型配合物。
本发明还涉及新的式(1)亚磷酸酯化合物类,其中桥连基团R2柔韧至足以使该配位体的两个磷原子都与铑原子配位(如上所述)。
这些新的亚磷酸酯化合物可根据前述方法制备。
本发明将参照实施例进一步作详细描述,但应知道本发明决不受这些具体实施例的限制。
实施例1
式9的亚磷酸酯通过首先制备含4个醇官能团的芳族分子来制备。该分子是这样制得的:根据Vogel“A text-book ofpracticalorganic chemistry”,Longmans,1966,P718所述方法先将3,4-二甲氧基苯乙酮与3,4-二甲氧基苯甲醛反应,对于亚苄基乙酰苯,采用3,4-二甲氧基苯乙酮代替苯甲醛。所得的3,4-二甲氧基亚苄基-3,4-二甲氧基苯乙酮按J.Agric.Chem.Soc.Jpn.27(1953)491所述方法在乙酸乙酯/乙醇(3∶1)中用Pd/硅胶进行氢化,之后羰基官能团经克莱门逊裂解(ClemmensenCleavage)而被还原,用HI裂解掉甲氧基官能团后得到所需的醇,将2-叔丁基-4-甲氧基苯膦二氯化物与上述制备的醇在甲苯/二氯甲烷中反应得到亚磷酸酯。用柱色谱进行提纯(Al2O3,CH2C12)。
实施例2
式10的亚磷酸酯是这样制备的:根据G.R.Newkome等在J.Am.Chem.Soc.112(1990)8458所述的方法将1,6-二溴己烷与丙二酸二甲酯反应,首先制得含4个醇官能团的脂族分子。生成的分子中的酯基用LiAlH4还原得到醇。按US-A-5103035中实施例1的叙述来制备亚磷酸酯,其中用2-叔丁基-4-甲氧苯酚代替2,4-二叔丁基苯酚,并使用上述制备的醇,用柱色谱进行提纯(Al2O3,CH2Cl2)。
实施例3
式11的亚磷酸酯采用实施例1所述方法制备,用2,4,6三叔丁基苯膦二氯化物代替2-叔丁基-4-甲氧基苯膦二氯化物。
实施例4
式12的亚磷酸酯采用实施例2所述方法由1,3-二溴丙烷和丙二酸二甲酯起始制备。
实施例5
于内容积为150ml的哈斯特洛伊耐蚀镍基合金-碳-不锈钢(Hastelloy-C-steel)压热器中在氮气氛下装入5.8mg(2.25*10-5mol)Rh(acac)(CO)2,7.88*10-5mol式9的亚磷酸酯和60ml甲苯,将压热器关闭并用氮气吹洗。1.5小时内压热器加热至90℃,用H2/CO混合物(1∶1(mol∶mol))使其压力升至1.0MPa,随后注入5.1g(45mmol)3-戊烯酸甲酯和1g壬烷(气相色谱内标)及甲苯的共15ml混合物,1.5小时后该反应混合物用气相色谱分析,结果列于表1。
实施例6
用式10的亚磷酸酯配位体重复实施例5,铑用量与实施例5相同,二齿配位亚磷酸酯/Rh比例、反应时间和结果参见表1。
实施例7
用式11的亚磷酸酯配位体重复实施例5,结果参见表1。
实施例8a和8b
用式12的亚磷酸酯配位体重复实施例5,结果参见表1。
实施例9
用式3的亚磷酸酯配位体重复实施例5,结果列于表1。
实施例10
用式4的亚磷酸酯配位体重复实施例5,结果列于表1。
比较例A
比较例B
表1
(1) L/Rh配位体/Rh比例,mol/mol(2) 选择性=形成的醛mol/转化的作用物mol
实施例 | 亚磷酸酯配位体(L) | L/Rh(1) | 时间(小时) | 转化率(mol%) | 醛的选择性(mol%)(2) | 氢化率(mol%) |
5678a8b910AB | 910111212341314 | 3.51.07.82552255 | 1.52.524242520.541616 | 27.444.510.768.798.368.256.492.488.8 | 82.794.583.990.487.097.599.080.383.6 | 17.35.516.19.613.012.519.716.4 |
×100%
表1结果表明当使用本发明方法时,与使用本领域现有方法,如实验A和B例举的方法相比较,前者具有较低的氢化比率和对醛的较高选择性。
实施例11
用相同量的铑和铑/二齿配位亚磷酸酯比例为2重复实施例5。反式2-辛烯代替3-戊烯甲酯用作作用物,结果列于表2。
比较例C
用式14的亚磷酸酯重复实施例11,结果参见表2。
表2
实施例 | 配位体(L) | 时间(小时) | 转化率(mol%) | 醛的选择性(mol%) | 氢化率(mol%) |
11C | 1014 | 2094 | 30.749.3 | 99.298.9 | 0.81.1 |
实施例12
重复实施例5,其中使用式10的亚磷酸酯,L/Rh=2,1-辛烯为作用物,结果列于表3。
实施例13
用式3的亚磷酸酯重复实施例12,结果列于表3。
比较例D
用式14的亚磷酸酯重复实施例12,结果列于表3。
表3
实施例 | 配位体(L) | 时间(小时) | 转化率(mol%) | 醛的选择性(mol%) | 氢化率(mo1%) |
1213D | 10314 | 333 | 93.080.657.9 | 99.798.997.7 | 0.31.12.3 |
表3说明例如当按实施例12使用螯合物时,与使用非螯合型配合物(实施例13)相比,前者获得了对醛的较高转化率和选择性,以及较低的氢化比率。
Claims (11)
1.一种通过烯属不饱和有机化合物的加氢甲酰化作用来制备醛化合物的方法,该方法使用催化剂系统,其中所说的催化剂系统包括铑和一种亚磷酸酯二齿配位体,其特征在于该亚磷酸酯二齿配位体是式(1)的化合物,其中R1和R2是相同或不相同的有机基团,R2是四价有机基团。
2.如权利要求1所述的制备醛的方法,其特征在于R2是柔韧至足以使该亚磷酸酯配位体上的两个磷原子都与一个铑原子配位的基团。
3.如权利要求2所述的方法,其特征在于R2是含至少8个碳原子的四价有机基团。
4.如权利要求3所述的方法,其特征在于R2是烷四基基团,邻-亚芳基-(Q)n-邻-亚芳基基团,亚烷基-(Q)n-亚烷基基团或邻-亚芳基-(Q)n-亚烷基基团,其中n=0,1,2,3或4和Q是二价芳基基团或烷基基团。
5.如权利要求4所述的方法,其特征在于R2是邻-亚苯基-(Q)n-邻-亚苯基基团和Q是-(CR4R5)-基团,其中R4和R5各代表氢或含1-12个碳原子的烷基。
7.如权利要求1-6任一所述的方法,其特征在于烯属不饱和有机化合物是戊烯腈、戊烯酸或戊烯酸C1-C6烷基酯。
8.催化剂系统,包括一种如权利要求1-6任一所述的亚磷酸酯二齿配位体和一种第八族金属。
9.如权利要求8所述的催化剂系统,其特征在于第八族金属是铑。
10.如式(1)所述的亚磷酸酯化合物,其中桥连基团R2的柔性足以使该化合物的两个磷原子都与一个铑原子配位。
11.制备如权利要求10所述的一种亚磷酸酯化合物的方法,其中相应于R2有4个醇官能团的化合物与一种卤化亚磷化合物反应,所得有机卤化亚磷化合物再与相应于R1OH或R2OH的一元醇化合物反应。
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CN1116267C (zh) * | 1997-03-24 | 2003-07-30 | 可乐丽股份有限公司 | 支链醛的生产方法 |
CN100431701C (zh) * | 2004-06-12 | 2008-11-12 | Lg化学株式会社 | 含磷催化剂组合物及使用该含磷催化剂组合物的醛化方法 |
CN100496736C (zh) * | 2007-05-31 | 2009-06-10 | 南京大学 | 一种用于双环戊二烯氢甲酰化制醛的水溶性配体铑配合物催化剂 |
CN115894190A (zh) * | 2023-01-17 | 2023-04-04 | 山东京博石油化工有限公司 | 一种烯烃氢甲酰化合成醛、醇、烷烃的方法 |
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US5663403A (en) * | 1995-01-24 | 1997-09-02 | Mitsubishi Chemical Corporation | Bisphosphite compound and method for producing aldehydes |
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US4612402A (en) * | 1982-03-29 | 1986-09-16 | Allied Corporation | Oxidation of olefins using rhodium nitro complex |
US5103035A (en) * | 1990-04-05 | 1992-04-07 | Ethyl Corporation | Process for preparing bis(alkylphenyl)pentaerythritol diphosphites |
US5210243A (en) * | 1990-12-10 | 1993-05-11 | Ethyl Corporation | Hydrogenation of aromatic-substituted olefins using organometallic catalyst |
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CN1116267C (zh) * | 1997-03-24 | 2003-07-30 | 可乐丽股份有限公司 | 支链醛的生产方法 |
CN100431701C (zh) * | 2004-06-12 | 2008-11-12 | Lg化学株式会社 | 含磷催化剂组合物及使用该含磷催化剂组合物的醛化方法 |
CN100496736C (zh) * | 2007-05-31 | 2009-06-10 | 南京大学 | 一种用于双环戊二烯氢甲酰化制醛的水溶性配体铑配合物催化剂 |
CN115894190A (zh) * | 2023-01-17 | 2023-04-04 | 山东京博石油化工有限公司 | 一种烯烃氢甲酰化合成醛、醇、烷烃的方法 |
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