CN1132734A - 醛的制备方法 - Google Patents
醛的制备方法 Download PDFInfo
- Publication number
- CN1132734A CN1132734A CN95120115A CN95120115A CN1132734A CN 1132734 A CN1132734 A CN 1132734A CN 95120115 A CN95120115 A CN 95120115A CN 95120115 A CN95120115 A CN 95120115A CN 1132734 A CN1132734 A CN 1132734A
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- CN
- China
- Prior art keywords
- ion
- sulfonation
- formula
- multinomial method
- catalyzer
- Prior art date
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- 150000001299 aldehydes Chemical class 0.000 title description 16
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000003446 ligand Substances 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
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- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 20
- 239000010941 cobalt Substances 0.000 claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 11
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 31
- 239000010948 rhodium Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 229910052703 rhodium Inorganic materials 0.000 claims description 29
- -1 polyene hydrocarbon Chemical class 0.000 claims description 28
- 238000006277 sulfonation reaction Methods 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 16
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 16
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
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- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 claims description 2
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- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
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- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
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- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 claims description 2
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- 125000005023 xylyl group Chemical group 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 2
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical group C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 claims 1
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- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
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- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 19
- 239000002904 solvent Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 150000002460 imidazoles Chemical class 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
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- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
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- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
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- 238000005406 washing Methods 0.000 description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical class CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明涉及烯烃和烯属不饱和化合物在含有作为配合物配位体的杂环碳烯以及必需时还含有其它配位体的钴或铑配合物存在下的醛化反应。
Description
本发明涉及通过在含有作为配位体的杂环碳烯的钴或铑配位化合物存在下进行烯烃醛化制备醛的方法。烯烃与CO和H2的反应可以在均相或非均相中进行。
众所周知,CO和H2与烯烃之间的反应(醛化)可被用于制备含碳子数比原料烯烃多1的醛和醇。该反应采用氢化金属羰基试剂作为催化剂,其中金属以选用元素周期表中8,9,10族为佳(对应于IU PAC1985年推荐)。除了最初被用作催化剂金属和已被广泛地用于工业的钴以外,铑近来发挥着越来越重要的作用。与钴相对照,铑可以使反应在低压下进行。此外,α-烯烃优选形成正构醛并且仅产生少量异构醛。最后,烯烃经过加氢处理形成饱和烃,而这一过程在铑催化剂存在下进行的速度明显地低于采用钴催化剂时的情形。在工业生产中,铑催化剂的使用形式为含有附加配位体尤其是三元有机膦或亚磷酸盐的改进型氢化铑羰基试剂。钴催化剂同样以附加地含有作为配位体的膦或亚磷酸盐的羰基试剂这一形式被使用,不过这种醛化方法在工业上的重要性低于铑作为催化剂的方法。
用于控制催化剂金属活性的配位体(因此同时被称为控制配位体)的用量通常超过形成配位化合物所需数量,从而在质量作用定律的意义上讲起到了稳定配位化合物的作用。因此,该催化剂体系含有配位化合物和游离配位体,配位体的存在不仅对于特定的催化活性是重要的、同时对于配位化合物的稳定性也是不可或缺的。
醛化反应可以在均相或非均相体系中进行。在均相催化反应中,催化剂被均匀地溶于反应产物和可以同时存在的溶剂中。在使用钴催化剂或铑催化剂时均可以利用上述步骤。然而,在反应产物分离、以及借助铑催化剂进行反应的情况下催化剂回收方面遇到困难。可以采用蒸馏方法以常规方式将溶液中的催化剂与产物彼此分离。不过,由于所形成的醛与醇的热敏性,这一方式只能应用于低级烯烃,即C8以下烯烃的醛化过程。
采用水溶性铑配合物作为催化剂可以避免上述缺陷存在于铑催化的反应过程中。举例来说,这类方法被描述于DE-C2627354。铑配合物的溶解性通过采用磺化三芳基膦作为配合物组分来实现。在该方法实施方案中,待反应完全后催化剂与反应产物的分离过程简单地通过水相与有机相分离,也就是说无需蒸馏进而无需附加的热过程便可以完成。该过程的另一特征在于正构醛可以由a-烯烃以特别高的选择性形成,而异构醛的生成量却非常少。水溶性铑配合物的配合组分以磺化三芳基膦和附加羧基化三芳基膦为佳。
无论有机膦可溶于有机介质还是可溶于水,由于其种类多样、其催化活性与选择性,可被作为控制配位体用于工业生产。然而,其自身存在的一系列不足之处妨碍了其广泛应用。这些不足之处包括,具体地讲,尤其在金属和金属离子存在下发生的氧化敏感性。因此,当采用基于含膦配合物的催化剂时,不得不采用措施排除诸如氧气或空气之类的氧化剂以便降低通常以高成本方能制得的配位体的损耗。另一种所有有机膦共同具有的特性并且因此特性而限制其应用的是磷一碳键不可逆断裂,举例来说,于醛化反应期间依据膦的种类在温度高于一定数值时这种断裂达到较高的程度,这种断裂会减活催化剂并且大量消耗膦,从而提高生产成本。最后,诸如被类似地用作配位体的有机磷之类传统的烷基膦与芳基膦对于催化活性金属中心来说,无法完成全部可能的电子控制。具体地讲,缺乏一种能够抵抗氧化剂并且与金属形成稳定键的强亲核富电子配位体。
因此,本发明的目的是开发一种被用作醛化反应催化剂的新型金属配合物,它不具有上述不足之处,此外,能够容易地廉价地合成。再者,控制配位体的组成能够以简便方式改变从而可以制备应付各种不同催化剂问题的催化剂。
这一目的可通过下述方法实现,通过单烯烃、多烯烃、环烯烃或这些化合物的衍生物与CO和H2在20-180℃与0.1-30兆帕斯卡、在作为催化剂的钴或铑配合物存在下进行反应制备醛。在该方法中,配合物如下式所示:〔LaMbXc〕n(A)n,式中M为作为中心原子的钴或铑,X为与中心原子相连的单齿或多齿、带电或不带电配位体,L为与中心原子相连下式所示类似的配位体-单碳烯或二碳烯 式中R1、R2、R3、R4、R5和R6相同或不同,为C1-7直链或支链、磺化或非磺化烷基,C5-18磺化或非磺化脂族单环或多环基团,C2-5磺化或非磺化烯基,C6-14磺化或非磺化芳基,C7-19磺化或非磺化芳烷基,R1和/或R2还可以是-(CH2)mPR2,其中m=1,2,3或4,R=苄基、苯基、取代苯基、萘基,-(CH2)mNR’2,其中m如上所定义,R’=烷基、乙烯基、烯丙基、苄基与芳基,以及-(CH2)mOR”,其中m如上所定义,R”=烷基,尤其是甲基、乙烯基、烯丙基、苄基或苯基;R3,R4、R5和R6还可以是氢,R3与R4和R5与R6可以分别相同或不同,为稠合与磺化或非磺化C3-7基团,R1、R2、R4和R6与配位体X可以形成环,Y为饱和或不饱和、直链或支链C1-4亚烷基或二烷基亚甲硅基或四烷基二亚甲硅基,A为单一带电的阴离子或多重带电阴离子的化学等同物,b为整数1-3,a为整数1-4,b和c=0或整数1-4,b和n=0或整数1-6。
配合物中的单齿或多齿配位体除了碳烯与式I中X所定义的以外,还可以是氢或氢离子、卤素或卤离子、拟卤化物、羧酸盐离子、磺酸盐离子、C1-7烷基、酰胺基、烷氧化物基、乙酰丙酮化物基团、一氧化碳、一氧化氮、腈、异腈、单烯或二烯、炔与π-芳基。若配合物分子中存在多种这些配位体,它们可以相同或不同。
在与由咪唑、吡唑或其衍生物衍生的式(II)、(III)、(IV)和(V)对应的单碳烯或二碳烯中,R1至R6尤其是甲基、异丙基、叔丁基、苄基、三苯甲基、苯基、甲苯基、二甲苯基、2,4,6-三甲苯基、金刚烷基,R1和R2优选为甲基、叔丁基、苯基、苄基和邻甲苯基,R3和R4优选为氢和甲基。
R3和R4以及R5和R6可以与咪唑环中两个相邻碳原子或吡唑环中C-N部分形成环状体系。R3和R4或R5与R6优选为能够导致稠合芳族6元环形成的基团(CH)4、(CH2)4和(CH2)5。
式(IV)和(V)所示二碳烯中Y定义的桥基优选为亚甲基、二甲基基亚甲基、二苯基亚甲基、1,3-亚苯基和亚乙基。含硅桥基中,以二甲基亚甲硅基和四甲基二亚甲硅基为佳。
a优选为1或2,b以1为佳;n尤其为0-3。
A优选为卤化物、拟卤化物、四苯基硼酸盐、四氢硼酸盐、六氟磷酸盐和羧酸盐尤其是醋酸盐阴离子,此外,还有金属配合物阴离子如四羰基高钴酸盐、六氟高铁(III)酸盐、四氯高铁酸盐、四氯铝酸盐或四氯钯酸盐(II)阴离子。
被用作催化剂的钴与铑配合物可通过不同途径获得。其中一种制备方法是采用形成配合物中心原子的每一元素的盐或金属配合物(如乙酰丙酮化物、金属羰基化物)这类简单化合物为原料。根据另一变通方式,可以通过配位体交换或者通过消除和/或取代反应由配合物获得新化合物,举例来说,采用这些金属化合物的常见溶剂配合物为原料。要求保护的化合物同样可以通过将碳烯简单地加成到相应的金属组分上而形成,其中这一分子加成还可能伴随着桥结构的破裂。
依据其稳定性,碳烯的使用形式可以是游离状态如溶液或者,更经常地,它是由可于反应条件下被转化为碳烯的化合物制备,并处于反应混合物中。最重要的方法是咪唑或吡唑鎓盐的去质子化反应,必要时添加碱如金属氢化物、羰基metallate、金属羧酸盐、金属醇盐或金属酰胺化物。
原料即简单盐或配合物与碳烯必要时还包括配位体之间的反应通过将反应物与溶剂在室温或升温下混合来进行。反应速度很快,通常经过几分钟便基本上完成。不过,为了完成反应,建议反应时间长达数小时,当反应原料仅仅部分地溶于反应介质即它们于悬浮液中进行反应时尤为如此。
为了制备含有磺化配位体的水溶性配合物,所用原料包括至少一种其分子全部或部分被磺化的反应物。
为了使反应介质与新型配合物分离,业已发现适合在高真空条件下脱除溶剂。粗产物通过洗涤与在适宜溶剂或溶剂混合物中重结晶被纯化,所用溶剂及其混合物在各自情况下借助初始实验确定。
本发明中被用作醛化反应催化剂的钴和铑配合物可溶于无机溶剂,作为盐同样可溶于水,当它们含有被磺酸基取代的脂族或芳族基时尤为如此。它们的热稳定性很强并且通常即使在350℃以上仍然稳定。此外,值得注意的是它们几乎不发生氧化反应,这与膦和亚磷酸盐形成对照。最后,这些配合物不易分解。因此,通常不必以超出形成配合物所需化学计量的用量使用配位体控制催化剂活性和稳定性。即使发现使用过量配位体是适宜的,其数量仍然明显低于使用膦或亚膦酸盐的情况。
所用的钴或铑的催化活性配合物依据其溶解性可被均匀地溶于有机反应介质,该介质通常含有原料烯烃、反应产物、反应副产物与可能存在的溶剂。它们还可作为单独相被用于非均相反应体系中的水溶液。特别适宜的水溶性催化剂为含有被磺酸基取代的非均相碳烯配位体的配合物。
通常在实际反应之前合成钴或铑配合物,不过也可以在醛化反应混合物中即时制备。在这两种情况下,催化剂如上所述由金属钴或铑的盐或配合物制得。在合成气的作用下,原来被采用的钴或铑配合物被转化为活性醛化催化剂。
有机或含水催化剂溶液中金属(以配合物形式存在)的溶度以所用烯属不饱和化合物为基准计为10-6-1%(摩尔),以10-4-0.1%(摩尔)为佳。在此范围内,所需钴浓度比所需铑浓度高10倍。
烯属不饱和化合物与CO和H2的反应在约0.1-300兆帕以1-15兆帕为佳的压力下进行,钴催化剂所需压力高于铑催化剂。合成气的组成即CO与H2的体积比可以在宽范围内变化,例如1∶10-1 0∶1。一般情况下,使用CO/H2体积比约为1∶1或者稍微高于或低于该值的气体混合物。
反应温度在约20-180℃,以80-150℃为佳。钴催化剂所需温度高于铑基催化剂。
液相或气相中反应物的反应在常规反应器中进行。均相体系中气液相之间和非均相体系中两个液相与一个气相之间紧密接触对反应进程产生决定性影响。因此,有必要尽可能地促进相表面接触。所以,合成气以及,必要的话,还包括烯烃最好通过分布装置被导入液相。醛化反应借助非均相催化剂相进行,建议剧烈搅拌反应混合物。必要时,还可以在水相中添加增溶剂以便改善催化剂中烯属化合物的溶解性。反应可以分批进行或者,优选地,连续地进行。
本发明可被成功地应用于单烯烃、多烯烃、环烯烃及其衍生物的反应。至于分子大小,对所用烯烃未加限制,对于C2-40化合物可以成功地应用该方法。烯属不饱和化合物可以呈直链或支链,双键可以处于终端或内部。可被用于新方法的烯烃实例为乙烯、丙烯、1-丁烯、2-丁烯、1-戊烯、2-甲基-1-丁烯、1-己烯、2-己烯、1-庚烯、1-辛烯、3-辛烯、3-乙基-1-己烯、1-癸烯、3-十一碳烯、4,4-二甲基-1-壬烯、二聚环戊二烯、乙烯基环己烯、环辛二烯、苯乙烯、2-乙烯基萘。依据要求保护的方法可被醛化的具体烯烃衍生物有如醇、醛、羧酸、酯、腈与卤素化合物、烯丙醇、丙烯醛、甲基丙烯醛、巴豆醛、丙烯酸甲酯、巴豆酸乙酯、富马酸二乙酯、马来酸二乙酯、丙烯腈。对于C2-20烯烃及其衍生物的醛化过程,该方法特别成功。
若用作催化剂的配合物中碳烯配位体之一具备手性,即它不具备Schonflies体系中第二类对称要素的话,在原料具备前手性并且采用以光学纯形式存在的金属配合物催化剂的条件下会在醛化产物中发生不对称诱导过程。这样便可以制备手性产物。
下面首先描述新型催化剂的制备方法,实施例仅供描述本发明,并不对其构成限制。
实施例1
氯代(η4-1,5-环辛二烯)(1,3-二甲基咪唑啉-2-亚基)合铑(I)(催化剂1)的制备方法。
a)1,3-二甲基咪唑-2-亚基(1,3-Dimethylimidazolin-2-ylidene)
将8.69克(38.8毫摩尔)碘化(1,3-二甲基咪唑鎓)盐与1.03克(42.7毫摩尔)氢化钠和0.2克(1.8毫摩尔)叔丁醇钾溶于50毫升四氢呋喃(THF)并且在室温下在配备有石蜡油止逆阀的Schlenk管中搅拌4小时。由于形成的游离碳烯而使溶液变黄。高真空脱除溶剂并且在一微型蒸馏装置中真空蒸馏残余物。得到黄色油状1,3-二甲基咪唑啉-2-亚基后,立即将其溶于60毫升THF并且在-30℃贮存。
b)氯代(η4-1,3-环辛二烯)(1,3-二甲基咪唑啉-2-亚基)合铑(I)
将247毫克(0.5毫摩尔)二(μ-氯)二(η4-1,5-环辛二烯)合二铑于室温下溶于20毫升无水THF并且与192毫克(1毫摩尔)1,3-二甲基咪唑啉-2-亚基混合。通过其颜色由浅黄变为深黄表明反应立即发生。室温下将该混合物进一步搅拌15分钟,高真空蒸除溶剂并且通过用10毫升乙醚洗涤来纯化残余物。将产物溶于10毫升二氯甲烷并且用30毫升戊烷仔细地使该产物结晶。通过倾析脱除所形成的黄色晶体中的溶剂混合物并且在高真空中干燥。该化合物极易溶于氯仿与二氯甲烷,易溶于THF和甲苯,少量溶于乙醚与戊烷,呈黄色。即使在雾状甲苯和氧气氛中加热数小时后,也未发生分解。产率:310毫克(91%)。
5.0-20.0毫克(0.015-0.058毫摩尔)该化合物被用作催化剂(见表)。
实施例2:〔(η4-1,5-环辛二烯)-二(1,3-二甲基咪唑啉-2-亚基)合铑(1)〕氯化物(催化剂2)的制备方法
将247毫克(0.5毫摩尔)=(μ-氯)二(η4-1,5-环辛二烯)合二铑于室温下溶于20毫升无水THF并且与279毫克(3毫摩尔)1,3-二甲基咪唑啉-2-亚基混合。其颜色由浅黄变为深黄表明反应立即发生。室温下继续搅拌该混合物3小时,高真空脱除溶剂并且通过用30毫升乙醚洗涤纯化残余物。将产物溶于10毫升二氯甲烷并且用10毫升戊烷仔细地使该产物结晶。所得黄色晶体通过倾析脱除溶混合物并且高真空干燥。该化合物易溶于氯仿和二氯甲烷,适度溶于THF、水和甲苯,不溶于乙醚和戊烷。产率为410毫克(93%)。
5.0-20.0毫克(0.011-0.046毫摩尔)该化合物被用作催化剂(见表)。
实施例3:即时制备催化剂3
a)1-甲基-3-(乙磺酸钠盐)咪唑鎓溴化物
在不采用溶剂的条件下在70℃将205毫克(2.5毫摩尔)甲基咪唑与210毫克(1毫摩尔)2-溴乙磺酸钠盐搅拌3天。冷却后,用30毫升乙醚洗涤3次残余物以便脱除过量甲基咪唑。经高真空干燥(70℃)10小时后,得到的白色固体非常易溶于水、几乎不溶于有机溶剂(如THF、甲苯、戊烷)。产率:280毫克(96%)。
b.催化剂3
将100毫克醋酸铑(III)(0.357毫摩尔)溶于25毫升除气水并且与314毫克(1.07毫摩尔)溴化(1-甲基-3-(乙基-2-磺酸钠盐)咪唑鎓)盐的25毫升脱气水溶液混合。1.0-5.0毫升(0.00714-0.0357毫摩尔)该溶液(相对于每10毫升水铑含量为0.0714毫摩尔)被用作催化剂(见表),在醛化条件下形成活性醛化催化剂。
实施例4:即时制备催化剂4
a)1-(乙基-2-磺酸钠盐)-3-(乙基-2-磺酸盐)咪唑甜菜碱
将557毫克(8.2毫摩尔)溶于20毫升二甲基乙酰胺的咪唑与1.5毫升(10.25毫摩尔)三乙胺和3.45克(16.3毫摩尔)2-溴乙磺酸钠盐混合。待加热至120℃,原悬浮液变清。进一步加热至160℃之后,开始形成白色沉淀。为了完成反应,将混合物加热回流4小时。待将溶液冷却至室温后,滤除白色沉淀,用20毫升乙醇洗涤二次并且每次用醚洗涤。
b)催化剂4
将100毫克醋酸铑(III)(0.357毫摩尔)溶于25毫升脱气水并且与328毫克(1.07毫摩尔)1-(乙基-2-磺酸钠盐)-3-(乙基-2-磺酸盐)咪唑鎓甜菜碱的25毫升气水溶液混合。1.0-5.0毫升(0.00714-0.0357毫摩尔)该溶液(相对于每10毫升水铑含量为0.0714毫摩尔)被用作催化剂(见表),在醛化反应条件下形成活性醛化催化剂。
实施例5:即时制备催化剂5
a)1-甲基-3-(丁基-4-磺酸盐)咪唑鎓甜菜碱
在不使用溶剂的条件下于室温将甲基咪唑(8.21毫克,10毫摩尔)与1,4-丁基磺内酯(1.36克,10毫摩尔)搅拌3天。待固化后,用甲苯洗涤3次,并进行高真空干燥。白色固体易溶于水,比较不易溶于有机溶剂。产率:2.100克(96%)。
b)催化剂5
将100毫克醋酸铑(III)(0.357毫摩尔)溶于25毫升脱气水并且与234毫克(1.07毫摩尔)1-甲基-3-(丁基-4-磺酸盐)咪唑鎓甜菜碱的35毫升去脱气水溶液混合。1.0-5.0毫升(0.02975-0.00595毫摩尔)该溶液(相对于每10毫升水铑含量为0.0595毫摩尔)被用作催化剂(见表),在醛化反应条件下形成活性醛化催化剂。
实施例6:即时制备催化剂6
称量10.0毫克己酸铑(III)(0.0223毫摩尔)和14.6毫克(0.0669毫摩尔)1,3-二甲基咪唑鎓溴化物并将其装入高压釜的玻璃插入物,与25毫升甲苯混合。该悬浮液被直接用作催化剂(见表),在醛化反应条件下形成活性醛化催化剂。
实施例7:烯烃的醛化
1000-100000当量烯烃在搅拌下(约1500分钟-1)于250毫升搅拌高压釜中(Roth实验室高压釜H10781,配有玻璃插入物)在5-20毫克实施例1和2制备的并且溶于甲苯的催化剂或者1.0-5.0毫升实施例3-5制备的催化剂水溶液存在下与合成气反应。合成气中H2和CO体积比为1∶1,总压力10兆帕,丙烯分压(使用丙烯作为烯烃时)为1.2兆帕。反应过程中一旦压力降至约3.0-4.0兆帕,便须再注入合成气。
待冷却至室温后,借助气相色谱/质谱分析产物和/或通过蒸馏纯化产物并且估评其特征。
表注
*借助气相色谱/质谱,仅有3,4-二甲基戊醛被视作产物。
**通过气相色谱/质谱分析,正庚醛(33.8%)和2-甲基己醛(66.2%)可被视为产物。
表烯烃醛化
No. | 催化剂 | 烯烃 | 催化剂/烯烃 | 溶剂 | 正构/异构比值 | 转化率(%) | 观察结果 |
1 | 1 | 丙烯 | 1∶100,000 | 甲苯 | 1.0∶1.0 | >99(60小时) | |
2 | 1 | 1-己烯 | 1∶100,000 | 甲苯 | 1.0∶1.0 | 85(60小时) | |
3 | 1 | 苯乙烯 | 1∶2000 | 甲苯 | 1.16∶1.0 | 100(2小时) | |
1 | 四甲基乙烯 | 1∶1000 | 甲苯 | . | 82(20小时) | 原料异构化 | |
5 | 1 | 2-己烯 | 1∶2500 | 甲苯 | .. | 95(20小时) | 原料异构化 |
6 | 2 | 1-已烯 | 1∶2500 | 甲苯 | 2.0∶1.0 | 85(20小时) | 催化剂不易溶于甲苯 |
7 | 2 | 丙烯 | 1∶10000 | 水 | 1.2∶1 | 85(20小时) | 催化完成后,催化剂可溶于丁醛相 |
8 | 3 | 丙烯 | 1∶10,000 | 水 | 2.1∶1 | 85(20小时) | 催化完成后,催化剂可溶于丁醛相红色 |
9 | 4 | 丙烯 | 1 ∶10,000 | 水 | 1.9∶1 | 92(20小时) | 催化完成后,催化剂可溶于丁醛相,红色 |
10 | 5 | 丙烯 | 1∶10,000 | 水 | 1.4∶1 | 65(20小时) | 催化完成后,催化剂同样溶于水相,红色 |
11 | 6 | 丙烯 | 1∶10,000 | 甲苯 | 1.4∶1 | 70(20小时) |
Claims (16)
1.通过单烯烃、多烯烃、环烯烃或这些化合物的衍生物与CO和H2在20-180℃与0.1-30兆帕斯卡、在作为催化剂的钴或铑配合物存在下进行反应制备醛的方法,其中,配合物如下式所示:〔LaMbXc〕n(A)n,式中M为作为中心原子的钴或铑,X为与中心原子相连的单齿或多齿、带电或不带电配位体,L为与中心原子M相连下式所示类似的配位体-单碳烯或二碳烯 式中R1、R2、R3、R4、R5和R6相同或不同,为C1-7直链或支链、磺化或非磺化烷基,C5-18磺化或非磺化脂族单环或多环基团,C2-5磺化或非磺化烯基,C6-14磺化或非磺化芳基,C7-19磺化或非磺化芳烷基,R1和/或R2还可以是-(CH2)mPR2,其中m=1,2,3或4,R=苄基、苯基、取代苯基、萘基,-(CH2)mNR’2,其中m如上所定义,R’=烷基、乙烯基、烯丙基、苄基与芳基,以及-(CH2)mOR”,其中m如上所定义,R”=烷基尤其是甲基、乙烯基、烯丙基、苄基或苯基;R3,R4、R5和R6还可以是氢,R3与R4和R5与R6可以分别相同或不同,为稠合与磺化或非磺化C3-7基团,R1、R2、R4或R6与配位体X可以形成环,Y为饱和或不饱和、直链或支链C1-4亚烷基或二烷基亚甲硅基或四烷基二亚甲硅基,A为单一带电的阴离子或多重带电阴离子的化学等同物,b为整数1-3,a为整数1-4,b和c=0或整数1-4,b和n=0或整数1-6。
2.按照权利要求1的方法,其中式(I)中的X为氢、氢离子、卤素、卤离子、拟卤化物、羧酸盐离子、磺酸盐离子、C1-7烷基、酰胺基、烷氧化物基、乙酰丙酮化物基团、一氧化碳、一氧化氮、腈、异腈、单烯或二烯、炔与π-芳基。
3.按照权利要求1或2的方法,其中在式(II)、(III)、(IV)和(V)中,R1至R6是甲基、异丙基、叔丁基、苄基、三苯甲基、苯基、甲苯基、二甲苯基、2,4,6-三甲苯基。
4.按照权利要求1至3中一项或多项的方法,其中在式(II)、(III)、(IV)和(V)中,R3和R4为氢和甲基。
5.按照权利要求1至3中一项或多项的方法,其中在式(II)、(III)、(IV)和(V)中,R3与R4以及R5与R6形成基团(CH)4、(CH2)4和(CH)2)5。
6.按照权利要求1至5中一项或多项的方法,其中在式(IV)和(V)中,Y为亚甲基、二甲基亚甲基、二苯基亚甲基、1,3-亚苯基和亚乙基。
7.按照权利要求1至5中一项或多项的方法,其中在式(IV)和(V)中,Y为二甲基亚甲硅基与四甲基二亚甲硅基。
8.按照权利要求1至7中一项或多项的方法,其中式(I)中a=1或2。
9.按照权利要求1至8中一项或多项的方法,其中式(I)中b=1。
10.按照权利要求1至9中一项或多项的方法,其中式(I)中n=0-3。
11.按照权利要求1至10中一项或多项的方法,其中式(I)中A为卤化物或拟卤化物离子、四苯基硼酸盐离子,四氟硼酸盐离子,六氟磷酸盐离子和乙酸盐离子,四羰基高钴酸盐离子,六氟高铁(III)酸盐离子、四氯高铁酸盐离子、四氯铝酸盐离子和四氯钯酸盐(II)离子。
12.按照权利要求1至11中一项或多项的方法,其中烯烃与CO和H2的反应在均匀地溶于反应介质的催化剂存在下进行。
13.按照权利要求1至11中一项或多项的方法,其中烯烃与CO和H2的反应在催化剂水溶液存在下进行。
14.按照权利要求1至13中一项或多项的方法,其中在水相或有机相中的金属浓度以所用烯属不饱和化合物为基准计为10-6-1%(摩尔)。
15.按照权利要求14的方法,其中在水相或有机相中金属的浓度为10-4-10-1%(摩尔)。
16.按照权利要求1至15中一项或多项的方法,其中反应在80-150℃下进行。
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CN115650835A (zh) * | 2022-09-30 | 2023-01-31 | 万华化学集团股份有限公司 | 一种由巴豆醛和烯丙醇合成正庚醛的方法 |
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DE19654908A1 (de) * | 1996-06-24 | 1998-01-29 | Hoechst Ag | Verfahren zur Herstellung von Aldehyden in Gegenwart eines neuen Katalysators |
AU5530998A (en) * | 1996-12-18 | 1998-07-15 | E.I. Du Pont De Nemours And Company | Relatively stable (1,3-disubstitutedimidazol-2-ylidene)-type carbenes |
DE19730783A1 (de) * | 1997-07-18 | 1999-01-21 | Studiengesellschaft Kohle Mbh | Hydroformylierung mit unmodifizierten Rhodiumkatalysatoren in überkritischem Kohlendioxid |
US6316380B1 (en) * | 1998-09-10 | 2001-11-13 | University Of New Orleans Research & Technology Foundation | Catalyst system comprising transition metal and imidazoline-2-ylidene or imidazolidine-2-ylidene |
DE10040972C2 (de) * | 2000-08-22 | 2003-11-20 | Wolf Peter Fehlhammer | Metallkomplexe mit Bis(imidazolin-2-yliden-1-yl) borat-Liganden und deren Verwendung in der homogenen Katalyse |
DE10231368A1 (de) * | 2002-07-11 | 2004-02-05 | Studiengesellschaft Kohle Mbh | Verfahren zur Herstellung von Imidazoliumsalzen |
CN112457178B (zh) * | 2020-11-26 | 2022-08-12 | 上海簇睿低碳能源技术有限公司 | 一种合成戊醛的方法 |
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US4248802A (en) | 1975-06-20 | 1981-02-03 | Rhone-Poulenc Industries | Catalytic hydroformylation of olefins |
JPS5283311A (en) * | 1975-12-27 | 1977-07-12 | Mitsui Petrochem Ind Ltd | Preparation of aldehydes |
JPH06262086A (ja) * | 1993-03-09 | 1994-09-20 | Daicel Chem Ind Ltd | アルデヒド合成用触媒及びアルデヒドの製造法 |
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- 1994-12-29 DE DE4447067A patent/DE4447067A1/de not_active Withdrawn
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- 1995-12-21 CA CA002165891A patent/CA2165891C/en not_active Expired - Fee Related
- 1995-12-21 ZA ZA9510938A patent/ZA9510938B/xx unknown
- 1995-12-21 BR BR9505989A patent/BR9505989A/pt not_active Application Discontinuation
- 1995-12-22 KR KR1019950054213A patent/KR960022426A/ko not_active Application Discontinuation
- 1995-12-22 FI FI956233A patent/FI956233A/fi not_active Application Discontinuation
- 1995-12-22 PL PL95312033A patent/PL312033A1/xx unknown
- 1995-12-27 DE DE59505586T patent/DE59505586D1/de not_active Expired - Fee Related
- 1995-12-27 ES ES95120578T patent/ES2132508T3/es not_active Expired - Lifetime
- 1995-12-27 AT AT95120578T patent/ATE178580T1/de not_active IP Right Cessation
- 1995-12-27 EP EP95120578A patent/EP0719753B1/de not_active Expired - Lifetime
- 1995-12-27 CN CN95120115A patent/CN1132734A/zh active Pending
- 1995-12-28 AU AU40705/95A patent/AU694819B2/en not_active Ceased
- 1995-12-28 JP JP7343035A patent/JP2834700B2/ja not_active Expired - Fee Related
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1909964B (zh) * | 2004-09-15 | 2011-12-28 | Lg化学株式会社 | 含磷催化剂组合物以及使用该组合物的醛化反应的方法 |
CN115650835A (zh) * | 2022-09-30 | 2023-01-31 | 万华化学集团股份有限公司 | 一种由巴豆醛和烯丙醇合成正庚醛的方法 |
CN115650835B (zh) * | 2022-09-30 | 2024-05-03 | 万华化学集团股份有限公司 | 一种由巴豆醛和烯丙醇合成正庚醛的方法 |
Also Published As
Publication number | Publication date |
---|---|
DE4447067A1 (de) | 1996-07-04 |
FI956233A (fi) | 1996-06-30 |
ZA9510938B (en) | 1996-07-16 |
EP0719753B1 (de) | 1999-04-07 |
ATE178580T1 (de) | 1999-04-15 |
CA2165891C (en) | 1999-10-26 |
FI956233A0 (fi) | 1995-12-22 |
ES2132508T3 (es) | 1999-08-16 |
EP0719753A1 (de) | 1996-07-03 |
AU694819B2 (en) | 1998-07-30 |
CA2165891A1 (en) | 1996-06-30 |
MY131691A (en) | 2007-08-30 |
AU4070595A (en) | 1996-07-04 |
PL312033A1 (en) | 1996-07-08 |
BR9505989A (pt) | 1997-12-23 |
JP2834700B2 (ja) | 1998-12-09 |
DE59505586D1 (de) | 1999-05-12 |
TW300884B (zh) | 1997-03-21 |
KR960022426A (ko) | 1996-07-18 |
US5663451A (en) | 1997-09-02 |
JPH08231459A (ja) | 1996-09-10 |
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