CN1042102C - 羰基化催化剂体系 - Google Patents
羰基化催化剂体系 Download PDFInfo
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- CN1042102C CN1042102C CN92100820A CN92100820A CN1042102C CN 1042102 C CN1042102 C CN 1042102C CN 92100820 A CN92100820 A CN 92100820A CN 92100820 A CN92100820 A CN 92100820A CN 1042102 C CN1042102 C CN 1042102C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000005810 carbonylation reaction Methods 0.000 title claims description 32
- 230000006315 carbonylation Effects 0.000 title claims description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 125000005843 halogen group Chemical group 0.000 claims abstract description 9
- 125000002252 acyl group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 55
- -1 acidic group Chemical group 0.000 claims description 43
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- 125000004429 atom Chemical group 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
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Abstract
本发明涉及一种羰基化催化剂体系,它包括a)第VIII族金属源,b)具有下列通式(I)的多膦。式中每个R可独立地任意选自烷基,环烷基,芳基或杂环芳基;每个A,X和Z可独立地选自氮原子,CH基,具有通式C-PR2的基团,其中R的意义同前,以及具有通式CR′的基团,其中R′代表羟基,氨基,酰氨基,氰基,酰基,酸基,卤原子,一个任意取代的烃基,一个任意取代的杂环芳基或一个任意取代的烃氧基,也可能由两个相邻的CR′基团形成一个环。
Description
本发明涉及一种含有多膦的新的催化剂体系,涉及一些新的多膦以及这一催化剂体系用于烯属或炔属不饱和化合物的羰基化反应。
烯或炔属不饱和化合物的羰基化反应已知有许多的方法。J.Falbe有“New Syntheses With Carbon Monoxide”一书中(1980,Springer-Verlag,Berlin Heidelberg New York出版)对这些工艺进行了综述。一般,这类方法包括在羰基化催化剂体系存在的条件下,使烯属或炔属不饱和化合物与一氧化碳进行反应,在一些情况下还含有氢或有可移去氢原子的亲核化合物。在许多实例中,羰基化催化剂体系包含第Ⅷ族金属源,以及一种配位体如膦类。
近年来已公开的一类催化剂体系包括第Ⅷ族金属和一种吡啶基膦。
Kurti Kurtev专人在Journal of the Chemical Society,Dalton Transactions,1980第55至58页公开了一种包含铑或钌化合物及一种吡啶基膦的催化剂体系,以及这些催化剂体系在1-己烯的羰基化反应中的应用。
欧洲专利申请EP-A1-0259914公开了一种含有钯化合物,吡啶基膦,一种酸和一种醌的催化剂体系,以及它们在烯烃的羰基化以提供聚合物过程中的应用。
欧洲专利申请EP-A1-0271144公开了把一种含有钯化合物,吡啶基膦和一种酸的催化剂体系用于炔属化合物与含羟基化合物进行的羰基化反应中。
欧洲专利申请EP-A1-0282142公开了将一种含有钯化合物,一种吡啶基膦和一种酸的催化剂体系应用于烯属化合物与含羟基化合物进行的羰基化反应中。
欧洲专利申请EP-A1-0386833公开了一种含有钯化合物和一种(取代的2-吡啶基)膦的催化剂体系,作为合适的取代基,提到了羟基,氨基,酰氨基,氰基,酰基,酸基,烃基和烃氧基,还有卤原子。
上述这些参考文献中没有一个叙述应用含有多膦基-取代的N-杂环芳基化合物的催化剂体系进行的实验。
Newkome等在J.Org.Chem.,43,947(1978)公开了2,6-双(二苯膦基)吡啶的制备方法。
现在已经发现,用含有某些多膦基-取代的N-杂环芳基化合物的催化剂体系,特别当膦配位体对作为催化剂的金属组份的比例很低时,羰基化反应能以极高的速率进行。此外,当一种α-不饱和烃,特别是丙炔,用这种催化剂体系进行羰基化反应时,可以非常高的选择性得到β-羰基化的产物。
按此,本发明提供一种催化剂体系,它包含:
a)第Ⅷ族金属源,
b)一种具有下列通式(Ⅰ)的多膦:式中R可独立地选自任意取代的烷基,环烷基,芳基或杂环芳基;每个A,X和Z独立地选自氮原子,CH基,具有通式为C-PR2的基团,其中R的定义同前,具有通式为CR′的基团,其中的R′代表羟基,氨基,酰氨基,氰基,酰基,酸基,卤原子,任意取代的烃基,任意取代的杂环芳基或任意取代的烃氧基,也可能由两个相邻的CR′基形成一个环;或者式(Ⅰ)化合物与酸加成所形成的盐。
已经发现,含有第Ⅷ族金属和具有通式(Ⅰ)的多膦或它们的盐的催化剂体系,能使丙炔的羰基化反应在45℃的反应温度时,以高达100,000摩尔丙炔每克原子钯每小时的转化速率进行。此外,用具有相对低的多膦对钯比例的催化剂,能够得到优良的转化速率,此外,已发现用现在的催化剂体系能由α-不饱和烃类如丙炔,以很高的选择性(99.9%以上)得到β-羰基化的产物。
不想被理论所束缚,相信是由于N-芳香六元环的空间限制,妨碍了具有通式(Ⅰ)的多膦与单个第Ⅷ族金属原子配位形成P,P-二齿配位体。因此,本催化剂体系,含有比别的单齿膦配位体更低的膦配位体对钯的比例,却很有效,是令人惊讶的。进一步相信,第二个膦基在α-不饱和化合物的羰基化过程中产生空间效应,从而有利于形成β-羰基化产物。
具有通式(Ⅰ)的多膦可被看作是由至少有一个与各带膦取代基的两个碳原子邻接的氮环原子的N-芳香六元环衍生而来的。具有通式(Ⅰ)的多膦中组成适当的环核的N-芳香化合物的实例包括吡啶,嘧啶,吡嗪,异喹啉,1,3,5-三嗪,1,2,4-三嗪和喹唑啉。
一个优选的实例是吡啶,即在式(Ⅰ)中,每个X,Z和A独立地选自CH基和具有通式CR′的基团。另外的优选实例包括嘧啶和1,3,5-三嗪,特别是在2-,4-和6-位取代有三个膦基时,即在式(Ⅰ)中,X和Z中至少有一个是氮,并且A是C-PR2基团。
当在本说明书中说到一个任意取代的基团时,一般这基团可以被一个或多个,比如一个,两个或三个,选自卤原子,烷基,芳基,卤代烷基,烷氧基和卤代烷氧基这类取代基所取代。
在说到氨基时,它优先意味着NH2基,烷基氨基或二烷基氨基。
一个酰基可以是,例如,一个烷基酰基,例如乙酰基。
一个酰氨基可以是,例如一个酰氨基例如乙酰氨基。
两个相邻的CR′基形成的环最好是一个任意取代的烃基环,例如一个任意取代的苯环。含有两个相邻的CR′基形成一个环的N-芳香化合物的实例有异喹啉和喹唑啉。
在说到任意取代的烃基或烃氧基时,烃基部份最好代表一个烷基,一个环烷基或一个苯基。
一个烷基较好有最多20个碳原子,更好是最多12个碳原子,特别是1至4个碳原子。例如一个烷基可以是一个甲基,乙基,正丙基,异丙基,正丁基,异丁基或叔丁基。
一个环烷基最好有3至6个碳原子。
一个卤原子优先意味着一个氟,氯或溴原子。
一个芳基最好是一个苯基或萘基。
一个杂环芳基可由上述任何一种N-芳香化合物衍生而来,但也可包括别的杂原子如氧,和/或是一个五元或七元环。
一个杂环芳基可以具体地是一个由上述具有通式(Ⅰ)的化合物中,从A,X或Z所代表的CH基中除去一个氢原子而衍生的基。当这样一个杂环芳基用R代表时,上面的式(Ⅰ)就代表一个包含重复的膦基吡啶部分被桥连的膦基相互连接所形成的链的低聚物,如在双〔6-(二苯膦基)2-吡啶基〕苯膦或2,6-双{〔6-(二苯膦基)2-吡啶基〕苯膦基}吡啶中那样。当这样一个杂环芳基用R′来代表,则上面的式(Ⅰ)就代表带有至少四个膦取代基的双-杂环芳香化合物,如在4,4′-双〔2,6-双(二苯膦基)吡啶基〕中那样。
较好是每个R′基独立地选自卤原子,C1-4烷基和C1-4烷氧基。更好是,每个R′代表一个C1-4烷基。
最好是膦取代基上的每个R基代表一个任意取代的苯基。
最好是,具有通式(Ⅰ)的多膦是2,6-双(二烃基膦基)吡啶,尤其是2,6-双(二芳基膦基)吡啶。
具有通式(Ⅰ)的多膦的实例有:2,6-双(二苯膦基)吡啶,2,6-双(二-对-甲苯膦基)吡啶,2,6-双(甲基苯膦基)吡啶,2,6-双(二环己膦基)吡啶,2,6-双(二-对甲氧基苯膦基)吡啶,3,4′-双〔2,6-双(二苯膦基)吡啶基〕,2,6-双(二苯膦基)吡嗪,2,2′-双〔3,5-双(二苯膦基)吡嗪〕,1,3-双(二苯膦基)异喹啉,2,4-双(二苯膦基)1,3,5-三嗪,2,4,6-三(二苯膦基)1,3,5-三嗪,2-氯4,6-双(二苯膦基)1,3,5-三嗪,1,3-双(二苯膦基)喹唑啉,2,4-双(二苯膦基)嘧啶和2,4,6-三(二苯膦基)嘧啶。
优选的,具有通式(Ⅰ)的多膦与酸加成形成的盐包括与下列酸所形成的盐;硫酸;磺酸,即任意取代的烃基磺酸如一种任意取代的芳基磺酸,如苯磺酸,对甲苯磺酸,或萘磺酸;一种任意取代的烷基磺酸如一种烷基磺酸,例如甲磺酸或叔丁基磺酸,或一种取代的烷基磺酸如2-羟基丙磺酸,三氟甲磺酸,氯磺酸或氟磺酸;一种膦酸,如正膦酸,焦膦酸或苯膦酸;一种羧酸如氯乙酸,二氯乙酸,三氯乙酸,三氟乙酸,草酸或对苯二甲酸;或一种过卤酸如过氯酸。
第Ⅷ族金属的实例有铁、钴、镍、钌、铑、钯、铱和铂。
按照本发明的催化剂体系,最好包含一个钯源。
第Ⅷ族金属源可以是,例如金属元素或第Ⅷ族金属的一种化合物。第Ⅷ族金属源较好是第Ⅷ族金属的一种化合物,最好是一种钯的化合物。
第Ⅷ族金属化合物的实例包括盐类,例如硝酸的盐;硫酸的盐;羧酸如不超过12个碳原子的烷羧酸,如醋酸的盐;以及氢卤酸的盐。盐类的其它实例还有那些与具有通式(Ⅰ)的多膦加成形成盐时所述的酸的盐。因为卤离子是有腐蚀性的,因而不宜用氢卤酸的盐。第Ⅷ族金属化合物的其它实例包括络合物,例如与β-羰基烯醇化物(例如乙酰丙酮化物),膦(例如具有通式Ⅰ的膦),和/或-氧化碳形成的络合物。例如第Ⅷ族金属的化合物可以是乙酰丙酮钯,四-三苯膦钯,醋酸双-三-邻-甲苯膦钯,醋酸双-二苯基-2-吡啶基膦钯,四-二苯基-2-吡啶膦钯,双-二-邻-甲苯基-吡啶基膦钯或醋酸双-二苯基吡啶基膦钯。
按照本发明的催化剂体系中,对应于每克原子第Ⅷ族金属的具有通式(Ⅰ)的多膦的摩尔数,并不特别重要。它依赖于具体的第Ⅷ族金属源以及具体的羰基化反应物。一般可把具有通式(Ⅰ)的多膦的摩尔数对每克原子第Ⅷ族金属的比例保持在1至50范围内。为提供很高的羰基化反应速率并节省使用多膦配位体,最好把上述比例的范围维持在2至20之间。因为相信多膦是以P-单齿配位体的形式配位,这些比例是指具有通式(Ⅰ)的化合物的摩尔数而不管它含有两个或更多个膦基。当然,在R和/或R′代表具有上面指出的式(Ⅰ)中的杂环芳基的情况下,式(Ⅰ)化合物中会含有许多膦基取代的N-芳香化合物部份,从而可以络合许多第Ⅷ族金属原子,因此可采用较低的配体对金属的比例。
在本发明的催化剂体系中还最好含有一种质子酸,它的作用是提供一种质子源。在例如丙炔的羰基化反应中,相信络合物具有阳离子的性质,这时质子酸也可以为催化活性的钯络合物提供一种阴离子源。优选的阴离子对钯阳离子是弱配位或不能配位的,因此它最好是由pKa值小于2(在18℃,在水中测定)的质子酸衍生而来的。质子酸可以直接加入体系中,也可以现场临时生成,例如可通过把BF3,AsF5,SbF5,PF5,TaF5或NbF5这类Lewis酸,与氢卤酸,水,烷醇如甲醇这类Broensted酸相互作用而形成,在甲基丙烯酸甲酯的制备中甲醇是反应物之一,最好是,所用的质子酸是那些上面在具有通式(Ⅰ)的多膦和酸加成形成盐时提到的有关的酸中的一种。它也可以是,例如,一种酸性离子交换树脂,例如磺酸型的离子交换树脂或一种硼酸衍生物如H〔B(O2C6H4)2〕或者H〔B(OC6H4CO2)2〕。
应该知道,包含具有通式(Ⅰ)的多膦与酸加成所形成的盐的催化剂体系一定包含一种质子酸。
当催化剂体系含有质子酸时,每当量具有通式(Ⅰ)的多膦对应的质子酸当量数的比例可在很宽的范围内变化。质子酸对具有通式(Ⅰ)的多膦的最优比例将依赖于催化剂组成物所应用的具体反应。一般每当量具有通式(Ⅰ)的多膦所用的质子酸的当量数目约在0.1至50的范围内,最好在0.5至5的范围内。
本发明的催化剂体系可以方便地在液相中组成。液相可以由包括一种或多种反应物的所用的催化剂体系所形成。另外,它也可以用溶剂形成。它还可以用催化剂体系中的一种组份形成。
本发明的催化剂体系可以是均相或非均相的,但最好是均相的。
本发明的催化剂体系可通过任意方便的方法产生。例如它可以在液相中把一种第Ⅷ族金属化合物,一种具有通式(Ⅰ)的多膦,如果合适,还有一种质子酸混合在一起而制得。另外,它也可以在液相中把一种第Ⅷ族金属化合物和一种具有通式(Ⅰ)的化合物与酸加成形成的盐混合在一起而制得。另外,它还可以在液相中把一种由第Ⅷ族金属和具有通式(Ⅰ)的多膦形成的络合物这样一种第Ⅷ族金属化合物,以及如果合适,一种质子酸混合一起而制得。
像上面已经讲过的,2,6-双(二苯膦基)吡啶已被Newkome等人在J.Org,Chem,43,947(1978)中公开,具有通式(Ⅰ)的其它多膦相信都是新的化合物。
具有通式(Ⅰ)的多膦可通过下面的方法来制备,它包括把一种具有通式(Ⅱ)或(Ⅲ)的化合物:式中M代表一个金属原子或一个离去原子或基团,与二或三当量的具有通式M′-PRR(Ⅳ)的一种适当的化合物,其中M′代表一个离去原子或基团,或一个金属原子,进行反应,然后任意地和酸加成形成盐。应当了解,当M代表一个金属原子时,具有通式(Ⅳ)的适当化合物中的M′就应当代表一个离去原子或基团。相似地,当M代表一个离去原子或基团时,具有通式(Ⅳ)的化合物中的M′就应当代表一个金属原子。具有式(Ⅱ)或式(Ⅲ)的化合物和具有式(Ⅳ)的化合物之间的反应,可以方便地在-80°至100℃的温度范围内,在一种溶剂如液氨,烃类,或一种醚存在的条件下进行。
具有通式(Ⅰ)的多膦,也可以通过一种类似于在我们的共同未决的英国专利申请9103214.4中所描述的方法来制备,该专利申请是1991年2月15日提出的,它的内容作为参考文献编入此文。
像前面已经讲过的,已经令人惊讶地发现,本发明的组合物在不饱和烃的羰基化反应中具有高度的选择性。
按此,本发明进一步把上面定义的催化剂组合物用于炔属或烯属不饱和烃的羰基化反应中。
另一方面,本发明提供一种炔属或烯属不饱和化合物的羰基化方法,它包括在液相中把炔属或烯属不饱和化合物在上面定义的催化剂体系存在的条件下与一氧化碳反应。
烯属不饱和化合物最好是在每个分子中具有2至30个,更好是3至20个碳原子的取代或未取代的烯烃或环烯烃。
炔属不饱和化合物最好是在每个分子中具有2至20个,特别是2至10个碳原子的取代或未取代的炔烃。
这种炔属或烯属的不饱和化合物可以包含一个或多个炔或烯键,例如一个、两个或三个炔或烯键。
这种烯烃或炔烃可以被例如下述基团所取代:卤原子、氰基、酰基如乙酰基、酸基如乙酸基、氨基如二烷氨基、烷氧基如甲氧基、卤代烷基如三氟甲基、卤代烷氧基如三氟甲氧基、酰氨基如乙酰基,或羟基。这些基团中有些依赖于精确的反应条件可以参与反应。例如在某些炔属不饱和醇如3-丁炔-1-醇、4-戊炔-1-醇或3-戊炔-1-醇的羰基化反应中,可以获得内酯。这样,可将3-丁炔-1-醇转化为α-亚甲基-γ-丁内酯。
炔烃的实例有:乙炔、丙炔、苯基乙炔、1-丁炔、2-丁炔、1-戊炔、1-己炔、1-庚炔、1-辛炔、2-辛炔、4-辛炔、1,7-辛二炔、5-甲基-3-庚炔、4-丙基-2-戊炔、1-壬炔、苄基乙炔、和环己基乙炔。
烯烃的实例有:乙烯、丙烯、苯乙烯、1-丁烯、2-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、2-辛烯、4-辛烯、环己烯和降冰片二烯。
不饱和化合物可以单独被羰基化,也可以在另一种反应物例如氢或一种具有可移去氢原子的亲核化合物存在的条件下被羰基化。具有可移去氢原子的亲核化合物的实例是含羟基的化合物。
含羟基的化合物最好是醇,水或羧酸。
任何使用的醇可以是脂族的、环脂族的或者芳族的,并可以带有一个或多个取代基。醇最好每分子含有至多20个碳原子。它可以是例如烷醇、环烷醇或酚。可以有一个或多个羟基,这时依赖于所用反应物的摩尔比可以有多种产物形成。烷醇的实例包括甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、2-甲基丙醇和2-甲基-2-丙醇。
按照本发明的方法,可以用多种羧酸来进行反应。例如,羧酸可以是脂族的、环脂族的或芳族的,并且可以带有一个或多个取代基,就像在有关炔属和烯属不饱和化合时提到的那些取代基。用于本发明的方法中的羧酸最好含有最多20个碳原子,诸如甲酸、乙酸、丙酸、苯甲酸或己二酸。
当炔属不饱和化合物与水和一氧化碳反应时,将形成α,β-不饱和羧酸。如果用醇代替水,就形成α,β-不饱和羧酸的酯。如果用羧酸代替水,就形成α,β-不饱和羧酸酐。这种α,β-不饱和产物依赖于所用的反应条件可发生进一步的反应。
已经发现本发明的催化剂组合物在α-炔烃与含羟基的化合物进行羰基化反应时特别有用。
因此,本发明优选提供一种制备α,β-烯属不饱和化合物的方法,它包括在液相,在上述羰基化催化剂存在的条件下,把一种α-炔烃与一氧化碳和一种含羟基的化合物进行反应。
在这个方法中,羰基化催化剂最好是上述的钯催化剂,即包含下列组份的催化剂:
a)一种钯化合物,
b)一种具有通式(Ⅰ)的多膦,
c)一种质子酸。
在本发明的方法中应用单独的溶剂不是必要的。
大为过量的产物或一种反应物,例如一种醇,常可形成适当的液相。但是在某些情况下,最好还是用一种单独的溶剂。任何一种惰性溶剂都可用于这一目的。例如所说的溶剂包括亚砜、砜、芳烃、酯类、酮类、醚类和酰胺类。
本发明的方法可以方便地在10℃至200℃的温度范围,特别是20℃至130℃、更好是25-80℃范围内进行反应。
本发明的方法最好是在1-70巴的压力条件下进行反应。可以用高于100巴的压力,可是因为特殊设备要求,通常在经济上是没有吸引力的。
含羟基的化合物对于不饱和烃的摩尔比,可以在很宽的范围内变化,一般是在0.01∶1至100∶1的范围内。
第Ⅷ族金属的用量不是关键性的,最好是每摩尔不饱和化合物所用的第Ⅷ族金属的量在10-7至10-1克原子的范围内。
按照本发明的方法,一氧化碳可以实际上纯净的形式,也可用一种经惰性气体如氮气稀释的方式使用。在气流中不应有较多量的氢气,因为在反应条件下会发生不饱和烃的氢化反应,一般所用气流中氢气的量最好是小于5%(体积)。
转化为α,β-烯属不饱和化合物的选择性,用百分数表示,被定义为
(a/b)×100式中“a”为炔属不饱和化合物转化为α,β-烯属不饱和化合物的量,“b”为已转化的炔属不饱和化合物的总量。
现在用下面的制备和实施例对本发明做具体说明。
除非另有说明,用于下面实施例中的丙炔中所含丙二烯的含量均小于50ppm。
2,6-双(二苯膦基)吡啶的制备
在氩气保护下,把0.75克金属锂(107毫摩尔)加到有效地搅拌着的13.1克三苯膦(50毫摩尔)在150毫升干燥四氢呋喃的溶液中。当反应在2小时之后完成时(如以31P NMR所证实),除去过量的锂,然后把深棕色的溶液冷却到0℃。随即加入与存在的苯基锂等当量的3.4克叔丁醇(45.8毫摩尔),这时温度升至大约15℃。然后加入3.52克的2,6-二氯吡啶(23.8毫摩尔)并允许温度上升。得到的反应混合物在回流和大气压力下蒸出四氢呋喃,真空干燥,加入50毫升3M氯化铵水溶液和50毫升二氯甲烷,分相,洗涤,把汇合的有机相过滤,真空浓缩,然后由沸腾的己烷中重结晶,冷却到室温后过滤收集,得到7.8克白色结晶状的2,6-双(二苯膦基)吡啶(收率73.4%,纯度97.5%)。
实施例1
往装有磁搅拌器的250毫升不锈钢高压釜中顺序加入0.025毫摩尔醋酸钯(Ⅱ),1毫摩尔2,6-双(二苯膦基)吡啶,1毫摩尔甲磺酸和50毫升甲醇。从高压釜中抽出空气,随即加入30毫升丙炔。然后充一氧化碳至压力为60巴。密封高压釜,这时观测到放热现象,它在反应期间加热反应混合物,使平均温度为45℃。等反应完成后将丙炔放空,借助气液色谱分析反应内容物取样,测得丙炔转化为甲基丙烯酸甲酯的选择性为99.92%,平均转化速率经计算高于每克原子钯每小时100,000摩尔丙炔。
实施例2
用基本相同的方式重复实施例1中的实验,所用的催化剂体系包括0.025毫摩尔醋酸钯(Ⅱ),0.25毫摩尔2,6-双(二苯膦基)吡啶,和0.25毫摩尔甲磺酸。在密封高压釜时,可观察到放热现象使温度平均升高到50℃。在反应0.25小时之后,对内容物取样进行分析,表明丙炔转化为甲基丙烯酸甲酯的选择性为99.92%,计算的平均转化速率为50,000摩尔/克原子钯/小时。
实施例3至4以及比较实例A至B
按指出的用量,用2,6-双(二苯膦基)吡啶(2,6-PNP),并且为了比较,也用2-二苯膦基吡啶(2-PN)分别作为催化剂体系的配位体,反应温度22℃,重复实施例2的方法。由反应最初三小时一氧化碳压力的变化计算出转化速率,并由气液色谱分析测得选择性,结果总结于表1中。
将实施例4与比较实例A比较,可以看出在用本发明所说的多膦配位体,并且配位体对钯的摩尔比为10∶1时,具有高出十倍以上的转化速率。由实施例3可以看出,2,6-PNP对钯的比例可降低至5∶1而仍然有很好的丙炔转化速率。比较实例B指出,在所说的羰基化条件下,每克原子钯每小时用20摩尔2-PN所得到的转化速率与用本发明的配位体所得的结果比较时仍然较差。
实施例5
用由0.025毫摩尔醋酸钯(Ⅱ),0.25毫摩尔2,6-双(二苯膦基)吡啶和1毫摩尔BF3·Et2O(由它在现场与甲醇反应而形成质子酸H+BF3(CH3O)-)所组成的催化剂体系重复实施例3的方法,在25℃反应3小时后,观察到丙炔转化速率为2700摩尔/克原子钯/小时,转化成甲基丙烯酸甲酯的选择性为99.92%。
实施例6
往装有磁搅拌器的250毫升不锈钢高压釜中顺序加入0.025毫摩尔醋酸钯(Ⅱ),0.25毫摩尔2,6-双(二苯膦基)吡啶,0.25毫摩尔甲磺酸,30毫升苯基乙炔和30毫升甲醇。从高压釜中抽出空气,充入一氧化碳至压力为60巴。密封高压釜,可观察到放热的反应把反应混合物的温度在整个反应期间加热到平均32℃。反应0.5小时之后,借助气液色谱测定反应内容物取样。丙炔转化为1-苯基丙烯酸甲酯的选择性为99.93%,而平均转化速率经计算为20,000摩尔丙炔每克原子钯每小时。
表1丙炔和甲醇羰基化成为甲基丙烯酸甲酯
实施例 | 配位体(毫摩尔) | 酸(毫摩尔) | 选择性(%) | 平均转化速率摩尔丙炔/克原子·钯/小时 |
3 | 2,6-PNP(0.125) | CH3SO3H(0.125) | 99.92 | 3,000 |
4 | 2,6-PNP(0.25) | CH3SO3H(0.25) | 99.92 | 5,000 |
A | 2-PN(0.25) | CH3SO3H(0.25) | 99.3 | <500 |
B | 2-PN(0.5) | CH3SO3H(0.25) | 99.4 | 1,000 |
注:用0.025毫摩尔Pd(OAC)2,30毫升丙炔,
50毫升甲醇,60巴CO,22℃
Claims (13)
2.权利要求1的催化剂体系,其中的X和Z中至少有一个是氮原子,并且A是一个C-PR2基。
3.权利要求1的催化剂体系,其中每个X,Z和A是独立地选自CH基和具有通式CR′的基。
4.权利要求1-3中任一项的催化剂体系,其中每个R′基团独立地选自卤原子、C1-4烷基、和C1-4烷氧基。
5.权利要求1-3任一项的催化剂体系,其中每个R基团独立地代表取代或非取代的苯基。
6.权利要求1-3中任一项的催化剂体系,其中第Ⅷ族金属源是一种钯的化合物。
7.权利要求1-3中任一项的催化剂体系,其中每克原子第Ⅷ族元素的具有通式(Ⅰ)的多膦的摩尔数在1至50。
8.权利要求1-3中任一项的催化剂体系,其中每克原子第Ⅷ族元素的具有通式(Ⅰ)的多膦的摩尔数在2至20的范围内。
9.权利要求1-3中任一项的催化剂体系,其中每当量具有通式(Ⅰ)的多膦有0.5至5当量范围的一种质子酸存在。
10.把权利要求1中所定义的催化剂体系用于炔属或烯属不饱和烃的羰基化反应的应用。
11.制备α,β-烯属不饱和化合物的方法,包括在权利要求1中所定义的羰基化催化剂体系存在的条件下,把α-炔属化合物与一氧化碳以及一种含羟基的化合物进行反应。
12.权利要求11的方法,其中的羰基化催化剂体系包括:
a)一种钯的化合物,
b)一种权利要求1中所定义的具有通式(Ⅰ)的多膦,
c)一种质子酸。
13.权利要求11或12中所述的方法,其中是使丙炔与一氧化碳和甲醇进行反应。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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GB9103214.4 | 1991-02-15 | ||
GB919103214A GB9103214D0 (en) | 1991-02-15 | 1991-02-15 | Process for the preparation of diarylphosphino pyridines |
GB919111583A GB9111583D0 (en) | 1991-05-30 | 1991-05-30 | Carbonylation catalyst system |
GB9111583.2 | 1991-05-30 |
Publications (2)
Publication Number | Publication Date |
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CN1067190A CN1067190A (zh) | 1992-12-23 |
CN1042102C true CN1042102C (zh) | 1999-02-17 |
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CN92100820A Expired - Fee Related CN1042102C (zh) | 1991-02-15 | 1992-02-13 | 羰基化催化剂体系 |
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EP (1) | EP0499329B1 (zh) |
JP (1) | JPH0584442A (zh) |
KR (1) | KR100230139B1 (zh) |
CN (1) | CN1042102C (zh) |
DE (1) | DE69200122T2 (zh) |
ES (1) | ES2054519T3 (zh) |
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TW272949B (zh) * | 1994-07-22 | 1996-03-21 | Taishal Kagaku Kogyo Kk | |
DE69607653T2 (de) * | 1995-12-07 | 2000-11-23 | Shell Int Research | Verfahren zur carbonylierung von ungesättigten acetylenverbindungen |
US5686613A (en) * | 1996-01-16 | 1997-11-11 | Wheelabrator Clean Air Systems Inc. | Tridentate metal ligands of certain pyridine phosphonic acids |
DE10048874A1 (de) | 2000-09-29 | 2002-04-11 | Basf Ag | Katalysatorsystem und Verfahren zur Carbonylierung |
TWI301481B (en) | 2002-08-10 | 2008-10-01 | Lucite Int Uk Ltd | A catalyst system |
PL213201B1 (pl) * | 2002-09-12 | 2013-01-31 | Lucite Int Uk Ltd | Zwiazek nadajacy sie w szczególnosci do katalizowania reakcji karbonylowania nienasyconych zwiazków, sposób wytwarzania tych zwiazków, kompozycja zawierajaca takie zwiazki, sposób karbonylowania etylenowo nienasyconych zwiazków z zastosowaniem tych zwiazków, a takze ich zastosowanie |
AU2003299066A1 (en) * | 2002-09-26 | 2004-04-19 | Shell Internationale Research Maatschappij B.V. | Process for the hydroformylation of an ethylenically unsaturated compound using a bidentate diphosphine composition with a bridging group comprising sp2 hybridized carbon atoms bound to the phosphorous atoms |
AU2003299094A1 (en) | 2002-09-26 | 2004-04-19 | Shell Internationale Research Maatschappij B.V. | Process for the production of primary alcohols |
WO2005003070A1 (en) | 2003-07-03 | 2005-01-13 | Lucite International Uk Limited | Process for the hydroformylation of ethylenically unsaturated compounds |
GB0403592D0 (en) | 2004-02-18 | 2004-03-24 | Lucite Int Uk Ltd | A catalyst system |
GB0411951D0 (en) | 2004-05-28 | 2004-06-30 | Lucite Int Uk Ltd | Carbonylation of ester |
GB0516556D0 (en) | 2005-08-12 | 2005-09-21 | Lucite Int Uk Ltd | Improved catalyst system |
EA025600B1 (ru) | 2005-11-17 | 2017-01-30 | ЛУСАЙТ ИНТЕРНЕЙШНЛ Ю Кей ЛИМИТЕД | Способ карбонилирования этиленненасыщенных соединений, каталитическая система и бидентатный лиганд |
GB0607494D0 (en) * | 2006-04-13 | 2006-05-24 | Lucite Int Uk Ltd | Metal complexes |
GB2437930A (en) | 2006-05-10 | 2007-11-14 | Lucite Int Uk Ltd | Mixing apparatus |
EP2097429B1 (en) | 2006-12-02 | 2019-03-06 | Lucite International UK Limited | Novel carbonylation ligands and their use in the carbonylation of ethylenically unsaturated compounds |
GB0812297D0 (en) | 2008-07-04 | 2008-08-13 | Lucite Int Uk Ltd | Novel carbonylation ligand sand thier use of in the carbonylation of ethylenically unsaturated compounds |
GB0921876D0 (en) | 2009-12-15 | 2010-01-27 | Lucite Int Uk Ltd | Improved carbonylation process |
GB0921875D0 (en) | 2009-12-15 | 2010-01-27 | Lucite Int Uk Ltd | A continuous process for the carbonylation of ethylene |
GB201000078D0 (en) * | 2010-01-05 | 2010-02-17 | Lucite Int Uk Ltd | Process for the carbonylation of ethylenically unsaturated compounds, novel carbonylation ligands and catalyst systems incorporatng such ligands |
CN102190583A (zh) * | 2010-03-08 | 2011-09-21 | 中国科学院成都有机化学有限公司 | 一种钯膦络合物催化乙炔羰基合成丙烯酸低碳醇酯的方法 |
SG194984A1 (en) | 2011-06-10 | 2013-12-30 | Procter & Gamble | Absorbent structure for absorbent articles |
GB201122054D0 (en) | 2011-12-21 | 2012-02-01 | Lucite Int Uk Ltd | A continuous process for the carbonylation of ethylene |
US9987176B2 (en) | 2013-08-27 | 2018-06-05 | The Procter & Gamble Company | Absorbent articles with channels |
US11207220B2 (en) | 2013-09-16 | 2021-12-28 | The Procter & Gamble Company | Absorbent articles with channels and signals |
EP3351225B1 (en) | 2013-09-19 | 2021-12-29 | The Procter & Gamble Company | Absorbent cores having material free areas |
CN109092366B (zh) * | 2017-06-21 | 2021-05-28 | 中国石油化工股份有限公司 | 催化剂组合物及2-丁烯酸的制备方法 |
CN111087306B (zh) | 2019-12-27 | 2021-08-03 | 南京诚志清洁能源有限公司 | 芳基双齿膦配体组合催化制备有机羧酸酯的方法 |
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PT76061A (en) * | 1982-12-30 | 1983-01-01 | Stable homogeneous hydrogenation rhodium catalyst - useful in high yield prodn. of doxycycline by stereospecific hydrogenation | |
DE3660719D1 (en) * | 1985-03-27 | 1988-10-20 | Hoechst Ag | Supported catalyst and procedure for the production of monocarboxylic acid anhydrides |
DE3685713D1 (de) * | 1985-10-18 | 1992-07-23 | Hoffmann La Roche | Chirale rhodium-diphosphinkomplexe fuer asymmetrische hydrierungen. |
US4880902A (en) * | 1987-08-27 | 1989-11-14 | Shell Oil Company | Copolymerization of carbon monoxide and olefin with diphosphine having heterocyclic substituents as catalyst |
CA2034971A1 (en) * | 1990-02-05 | 1991-08-06 | Eit Drent | Carbonylation catalyst system |
-
1992
- 1992-02-11 DE DE69200122T patent/DE69200122T2/de not_active Expired - Fee Related
- 1992-02-11 ES ES92200389T patent/ES2054519T3/es not_active Expired - Lifetime
- 1992-02-11 EP EP92200389A patent/EP0499329B1/en not_active Expired - Lifetime
- 1992-02-11 KR KR1019920002118A patent/KR100230139B1/ko not_active IP Right Cessation
- 1992-02-13 CN CN92100820A patent/CN1042102C/zh not_active Expired - Fee Related
- 1992-02-13 JP JP4058799A patent/JPH0584442A/ja active Pending
Also Published As
Publication number | Publication date |
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EP0499329B1 (en) | 1994-05-04 |
EP0499329A1 (en) | 1992-08-19 |
JPH0584442A (ja) | 1993-04-06 |
CN1067190A (zh) | 1992-12-23 |
DE69200122T2 (de) | 1994-09-29 |
ES2054519T3 (es) | 1994-08-01 |
KR920016142A (ko) | 1992-09-24 |
DE69200122D1 (de) | 1994-06-09 |
KR100230139B1 (ko) | 1999-11-15 |
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