CN1207277C - 戊烯酸及其衍生物的羰基化方法 - Google Patents
戊烯酸及其衍生物的羰基化方法 Download PDFInfo
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- CN1207277C CN1207277C CNB018199887A CN01819988A CN1207277C CN 1207277 C CN1207277 C CN 1207277C CN B018199887 A CNB018199887 A CN B018199887A CN 01819988 A CN01819988 A CN 01819988A CN 1207277 C CN1207277 C CN 1207277C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
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Abstract
本发明涉及式(I)的正戊烯酸或其衍生物的羰基化方法,其中R1代表-CN或COOR2,R2代表氢、烷基或芳基。根据所述方法,使式(I)的化合物与一氧化碳和含有羟基的化合物(II)在催化剂体系存在下反应。该方法的特征在于所述催化剂体系通过a)元素周期表的第8副族的金属(III)的金属离子源,与b)式(IV)的双齿膦配体反应获得,其中R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14彼此独立地代表在各种情况下含有碳原子的有机基团,经由该碳原子将相应的基团连接于式(IV)中的相关叔碳原子,L1、L2彼此独立地代表低级亚烷基,X代表亚芳基。
Description
本发明涉及式(I)的正戊烯酸或其衍生物的羰基化方法,
C4H7-R1 (I)
其中R1是-CN或COOR2,其中R2是氢、烷基或芳基,
该方法在于使式(I)的化合物与一氧化碳和含有羟基的化合物(II)在催化剂体系存在下反应,其中所述催化剂体系通过以下组分的反应获得:
a)元素周期表的第8副族的金属(III)的金属离子源,
b)式(IV)的双齿膦配体,
(R3R4R5C)(R6R7R8C)P-L1-X-L2-P(CR9R10R11)(CR12R13R14) (IV)
其中
R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14彼此独立地是在各种情况下含有碳原子的有机基团,经由该碳原子将相应的基团连接于式(IV)中的相关叔碳原子;
L1、L2彼此独立地是低级亚烷基;
X是亚芳基。
正戊烯酸或其衍生物的羰基化方法是公知的,例如GB-1497046、DE-A-2541640、US 4508660、EP-A-373579、US 4933483、EP-A-450577、US 4257973、WO 2000/14055、EP-A-577204、WO 2000/56695、EP-A-662467或WO 2000/42717所述。
在这些方法中,获得了直链或支化产物。
式(I)化合物的羰基化的直链产物是己二酸或其衍生物,大量用于制备工业上重要的聚合物,特别是聚酰胺,而支化产物没有价值或重要性仅仅很小。
所以,希望在高产率的同时获得高的n/i比率。n/i比率理解为代表直链产物的选择性与支化产物的选择性之比。在现有技术中提到的线性指直链产物的选择性。n/i比率根据下面的等式从线性来计算:
n/i比率=线性[%]/(100%-线性[%])
在获得高产率的同时,上述方法的n/i比率不令人满意。
所以,根据US 4933483的实施例6,在获得仅仅70%产率的同时,达到的n/i比率是24(线性96%)。
WO 98/42717的实施例7公开了产率为84%(转化率100%,选择性84%);但是,n/i比率仅为5.25(84%的线性产物,其余的16%是支化产物)。
本发明的目的是提供式(I)的正戊烯酸或其衍生物的羰基化方法,该方法以技术简易和经济的方式避免了上述缺点。
相应地,在开始时已经定义了本发明。
根据本发明,使用式(I)的正戊烯酸或其衍生物,
C4H7-R1 (I)
其中为了本发明的目的,在这里也可以理解为这些化合物的混合物。
适宜的基团R1是-CN或COOR2,其中R2可以是氢、烷基或芳基,有利地是氢或烷基,优选氢、甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基,特别是氢、甲基、乙基,特别优选氢或甲基。
如果R2是烷基或芳基,则它可以携带取代基,例如官能团或其它烷基或芳基。优选,在烷基或芳基的情况下,R2不带取代基。
适宜的式(I)的正戊烯酸或其衍生物是基本上所有的异构体,例如顺-2-、反-2-、顺-3-、反-3-和4-异构体,以及它们的混合物。这些混合物可以含有相同或不同的基团R1。含有相同的基团R1的那些混合物是优选的。
有利的是,使用顺-2-、反-2-、顺-3-、反-3-或4-戊烯腈以及它们的混合物是合适的。在这里,优选含有至少80%重量的3-戊烯腈(即顺-3-戊烯腈和反-3-戊烯腈的总和)的那些混合物。
在进一步有利的实施方案中,使用顺-2-、反-2-、顺-3-、反-3-或4-戊烯酸以及它们的混合物是合适的。在这里,优选含有至少80%重量的3-戊烯酸(即顺-3-戊烯酸和反-3-戊烯酸的总和)的那些混合物。
在进一步有利的实施方案中,使用顺-2-、反-2-、顺-3-、反-3-或4-戊烯酸甲酯以及它们的混合物是合适的。在这里,优选含有至少80%重量的3-戊烯酸甲酯(即顺-3-戊烯酸甲酯和反-3-戊烯酸甲酯的总和)的那些混合物。
式(I)中的戊烯酸及其衍生物可以根据本身已知的方法来获得,例如通过在催化剂的存在下将一氧化碳和含有羟基的化合物或氰化氢加成到丁二烯上。
根据本发明,式(I)的化合物与一氧化碳反应。在该方法中,一氧化碳可以作为纯化合物使用或在基本对本发明方法无不利影响、特别是对其呈惰性的气体存在下使用。合适的这种惰性物质是例如氮气、氢气、二氧化碳、甲烷和稀有气体,例如氩气。
有利的是,化合物(I)与一氧化碳之间的摩尔比可以是至少1∶1,优选至少3∶1,特别是至少5∶1,优选在5∶1至50∶1的范围内,特别优选在7∶1至15∶1的范围内。如果在化合物(I)与一氧化碳之间的摩尔比小于5∶1、特别是小于3∶1、尤其小于1∶1的情况下进行本发明方法,则可能导致催化剂体系的性能迅速变差。
根据本发明,式(I)的化合物与含有羟基的式(II)化合物反应。在本发明中,化合物(II)理解为表示单独的化合物(II)以及各种此类化合物的混合物。
化合物(II)的性质至少部分地决定了本发明方法的最终产物。如果水用作化合物(II),则获得相应的酸,而当使用醇例如链烷醇时,获得了相应的酯。适宜的醇是伯醇、仲醇或叔醇,优选伯醇,有利地是C1-C30链烷醇,其可以任选地携带取代基,例如一个或多个卤素、腈、羰基、烷氧基或芳基。有利的是,适宜的链烷醇是甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、叔丁醇、正己醇、正辛醇、异辛醇、2-乙基己醇、环己醇、苄基醇、苯乙醇、乙二醇、1,2-丙二醇、1,3-丙二醇、新戊二醇、三羟甲基丙烷、季戊四醇,优选甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、叔丁醇,特别优选甲醇或乙醇,特别是甲醇。
化合物(I)与化合物(II)的摩尔比本身不是关键的,可以处于宽范围内,有利地在0.001∶1至100∶1摩尔/摩尔的范围内。
根据本发明的方法在催化剂体系的存在下进行,该催化剂体系可以通过金属(III)的金属离子源与式(IV)的双齿膦配体反应来获得。
合适的金属(III)是元素周期表的第8副族的元素,例如铁、钴、镍、钌、铑、钯、锇、铱、铂,优选钯、铂、铑、铱,特别是钯,以及它们的混合物。
这种金属的金属离子源可以有利地是这些金属与阴离子的盐,或其中弱配位键接这种金属的化合物与阴离子的盐,所述阴离子衍生自无机酸,例如硝酸、硫酸、磷酸,羧酸,有利地是C1-C12羧酸,优选乙酸、丙酸、丁酸,磺酸,例如甲磺酸、氯磺酸、氟磺酸、三氟甲磺酸、苯磺酸、萘磺酸、甲苯磺酸(特别是对甲苯磺酸)、叔丁基磺酸、2-羟基丙磺酸、磺化离子交换剂,卤代过酸,例如高氯酸、全氟化羧酸,例如三氟乙酸、九氟丁磺酸、三氯乙酸,膦酸,例如苯膦酸,由路易斯酸与布朗斯台德酸的相互作用获得的酸,阴离子,例如四苯基硼酸盐及其衍生物,或它们的混合物。
同样,可以有利地使用这样的化合物,其中这种金属以零化合价的形式与可去除的配体一起存在,所述配体例如是三(二亚苄基丙酮)-钯、四(三苯基磷烷(phosphan))钯、二(三-邻-甲苯基磷烷)钯。
金属(III)与化合物(I)的摩尔比本身不是关键的。已经证明了金属(III)与化合物(I)的摩尔比在10-7∶1至10-1∶1、优选10-6∶1至10-2∶1的范围内是有利的。
根据本发明,所用的化合物(IV)是下式的双齿膦配体,
(R3R4R5C)(R6R7R8C)P-L1-X-L2-P(CR9R10R11)(CR12R13R14)(IV)
其中
R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14彼此独立地是在各种情况下含有碳原子的有机基团,经由该碳原子将相应的基团连接于式(IV)中的相关叔碳原子;
L1、L2彼此独立地是低级亚烷基;
X是亚芳基。
R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14可以彼此独立地在宽范围的有机基团范围内选择。优选的有机基团是低级烷基,优选直链或支链C1-C4烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基。
特别优选的基团R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14是这样的,它们与和它们直接相连的叔碳原子一起形成这样的基团,在每种情况下该基团具有至少一个空间位阻条件,例如叔丁基。在本发明中,空间位阻条件理解为表示术语“空间位阻”,论述于“HomogeneousTransition Metal Catalysis-A Gentle Art”(C Masters,Chapman and Hall出版,1981,14页起)中。
基团L1和L2可以彼此独立地是低级亚烷基,优选C1-C4-亚烷基,例如亚甲基、亚乙基、亚正丙基、亚丁基,它们可以被取代或未取代。L1和L2在每种情况下特别优选是亚甲基。
适合的X是亚芳基,例如亚苯基,其可以被取代或未取代。特别优选的亚芳基是其中L1和L2经由邻碳原子与X相连的那些。在X上有取代基的情况下,合适的取代基是烷基基团,特别是C1-C4烷基基团,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基,烷氧基,烷氧羰基,卤素,硝基,三卤代甲基或氰基。此外,X可以是饱和或不饱和多环体系的组分,例如萘、1,2,3,4-四氢化萘、联苯、茚。
有利的是,所用的化合物(IV)可以是二(二-叔丁基膦基)-邻二甲苯(“1,2-二(二-叔丁基膦基)-苯”),二(二-叔戊基膦基)-邻二甲苯和1,2-二(二-叔丁基-膦基)萘。
此外,合适的化合物(IV)是优选经由X、L1或L2与聚合物相连的那些双齿膦。因此,例如二(二-叔丁基膦基)-邻二甲苯可以经由邻二甲苯基团与聚苯乙烯键接。在这种情况下,获得了非均相催化剂体系。
配体(IV)与金属(III)的摩尔比可以在宽范围内选择。有利的是,该比率在0.5-50、优选0.5-20、特别优选0.5-10、尤其1-5摩尔/摩尔范围内是合适的。
在优选的实施方案中,催化剂体系在阴离子源(V)的存在下获得。
所用的阴离子源可以是已经含有阴离子的化合物,例如盐,或能通过化学反应释放出阴离子的化合物,例如键的异裂。
合适的阴离子源是公知的,例如描述在EP-A-495 547中。阴离子源(V)可以有利地是在去除H+离子时能获得阴离子的化合物,例如硝酸、硫酸、磷酸,羧酸,有利地是C1-C12羧酸,优选乙酸、丙酸、2,4,6-三甲基苯甲酸、2,6-二氯苯甲酸、9-蒽甲酸、新戊酸、1,2,3-苯三甲酸、1,2,3-苯三甲酸-1,3-二酯、2-乙氧基-1-萘甲酸、2,6-二甲氧基苯甲酸、5-氰基戊二酸,磺酸,例如甲磺酸、氯磺酸、氟磺酸、三氟甲磺酸、苯磺酸、萘磺酸、甲苯磺酸(特别是对甲苯磺酸)、叔丁基磺酸、2-羟基丙磺酸、磺化离子交换剂,卤代过酸,例如高氯酸、全氟化羧酸,例如三氟乙酸、九氟丁磺酸、三氯乙酸,膦酸,例如苯膦酸,由路易斯酸(例如BF3、PF5、AsF5、SbF5、TaF5或NbF5)与布朗斯台德酸(例如HF,例如氟硅酸、HBF4、HPF6、HSbF6、四苯基硼酸和其衍生物)的相互作用获得的酸,或它们的混合物。
在去除H+离子时能获得阴离子的化合物(V)中,pKa值至多为3.5、特别是至多2的那些是优选的。
化合物(V)与金属(III)的摩尔比本身不是关键的。有利的是,化合物(V)与金属(III)的摩尔比可以在0.5-100、优选1-20摩尔/摩尔的范围内。
催化剂体系可以在用于本发明方法之前制备,或在根据本发明方法本身中制备。
如果在根据本发明方法本身中制备催化剂体系,则已经证明使用这样的金属(III)的化合物是有利的,它们在反应混合物中的溶解程度能使其与其它组分形成活性催化剂体系。
在本发明方法中使用的催化剂体系可以在均相或非均相、优选均相中使用。
催化剂体系可以有利地在液相中获得。在这种情况下,液相可以通过一种或多种能获得或获得催化剂体系的组分形成。同样,可以通过无机或有机液体稀释剂、优选有机液体稀释剂来制备液相。
合适的液体稀释剂有利地是非质子液体稀释剂,例如醚类,例如二乙醚、二甲醚、乙二醇二甲醚、二甘醇二甲醚、四氢呋喃、聚醚、官能化聚醚、茴香醚、2,5,8-三氧杂壬烷、二异丙醚、二苯醚;例如芳族化合物,包括卤代芳族化合物,例如苯、甲苯、邻二甲苯、间二甲苯、对二甲苯、氯苯、邻二氯苯、间二氯苯、对二氯苯;例如烷烃,包括卤代烷烃,例如己烷、庚烷、2,2,3-三甲基戊烷、二氯甲烷、四氯甲烷;例如腈类,例如苯甲腈、乙腈;例如酯类,例如苯甲酸甲酯、乙酸甲酯、邻苯二甲酸二甲酯、丁内酯;例如砜类,例如二乙基砜、二异丙基砜、四氢噻吩1,1-二氧化物(“环丁砜”)、2-甲基环丁砜、3-甲基环丁砜、2-甲基-4-丁基环丁砜;例如亚砜类,例如二甲基亚砜;例如酰胺类,包括卤代酰胺,例如二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮;例如酮类,例如丙酮、甲乙酮、甲基异丁基酮,以及它们的混合物。
特别优选的液体稀释剂是沸点高于通过本发明方法获得的相应产物的沸点的那些。通过该方法可以促进从剩余的反应混合物中除去产物,例如通过蒸馏进行。
根据本发明的方法可以有利地在20-250℃的温度下进行,优选40-200℃,特别优选70-170℃,特别是80-140℃。
本发明方法可以有利地在总压力为1×105至200×105Pa下进行,优选5×105至70×105Pa,特别是6×105至20×105Pa。
本发明方法可以连续地、间歇地或半连续地进行。
产物可以通过本身已知的方法从其它组分中分离出来,例如萃取或蒸馏。
由于本发明方法的高n/i比率,明显减少了随后的纯化费用,这是由于获得了较少的不希望的副产物。
本发明方法的另一个优点在于含有催化剂体系的残余组分可以返回到本发明方法中。同时,如果需要,可以加入新催化剂。
实施例
实施例1
将70mg(0.31mmol)乙酸钯、244mg(0.62mmol)二(二叔丁基膦基)-邻-二甲苯(“配体1”)、590mg(3.1mmol)对甲苯磺酸、80ml(830mmol)3-戊烯腈(“3-PN”)和34ml甲醇加入配有充气搅拌器的400ml玻璃高压釜中,密封后,注入一氧化碳达到4×105Pa压力,将高压釜加热到90℃。在此过程中,将总压力调节到7×105Pa。在如表1列出的反应时间后,冷却高压釜,通过气相色谱分析反应混合物。结果列在表1中。
实施例2
工艺过程如实施例1所述,区别在于用102ml(840mmol)3-戊烯酸甲酯(“3-PSE”)代替3-戊烯腈。
结果列在表1中。
实施例3
工艺过程如实施例1所述,区别在于用192mg(0.31mmol)乙酸钯-配体1配合物代替乙酸钯和配体1。
关于乙酸钯-配体1配合物的制备,将1.0g(4.4mmol)的乙酸钯溶解于50ml丙酮中,使该溶液经过塞里塑料(煅烧的硅胶)过滤。将1.73g(4.4mmol)在50ml丙酮中的悬浮液加入该溶液中,在室温下搅拌混合物1小时。过滤出所得的浅黄色固体,真空干燥。产率是2.57g(94%)。
结果列在表1中。
实施例4
工艺过程如实施例3所述,区别在于用102ml(840mmol)3-戊烯酸甲酯代替3-戊烯腈。
结果列在表1中。
表1
实施例 | 反应时间[h] | 转化率[%]3-PN/3-PSE | TOF[h-1] | 羰基化选择性[%] | n/i比率 |
1 | 1 | 90 | 2400 | >99 | 65.7 |
2 | 1 | 92 | 2500 | >99 | 61.5 |
3 | 1 | >99 | 2650 | >99 | 70.4 |
4 | 1 | >99 | 2700 | >99 | 65.7 |
TOF:(原料转化率(3-PN/3-PSE)摩尔/小时)/(催化剂的摩尔量)
Claims (9)
1、式(I)的正戊烯酸或其衍生物的羰基化方法,
C4H7-R1 (I)
其中R1是-CN或COOR2,其中R2选自氢、甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基,
该方法在于使式(I)的化合物与一氧化碳和含有羟基的化合物(II)在催化剂体系存在下反应,其中所述催化剂体系通过以下组分的反应获得:
a)元素周期表的第8副族的金属(III)的金属离子源,其中金属(III)选自钯、铂、铑和铱,
b)式(IV)的双齿膦配体,
(R3R4R5C)(R6R7R8C)P-L1-X-L2-P(CR9R10R11)(CR12R13R14) (IV)
其中
R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14彼此独立地在各种情况下是C1-C4烷基;
L1、L2彼此独立地是C1-C4亚烷基;
X是亚苯基、萘、1,2,3,4-四氢化萘、联苯或茚。
2、根据权利要求1的方法,其中所用的式(I)化合物是至少80%重量的3-戊烯腈。
3、根据权利要求1的方法,其中所用的式(I)化合物是至少80%重量的3-戊烯酸甲酯。
4、根据权利要求1的方法,其中使用的金属(III)是钯。
5、根据权利要求1或2的方法,其中基团R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14与和它们直接相连的叔碳原子一起形成这样的基团,在每种情况下该基团具有至少一个空间位阻条件。
6、根据权利要求5的方法,其中基团R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14与和它们直接相连的叔碳原子一起形成叔丁基。
7、根据权利要求1或2的方法,其中L1和L2在每种情况下是亚甲基。
8、根据权利要求1或2的方法,其中催化剂体系是在阴离子源(V)的存在下获得的。
9、根据权利要求8的方法,其中所用的阴离子源(V)是在去除H+离子时能获得阴离子的化合物。
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MY154959A (en) | 2005-11-17 | 2015-08-28 | Lucite Int Uk Ltd | Carbonylation of ethylenically unsaturated compounds |
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AU2007327051B2 (en) | 2006-12-02 | 2013-07-04 | Lucite International Uk Limited | Novel carbonylation ligands and their use in the carbonylation of ethylenically unsaturated compounds |
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DE2541640C2 (de) | 1975-09-18 | 1983-12-08 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von 5-Cyanvaleriansäure bzw. ihren Estern |
US4508660A (en) * | 1983-03-14 | 1985-04-02 | E. I. Du Pont De Nemours And Company | Carbonylation of olefinically unsaturated nitriles and acids using a sulfone solvent |
US4950778A (en) | 1988-12-12 | 1990-08-21 | E. I. Du Pont De Nemours & Company | Manufacture of 5-cyanovaleric acid and its esters using cyclic cosolvents |
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