CN1045300C - 含磷环芳烃、其制备方法及其应用 - Google Patents

含磷环芳烃、其制备方法及其应用 Download PDF

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CN1045300C
CN1045300C CN94192576A CN94192576A CN1045300C CN 1045300 C CN1045300 C CN 1045300C CN 94192576 A CN94192576 A CN 94192576A CN 94192576 A CN94192576 A CN 94192576A CN 1045300 C CN1045300 C CN 1045300C
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R·帕西罗
M·勒帕
H·-J·努伊帕
E·兰古思
P·M·洛兹
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Abstract

通式(Ⅰ)所示含磷的环芳烃及其制备方法以及利用铑-或钌-羰基配合物通过C3-C20-烯烃的羰基化制备醛的方法，其中使用式(Ⅰ)所示含磷的环芳烃作配位体。

Description

含磷环芳烃、其制备方法及其应用
本发明涉及含磷的环芳烃(phosphorhaltige Calixarene)。
人们把羰基化反应理解为：通过有机化合物与一氧化事并优选另一种反应物—特别是氢—在催化剂存在下反应来生产含氧产物。一种技术上特别重要的反应是链烯烃羰基化反应，它通过与一氧化碳和氢反应生成比离折物多一个碳原子的醛。作为催化剂使用第Ⅷ族过渡金属的配合物，该配合物含有含磷的配位体，例如亚磷酸盐类(参见J.Falbe,New Synthesiswith Carbon Monoxide,Springer Verlag,New York 1980)。
在近几年，除钴催化剂外，用于低级α-烯烃羰基化愈来愈多的铑催化剂获得重要意义，因为铑催化剂使反应在低压下进行。磷配位体通常使用过量的三苯膦，此时高的配位体/铑比率是必需的，这样才能提高商业上所需的n-醛产品的反应选择性。
近几年进行了实验，找到对羰基化更有效的磷配位体。除了不同取代的亚磷酸盐外，也对亚磷酸盐作为催化剂的适宜性进行了探讨。亚磷酸盐在其与一过渡金属中心配位时，产生的催化剂活性有所提高，但这种催化剂体系的寿命由于亚磷酸盐配位体的强水解敏感性而不令人满意。由双芳基二醇取代的螯合多亚磷酸盐，如在EP-A214622所描叙的，据说具有急剧减少的水解敏感性。这种配位体的铑配合物应构成最具活性的羰基化催化剂。EP-A213639记述了螯合物-双亚磷酸盐，该螯合物—双亚磷酸盐在一个磷原子上有二个有机基亚磷酸盐官能度，在第二个磷原子上有三个有机基亚磷酸盐官能度。另外，由EP-A155508还已知，在立体受阻的烯烃如异丁烯的铑催化羰基化时，用了双芳基二醇取代的单亚磷酸盐。EP-A472071中公开了螯合物-双亚磷酸盐-配位体，其中双芳基二醇是经由双亚磷酸酯-桥键与烷二醇或o-芳基二醇联结在一起的。二醇-和三醇-取代的单亚磷酸盐及其羰基化插入物终于在EP-A149894、EP-A96988和EP-A96986中予以记叙。
在烯烃羰基化时，按一氧化碳加在双键的位置而定，生成直链醛(称为n-醛)或支链醛(所谓的异-醛)。这可概括地用反应式(1)表示：
Figure C9419257600071
但现在通常希望，在羰基化产物中n-醛部分(下面以n-部分表示)尽可能比异醛部分多，因为在将醛进一步加工成增塑剂-醇和增塑剂时，n-醛能生成具特别优良增塑剂性能的产品(参见例如US-A4426542)。
在使用前述现有技术的螯合物-双亚磷酸盐-配位体时，在进行烯烃铑催化羰基化时可得到具有很高n-部分(最高达96％)的羰基化产物。
本发明的任务是，找到烯烃铑催化或钌催化羰基化用的配位体，借助该配位体可使羰基化产物中的n-部分进一步地提高。
与此相应的是通式(Ⅰ)所示含磷的环芳烃(Calixarene)：
Figure C9419257600081
式中n为2至4的整数，R1为氢、C1-C20-烷基、C1-C20-烷氧基、磺酸盐基或羧酸盐基，R2可同可不同，并为氢或C1-C20-烷基，和X为氢、C1-C20-烷基、C1-C20-烷氧基，或者未取代的或以1至3个C1-C20-烷基、C1-C20-烷氧基、磺酸盐基、羧酸盐基、C1-C20-烷硫基和/或C2-C20-二烷基氨基取代的苯基或苯氧基。
另外，找到一种制备式Ⅰ所示含磷环芳烃的方法，其特征是，使通式Ⅳ的环芳烃与通式Ⅴ的磷化合物在碱存在下反应，式Ⅳ中，n和基团R2和R4符合上述含义，
             XPHal2                Ⅴ式Ⅴ中，X具有上述含义，并且Hal为氟、氯、溴或碘。
另外，还找到一种用CO/H2-气体混合物，在具有含磷配位体的铑-或钌-羰基配合物和溶剂存在下，通过C2-C20-烯烃的羰基化来制备醛的方法，其特征在于，使用式Ⅰ的含磷环芳烃作配位体。
本发明的含磷环芳烃涉及羟基化环芳烃的环状的亚磷酸盐类和磷酸盐类(Phosphonite)。
在由通式Ⅰ所示的本发明含磷环芳烃中，R1基团可以是氢或C1-C20-烷基，优选为C1-C5-烷基，C1-C20-烷氧基，优选为C1-C6-烷氧基，磺酸盐基或羧酸盐基。作为R1基团特别优选的为叔-丁基、磺酸盐基或羧酸盐基。
式Ⅰ所示的本发明含磷环芳烃中，基团R2可同可不同，并可为氢或C1-C20-烷基，优选为C1-C6-烷基。R2特别优选为氢。
式Ⅰ所示的本发明含磷环芳烃中，X基团可以是氢、C1-C20-烷基(优选C1-C6-烷基)、C1-C20-烷氧基(优选C1-G5-烷氧基)或未取代的或用1至3个(优选用1或2个)C1-C20-烷基(优选C1-C5-烷基)、C1-C20-烷氧基(优选C1-C6-烷氧基)、C1-C20-烷硫基(优选C1-C6-烷硫基)、C2-C20-(优选C2-C10-)二烷基氨基、磺酸盐基或羧酸盐基取代的苯基或苯氧基。优选的含磷环芳烃是其中X基团为通式Ⅱ所示苯氧基者：
式中基团R3和R4可同可不同，并可为氢、C1-C20-(优选C1-C5-)烷基、C1-C20-(优选C1-C5-)烷氧基、C1-C20-(优选C1-C5-)烷硫基和/或C2-C20-(优选C2-C10-)二烷基氨基，其中R4基团还另可为磺酸盐基或羧酸盐基。
在本发明环芳烃衍生物中，磺酸盐基和羧酸盐基不仅可以质子化的形式存在，也就是作为磺酸基团或羧酸基团存在，优选的是这种环芳烃，其中这些基团以盐的形式存在，例如作为碱金属盐，碱土金属盐或鎓盐，特别是作为铵盐或鏻盐。在本发明含磷环芳烃中，磺酸盐基或羧酸盐基的存在提高了其水溶性，并以这种方式促进了在含水介质中进行羰基化。
式Ⅲ示出特别优选的含磷环芳径：
Figure C9419257600111
本发明的含磷环芳烃可经通式Ⅳ所示带羟基的环芳烃与通式Ⅴ所示的磷化合物在碱存在下进行反应而制得，式Ⅳ中，n和基团R1和R2具有上述含义，
           XPHal2        Ⅴ式Ⅴ中，X基团具有上述含义，并且Hal为氟、氯、溴或碘，优选为氯。
由对位上取代的酚和醛(优选甲醛)生成的环状缩合产物称作环芳烃(参见Chemie in unserer Zeit25,195(1991))。它们可按本身已知的方法制备，例如在Gutsche,“Calixarenes”,Kapitel2,S.27-66，化学皇家协会，Cambridge1989所记叙者。
制备环芳烃亚磷酸盐(Calixarenphosphite)所需的式Ⅴ所示含磷化合物可按本身为已知的方法(参见Houben Weyl,Methoden derOrg.Chemie BandⅫ/2,Kapitel2,Thieme,Stuttgart1964),例如通过三卤化磷，如三氯化磷、三溴化磷或三碘化磷，与醇或酚在碱，如碱金属氢氧化物或碱土金属氢氧化物或其碳酸盐或优选权胺存在下进行反应来制备。
制备环芳烃膦酸盐(Calixarenphosphonite)所需的式Ⅴ所示含磷化合物，同样可按已知方法(参见Houben-Weyl,Methoden derOrg.Chemie BandⅫ/1，S.302-318,Thieme Stuttgart1963)，例如通过三卤化磷(如三氯化磷)与芳族化合物，如苯，在Friedel-Crafts-催化剂如氯化铝存在下，进行反应而生产出来。
为制备本发明的环芳烃衍生物，可使相关的环芳烃Ⅳ与每所用环芳烃单体单元的含磷化合物Ⅴ优选以化学计算量进行反应。化学式单元，如它在方括号内按式Ⅳ所描叙的，被定义为环芳烃单体单元。
环芳烃Ⅳ与磷化合物Ⅴ是在碱存在下进行反应的。
作为碱可使用无机碱，例如碱金属或碱土金属的氧化物、碱金属或碱土金属的氢氧化物，或者碱金属或碱土金属的碳酸盐，但优选在叔胺存在下，优选具有3至30个碳原子的叔脂肪胺，例如用三甲基胺、三乙基胺、三正丙基胺、乙基二异丙基胺、三异丙基胺、三丁基胺等进行反应。以所用磷化合物Ⅴ的量为准计，碱按1至200的摩尔比添加，优选按1.5至100的摩尔比，并特别优选按2至10的摩尔比添加。
制备本发明的环芳烃衍生物适宜的方式是在溶剂中进行。溶剂可用在反应条件下是惰性的所有溶剂，优选芳族烃如苯、甲苯、二甲苯，或者醚如二乙基醚、二异丙基醚、甲基叔丁基醚、四氢呋喃、二噁烷、乙二醇二甲基醚等。
一般，在温度为-40℃至100℃时进行反应。反应使用的压力一般不是关键性的，但适宜在大气压时或在反应体系本身压力下工作。
本发明的含磷环芳烃在铑或钌催化的C3-C20-烯烃的羰基化中用作铑和钌的配位体。作为烯烃可使用内部具有双键的烯烃，按照本方法优选羰基化α-烯烃。
铑和钌以本身属常规的方式以盐的形式，例如以铑或钌的乙酸盐或丙酮基丙酮酸盐的形式，以铑或钌的氧化物形式，或者以羰基铑(Rhodiumcarbonyle)或羰基钌(Rutheniumcarbonyle)的形式用于本发明的方法。用于本发明方法中的铑化合物或钌化合物的种类，一般不是关键的，因这些化合物在所用羰基化条件下，在CO/H2-反应气体存在下，全都转化成具催化活性、均匀溶于羰基化介质中的含铑物质或含钌物质(Rhodium-oder Rutheniumspecies)，该含铑物质或含钌物质就被含磷环芳烃络合并稳定化。尽管在专业界关于其化学结构有一系列的推测，但所有的都还没有最后证实，所以这种催化活性的含铑物质和含钌物质的化学性能也不能最终得以弄清。
因为有催化活性的铑化合物或钌化合物是真正的催化剂，也就是说，反应时实际上不被消耗，并本身具有很高活性，很少量的铑化合物或钌化合物就足以对羰基化反应以满意的转化率进行催化。一般，在反应状态固定时铑-或钌与所用烯烃的摩尔比为1∶1000至1∶50000，优选1∶1000至1∶5000。
本发明含磷环芳烃，以所用铑或钌为准计，所用环芳烃与铑或钌的摩尔比一般为1∶1至100∶1，饱选从1∶1至20∶1，特别优选从1∶1至5∶1。
供羰基化用的CO/H2-混合物中，CO/H2-摩尔比可为20∶1至1∶20，优选1∶1至20∶1，并特别优选1∶1。
本发明的羰基化方法一般在溶剂存在下进行。作为溶剂，实际上可使用在羰基化条件下为惰性的所用溶剂，例如烃、酯或醇，但优选在羰基化时用相关的烯烃在羰基化时产生的醛作溶剂。另一种特别优选的溶剂是所谓的“高沸物”，该高沸物是由高沸化合物组成的混合物，如它在羰基化反应中作为副产物在一系列副反应中，如醇醛缩合、消除、歧化和加氢，由羰基化时产生的醛生成。这样的高沸物系列和种类及其生成方法在US-A4148830中对制备丁醛的情况予以示范性记叙。
本发明方法一般在30至150℃，优选从60至130℃，特别优选从90至110℃的温度下，并且一般在1×103至1×107Pa，优选从1×105至5×106Pa，并且特别优选从5×105至3×106Pa的压力下进行。
本发明的羰基化方法可以间歇方式进行，优选以连续方式进行。在这当中可使用本身已知的工艺技术，例如在US-A4148830、US-A4329511或EP-A313559中所记述者。
用本发明的含磷环芳烃作为催化活性的铑化合物或钌化合物的配位体，成功地在本发明的羰基化方法中出人意料地使羰基化产物的n-部分提高到99.5％。
实施例
制备含磷的环芳烃Ⅲ
阶段1：
Figure C9419257600151
使23.6g(0.1Mol)3,5-二叔丁基-4-羟基苯甲醚(可市购得到或按J.Am.Chem.Soc.77,1672(1955)制备)溶于500ml甲苯，并从此混合物中馏除50ml甲苯。冷却后的溶液在室温下掺加68.2ml(0.5Mol)三乙胺，接着定量加到预冷至-40℃的8.8ml(0.1Mol)三氯化磷溶于1L甲苯所成的溶液中。将所得溶液缓缓温热至室温，在室温下搅拌1小时，接着再以100℃加热10小时。将如此制得的化合物Ⅵ的溶液以此形式供阶段2用。
Figure C9419257600161
将32.4g(0.05Mo)环-4-芳烃(Calix-4-Aren)Ⅶ(可按下列文献制得：Gutsche“Calixarenes”，Kapitel2, Seite27-66)以粉末形式加到由阶段1所得化合物Ⅵ的溶液中，并将此混合物冷至-40℃。在此混合物中定量加入136.5ml(1Mol)三乙胺溶于500ml甲苯所成的溶液。将反应混合物慢慢温热至室温，在室温搅拌1小时，并在100℃继续搅拌10小时。接着，将沉淀出的氯化三乙基铵从反应液中过滤出来，并用甲苯洗涤。从合并后的甲苯抽提物中馏除甲苯，剩下淡褐色粘稠状残留物。用戊烷洗涤该残余物，再用400ml乙腈在沸腾回流下进行萃取。在部分留余物溶解以后，过滤分离出余下的粉末，用戊烷洗涤并干燥之。
1H-和13C-NMR-谱证明了式Ⅲ的结构。在31P-NMR-谱中以磷酸为标准，在121ppm处观察到一信号。
元素分析[实测值(理论值)]：C75.5％(76.2％)；H8.3％(8.9％)；O10.9％(9.9％)；P5.3％(5.1％)。
式Ⅲ所示物质的质谱在1176道尔顿处有主成分分子峰。
实施例2
1-辛烯的羰基化
在0.35L的压热器中，将由56.9g1-辛烯(508mmol)、0.032g(0.124mmol)铑[以Rh(CO)2(acac)配合物形式(acac=乙酰丙酮酸盐)]和0.7098g(0.604mmol)化合物Ⅲ溶于70mlTexanol(2,24-三甲基戊烷-l,3-二醇单异丁酸酯)所成溶液组成的混合物加热到100℃，并将CO/H2-混合物(体积比CO/H2=1/1)引入压热器，以此将压力调至2×106Pa，该压力在整个反应期间通过这种气体混合物的补充加压保持恒定。经8小时反应时间后，对羰基化的混合物进行气相色谱分析。分析结果列于下表。
                      表
内(int.)C8-烯烃  3,41％(重量) 0,0386Mol
1-辛烯  16,58″ 0,1879Mol
辛烷  7,84″ 0,0873Mol
2-丙基己醛  0,00″
2-乙基庚醛  0,00″
2-甲基辛醛  0,1l″ 0,001Mol
n-壬醛  21,84″ 0,1952Mol
Texanol  45,8″
其他(Sonstige)  0,0″
总合(Sonstige)  95,6″
转化率 63Mo1.-％
壬醛产率 39Mol.-％
辛烷产率 17Mol.-％
      选择性(以转化的1-辛烯为准计)
壬醛 61％
辛烷 27％
内烯烃 12％
1-壬醛与全部壬醛类的摩尔比为99.5∶0.5。
通过增加反应时间可进一步提高转化率，而不会在此情况下降低催化剂对n-醛的选择性。

Claims (11)

1．通式Ⅰ所示含磷的环芳烃
Figure C9419257600021
式中n是2至4的整数，
R1为氢、C1-C20烷基、C1-C20烷氧基、磺酸盐基或羧酸盐基，
R2可同可不同，并为氢或C1-C20烷基，和
X为氢、C1-C20烷基、C1-C20烷氧基，或未取代的或以1至3个
C1-C20烷基、C1-C20烷氧基、磺酸盐基、羧酸盐基、C1-C20烷
硫基和/或C2-C20二烷基氨基取代的苯基或苯氧基。
2．权利要求1所述的含磷环芳烃，其中X基是通式Ⅱ所述的苯氧基，式中，R3和R4可同可不同，并为氢、C1-C20烷基、C1-C20烷氧基、C1-C20烷硫基、和/或为C2-C20二烷基氨基，并且式中R4还另可为磺酸盐基或羧酸盐基。
3．权利要求1所述的含磷环芳烃，其中R1基为氢、C1-C6烷基，C1-C6烷氧基，磺酸盐基或羧酸盐基，R2为氢，并且X的含义为权利要求2中所提到者。
4．权利要求1所述的含磷环芳烃，其具有式Ⅲ结构：
Figure C9419257600031
5．制备权利要求1所述含磷环芳烃的方法，其特征在于，使通式Ⅳ所示环芳烃在碱存在下、并且在溶剂存在下、在-40℃至100℃之间的温度下，与通式Ⅴ所示的磷化合物反应，其中以所用磷化合物V的量为准计，碱按1至200的摩尔比添加，
Figure C9419257600041
式Ⅳ中，n和基团R1和R2的含义为权利要求1中所提到者，
             XPHal2                Ⅴ
式Ⅴ中X的含义为权利要求1中所提到者，并Hal为氟、氯、溴和碘。
6．权利要求5所述的方法，其特征在于，使用C3-C30三烷基胺作为所述碱。
7．制备醛的方法，通过C3-C20-烯烃羰基化利用CO/H2-气体混合物在具有含磷配位体的铑-或钌-羰基-配合物和溶剂存在下进行，其特征在于，使用权利要求1至4所述含磷的环芳烃作为配位体。
8．权利要求7所述的方法，其特征在于，所述羰基化反应在30至150℃温度和1×103至1×107Pa压力下进行。
9．权利要求7或8所述的方法，其特征在于，使用由各次所用烯烃的羰基化产生的醛作为溶剂。
10．权利要求7或8所述的方法，其特征在于，使用高沸点化合物作溶剂，该高沸点化合物是在羰基化进程中通过缩合在羰基化时生成的醛产生的。
11．权利要求7至10所述的方法，其特征在于，对α-烯烃进行羰基化。
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