CN108689823A - 使用三联苯-2`-基氧基-s-二萘并二氧磷杂环庚三烯将环辛二烯加氢甲酰化的方法 - Google Patents

使用三联苯-2`-基氧基-s-二萘并二氧磷杂环庚三烯将环辛二烯加氢甲酰化的方法 Download PDF

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CN108689823A
CN108689823A CN201810314874.2A CN201810314874A CN108689823A CN 108689823 A CN108689823 A CN 108689823A CN 201810314874 A CN201810314874 A CN 201810314874A CN 108689823 A CN108689823 A CN 108689823A
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octadiene
cyclo
hydroformylation
cycloheptatriene
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K.M.迪巴拉
R.弗兰克
D.弗里达格
D.黑斯
D.泽伦特
A.伯纳
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Abstract

本发明涉及使用4‑([1,1':3',1''‑三联苯]‑2'‑基氧基)‑S‑二萘并[2,1‑d:1',2'‑f][1,3,2]二氧磷杂环庚三烯将环辛二烯加氢甲酰化的方法。

Description

使用三联苯-2'-基氧基-S-二萘并二氧磷杂环庚三烯将环辛 二烯加氢甲酰化的方法
技术领域
本发明涉及使用4-([1,1':3',1''-三联苯]-2'-基氧基)-S-二萘并[2,1-d:1',2'-f][1,3,2]二氧磷杂环庚三烯将环辛二烯（COD）加氢甲酰化的方法。
背景技术
含磷化合物作为配体在许多反应中起到关键作用。所述化合物包括用于氢化、氢氰化，尤其是加氢甲酰化的亚磷酸酯配体，即包含P-O键的化合物。
在催化剂存在下烯烃化合物、一氧化碳和氢气之间反应产生多一个碳原子的醛被称作加氢甲酰化或羰基合成法。在这些反应中，通常使用元素周期表第VIII族的过渡金属的化合物作为催化剂。已知配体是例如选自各自具有三价磷PIII的膦、亚磷酸酯和亚膦酸酯（Phosphonite）类的化合物。烯烃的加氢甲酰化现状的优秀综述可见于R. Franke、D.Selent、A. Börner, "Applied Hydroformylation", Chem. Rev., 2012, DOI:10.1021/cr3001803。
发明内容
本发明的目的是提供将环辛二烯加氢甲酰化的方法，其提供环辛二烯的良好转化率。
通过根据权利要求1的方法实现该目的。
将环辛二烯加氢甲酰化的方法，其包括方法步骤：
a) 预先装载环辛二烯；
b) 添加络合物，其包含：
- 选自Rh、Ru、Co、Ir的金属原子，和
- 具有结构(1)的配体：
；或
添加包含选自Rh、Ru、Co、Ir的金属原子的络合物前体和具有结构(1)的化合物：
c) 供入H2和CO，
d) 加热所述反应混合物，由此将所述环辛二烯转化成醛。
在此，方法步骤a)至d)可以以任意顺序进行。
在该方法的一个变体中，该金属原子是Rh。
在该方法的一个变体中，该络合物前体包含环辛二烯。
在该方法的一个变体中，该络合物前体是[(acac)Rh(COD)]。
在这种情况下，“acac”是乙酰丙酮阴离子且“COD”是环辛二烯。
在该方法的一个变体中，在方法步骤d)中将反应混合物加热到50℃至70℃的温度。
具体实施方式
下面通过实施例详细阐释本发明。
分析
色谱法
在来自Macherey-Nagel GmbH & Co, Düren公司的60 M硅胶（0.040-0.063 mm）上用1.6巴的最大压力进行经由“快速色谱法”的制备型液相色谱分离。在来自Merck KGaA,Darmstadt公司的Geduran Si 60硅胶（0.063-0.200 mm）上进行无加压的分离。用作洗脱剂的溶剂（乙酸乙酯（技术级）、环己烷（技术级））预先在旋转蒸发器上通过蒸馏提纯。
对于薄层色谱法（DC），使用来自Merck KGaA, Darmstadt公司的现成PSC硅胶60F254板。根据所用洗脱剂混合物，给出Rf值。为了将该DC板染色，使用铈/钼磷酸溶液作为浸渍剂。铈/钼磷酸试剂：5.6克钼磷酸、2.2克四水合硫酸铈(IV)和13.3克浓硫酸在200毫升水中。
气相色谱法（GC/GCMS）
借助来自Shimadzu, Japan公司的GC-2010气相色谱仪进行产物混合物和纯物质的气相色谱研究（GC）。在来自Agilent Technologies, USA公司的HP-5石英毛细管柱（长度：30m；内径：0.25 mm；共价结合的固定相的薄膜厚度：0.25 μm；载气：氢气；注射器温度：250℃；检测器温度：310℃；程序：“硬（hart）”方法：开始温度50℃ 1分钟，加热速率：15℃/min，最终温度290℃ 8分钟）上进行测量。借助与来自Shimadzu, Japan公司的GCMS-QP2010质量检测器结合的GC-2010气相色谱仪记录产物混合物和纯物质的气相色谱-质谱（GCMS）。在来自Agilent Technologies, USA公司的HP-1石英毛细管柱（长度：30 m；内径：0.25 mm；共价结合的固定相的薄膜厚度：0.25 μm；载气：氢气；注射器温度：250℃；检测器温度：310℃；程序：“硬”方法：开始温度50℃ 1分钟，加热速率：15℃/min，最终温度290℃ 8分钟；GCMS：离子源温度：200℃）上进行测量。
熔点
借助来自HW5, Mainz公司的SG 2000熔点测定仪器测量熔点并且未校正。
元素分析
在Johannes Gutenberg-Universität Mainz的有机化学系的分析部门中在来自Foss-Heraeus, Hanau公司的Vario EL Cube上进行元素分析。
质谱法
在来自Waters Micromasses, Milford, Massachusetts公司的QTof Ultima 3上进行所有电喷雾电离测量（ESI+）。在来自ThermoFinnigan, Bremen公司的MAT 95 XL扇形场仪器类型的仪器上测量EI质谱和高分辨率EI谱。
NMR谱法
在来自Bruker, Analytische Messtechnik, Karlsruhe公司的AC 300或AV II 400型多核共振谱仪上进行NMR谱法研究。所用溶剂是CDCl3。使用来自Cambridge IsotopesLaboratories, USA公司的NMR Solvent Data Chart根据未氘化溶剂的残留含量校准1H和13C谱。借助H,H-COSY、H,H-NOESY、H,C-HSQC和H,C-HMBC谱进行一些1H和13C信号的赋值。化学位移作为以ppm为单位的δ值给出。关于NMR信号的多重性，使用下列缩写：s（单峰）、bs（宽单峰）、d（双重峰）、t（三重峰）、q（四重峰）、m（多重峰）、dd（双重双峰）、dt（双重三峰），tq（三重四峰）。所有偶合常数J与包括的键数一起以赫兹（hz）为单位给出。信号赋值中给出的编号对应于式图中所示的编号，其不必对应于IUPAC命名。
一般程序说明
所有制备操作使用Schlenk技术用氩气作为保护性气体进行。甲苯和四氢呋喃用PureSolv MD-7 System提纯并在使用前储存在氩气下。三乙胺在使用前在氩气下从羰游基钠（Natiumketyl）中蒸馏。三氯化磷（Aldrich）在使用前在氩气下蒸馏。所有制备操作在经加热的容器中进行。在Bruker Avance 300或Bruker Avance 400上进行核磁共振谱的记录，在Agilent GC 7890A上进行气相色谱分析，在Leco TruSpec CHNS和Varian ICP-OES 715上进行元素分析，并在Thermo Electron Finnigan MAT 95-XP和Agilent 6890 N/5973仪器上进行ESI-TOF质谱法，在Teledyne Isco Combiflash Rf+上进行半自动柱色谱法。
合成
a) (蒽-9-基氧基)二氯磷烷（前体）
在10℃下在90分钟内向PCl3（5.16克；37.6毫摩尔）在THF（25毫升）中的搅拌溶液中逐滴加入蒽酮（2.03克；10.44毫摩尔）和三乙胺（2毫升）在THF（80毫升）中的混合物。在静置整夜后过滤，滤液在真空中变干并将所得残留物置于甲苯（50毫升）中。再过滤，在真空中除去溶剂，该黄色残留物在50℃/0.1毫巴下干燥。随后，所得固体在室温下与己烷（30毫升）一起搅拌整夜。过滤，滤饼再用己烷（3 x 20毫升）洗涤并干燥。产量：2.27 g (73%). 31P-NMR(CD2Cl2): 202.5 (s) ppm。
b) 4-([1,1':3',1''-三联苯]-2'-基氧基)-S-二萘并[2,1-d:1',2'-f][1,3,2] 二氧磷杂环庚三烯（配体1）
在-20℃下在搅拌下向2,6-二苯基苯酚（0.568克；2.30毫摩尔）在THF（7毫升）中的溶液中加入正丁基锂在庚烷（7.2毫升；2.30毫摩尔）中的0.32M溶液。搅拌20分钟，使其达到室温，将所得溶液在搅拌下逐滴加入冷却至-20°C的4-氯-S-二萘并[2,1-d:1',2'-f][1,3,2]二氧磷杂环庚三烯（0.849克；2.42毫摩尔）在THF（8毫升）中的溶液。在-20°C下搅拌20分钟，随后在室温下过夜。在真空中除去溶剂，残余物置于甲苯（14毫升）中，过滤，浓缩至干，所得固体在50℃/0.1毫巴下干燥1小时。在除去溶剂和在50℃/0.1毫巴下干燥3小时后，通过柱色谱法（己烷/甲苯，梯度己烷100 → 0 %; 洗脱剂的1:2混合物的R f = 0.6）后处理产生1.066克（1.90毫摩尔；82%）。元素分析（对C38H25O3P的计算值 = 560.586 g/mol）: C 81.30(81.42); H 4.71 (4.49); P 5.56 (5.53) %. ESI-TOF/HRMS: m/e 561.16060 (M+H)+。
31P-NMR (CD2Cl2): 146.4 (s) ppm。
1H-NMR (CD2Cl2): 5.97 (d, J HH= 8.8 Hz, 1H); 6.86 (d, J HH= 8.8 Hz, 1H);7.22-7.32 (m, 4H); 7.34-7.39 (m, 1H); 7.42-7.50 (m, 4H); 7.54-7.64 (m, 10H);7.71 (d, J HH= 8.8 Hz, 1H); 7.88-7.98 (m, 3H) ppm。
13C-NMR (CD2Cl2):121.9; 122.2; 122.4; 124.6; 125.1; 125.2; 125.5;126.4; 126.6; 127.0; 127.1; 127.); 128.6; 128.7; 128.9; 129.2; 129.4; 130.1;130.6; 131.0; 131.2; 131.4; 131.9; 132.5; 132.9; 136.4; 138.8; 146.4 (d, J CP=8.3 Hz); 147.0; 148.2 (d, J CP= 4.8 Hz) ppm。
c) 4-(蒽-9-基氧基)-S-二萘并[2,1-d:1',2'-f][1,3,2]二氧磷杂环庚三烯（配 体2）
向在-20℃下搅拌的蒽酮（0.447克；2.30毫摩尔）在THF（5毫升）中的悬浮液中逐滴加入正丁基锂在庚烷（7.2毫升；2.30毫摩尔）中的0.32M溶液。使该混合物达到室温，然后在搅拌下逐滴加入4-氯-S-二萘并[2,1-d:1',2'-f][1,3,2]二氧磷杂环庚三烯（0.807克；2.30毫摩尔）在THF（6毫升）中的溶液。搅拌整夜并过滤。在真空中除去滤液的挥发性成分，将所得黄色固体置于甲苯（10毫升）中，经硅胶涂覆的G4玻璃料过滤并将滤液在真空中浓缩。所得固体在50℃/0.1毫巴下干燥3小时。通过柱色谱法（己烷/CH2Cl2，梯度己烷100 → 0 %; 洗脱剂的1:1混合物的R f = 0.5）后处理产生0.55克（1.08毫摩尔；47%）纯产物。元素分析（对C34H21O3P的计算值 = 508.511 g/mol）: C 80.80 (80.31); H 3.89 (4.16); P 6.02(6.09) %. ESI-TOF/HRMS: m/e 509.12979 (M+H)+。
31P-NMR (CD2Cl2): 149.7 (s) ppm。
1H-NMR (CD2Cl2): 7.37-7.42 (m, 2H); 7.51-7.65 (m, 9H); 7.87 (d, J HH=8.9 Hz, 1H); 8.02-8.14 (m, 6H); 8.40 (s, 1H); 8.57 (d, J HH= 8.9 Hz, 2H) ppm。
13C-NMR (CD2Cl2): 122.1; 122.4; 123.0; 123.6; 123.8; 124.7; 125.0;125.7; 126.1; 126.5; 127.0; 127.3; 128.6; 128.9; 130.6; 131.1; 131.9; 132.3;132.6; 133.1; 133.4; 143.5 (d, J CP= 6.1 Hz); 147.4 (d, J CP= 2.7 Hz); 148.3 (d,J CP= 5.2 Hz) ppm。
d) 2-([1,1':3',1''-三联苯]-2'-基氧基)-4,4,5,5-四甲基-1,3,2-二氧磷杂环 戊烷（配体3）
所需2,6-二苯基苯-1-氧基二氯膦如W. Maringgele, A. Meller, Phosphorus, Sulfur and Silicon 1994, 90, 235-241中所述制备。
向在0℃下搅拌的2,6-二苯基苯-1-氧基二氯膦（1.048克；3.018毫摩尔）在甲苯（18毫升）中的溶液中逐滴加入频哪醇（0.3405克；2.881毫摩尔）和三乙胺（3.65毫升）在甲苯（12毫升）中的混合物。使该混合物达到室温，搅拌整夜并过滤。浓缩滤液，所得残留物从热庚烷中结晶多次。产量：0.295克（0.752毫摩尔；26%）。元素分析（对C24H25O3P的计算值 =392.41 g/mol）: C 73.31 (73.45); H 6.42 (6.42); P 7.53 (7.89) %. ESI-TOF/HRMS:m/e 393.16143, (M+H)+。
31P-NMR (CD2Cl2): 142.9 (s) ppm。
1H-NMR (CD2Cl2): 1.17 (s, 6H), 1.31 (s, 6H), 7.34-7.72 (m, 13H) ppm。
13C-NMR (CD2Cl2) δ 147.4 (d, J CP= 6.5 Hz); 139.4; 136.6; 130.9; 130.8;128.5; 127.6; 124.7; 85.3 (d, J CP= 8.0 Hz); 25.5; 24.8 ppm。
加氢甲酰化
在来自Premex Reactor AG, Lengau, 瑞士公司的配备有保压阀（Druckkonstanthaltung）、气体流量计、鼓泡搅拌器和压力吸移管的200毫升高压釜中进行加氢甲酰化反应。用作溶剂的甲苯使用Pure Solv MD-7 System提纯并储存在氩气下。
对于该实验，在高压釜中在氩气气氛下混合络合物前体（= 催化剂前体）和配体的溶液。使用[(acac)Rh(COD)]（Umicore，acac = 乙酰丙酮阴离子；COD = 1,5-环辛二烯）作为络合物前体。对于在100 ppm-m铑浓度下的实验，将5毫升4.32毫摩尔溶液置于高压釜中。随后，将与比率L/Rh = 5:1对应的质量的配体溶解和混合在20毫升甲苯中。向耐压吸移管中装入2.69克（24.86毫摩尔）COD-1,5。用合成气（Linde; H2（品质5.0）: CO（品质4.7）= 1:1）使该高压釜达到42巴压力并加热至60℃。在达到反应温度后，将二烯烃压到高压釜中。该反应在50巴恒压下进行（来自Bronkhorst, NL公司的后压力调节器（Nachdruckregler））。在反应时间经过后，将该高压釜冷却至室温，在搅拌的同时减压并用氩气吹扫。在关闭搅拌器后立即取出1毫升各反应混合物，用5毫升戊烷稀释并通过气相色谱法分析：HP 5890Series II plus, PONA, 50 m x 0.2 mm x 0.5 µm。
加氢甲酰化实验的结果汇集在下表中。给出的转化率在这种情况下包括单醛和二醛。
标准实验条件: [Rh] = 0.717 x 10-4 M，Rh/配体/COD-1,5 = 1:5:1151，溶剂甲苯。
表1:
配体 p [bar] T [℃] t [h] 转化率COD-1,5 [%]
1* 50 60 4 95
2 50 60 4 54
3 50 60 4 76
*根据本发明的方法。
如实验结果所示，通过本发明的方法实现该目的。

Claims (5)

1.将环辛二烯加氢甲酰化的方法，其包括方法步骤：
a) 预先装载环辛二烯；
b) 添加络合物，其包含：
- 选自Rh、Ru、Co、Ir的金属原子，和
- 具有结构(1)的配体：
；或
添加包含选自Rh、Ru、Co、Ir的金属原子的络合物前体和具有结构(1)的化合物：
c) 供入H2和CO，
d) 加热所述反应混合物，由此将所述环辛二烯转化成醛。
2.根据权利要求1的方法，
其中所述金属原子是Rh。
3.根据权利要求1或2任一项的方法，
其中所述络合物前体包含环辛二烯。
4.根据权利要求1至3任一项的方法，
其中所述络合物前体是[(acac)Rh(COD)]。
5.根据权利要求1至4任一项的方法，
其中在方法步骤d)中将所述反应混合物加热到50℃至70℃的温度。
CN201810314874.2A 2017-04-11 2018-04-10 使用三联苯-2`-基氧基-s-二萘并二氧磷杂环庚三烯将环辛二烯加氢甲酰化的方法 Pending CN108689823A (zh)

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