CN118255813A - 具有顺式位置的取代基的二亚磷酸酯 - Google Patents
具有顺式位置的取代基的二亚磷酸酯 Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 17
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 8
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- BUYVJWVYKPKZEX-DWVXZKBMSA-N (1z,5z)-cycloocta-1,5-diene;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\1C\C=C/CC\C=C/1 BUYVJWVYKPKZEX-DWVXZKBMSA-N 0.000 claims description 3
- POILWHVDKZOXJZ-ONEGZZNKSA-M (E)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C/C(C)=O POILWHVDKZOXJZ-ONEGZZNKSA-M 0.000 claims description 3
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 3
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 238000007037 hydroformylation reaction Methods 0.000 abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000003446 ligand Substances 0.000 description 5
- -1 olefin compound Chemical class 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QMMOXUPEWRXHJS-HWKANZROSA-N (e)-pent-2-ene Chemical compound CC\C=C\C QMMOXUPEWRXHJS-HWKANZROSA-N 0.000 description 2
- QMMOXUPEWRXHJS-HYXAFXHYSA-N (z)-pent-2-ene Chemical compound CC\C=C/C QMMOXUPEWRXHJS-HYXAFXHYSA-N 0.000 description 2
- RRTJOAHJZQVSSE-UHFFFAOYSA-N 1,3,2-dioxaphosphepine Chemical compound C=1C=COPOC=1 RRTJOAHJZQVSSE-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 235000010292 orthophenyl phenol Nutrition 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005669 hydrocyanation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
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Abstract
本发明涉及具有顺式位置的取代基的二亚磷酸酯及其在加氢甲酰化中的用途。
Description
技术领域
本发明涉及具有顺式位置的取代基的二亚磷酸酯及其在加氢甲酰化中的用途。
背景技术
含磷化合物作为配体在各种反应中发挥着至关重要的作用，例如在氢化、氢氰化以及加氢甲酰化中。
烯烃化合物、一氧化碳和氢气之间在催化剂存在下产生多一个碳原子的醛的反应称为加氢甲酰化或羰基合成(Oxierung)。元素周期表第VIII族过渡金属的化合物通常用作这些反应中的催化剂。已知的配体例如为膦、亚磷酸酯和亚膦酸酯类的化合物，其各自具有三价磷PIII。关于烯烃的加氢甲酰化现状的良好概述可以在R.Franke,D.Selent,A.”Applied Hydroformylation“,Chem.Rev.,2012(112),11,5675–5732,DOI:10.1021/cr3001803中找到。
发明内容
本发明的技术目的是提供一种化合物，利用该化合物可以在烯烃的加氢甲酰化中实现增加的n-选择性。这意味着，n-产物与iso-产物的比率应增加。
该目的通过根据权利要求1的化合物来实现。
根据式(I)的化合物：
其中R1、R2、R3、R4选自：-(C1-C12)-烷基、-O-(C1-C12)-烷基，并且
R5选自：-(C1-C12)-烷基、-O-(C1-C12)-烷基、-Ph。
在一个实施方案中，R1选自：-CH3、-OCH3、-tBu。
在一个实施方案中，R1代表-tBu。
在一个实施方案中，R2选自：-CH3、-OCH3、-tBu。
在一个实施方案中，R2代表-tBu。
在一个实施方案中，R3选自：-CH3、-OCH3、-tBu。
在一个实施方案中，R3代表-tBu。
在一个实施方案中，R4选自：-CH3、-OCH3、-tBu。
在一个实施方案中，R4代表-tBu。
在一个实施方案中，R5选自：-CH3、-OCH3、-tBu、-Ph。
在一个实施方案中，R5代表-Ph：
在一个实施方式中，该化合物具有结构(1)：
除了该化合物本身之外，还要求保护其中使用前述化合物的方法。
方法，其包括以下方法步骤：
a)预先放置烯烃；
b)添加前述化合物；
c)添加Rh化合物；
d)供应H2和CO；
e)将来自a)至d)的反应混合物加热，由此将烯烃转化为醛。
在该方法的一个变体中，Rh化合物选自：Rh(acac)(CO)2、[(acac)Rh(COD)](Umicore，acac＝乙酰丙酮阴离子；COD＝1,5-环辛二烯)、Rh4CO12。
在该方法的一个变体中，Rh化合物是Rh(acac)(COD)。
在该方法的一个变体中，在方法步骤d)中以1至6MPa(10至60巴)的压力供应H2和CO。
在该方法的一个变体中，在方法步骤d)中以1.5至4.5MPa(15至45巴)的压力供应H2和CO。
在该方法的一个变体中，在方法步骤e)中将反应混合物加热至80℃至160℃的温度。
在该方法的一个变体中，在方法步骤e)中将反应混合物加热至100℃至140℃的温度。
具体实施方式
下面应借助实施例更详细地解释本发明。
合成(1)：2,4,8,10-四叔丁基-6-((3,3',5,5'-四叔丁基-2'-(((4S,5R)-4,5-二
苯基)-1,3,2-二氧磷杂环戊烷-2-基)氧基)-[1,1'-联苯]-2-基)氧基)二苯并[d,f][1,3,
2]二氧磷杂环庚二烯
在-20℃下向3,3',5,5'-四叔丁基-2'-((2,4,8,10-四叔丁基二苯并[d,f][1,3,2]二氧磷杂环庚二烯-6-基)氧基)-[1,1'-联苯]-2-醇(0.430g，0.506mmol)在THF(3ml)中的溶液中滴加正丁基锂溶液(0.532M的己烷溶液，1.00ml，0.532mmol)。20分钟后，将反应溶液加热至0℃，随后向其中逐滴加入(4R,5S)-2-氯-4,5-二苯基-1,3,2-二氧磷杂环戊烷(0.148g，0.532mmol)在THF(2ml)中的溶液。在室温下搅拌过夜后，真空除去溶剂，将甲苯(6ml)加入到白色残余物中，过滤出不溶解的成分。将滤液再次真空浓缩并将粗产物在60℃下干燥。为了纯化，将其溶解在处于沸点的乙腈(5ml)中，冷却后过滤出沉淀的沉淀物，并分离出产物，其为白色固体(0.22g，0.202mmol，40％产率)。
元素分析(以C70H92O6P2＝1091.448g/mol计算):C＝77.22％(77.03％)；H＝8.45％(8.50％)；P＝5.68％(5.68％).
ESI-TOF HRMS:m/z＝1090.6369
[M++H],计算值m/z＝1091.6448(实际值1091.6442)
[M++Na],计算值m/z＝1113.6262(实际值1113.6256)
合成(2)：2,4,8,10-四叔丁基-6-((3,3',5,5'-四叔丁基-2'-(((4R,5R)-4,5-二
苯基)-1,3,2-二氧磷杂环戊烷-2-基)氧基)-[1,1'-联苯]-2-基)氧基)二苯并[d,f][1,3,
2]二氧磷杂环庚二烯
在-20℃下向3,3',5,5'-四叔丁基-2'-((2,4,8,10-四叔丁基二苯并[d,f][1,3,2]二氧磷杂环庚二烯-6-基)氧基)-[1,1'-联苯]-2-醇(0.474g，0.558mmol)在THF(3ml)中的溶液中滴加正丁基锂溶液(0.533M的己烷溶液，1.10ml，0.587mmol)。20分钟后，将反应溶液加热至0℃，随后向其中逐滴加入(4R,5R)-2-氯-4,5-二苯基-1,3,2-二氧磷杂环戊烷(0.163g，0.587mmol)在THF(3ml)中的溶液。在室温下搅拌过夜后，真空除去溶剂，将甲苯(7ml)加入到白色残余物中，过滤出不溶解的成分。将滤液再次真空浓缩并将粗产物在60℃下干燥。为了纯化，将其溶解在处于沸点的乙腈中，冷却后过滤出沉淀的沉淀物，并分离出产物，其为白色固体(0.39g，0.357mmol，64％产率)。
元素分析(以C70H92O6P2＝1091.448g/mol计算)：C＝77.22％(77.03％)；H＝8.57％(8.50％)；P＝5.50％(5.68％).
ESI-TOF HRMS:m/z＝1090.6369
[M++H],计算值m/z＝1091.6448(实际值1091.6449)
[M++Na],计算值m/z＝1113.6262(实际值1113.6276)
催化实验
加氢甲酰化在瑞士Lengau的Premex Reactor AG公司的配备有保压阀、气体流量计、充气搅拌器和压力移液管的200ml高压釜中进行。为了最大限度地减少水分和氧气的影响，用作溶剂的甲苯在Pure Solv.MD-7系统中纯化和在氩气下储存。用作底物的烯烃顺/反-2-戊烯(Aldrich)在钠上回流加热并在氩气下蒸馏。将催化剂前体和配体各自的甲苯溶液在高压釜中在氩气气氛下混合。Rh(acac)(COD)(Umicore，acac＝乙酰丙酮阴离子；COD＝1,5-环辛二烯)用作催化剂前体。将高压釜在12巴下在搅拌(1500转/分钟)的同时加热至20巴的最终压力。达到反应温度后，使用压力移液管中设定的超压将烯烃压入高压釜中。反应在恒压(20巴)(来自荷兰Bronkhorst公司的后续压力调节器)下进行4小时。反应时间结束后，将高压釜冷却至室温，在搅拌的同时减压并用氩气吹扫。关闭搅拌器后立即取出1ml反应混合物，用10ml戊烷稀释并通过气相色谱分析：HP 5890系列II plus，PONA，50m x 0.2mmx 0.5μm。
使用化合物(1)和(2)进行实验。
化合物(2)在此用作对比配体。
催化实验结果
[Rh]：100ppm，p：20巴，T：120℃；时间：4小时；Rh:L＝1:2
表：顺/反-2-戊烯的加氢甲酰化
| 配体 | n-选择性[％] |
| (1)* | 83.6 |
| (2) | 74.1 |
*根据本发明的化合物
进行的实验证明，根据本发明的化合物实现了所提出的目的。
Claims (15)
1.根据式(I)的化合物：
其中R1、R2、R3、R4选自：-(C1-C12)-烷基、-O-(C1-C12)-烷基，并且
R5选自：-(C1-C12)-烷基、-O-(C1-C12)-烷基、-Ph。
2.根据权利要求1所述的化合物，
其中R1选自：-CH3、-OCH3、-tBu。
3.根据权利要求1或2中任一项所述的化合物，
其中R1代表-tBu。
4.根据权利要求1至3中任一项所述的化合物，
其中R2选自：-CH3、-OCH3、-tBu。
5.根据权利要求1至4中任一项所述的化合物，
其中R2代表-tBu。
6.根据权利要求1至5中任一项所述的化合物，
其中R3选自：-CH3、-OCH3、-tBu。
7.根据权利要求1至6中任一项所述的化合物，
其中R3代表-tBu。
8.根据权利要求1至7中任一项所述的化合物，
其中R4选自：-CH3、-OCH3、-tBu。
9.根据权利要求1至8中任一项所述的化合物，
其中R4代表-tBu。
10.根据权利要求1至9中任一项所述的化合物，
其中R5选自：-CH3、-OCH3、-tBu、-Ph。
11.根据权利要求1至10中任一项所述的化合物，
其中R5代表-Ph。
12.根据权利要求1至11中任一项所述的化合物，
其中所述化合物具有结构(1)：
13.方法，其包括以下方法步骤：
a)预先放置烯烃；
b)添加根据权利要求1至12中任一项所述的化合物；
c)添加Rh化合物；
d)供应H2和CO；
e)将来自a)至d)的反应混合物加热，由此将烯烃转化为醛。
14.根据权利要求13所述的方法，
其中Rh化合物选自：Rh(acac)(CO)2、[(acac)Rh(COD)](Umicore，acac＝乙酰丙酮阴离子；COD＝1,5-环辛二烯)、Rh4CO12。
15.根据权利要求13或14中任一项所述的方法，
其中Rh化合物为Rh(acac)(COD)。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP22216759.5A EP4393900A1 (de) | 2022-12-27 | 2022-12-27 | Diphosphite mit cis-ständigen substituenten |
| EP22216759.5 | 2022-12-27 |
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| DE102006058682A1 (de) * | 2006-12-13 | 2008-06-19 | Evonik Oxeno Gmbh | Bisphosphitliganden für die übergangsmetallkatalysierte Hydroformylierung |
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- 2022-12-27 EP EP22216759.5A patent/EP4393900A1/de active Pending
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| EP4393900A1 (de) | 2024-07-03 |
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