CN1045445C - 三芳基硼烷的制备 - Google Patents
三芳基硼烷的制备 Download PDFInfo
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- CN1045445C CN1045445C CN95193748A CN95193748A CN1045445C CN 1045445 C CN1045445 C CN 1045445C CN 95193748 A CN95193748 A CN 95193748A CN 95193748 A CN95193748 A CN 95193748A CN 1045445 C CN1045445 C CN 1045445C
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- triarylborane
- bph
- phenyl
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- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000009833 condensation Methods 0.000 claims abstract description 4
- 230000005494 condensation Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 150000002815 nickel Chemical class 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 12
- 238000005669 hydrocyanation reaction Methods 0.000 description 11
- ISBHMJZRKAFTGE-UHFFFAOYSA-N pent-2-enenitrile Chemical compound CCC=CC#N ISBHMJZRKAFTGE-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- -1 hexichol boron derivative Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 2
- ISBHMJZRKAFTGE-ONEGZZNKSA-N (e)-pent-2-enenitrile Chemical compound CC\C=C\C#N ISBHMJZRKAFTGE-ONEGZZNKSA-N 0.000 description 1
- GDCJAPJJFZWILF-UHFFFAOYSA-N 2-ethylbutanedinitrile Chemical compound CCC(C#N)CC#N GDCJAPJJFZWILF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CGXMHTSTPOVZJU-UHFFFAOYSA-N P(O)(O)O.CC=1C(=C(C=CC1)C)C Chemical compound P(O)(O)O.CC=1C(=C(C=CC1)C)C CGXMHTSTPOVZJU-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
从含有镍配合物和三芳基硼烷的催化剂残渣中制备三芳基硼烷，该方法是在减压下加热该配合物，和通过冷凝回收三芳基硼烷。
Description
发明领域
本发明涉及由通式为Ni(NC(CH2)4CN)2(NCBAr3)2的镍配合物制备三芳基硼烷，式中Ar为苯基或被含有1-4个碳原子的烷基取代的苯基，其中的烷基可以含有一个或多个氟原子。这些镍配合物可包含在催化剂残渣中，该残渣是在采用有机磷的镍配合物作催化剂和采用三芳基硼烷作助催化剂时，在烯烃氢氰化(例如丁二烯氢氰化)过程中产生的。
发明背景
King等人的美国专利3,798,256公开了采用镍配合物作催化剂和采用有机硼化合物作助催化剂，产生己二腈的3-戊烯腈氢氰化反应。这种氢氰化反应产生的催化剂残渣主要为Ni(NCR)4(NCBAr3)2，下文称作NCBC。Shook的美国专利4,082,811公开了采用氢氧化铵处理这种残渣以沉淀三芳基硼烷胺加成物的方法。用金属氢氧化物处理，可从加成物中回收三芳基硼烷-见Shook的美国专利4,134,923。
本发明是一种直接从催化剂残渣中回收三芳基硼烷助催化剂的方法。
发明概述
本发明是一种制备通式为BAr3的三芳基硼烷的方法，式中Ar为苯基或被含1-4个碳原子的烷基取代的苯基，其中的烷基可以含有一个或多个氟原子，该方法包括在惰性气氛中、在负压下将通式Ni(NC(CH2)4CN)2(NCBAr3)2的配合物加热到温度为120℃-300℃，式中Ar与上述的相同；从而产生含有三芳基硼烷的蒸气，和从蒸气中冷凝三芳基硼烷。在该方法优选的实施方案中，惰性气流把含三芳基硼烷的蒸气推移到其冷凝区。
附图描述
该附图是适用于实施本发明方法的装置的横截面示意图。
发明详述
在本发明的一个实施方案中，将催化剂残渣或NCBC放在常规的升华装置中，然后在惰性气氛中例如在氮气或氩气中，或优选在减压下将其加热，使催化剂残渣或NCBC分解并释放出BAr3和RCN。BAr3和RCN在升华器的冷凝管上固化。可以采用的温度为120-300℃，优选为170℃-230℃。可以采用的压力为0-760乇，优选的压力为0.001-40乇。
在本发明的第二个实施方案中，将催化剂残渣或NCBC放在管中，然后将其加热，优选在减压下加热，同时使惰性载体气流，例如氮气或氩气流在催化剂残渣或NCBC上流过且通往一个冷阱。在该过程中释放出的BAr3和RCN被载体气体吹入冷阱并在其表面上冷凝。
催化剂残渣是从烯烃，优选从3-戊烯腈(3PN)氢氰化得到的，氢氰化是在活性Ni催化剂Ni[P(OR)3]4和通式BAr3的三芳基硼烷助催化剂存在下进行的，式中R是含有最高达18个碳原子的芳基和Ar是含有最高达10个碳原子的芳基，优选BPh3(Ph=苯基)。这类典型的Ni催化剂包括Ni[P(OC6H5)3]4、Ni[P(O-p-C6H4CH3)]4、Ni[P(O-m-C6H4CH3)3]4和Ni[P(O-m&p-C6H4CH3)3]4。所用助催化剂的量是与催化剂的摩尔比一般为约1∶16-50∶1。在美国专利4,082,811中对催化剂残渣的生成有详细的叙述。
可以按照Cone的美国专利4,394,321所述的方法制备NCBC。
实施例
在下列各实施例中，除非另有说明，所有的操作都是在氮气气氛下采用干箱或标准的Schlenk技术进行的。三苯基硼暴露在空气或湿气中通常会导致生成二苯硼衍生物。ADN-NCBC是指由己二腈(ADN)，特别是Ni(NC(CH2)4CN)2(NCBPh3)2衍生的NCBC。对催化剂残渣和ADN-NCBC的元素分析如下。Ni催化剂残渣：C,72.96；H,5.66；N,10.53。ADN-NCBC:C,72.14；H,5.70；N,11.71；Ni,6.56；B,4.26。
实施例1
将0.158g(0.195mmol)的ADN-NCBC放在装设有干冰冷凝管的升华器内，然后在150℃和0.004乇下将其加热15分钟，随后白色固体开始在冷凝管上生成。将温度提高到190℃保持30分钟，然后最终达200℃保持4个小时。将该装置冷却到室温且从冷凝管上收集白色固体。产量为0.133g。这些固体的1HNMR光谱分析表明，它们是ADN比Bph3为1.5∶1的混合物以及少量的二苯酮衍生物。Bph3的产率为83％。
实施例2
将2.0g Ni催化剂残渣在装设有干冰冷凝管的升华器中在约0.004乇下加热到210℃。一天后，将温度升高到约230℃，保持几个小时。在该装置冷却到室温以后，从冷凝管上收集到1.192g白色固体，并用1HNMR谱仪进行分析。该样品含有Bph3与己二腈比例为1.0∶1.1的混合物以及少量的二苯硼衍生物。BPh3的产率为71％。
实施例3
如图所示，将5.0g Ni催化剂残渣放在玻璃管2内的瓷舟1中。将系统内的压力降到约20乇，同时使氮气气流4以约200ml/min的速率在催化剂残渣上流过。将该管加热到190℃保持约5小时且收集干冰冷阱3中的挥发产物。从冷阱中收集到3.4g浅黄色的固体。该产品的1H NMR光谱分析表明，它们是BPh3和ADN的混合物，其中BPh3占65％(重量)。
从劣化催化剂制得的BPh3的氢氰化性能
对用上述方法从劣化的氢氰化催化剂中回收的含有三苯基硼材料的氢氰化活性的评价，是在单级、22ml玻璃连续搅拌槽反应器中进行的。美国专利4,874,884叙述了采用连续搅拌槽反应器评价助催化剂的性能，在此引入作为参考。连续氢氰化的稳态条件如下：
反应速率=1.0×10E-4摩尔ADN/升-秒
3PN的转化率为20％
加料0.1摩尔Ni(TTP)4催化剂/摩尔HCN
(其中TTP表示三甲苯亚磷酸根)
加料0.12摩尔TTP/摩尔HCN
加料0.0065摩尔BPh3/摩尔HCN
温度=40℃
反应器初始装入含有24％(重量)Ni(TTP)4催化剂，6.3％TTP和0.28％BPh3的3PN溶液。以连续方式泵送下列溶液41小时达到稳态条件：试剂 加料速率含25％(重量)HCN的3PN 0.88g/hr含224％BPh3的3PN 0.57g/hr含35％TTP的3PN 0.66g/hr含51％Ni(TTP)4、 2.39g/hr3.7％TTP的3PN3PN 0.80g/hr
BPh3助催化剂溶液是用52.0g 3PN和2.1g升华材料制备的该材料是以实施例2叙述的方法从劣化的Ni催化剂中回收的。用液相色谱法分析该溶液表明，该溶液含2.24％(重量)的BPh3。
从反应器的溢流采集反应器的产物用于气相色谱法分析。可以用下面所示的产率和选择性表示给定助催化剂的反应特征。所示的结果是从连续流动开始17-41小时所取样品的平均值。除了示出用在市场上购买的BPh3作助催化剂的结果以外，还示出了在同样条件下连续氢氰化的结果作为比较。
回收的BPh3 购买的BPh3
ADN产率 92.6％ 92.9％
线性度 96.2％ 96.3％
2PN产率 3.7％ 3.6％
VN产率 0.04％ 0.04％定义：
转化率=已反应的摩尔数/加料的摩尔数
VN=戊腈
2PN=2-戊烯腈
MGN=甲基戊二腈
ESN=乙基丁二腈
ADN(2PN/VN)产率=产生的ADN(2PN/VN)摩尔数/
已反应的3PN摩尔数
线性度=ADN摩尔数/ADN+MGN+ESN的摩尔数。
Claims (4)
1．一种制备通式为BAr3的三芳基硼烷的方法，式中Ar为苯基或被含1-4个碳原子的烷基取代的苯基，其中的烷基可以被氟化，该法包括在惰性气氛中在负压下将通式为Ni(NC(CH2)4CN)2(NCBAr3)2的配合物加热到温度为120℃-300℃，式中Ar如上定义；从而生成含有三芳基硼烷的蒸气，和从蒸气中冷凝三芳基硼烷。
2．权利要求1的方法，其中惰性气流将含有三芳基硼烷的蒸气推移到三芳基硼烷的冷凝区。
3．权利要求1的方法，其中配合物包含在催化剂残渣中。
4．权利要求1的方法，其中Ar是苯基。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/264,275 US5382697A (en) | 1994-06-23 | 1994-06-23 | Preparation of triarylborane |
| US08/264,275 | 1994-06-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1151163A CN1151163A (zh) | 1997-06-04 |
| CN1045445C true CN1045445C (zh) | 1999-10-06 |
Family
ID=23005324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95193748A Expired - Lifetime CN1045445C (zh) | 1994-06-23 | 1995-06-19 | 三芳基硼烷的制备 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5382697A (zh) |
| EP (1) | EP0766686B1 (zh) |
| JP (1) | JP3701677B2 (zh) |
| KR (1) | KR100353777B1 (zh) |
| CN (1) | CN1045445C (zh) |
| DE (1) | DE69502395T2 (zh) |
| MX (1) | MX9606723A (zh) |
| TW (1) | TW320633B (zh) |
| WO (1) | WO1996000227A1 (zh) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2849027B1 (fr) * | 2002-12-23 | 2005-01-21 | Rhodia Polyamide Intermediates | Procede de synthese de composes comprenant des fonctions nitriles a partir de composes a insaturations ethyleniques |
| FR2850966B1 (fr) | 2003-02-10 | 2005-03-18 | Rhodia Polyamide Intermediates | Procede de fabrication de composes dinitriles |
| FR2854892B1 (fr) * | 2003-05-12 | 2005-06-24 | Rhodia Polyamide Intermediates | Procede de fabrication de dinitriles |
| FR2854891B1 (fr) | 2003-05-12 | 2006-07-07 | Rhodia Polyamide Intermediates | Procede de preparation de dinitriles |
| BRPI0709313A2 (pt) * | 2006-03-17 | 2011-07-05 | Invista Tech Sarl | método de separação e método para a preparação de triorganofosfitos |
| US7709674B2 (en) * | 2006-07-14 | 2010-05-04 | Invista North America S.A R.L | Hydrocyanation process with reduced yield losses |
| CN102241698B (zh) * | 2011-05-23 | 2013-12-25 | 中国科学院理化技术研究所 | 星形三芳基硼烷类化合物及其制备方法和用途 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4082811A (en) * | 1977-02-23 | 1978-04-04 | E. I. Du Pont De Nemours And Company | Recovery of metal and triarylborane catalyst components from olefin hydrocyanation residue |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3798256A (en) * | 1971-08-02 | 1974-03-19 | Du Pont | Hydrocyanation of olefins |
| US4134923A (en) * | 1977-09-02 | 1979-01-16 | E. I. Du Pont De Nemours And Company | Process for producing a metal hydroxide adduct of a triarylborane |
| US4394321A (en) * | 1981-11-12 | 1983-07-19 | E. I. Du Pont De Nemours And Company | Triarylboraneisocy ano metal compounds |
| US4416824A (en) * | 1981-12-21 | 1983-11-22 | E. I. Du Pont De Nemours & Co. | Recovery of triarylboranes by forming boron-containing metal compounds |
| US4749801A (en) * | 1986-06-04 | 1988-06-07 | E. I. Du Pont De Nemours And Company | [Hexakis(pentenenitrilo)nickel II]bis-[μ-(cyano) bis(triphenylborane) (I)], its method of preparation and its use |
| US4847399A (en) * | 1987-01-23 | 1989-07-11 | Morton Thiokol, Inc. | Process for preparing or purifying Group III-A organometallic compounds |
-
1994
- 1994-06-23 US US08/264,275 patent/US5382697A/en not_active Expired - Lifetime
-
1995
- 1995-05-31 TW TW084105504A patent/TW320633B/zh not_active IP Right Cessation
- 1995-06-19 CN CN95193748A patent/CN1045445C/zh not_active Expired - Lifetime
- 1995-06-19 KR KR1019960707332A patent/KR100353777B1/ko not_active IP Right Cessation
- 1995-06-19 EP EP95922972A patent/EP0766686B1/en not_active Expired - Lifetime
- 1995-06-19 MX MX9606723A patent/MX9606723A/es not_active Application Discontinuation
- 1995-06-19 WO PCT/US1995/007127 patent/WO1996000227A1/en active IP Right Grant
- 1995-06-19 DE DE69502395T patent/DE69502395T2/de not_active Expired - Lifetime
- 1995-06-19 JP JP50317896A patent/JP3701677B2/ja not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4082811A (en) * | 1977-02-23 | 1978-04-04 | E. I. Du Pont De Nemours And Company | Recovery of metal and triarylborane catalyst components from olefin hydrocyanation residue |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1996000227A1 (en) | 1996-01-04 |
| JP3701677B2 (ja) | 2005-10-05 |
| EP0766686B1 (en) | 1998-05-06 |
| MX9606723A (es) | 1997-03-29 |
| CN1151163A (zh) | 1997-06-04 |
| JPH10502080A (ja) | 1998-02-24 |
| KR100353777B1 (ko) | 2003-01-06 |
| US5382697A (en) | 1995-01-17 |
| EP0766686A1 (en) | 1997-04-09 |
| DE69502395T2 (de) | 1999-01-07 |
| TW320633B (zh) | 1997-11-21 |
| DE69502395D1 (de) | 1998-06-10 |
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