CN109553639B - 一种合成三叔丁基膦的方法 - Google Patents
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- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- PGYDGBCATBINCB-UHFFFAOYSA-N 4-diethoxyphosphoryl-n,n-dimethylaniline Chemical compound CCOP(=O)(OCC)C1=CC=C(N(C)C)C=C1 PGYDGBCATBINCB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006009 Calcium phosphide Substances 0.000 claims abstract description 10
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 8
- DRZUOPCJWAJOAG-UHFFFAOYSA-N CC(=O)C.CC(=O)C.[Ni] Chemical group CC(=O)C.CC(=O)C.[Ni] DRZUOPCJWAJOAG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- CQRPUKWAZPZXTO-UHFFFAOYSA-M magnesium;2-methylpropane;chloride Chemical compound [Mg+2].[Cl-].C[C-](C)C CQRPUKWAZPZXTO-UHFFFAOYSA-M 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 phosphine compound Chemical class 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5004—Acyclic saturated phosphines
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种合成三叔丁基膦的方法,属于有机合成领域。在无水无氧氛围中,以溴代叔丁烷为原料,在镍催化剂的催化作用下,与磷化钙反应生成三叔丁基膦。与现有技术相比本发明反应条件温和,操作简单,产率高,原料简单易得,降低了生产成本,适合工业化生产。
Description
技术领域
本发明属于有机合成领域,涉及一类有机膦化合物的合成方法,尤其涉及三叔丁基膦的合成方法。
背景技术
过渡金属催化的偶联反应在最近的几十年被广泛应用于医药和石化行业,其中钯催化剂可以有效地催化多取代的卤代芳烃或卤代杂芳烃的Suzuki、Negishi、Stille、Heck等偶联反应,其衍生的催化剂最为常用。在钯催化剂催化各种偶联反应过程中 , 通过选择合适的配体 往往能获得较高的收率和较好的反应选择性。三叔丁基膦做为新兴的第三代膦配体,近年来在钯催化偶联反应中的性能得到了广泛的研究。这主要是由于三叔丁基膦富电子和具有大的空间位阻,既加速了氧化加成反应, 又利于原消除反应, 从而加速了偶联反应进程。
到目前为止,文献报道的关于三叔丁基膦的合成方法主要是通过叔丁基锂与三氯化磷反应得到 (文献Chemische Berichte, vol. 100, p. 692 - 693),该方法的主要弊端在于使用了叔丁基锂作为反应原料,对空气敏感,易自然,使得反应条件控制要求较高。另外一种方法是通过叔丁基氯化镁与三氯化磷在碘化铜和溴化锂的催化作用下反应得到(文献 US2003/229240 A1, 2003),该路线后处理过程中有大量无机盐存在,后处理困难,限制了其进一步应用。鉴于该类化合物优越的催化活性及广阔的市场应用前景,探索更加高效、实用的三叔丁基膦的合成方法十分必要。
发明内容
本发明目的在于提供一种收率高、生产成本低、反应条件温和,操作简单,适合工业化生产三叔丁基膦的新方法。
为实现本发明目的,本发明的反应路线如下:
本发明的反应步骤如下:
在氩气保护下,向干燥反应器中加入反应溶剂四氢呋喃,然后依次加入磷化钙、溴代叔丁烷以及镍催化剂,而后升温至60-80 ºC反应,然后加入水淬灭反应,萃取,干燥,减压蒸馏得到三叔丁基膦;
所述镍催化剂为二乙酰丙酮镍。
所述的磷化钙、溴代叔丁烷与镍催化剂的摩尔比为1 : 6-12 : 0.01-0.1。
本发明有益效果在于:本发明使用溴代叔丁烷和磷化钙作为起始原料,避免了对空气敏感的叔丁基锂和叔丁基氯化镁的使用,操作更加简单。该发明优化了反应过程,反应条件温和,收率高,达90 %以上,更适合于工业化生产。
具体实施方式
为更好地对本发明进行详细说明,举实例如下:
实施例一:三叔丁基膦的合成
在氩气保护下,向干燥反应器中加入2L四氢呋喃,然后依次加入磷化钙(182 g, 1mol)、溴代叔丁烷(816 g, 6mol)、以及二乙酰丙酮镍(12.8 g, 0.05mol),而后升温至60 ºC反应12小时,反应结束后加入1L水淬灭反应,然后萃取,有机层用无水硫酸镁干燥,过滤,减压蒸馏得到无色液体三叔丁基膦367 g,收率91%。1H NMR (400 MHz, C6D6) δ: 3.28 (d,J= 199 Hz, 1H), 1.29 (d, J = 11.3 Hz, 18H). 31P NMR (162 MHz, C6D6) δ: 33.2 (J= 200 Hz).。
实施例二:三叔丁基膦的合成
在氩气保护下,向干燥反应器中加入2L四氢呋喃,然后依次加入磷化钙(182 g, 1mol)、溴代叔丁烷(1224 g, 9 mol)、以及二乙酰丙酮镍(12.8 g, 0.05 mol),而后升温至70 ºC反应10小时,反应结束后加入1L水淬灭反应,然后萃取,有机层用无水硫酸镁干燥,过滤,减压蒸馏得到无色液体三叔丁基膦384 g,收率95%。
实施例三:三叔丁基膦的合成
在氩气保护下,向干燥反应器中加入2L四氢呋喃,然后依次加入磷化钙(182 g, 1mol)、溴代叔丁烷(1088 g, 8 mol)、以及二乙酰丙酮镍(2.6 g, 0.01 mol),而后升温至60ºC反应12小时,反应结束后加入1L水淬灭反应,然后萃取,有机层用无水硫酸镁干燥,过滤,减压蒸馏得到无色液体三叔丁基膦372 g,收率92%。
实施例四:三叔丁基膦的合成
在氩气保护下,向干燥反应器中加入2L四氢呋喃,然后依次加入磷化钙(182 g, 1mol)、溴代叔丁烷(1088 g, 8 mol)、以及二乙酰丙酮镍(25.6 g, 0.1 mol),而后升温至80ºC反应10小时,反应结束后加入1L水淬灭反应,然后萃取,有机层用无水硫酸镁干燥,过滤,减压蒸馏得到无色液体三叔丁基膦376 g,收率93%。
Claims (1)
1.一种合成三叔丁基膦的方法,其特征在于,通过如下方法实现:在氩气保护下,向干燥反应器中加入反应溶剂四氢呋喃,然后依次加入磷化钙、溴代叔丁烷、以及镍催化剂,而后升温至60-80℃反应,然后加入水淬灭反应,萃取,干燥,减压蒸馏得到三叔丁基膦;
所述镍催化剂为二乙酰丙酮镍;
所述的磷化钙、溴代叔丁烷与镍催化剂的摩尔比为1 : 6-12 : 0.01-0.1。
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JPH0374395A (ja) * | 1989-08-11 | 1991-03-28 | Nippon Chem Ind Co Ltd | 有機ホスホニウム塩の製造方法 |
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