CN104861001A - Method for preparing ferrocene diphosphine ligand - Google Patents
Method for preparing ferrocene diphosphine ligand Download PDFInfo
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- CN104861001A CN104861001A CN201510317983.6A CN201510317983A CN104861001A CN 104861001 A CN104861001 A CN 104861001A CN 201510317983 A CN201510317983 A CN 201510317983A CN 104861001 A CN104861001 A CN 104861001A
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- ferrocene
- phosphine oxide
- boron trifluoride
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- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
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Abstract
The invention discloses a method for preparing ferrocene diphosphine ligand, and belongs to the field of organic synthesis. The method comprises the following steps: by taking ferrocene as an initial raw material and boron trifluoride diethyl etherate as a catalyst, reacting with diaryl phosphine oxide or dialkyl phosphine oxide, hydrolyzing so as to obtain tertfluoborate of a ferrocene diphosphine compound, and performing heating backflow deprotection in methanol, thereby obtaining the ferrocene diphosphine compound. Compared with the prior art, the method is gentle in reaction condition, simple in aftertreatment, and relatively applicable to industrial production, and the yield is greater than 90%. The prepared ferrocene diphosphine can be used as ligand of a metal catalyst, and can be used in the fields such as organic optoelectronic materials and medicines.
Description
Technical field
The invention belongs to organic synthesis field, relate to the synthetic method of a class organic phosphine compound, particularly relate to the synthetic method of ferrocene diphosphine compound.
Background technology
Ferrocene diphosphine compound has purposes widely as the important intermediate of a class and catalyst ligand in synthesis of natural product, medicine, functional materials, liquid crystal molecule and bioactive compounds.The electronic effect of ferrocene frame having ferrocene frame uniqueness and space structure make to show good activity when being applied to catalyzed coupling reaction based on the Phosphine ligands of ferrocene.Such as, 1, can as the effective catalyst constructing C-C/ C-N/ C-O key in organic synthesis after two (diphenylphosphine) ferrocene (DPPF) of 1'-and transition metal complex, 1,1'-two (di-t-butyl phosphine) ferrocene (DtBPF) is due to sterically hindered larger on phosphine, this makes it have good activity when activated carbon chlorine key, can accelerate catalytic cycle and Reaction time shorten.
At present, the method of the synthesis ferrocene biphosphine ligand of bibliographical information is all generally obtained by the two lithiumation of ferrocene, this route be with to the butyllithium of air-sensitive and diaryl phosphonium chloride or dialkyl group phosphonium chloride for raw material, make to react during industrial production to be difficult to control, higher (J. Organometal. Chem. is required to production unit, 1971,27,241-249; Chem. Eur. J. 2012,18,12267-12277).In addition, in the method can there is polymerization and cause reaction yield lower (60 % ~ 70 %) in ferrocene self, and ferrocene polymer also can have an impact to the ligand catalysis activity generated.Document (Organometallics, 1983,2,714-719; J. Am. Chem. Soc., 1998,120 (29); 7369-7370) report the synthetic method of DtBPF, but due to DtBPF easily oxidized, cause its when separating-purifying must noble gas protection under carry out; make troubles to operation, the demand of industrial applications cannot be met.The catalytic activity superior in view of this compounds and wide market application foreground, the synthetic method exploring more efficient, practical ferrocene biphosphine ligand is very necessary.
Summary of the invention
The novel synthesis that the object of the invention is to provide that a kind of yield is high, mild condition, aftertreatment are simple, be applicable to suitability for industrialized production ferrocene biphosphine ligand.
For realizing the object of the invention, reaction scheme of the present invention is as follows:
Reactions steps of the present invention is as follows:
1) under noble gas protection, ferrocene, solvent 1 is added in dry reactor, after 2-ethylene dichloride and diaryl phosphine oxide or dialkyl group phosphine oxide, in system, boron trifluoride ether solution is dripped under-10 ~ 10 DEG C of conditions, 60 ~ 80 DEG C of reactions are warming up to after dropwising, then cooling down, drips water hydrolysis in system, by a tetrafluoro borate extracted, dry, recrystallization obtains ferrocene diphosphine compound;
2) in a tetrafluoro borate of ferrocene diphosphine compound, add methyl alcohol, reflux, then the lower crystallisation by cooling of noble gas protection obtains target product ferrocene diphosphine compound.
The diaryl phosphine oxide that the present invention relates to or dialkyl group phosphine oxide comprise diphenyl phosphine oxide, di-t-butyl phosphine oxide, di-isopropyl phosphine oxide or dicyclohexyl phosphine oxide.
The ferrocene biphosphine ligand that the present invention relates to comprises 1,1 '-bis-(diphenylphosphine) ferrocene, 1,1 '-bis-(di-t-butyl phosphine) ferrocene, 1,1 '-bis-(diisopropyl phosphine) ferrocene, 1,1 '-bis-(dicyclohexylphosphontetrafluoroborate) ferrocene.
The mol ratio of ferrocene of the present invention and diaryl phosphine oxide or dialkyl group phosphine oxide is 1:2-3, and described ferrocene and the mol ratio of boron trifluoride diethyl etherate are 1:5-10.
Beneficial effect of the present invention is: 1) with diaryl phosphine oxide stable in air or dialkyl group phosphine oxide for starting raw material, utilize secondary phosphine oxide compound can tautomerize to the characteristic of phosphinous acid, adopt boron trifluoride diethyl etherate as catalyzer and dewatering agent, change the rigors of traditional technology to equipment, avoid the polymerization of ferrocene self in reaction process, the yield generating ferrocene biphosphine ligand reaches 90 more than % simultaneously; 2) boron trifluoride hydrolysis generate after Tetrafluoroboric acid with the complexing of ferrocene biphosphine ligand; the two phosphine a tetrafluoro borate of the intermediate ferrocene obtained in atmosphere can stable existence; then the deprotection that refluxes in methyl alcohol can obtain target product, optimizes separation and purification process.This reaction conditions is gentle, easy handling, and separation and purification is simple, is easier to suitability for industrialized production.The two phosphine of obtained ferrocene can be used as the part of metal catalyst, for organic photoelectrical material and medicine and other fields.
Embodiment
For the present invention is described in detail better, give an actual example as follows:
Embodiment 11, the synthesis of 1 '-bis-(diphenylphosphine) ferrocene
Under argon shield, ferrocene (1 mol is added in dry reactor, 186 g), 1 L 1, 2-ethylene dichloride and diphenyl phosphine oxide (2 mol, 405 g), in system, mass percent 47 % boron trifluoride ether solution (5 mol are dripped under 0 DEG C of condition, 1.52 kg), 60 DEG C of reaction 10 h are warming up to after dropwising, then be cooled to 0 DEG C and drip water in system, hydrolysis, then separatory, organic over anhydrous dried over mgso, filter, underpressure distillation obtains yellow solid except after desolventizing, methylene dichloride and normal hexane recrystallization can obtain 1, a tetrafluoro borate 686 g(of 1 '-bis-(diphenylphosphine) ferrocene
31p NMR (400 MHz, CDCl
3), δ: 4.0 ppm), 2 L methyl alcohol are added, reflux 8 h, then crystallisation by cooling under argon shield in above-mentioned a tetrafluoro borate, suction filtration drying obtains yellow solid 1, 1 '-bis-(diphenylphosphine) ferrocene 510 g, productive rate 92 %, content 98.3 % (HPLC).
31p NMR (400 MHz, CDCl
3), δ :-16.6,
1h NMR (400 MHz, CDCl3), δ: 8.03-7.14 (m, 10H, Ph), 4.56-4.14 (m, 8H, Fc-H). HRMS:Calcd for C
34h
28feP
2554.1016, Found 554.1013. ultimate analysis measured value (calculated value)/%: C 73.65 (73.66), H 5.07 (5.09).
Embodiment 21, the synthesis of 1 '-bis-(di-t-butyl phosphine) ferrocene
Under argon shield, ferrocene (1 mol is added in dry reactor, 186 g), 1 L 1, 2-ethylene dichloride and di-t-butyl phosphine oxide (4 mol, 648 g), in system, mass percent 47 % boron trifluoride ether solution (8 mol are dripped under-10 DEG C of conditions, 2.4 kg), 80 DEG C of reaction 10 h are warming up to after dropwising, then be cooled to 0 DEG C and drip water in system, hydrolysis, then separatory, organic over anhydrous dried over mgso, filter, underpressure distillation obtains yellow solid except after desolventizing, methylene dichloride and normal hexane recrystallization can obtain 1, a tetrafluoro borate 618 g(of 1 '-bis-(di-t-butyl phosphine) ferrocene
31p NMR (400 MHz, CDCl
3), δ: 39.9 ppm), 2 L methyl alcohol are added, reflux 12 h, then crystallisation by cooling under argon shield in above-mentioned a tetrafluoro borate, suction filtration drying obtains yellow solid 1, 1 '-bis-(di-t-butyl phosphine) ferrocene 431 g, productive rate 91 %, content 98.5 % (HPLC).
31p NMR (400 MHz, CDCl
3), δ: 20.8,
1h NMR (400 MHz, CDCl3), δ:
1h NMR (400 MHz, CDCl
3) δ: 4.38-4.16 (m, 8H, Fc-H), 1.56 (d,
3 j=17.0 Hz, 36H ,-Me) HRMS:Calcd for C
26h
44feP
2474.2268, Found 474.2264. ultimate analysis measured value (calculated value)/%: C 65.80 (65.82), H 9.36 (9.35).
Embodiment 31, the synthesis of 1 '-bis-(diisopropyl phosphine) ferrocene
Under argon shield, ferrocene (1 mol is added in dry reactor, 186 g), di-isopropyl phosphine oxide (4 mol, 536 g) (according to document Organometallics, 2009, 28, the method synthesis of 6383 ~ 6401) and 1 L 1, 2-ethylene dichloride, in system, mass percent 47 % boron trifluoride ether solution (8 mol are dripped under 10 DEG C of conditions, 2.4 kg), 70 DEG C of reaction 12 h are warming up to after dropwising, then be cooled to 0 DEG C and drip water in system, hydrolysis, then separatory, organic over anhydrous dried over mgso, filter, underpressure distillation obtains yellow solid except after desolventizing, methylene dichloride and normal hexane recrystallization can obtain 1, a tetrafluoro borate 552 g of 1 '-bis-(diisopropyl phosphine) ferrocene, 1 L methyl alcohol is added, reflux 12 h, then crystallisation by cooling under argon shield in above-mentioned a tetrafluoro borate, suction filtration drying obtains yellow solid 1, 1 '-bis-(diisopropyl phosphine) ferrocene 377 g, productive rate 90 %, content 98.1 % (HPLC).
31p NMR (400 MHz, CDCl
3), δ: 0.9,
1h NMR (400 MHz, CDCl
3), δ:
1h NMR (400 MHz, CDCl
3) δ: 4.35-4.12 (m, 8H, Fc-H), 1.63 (m, 4H ,-CH) 1.27 (d,
3 j=15.2 Hz, 24H ,-Me) HRMS:Calcd for C
22h
36feP
2418.1642, Found 418.1645. ultimate analysis measured value (calculated value)/%: C 63.14 (63.17), H 8.68 (8.67).
Embodiment 41, the synthesis of 1 '-bis-(dicyclohexylphosphontetrafluoroborate) ferrocene
Under argon shield, ferrocene (1 mol is added in dry reactor, 186 g), 1 L 1, 2-ethylene dichloride and dicyclohexyl phosphine oxide (4 mol, 856 g), in system, mass percent 47 % boron trifluoride ether solution (10 mol are dripped under 0 DEG C of condition, 3.0 kg), 80 DEG C of reaction 12 h are warming up to after dropwising, then be cooled to 0 DEG C and drip water in system, hydrolysis, then separatory, organic over anhydrous dried over mgso, filter, underpressure distillation obtains yellow solid except after desolventizing, methylene dichloride and normal hexane recrystallization can obtain 1, a tetrafluoro borate 716 g of 1 '-bis-(dicyclohexylphosphontetrafluoroborate) ferrocene, 1 L methyl alcohol is added, reflux 12 h, then crystallisation by cooling under argon shield in above-mentioned a tetrafluoro borate, suction filtration drying obtains yellow solid 1, 1 '-bis-(dicyclohexylphosphontetrafluoroborate) ferrocene 532 g, productive rate 92 %, content 98.6 % (HPLC).
31p NMR (400 MHz, CDCl
3), δ :-7.8,
1h NMR (400 MHz, CDCl
3), δ:
1h NMR (400 MHz, CDCl
3) δ: 4.36-4.11 (m, 8H, Fc-H), 1.68-1.16 (m, 44H) HRMS:Calcd for C
34h
52feP
2578.2894, Found 578.2891. ultimate analysis measured value (calculated value)/%: C 70.59 (70.58), H 9.03 (9.06)..
Claims (2)
1. the preparation method of a ferrocene biphosphine ligand, it is characterized in that, realize as follows: 1) under noble gas protection, ferrocene, solvent 1 is added in dry reactor, 2-ethylene dichloride and diaryl phosphine oxide or dialkyl group phosphine oxide, then under-10 ~ 10 DEG C of conditions, in system, boron trifluoride ether solution is dripped, 60 ~ 80 DEG C of reactions are warming up to after dropwising, then cooling down, water is dripped in system, hydrolysis, by a tetrafluoro borate extracted, dry, recrystallization obtains ferrocene diphosphine compound;
2) in a tetrafluoro borate of ferrocene diphosphine compound, add methyl alcohol, reflux, then the lower crystallisation by cooling of noble gas protection obtains target product ferrocene diphosphine compound;
Described diaryl phosphine oxide or dialkyl group phosphine oxide are diphenyl phosphine oxide, di-t-butyl phosphine oxide, di-isopropyl phosphine oxide or dicyclohexyl phosphine oxide.
2. the preparation method of ferrocene biphosphine ligand as claimed in claim 1, it is characterized in that, the mol ratio of described ferrocene and diaryl phosphine oxide or dialkyl group phosphine oxide is 1:2-3, and described ferrocene and the mol ratio of boron trifluoride diethyl etherate are 1:5-10.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237379A (en) * | 2015-10-29 | 2016-01-13 | 河南省科学院化学研究所有限公司 | Production method for 4-bromo fluorenone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070161762A1 (en) * | 2004-01-14 | 2007-07-12 | Phoenix Chemicals Limited | Metallocene-based chiral phosphine or arsine ligands |
| CN101421285A (en) * | 2006-04-12 | 2009-04-29 | 索尔维亚斯股份公司 | Ferrocenediphosphines |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070161762A1 (en) * | 2004-01-14 | 2007-07-12 | Phoenix Chemicals Limited | Metallocene-based chiral phosphine or arsine ligands |
| CN101421285A (en) * | 2006-04-12 | 2009-04-29 | 索尔维亚斯股份公司 | Ferrocenediphosphines |
Non-Patent Citations (1)
| Title |
|---|
| BLAKE C. HAMANN ET AL.: "Sterically Hindered Chelating Alkyl Phosphines Provide Large Rate Accelerations in Palladium-Catalyzed Amination of Aryl Iodides, Bromides, and Chlorides, and the First Amination of Aryl Tosylates", 《J. AM. CHEM. SOC.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237379A (en) * | 2015-10-29 | 2016-01-13 | 河南省科学院化学研究所有限公司 | Production method for 4-bromo fluorenone |
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Inventor after: Chen Hui Inventor after: Yang Ruina Inventor after: Yang Zhenqiang Inventor after: Zhang Yinlong Inventor after: Zhou Duo Inventor after: Sun Minqing Inventor after: Qu Fengbo Inventor after: Duan Zheng Inventor after: Xi Zhenfeng Inventor before: Chen Hui Inventor before: Yang Ruina Inventor before: Yang Zhenqiang Inventor before: Zhang Yinlong Inventor before: Zhou Duo Inventor before: Sun Minqing Inventor before: Qu Fengbo |
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Effective date of registration: 20200628 Address after: 457000 west section of Shengli Road, Henan, Puyang Patentee after: PUYANG HUICHENG ELECTRONIC MATERIAL Co.,Ltd. Address before: 450002 Henan Province, Zhengzhou City Red Road No. 56 Patentee before: HENAN ACADEMY OF SCIENCES CHEMICAL RESEARCH INSTITUTE Co.,Ltd. |
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Effective date of registration: 20210114 Address after: 457000 No.30, North Road, 1000m West, intersection of Shengli Road and Hua'an Road, Puyang City, Henan Province Patentee after: PUYANG HUICHENG NEW MATERIAL INDUSTRY TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. Address before: 457000 west section of Shengli Road, Puyang City, Henan Province Patentee before: PUYANG HUICHENG ELECTRONIC MATERIAL Co.,Ltd. |