CN104861001B - A kind of preparation method of ferrocene biphosphine ligand - Google Patents
A kind of preparation method of ferrocene biphosphine ligand Download PDFInfo
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- CN104861001B CN104861001B CN201510317983.6A CN201510317983A CN104861001B CN 104861001 B CN104861001 B CN 104861001B CN 201510317983 A CN201510317983 A CN 201510317983A CN 104861001 B CN104861001 B CN 104861001B
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- ferrocene
- phosphine oxide
- tetrafluoroborate
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Abstract
The invention discloses a kind of preparation method of ferrocene biphosphine ligand, belong to organic synthesis field.This method is using ferrocene as initiation material; BFEE is catalyst; tetrafluoroborate with obtaining ferrocene diphosphine compound after diaryl phosphine oxide or dialkyl group oxidation phosphine reaction through hydrolysis, is then heated to reflux deprotection and obtains ferrocene diphosphine compound in methyl alcohol.Reaction condition is gentle compared with prior art by the present invention, and yield is up to more than 90%, and post processing is simple, is more suitable for industrialized production.The double phosphines of obtained ferrocene can as metallic catalyst part, for organic photoelectrical material and medicine and other fields.
Description
Technical field
The invention belongs to organic synthesis field, it is related to the synthetic method of a class organic phosphine compound, more particularly to ferrocene
The synthetic method of diphosphine compound.
Background technology
Ferrocene diphosphine compound as the important intermediate of a class and catalyst ligand synthesis of natural product, medicine,
There is purposes widely in functional material, liquid crystal molecule and bioactive compound.The unique electronics of ferrocene frame having ferrocene frame
Effect and space structure make the Phosphine ligands based on ferrocene show good activity when applied to catalyzed coupling reaction.Than
Such as, double (diphenylphosphine) ferrocene of 1,1'-（DPPF）With can be as constructing C-C/ in organic synthesis after transition metal complex
The effective catalyst of C-N/ C-O keys, 1,1'- double (di-t-butyl phosphine) ferrocene (DtBPF) due on phosphine steric hindrance compared with
Greatly, this causes it to possess preferable activity in activated carbon chlorine key, can speed up catalytic cycle and shortens the reaction time.
At present, the method for the synthesis ferrocene biphosphine ligand of document report is typically all to be obtained by the double lithiumations of ferrocene,
The route is using the butyl lithium and diaryl phosphonium chloride or dialkyl group phosphonium chloride to air-sensitive as raw material so that industrial production
Shi Fanying is difficult to control to, and requires higher to production equipment（J. Organometal. Chem., 1971, 27, 241-249；
Chem. Eur. J. 2012, 18, 12267-12277）.In addition, ferrocene itself can occur polymerization and cause in this method
Reaction yield is relatively low（60 % ~ 70 %）, ferrocene polymer can also be produced on the ligand catalysis activity of generation to be influenceed.Document
（Organometallics, 1983, 2, 714-719；J. Am. Chem. Soc., 1998, 120(29), 7369-
7370）DtBPF synthetic method is reported, but because DtBPF is oxidized easily, causes it must be in noble gas in separating-purifying
Protection is lower to be carried out, and is made troubles to operation, it is impossible to meet the demand of industrial applications.In view of the superior catalysis of such compound is lived
Property and wide market application foreground, explore more efficiently, the synthetic method of practical ferrocene biphosphine ligand it is very necessary.
The content of the invention
Present invention aims at provide a kind of high income, mild condition, simple, the suitable industrialized production ferrocene of post processing
The novel synthesis of biphosphine ligand.
To realize the object of the invention, reaction scheme of the present invention is as follows：
Reactions steps of the present invention are as follows：
1）Under noble gas protection, ferrocene, solvent 1,2- dichloroethanes and diaryl oxygen are added into dry reactor
Change after phosphine or dialkyl group phosphine oxide, boron trifluoride ether solution is added dropwise into system under the conditions of -10 ~ 10 DEG C, drips
60 ~ 80 DEG C of reactions are warming up to after finishing, then cooling down, water hydrolysis is added dropwise into system, by extraction, dry, recrystallization
Obtain the tetrafluoroborate of ferrocene diphosphine compound；
2）Methanol is added into the tetrafluoroborate of ferrocene diphosphine compound, is heated to reflux, it is then cold under noble gas protection
But crystallization obtains target product ferrocene diphosphine compound.
Diaryl phosphine oxide or dialkyl group phosphine oxide of the present invention include diphenyl phosphine oxide, di-t-butyl and aoxidized
Phosphine, diisopropyl phosphine oxide or dicyclohexyl phosphine oxide.
Ferrocene biphosphine ligand of the present invention includes 1,1 '-bis- (diphenylphosphine) ferrocene, 1,1 '-bis- (two tertiary fourths
Base 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, it is described
Ferrocene and BFEE mol ratio be 1：5-10.
Beneficial effect of the present invention is：1）Stable diaryl phosphine oxide or dialkyl group phosphine oxide is startings using in air
Raw material, the characteristic of phosphinous acid can be tautomerized to using secondary phosphine oxide, using BFEE as catalyst and dehydrating agent,
Rigors of the traditional handicraft to equipment are changed, while the polymerization of ferrocene itself in course of reaction is avoided, the cyclopentadienyl of generation two
The yield of iron biphosphine ligand is up to 90 more than %；2）It is complexed after boron trifluoride hydrolysis generation tetrafluoro boric acid with ferrocene biphosphine ligand,
The obtained double phosphine tetrafluoroborates of intermediate ferrocene can be stabilized in atmosphere, and then backflow deprotection is in methyl alcohol
Target product is can obtain, the process of isolating and purifying is optimized.The reaction condition is gentle, it is easy to operate, and isolates and purifies simple, it is easier to
Industrialized production.The double phosphines of obtained ferrocene can as metallic catalyst part, for the neck such as organic photoelectrical material and medicine
Domain.
Embodiment
For preferably the present invention is described in detail, give an actual example as follows：
The synthesis of embodiment 1 1,1 '-bis- (diphenylphosphine) ferrocene
Under argon gas protection, ferrocene is added into dry reactor（1 mol, 186 g）, 1 L 1,2- dichloroethanes
And (2 mol, 405 g), and the % boron trifluorides of mass percent 47 are added dropwise into system under the conditions of 0 DEG C for diphenyl phosphine oxide
60 DEG C of 10 h of reaction are warming up to after diethyl ether solution (5 mol, 1.52 kg), completion of dropping, 0 DEG C are then cooled into system
Water is added dropwise, then hydrolysis divides liquid, organic layer is dried with anhydrous magnesium sulfate, filtered, obtaining yellow after vacuum distillation removing solvent consolidates
The g of tetrafluoroborate 686 of body, dichloromethane and n-hexane recrystallization i.e. available 1,1 '-bis- (diphenylphosphine) ferrocene（31P
NMR (400 MHz, CDCl3), δ: 4.0 ppm）；2 L methanol are added into above-mentioned tetrafluoroborate, 8 h are heated to reflux,
Then argon gas protects lower crystallisation by cooling, and suction filtration is dried to obtain yellow solid 1,1 '-g of bis- (diphenylphosphines) ferrocene 510, yield
92 %, content 98.3 % (HPLC)31P NMR (400 MHz, CDCl3), 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
C34H28FeP2 554.1016, Found 554.1013. elementary analyses measured values (calculated value)/%: C 73.65
(73.66), H 5.07 (5.09).
The synthesis of embodiment 2 1,1 '-bis- (di-t-butyl phosphine) ferrocene
Under argon gas protection, ferrocene is added into dry reactor（1 mol, 186 g）, 1 L 1,2- dichloroethanes
And (4 mol, 648 g), and the % trifluoros of mass percent 47 are added dropwise into system under the conditions of -10 DEG C for di-t-butyl phosphine oxide
Change and 80 DEG C of 10 h of reaction are warming up to after borate ether solution (8 mol, 2.4 kg), completion of dropping, be then cooled to 0 DEG C to system
Middle dropwise addition water, hydrolysis, then divides liquid, organic layer is dried with anhydrous magnesium sulfate, filtered, and vacuum distillation obtains yellow after removing solvent
The tetrafluoroborate 618 of solid, dichloromethane and n-hexane recrystallization i.e. available 1,1 '-bis- (di-t-butyl phosphine) ferrocene
g（31P NMR (400 MHz, CDCl3), δ: 39.9 ppm）；2 L methanol are added into above-mentioned tetrafluoroborate, are heated back
12 h are flowed, then the lower crystallisation by cooling of argon gas protection, suction filtration is dried to obtain yellow solid 1,1 '-bis- (di-t-butyl phosphines) ferrocene
431 g, the % of yield 91, content 98.5 % (HPLC)31P NMR (400 MHz, CDCl3), δ: 20.8;1H NMR (400
MHz, CDCl3), δ: 1H NMR (400 MHz, CDCl3) δ: 4.38-4.16 (m, 8H, Fc-H), 1.56 (d,3 J = 17.0 Hz, 36H, -Me) HRMS: Calcd for C26H44FeP2 474.2268, Found 474.2264. members
Element analysis measured value (calculated value)/%: C 65.80 (65.82), H 9.36 (9.35).
The synthesis of embodiment 3 1,1 '-bis- (diisopropyl phosphine) ferrocene
Under argon gas protection, ferrocene is added into dry reactor（1 mol, 186 g）, diisopropyl phosphine oxide (4
Mol, 536 g) (according to document Organometallics, 2009,28,6383 ~ 6401 method synthesis) and 1 L
1,2- dichloroethanes, be added dropwise under the conditions of 10 DEG C into system mass percent 47 % boron trifluoride ether solutions (8 mol,
2.4 kg), 70 DEG C of 12 h of reaction are warming up to after completion of dropping, 0 DEG C is then cooled to and water is added dropwise into system, hydrolyze, Ran Houfen
Liquid, organic layer is dried with anhydrous magnesium sulfate, filtered, and vacuum distillation obtains yellow solid after removing solvent, dichloromethane and just oneself
The g of tetrafluoroborate 552 of alkane recrystallization i.e. available 1,1 '-bis- (diisopropyl phosphine) ferrocene；To above-mentioned tetrafluoroborate
1 L methanol of middle addition, is heated to reflux 12 h, then the lower crystallisation by cooling of argon gas protection, and suction filtration is dried to obtain yellow solid 1,1 '-bis-
(diisopropyl phosphine) ferrocene 377 g, % of yield 90, content 98.1 % (HPLC)31P NMR (400 MHz, CDCl3),
δ: 0.9 ;1H NMR (400 MHz, CDCl3), δ: 1H NMR (400 MHz, CDCl3) 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
C22H36FeP2 418.1642, Found 418.1645. elementary analyses measured values (calculated value)/%: C 63.14
(63.17), H 8.68 (8.67).
The synthesis of embodiment 4 1,1 '-bis- (dicyclohexylphosphontetrafluoroborate) ferrocene
Under argon gas protection, ferrocene is added into dry reactor（1 mol, 186 g）, 1 L 1,2- dichloroethanes
And (4 mol, 856 g), and into system, dropwise addition mass percent 47 % is borontrifluoride under the conditions of 0 DEG C for dicyclohexyl phosphine oxide
80 DEG C of 12 h of reaction are warming up to after borate ether solution (10 mol, 3.0 kg), completion of dropping, 0 DEG C are then cooled to system
Middle dropwise addition water, hydrolysis, then divides liquid, organic layer is dried with anhydrous magnesium sulfate, filtered, and vacuum distillation obtains yellow after removing solvent
The tetrafluoroborate 716 of solid, dichloromethane and n-hexane recrystallization i.e. available 1,1 '-bis- (dicyclohexylphosphontetrafluoroborate) ferrocene
g；1 L methanol is added into above-mentioned tetrafluoroborate, 12 h are heated to reflux, then the lower crystallisation by cooling of argon gas protection, suction filtration is dried
Obtain yellow solid 1,1 '-bis- (dicyclohexylphosphontetrafluoroborates) ferrocene 532 g, the % of yield 92, content 98.6 % (HPLC)31P NMR
(400 MHz, CDCl3), δ: -7.8 ;1H NMR (400 MHz, CDCl3), δ: 1H NMR (400 MHz, CDCl3)
δ: 4.36-4.11 (m, 8H, Fc-H), 1.68-1.16 (m, 44H) HRMS: Calcd for C34H52FeP2
578.2894, Found 578.2891. elementary analyses measured values (calculated value)/%: C 70.59 (70.58), H 9.03
(9.06).。
Claims (2)
1. a kind of preparation method of ferrocene biphosphine ligand, it is characterised in that be achieved by the steps of：
1）Under noble gas protection, ferrocene, solvent 1,2- dichloroethanes and diaryl phosphine oxide are added into dry reactor
Or dialkyl group phosphine oxide, boron trifluoride ether solution, completion of dropping is then added dropwise into system under the conditions of -10 ~ 10 DEG C
After be warming up to 60 ~ 80 DEG C of reactions, then cooling down, water is added dropwise into system, hydrolysis, by extraction, dry, recrystallize
To the tetrafluoroborate (II) of ferrocene diphosphine compound；
2）Methanol is added into the tetrafluoroborate (II) of ferrocene diphosphine compound, is heated to reflux, it is then cold under noble gas protection
But crystallization obtains target product ferrocene diphosphine compound (III)；
Described diaryl phosphine oxide or dialkyl group phosphine oxide are diphenyl phosphine oxide, di-t-butyl phosphine oxide, diisopropyl
Phosphine oxide or dicyclohexyl phosphine oxide.
2. the preparation method of ferrocene biphosphine ligand as claimed in claim 1, it is characterised in that described ferrocene and two virtues
The mol ratio of base phosphine oxide or dialkyl group phosphine oxide is 1:2-3, described ferrocene and the mol ratio of BFEE are
1：5-10.
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| CN101421285A (en) * | 2006-04-12 | 2009-04-29 | 索尔维亚斯股份公司 | Ferrocenediphosphines |
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| 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;Blake C. Hamann et al.;《J. Am. Chem. Soc.》;19980711;第120卷;第7369-7370页 * |
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