CN106478716B - A kind of synthetic method of organic phosphorus compound - Google Patents

A kind of synthetic method of organic phosphorus compound Download PDF

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CN106478716B
CN106478716B CN201610826929.9A CN201610826929A CN106478716B CN 106478716 B CN106478716 B CN 106478716B CN 201610826929 A CN201610826929 A CN 201610826929A CN 106478716 B CN106478716 B CN 106478716B
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added
spares
synthetic method
reaction
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CN106478716A (en
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赵晓宝
张志平
陈虎
孙明明
李娟�
鲁晓凤
王进华
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JIANGSU SINOCOMPOUND CATALYST CO Ltd
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JIANGSU SINOCOMPOUND CATALYST CO Ltd
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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 System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
    • 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 System
    • 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
    • C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
    • C07F9/5072—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure P-H

Abstract

The invention discloses the synthetic methods of one kind 5,5', 6,6', 7,7', 8,8' octahydros [1,1' dinaphthalene] 2,2' bis- [diphenylphosphines], belong to organic synthesis field.This method through catalytic hydrogenation, esterification, then under palladium catalyst and Phosphine ligands co-catalysis, carries out C P key coupling reactions with diphenylphosphine, obtains target product, yield reaches 35% using dinaphthol as starting material.The present invention has step few compared with the prior art, avoids using high poison reaction raw materials, and it is easy to isolate and purify, and is suitble to industrialized production.The target product being prepared has chiral catalysis and Asymmetrical annular-addition field to have unique catalytic activity, has broad application prospects in medicine and natural products synthesis field.

Description

A kind of synthetic method of organic phosphorus compound
Technical field
The present invention relates to technical field of organic synthesis, are related to a kind of synthetic method of organic phosphorus compound, and in particular to and 5, The preparation of 5', 6,6', 7,7', 8,8'- octahydro-[1,1'- dinaphthalenes] -2,2'- bis- [diphenylphosphines] (hereinafter referred to as H8-BINAP) Method.
Background technology
The double diphenylphosphine compounds of dinaphthalene are a kind of important catalyst ligands, in synthesis of natural product, drug, function material There is extensive purposes in material and bioactive compound, with the metal catalyst complex catalyst system and catalyzing such as Ru, Rh, Pd, is being catalyzed C-C keys are coupled【J.Am.Chem.Soc.1998,120 (22), 5579~5580】, chiral hydrogenation【J.Am.Chem.Soc.1995, 117 (9), 2675~2676】, cycloaddition【Angew.Chem.Int.Ed.1997,36 (5), 518~521】Equal reactions have it solely Special catalytic activity.H8-BINAP has the chelating angle of bigger, chiral induction effect more prominent relative to the double diphenylphosphines of dinaphthalene Go out, such as Pd (CF3COO)2Catalyst system and catalyzing with (R)-H8-BINAP compositions is shown high in catalytic hydrogenation indole derivatives Specificity, ee values are up to 98%【J.Am.Chem.Soc.2014,136 (21), 7688~7700】.The prochiral H8- of mesh BINAP methods are reported by EP839819, are esterified and spares two and two are made by adding hydrogen as starting material using dinaphthol Phenyl phosphine oxide coupling reaction, trichlorine silicon hydrogen reduction, then with diphenyl phosphine oxide coupling reaction, trichlorine silicon hydrogen reduction, reaction route compared with It is long, it is more demanding to production equipment wherein use the high poison trichlorine silicon hydrogen of highly volatile, and also to be both needed to silica gel column chromatography pure for product Change, cannot be satisfied the demand of industrial applications.
It, can the present invention provides another in view of the unique catalytic activity of H8-BINAP compounds and vast market prospect Capable reaction route.
Invention content
First problem to be solved by this invention is to provide a kind of mild condition, post-process simply, is suitble to industry metaplasia Produce the preparation method of H8-BINAP ligands.
In order to solve the problems, such as it is in the prior art these, the present invention provides 5,5', 6,6', 7,7', 8,8'- octahydros-[1, 1'- dinaphthalenes] -2,2'- bis- [diphenylphosphines] (hereinafter referred to as H8-BINAP) synthetic method, which is characterized in that it includes as follows Step：
(1) dinaphthol (BINOL) is added in ethanol, catalyst Pd/C is added, one section is reacted under high pressure hydrogen atmosphere Time is cooled to room temperature after completion of the reaction, filters off insoluble matter, and filtrate is concentrated to dryness to obtain spares one, and reaction equation is as follows；
(2) in methylene chloride by the dissolving of above-mentioned spares one, pyridine and trifluoroacetic anhydride is added, it is small that 8-24 is stirred at room temperature When, insoluble matter is filtered off, filtrate is concentrated, carries out crystallization filtering, dries and spares two is made, reaction equation is as follows；
(3) under an inert atmosphere by above-mentioned spares two, palladium catalyst, ligand, diphenylphosphine, basic specie, big is added Polar solvent, reaction temperature react 48~96 hours between 110~130 DEG C, reaction solution are cooled to room temperature, methanol is poured into In, solid, filtering is precipitated, filter cake is eluted with a small amount of methanol, and drying obtains target product, and reaction equation is as follows：
Preferably, the dinaphthol in the step (1) is selected from the mixture of R configurations, S configurations or both.
Preferably, reaction carries out under 60atm hydrogen atmospheres in the step (1), and 75~80 DEG C are reacted 6~8 hours.
Preferably, in the step (2), when concentration filtrate remains a small amount of solvent, methanol is added and is crystallized.
Preferably, in the step (2), after the dissolving in methylene chloride of spares one, pyridine is added, is cooled to 5 DEG C Hereinafter, stirring instills trifluoroacetic anhydride, system temperature is kept to be no more than 25 DEG C.
Preferably, in the step (3), palladium metal catalyst is selected from Pd (OAc)2, PdCl2, Pd2(dba)3, Pd (PPh)4 Or PdCl2(PPh3)2In one or more combinations.
Preferably, in the step (3), the ligand is Phosphine ligands, is selected from DPPE, DPPP, DPPB, P (t-Bu)3Or P(Ch)3In one or more combinations.
Preferably, in the step (3), the basic specie is selected from DIPEA, DBU, DMAP or N, N- dicyclohexylmethylamines In one or more combinations.
Preferably, in the step (3), the big polar solvent is selected from n,N dimethylformamide, N, N dimethyl acetyl One or more combinations in amine, N-Methyl pyrrolidone or 1,4- dioxane.
The net reaction of the present invention is as follows：
Present invention aims at a kind of mild condition is provided, post-processing is simple, is suitble to industrialized production H8-BINAP ligands New method.
Invention route is as described below, and dinaphthol (BINOL) and 5%Pd/C (50%wet), 60atm hydrogen are added in ethanol Under gas atmosphere, 75~80 DEG C are reacted 6~8 hours, are cooled to room temperature, and insoluble matter is filtered off, and filtrate is concentrated to dryness to obtain spares one. The dinaphthol can be the mixture of R configurations, S configurations or both.
Spares one dissolve in methylene chloride, and pyridine and trifluoroacetic anhydride is added, is stirred at room temperature 24 hours, filter off insoluble Object concentrates filtrate, and when remaining a small amount of solvent, methanol crystallization is added, and filtering dries and spares two are made, and is yellow crystalline solid
Under an inert atmosphere, it is molten that palladium catalyst, Phosphine ligands, diphenylphosphine, basic specie, big polarity is added in spares two Agent, diphenylphosphine, reaction temperature react 48~96 hours between 110~130 DEG C, reaction solution are cooled to room temperature, first is poured into In alcohol, solid, filtering is precipitated, filter cake is eluted with a small amount of methanol, and drying obtains target product.The big polar solvent is N, N Dimethylformamide, N, N dimethyl acetamide, N-Methyl pyrrolidone or 1,4- dioxane are chosen any one kind of them；Palladium metal is catalyzed Agent is Pd (OAc)2, PdCl2, Pd2(dba)3, Pd (PPh)4Or PdCl2(PPh3)2It chooses any one kind of them；The Phosphine ligands are DPPE, DPPP, DPPB, P (t-Bu)3Or P (Ch)3It chooses any one kind of them；The basic specie is DIPEA, DBU, DMAP or N, bis- hexamethylenes of N- Base methylamine is chosen any one kind of them.
Solution in compared with the prior art, the beneficial effects of the invention are as follows：Using spares two directly with phosphine hydrogen Target product is prepared in reaction, has step few relative to EP839819, avoids using high poison trichlorine silicon hydrogen, isolates and purifies appearance Easily, it is suitble to industrialized production.This method through catalytic hydrogenation, esterification, then is matched using dinaphthol as starting material in palladium catalyst and phosphine Under body co-catalysis, C-P key coupling reactions are carried out with diphenylphosphine, obtain target product, yield reaches 35%.It is prepared by the present invention Obtained target product has chiral catalysis and Asymmetrical annular-addition field to have unique catalytic activity, in medicine and natural production Object synthesis field has broad application prospects.
Specific implementation mode
In order to make it easy to understand, the present invention will be described in detail by specific embodiment below.It needs to refer in particular to Go out, these descriptions are only exemplary description, and are not meant to limit the scope of the invention.Opinion according to this specification It states, many variations of the invention, change will be apparent from for those skilled in the art.
Embodiment 1
50g (R)-BINOL, 15g 5%Pd/C (50%wet) is added in 1L autoclaves, 300mL ethyl alcohol seals high pressure Kettle vacuumizes, and nitrogen displacement is primary, then hydrogen is replaced 3 times, adjustment pressure to 60atm, temperature is risen to 75~80 DEG C, heat preservation Reaction 8 hours, autoclave is cooled to room temperature, and is filtered, and filtrate is concentrated to dryness spare, obtained thick spares one.
Embodiment 2
Spares one in example 1 are dissolved in 300mL dichloromethane, are added in 32mL pyridine solutions, be cooled to 5 DEG C with Under, 108g trifluoroacetic anhydride is added dropwise, temperature is no more than 25 DEG C when dropwise addition, is added dropwise and is stirred at room temperature 24 hours, filters off insoluble matter, Filtrate is concentrated, when remaining a small amount of solvent, methanol crystallization is added, filters, vacuum drying at 60~70 DEG C obtains 70g yellow spares Two, yield 72%, purity 99.2%.
Embodiment 3
By 1.1g spares two in example 2,0.0448gPd (OAc) (10mol%), 0.085gDPPE (10mol%) add Enter into 5mLDMF solvents, vacuumize, argon gas is replaced into reaction kettle, is then added 0.57gDIPEA and 0.82g diphenylphosphines Enter into reaction system, 120 DEG C are warming up under stirring, heat preservation reflux 72 hours is cooled to room temperature, reaction solution is added to 30mL In methanol, filtering, filter cake is eluted with a small amount of methanol, and vacuum drying at 60~70 DEG C obtains 0.58g off-white powders, yield 46%, 207~208 DEG C of fusing point,31P-NMR(CDCl3):- 16.31 (S), []D+69.7(C 0.5Toluene)。
Embodiment 4-14
Embodiment 4-14 does conditional filtering based on the operation of example 3, only carries out liquid yield statistics.
Embodiment 15
5g (S)-BINOL, 1.5g 5%Pd/C (50%wet), 30mL ethyl alcohol, sealing height are added in 100mL autoclaves Kettle is pressed, is vacuumized, nitrogen displacement is primary, then hydrogen is replaced 3 times, adjustment pressure to 80atm, and temperature is risen to 75~80 DEG C, is protected Temperature reaction 8 hours, autoclave is cooled to room temperature, and is filtered, and filtrate is concentrated to dryness spare, obtained thick spares one
Embodiment 16
Spares one in example 1 are dissolved in 30mL dichloromethane, are added in 3.2mL pyridine solutions, be cooled to 5 DEG C with Under, 10.8g trifluoroacetic anhydride is added dropwise, temperature is no more than 25 DEG C when dropwise addition, is added dropwise and is stirred at room temperature 24 hours, filters off insoluble Object concentrates filtrate, and when remaining a small amount of solvent, methanol crystallization is added, filters, and it is standby to obtain 7.0g yellow for vacuum drying at 60~70 DEG C With object two, yield 74%, purity 99.5%.
Embodiment 17
By 5.5g spares two, 0.224gPd (OAc)2(10mol%), 0.426g DPPP (10mol%), is added to It in 30mLDMF solvents, vacuumizes, argon gas is replaced into reaction kettle, is then added to 2.85gDIPEA and 4.1g diphenylphosphines In reaction system, 120 DEG C are warming up under stirring, heat preservation reflux 72 hours is cooled to room temperature, reaction solution is added to 150mL first In alcohol, filtering, filter cake is eluted with a small amount of methanol, and vacuum drying at 60~70 DEG C obtains 3.2g off-white powders, yield 51.5%, 209~210 DEG C of fusing point, 31P-NMR (CDCl3):- 16.31 (S), [] D-71.2 (C 0.5Toluene).
The foregoing examples are merely illustrative of the technical concept and features of the invention, its object is to allow the person skilled in the art to be It cans understand the content of the present invention and implement it accordingly, it is not intended to limit the scope of the present invention.It is all smart according to the present invention The equivalent transformation or modification that refreshing essence is done, should be covered by the protection scope of the present invention.

Claims (5)

  1. The synthetic method of 1.5,5', 6,6', 7,7', 8,8'- octahydros-[1,1'- dinaphthalene] -2,2'- bis- [diphenylphosphines], feature It is comprising following steps：
    (1) dinaphthol is added in ethanol, catalyst Pd/C is added, a period of time is reacted under 60atm high pressure hydrogen atmosphere, instead It is cooled to room temperature after answering, filters off insoluble matter, filtrate is concentrated to dryness to obtain spares one, and reaction equation is as follows；
    (2) in methylene chloride by the dissolving of above-mentioned spares one, pyridine and trifluoroacetic anhydride is added, is stirred at room temperature 8-24 hours, Insoluble matter is filtered off, filtrate is concentrated, carries out crystallization filtering, dries and spares two is made, reaction equation is as follows；
    (3) under an inert atmosphere by above-mentioned spares two, be added palladium metal catalyst, Phosphine ligands, diphenylphosphine, basic specie, Big polar solvent, reaction temperature react 48~96 hours between 110~130 DEG C, reaction solution are cooled to room temperature, first is poured into In alcohol, solid, filtering is precipitated, filter cake is eluted with a small amount of methanol, and drying obtains target product, and reaction equation is as follows：
    Palladium metal catalyst is selected from Pd (OAc)2, PdCl2, Pd2(dba)3, Pd (PPh)4Or PdCl2(PPh3)2In one kind or more The combination of kind；
    The basic specie is selected from DIPEA, DBU, DMAP or N, one or more combinations in N- dicyclohexylmethylamines；
    The big polar solvent is selected from N, N-dimethylformamide, N, N dimethyl acetamide, N-Methyl pyrrolidone or 1,4- bis- One or more combinations in six ring of oxygen.
  2. 2. synthetic method according to claim 1, which is characterized in that the dinaphthol in the step (1) is selected from R configurations, S The mixture of configuration or both.
  3. 3. synthetic method according to claim 1, which is characterized in that in the step (1) reaction in a hydrogen atmosphere into Row, 75~80 DEG C are reacted 6~8 hours.
  4. 4. synthetic method according to claim 1, which is characterized in that in the step (2), spares one are dissolved in dichloro After in methane, pyridine is added, is cooled to 5 DEG C hereinafter, stirring instills trifluoroacetic anhydride, holding system temperature is no more than 25 DEG C.
  5. 5. synthetic method according to claim 1, which is characterized in that in the step (3), the Phosphine ligands are selected from DPPE, DPPP, DPPB, P (t-Bu)3Or P (Cy)3In one or more combinations.
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JP2681057B2 (en) * 1990-10-01 1997-11-19 高砂香料工業株式会社 2,2'-bis (diphenylphosphino) -5,5 ', 6,6', 7,7 ', 8,8'-octahydro-1,1'-binaphthyl and transition metal having this as a ligand Complex
JP3437623B2 (en) * 1994-01-12 2003-08-18 高砂香料工業株式会社 Method for producing ruthenium-iodo-optically active phosphine complex and method for producing optically active 4-methyl-2-oxetanone using this complex
JP3020128B2 (en) * 1994-03-08 2000-03-15 高砂香料工業株式会社 Method for producing optically active carboxylic acid
JP3445451B2 (en) * 1996-10-24 2003-09-08 高砂香料工業株式会社 Method for producing optically active diphosphine ligand
JP2001122847A (en) * 1999-10-28 2001-05-08 Central Glass Co Ltd Production of binaphthyl derivative
JP4416466B2 (en) * 2003-10-02 2010-02-17 高砂香料工業株式会社 Method for producing benzene derivatives
DE10349399A1 (en) * 2003-10-21 2005-06-02 Degussa Ag Process for the reduction of binaphthyl derivatives

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