CN101747125B - Methods for preparing biaryl compound and diolefin compound - Google Patents

Methods for preparing biaryl compound and diolefin compound Download PDF

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CN101747125B
CN101747125B CN200910260220A CN200910260220A CN101747125B CN 101747125 B CN101747125 B CN 101747125B CN 200910260220 A CN200910260220 A CN 200910260220A CN 200910260220 A CN200910260220 A CN 200910260220A CN 101747125 B CN101747125 B CN 101747125B
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CN101747125A (en
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韩福社
高连勋
赵玉龙
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Changzhou Institute of Energy Storage Materials & Devices
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention discloses a method for preparing a biaryl compound, comprising the following steps: a) adding a phenol compound, phosphorus oxide halide and solvent in a reactor to form reacting solution and stirring the solution to obtain an intermediate product; and b) mixing the intermediate product with organic boric acid, transition metal salt catalyst, ligand, basic metal salt and solvent to perform coupling reaction. The invention also discloses a method for preparing a diolefin compound, comprising the following steps: a) adding an enol compound, phosphorus oxide halide and solvent in a reactor to form reacting solution, and stirring the solution to obtain an intermediate; and b) mixing the intermediate with organic boric acid, transition metal salt catalyst, ligand, basic metal salt and solvent to perform coupling reaction. Compared with the prior art, the invention uses the phosphorus oxide halide compound to activate the phenol compound or the enol compound to obtain an activated product which is relatively stable, has stronger reaction activity and is in favor of subsequent coupling reaction.

Description

The preparation method of a kind of biaryl hydro carbons and diolefin compounds
Technical field
The present invention relates to a kind of preparation method of hydrocarbon compound, relate in particular to the preparation method of a kind of biaryl hydro carbons and diolefin compounds.
Background technology
The biaryl compounds is widely used in macromolecular material, liquid crystal material or medicine intermediate, as: 3,3,3 ', 4 '-the tetramethyl-terphenyl is used for conducting polymer composite, 4 '-methyl diphenyl-2-formonitrile HCN is the midbody of sartans.
Prior art discloses the multiple method for preparing the biaryl compounds.Wherein, Comparatively commonly used is to be that raw material, transition metal are catalyzer with the phenolic cpd; Make the biaryl compounds through linked reaction; Canonical process is following: earlier with the phenolic hydroxyl group activation of phenolic cpd, coupling under the katalysis of the transition metal of part complexing obtains the biaryl compounds again.
In the prior art, generally generate corresponding ester with the phenolic hydroxyl group activation through acvator and phenolic cpd, acvator commonly used is trifluoromethanesulfchloride chloride (CF 3SO 2Cl), p-toluenesulfonyl chloride, methylsulfonyl chloride, alkyl acyl chloride (RCOCl) or sulfamic acid chloride etc.But, these acvators or cost an arm and a leg, the Ester of generation is unstable, as by the triflate that generates after the trifluoromethanesulfchloride chloride activation, follow-up linked reaction is impacted; To the poor compatibility of raw material, can only be used for the compound of one type of ad hoc structure.Simultaneously, prior art is used the palladium or the nickel of part complexing mostly, like Ni [COD] 2, Ni [P (Cy 3) 2] Cl 2Deng as catalyzer, this type catalyzer not only costs an arm and a leg, and reaction conditions is had relatively high expectations, and needs secluding air and water, has increased operation easier.
Because enols used have identical SP2 hydridization atomic structure of carbon with phenolic cpd; And the diolefin compounds that generates after the enols used coupling is used comparatively extensive; Therefore; The inventor considers, can select suitable acvator, catalyzer and part, with phenols or enols used be feedstock production biaryl or diolefin compounds.
Summary of the invention
In view of this; The technical problem that the present invention will solve is to provide the preparation method of a kind of biaryl and diolefin; This method with phenols or enols used be raw material, use that compatible acvator, cheap catalyzer and part prepare biaryl and diolefin preferably.
The invention provides a kind of preparation method of biaryl compounds, comprising:
A) in reactor drum, add phenolic cpd, acvator and solvent, form reaction soln, stir said reaction soln, obtain intermediate product;
The compound of said acvator for having formula (I) structure:
Figure G2009102602207D00021
Wherein, X is Cl, Br or I;
Y is N, O or S;
B) intermediate product and organic boronic, transition metal salt catalyst, part, alkaline metal salt and the solvent that step a) are obtained are carried out linked reaction.
Preferably, said acvator is two (2-oxo-3-oxazolidinyl) inferior phosphoryl chlorides.
Preferably, said catalyzer is NiCl 2, NiBr 2, NiI 2, NiSO 4Or Ni (OAc) 2
Preferably, the compound of said part for having formula (II) structure:
Figure G2009102602207D00022
Wherein, n=1,2,3 or 4.
Preferably, said solvent is methyl-sulphoxide, N, dinethylformamide, DMAC N,N, dioxane, THF, toluene, dimethyl-terepthaloyl moietie or n-butyl ether.
Preferably, said phenolic cpd and acvator are 1 in molar ratio: 1-3.Preferably, in the said step b), said intermediate product and organic boronic are 1 in molar ratio: 1-3.Preferably, the compound of said organic boronic for having formula (III) structure or formula (IV) structure:
Wherein, R is phenyl, naphthyl or heterocyclic aromatic base;
R 1Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl;
R 2Be hydrogen or alkyl;
R 3Be hydrogen or alkyl;
R 4Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl;
R 5Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl;
R 6Be hydrogen or alkyl;
R 7Be hydrogen or alkyl.
Preferably, the temperature of said linked reaction is 50 ℃-150 ℃.
The present invention also provides a kind of preparation method of diolefin compounds, comprising:
1) in reactor drum, adds enols used, acvator and solvent, form mixing solutions, stir said mixing solutions, obtain midbody;
The compound of said acvator for having formula (I) structure:
Figure G2009102602207D00032
Wherein, X is Cl, Br or I;
Y is N, O or S;
2) midbody and organic boronic, transition metal salt catalyst, part, alkaline metal salt and the solvent that step 1) are obtained are carried out linked reaction.
Compared with prior art, the present invention is an acvator activation phenols or enols used with commercial phosphoryl halogen compounds, and the activation products that obtain are comparatively stable, and reactive behavior is higher, helps carrying out follow-up linked reaction, can improve productive rate.Simultaneously, the phosphoryl halogen compounds is compatible better, can the most of phenols of activation or enols used, also can activation have the compound of ester group, cyanic acid isoreactivity functional group.In addition, that the present invention also adopts is cheap, the catalyzer and the part of good stability, makes reaction need not under the condition of secluding air and water, to carry out, and has reduced cost, has reduced operation easier.
Embodiment
The invention provides a kind of preparation method of biaryl compounds, comprising:
A) in reactor drum, add phenolic cpd, acvator and solvent, form reaction soln, stir said reaction soln, obtain intermediate product;
The compound of said acvator for having formula (I) structure:
Figure G2009102602207D00041
Wherein, X is Cl, Br or I;
Y is N, O or S;
B) intermediate product and organic boronic, transition metal salt catalyst, part, alkaline metal salt and the solvent that step a) are obtained are carried out linked reaction.
Raw material of the present invention is a phenolic cpd, after phenolic cpd is activated the agent activation, under the effect of transition metal salt catalyst, with organic boronic generation linked reaction, generates biaryl compounds or aromatic hydrocarbons-alkenes compounds.
According to the present invention, said phenolic cpd is for having R 1The compound of '-R '-OH structure, wherein, R ' is phenyl, naphthyl or heterocyclic aromatic base; R 1' be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl.
The present invention does not have particular restriction to the source of phenolic cpd, is preferably mode well known to those skilled in the art and obtains or buy from market.
According to the present invention, the compound of said acvator for having formula (I) structure:
Figure G2009102602207D00051
Wherein, X is Cl, Br or I;
Y is N, O or S;
According to the present invention, said acvator includes but not limited to the compound that following table is listed:
Figure G2009102602207D00061
Said acvator is preferably two (2-oxo-3-oxazolidinyl) inferior phosphoryl chlorides.The present invention does not have particular restriction to the source of said acvator, is preferably mode well known to those skilled in the art and prepares or buy from market.
The present invention does not have particular restriction to said solvent, is preferably methyl-sulphoxide, N, dinethylformamide, DMAC N,N, dioxane, THF, toluene, dimethyl-terepthaloyl moietie or n-butyl ether.
According to the present invention, said phenolic cpd and said acvator at room temperature stir, and react, and obtain the activatory intermediate product, react as follows:
Figure G2009102602207D00062
Wherein, X is Cl, Br or I; Y is N, O or S; R ' is phenyl, naphthyl or heterocyclic aromatic base; R 1' be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl.
According to the present invention, said phenolic cpd and said acvator are preferably 1 in molar ratio: 1-5, and more preferably 1: 1-3 most preferably is 1: 1-2; Said churning time is preferably 2-20 hour, more preferably 3-20 hour, most preferably is 3-15 hour.
According to the present invention, obtain intermediate product after, with said intermediate product and organic boronic, transition metal salt catalyst, part, alkaline metal salt and solvent, carry out linked reaction.
According to the present invention, said transition metal salt catalyst is preferably NiCl 2, NiBr 2, NiI 2, NiSO 4Or Ni (OAc) 2Said part is preferably the compound of (II) structure that has formula:
Figure G2009102602207D00071
Wherein, n=1,2,3 or 4; Said catalyzer and part form complex compound and play katalysis.
According to the present invention, said alkaline metal salt is preferably Na 2CO 3, K 2CO 3, NaOAc, KOAc, Na 3PO 4Or K 3PO 4Said solvent is preferably methyl-sulphoxide, N, dinethylformamide, DMAC N,N, dioxane, THF, toluene, dimethyl-terepthaloyl moietie or n-butyl ether.
The present invention does not have particular restriction to organic boronic, is preferably the compound of (III) structure that has formula or formula (IV) structure:
Figure G2009102602207D00072
Wherein, R is phenyl, naphthyl or heterocyclic aromatic base;
R 1Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl;
R 2Be hydrogen or alkyl;
R 3Be hydrogen or alkyl;
R 4Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl;
R 5Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl;
R 6Be hydrogen or alkyl;
R 7Be hydrogen or alkyl.
According to the present invention, linked reaction takes place in said organic boronic and said intermediate product in solvent under the effect of catalyzer, part, alkaline metal salt.
When organic boric acid was the compound of formula (III) structure, linked reaction generated biaryl, reacted as follows:
Figure G2009102602207D00073
Wherein, X is Cl, Br or I; Y is N, O or S; R ' is phenyl, naphthyl or heterocyclic aromatic base; R 1' be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl; R is phenyl, naphthyl or heterocyclic aromatic base; R 1Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl; R 2Be hydrogen or alkyl; R 3Be hydrogen or alkyl;
When organic boric acid was the compound of formula (IV) structure, linked reaction generated the compound of aromatic hydrocarbons-alkene structures, reacted as follows:
Figure G2009102602207D00081
Wherein, X is Cl, Br or I; Y is N, O or S; R ' is phenyl, naphthyl or heterocyclic aromatic base; R 1' be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl; R 4Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl; R 5Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl; R 6Be hydrogen or alkyl; R 7Be hydrogen or alkyl.
According to the present invention, said intermediate product and organic boronic are preferably 1 in molar ratio: 1-5, and more preferably 1: 1-3 most preferably is 1: 1-2; The temperature of reaction of said linked reaction is preferably 20 ℃-180 ℃, more preferably 30 ℃-160 ℃, most preferably is 50 ℃-150 ℃; The reaction times of said linked reaction is preferably 2-50 hour, more preferably 3-50 hour, most preferably is 5-50 hour.
The present invention also provides a kind of preparation method of diolefin compounds, comprising:
1) in reactor drum, adds enols used, acvator and solvent, form mixing solutions, stir said mixing solutions, obtain midbody;
The compound of said acvator for having formula (I) structure:
Figure G2009102602207D00082
Wherein, X is Cl, Br or I;
Y is N, O or S;
2) midbody and organic boronic, transition metal salt catalyst, part, alkaline metal salt and the solvent that step 1) are obtained are carried out linked reaction.
Preparing method provided by the invention is to be raw material with enols used, be activated the agent activation after, under the effect of catalyzer,, generate diolefin compounds or aromatic hydrocarbons-alkenes compounds with organic boronic generation linked reaction.
Because enol is unstable, the form with aldehydes or ketones exists usually, therefore enols usedly comprises compound with formula V structure and the compound with formula (VI) structure, and the compound of the compound of formula V structure and formula (VI) structure is a tautomer:
Figure G2009102602207D00091
Wherein, R 8Be hydrogen or alkyl; R 9Be hydrogen or alkyl.
The present invention does not have particular restriction to enols used source, is preferably mode well known to those skilled in the art and obtains or buy from market.
According to the present invention, the compound of said acvator for having formula (I) structure:
Figure G2009102602207D00092
Wherein, X is Cl, Br or I;
Y is N, O or S;
According to the present invention, said acvator includes but not limited to the compound that following table is listed:
Figure G2009102602207D00101
Said acvator is preferably two (2-oxo-3-oxazolidinyl) inferior phosphoryl chlorides.The present invention does not have particular restriction to the source of said acvator, is preferably mode well known to those skilled in the art or buys from market.
The present invention does not have particular restriction to said solvent, is preferably methyl-sulphoxide, N, dinethylformamide, DMAC N,N, dioxane, THF, toluene, dimethyl-terepthaloyl moietie or n-butyl ether.
According to the present invention, said enols used and said acvator at room temperature stirs, and reacts, and obtains the activatory intermediate product, when enols used when having the compound of formula V structure, reaction as follows:
Figure G2009102602207D00102
Wherein, X is Cl, Br or I; Y is N, O or S; R 8Be hydrogen or alkyl; R 9Be hydrogen or alkyl;
When having the compound of formula (VI) structure, reaction as follows takes place when enols used:
According to the present invention, said enols used and said acvator is preferably 1 in molar ratio: 1-5, and more preferably 1: 1-3 most preferably is 1: 1-2; Said churning time is preferably 2-20 hour, more preferably 3-20 hour, most preferably is 3-15 hour.
According to the present invention, obtain intermediate product after, with said intermediate product and organic boronic, transition metal salt catalyst, part, alkaline metal salt and solvent, carry out linked reaction.
According to the present invention, said catalyzer is preferably NiCl 2, NiBr 2, NiI 2, NiSO 4Or Ni (OAc) 2Said part is preferably the compound of (II) structure that has formula:
Figure G2009102602207D00112
Wherein, n=1,2,3 or 4; Said catalyzer and part form complex compound and play katalysis.
According to the present invention, said alkaline metal salt is preferably Na 2CO 3, K 2CO 3, NaOAc, KOAc, Na 3PO 4Or K 3PO 4Said solvent is preferably methyl-sulphoxide, N, dinethylformamide, DMAC N,N, dioxane, THF, toluene, dimethyl-terepthaloyl moietie or n-butyl ether.
The present invention does not have particular restriction to organic boronic, is preferably the compound of (III) structure that has formula or formula (IV) structure:
Wherein, R is phenyl, naphthyl or heterocyclic aromatic base;
R 1Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl;
R 2Be hydrogen or alkyl;
R 3Be hydrogen or alkyl;
R 4Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl;
R 5Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl;
R 6Be hydrogen or alkyl;
R 7Be hydrogen or alkyl.
According to the present invention, linked reaction takes place in said organic boronic and said intermediate product in solvent under the effect of transition metal salt catalyst, part, alkaline metal salt.
When organic boric acid is the compound of formula (III) structure, generate the compound of aromatic hydrocarbons-alkene structures, react as follows:
Figure G2009102602207D00121
Wherein, X is Cl, Br or I; Y is N, O or S; R is phenyl, naphthyl or heterocyclic aromatic base; R 1Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl; R 2Be hydrogen or alkyl; R 3Be hydrogen or alkyl; R 8Be hydrogen or alkyl; R 9Be hydrogen or alkyl;
When organic boric acid is the compound of formula (IV) structure, generate the compound of diolefin structure, react as follows:
Wherein, X is Cl, Br or I; Y is N, O or S; R 4Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl; R 5Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl; R 6Be hydrogen or alkyl; R 7Be hydrogen or alkyl; R 8Be hydrogen or alkyl; R 9Be hydrogen or alkyl.
According to the present invention, said intermediate product and organic boronic are preferably 1 in molar ratio: 1-5, and more preferably 1: 1-3 most preferably is 1: 1-2; The temperature of reaction of said linked reaction is preferably 20 ℃-180 ℃, more preferably 30 ℃-160 ℃, most preferably is 50 ℃-150 ℃; The reaction times of said linked reaction is preferably 2-50 hour, more preferably 3-50 hour, most preferably is 5-50 hour.
Compared with prior art, the present invention is an acvator activation phenols or enols used with commercial phosphoryl halogen compounds, and the activation products that obtain are comparatively stable, and have high reaction activity and high, helps carrying out follow-up linked reaction, can improve productive rate.Simultaneously, the phosphoryl halogen compounds is compatible better, can the most of phenols of activation or enols used, also can activation have the compound of ester group, cyanic acid isoreactivity functional group.In addition, that the present invention also adopts is cheap, the catalyzer and the part of good stability, makes reaction need not under the condition of secluding air and water, to carry out, and has reduced cost, has reduced operation easier.
In order further to understand the present invention, the preparation method of biaryl provided by the invention and diolefin is described below in conjunction with embodiment.
Embodiment 1
In 50 milliliters of round-bottomed flasks, add 5.0 mmoles (540 milligrams) p-methyl phenol, the inferior phosphoryl chloride of 6.0 mmoles (1524 milligrams) two (2-oxo-3-oxazolidinyl), 0.5 mmole 4-dimethylamino pyridine (DMAP) and 20mL dichloromethane solution, form mixing solutions;
Under the stirring at room, to said mixed solution and dripping 6.0 mmole triethylamine (NEt 3), continue at normal temperatures then to stir 3 hours, carry out thin-layer chromatographic analysis (TLC), confirm that p-methyl phenol reacts completely;
Reaction mixture is poured in the 100mL water; Use dichloromethane extraction; Steam down with anhydrous sodium sulfate drying, underpressure distillation then and desolventize; Residuum is carried out silica gel column chromatography separate, elutriant is the mixed solution of sherwood oil, ETHYLE ACETATE and methylene dichloride, and sherwood oil, ETHYLE ACETATE and methylene dichloride are 1: 1: 3 by volume; Finally obtain 1581 milligrams of phosphotidic compounds, productive rate 97%.Reaction as shown in the formula:
Figure G2009102602207D00141
Embodiment 2
In 50 milliliters of round-bottomed flasks, add 5.0 mmoles (540 milligrams) ortho-methyl phenol, the inferior phosphoryl chloride of 6.0 mmoles (1524 milligrams) two (2-oxo-3-oxazolidinyl), 0.5 mmole 4-dimethylamino pyridine (DMAP) and 20mL dichloromethane solution, form mixing solutions;
Under the stirring at room,, continue at normal temperatures then to stir 4 hours, carry out thin-layer chromatographic analysis (TLC), confirm that p-methyl phenol reacts completely to said mixed solution and dripping 6.0 mmole triethylamines (NEt3);
Reaction mixture is poured in the 100mL water; Use dichloromethane extraction; Steam down with anhydrous sodium sulfate drying, underpressure distillation then and desolventize; Residuum is carried out silica gel column chromatography separate, elutriant is the mixed solution of sherwood oil, ETHYLE ACETATE and methylene dichloride, and sherwood oil, ETHYLE ACETATE and methylene dichloride are 1: 1: 3 by volume; Finally obtain 1467 milligrams of phosphotidic compounds, productive rate 90%.Reaction as shown in the formula:
Figure G2009102602207D00142
Embodiment 3
In 50 milliliters of round-bottomed flasks, add 5.0 mmoles (685 milligrams) 3-dimethylamino phenol, the inferior phosphoryl chloride of 6.0 mmoles (1524 milligrams) two (2-oxo-3-oxazolidinyl), 0.5 mmole 4-dimethylamino pyridine (DMAP) and 20mL dichloromethane solution, form mixing solutions;
Under the stirring at room, to said mixed solution and dripping 6.0 mmole triethylamine (NEt 3), continue at normal temperatures then to stir 3 hours, carry out thin-layer chromatographic analysis (TLC), confirm that 3-dimethylamino phenol reactant is complete;
Reaction mixture is poured in the 100mL water; Use dichloromethane extraction; Steam down with anhydrous sodium sulfate drying, underpressure distillation then and desolventize; Residuum is carried out silica gel column chromatography separate, elutriant is the mixed solution of sherwood oil, ETHYLE ACETATE and methylene dichloride, and sherwood oil, ETHYLE ACETATE and methylene dichloride are 1: 1: 3 by volume; Finally obtain 1633 milligrams of phosphotidic compounds, productive rate 92%.Reaction as shown in the formula:
Figure G2009102602207D00151
Embodiment 4
In 50 milliliters of round-bottomed flasks, add 5.0 mmoles (470 milligrams) phenol, the inferior phosphoryl chloride of 6.0 mmoles (1524 milligrams) two (2-oxo-3-oxazolidinyl), 0.5 mmole 4-dimethylamino pyridine (DMAP) and 20mL dichloromethane solution, form mixing solutions;
Under the stirring at room, to said mixed solution and dripping 6.0 mmole triethylamine (NEt 3), continue at normal temperatures then to stir 3 hours, carry out thin-layer chromatographic analysis (TLC), confirm that phenol reactant is complete;
Reaction mixture is poured in the 100mL water; Use dichloromethane extraction; Steam down with anhydrous sodium sulfate drying, underpressure distillation then and desolventize; Residuum is carried out silica gel column chromatography separate, elutriant is the mixed solution of sherwood oil, ETHYLE ACETATE and methylene dichloride, and sherwood oil, ETHYLE ACETATE and methylene dichloride are 1: 1: 3 by volume; Finally obtain 1467 milligrams of phosphotidic compounds, productive rate 94%.Reaction as shown in the formula:
Figure G2009102602207D00152
Embodiment 5
In 50 milliliters of round-bottomed flasks, add 5.0 mmoles (595 milligrams) 4-hydroxybenzonitrile, the inferior phosphoryl chloride of 6.0 mmoles (1524 milligrams) two (2-oxo-3-oxazolidinyl), 0.5 mmole 4-dimethylamino pyridine (DMAP) and 20mL dichloromethane solution, form mixing solutions;
Under the stirring at room, to said mixed solution and dripping 6.0 mmole triethylamine (NEt 3), continue at normal temperatures then to stir 3 hours, carry out thin-layer chromatographic analysis (TLC), confirm that 4-hydroxybenzonitrile reacts completely;
Reaction mixture is poured in the 100mL water; Use dichloromethane extraction; Steam down with anhydrous sodium sulfate drying, underpressure distillation then and desolventize; Residuum is carried out silica gel column chromatography separate, elutriant is the mixed solution of sherwood oil, ETHYLE ACETATE and methylene dichloride, and sherwood oil, ETHYLE ACETATE and methylene dichloride are 1: 1: 3 by volume; Finally obtain 1550 milligrams of phosphotidic compounds, productive rate 92%.Reaction as shown in the formula:
Embodiment 6
In 50 milliliters of round-bottomed flasks, add pyridone, the inferior phosphoryl chloride of 6.0 mmoles (1524 milligrams) two (2-oxo-3-oxazolidinyl), 0.5 mmole 4-dimethylamino pyridine (DMAP) and 20mL dichloromethane solution between 5.0 mmoles (475 milligrams), form mixing solutions;
Under the stirring at room, to said mixed solution and dripping 6.0 mmole triethylamine (NEt 3), continue at normal temperatures then to stir 3 hours, carry out thin-layer chromatographic analysis (TLC), pyridone reacts completely between confirming;
Reaction mixture is poured in the 100mL water; Use dichloromethane extraction; Steam down with anhydrous sodium sulfate drying, underpressure distillation then and desolventize; Residuum is carried out silica gel column chromatography separate, elutriant is the mixed solution of sherwood oil, ETHYLE ACETATE and methylene dichloride, and sherwood oil, ETHYLE ACETATE and methylene dichloride are 1: 1: 3 by volume; Finally obtain 1346 milligrams of phosphotidic compounds, productive rate 86%.Reaction as shown in the formula:
Figure G2009102602207D00171
Embodiment 7
In 50 milliliters of round-bottomed flasks, add 5.0 mmoles (720 milligrams) beta naphthal, the inferior phosphoryl chloride of 6.0 mmoles (1524 milligrams) two (2-oxo-3-oxazolidinyl), 0.5 mmole 4-dimethylamino pyridine (DMAP) and 20mL dichloromethane solution, form mixing solutions;
Under the stirring at room, to said mixed solution and dripping 6.0 mmole triethylamine (NEt 3), continue at normal temperatures then to stir 3 hours, carry out thin-layer chromatographic analysis (TLC), confirm that beta naphthal reacts completely;
Reaction mixture is poured in the 100mL water; Use dichloromethane extraction; Steam down with anhydrous sodium sulfate drying, underpressure distillation then and desolventize; Residuum is carried out silica gel column chromatography separate, elutriant is the mixed solution of sherwood oil, ETHYLE ACETATE and methylene dichloride, and sherwood oil, ETHYLE ACETATE and methylene dichloride are 1: 1: 3 by volume; Finally obtain 1720 milligrams of phosphotidic compounds, productive rate 95%.Reaction as shown in the formula:
Embodiment 8
In 50 milliliters of round-bottomed flasks, add 5.0 mmoles (720 milligrams) 1-naphthols, the inferior phosphoryl chloride of 6.0 mmoles (1524 milligrams) two (2-oxo-3-oxazolidinyl), 0.5 mmole 4-dimethylamino pyridine (DMAP) and 20mL dichloromethane solution, form mixing solutions;
Under the stirring at room, to said mixed solution and dripping 6.0 mmole triethylamine (NEt 3), continue at normal temperatures then to stir 3 hours, carry out thin-layer chromatographic analysis (TLC), confirm that the 1-naphthol reaction is complete;
Reaction mixture is poured in the 100mL water; Use dichloromethane extraction; Steam down with anhydrous sodium sulfate drying, underpressure distillation then and desolventize; Residuum is carried out silica gel column chromatography separate, elutriant is the mixed solution of sherwood oil, ETHYLE ACETATE and methylene dichloride, and sherwood oil, ETHYLE ACETATE and methylene dichloride are 1: 1: 3 by volume; Finally obtain 1629 milligrams of phosphotidic compounds, productive rate 90%.Reaction as shown in the formula:
Figure G2009102602207D00181
Embodiment 9
In 50 milliliters of round-bottomed flasks, add 5.0 mmoles (870 milligrams) 4-methoxyl group-1-naphthols, the inferior phosphoryl chloride of 6.0 mmoles (1524 milligrams) two (2-oxo-3-oxazolidinyl), 0.5 mmole 4-dimethylamino pyridine (DMAP) and 20mL dichloromethane solution, form mixing solutions;
Under the stirring at room,, continue at normal temperatures then to stir 3 hours, carry out thin-layer chromatographic analysis (TLC), confirm that 4-methoxyl group-1-naphthol reaction is complete to said mixed solution and dripping 6.0 mmole triethylamines (NEt3);
Reaction mixture is poured in the 100mL water; Use dichloromethane extraction; Steam down with anhydrous sodium sulfate drying, underpressure distillation then and desolventize; Residuum is carried out silica gel column chromatography separate, elutriant is the mixed solution of sherwood oil, ETHYLE ACETATE and methylene dichloride, and sherwood oil, ETHYLE ACETATE and methylene dichloride are 1: 1: 3 by volume; Finally obtain 1629 milligrams of phosphotidic compounds, productive rate 90%.Reaction as shown in the formula:
Figure G2009102602207D00182
Embodiment 10
In 30 milliliters of reaction vessels, add the anhydrous Nickel Chloride of 0.05 mmole, 0.1 mmole (41.2 milligrams) 1; 3-two (diphenylphosphine) propane (dppp), 0.5 mmole (181 milligrams) are implemented phosphotidic compound, 1.0 mmole 4-methoxyphenylboronic acids, 2.0 mmole Anhydrous potassium carbonates and 5mL dioxane (dioxane) solution of 8 preparations, form mixing solutions;
Under the nitrogen protection condition, said mixing solutions was heated 24 hours down at 100 ℃, carry out thin-layer chromatographic analysis (TLC), confirm that the phosphotidic compound reacts completely;
Reaction mixture is poured in the 20mL water; Use dichloromethane extraction, desolventize with steaming under anhydrous sodium sulfate drying, the underpressure distillation then, residuum is carried out silica gel column chromatography separate; Elutriant is the mixed solution of sherwood oil and methylene dichloride, and sherwood oil, methylene dichloride are 10: 1 by volume; Finally obtain 112 milligrams of biphenol compounds, productive rate 96%.Reaction as shown in the formula:
Figure G2009102602207D00191
Embodiment 11
In 30 milliliters of reaction vessels, add the anhydrous Nickel Chloride of 0.05 mmole, 0.1 mmole (41.2 milligrams) 1; 3-two (diphenylphosphine) butane (dppb), 0.5 mmole (181 milligrams) are implemented phosphotidic compound, 1.0 mmole 4-methoxyphenylboronic acids, 2.0 mmole Anhydrous potassium carbonates and 5mL dioxane (dioxane) solution of 8 preparations, form mixing solutions;
Under the nitrogen protection condition, said mixing solutions was heated 24 hours down at 100 ℃, carry out thin-layer chromatographic analysis (TLC), confirm that the phosphotidic compound reacts completely;
Reaction mixture is poured in the 20mL water; Use dichloromethane extraction, desolventize with steaming under anhydrous sodium sulfate drying, the underpressure distillation then, residuum is carried out silica gel column chromatography separate; Elutriant is the mixed solution of sherwood oil and methylene dichloride, and sherwood oil, methylene dichloride are 10: 1 by volume; Finally obtain 98.3 milligrams of biphenol compounds, productive rate 84%.Reaction as shown in the formula:
Figure G2009102602207D00201
Embodiment 12
In 30 milliliters of reaction vessels, add the anhydrous Nickel Chloride of 0.05 mmole, 0.1 mmole (41.2 milligrams) 1; 2-two (diphenylphosphine) ethane (dppe), 0.5 mmole (181 milligrams) are implemented phosphotidic compound, 1.0 mmole 4-methoxyphenylboronic acids, 2.0 mmole Anhydrous potassium carbonates and 5mL dioxane (dioxane) solution of 8 preparations, form mixing solutions;
Under the nitrogen protection condition, said mixing solutions was heated 24 hours down at 100 ℃, carry out thin-layer chromatographic analysis (TLC), confirm that the phosphotidic compound reacts completely;
Reaction mixture is poured in the 20mL water; Use dichloromethane extraction, desolventize with steaming under anhydrous sodium sulfate drying, the underpressure distillation then, residuum is carried out silica gel column chromatography separate; Elutriant is the mixed solution of sherwood oil and methylene dichloride, and sherwood oil, methylene dichloride are 10: 1 by volume; Finally obtain 88.9 milligrams of biphenol compounds, productive rate 76%.Reaction as shown in the formula:
Figure G2009102602207D00202
Embodiment 13
In 30 milliliters of reaction vessels, add the anhydrous Nickel Chloride of 0.05 mmole, 0.1 mmole (41.2 milligrams) 1; 3-two (diphenylphosphine) propane (dppp), 0.5 mmole (181 milligrams) are implemented phosphotidic compound, 1.0 mmole 4-methoxycarbonyl phenylo boric acids, 2.0 mmole Anhydrous potassium carbonates and 5mL dioxane (dioxane) solution of 8 preparations, form mixing solutions;
Under the nitrogen protection condition, said mixing solutions was heated 24 hours down at 100 ℃, carry out thin-layer chromatographic analysis (TLC), confirm that the phosphotidic compound reacts completely;
Reaction mixture is poured in the 20mL water; Use dichloromethane extraction, desolventize with steaming under anhydrous sodium sulfate drying, the underpressure distillation then, residuum is carried out silica gel column chromatography separate; Elutriant is the mixed solution of sherwood oil and methylene dichloride, and sherwood oil, methylene dichloride are 10: 1 by volume; Finally obtain 121 milligrams of biphenol compounds, productive rate 92%.Reaction as shown in the formula:
Figure G2009102602207D00211
Embodiment 14
In 30 milliliters of reaction vessels, add the anhydrous Nickel Chloride of 0.05 mmole, 0.1 mmole (41.2 milligrams) 1; 3-two (diphenylphosphine) propane (dppp), 0.5 mmole (181 milligrams) are implemented phosphotidic compound, 1.0 mmole phenylo boric acids, 2.0 mmole Anhydrous potassium carbonates and 5mL dioxane (dioxane) solution of 8 preparations, form mixing solutions;
Under the nitrogen protection condition, said mixing solutions was heated 24 hours down at 100 ℃, carry out thin-layer chromatographic analysis (TLC), confirm that the phosphotidic compound reacts completely;
Reaction mixture is poured in the 20mL water; Use dichloromethane extraction, desolventize with steaming under anhydrous sodium sulfate drying, the underpressure distillation then, residuum is carried out silica gel column chromatography separate; Elutriant is the mixed solution of sherwood oil and methylene dichloride, and sherwood oil, methylene dichloride are 10: 1 by volume; Finally obtain 121 milligrams of biphenol compounds, productive rate 92%.Reaction as shown in the formula:
Figure G2009102602207D00212
Embodiment 15
In 30 milliliters of reaction vessels, add the anhydrous Nickel Chloride of 0.05 mmole, 0.1 mmole (41.2 milligrams) 1; 3-two (diphenylphosphine) propane (dppp), 0.5 mmole (181 milligrams) are implemented phosphotidic compound, 1.0 mmole 4-methoxyphenylboronic acids, 2.0 mmole Anhydrous potassium carbonates and 5mL dioxane (dioxane) solution of 1 preparation, form mixing solutions;
Under the nitrogen protection condition, said mixing solutions was heated 24 hours down at 100 ℃, carry out thin-layer chromatographic analysis (TLC), confirm that the phosphotidic compound reacts completely;
Reaction mixture is poured in the 20mL water; Use dichloromethane extraction, desolventize with steaming under anhydrous sodium sulfate drying, the underpressure distillation then, residuum is carried out silica gel column chromatography separate; Elutriant is the mixed solution of sherwood oil and methylene dichloride, and sherwood oil, methylene dichloride are 10: 1 by volume; Finally obtain 74.3 milligrams of biphenol compounds, productive rate 75%.Reaction as shown in the formula:
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.

Claims (6)

1. the preparation method of a biaryl compounds is characterized in that, comprising:
A) in reactor drum, add phenolic cpd, acvator and solvent, form reaction soln, stir said reaction soln, obtain intermediate product; Said solvent is methyl-sulphoxide, N, dinethylformamide, DMAC N,N, dioxane, THF, toluene, dimethyl-terepthaloyl moietie, n-butyl ether or methylene dichloride;
The compound of said acvator for having formula (I) structure:
Figure FDA0000126063380000011
Wherein, X is Cl, Br or I;
Y is N, O or S;
B) intermediate product and organic boronic, transition metal salt catalyst, part, alkaline metal salt and the solvent that step a) are obtained are carried out linked reaction;
Said solvent is methyl-sulphoxide, N, dinethylformamide, DMAC N,N, dioxane, THF, toluene, dimethyl-terepthaloyl moietie or n-butyl ether;
The compound of said organic boronic for having formula (III) structure or formula (IV) structure:
Figure FDA0000126063380000012
Wherein, R is phenyl, naphthyl or heterocyclic aromatic base;
R 1Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl;
R 2Be hydrogen or alkyl;
R 3Be hydrogen or alkyl;
R 4Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl;
R 5Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl;
R 6Be hydrogen or alkyl;
R 7Be hydrogen or alkyl;
Said transition metal salt catalyst is NiCl 2, NiBr 2, NiI 2, NiSO 4Or Ni (OAc) 2
The compound of said part for having formula (II) structure:
Figure FDA0000126063380000021
Wherein, n=1,2,3 or 4.
2. method according to claim 1 is characterized in that, said acvator is two (2-oxo-3-oxazolidinyl) inferior phosphoryl chlorides.
3. method according to claim 1 is characterized in that, said phenolic cpd and acvator are 1 in molar ratio: 1-3.
4. method according to claim 1 is characterized in that, in the said step b), said intermediate product and organic boronic are 1 in molar ratio: 1-3.
5. method according to claim 1 is characterized in that, the temperature of said linked reaction is 50 ℃-150 ℃.
6. the preparation method of a diolefin compounds is characterized in that, comprising:
1) in reactor drum, adds enols used, acvator and solvent, form mixing solutions, stir said mixing solutions, obtain midbody; Said solvent is methyl-sulphoxide, N, dinethylformamide, DMAC N,N, dioxane, THF, toluene, dimethyl-terepthaloyl moietie or n-butyl ether;
The compound of said acvator for having formula (I) structure:
Figure FDA0000126063380000022
Wherein, X is Cl, Br or I;
Y is N, O or S;
2) midbody and organic boronic, transition metal salt catalyst, part, alkaline metal salt and the solvent that step 1) are obtained are carried out linked reaction;
Said solvent is methyl-sulphoxide, N, dinethylformamide, DMAC N,N, dioxane, THF, toluene, dimethyl-terepthaloyl moietie or n-butyl ether;
The compound of said organic boronic for having formula (III) structure or formula (IV) structure:
Figure FDA0000126063380000031
Wherein, R is a phenyl or naphthyl;
R 1Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl;
R 2Be hydrogen or alkyl;
R 3Be hydrogen or alkyl;
R 4Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl;
R 5Be hydrogen, alkyl, ester group, carboxyl, hydroxyl, amido, itrile group, aldehyde radical or carbonyl;
R 6Be hydrogen or alkyl;
R 7Be hydrogen or alkyl;
Said transition metal salt catalyst is NiCl 2, NiBr 2, NiI 2, NiSO 4Or Ni (OAc) 2
The compound of said part for having formula (II) structure:
Figure FDA0000126063380000032
Wherein, n=1,2,3 or 4.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2002774A (en) * 1977-08-11 1979-02-28 Antibioticos Sa P-substituted n,n'-bis-(3-oxazolidin-yl-2-one)phosphoramides and process for the preparation thereof
CN1416954A (en) * 2002-12-06 2003-05-14 中国科学院上海有机化学研究所 Phosphinidene amide and transition metal complex catalyst and its synthesis process and application in C-C and C-N bond forming reaction

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2002774A (en) * 1977-08-11 1979-02-28 Antibioticos Sa P-substituted n,n'-bis-(3-oxazolidin-yl-2-one)phosphoramides and process for the preparation thereof
CN1416954A (en) * 2002-12-06 2003-05-14 中国科学院上海有机化学研究所 Phosphinidene amide and transition metal complex catalyst and its synthesis process and application in C-C and C-N bond forming reaction

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
J. DIAGO-MESEGUER ET AL.A New Reagent for Activating Carboxyl Groups;Preparation and Reactions of N,N-Bis[2-oxo-3-ox-azolidinyl]phosphorodiamidic Chloride.《SYNTHESIS》.1980,(第7期),547-551. *
TOMOHISA NAGAMATSU ET AL.ARYL BIS(2-OXO-3-BENZOXAZOLINYL) PHOSPHINATE AND TRIS(2-OXO-3-BENZOXAZOLINYL) PHOSPHINE OXIDE: NEW CONDENSING REAGENTS FOR BETA-LACTAM FORMATION FROM BETA-AMINO ACIDS.《Chemical & Pharmaceutical Bulletin》.1988,第36卷(第3期),1249-1251. *

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