CN102603527A - Preparation method of functionalized aryl acetate compound - Google Patents
Preparation method of functionalized aryl acetate compound Download PDFInfo
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- CN102603527A CN102603527A CN2011100243993A CN201110024399A CN102603527A CN 102603527 A CN102603527 A CN 102603527A CN 2011100243993 A CN2011100243993 A CN 2011100243993A CN 201110024399 A CN201110024399 A CN 201110024399A CN 102603527 A CN102603527 A CN 102603527A
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Abstract
The invention provides a preparation method of a functionalized aryl acetate compound. The preparation method comprises the following step of carrying out decarboxylation coupling reaction on a decarboxylation coupling reagent and an electrophilic substrate in an organic solvent in the presence of a palladium catalyst and a phosphine ligand under the protection of inert gas to obtain the functionalized aryl acetate compound. According to the preparation method, the conjugation use of the palladium catalyst and the phosphine ligand can well catalyze the decarboxylation coupling reagent and the electrophilic substrate, and alkali does not need to be added in the reaction process, thus the method provided by the invention has good compatibility with a reactant sensitive to alkali. In addition, the yield of the functionalized aryl acetate compound prepared by using the preparation method provided by the invention is high; and an experiment proves that the yield of a target product reaches more than 78%.
Description
Technical field
The present invention relates to the organic synthesis field, particularly a kind of preparation method of aryl acetate compounds of functionalization.
Background technology
Aryl acetate is the compound with (I) structure, and R is an alkyl in the formula (I), on the aryl acetate phenyl ring, inserts functionalized group, obtains the aryl acetate compounds of functionalization.Functionalized aryl acetate compounds is the important intermediate of anti-inflammatory analgesiies such as Ibuprofen BP/EP; Like 2-(4 '-isobutyl phenenyl) ethyl propionate is the important intermediate of Ibuprofen BP/EP 2-(4 '-isobutyl phenenyl) propionic acid, 2-(3 '-fluoro-4 '-phenyl) ethyl propionate be FLURBIPROFEN USP24 2-(3 '-fluoro-4 '-phenyl) important intermediate of propionic acid.
The preparation method of the aryl acetate compounds of the functionalization of having reported at present, mainly contains following two kinds:
First method is that phenylo boric acid and METHYL BROMOACETATE close under the catalysis of palladium and Red copper oxide at four (triphenyl phosphorus); In organic solvent, reacting by heating obtains aryl acetate compounds (Bull.Chem.Soc.Jpn, 58 of functionalization under the alkaline sublimity; 3383-3384), its reaction formula is following:
Second method be aryl bromide or iodo aromatic hydrocarbons with the catalysis of ethyl malonate of handling through highly basic at cuprous bromide under in 1; Back flow reaction obtains the aryl acetate compounds (CHEM.COMMUN. of functionalization in the 4-dioxane; 2002,622-623), its reaction formula is following:
Above-mentioned two kinds of methods all must under alkaline condition, react, so aforesaid method are higher to the selectivity of reactant, are not suitable for the compound that contains the unstable group of alkali as reactant, and the scope of application is narrower.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of preparation method of aryl acetate compounds of functionalization, and this method reaction conditions is gentle, and alkali-sensitive reactant has favorable compatibility.
In view of this, the present invention provides a kind of preparation method of aryl acetate compounds of functionalization, comprising:
Under the condition of palladium catalyst and the existence of phosphine part, under protection of inert gas, the decarboxylation linked reaction takes place in decarboxylation coupling reagent and close electric substrate in organic solvent, obtain the aryl acetate compounds of functionalization; Said decarboxylation coupling reagent is compound with structure shown in the formula (II), and the electric substrate of said parent is for having the compound of formula (III) to structure shown in any one of the formula (X);
R in the formula (II)
0, R
1, R
2Independent separately is the aryl of Wasserstoffatoms, C6～C18, alkyl, ester group, carboxamido-group, amino, hydroxyl, nitro, cyanic acid, carbonyl, halogen, two key, triple bond or the heteroatoms of C1～C18, M
+Be H
+, Li
+, Na
+, K
+, Cs
+Or NH
4 +
Formula (III) to formula (X), Q
(m)And Q
(n)Middle Q is a substituting group, and m and n are the substituting group number, and said substituting group is identical or different alkyl, ether, alkylthio, carbonyl, ester group, tolysulfonyl oxygen base, cyanic acid, acetal radical or ketal group, and m is 0～5 integer, and n is 0～3 integer; X is halogen, trifluoro-methanesulfonyl oxy or tolysulfonyl oxygen base.
Preferably, said palladium catalyst is one or more in acid chloride, Palladous chloride, two (acetonitrile) Palladous chloride, palladium trifluoroacetate, two (methyl ethyl diketone) palladium, allyl palladium chloride, three (dibenzalacetone) two palladiums and two (dibenzalacetone) palladium.
Preferably, said phosphine part is triphenylphosphine, tricyclohexyl phosphine, tri-butyl phosphine, 2-dicyclohexylphosphontetrafluoroborate-2,4; 6-tri isopropyl biphenyl, 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl, 2-dicyclohexyl phosphine-2 ', 6 '-diisopropoxy biphenyl, 2-(di-t-butyl phosphino-) biphenyl, 2-(dicyclohexyl phosphino-) biphenyl, 2-dicyclohexylphosphontetrafluoroborate-2-(N; The N-dimethyl amido) biphenyl, 9,9-dimethyl--4,5-two (diphenylphosphino) xanthene, 9; 9-dimethyl--4,5-two (di-t-butyl phosphino-) xanthene, (±)-2,2 '-two-(diphenyl phosphine)-1; 1 '-dinaphthalene, (±)-2; 2 '-two-(di-p-tolyl phosphino-)-1,1 '-dinaphthalene or 1,1 '-in two (diphenylphosphino) ferrocene one or more.
Preferably, the mol ratio of said palladium catalyst and phosphine part is 1: 0.5～6.
Preferably, the mol ratio of said palladium catalyst and phosphine part is 1: 2～4.
Preferably, the mol ratio of said decarboxylation coupling reagent and close electric substrate is 0.25～3: 1.
Preferably, the mol ratio of said decarboxylation coupling reagent and close electric substrate is 1.2～2: 1.
Preferably, the mol ratio of said palladium catalyst and close electric substrate is 0.01～10: 100.
Preferably, said temperature of reaction is 120 ℃～140 ℃.
Preferably; Said organic solvent is a benzene,toluene,xylene, 1; 3; 5-trimethylbenzene, DMSO 99.8MIN., N, dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dme or dipropylene glycol diethyl ether.
The present invention provides a kind of preparation method of aryl acetate compounds of functionalization, and this method is that palladium catalyst and phosphine part are catalyzer, under protection of inert gas, makes decarboxylation coupling reagent and close electric substrate that the decarboxylation linked reaction take place in organic solvent.Palladium catalyst and phosphine part are used has good catalytic effect to above-mentioned decarboxylation coupling reagent and close electric substrate, and reaction process need not to add alkali, and therefore method provided by the invention pair also has favorable compatibility with the reactant of alkali sensitivity.In addition, the aryl acetate compounds productive rate that is prepared functionalization by method provided by the invention is higher, experiment showed, that the title product productive rate reaches more than 78%.
Description of drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 1 product;
Fig. 2 is the carbon-13 nmr spectra figure of embodiment 1 product;
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 2 products;
Fig. 4 is the carbon-13 nmr spectra figure of embodiment 2 products;
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 3 products;
Fig. 6 is the carbon-13 nmr spectra figure of embodiment 3 products.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of preparation method of aryl acetate compounds of functionalization; It is under the condition of the catalysis existence of palladium catalyst and phosphine part; The decarboxylation linked reaction takes place in decarboxylation coupling reagent and close electric substrate in organic solvent, obtain the aryl acetate compounds of functionalization; Said decarboxylation coupling reagent has the compound of structure shown in the formula (II), and the electric substrate tool of said parent formula (III) is to the compound of structure shown in any one of the formula (X).
R in the formula (II)
0, R
1, R
2Independent separately is the aryl of Wasserstoffatoms, C6～C18, alkyl, ester group, carboxamido-group, amino, hydroxyl, nitro, cyanic acid, carbonyl, halogen, two key, triple bond or the heteroatoms of C1～C18, M
+Be H
+, Li
+, Na
+, K
+, Cs
+Or NH
4 +
Formula (III) to formula (X), Q
(m)And Q
(n)Middle Q is a substituting group, and m and n are the substituting group number, and said substituting group is identical or different alkyl, ether, alkylthio, carbonyl, ester group, tolysulfonyl oxygen base, cyanic acid, acetal radical or ketal group, and m is 0～5 integer, and n is 0～3 integer; X is halogen, trifluoro-methanesulfonyl oxy or tolysulfonyl oxygen base.
The inventor finds; With palladium catalyst and phosphine part is catalyzer; To decarboxylation coupling reagent with formula (II) structure with have the reaction of formula (III) and have good catalytic effect to the close electric substrate of structure shown in any one of the formula (X); And because reaction process need not to add alkali, therefore method provided by the invention pair has favorable compatibility with the responsive close electric substrate of alkali, like this method applicable to the decarboxylation coupling reagent that contains carboxyl with contain the close electric substrate of ester group.
For having structural compounds shown in the formula (II) as the decarboxylation coupling reagent, be the decarboxylation linked reaction that close electric substrate takes place with the compound of formula (III) structure, its reaction formula is following:
For having structural compounds shown in the formula (II) as the decarboxylation coupling reagent, be the decarboxylation linked reaction that close electric substrate takes place with the compound of formula (IV) structure, its reaction formula is following:
For having structural compounds shown in the formula (II) as the decarboxylation coupling reagent, be the decarboxylation linked reaction that close electric substrate takes place with the compound of formula V structure, its reaction formula is following:
For having structural compounds shown in the formula (II) as the decarboxylation coupling reagent, be the decarboxylation linked reaction that close electric substrate takes place with the compound of formula (VI) structure, its reaction formula is following:
For having structural compounds shown in the formula (II) as the decarboxylation coupling reagent, be the decarboxylation linked reaction that close electric substrate takes place with the compound of formula (VII) structure, its reaction formula is following:
For having structural compounds shown in the formula (II) as the decarboxylation coupling reagent, be the decarboxylation linked reaction that close electric substrate takes place with the compound of formula (VIII) structure, its reaction formula is following:
For having structural compounds shown in the formula (II) as the decarboxylation coupling reagent, be the decarboxylation linked reaction that close electric substrate takes place with the compound of formula (IX) structure, its reaction formula is following:
For having structural compounds shown in the formula (II) as the decarboxylation coupling reagent, be the decarboxylation linked reaction that close electric substrate takes place with the compound of formula (X) structure, its reaction formula is following:
The palladium catalyst that uses in the above-mentioned reaction is preferably from acid chloride (Pd (OAc)
2), Palladous chloride (PdCl
2), two (acetonitrile) Palladous chloride (Pd (MeCN)
2Cl
2), palladium trifluoroacetate (Pd (OTFA)
2), two (methyl ethyl diketone) palladium (Pd (acac)
2), allyl palladium chloride (Pd
2(p-allyl)
2Cl
2), three (dibenzalacetone) two palladium (Pd
2(dba)
3) and two (dibenzalacetone) palladium (Pd (dba)
2) at least a; More preferably three (dibenzalacetones), two palladiums and allyl palladium chloride.
Be preferably triphenylphosphine, tricyclohexyl phosphine, tri-butyl phosphine, 2-dicyclohexylphosphontetrafluoroborate-2,4 with the phosphine part that uses catalyzer collocation, 6-tri isopropyl biphenyl (X-Phos), 2-dicyclohexyl phosphine-2 '; 6 '-dimethoxy-biphenyl (S-Phos), 2-dicyclohexyl phosphine-2 '; 6 '-diisopropoxy biphenyl (Ru-Phos), 2-(di-t-butyl phosphino-) biphenyl (JohnPhos), 2-(dicyclohexyl phosphino-) biphenyl (Cy-JohnPhos), 2-dicyclohexylphosphontetrafluoroborate-2-(N, N-dimethyl amido) biphenyl (DavePhos), 9,9-dimethyl--4; 5-two (diphenylphosphino) xanthene (Xant-Phos), 9; 9-dimethyl--4,5-two (di-t-butyl phosphino-) xanthene (tBu-XantPhos), (±)-2,2 '-two-(diphenyl phosphine)-1; 1 '-dinaphthalene (BINAP), (±)-2; 2 '-two-(di-p-tolyl phosphino-)-1,1 '-dinaphthalene (Tol-BINAP) and 1,1 '-at least a in two (diphenylphosphino) ferrocene (DPPF).More preferably 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (S-Phos), 2-dicyclohexyl phosphine-2 ', 6 '-diisopropoxy biphenyl (Ru-Phos), 2-dicyclohexylphosphontetrafluoroborate-2,4, at least a in the 6-tri isopropyl biphenyl (X-Phos).
The mol ratio of preferred above-mentioned decarboxylation coupling reagent of control and close electric substrate is 0.25～3: 1 in the reaction process.Because close electric substrate structure is generally comparatively complicated, price is higher relatively, and the electric substrate reactions of its part parent site is other to have the group that hinders reaction, so the present invention more preferably increases the decarboxylation coupling reagent in reaction amount guarantees that close electric substrate reactions is complete.Thus, the mol ratio that the present invention more preferably controls above-mentioned decarboxylation coupling reagent and close electric substrate is 1.2～2: 1, most preferably is 1.3～1.6: 1.
In the catalyzer mol ratio of palladium catalyst and phosphine part be preferably 1: 0.5～6, more preferably 1: 2～4.The mol ratio of said palladium catalyst and close electric substrate is 0.01～10: 100, more preferably 0.5～2: 100.If palladium catalyst and phosphine part are very few, speed of response is slack-off, needs time expand to guarantee to react and carries out fully.
Among the preparation method provided by the invention; Preferably place following organic solvent to react above-mentioned reactant: benzene,toluene,xylene, 1; 3; 5-trimethylbenzene, DMSO 99.8MIN., N, dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dme or dipropylene glycol diethyl ether.Rare gas element can be gas well known to those skilled in the art, like argon gas or nitrogen atmosphere.Temperature of reaction is preferably 120 ℃～140 ℃, finishes reaction after 10～30 hours reaction times, according to following mode product is purified then:
After the reaction system mixture that reaction is finished filters; Use quick silica gel column chromatography that filtrating is carried out chromatography; Earlier washing away reaction solvent, use the mixed solvent eluent of sherwood oil and ETHYLE ACETATE again with sherwood oil, the volume ratio of used sherwood oil and eluent ethyl acetate agent is preferably 1: 1～and 100: 1; Steaming is sauted and is removed eluent, obtains title product after the vacuum-drying.
If prepare aryl acetate compounds in a large number, also can be without silica gel column chromatography, and adopt conventional distillation under vacuum, directly obtain title product.
In order further to understand the present invention, the preparation method of the aryl acetate compounds of functionalization provided by the invention is described below in conjunction with embodiment.Protection scope of the present invention is not limited by the following examples.
1, the monoethyl malonate acid potassium salt that in vacuum reactor, adds 0.75mmol; 0.01mmol allyl palladium chloride and 0.03mmol 2-dicyclohexyl phosphine-2 ', 6 '-diisopropoxy biphenyl, vacuumize; Logical high-purity argon gas; Replace three times, the chlorobenzene that under the protection of argon gas stream, adds 0.5mmol with the organic solvent trimethylbenzene, the add-on of organic solvent adds 2 milliliters of solvents by the electric substrate of every mmole parent; With mixture heating up to 120 in the reactor drum ℃, heated and stirred finishes reaction after 10 hours.The reaction formula in this step is following:
2, the reaction system mixture that reaction is finished is purified with quick silica gel column chromatography; Use 50mL sherwood oil eluting solvent trimethylbenzene earlier; Using sherwood oil and ETHYLE ACETATE volume ratio again is 50: 1 eluent wash-out, obtains the product Phenylacetic acid ethylester, and the productive rate of this product is 83%.
Referring to shown in Figure 1 be the hydrogen nuclear magnetic resonance spectrogram of this product, referring to shown in Figure 2 be this product carbon-13 nmr spectra figure.
Embodiment 2 preparation 2-(2-thienyl) ETHYLE ACETATE
1, the monoethyl malonate acid potassium salt that in vacuum reactor, adds 0.75mmol, the 2-dicyclohexyl phosphine-2 of the allyl palladium chloride of 0.01mmol (Pd2 (p-allyl) 2Cl2) and 0.03mmol ', 6 '-diisopropoxy biphenyl; Vacuumize; Logical high-purity argon gas replace three times, under the protection of argon gas stream the close 2-chlorothiophene of adding 0.5mmol with the organic solvent trimethylbenzene; The add-on of organic solvent adds 2 milliliters of solvents by the electric substrate of every mmole parent; With mixture heating up to 140 in the reactor drum ℃,, heated and stirred finishes reaction after 20 hours.The reaction formula in this step is following:
2, the reaction system mixture that reaction is finished is purified with quick silica gel column chromatography; Use 50mL sherwood oil eluting solvent trimethylbenzene earlier; Using sherwood oil and ETHYLE ACETATE volume ratio again is 50: 1 eluent wash-out; Obtain product 2-(2-thienyl) ETHYLE ACETATE, the productive rate of this product is 78%.
Referring to shown in Figure 3 be the hydrogen nuclear magnetic resonance spectrogram of this product, referring to shown in Figure 4 be this product carbon-13 nmr spectra figure.
Embodiment 3 preparation 2-(3-pyridyl) n-butyl acetates
1, the positive butyl ester acid potassium salt of propanedioic acid list that in vacuum reactor, adds 0.75mmol, the 2-dicyclohexyl phosphine-2 of the allyl palladium chloride of 0.01mmol (Pd2 (p-allyl) 2Cl2) and 0.03mmol ', 6 '-diisopropoxy biphenyl; Vacuumize; Logical high-purity argon gas is replaced three times, and the 3-chloropyridine that under the protection of argon gas stream, adds 0.5mmol adds 2 milliliters of solvents in the add-on with organic solvent trimethylbenzene organic solvent by the electric substrate of every mmole parent; With mixture heating up to 140 in the reactor drum ℃;, heated and stirred finished reaction after 10 hours.The reaction formula in this step is following:
2, the reaction system mixture that reaction is finished is purified with quick silica gel column chromatography; Use 50mL sherwood oil eluting solvent trimethylbenzene earlier; Using sherwood oil and ETHYLE ACETATE volume ratio again is 50: 1 eluent wash-out; Obtain product 2-(3-pyridyl) n-butyl acetate, the productive rate of this product is 93%.
Referring to shown in Figure 5 be the hydrogen nuclear magnetic resonance spectrogram of this product, referring to shown in Figure 6 be this product carbon-13 nmr spectra figure.
Embodiment 5
1, the monoethyl malonate acid potassium salt that in vacuum reactor, adds 0.75mmol; 0.01mmol allyl palladium chloride (Pd2 (p-allyl) 2Cl2) and 0.03mmol 2-dicyclohexyl phosphine-2 ', 6 '-diisopropoxy biphenyl, vacuumize; Logical high-purity argon gas; Replace three times, the 1-chloronaphthalene that under the protection of argon gas stream, adds 0.5mmol with the organic solvent trimethylbenzene, the add-on of organic solvent adds 2 milliliters of solvents by the electric substrate of every mmole parent; With mixture heating up to 120 in the reactor drum ℃, heated and stirred finishes reaction after 10 hours.The reaction formula in this step is following:
2, the reaction system mixture that reaction is finished is purified with quick silica gel column chromatography, uses earlier 50mL sherwood oil eluting solvent trimethylbenzene, and using sherwood oil and ETHYLE ACETATE volume ratio again is 50: 1 eluent wash-out, obtains product 1-naphthalene ethyl acetate.The productive rate of this product is 78%.
Embodiment 6
1, the monoethyl malonate acid potassium salt that in vacuum reactor, adds 0.75mmol; 0.01mmol allyl palladium chloride (Pd2 (p-allyl) 2Cl2) and 0.03mmol 2-dicyclohexyl phosphine-2 ', 6 '-diisopropoxy biphenyl, vacuumize; Logical high-purity argon gas; Replace three times, the 6-SN-7618 that under the protection of argon gas stream, adds 0.5mmol with the organic solvent trimethylbenzene, the add-on of organic solvent adds 2 milliliters of solvents by the electric substrate of every mmole parent; With mixture heating up to 140 in the reactor drum ℃, heated and stirred finishes reaction after 20 hours.The reaction formula in this step is following:
2, the reaction system mixture that reaction is finished is purified with quick silica gel column chromatography, uses earlier 50mL sherwood oil eluent trimethylbenzene, and using sherwood oil and ETHYLE ACETATE volume ratio again is 3: 1 eluent wash-out, obtains product 6-quinoline ETHYLE ACETATE.The productive rate of this product is 84%.
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.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. the preparation method of the aryl acetate compounds of a functionalization comprises:
Under the condition of palladium catalyst and the existence of phosphine part, under protection of inert gas, the decarboxylation linked reaction takes place in decarboxylation coupling reagent and close electric substrate in organic solvent, obtain the aryl acetate compounds of functionalization; Said decarboxylation coupling reagent is compound with structure shown in the formula (II), and the electric substrate of said parent is for having the compound of formula (III) to structure shown in any one of the formula (X);
R in the formula (II)
0, R
1, R
2Independent separately is the aryl of Wasserstoffatoms, C6～C18, alkyl, ester group, carboxamido-group, amino, hydroxyl, nitro, cyanic acid, carbonyl, halogen, two key, triple bond or the heteroatoms of C1～C18, M
+Be H
+, Li
+, Na
+, K
+, Cs
+Or NH
4 +
Formula (III) to formula (X), Q
(m)And Q
(n)Middle Q is a substituting group, and m and n are the substituting group number, and said substituting group is identical or different alkyl, ether, alkylthio, carbonyl, ester group, tolysulfonyl oxygen base, cyanic acid, acetal radical or ketal group, and m is 0～5 integer, and n is 0～3 integer; X is halogen, trifluoro-methanesulfonyl oxy or tolysulfonyl oxygen base.
2. according to the said preparation method of claim 1, said palladium catalyst is one or more in acid chloride, Palladous chloride, two (acetonitrile) Palladous chloride, palladium trifluoroacetate, two (methyl ethyl diketone) palladium, allyl palladium chloride, three (dibenzalacetone) two palladiums and two (dibenzalacetone) palladium.
3. preparation method according to claim 2 is characterized in that, said phosphine part is triphenylphosphine, tricyclohexyl phosphine, tri-butyl phosphine, 2-dicyclohexylphosphontetrafluoroborate-2; 4,6-tri isopropyl biphenyl, 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl, 2-dicyclohexyl phosphine-2 '; 6 '-diisopropoxy biphenyl, 2-(di-t-butyl phosphino-) biphenyl, 2-(dicyclohexyl phosphino-) biphenyl, 2-dicyclohexylphosphontetrafluoroborate-2-(N, N-dimethyl amido) biphenyl, 9,9-dimethyl--4; 5-two (diphenylphosphino) xanthene, 9,9-dimethyl--4,5-two (di-t-butyl phosphino-) xanthene, (±)-2; 2 '-two-(diphenyl phosphine)-1,1 '-dinaphthalene, (±)-2,2 '-two-(di-p-tolyl phosphino-)-1; 1 '-dinaphthalene or 1,1 '-in two (diphenylphosphino) ferrocene one or more.
4. preparation method according to claim 3 is characterized in that, the mol ratio of said palladium catalyst and phosphine part is 1: 0.5～6.
5. preparation method according to claim 3 is characterized in that, the mol ratio of said palladium catalyst and phosphine part is 1: 2～4.
6. preparation method according to claim 3 is characterized in that, the mol ratio of said decarboxylation coupling reagent and close electric substrate is 0.25～3: 1.
7. preparation method according to claim 3 is characterized in that, the mol ratio of said decarboxylation coupling reagent and close electric substrate is 1.2～2: 1.
8. preparation method according to claim 3 is characterized in that, the mol ratio of said palladium catalyst and close electric substrate is 0.01～10: 100.
9. preparation method according to claim 3 is characterized in that, said temperature of reaction is 120 ℃～140 ℃.
10. according to any described preparation method of claim 1～9; It is characterized in that; Said organic solvent is a benzene,toluene,xylene, 1,3,5-trimethylbenzene, DMSO 99.8MIN., N; Dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dme or dipropylene glycol diethyl ether.
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| CN105367390A (en) * | 2015-11-25 | 2016-03-02 | 湖南中医药大学 | Method for synthesizing pterostilbene and derivatives thereof |
| CN105367390B (en) * | 2015-11-25 | 2018-07-06 | 湖南中医药大学 | A kind of method for synthesizing pterostilbene and its derivative |
| CN109384664A (en) * | 2018-11-20 | 2019-02-26 | 成都正善达生物医药科技有限公司 | A kind of Ai Le replaces the preparation method of Buddhist nun's intermediate |
| CN109384664B (en) * | 2018-11-20 | 2021-04-13 | 成都正善达生物医药科技有限公司 | Preparation method of erlotinib intermediate |
| CN110483351A (en) * | 2019-09-18 | 2019-11-22 | 中国科学技术大学 | The method for preparing thioesters by oxo thioacetic acid compound |
| CN110483351B (en) * | 2019-09-18 | 2021-08-13 | 中国科学技术大学 | Process for preparing thioesters via oxomercaptoacetic acid compounds |
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