CN102603527B - Preparation method of functionalized aryl acetate compound - Google Patents
Preparation method of functionalized aryl acetate compound Download PDFInfo
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- CN102603527B CN102603527B CN201110024399.3A CN201110024399A CN102603527B CN 102603527 B CN102603527 B CN 102603527B CN 201110024399 A CN201110024399 A CN 201110024399A CN 102603527 B CN102603527 B CN 102603527B
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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 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 in formula (I), R is alkyl, aryl acetate phenyl ring accesses functionalizing group, obtains the aryl acetate compounds of functionalization.Functionalized aryl acetate compounds is the important intermediate of the anti-inflammatory analgesiies such as Ibuprofen BP/EP, as the important intermediate that 2-(4 '-isobutyl phenenyl) ethyl propionate is Ibuprofen BP/EP 2-(4 '-isobutyl phenenyl) propionic acid, 2-(3 '-fluoro-4 '-phenyl) ethyl propionate is the important intermediate of flurbiprofen 2-(3 '-fluoro-4 '-phenyl) propionic acid.
At present, the preparation method of the aryl acetate compounds of the functionalization reported mainly contains the following two kinds:
First method is that phenylo boric acid and ethyl bromoacetate are under four (triphenyl phosphorus) close the catalysis of palladium and Red copper oxide, in organic solvent, under alkalescence sublimity, reacting by heating obtains the aryl acetate compounds (Bull.Chem.Soc.Jpn of functionalization, 58,3383-3384), its reaction formula is as follows:
Second method be aryl bromide or iodo aromatic hydrocarbon and under the catalysis at cuprous bromide of the diethyl malonate of highly basic process in 1, in 4-dioxane, back flow reaction obtains the aryl acetate compounds (CHEM.COMMUN. of functionalization, 2002,622-623), its reaction formula is as follows:
Above-mentioned two kinds of methods, all must react in the basic conditions, and therefore the selectivity of aforesaid method to reactant is higher, be not suitable for containing to the compound of the unstable group of alkali as reactant, the scope of application is narrower.
Summary of the invention
The technical problem that the present invention solves is the preparation method of the aryl acetate compounds providing a kind of functionalization, and the method reaction conditions is gentle, and alkali-sensitive reactant has good compatibility.
In view of this, the invention provides a kind of preparation method of aryl acetate compounds of functionalization, comprising:
Under palladium catalyst and Phosphine ligands existent condition, under protection of inert gas, there is decarboxylation linked reaction in decarboxylation coupling reagent and parent's electricity substrate, obtains the aryl acetate compounds of functionalization in organic solvent; Described decarboxylation coupling reagent is for having the compound of structure shown in formula (II), and the electric substrate of described parent is for having the compound of structure shown in formula (III) to formula (X) any one;
R in formula (II)
0, R
1, R
2respective is independently hydrogen atom, the aryl of C6 ~ C18, the alkyl of C1 ~ C18, ester group, amide group, amino, hydroxyl, nitro, cyano group, carbonyl, halogen, double bond, triple bond or heteroatoms, M
+for H
+, Li
+, Na
+, K
+, Cs
+or NH
4 +;
Formula (III) in formula (X), Q
(m)and Q
(n)middle Q is substituting group, m and n is substituting group number, and described substituting group is identical or different alkyl, ether, alkylthio, carbonyl, ester group, tolysulfonyl oxygen base, cyano group, acetal radical or ketal group, and m is the integer of 0 ~ 5, and n is the integer of 0 ~ 3; X is halogen, trifluoro-methanesulfonyl oxy or tolysulfonyl oxygen base.
Preferably, described palladium catalyst is one or more in palladium and two (dibenzalacetone) palladium of acid chloride, Palladous chloride, two (acetonitrile) Palladous chloride, palladium trifluoroacetate, two (methyl ethyl diketone) palladium, allyl palladium chloride, three (dibenzalacetone) two.
Preferably, described Phosphine ligands 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-bis-(diphenylphosphino) xanthene, 9, 9-dimethyl-4, 5-bis-(di-t-butyl phosphino-) xanthene, (±)-2, 2 '-bis--(diphenyl phosphine)-1, 1 '-dinaphthalene, (±)-2, 2 '-bis--(di-p-tolyl phosphino-)-1, 1 '-dinaphthalene or 1, one or more in 1 '-bis-(diphenylphosphino) ferrocene.
Preferably, the mol ratio of described palladium catalyst and Phosphine ligands is 1: 0.5 ~ 6.
Preferably, the mol ratio of described palladium catalyst and Phosphine ligands is 1: 2 ~ 4.
Preferably, the mol ratio of described decarboxylation coupling reagent and parent's electricity substrate is 0.25 ~ 3: 1.
Preferably, the mol ratio of described decarboxylation coupling reagent and parent's electricity substrate is 1.2 ~ 2: 1.
Preferably, the mol ratio of described palladium catalyst and parent's electricity substrate is 0.01 ~ 10: 100.
Preferably, described temperature of reaction is 120 DEG C ~ 140 DEG C.
Preferably, described organic solvent is benzene,toluene,xylene, 1,3,5-trimethylbenzene, dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, TRIGLYME or dipropylene glycol diethyl ether.
The invention provides a kind of preparation method of aryl acetate compounds of functionalization, the method is palladium catalyst and Phosphine ligands is catalyzer, under protection of inert gas, makes decarboxylation coupling reagent and parent's electricity substrate that decarboxylation linked reaction occur in organic solvent.Palladium catalyst and Phosphine ligands have good catalytic effect with the use of to above-mentioned decarboxylation coupling reagent and parent's electricity substrate, and reaction process is without the need to adding alkali, and therefore the reactant of method provided by the invention pair and alkali sensitivity also has good compatibility.In addition, the aryl acetate compounds productive rate being prepared functionalization by method provided by the invention is higher, and experiment proves, target product productive rate reaches more than 78%.
Accompanying drawing explanation
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 product;
Fig. 4 is the carbon-13 nmr spectra figure of embodiment 2 product;
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 3 product;
Fig. 6 is the carbon-13 nmr spectra figure of embodiment 3 product.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of preparation method of aryl acetate compounds of functionalization, it is under the catalysis existent condition of palladium catalyst and Phosphine ligands, there is decarboxylation linked reaction in decarboxylation coupling reagent and parent's electricity substrate, obtains the aryl acetate compounds of functionalization in organic solvent; Described decarboxylation coupling reagent has the compound of structure shown in formula (II), the compound of structure shown in described parent electric substrate tool formula (III) to formula (X) any one.
R in formula (II)
0, R
1, R
2respective is independently hydrogen atom, the aryl of C6 ~ C18, the alkyl of C1 ~ C18, ester group, amide group, amino, hydroxyl, nitro, cyano group, carbonyl, halogen, double bond, triple bond or heteroatoms, M
+for H
+, Li
+, Na
+, K
+, Cs
+or NH
4 +;
Formula (III) in formula (X), Q
(m)and Q
(n)middle Q is substituting group, m and n is substituting group number, and described substituting group is identical or different alkyl, ether, alkylthio, carbonyl, ester group, tolysulfonyl oxygen base, cyano group, acetal radical or ketal group, and m is the integer of 0 ~ 5, and n is the integer of 0 ~ 3; X is halogen, trifluoro-methanesulfonyl oxy or tolysulfonyl oxygen base.
The present inventor finds, with palladium catalyst and Phosphine ligands for catalyzer, with the reaction of parent's electricity substrate with structure shown in formula (III) to formula (X) any one, there is good catalytic effect to the decarboxylation coupling reagent with formula (II) structure, and because reaction process is without the need to adding alkali, therefore parent's electricity substrate of method provided by the invention pair and alkali sensitivity has good compatibility, as the method is applicable to the decarboxylation coupling reagent containing carboxyl and the electricity of the parent containing ester group substrate.
For to have structural compounds shown in formula (II) as decarboxylation coupling reagent, be the decarboxylation linked reaction that close electric substrate occurs with the compound of formula (III) structure, its reaction formula is as follows:
For to have structural compounds shown in formula (II) as decarboxylation coupling reagent, be the decarboxylation linked reaction that close electric substrate occurs with the compound of formula (IV) structure, its reaction formula is as follows:
For to have structural compounds shown in formula (II) as decarboxylation coupling reagent, be the decarboxylation linked reaction that close electric substrate occurs with the compound of formula (V) structure, its reaction formula is as follows:
For to have structural compounds shown in formula (II) as decarboxylation coupling reagent, be the decarboxylation linked reaction that close electric substrate occurs with the compound of formula (VI) structure, its reaction formula is as follows:
For to have structural compounds shown in formula (II) as decarboxylation coupling reagent, be the decarboxylation linked reaction that close electric substrate occurs with the compound of formula (VII) structure, its reaction formula is as follows:
For to have structural compounds shown in formula (II) as decarboxylation coupling reagent, be the decarboxylation linked reaction that close electric substrate occurs with the compound of formula (VIII) structure, its reaction formula is as follows:
For to have structural compounds shown in formula (II) as decarboxylation coupling reagent, be the decarboxylation linked reaction that close electric substrate occurs with the compound of formula (IX) structure, its reaction formula is as follows:
For to have structural compounds shown in formula (II) as decarboxylation coupling reagent, be the decarboxylation linked reaction that close electric substrate occurs with the compound of formula (X) structure, its reaction formula is as follows:
The palladium catalyst used in 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 one; Be more preferably three (dibenzalacetone) two palladium and allyl palladium chloride.
Triphenylphosphine is preferably with the Phosphine ligands used that catalyzer is arranged in pairs or groups, tricyclohexyl phosphine, tri-butyl phosphine, 2-dicyclohexylphosphontetrafluoroborate-2,4,6-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-bis-(diphenylphosphino) xanthene (Xant-Phos), 9,9-dimethyl-4,5-bis-(di-t-butyl phosphino-) xanthene (tBu-XantPhos), (±)-2,2 '-bis--(diphenyl phosphine)-1,1 '-dinaphthalene (BINAP), at least one in (±)-2,2 '-bis--(di-p-tolyl phosphino-)-1,1 '-dinaphthalene (Tol-BINAP) and 1,1 '-bis-(diphenylphosphino) ferrocene (DPPF).Be more preferably 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (S-Phos), 2-dicyclohexyl phosphine-2 ', at least one in 6 '-diisopropoxy biphenyl (Ru-Phos), 2-dicyclohexylphosphontetrafluoroborate-2,4,6-tri isopropyl biphenyl (X-Phos).
The mol ratio preferably controlling above-mentioned decarboxylation coupling reagent and parent's electricity substrate in reaction process is 0.25 ~ 3: 1.Due to the general comparatively complexity of the electric substrate structure of parent, price is relatively high, and the close electric substrate reactions site of its part is other the group hindering reaction, and therefore more preferably the close electric substrate reactions of amount guarantee of increase decarboxylation coupling reagent is complete in the reaction in the present invention.Thus, the mol ratio that the present invention more preferably controls above-mentioned decarboxylation coupling reagent and parent's electricity substrate is 1.2 ~ 2: 1, most preferably is 1.3 ~ 1.6: 1.
In catalyzer, the mol ratio of palladium catalyst and Phosphine ligands is preferably 1: 0.5 ~ 6, is more preferably 1: 2 ~ 4.The mol ratio of described palladium catalyst and parent's electricity substrate is 0.01 ~ 10: 100, is more preferably 0.5 ~ 2: 100.If palladium catalyst and Phosphine ligands very few, speed of response is slack-off, and reaction is carried out completely to need time expand to guarantee.
In preparation method provided by the invention, preferably above-mentioned reactant is placed in following organic solvent to react: benzene,toluene,xylene, 1,3,5-trimethylbenzene, dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, TRIGLYME or dipropylene glycol diethyl ether.Rare gas element can be gas well known to those skilled in the art, as argon gas or nitrogen atmosphere.Temperature of reaction is preferably 120 DEG C ~ 140 DEG C, terminates reaction, then purify to product in the following manner after 10 ~ 30 hours reaction times:
After the complete reaction system mixture of reaction is filtered, Flash silica column chromatography is used to carry out chromatography to filtrate, first wash away reaction solvent with sherwood oil, use the mixed solvent eluent of sherwood oil and ethyl acetate again, the volume ratio of sherwood oil used and eluent ethyl acetate agent is preferably 1: 1 ~ 100: 1, removing eluent is sauted in steaming, obtains target product after vacuum-drying.
If prepare aryl acetate compounds in a large number, also without silica gel column chromatography, and conventional distillation under vacuum can be adopted, directly obtain target product.
In order to understand the present invention further, below in conjunction with embodiment, the preparation method to the aryl acetate compounds of functionalization provided by the invention is described.Protection scope of the present invention is not limited by the following examples.
Embodiment 1 prepares Phenylacetic acid ethylester
1, in vacuum reactor, add the monoethyl malonate acid potassium salt of 0.75mmol; the 2-dicyclohexyl phosphine-2 of the allyl palladium chloride of 0.01mmol and 0.03mmol '; 6 '-diisopropoxy biphenyl; vacuumize; logical high-purity argon gas; replace three times; the chlorobenzene adding 0.5mmol under the protection of argon gas stream with organic solvent trimethylbenzene; the add-on of organic solvent adds 2 milliliters of solvents by the electric substrate of every mmole parent; mixture in reactor is heated to 120 DEG C, and heated and stirred terminates reaction after 10 hours.The reaction formula of this step is as follows:
2, reaction system mixture Flash silica column chromatography complete for reaction is purified, first use 50mL sherwood oil eluting solvent trimethylbenzene, be the eluent wash-out of 50: 1 again with sherwood oil and ethyl acetate volume ratio, obtain product Phenylacetic acid ethylester, the productive rate of this product is 83%.
Shown in Figure 1 is the hydrogen nuclear magnetic resonance spectrogram of this product, and shown in Figure 2 is this product carbon-13 nmr spectra figure.
Embodiment 2 prepares 2-(2-thienyl) ethyl acetate
1, in vacuum reactor, add the monoethyl malonate acid potassium salt of 0.75mmol; the 2-dicyclohexyl phosphine-2 of the allyl palladium chloride (Pd2 (p-allyl) 2Cl2) of 0.01mmol and 0.03mmol '; 6 '-diisopropoxy biphenyl; vacuumize; logical high-purity argon gas; replace three times; the close 2-chlorothiophene adding 0.5mmol under the protection of argon gas stream with organic solvent trimethylbenzene; the add-on of organic solvent adds 2 milliliters of solvents by the electric substrate of every mmole parent; mixture in reactor is heated to 140 DEG C;, heated and stirred terminates reaction after 20 hours.The reaction formula of this step is as follows:
2, reaction system mixture Flash silica column chromatography complete for reaction is purified, first use 50mL sherwood oil eluting solvent trimethylbenzene, be the eluent wash-out of 50: 1 again with sherwood oil and ethyl acetate volume ratio, obtain product 2-(2-thienyl) ethyl acetate, the productive rate of this product is 78%.
Shown in Figure 3 is the hydrogen nuclear magnetic resonance spectrogram of this product, and shown in Figure 4 is this product carbon-13 nmr spectra figure.
Embodiment 3 prepares 2-(3-pyridyl) n-butyl acetate
1, in vacuum reactor, add the positive butyl ester acid potassium salt of propanedioic acid list of 0.75mmol; the 2-dicyclohexyl phosphine-2 of the allyl palladium chloride (Pd2 (p-allyl) 2Cl2) of 0.01mmol and 0.03mmol '; 6 '-diisopropoxy biphenyl; vacuumize; logical high-purity argon gas; replace three times; the 3-chloropyridine of 0.5mmol is added to add 2 milliliters of solvents with the add-on of organic solvent trimethylbenzene organic solvent by the electric substrate of every mmole parent under the protection of argon gas stream; mixture in reactor is heated to 140 DEG C; heated and stirred, after 10 hours, terminates reaction.The reaction formula of this step is as follows:
2, reaction system mixture Flash silica column chromatography complete for reaction is purified, first use 50mL sherwood oil eluting solvent trimethylbenzene, be the eluent wash-out of 50: 1 again with sherwood oil and ethyl acetate volume ratio, obtain product 2-(3-pyridyl) n-butyl acetate, the productive rate of this product is 93%.
Shown in Figure 5 is the hydrogen nuclear magnetic resonance spectrogram of this product, and shown in Figure 6 is this product carbon-13 nmr spectra figure.
Embodiment 5
1, in vacuum reactor, add the monoethyl malonate acid potassium salt of 0.75mmol; the allyl palladium chloride (Pd2 (p-allyl) 2Cl2) of 0.01mmol and 0.03mmol 2-dicyclohexyl phosphine-2 '; 6 '-diisopropoxy biphenyl; vacuumize; logical high-purity argon gas; replace three times; the 1-chloronaphthalene adding 0.5mmol under the protection of argon gas stream with organic solvent trimethylbenzene; the add-on of organic solvent adds 2 milliliters of solvents by the electric substrate of every mmole parent; mixture in reactor is heated to 120 DEG C, and heated and stirred terminates reaction after 10 hours.The reaction formula of this step is as follows:
2, reaction system mixture Flash silica column chromatography complete for reaction is purified, first use 50mL sherwood oil eluting solvent trimethylbenzene, then be the eluent wash-out of 50: 1 with sherwood oil and ethyl acetate volume ratio, obtain product 1-naphthalene ethyl acetate.The productive rate of this product is 78%.
Embodiment 6
1, in vacuum reactor, add the monoethyl malonate acid potassium salt of 0.75mmol; the 2-dicyclohexyl phosphine-2 of the allyl palladium chloride (Pd2 (p-allyl) 2Cl2) of 0.01mmol and 0.03mmol '; 6 '-diisopropoxy biphenyl; vacuumize; logical high-purity argon gas; replace three times; the 6-chloroquinoline adding 0.5mmol under the protection of argon gas stream with organic solvent trimethylbenzene; the add-on of organic solvent adds 2 milliliters of solvents by the electric substrate of every mmole parent; mixture in reactor is heated to 140 DEG C, and heated and stirred terminates reaction after 20 hours.The reaction formula of this step is as follows:
2, reaction system mixture Flash silica column chromatography complete for reaction is purified, first use 50mL sherwood oil eluent trimethylbenzene, then be the eluent wash-out of 3: 1 with sherwood oil and ethyl acetate volume ratio, obtain product 6-quinoline ethyl acetate.The productive rate of this product is 84%.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (8)
1. a preparation method for the aryl acetate compounds of functionalization, comprising:
Under palladium catalyst and Phosphine ligands existent condition, under protection of inert gas, there is decarboxylation linked reaction in decarboxylation coupling reagent and parent's electricity substrate, obtains the aryl acetate compounds of functionalization in organic solvent; Described decarboxylation coupling reagent is for having the compound of structure shown in formula II, and the electric substrate of described parent is for having the compound of structure shown in formula III to formula (Ⅹ) any one;
R in formula II
0, R
1, R
2respective is independently hydrogen atom, the aryl of C6 ~ C18, the alkyl of C1 ~ C18, ester group, amide group, amino, hydroxyl, nitro, cyano group, carbonyl or halogen, M
+for H
+, Li
+, Na
+, K
+, Cs
+or NH
4 +;
Formula III in formula (Ⅹ), Q
(m)and Q
(n)middle Q is substituting group, m and n is substituting group number, and described substituting group is identical or different alkyl, ether, alkylthio, carbonyl, ester group, tolysulfonyl oxygen base, cyano group, acetal radical or ketal group, and m is the integer of 0 ~ 5, and n is the integer of 0 ~ 3; X is halogen, trifluoro-methanesulfonyl oxy or tolysulfonyl oxygen base;
Described palladium catalyst is allyl palladium chloride;
Described Phosphine ligands is 2-dicyclohexyl phosphine-2', 6'-diisopropoxy biphenyl.
2. preparation method according to claim 1, is characterized in that, the mol ratio of described palladium catalyst and Phosphine ligands is 1:0.5 ~ 6.
3. preparation method according to claim 1, is characterized in that, the mol ratio of described palladium catalyst and Phosphine ligands is 1:2 ~ 4.
4. preparation method according to claim 1, is characterized in that, the mol ratio of described decarboxylation coupling reagent and parent's electricity substrate is 0.25 ~ 3:1.
5. preparation method according to claim 1, is characterized in that, the mol ratio of described decarboxylation coupling reagent and parent's electricity substrate is 1.2 ~ 2:1.
6. preparation method according to claim 1, is characterized in that, the mol ratio of described palladium catalyst and parent's electricity substrate is 0.01 ~ 10:100.
7. preparation method according to claim 1, is characterized in that, described temperature of reaction is 120 DEG C ~ 140 DEG C.
8. the preparation method according to claim 1 ~ 7 any one, it is characterized in that, described organic solvent is benzene,toluene,xylene, 1,3,5-trimethylbenzene, dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, TRIGLYME or dipropylene glycol diethyl ether.
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| CN101198581A (en) * | 2005-05-10 | 2008-06-11 | 科勒研究有限公司 | Method for decarboxylating C-C cross-linking of carboxylic acids with carbon electrophiles |
| CN101863826A (en) * | 2010-05-26 | 2010-10-20 | 中国科学技术大学 | Method for preparing 2-benzyl pyridine compound |
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| CN101198581A (en) * | 2005-05-10 | 2008-06-11 | 科勒研究有限公司 | Method for decarboxylating C-C cross-linking of carboxylic acids with carbon electrophiles |
| CN101863826A (en) * | 2010-05-26 | 2010-10-20 | 中国科学技术大学 | Method for preparing 2-benzyl pyridine compound |
Non-Patent Citations (1)
| Title |
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| Synthesis of aromatic esters via pd-catalyzed decarboxylative coupling of potassium oxalate monoesters with aryl bromides and chlorides;Rui Shang et al;《Journal of American chemical society》;2009;第131卷(第16期);表2 * |
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