CN108299140B - Synthetic method of biaryl compound - Google Patents
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Abstract
The invention discloses a synthetic method of a biaryl compound, which comprises the following steps: under the condition of the existence of a derivative catalyst of urea and an additive, the aryl iodide compound and the aryl compound react to obtain the biaryl compound. According to the synthetic method of the biaryl compound, all the steps are carried out in one reactor, no separation step is needed in the middle, the method belongs to one-pot reaction, the yield of the reaction is improved, and the reaction product is easy to purify. The synthetic method of the invention adopts a series of urea derivatives as catalysts, and the derivatives and reactants generate a single electron transfer process to form free radicals, thereby further catalyzing to form C-C bonds to generate biaryl. Compared with the traditional transition metal catalysis method, the catalyst has the advantages of low price, easy acquisition, good selectivity, high yield, strong applicability, simple treatment process after reaction, reduced cost and accelerated synthesis rate.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a synthetic method of a biaryl compound.
Background
Biaryl compounds are one of the important structures for constructing many natural organic compounds. It is widely used in the fields of organic functional materials (such as liquid crystal compounds, fluorescent compounds and the like), medicines, pesticides, organic synthesis intermediates and the like. For example: the biaryl compound can be used as a specific medicine for certain stubborn diseases and a food additive in the food industry, so the biaryl compound has a good development prospect.
Many documents about biaryl synthesis at home and abroad are reported, and each document has an independent advantage, and the document mainly comprises the following synthesis methods: fritz Ullmann et al, 1901 reported the formation of biaryl by using halogenated aromatic hydrocarbons as a starting material and excess fresh copper powder as a catalyst, followed by direct heating or by reaction with DMF. The method requires high temperature, strong base equivalent of copper or copper salt, long reaction time, severe reaction conditions and low yield. (II) Tanaka et al in 2003 reported aryl coupling reactions promoted by Pa (II) -TDAE catalysts. Various palladium reagents such as PdCl2(MeCN)2，PdCl3，Pd(hfacac)2And Pd2(dba)2The catalyst is used for forming a complex with TDAE to catalyze and reduce aryl halide, and can obtain good catalytic coupling yield. In 1972, Kumada et al reported the cross-coupling of Grignard reagents phenylmagnesium bromide with aromatic or vinyl halides to styrene under the action of nickel catalysts. The reaction has good chemical selectivity and simple operation, but the nickel catalyst can only be used for Grignard reagent and can not be used for organic matterLithium reagent, a later developed palladium catalyst, is expensive. (tetra) Negishi in 1977 reported a palladium catalyzed coupling reaction of an unsaturated organozinc reagent with aryl or ethyl halides, etc. The reaction has the advantages of good reaction selectivity, high catalytic efficiency, mild reaction conditions, abundant sources of reaction raw materials and the like, but the activity of an organic zinc reagent is not high, and the price of a palladium catalyst is high. Suzuki developed in 1981 that aryl boronic acids were coupled with aryl halides with the aid of Pd (0) -catalysts to form biaryls. The reaction condition is mild, and the aryl boric acid is economical and easy to obtain. However, the catalyst is expensive and difficult to react if the reactant is a chloride. (VI) Stille reports in 1986 that organotin derivatives catalyzed by palladium catalysts form aryl C-C bonds either by themselves or with organic halogens. But the synthesis process is complex, the cost is high and the atom economy is poor.
In summary, although there are many reports on the synthesis methods of biaryl compounds in the prior art, the problems of difficult availability of catalysts, high catalyst price, low reaction yield, poor selectivity, poor applicability, complex synthesis process and the like still exist. Therefore, it is necessary to find a new synthetic method of biaryl compounds which is more economical and environment-friendly.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a novel method for synthesizing biaryl compounds. The invention adopts a series of urea derivatives as catalysts, and the urea derivatives and reactants generate a single electron transfer process to form free radicals, so as to further catalyze and form C-C bonds to generate biaryl. Compared with the traditional transition metal catalysis method, the catalyst has the advantages of low price, easy acquisition, high reaction yield, good selectivity, strong applicability, simple treatment process after reaction, reduced cost and accelerated synthesis rate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a synthetic method of a biaryl compound comprises the following steps:
under the condition of the existence of a derivative catalyst of urea and an additive, reacting an aryl iodide compound with an aromatic compound to obtain a biaryl compound;
the structure of the urea derivative catalyst is shown as the formula (I):
wherein R is3Represents a hydrogen atom, a phenyl group, a methyl group, an ethyl group or a tert-butylphenyl group; r4Represents a hydrogen atom, a phenyl group, a methyl group, an ethyl group or a tert-butylphenyl group;
the additive is potassium tert-butoxide.
In the synthesis method, the aryl iodide compound is selected from a compound with a structure shown in a formula (II) or a thiophene iodide compound; the aromatic compound is selected from a compound with a structure shown in a formula (III) or pyrazine;
wherein R is1Represents a methyl group, a methoxy group, a fluorine atom, a chlorine atom, a cyano group or a hydrogen atom; r2Represents a methyl group, a methoxy group or a hydrogen atom;
x represents C or N.
Preferably, the iodoaromatic compound is any one of the following compounds:
p-iodoanisole, m-iodoanisole, o-iodoanisole, iodobenzene, p-iodotoluene, m-iodotoluene, 3, 5-dimethyliodobenzene, p-fluoroiodobenzene, p-chloroiodobenzene, 3-iodothiophene, p-iodobenzonitrile, 2-iodopyridine, 3-iodopyridine or 4-iodopyridine.
Preferably, the aromatic compound is any one of the following compounds:
benzene, toluene, xylene, pyridine or pyrazine.
In the synthesis method, the equivalent ratio of the iodo aromatic compound, the additive and the urea derivative catalyst is 1: (100-150): (3-4): (0.05-0.15); preferably, the iodo aromatic compound, the additive and the urea derivative catalyst are added in an equivalent ratio of 1: 100: 3: 0.1.
in the above synthesis method, the reaction temperature is 110-; most preferably 120 deg.c.
In the synthesis method, the reaction time is 18-24h, for example, 18h, 20h, 22h or 24 h; most preferably 24 h.
In the above synthesis method, the urea derivative catalyst is preferably diethyl urea.
The synthesis method further comprises the following steps: and (3) carrying out column chromatography separation on the obtained biaryl compound.
The biaryl compound synthesized by the method has a biaryl structure, so the biaryl compound has important application in the fields of organic functional materials, medicines, pesticides, organic synthesis intermediates and the like.
The invention has the beneficial effects that:
(1) the synthetic method of the biaryl compound provided by the invention has the advantages that all steps are carried out in one reactor, no separation step is needed in the middle, the method belongs to one-pot reaction, the reaction yield is greatly improved, the yield can reach more than 95%, and the reaction product is easy to purify.
(2) The invention adopts a series of urea derivatives as catalysts, and the urea derivatives and reactants generate a single electron transfer process to form free radicals, so as to further catalyze and form C-C bonds, replace the traditional multistep organic synthesis reaction, shorten the reaction time, reduce the energy consumption and improve the synthesis efficiency.
(3) The catalyst for the synthesis reaction is low in price, easy to obtain, low in toxicity and green and safe in synthesis reaction.
Drawings
FIG. 1: example 1 structural characterization of the prepared product.
FIG. 2: example 4 structural characterization of the prepared product.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As described in the background art, transition metal catalysts are mostly adopted in the synthesis method of biaryl compounds in the prior art, and the method is complex and has low yield. Based on the above, the invention provides a novel synthesis method of biaryl compounds, which adopts a series of urea derivatives as catalysts for the first time, and the urea derivatives and reactants generate a single electron transfer process to form free radicals, further form C-C bonds, generate biaryl, improve atom economy, and has the advantages of simple preparation method and high yield.
In one embodiment of the invention, the synthesis method of the biaryl compound is as follows:
(1) the method comprises the following steps of (1) mixing iodo aromatic hydrocarbon compounds, aromatic compounds, additives and urea derivative catalysts according to a molar ratio of 1: (100-150): (3-4): (0.05-0.15) is added into a reaction tube, and the mixture is heated and stirred for reaction at the temperature of 110 ℃ and 150 ℃ for 18-24 h.
(2) After the reaction is finished, the biaryl compound is obtained by column chromatographic separation.
The reaction formula of the synthesis is as follows:
in the synthesis system, the selection of the additive plays a crucial role in the yield of the product, and the invention optimally selects various additives in the test process, so that the result shows that the yield of the product can be greatly improved only by selecting potassium tert-butoxide as the additive; and the other substances are selected as additives, so that the yield of the product cannot be improved, and even the product cannot be obtained.
In the synthesis system of the present invention, the aromatic compound serves as both a reactant and a solvent. In organic chemistry, most reactions are carried out in solvents, which play a very important role in chemical synthesis reactions, and the reaction effects are very different when different solvents are used in the same reaction. The aromatic compound of the invention plays a dual role in the synthesis reaction, has good intermiscibility with the iodo-aromatic compound, the additive and the derivative catalyst of urea, is beneficial to the reaction and improves the yield of the product.
In the synthesis system, the reaction temperature and time are key factors influencing the yield of the reaction product, and the conditions of the reaction temperature and time are investigated and optimized, so that the result shows that the yield of the reaction product is higher when the reaction time is 18-24h at the temperature of 110-; when the reaction temperature is 120 ℃ and the reaction time is 24 hours, the optimal yield can be obtained, side reactions are not generated basically, and the purification of reaction products is convenient.
In conclusion, in the synthesis system of the invention, the addition proportion of the urea derivative catalyst, the additive potassium tert-butoxide, the iodo-aromatic compound and the aromatic compound, the reaction temperature and the reaction time are an organic whole, and the specific selection and combination of the conditions lead the urea derivative catalyst, the iodo-aromatic compound and the aromatic compound to mutually exert unique coordination action and effect, realize the generation of C-C bonds and form the biaryl compound. Omission or replacement of any one of the above-mentioned synthesis systems, or addition of reaction conditions to the reaction system, may decrease the yield of the product.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples and comparative examples of the present invention are conventional test materials in the art, and are commercially available; or prepared by conventional synthetic methods known in the art.
In the present invention, "10 mol%", "15 mol%" and the like each indicate the percentage of the added substance to the reaction equivalent of the "aromatic iodo compound". For example: in example 1, 10 mol% of diethyl urea means that "diethyl urea" was added in an amount of 10% of the amount of "p-iodoanisole", that is, 0.02 mmol.
Example 1:
(1) putting 10 mol% of diethyl urea (0.02mmol), 0.6mmol of potassium tert-butoxide, 0.2mmol of p-iodoanisole and 2ml of benzene into a reaction tube, heating and stirring for reaction at 120 ℃ for 24 h; .
(2) After the reaction is finished, the product 4-methoxybiphenyl can be obtained by column chromatography (the column packing is 300-400-mesh column chromatography silica gel, the eluant is petroleum ether and ethyl acetate which are 100:0.5, and v: v), and the yield is 94%. The structural characterization of the product is shown in figure 1.
The structural characterization data of the product are as follows:
1H NMR(400MHz,CDCl3)7.59–7.54(m,4H),7.44(t,J＝7.4Hz,2H),7.32(t,J＝7.36Hz,1H),7.00(t,J＝8.84Hz,2H),3.87(s,3H).MS(CI)Calcd for C13H12O:184；Found(M+H+):185.
example 2:
(1) 10 mol% of diethyl urea (0.02mmol), 0.6mmol of potassium tert-butoxide, 0.2mmol of m-iodoanisole and 2ml of benzene are put into a reaction tube to be heated and stirred for reaction, the heating and stirring temperature is 120 ℃, and the reaction time is 24 h.
(2) After the reaction is finished, the product 3-methoxybiphenyl can be obtained by column chromatography (the column packing is 300-mesh 400-mesh column chromatography silica gel, the eluant is petroleum ether and ethyl acetate which are 100:0.5, and v: v), and the yield is 51%.
The structural characterization data of the product are as follows:
1H NMR(400MHz,CDCl3)7.64–7.61(m,2H),7.47(t,J＝7.24Hz,2H),7.41–7.37(m,2H),7.23–7.16(m,2H),6.95–6.92(m,1H),3.89(s,3H).MS(CI)Calcd for C13H12O:184；Found(M+H+):185.
example 3:
(1) 10 mol% of diethyl urea (0.02mmol), 0.6mmol of potassium tert-butoxide, 0.2mmol of o-iodoanisole and 2ml of benzene are put into a reaction tube to be heated and stirred for reaction, the heating and stirring temperature is 120 ℃, and the reaction time is 24 h.
(2) After the reaction is finished, the product 2-methoxybiphenyl can be obtained by column chromatography (the column packing is 300-mesh 400-mesh column chromatography silica gel, the eluant is petroleum ether and ethyl acetate which are 100:0.5, and v: v), and the yield is 82%.
The structural characterization data of the product are as follows:
1H NMR(400MHz,CDCl3)7.57–7.54(m,2H),7.45–7.41(m,2H),7.36–7.33(m,3H),7.08–7.00(m,2H),3.83(s,3H).MS(CI)Calcd for C13H12O:184；Found(M+H+):185.
example 4:
(1) 10 mol% of diethyl urea (0.02mmol), 0.6mmol of potassium tert-butoxide, 0.2mmol of iodobenzene and 2ml of benzene are put into a reaction tube and heated and stirred for reaction at the temperature of 120 ℃ for 24 hours.
(2) After the reaction is finished, the product biphenyl can be obtained by column chromatography separation (the filler of the chromatographic column is 300-mesh 400-mesh column chromatography silica gel, the eluent is petroleum ether), and the yield is 95%. The structural characterization of the product is shown in figure 2.
The structural characterization data of the product are as follows:
1H NMR(400MHz,CDCl3)7.64–7.61(m,4H),7.49–7.44(m,4H),7.39–7.35(m,2H).MS(CI)Calcd for C12H10:154；Found(M+H+):155.
example 5:
(1) 15 mol% of diethyl urea (0.03mmol), 0.6mmol of potassium tert-butoxide, 0.2mmol of p-iodotoluene and 2ml of benzene are put into a reaction tube and heated and stirred for reaction at the temperature of 120 ℃ for 24 hours.
(2) After the reaction is finished, the product 4-methyl biphenyl can be obtained by column chromatography separation (the column packing of the column is 300-400 mesh column chromatography silica gel, the eluent is petroleum ether), and the yield is 82%.
The structural characterization data of the product are as follows:
1H NMR(400MHz,CDCl3)7.62–7.60(m,2H),7.53–7.51(m,2H),7.47–7.43(m,2H),7.37–7.33(m,1H),7.29–7.26(m,2H),2.42(s,3H).MS(CI)Calcd for C13H12:168；Found(M+H+):169.
example 6:
(1) 15 mol% of diethyl urea (0.03mmol), 0.6mmol of potassium tert-butoxide, 0.2mmol of m-iodotoluene and 2ml of benzene are put into a reaction tube and heated and stirred for reaction at the temperature of 120 ℃ for 24 hours.
(2) After the reaction is finished, the product 3-methyl biphenyl can be obtained by column chromatography separation (the column packing of the column is 300-400 mesh column chromatography silica gel, the eluent is petroleum ether), and the yield is 82%.
The structural characterization data of the product are as follows:
1H NMR(400MHz,CDCl3)7.63–7.60(m,2H),7.48–7.42(m,4H),7.38–7.34(m,2H),7.19(d,J＝7.5Hz,1H),2.45(s,3H).MS(CI)Calcd for C13H12:168；Found(M+H+):169.
example 7:
(1) 10 mol% of diethyl urea (0.02mmol), 0.6mmol of potassium tert-butoxide, 0.2mmol of 3, 5-dimethyl iodobenzene and 2ml of benzene are put into a reaction tube to be heated and stirred for reaction, the heating and stirring temperature is 130 ℃, and the reaction time is 24 h.
(2) After the reaction is finished, the product 3, 5-dimethyl biphenyl can be obtained by column chromatography separation (the column packing of the column is 300-mesh 400-mesh column chromatography silica gel, the eluent is petroleum ether), and the yield is 80%.
The structural characterization data of the product are as follows:
1H NMR(400MHz,CDCl3)7.62–7.59(m,2H),7.47–7.42(m,2H),7.35(t,J＝7.36Hz,1H),7.24(s,2H),7.03(s,1H),2.41(s,6H).MS(CI)Calcd for C14H14:182；Found(M+H+):183.
example 8:
(1) 10 mol% of diethyl urea (0.02mmol), 0.6mmol of potassium tert-butoxide, 0.2mmol of p-fluoroiodobenzene and 2ml of benzene are put into a reaction tube to be heated and stirred for reaction, the heating and stirring temperature is 130 ℃, and the reaction time is 24 h.
(2) After the reaction is finished, the product 4-fluorobiphenyl can be obtained by column chromatography separation (the column packing of the column is 300-400-mesh column chromatography silica gel, the eluent is petroleum ether), and the yield is 51%.
The structural characterization data of the product are as follows:
1H NMR(400MHz,CDCl3)7.62–7.53(m,4H),7.47–7.43(m,2H),7.38–7.34(m,1H),7.17–7.11(m,2H).MS(CI)Calcd for C12H9F:172；Found(M+H+):173.
example 9:
(1) 10 mol% of diethyl urea (0.02mmol), 0.6mmol of potassium tert-butoxide, 0.2mmol of p-chloroiodobenzene and 2ml of benzene are put into a reaction tube to be heated and stirred for reaction, the heating and stirring temperature is 130 ℃, and the reaction time is 24 h.
(2) After the reaction is finished, the product terphenyl can be obtained by column chromatography separation (the column packing of the chromatographic column is 300-mesh 400-mesh column chromatography silica gel, the eluent is petroleum ether), and the yield is 60%.
The structural characterization data of the product are as follows:
1H NMR(400MHz,CDCl3)7.70–7.65(m,8H),7.50–7.46(m,4H),7.40–7.36(m,2H).MS(CI)Calcd for C18H14:230；Found(M+H+):231.
example 10:
(1) 10 mol% of diethyl urea (0.02mmol), 0.6mmol of potassium tert-butoxide, 0.2mmol of p-iodobenzonitrile and 2ml of benzene were placed in a reaction tube, and heated and stirred for reaction at 130 ℃ for 24 hours.
(2) After the reaction is finished, the product 4-biphenylcarbonitrile can be obtained by column chromatography (the column packing is 300-400 mesh column chromatography silica gel, the eluent is petroleum ether), and the yield is 42%.
The structural characterization data of the product are as follows:
1H NMR(600MHz,CDCl3)7.74–7.68(m,4H),7.59(d,J＝7.14Hz,2H),7.49(t,J＝7.26Hz,2H),7.43(d,J＝7.32Hz,1H).MS(CI)Calcd for C13H9N:179；Found(M+H+):180.
example 11:
(1) 10 mol% of diethyl urea (0.02mmol), 0.6mmol of potassium tert-butoxide, 0.2mmol of 3-iodothiophene and 2ml of benzene are put into a reaction tube to be heated and stirred for reaction, the heating and stirring temperature is 130 ℃, and the reaction time is 24 h.
(2) After the reaction is finished, the product 3-phenyl thiophene can be obtained by column chromatography separation (the column packing of the column is 300-400-mesh column chromatography silica gel, the eluent is petroleum ether), and the yield is 85%.
The structural characterization data of the product are as follows:
1H NMR(400MHz,CDCl3)7.63–7.61(m,2H),7.48–7.46(m,1H),7.44–7.39(m,4H),7.33–7.29(t,J＝7.36Hz,1H).MS(CI)Calcd for C10H8S:160；Found(M+H+):161.
example 12:
(1) 10 mol% of diethyl urea (0.02mmol), 0.6mmol of potassium tert-butoxide, 0.2mmol of 2-iodopyridine and 2ml of benzene are put into a reaction tube and heated and stirred for reaction at the temperature of 110 ℃ for 24 hours.
(2) After the reaction is finished, the product 2-phenylpyridine can be obtained by column chromatography (the column packing is 300-mesh 400-mesh column chromatography silica gel, the eluent is ethyl acetate and petroleum ether is 1:4), and the yield is 72%.
The structural characterization data of the product are as follows:
1H NMR(400MHz,CDCl3)8.70(d,J＝4.64Hz,1H),7.99(d,J＝7.28Hz,2H),7.78–7.72(m,2H),7.50–7.40(m,3H),7.26–7.22(m,1H).MS(CI)Calcd for C11H9N:155；Found(M+H+):156.
example 13:
(1) 10 mol% of diethyl urea (0.02mmol), 0.6mmol of potassium tert-butoxide, 0.2mmol of 3-iodopyridine and 2ml of benzene are put into a reaction tube and heated and stirred for reaction at the temperature of 110 ℃ for 24 hours.
(2) After the reaction is finished, the product 3-phenylpyridine can be obtained by column chromatography (the column packing is 300-mesh 400-mesh column chromatography silica gel, the eluent is ethyl acetate and petroleum ether is 1:4), and the yield is 52%.
The structural characterization data of the product are as follows:
1H NMR(600MHz,CDCl3)8.85(d,J＝2.4Hz 1H),8.59(d,J＝3.36Hz,1H),7.89–7.87(m,1H),7.59–7.57(m,2H),7.50–7.47(m,2H),7.42–7.40(m,1H),7.38–7.34(m,1H).MS(CI)Calcd for C11H9N:155；Found(M+H+):156.
example 14:
(1) 10 mol% of diethyl urea (0.02mmol), 0.6mmol of potassium tert-butoxide, 0.2mmol of 4-iodopyridine and 2ml of benzene are put into a reaction tube and heated and stirred for reaction at the temperature of 110 ℃ for 24 hours.
(2) After the reaction is finished, the 4-phenylpyridine product can be obtained by column chromatography (the column packing is 300-mesh 400-mesh column chromatography silica gel, the eluent is ethyl acetate and petroleum ether is 1:4), and the yield is 49%.
The structural characterization data of the product are as follows:
1H NMR(600MHz,CDCl3)8.66(d,J＝5.6Hz,2H),7.65–7.63(m,2H),7.51–7.48(m,4H),7.45–7.43(m,1H).MS(CI)Calcd for C11H9N:155；Found(M+H+):156.
comparative example 1:
the product was prepared in the same manner as in example 1 except that the heating and stirring temperature in example 1 was adjusted to 100 c, and the yield of the product was calculated to be 12%.
Comparative example 2:
the catalyst "diethyl urea" in example 1 was adjusted to "dimethyl urea", and the product yield was calculated to be 76% as in example 1.
Comparative example 3:
the catalyst "diethyl urea" in example 1 was adjusted to "diphenyl urea", and the yield of the product was calculated to be 57% as in example 1.
Comparative example 4:
the catalyst "diethyl urea" in example 1 was adjusted to "ethyl urea", and the product yield was calculated to be 84% as in example 1.
Comparative example 5:
the additive "potassium tert-butoxide" in example 1 was adjusted to "potassium hydroxide", and the product was not prepared and the yield was 0 as determined in example 1.
Comparative example 6:
the additive "potassium tert-butoxide" in example 1 was adjusted to "sodium tert-butoxide", and otherwise as in example 1, no product was prepared and the yield of product was 0.
Comparative example 7:
the catalyst "diethylurea" added in example 1 was adjusted to not add any catalyst, and the product yield was calculated to be 3% as in example 1.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (2)
1. A synthetic method of a biaryl compound is characterized by comprising the following steps: under the condition of the existence of a derivative catalyst of urea and an additive, reacting an iodo-aromatic compound or an iodo-heteroaromatic compound with an aromatic compound to obtain a biaryl compound; and (3) carrying out column chromatography separation on the obtained biaryl compound, wherein the filler of a chromatographic column is 300-400-mesh column chromatography silica gel, and the eluent is a mixture of the following components in a volume ratio of 100:0.5 of petroleum ether-ethyl acetate, or the eluent is petroleum ether, or the eluent is ethyl acetate-petroleum ether with the volume ratio of 1: 4;
the derivative catalyst of the urea is diethyl urea;
the additive is potassium tert-butoxide;
the molar ratio of the iodo-aromatic hydrocarbon compound or iodo-heteroaromatic hydrocarbon compound, the aromatic compound, the additive and the urea derivative catalyst is 1: (100-150): (3-4): (0.05-0.15);
the reaction temperature is 110-150 ℃, and the reaction time is 18-24 h;
the iodo-aromatic hydrocarbon compound or the iodo-heteroaromatic hydrocarbon compound is any one of the following compounds: p-iodoanisole, m-iodoanisole, o-iodoanisole, iodobenzene, p-iodotoluene, m-iodotoluene, 3, 5-dimethyliodobenzene, p-fluoroiodobenzene, p-chloroiodobenzene, 3-iodothiophene, p-iodobenzonitrile, 2-iodopyridine, 3-iodopyridine or 4-iodopyridine;
the aromatic compound is any one of the following compounds: benzene, toluene, xylene, pyridine or pyrazine.
2. The synthesis method according to claim 1, wherein the iodoaromatic or iodoheteroaromatic compound, the aromatic compound, the additive and the urea derivative catalyst are added in a molar ratio of 1: 100: 3: 0.1.
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Non-Patent Citations (4)
| Title |
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| "A Foldamer-Based Organocatalyst for Direct Arylations of Unactivated Arenes";Huaiqing Zhao等;《Organic Letters》;20170405;第19卷;第2192页左栏table2、右栏table3、Scheme2 * |
| "A macrocyclic aromatic pyridone pentamer as a highly efficient organocatalyst for the direct arylations of unactivated arenes";Huaiqing Zhao等;《Chemical Communication》;20130204;第49卷;第2324页左栏table2、右栏table3，第2325页左栏第1段、scheme2 * |
| "Organocatalysis in Cross-Coupling: DMEDA-Catalyzed Direct C-H Arylation of Unactivated Benzene";wei liu等;《Journal of America Chemical Society》;20100802;第132卷;第16738页左栏table2，第16739页左栏第2段、Scheme 3 * |
| "Urea-based organocatalyst catalyzed direct C-H bond arylations of unactivated arenes";Huaiqing Zhao等;《Catalysis Communications》;20180410;第111卷;全文 * |
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