CN102329199B - Method for synthesizing biphenyl compounds under composite catalytic actions of Pd/C and crown ether - Google Patents
Method for synthesizing biphenyl compounds under composite catalytic actions of Pd/C and crown ether Download PDFInfo
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Abstract
The invention relates to a method for synthesizing biphenyl compounds under composite catalytic actions of Pd/C and crown ether, belonging to the field of synthesis of biphenyl compounds. The invention aims to solve the problems that the Pd/C catalyst used in the Pd/C catalyzed Suzuki coupling reaction can not be used cyclically, the cost for producing the biphenyl compounds is high, and the yield of the biphenyl compounds can not be higher than 95%. The method comprises the following steps: adding aryl halide and arylboric acid as reaction substrates in a mol ratio of 1:(0.8-4) into a reaction kettle; adding Pd/C and crown ether as a composite catalyst, adding potassium carbonate and adding methanol water solution; under inert gas shielding conditions, reacting at room temperature for 12-36 hours; and extracting, drying, filtering, carrying out vacuum concentration, carrying out chromatography, and eluting to obtain the biphenyl compounds. The invention is mainly used for synthesizing biphenyl compounds.
Description
Technical field
The present invention relates to a kind of synthetic field of biphenyl compound.
Background technology
Biphenyl compound structure is extensively present in natural product, as terpene (terpenes), and lignanoid (lignans), flavonoid compound (flavonoids), in peptide (petides) and alkaloid (alkaloids).Many biphenyl compounds have certain biological activity, if significantly reduce serum glutamic pyruvic transminase, alleviate hepatic pathology damage and strengthen liver detoxification function etc.Biphenyl structural is also the common structure unit such as agricultural chemicals and dyestuff simultaneously, and wherein polyaromatic, due to its special physics and characteristic electron, has been used as organic conductor, semi-conductor and liquid crystal material.Because biphenyl compound has these functions, paid close attention to more and more widely, therefore adopt new synthetic method can synthesize efficiently, fast and cheaply the work problem that biphenyl compound has become many researchers.
The formation of C-C is one of most basic organic chemical reactions process, is from simple precursor, to form the committed step of complicated molecule.The Suzuki linked reaction of the famous scientist's Suzuki Zhang Faming of Japan is one of important method of preparing biphenyl compound, and this reaction has realized to be carried out cross-coupling by halogenated aryl hydrocarbon and aryl boric acid and form new C-C and synthesize biphenyl compound.In recent years, this reaction has obtained impressive progress at the aspects such as innovation of mechanism research, substrate expansion, catalyzer and catalyst system.This catalyzed reaction not only reaction conditions is gentle, and has chemistry highly, three-dimensional and selectivity region, in organic synthesis, is widely used.In this reaction, the title complex of palladium is custom catalysts group, and palladium belongs to d
10transition metal, oxidation addition easily occurs palladium complex when catalyzed reaction makes reaction substrate activation, then is eliminated and obtained biphenyl product by reduction, thereby completes catalytic cycle.Simultaneously the title complex of palladium is also widely used in the formation of catalysis C-C key, C-N key, C-S key, C-P key and C-O key etc., makes over that some are accomplished with the reaction that ordinary method is difficult to realization.Although oneself obtains larger development to the title complex of palladium in catalysis Suzuki linked reaction, also there is following problems: the one, conventionally need to use the organic ligand of large steric hindrance, electron rich, the numerous and diverse difficult acquisition of synthesis step of these organic ligands, price is high; The 2nd, use volatile, poisonous in a large number organic solvent and cause environmental pollution.
Therefore, explore without additional part, simple to operate, efficient and eco-friendly palladium catalysis Suzuki linked reaction system is synthesized biphenol compound becomes significant research topic.
1994, Marck etc. (TetrahedronLett.1994,35,3277) reported first the Suzuki linked reaction of Pd/C catalysis, be that to take aryl bromide and trifluoro sulphonate be substrate, reaction yield is greater than 80%, but need to add PhP
3as part, and temperature requirement is higher; Calendar year 2001, (the Org.Lett. such as Sun, 2001,3,1555), under the inspiration of the work such as Marck, the aqueous solution of N,N-dimethylacetamide (DMA) of take has been furtherd investigate and has not been added the Suzuki linked reaction that the Pd/C catalyst system catalysis chlorinated aromatic hydrocarbons of phosphine part participates in as solvent, research shows can reach more than 79% with the reaction yield of the chlorinated aromatic hydrocarbons of electron withdrawing group, but not high with the reaction yield of the chlorinated aromatic hydrocarbons of donor residues; 2002 subsequently,
deng (Synlett 2002,1118) further to not adding the aryl bromide of Pd/C catalyst and the Suzuki linked reaction of chlorinated aromatic hydrocarbons of part, be studied, by add a certain proportion of water in organic solvent, obtained higher reaction yield, but temperature of reaction needs 100 ℃; (the Synthesis2005 such as Sajiki in 2005,537 and Synthesis2005,852) adopt 10% Pd/C of industrial use to make catalyzer, take ethanol/water as solvent, sodium carbonate is alkali, just can catalysis aryl bromide under room temperature and the reacting of aryl boric acid, obtain target product yield < 95%.
But prior art adopts the Pd/C catalyzer using in the Suzuki linked reaction of Pd/C catalysis not realize and can be recycled, and the cost of producing biphenyl compound is high, and the yield of biphenyl compound can not reach the problem that is greater than 95%.
Summary of the invention
The present invention will solve prior art and adopt the Pd/C catalyzer using in the Suzuki linked reaction of Pd/C catalysis not realize to can be recycled, the cost of producing biphenyl compound is high, and the yield of biphenyl compound can not reach the problem that is greater than 95%, and provide a kind of method that adopts palladium/carbon and the synthetic biphenyl compound of crown ether composite catalyzing.
Adopt the method for the synthetic biphenyl compound of palladium/carbon and crown ether composite catalyzing, specifically complete according to the following steps: using the halogenated aryl hydrocarbon as reaction substrate and aryl boric acid, be first 1:(0.8～4 in molar ratio) ratio put in reactor, then add palladium/carbon and crown ether as composite catalyst, add salt of wormwood, add again methanol aqueous solution, under protection of inert gas condition, room temperature reaction 12～36h, then obtain biphenyl compound through extraction → dry → filtration → vacuum concentration → chromatography → wash-out; The general formula of described halogenated aryl hydrocarbon is:
wherein R is hydrogen, 4-nitro, 4-aldehyde radical, 4-methoxyl group, 3,4-dimethoxy, 2-benzyloxy-4-methyl, 2-nitro-5-methoxyl group or 3,4-methylene-dioxy; The general formula of described aryl boric acid is:
r wherein
1for alkyl, alkoxyl group, replacement alkane or aryl; In described palladium/carbon, the palladium metal of load accounts for 10% of palladium/carbon total mass; Described crown ether be 18-hat (ether)-6,15-hat (ether)-5 or two cyclohexanes also-18-is preced with (ether)-6; The described amount that adds palladium/carbon species is 0.1～15% of halogenated aryl hydrocarbon amount of substance; The described crown ether amount of substance that adds is 0.5～3.0 times of halogenated aryl hydrocarbon amount of substance; The described amount of substance that adds salt of wormwood is 1～5 times of halogenated aryl hydrocarbon amount of substance; Described methanol aqueous solution and the mass ratio of halogenated aryl hydrocarbon are (10～40): 1, and methanol aqueous solution is by anhydrous methanol and distilled water (0.1～10) by volume: 1 mixes; Described rare gas element is nitrogen or argon gas.
Advantage of the present invention: one, use palladium/carbon and crown ether as composite catalyst, without using any palladium catalyst containing part, cost-saving, simple to operate; Two, this synthesising method reacting condition is gentle, and the time is short, and yield is high; Three, composite catalyst of the present invention is capable of circulation makes; Four, the yield of the synthetic biphenyl compound of the present invention reaches 95%～99.9%.
Embodiment
Embodiment one: present embodiment provides a kind of method that adopts palladium/carbon and the synthetic biphenyl compound of crown ether composite catalyzing, specifically completes according to the following steps:
First using the halogenated aryl hydrocarbon as reaction substrate and aryl boric acid, be 1:(0.8～4 in molar ratio) ratio put in reactor; then add palladium/carbon and crown ether as composite catalyst; add salt of wormwood; add again methanol aqueous solution; under protection of inert gas condition; room temperature reaction 12～36h, then obtain biphenyl compound through extraction → dry → filtration → vacuum concentration → chromatography → wash-out.
The general formula of the halogenated aryl hydrocarbon described in present embodiment is:
r can be hydrogen, 4-nitro, 4-aldehyde radical, 4-methoxyl group, 3,4-dimethoxy, 2-benzyloxy-4-methyl, 2-nitro-5-methoxyl group or 3,4-methylene-dioxy.
The general formula of the aryl boric acid described in present embodiment is:
r
1can be alkyl, alkoxyl group, replacement alkane or aryl.
In palladium/carbon described in present embodiment, the palladium metal of load accounts for 10% of palladium/carbon total mass.
Crown ether described in present embodiment be 18-hat (ether)-6,15-hat (ether)-5 or two cyclohexanes also-18-is preced with (ether)-6.
The amount that adds palladium/carbon species described in present embodiment is 0.1～15% of halogenated aryl hydrocarbon amount of substance.
The crown ether amount of substance that adds described in present embodiment is 0.5～3.0 times of halogenated aryl hydrocarbon amount of substance.
The amount of substance that adds salt of wormwood described in present embodiment is 1～5 times of halogenated aryl hydrocarbon amount of substance.
Methanol aqueous solution described in present embodiment and the mass ratio of halogenated aryl hydrocarbon are (10～40): 1, and methanol aqueous solution is by anhydrous methanol and distilled water (0.1～10) by volume: 1 mixes.
Rare gas element described in present embodiment is nitrogen or argon gas.
The reaction expression of present embodiment is:
The yield of the biphenyl compound that present embodiment is synthetic reaches 95%～99.9%.
Present embodiment is used palladium/carbon and crown ether as composite catalyst, without using any palladium catalyst containing part, cost-saving, simple to operate.
The synthesising method reacting condition of present embodiment is gentle, and the time is short, and yield is high.
Composite catalyst palladium/the carbon of present embodiment and crown ether recycle 10 times, and its catalytic efficiency is not decreased significantly, so composite catalyst palladium/carbon and crown ether are capable of circulation, make.
Embodiment two: present embodiment and embodiment one difference are: the described amount that adds palladium/carbon species is 1～10% of halogenated aryl hydrocarbon amount of substance.Other is identical with embodiment one.
Embodiment three: present embodiment and one of embodiment one or two difference are: the described amount that adds palladium/carbon species is 2～8% of halogenated aryl hydrocarbon amount of substance.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three difference is: the described amount that adds palladium/carbon species is 5% of halogenated aryl hydrocarbon amount of substance.Other is identical with embodiment one or three.
Embodiment five: one of present embodiment and embodiment one to four difference is: the described crown ether amount of substance that adds is 2.2～2.8 times of halogenated aryl hydrocarbon amount of substance.Other is identical with embodiment one or four.
Embodiment six: one of present embodiment and embodiment one to five difference is: the described crown ether amount of substance that adds is 2.5 times of halogenated aryl hydrocarbon amount of substance.Other is identical with embodiment one or five.
Embodiment seven: one of present embodiment and embodiment one to six difference is: the described amount of substance that adds salt of wormwood is 3～4 times of halogenated aryl hydrocarbon amount of substance.Other is identical with embodiment one or six.
Embodiment eight: one of present embodiment and embodiment one to seven difference is: the described amount of substance that adds salt of wormwood is 3.5 times of halogenated aryl hydrocarbon amount of substance.Other is identical with embodiment one or seven.
Embodiment nine: one of present embodiment and embodiment one to eight difference is: described methanol aqueous solution and the mass ratio of halogenated aryl hydrocarbon are (15～35): 1, and methanol aqueous solution is by anhydrous methanol and distilled water (0.3～5) by volume: 1 mixes.Other is identical with embodiment one or eight.
Embodiment ten: one of present embodiment and embodiment one to nine difference is: described methanol aqueous solution and the mass ratio of halogenated aryl hydrocarbon are (20～30): 1, and methanol aqueous solution is by anhydrous methanol and distilled water (0.5～2) by volume: 1 mixes.Other is identical with embodiment one or nine.
Embodiment 11: one of present embodiment and embodiment one to ten difference is: described methanol aqueous solution and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.Other is identical with embodiment one or ten.
Embodiment 12: one of present embodiment and embodiment one to 11 difference is: under protection of inert gas condition, room temperature reaction 24h.Other is identical with embodiment one or 11
Embodiment 13: present embodiment adopts the method for palladium/carbon and the synthetic biphenyl compound of crown ether composite catalyzing to synthesize 3,4-dimethoxy-4 ' '-trifluoromethyl-biphenyl, specifically completes according to the following steps:
First using as 3 of reaction substrate; 4-dimethoxy bromobenzene and 4-trifluoromethyl the phenylo boric acid in molar ratio ratio of 5:6 are put in reactor; then add palladium/carbon and 18-hat (ether)-6 as composite catalyst; add salt of wormwood; add again methanol aqueous solution, under nitrogen protection condition, room temperature reaction 24h; then through extraction → dry → filtration → vacuum concentration → chromatography → wash-out, obtain 3,4-dimethoxy-4 ' '-trifluoromethyl-biphenyl.
In palladium/carbon described in present embodiment, the palladium metal of load accounts for 10% of palladium/carbon total mass.
The amount that adds palladium/carbon species described in present embodiment is 5% of 3,4-dimethoxy bromobenzene amount of substance.
18-hat (ether)-6 amount of substance that adds described in present embodiment is 2.5 times of 3,4-dimethoxy bromobenzene amount of substance.
The amount of substance that adds salt of wormwood described in present embodiment is 3.5 times of 3,4-dimethoxy bromobenzene amount of substance.
Methanol aqueous solution described in present embodiment and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
Present embodiment synthetic 3,4-dimethoxy-4 ' '-trifluoromethyl-biphenyl yield reaches 99.2%.
To present embodiment synthetic 3,4-dimethoxy-4 ' '-trifluoromethyl-biphenyl carries out magnetic resonance detection, its data are:
1HNMR(400MHz,CDCl
3)δ7.72–7.61(m,4H),7.17(dd,J=8.3,2.1Hz,1H),7.10(d,J=2.1Hz,1H),6.97(d,J=8.3Hz,1H),3.96(s,3H),3.94(s,3H).
13CNMR(100MHz,CDCl3)δ149.49,149.41,144.55,132.68,127.06,125.71,125.67,1,121.44,119.77,111.61,110.48,56.04,29.71.
HRMS(EI)calcdforC
15H
13F
2O
2(M-):282.0957.Found:242.0948.
By the known present embodiment of magnetic resonance detection synthetic 3, the structure of 4-dimethoxy-4 ' '-trifluoromethyl-biphenyl is
Embodiment 14: present embodiment adopts the method for palladium/carbon and the synthetic biphenyl compound of crown ether composite catalyzing to synthesize 4-formyl biphenyl, specifically completes according to the following steps:
First using the bromobenzaldehyde as reaction substrate and phenylo boric acid in molar ratio the ratio of 5:6 put in reactor; then add palladium/carbon and 18-hat (ether)-6 as composite catalyst; add salt of wormwood; add again methanol aqueous solution; under nitrogen protection condition; room temperature reaction 24h, then obtain 4-formyl biphenyl through extraction → dry → filtration → vacuum concentration → chromatography → wash-out.
Adopt the palladium/carbon of embodiment 13 recovery as the raw material of present embodiment composite catalyst, what not enough employing was new supplements, and 18-hat (ether)-6 cannot be reclaimed, and need to again add.
In palladium/carbon described in present embodiment, the palladium metal of load accounts for 10% of palladium/carbon total mass.
The amount that adds palladium/carbon species described in present embodiment is 5% of bromobenzaldehyde amount of substance.
18-hat (ether)-6 amount of substance that adds described in present embodiment is 2.5 times of bromobenzaldehyde amount of substance.
The amount of substance that adds salt of wormwood described in present embodiment is 3.5 times of bromobenzaldehyde amount of substance.
Methanol aqueous solution described in present embodiment and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
The synthetic 4-formyl biphenyl yield of present embodiment reaches 99.0%.
The 4-formyl biphenyl synthetic to present embodiment carries out magnetic resonance detection, and its data are:
1HNMR(400MHz,CDCl
3)δ10.06(s,1H),7.95(d,J=8.4Hz,2H),7.75(d,J=8.2Hz,2H),7.66–7.61(m,2H),7.48(t,J=7.3Hz,2H),7.45–7.39(m,1H).
Structure by the synthetic 4-formyl biphenyl of the known present embodiment of magnetic resonance detection is
Embodiment 15: present embodiment adopts the method for palladium/carbon and the synthetic biphenyl compound of crown ether composite catalyzing to synthesize 4-methoxyl group-4 '-trifluoromethyl-biphenyl, specifically completes according to the following steps:
First using the bromoanisole as reaction substrate and 4-trifluoromethyl phenylo boric acid in molar ratio the ratio of 5:6 put in reactor; then add palladium/carbon and 18-hat (ether)-6 as composite catalyst; add salt of wormwood; add again methanol aqueous solution; under nitrogen protection condition; room temperature reaction 24h, then obtain 4-methoxyl group-4 '-trifluoromethyl-biphenyl through extraction → dry → filtration → vacuum concentration → chromatography → wash-out.
Adopt the palladium/carbon of embodiment 14 recovery as the raw material of present embodiment composite catalyst, what not enough employing was new supplements.
In palladium/carbon described in present embodiment, the palladium metal of load accounts for 10% of palladium/carbon total mass.
The amount that adds palladium/carbon species described in present embodiment is 5% of bromoanisole amount of substance.
18-hat (ether)-6 amount of substance that adds described in present embodiment is 2.5 times of bromoanisole amount of substance.
The amount of substance that adds salt of wormwood described in present embodiment is 3.5 times of bromoanisole amount of substance.
Methanol aqueous solution described in present embodiment and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
The synthetic 4-methoxyl group-4 '-trifluoromethyl-biphenyl yield of present embodiment reaches 98.6%.
4-methoxyl group-4 synthetic to present embodiment '-trifluoromethyl-biphenyl carries out magnetic resonance detection, and its data are:
1HNMR(400MHz,CDCl
3)δ7.54(t,J=8.3Hz,4H),7.42(d,J=7.5Hz,1H),7.40(d,J=7.8Hz,1H),7.30(t,J=7.4Hz,1H),6.98(d,J=8.7Hz,2H),3.85(s,3H).
Structure by the known present embodiment of magnetic resonance detection synthetic 4-methoxyl group-4 '-trifluoromethyl-biphenyl is
Embodiment 16: the method that present embodiment adopts palladium/carbon and crown ether composite catalyzing to synthesize biphenyl compound synthesized 3,4-dimethoxy-2 ', 5 '-dimethyl diphenyl, specifically completes according to the following steps:
First using as 3 of reaction substrate; 4-dimethoxy bromobenzene and 2; the 5-dimethylphenyl boronic acid in molar ratio ratio of 5:6 is put in reactor, then adds palladium/carbon and 15-hat (ether)-5 as composite catalyst, adds salt of wormwood; add again methanol aqueous solution; under nitrogen protection condition, room temperature reaction 24h, then obtain 3 through extraction → dry → filtration → vacuum concentration → chromatography → wash-out; 4-dimethoxy-2 ', 5 '-dimethyl diphenyl.
Adopt the palladium/carbon of embodiment 15 recovery as the raw material of present embodiment composite catalyst, what not enough employing was new supplements.
In palladium/carbon described in present embodiment, the palladium metal of load accounts for 10% of palladium/carbon total mass.
The amount that adds palladium/carbon species described in present embodiment is 5% of 3,4-dimethoxy bromobenzene amount of substance.
15-hat (ether)-5 amount of substance that adds described in present embodiment is 2.5 times of 3,4-dimethoxy bromobenzene amount of substance.
The amount of substance that adds salt of wormwood described in present embodiment is 3.5 times of 3,4-dimethoxy bromobenzene amount of substance.
Methanol aqueous solution described in present embodiment and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
Present embodiment synthetic 3,4-dimethoxy-2 ', 5 '-dimethyl diphenyl yield reaches 98.6%.
To present embodiment synthetic 3,4-dimethoxy-2 ', 5 '-dimethyl diphenyl carries out magnetic resonance detection, its data are:
1HNMR(400MHz,CDCl
3)δ7.13(d,J=7.5Hz,1H),7.04(d,J=9.8Hz,2H),6.91–6.87(m,1H),6.84(dd,J=5.8,1.7Hz,2H),3.88(s,3H),3.85(d,J=5.8Hz,3H),2.33(s,3H),2.23(s,3H).
13CNMR(100MHz,CDCl3)δ148.53,147.96,141.62,135.17,134.96,132.32,130.58,130.31127.84,121.40,112.72,110.94,55.92,20.95,20.08.
HRMS(EI)calcdforC
16H
8O
2(M-):242.1365.Found:242.1376.
By the known present embodiment of magnetic resonance detection synthetic 3,4-dimethoxy-2 ', the structure of 5 '-dimethyl diphenyl is
Embodiment 17: present embodiment adopts the method for palladium/carbon and the synthetic biphenyl compound of crown ether composite catalyzing to synthesize 2-nitro-4-methoxyl group-4 '-trifluoromethyl-biphenyl, specifically completes according to the following steps:
First using the 2-nitro-4-methoxyl group bromobenzene as reaction substrate and 4-trifluoromethyl phenylo boric acid in molar ratio the ratio of 5:6 put in reactor; then add palladium/carbon and 15-hat (ether)-5 as composite catalyst; add salt of wormwood; add again methanol aqueous solution; under nitrogen protection condition; room temperature reaction 24h, then obtain 2-nitro-4-methoxyl group-4 '-trifluoromethyl-biphenyl through extraction → dry → filtration → vacuum concentration → chromatography → wash-out.
Adopt the palladium/carbon of embodiment 16 recovery as the raw material of present embodiment composite catalyst, what not enough employing was new supplements.
In palladium/carbon described in present embodiment, the palladium metal of load accounts for 10% of palladium/carbon total mass.
The amount that adds palladium/carbon species described in present embodiment is 5% of 2-nitro-4-methoxyl group bromobenzene amount of substance.
15-hat (ether)-5 amount of substance that adds described in present embodiment is 2.5 times of 2-nitro-4-methoxyl group bromobenzene amount of substance.
The amount of substance that adds salt of wormwood described in present embodiment is 3.5 times of 2-nitro-4-methoxyl group bromobenzene amount of substance.
Methanol aqueous solution described in present embodiment and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
The synthetic 2-nitro-4-methoxyl group-4 '-trifluoromethyl-biphenyl yield of present embodiment reaches 97.6%.
2-nitro-4-methoxyl group-4 '-the trifluoromethyl-biphenyl synthetic to present embodiment carries out magnetic resonance detection, and its data are:
1HNMR(400MHz,CDCl
3)δ7.66(d,J=8.1Hz,2H),7.45(d,J=2.6Hz,1H),7.40(d,J=8.0Hz,2H),7.32(d,J=8.5Hz,1H),7.19(dd,J=8.6,2.6Hz,1H),3.92(s,3H).
13CNMR(100MHz,CDCl
3)δ159.76,149.43,141.28,132.71,128.55,127.36,125.63,125.59,25.55,125.52,125.47,118.9,109.49,56.02.
HRMS(EI)calcdforC
15H
10F
3NO
3(M-):297.0645.Found:297.0632.
Structure by the synthetic 2-nitro-4-methoxyl group-4 '-trifluoromethyl-biphenyl of the known present embodiment of magnetic resonance detection is
Embodiment 18: the method that present embodiment adopts palladium/carbon and crown ether composite catalyzing to synthesize biphenyl compound synthesized 2-nitro-4-methoxyl group-3 ', 4 '-dimethoxy-biphenyl, specifically completes according to the following steps:
First using the 2-nitro-4-methoxyl group bromobenzene and 3 as reaction substrate; the 4-dimethoxy phenylo boric acid in molar ratio ratio of 5:6 is put in reactor; then add as the palladium/carbon of composite catalyst and two cyclohexanes also-18-is preced with (ether)-6; add salt of wormwood; add again methanol aqueous solution, under nitrogen protection condition, room temperature reaction 24h; then through extraction → dry → filtration → vacuum concentration → chromatography → wash-out obtain 2-nitro-4-methoxyl group-3 ', 4 '-dimethoxy-biphenyl.
Adopt the palladium/carbon of embodiment 17 recovery as the raw material of present embodiment composite catalyst, what not enough employing was new supplements.
In palladium/carbon described in present embodiment, the palladium metal of load accounts for 10% of palladium/carbon total mass.
The amount that adds palladium/carbon species described in present embodiment is 5% of 2-nitro-4-methoxyl group bromobenzene amount of substance.
Described in present embodiment add two cyclohexanes also-18-hat (ether)-6 amount of substance is 2.5 times of 2-nitro-4-methoxyl group bromobenzene amount of substance.
The amount of substance that adds salt of wormwood described in present embodiment is 3.5 times of 2-nitro-4-methoxyl group bromobenzene amount of substance.
Methanol aqueous solution described in present embodiment and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
Synthetic 2-nitro-4-methoxyl group-3 of present embodiment ', 4 '-dimethoxy-biphenyl yield reaches 97.0%.
2-nitro-4-methoxyl group-3 synthetic to present embodiment ', 4 '-dimethoxy-biphenyl carries out magnetic resonance detection, and its data are:
1HNMR(400MHz,CDCl
3)δ7.35(d,J=8.6Hz,1H),7.31(d,J=2.6Hz,1H),7.13(dd,J=8.6,2.7Hz,1H),6.90(d,J=8.2Hz,1H),6.84(dd,J=8.2,2.0Hz,1H),6.79(d,J=2.0Hz,1H),3.91(s,3H),3.89(s,3H),3.87(s,3H).
13CNMR(100MHz,CDCl
3)δ158.92,149.85,149.00,148.95,132.72,129.72,128.25,120.47,118.51,111.38,111.31,108.83,55.92,55.95,29.71.HRMS(EI)calcdforC
15H
15NO
5(M-):289.1069.Found:289.1054.
By synthetic 2-nitro-4-methoxyl group-3 of the known present embodiment of magnetic resonance detection ', the structure of 4 '-dimethoxy-biphenyl is
Embodiment 19: the method that present embodiment adopts palladium/carbon and crown ether composite catalyzing to synthesize biphenyl compound synthesized 2-benzyloxy-4-methoxyl group-3 ', 4 '-dimethoxy-biphenyl, specifically completes according to the following steps:
First using the 2-benzyloxy-4-methoxyl group bromobenzene and 3 as reaction substrate; the 4-dimethoxy phenylo boric acid in molar ratio ratio of 5:6 is put in reactor; then add as the palladium/carbon of composite catalyst and two cyclohexanes also-18-is preced with (ether)-6; add salt of wormwood; add again methanol aqueous solution; under nitrogen protection condition; room temperature reaction 24h; then through extraction → dry → filtration → vacuum concentration → chromatography → wash-out obtain 2-benzyloxy-4-methoxyl group-3 ', 4 '-dimethoxy-biphenyl.
Adopt the palladium/carbon of embodiment 18 recovery as the raw material of present embodiment composite catalyst, what not enough employing was new supplements.
In palladium/carbon described in present embodiment, the palladium metal of load accounts for 10% of palladium/carbon total mass.
The amount that adds palladium/carbon species described in present embodiment is 5% of 2-benzyloxy-4-methoxyl group bromobenzene amount of substance.
Described in present embodiment add two cyclohexanes also-18-hat (ether)-6 amount of substance is 2.5 times of 2-benzyloxy-4-methoxyl group bromobenzene amount of substance.
The amount of substance that adds salt of wormwood described in present embodiment is 3.5 times of 2-benzyloxy-4-methoxyl group bromobenzene amount of substance.
Methanol aqueous solution described in present embodiment and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
Synthetic 2-benzyloxy-4-methoxyl group-3 of present embodiment ', 4 '-dimethoxy-biphenyl yield reaches 95.8%.
2-benzyloxy-4-methoxyl group-3 synthetic to present embodiment ', 4 '-dimethoxy-biphenyl carries out magnetic resonance detection, and its data are:
1HNMR(400MHz,CDCl
3)δ7.32(dt,J=12.3,8.2Hz,6H),7.16(d,J=1.7Hz,1H),7.06(dd,J=8.3,1.8Hz,1H),6.89(d,J=8.3Hz,1H),6.63(d,J=2.2Hz,1H),6.58(dd,J=8.4,2.3Hz,1H),5.04(s,2H),3.90(s,3H),3.82(s,3H),3.75(s,3H).
13CNMR(100MHz,CDCl
3)δ159.96,156.47,148.16,147.77,136.96,131.14,128.47,127.80,127.24,123.75,121.48,113.16,110.88,105.38,100.78,70.54,55.88,55.68,55.44,29.71.
HRMS(EI)calcdforC
22H
22O
4(M-):350.1582.Found:350.1571.
By synthetic 2-benzyloxy-4-methoxyl group-3 of the known present embodiment of magnetic resonance detection ', the structure of 4 '-dimethoxy-biphenyl is
Embodiment 20: the method that present embodiment adopts palladium/carbon and crown ether composite catalyzing to synthesize biphenyl compound synthesized 3,4-methylene-dioxy-3 ', 4 '-dimethoxy-biphenyl, specifically completes according to the following steps:
First using as 3 of reaction substrate; 4-methylene-dioxy bromobenzene and 3; the 4-dimethoxy phenylo boric acid in molar ratio ratio of 5:6 is put in reactor, then adds palladium/carbon and 18-hat (ether)-6 as composite catalyst, adds salt of wormwood; add again methanol aqueous solution; under nitrogen protection condition, room temperature reaction 24h, then obtain 3 through extraction → dry → filtration → vacuum concentration → chromatography → wash-out; 4-methylene-dioxy-3 ', 4 '-dimethoxy-biphenyl.
Adopt the palladium/carbon of embodiment 19 recovery as the raw material of present embodiment composite catalyst, what not enough employing was new supplements.
In palladium/carbon described in present embodiment, the palladium metal of load accounts for 10% of palladium/carbon total mass.
The amount that adds palladium/carbon species described in present embodiment is 5% of 3,4-methylene-dioxy bromobenzene amount of substance.
18-hat (ether)-6 amount of substance that adds described in present embodiment is 2.5 times of 3,4-methylene-dioxy bromobenzene amount of substance.
The amount of substance that adds salt of wormwood described in present embodiment is 3.5 times of 3,4-methylene-dioxy bromobenzene amount of substance.
Methanol aqueous solution described in present embodiment and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
Present embodiment synthetic 3,4-methylene-dioxy-3 ', 4 '-dimethoxy-biphenyl yield reaches 95.0%.
To present embodiment synthetic 3,4-methylene-dioxy-3 ', 4 '-dimethoxy-biphenyl carries out magnetic resonance detection, its data are:
1HNMR(400MHz,CDCl
3)δ7.08–6.99(m,4H),6.92(d,J=8.2Hz,1H),6.86(d,J=7.9Hz,1H),5.99(s,2H),3.94(s,3H),3.91(s,3H).
13CNMR(100MHz,CDCl
3)δ149.13,148.40,148.07,146.73,135.54,134.08,120.23,119.11,111.52,110.37,108.52,107.50,101.11,55.95,56.01.
HRMS(EI)calcdforC
15H
14O
4(M-):258.0943.Found:258.0923.
By the known present embodiment of magnetic resonance detection synthetic 3,4-methylene-dioxy-3 ', the structure of 4 '-dimethoxy-biphenyl is
Embodiment 21: the method that present embodiment adopts palladium/carbon and crown ether composite catalyzing to synthesize biphenyl compound synthesized 3,4-methylene-dioxy-2 ', 5 '-dimethyl diphenyl, specifically completes according to the following steps:
First using as 3 of reaction substrate; 4-methylene-dioxy bromobenzene and 2; the 5-dimethylphenyl boronic acid in molar ratio ratio of 5:6 is put in reactor, then adds palladium/carbon and 18-hat (ether)-6 as composite catalyst, adds salt of wormwood; add again methanol aqueous solution; under nitrogen protection condition, room temperature reaction 24h, then obtain 3 through extraction → dry → filtration → vacuum concentration → chromatography → wash-out; 4-methylene-dioxy-2 ', 5 '-dimethyl diphenyl.
Adopt the palladium/carbon of embodiment 20 recovery as the raw material of present embodiment composite catalyst, what not enough employing was new supplements.
In palladium/carbon described in present embodiment, the palladium metal of load accounts for 10% of palladium/carbon total mass.
The amount that adds palladium/carbon species described in present embodiment is 5% of 3,4-methylene-dioxy bromobenzene amount of substance.
18-hat (ether)-6 amount of substance that adds described in present embodiment is 2.5 times of 3,4-methylene-dioxy bromobenzene amount of substance.
The amount of substance that adds salt of wormwood described in present embodiment is 3.5 times of 3,4-methylene-dioxy bromobenzene amount of substance.
Methanol aqueous solution described in present embodiment and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
Present embodiment synthetic 3,4-methylene-dioxy-2 ', 5 '-dimethyl diphenyl yield reaches 98.0%.
To present embodiment synthetic 3,4-methylene-dioxy-2 ', 5 '-dimethyl diphenyl carries out magnetic resonance detection, its data are:
1HNMR(400MHz,CDCl
3)δ=7.13(d,J=7.6,1H),7.09–6.99(m,2H),6.85(d,J=7.9,1H),6.80(d,J=1.4,1H),6.75(dd,J=7.9,1.6,1H),5.99(s,2H),2.33(s,3H),2.22(s,3H).
13CNMR(100MHz,CDCl
3)δ147.26,146.36,141.39,136.07,135.16,132.29,130.57,130.24,127.84,122.46,109.81,107.99,100.97,20.89,19.97.
HRMS(EI)calcdforC
15H
14O
2(M-):226.1084.Found:226.1068.
By the known present embodiment of magnetic resonance detection synthetic 3,4-methylene-dioxy-2 ', the structure of 5 '-dimethyl diphenyl is
Embodiment 22: present embodiment adopts the method for palladium/carbon and the synthetic biphenyl compound of crown ether composite catalyzing to synthesize 3,4-methylene-dioxy-4 '-trifluoromethyl-biphenyl, specifically completes according to the following steps:
First using as 3 of reaction substrate; 4-methylene-dioxy bromobenzene and 4-trifluoromethyl the phenylo boric acid in molar ratio ratio of 5:6 are put in reactor; then add palladium/carbon and 15-hat (ether)-5 as composite catalyst; add salt of wormwood; add again methanol aqueous solution, under nitrogen protection condition, room temperature reaction 24h; then through extraction → dry → filtration → vacuum concentration → chromatography → wash-out to 3,4-methylene-dioxy-4 '-trifluoromethyl-biphenyl.
Adopt the palladium/carbon of embodiment 21 recovery as the raw material of present embodiment composite catalyst, what not enough employing was new supplements.
In palladium/carbon described in present embodiment, the palladium metal of load accounts for 10% of palladium/carbon total mass.
The amount that adds palladium/carbon species described in present embodiment is 5% of 3,4-methylene-dioxy bromobenzene amount of substance.
15-hat (ether)-5 amount of substance that adds described in present embodiment is 2.5 times of 3,4-methylene-dioxy bromobenzene amount of substance.
The amount of substance that adds salt of wormwood described in present embodiment is 3.5 times of 3,4-methylene-dioxy bromobenzene amount of substance.
Methanol aqueous solution described in present embodiment and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
Present embodiment synthetic 3,4-methylene-dioxy-4 '-trifluoromethyl-biphenyl yield reaches 98.4%.
To present embodiment synthetic 3,4-methylene-dioxy-4 '-trifluoromethyl-biphenyl carries out magnetic resonance detection, its data are:
1HNMR(400MHz,CDCl
3)δ7.63(dd,J=20.0,8.4Hz,4H),7.07(dt,J=4.4,2.2Hz,2H),6.94–6.86(m,1H),6.02(s,2H).
By the known present embodiment of magnetic resonance detection synthetic 3, the structure of 4-methylene-dioxy-4 '-trifluoromethyl-biphenyl is
Because from embodiment 14, the raw material of the composite catalyst using all adopts an embodiment to reclaim, palladium/carbon recovery method wherein: used solid palladium/carbon is washed respectively after three times with ethyl acetate and distilled water, place 24h, naturally dry and obtain palladium/carbon; Due to removal process loss, make the quantity not sufficient of palladium/carbon, therefore need to add palladium/carbon that a part is new, 1/100 of the quantity not sufficient total mass still newly adding.Yield by product is known, and the catalytic efficiency of composite catalyst is not decreased significantly.
Claims (10)
1. adopt the method for the synthetic biphenyl compound of palladium/carbon and crown ether composite catalyzing, it is characterized in that adopting the method for palladium/carbon and synthetic 3, the 4-dimethoxy-4 ' '-trifluoromethyl-biphenyl of crown ether composite catalyzing to complete according to the following steps:
First using as 3 of reaction substrate, 4-dimethoxy bromobenzene and 4-trifluoromethyl the phenylo boric acid in molar ratio ratio of 5:6 are put in reactor, then add palladium/carbon and hexaoxacyclooctadecane-6-6 as composite catalyst, add salt of wormwood, add again methanol aqueous solution, under nitrogen protection condition, room temperature reaction 24h, then through extraction → dry → filtration → vacuum concentration → chromatography → wash-out, obtain 3,4-dimethoxy-4 ' '-trifluoromethyl-biphenyl;
In described palladium/carbon, the palladium metal of load accounts for 10% of palladium/carbon total mass;
The described amount that adds palladium/carbon species is 5% of 3,4-dimethoxy bromobenzene amount of substance;
Described hexaoxacyclooctadecane-6-6 amount of substance that adds is 2.5 times of 3,4-dimethoxy bromobenzene amount of substance;
The described amount of substance that adds salt of wormwood is 3.5 times of 3,4-dimethoxy bromobenzene amount of substance;
Described methanol aqueous solution and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
2. adopt the method for the synthetic biphenyl compound of palladium/carbon and crown ether composite catalyzing, it is characterized in that adopting the method for palladium/carbon and the synthetic 4-formyl biphenyl of crown ether composite catalyzing to complete according to the following steps:
First using the bromobenzaldehyde as reaction substrate and phenylo boric acid in molar ratio the ratio of 5:6 put in reactor, then add palladium/carbon and hexaoxacyclooctadecane-6-6 as composite catalyst, add salt of wormwood, add again methanol aqueous solution, under nitrogen protection condition, room temperature reaction 24h, then obtain 4-formyl biphenyl through extraction → dry → filtration → vacuum concentration → chromatography → wash-out;
In described palladium/carbon, the palladium metal of load accounts for 10% of palladium/carbon total mass;
The described amount that adds palladium/carbon species is 5% of bromobenzaldehyde amount of substance;
Described hexaoxacyclooctadecane-6-6 amount of substance that adds is 2.5 times of bromobenzaldehyde amount of substance;
The described amount of substance that adds salt of wormwood is 3.5 times of bromobenzaldehyde amount of substance;
Described methanol aqueous solution and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
3. adopt the method for the synthetic biphenyl compound of palladium/carbon and crown ether composite catalyzing, it is characterized in that adopting the method for palladium/carbon and the synthetic 4-methoxyl group-4 '-trifluoromethyl-biphenyl of crown ether composite catalyzing to complete according to the following steps:
First using the bromoanisole as reaction substrate and 4-trifluoromethyl phenylo boric acid in molar ratio the ratio of 5:6 put in reactor, then add palladium/carbon and hexaoxacyclooctadecane-6-6 as composite catalyst, add salt of wormwood, add again methanol aqueous solution, under nitrogen protection condition, room temperature reaction 24h, then obtain 4-methoxyl group-4 '-trifluoromethyl-biphenyl through extraction → dry → filtration → vacuum concentration → chromatography → wash-out;
In described palladium/carbon, the palladium metal of load accounts for 10% of palladium/carbon total mass;
The described amount that adds palladium/carbon species is 5% of bromoanisole amount of substance;
Described hexaoxacyclooctadecane-6-6 amount of substance that adds is 2.5 times of bromoanisole amount of substance;
The described amount of substance that adds salt of wormwood is 3.5 times of bromoanisole amount of substance;
Described methanol aqueous solution and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
4. adopt the method for palladium/carbon and the synthetic biphenyl compound of crown ether composite catalyzing, it is characterized in that adopting palladium/carbon and crown ether composite catalyzing synthesize 3,4-dimethoxy-2 ', the method for 5 '-dimethyl diphenyl completes according to the following steps:
First using as 3 of reaction substrate, 4-dimethoxy bromobenzene and 2, the 5-dimethylphenyl boronic acid in molar ratio ratio of 5:6 is put in reactor, then adds palladium/carbon and 15-crown ether-5 as composite catalyst, adds salt of wormwood, add again methanol aqueous solution, under nitrogen protection condition, room temperature reaction 24h, then obtain 3 through extraction → dry → filtration → vacuum concentration → chromatography → wash-out, 4-dimethoxy-2 ', 5 '-dimethyl diphenyl;
In described palladium/carbon, the palladium metal of load accounts for 10% of palladium/carbon total mass;
The described amount that adds palladium/carbon species is 5% of 3,4-dimethoxy bromobenzene amount of substance;
Described 15-crown ether-5 amount of substance that adds is 2.5 times of 3,4-dimethoxy bromobenzene amount of substance;
The described amount of substance that adds salt of wormwood is 3.5 times of 3,4-dimethoxy bromobenzene amount of substance;
Described methanol aqueous solution and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
5. adopt the method for the synthetic biphenyl compound of palladium/carbon and crown ether composite catalyzing, it is characterized in that adopting the method for palladium/carbon and the synthetic 2-nitro-4-methoxyl group-4 '-trifluoromethyl-biphenyl of crown ether composite catalyzing to complete according to the following steps:
First using the 2-nitro-4-methoxyl group bromobenzene as reaction substrate and 4-trifluoromethyl phenylo boric acid in molar ratio the ratio of 5:6 put in reactor, then add palladium/carbon and 15-crown ether-5 as composite catalyst, add salt of wormwood, add again methanol aqueous solution, under nitrogen protection condition, room temperature reaction 24h, then obtain 2-nitro-4-methoxyl group-4 '-trifluoromethyl-biphenyl through extraction → dry → filtration → vacuum concentration → chromatography → wash-out;
In described palladium/carbon, the palladium metal of load accounts for 10% of palladium/carbon total mass;
The described amount that adds palladium/carbon species is 5% of 2-nitro-4-methoxyl group bromobenzene amount of substance;
Described 15-crown ether-5 amount of substance that adds is 2.5 times of 2-nitro-4-methoxyl group bromobenzene amount of substance;
The described amount of substance that adds salt of wormwood is 3.5 times of 2-nitro-4-methoxyl group bromobenzene amount of substance;
Described methanol aqueous solution and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
6. adopt the method for palladium/carbon and the synthetic biphenyl compound of crown ether composite catalyzing, it is characterized in that adopting palladium/carbon and crown ether composite catalyzing synthesize 2-nitro-4-methoxyl group-3 ', the method for 4 '-dimethoxy-biphenyl completes according to the following steps:
First using the 2-nitro-4-methoxyl group bromobenzene and 3 as reaction substrate, the 4-dimethoxy phenylo boric acid in molar ratio ratio of 5:6 is put in reactor, then add as the palladium/carbon of composite catalyst and two cyclohexanes also-hexaoxacyclooctadecane-6-6, add salt of wormwood, add again methanol aqueous solution, under nitrogen protection condition, room temperature reaction 24h, then through extraction → dry → filtration → vacuum concentration → chromatography → wash-out obtain 2-nitro-4-methoxyl group-3 ', 4 '-dimethoxy-biphenyl;
In described palladium/carbon, the palladium metal of load accounts for 10% of palladium/carbon total mass;
The described amount that adds palladium/carbon species is 5% of 2-nitro-4-methoxyl group bromobenzene amount of substance;
Described add two cyclohexanes also-hexaoxacyclooctadecane-6-6 amount of substance is 2.5 times of 2-nitro-4-methoxyl group bromobenzene amount of substance;
The described amount of substance that adds salt of wormwood is 3.5 times of 2-nitro-4-methoxyl group bromobenzene amount of substance;
Described methanol aqueous solution and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
7. adopt the method for palladium/carbon and the synthetic biphenyl compound of crown ether composite catalyzing, it is characterized in that adopting palladium/carbon and crown ether composite catalyzing synthesize 2-benzyloxy-4-methoxyl group-3 ', the method for 4 '-dimethoxy-biphenyl completes according to the following steps:
First using the 2-benzyloxy-4-methoxyl group bromobenzene and 3 as reaction substrate, the 4-dimethoxy phenylo boric acid in molar ratio ratio of 5:6 is put in reactor, then add as the palladium/carbon of composite catalyst and two cyclohexanes also-hexaoxacyclooctadecane-6-6, add salt of wormwood, add again methanol aqueous solution, under nitrogen protection condition, room temperature reaction 24h, then through extraction → dry → filtration → vacuum concentration → chromatography → wash-out obtain 2-benzyloxy-4-methoxyl group-3 ', 4 '-dimethoxy-biphenyl;
In described palladium/carbon, the palladium metal of load accounts for 10% of palladium/carbon total mass;
The described amount that adds palladium/carbon species is 5% of 2-benzyloxy-4-methoxyl group bromobenzene amount of substance;
Described add two cyclohexanes also-hexaoxacyclooctadecane-6-6 amount of substance is 2.5 times of 2-benzyloxy-4-methoxyl group bromobenzene amount of substance;
The described amount of substance that adds salt of wormwood is 3.5 times of 2-benzyloxy-4-methoxyl group bromobenzene amount of substance;
Described methanol aqueous solution and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
8. adopt the method for palladium/carbon and the synthetic biphenyl compound of crown ether composite catalyzing, it is characterized in that adopting palladium/carbon and crown ether composite catalyzing synthesize 3,4-methylene-dioxy-3 ', the method for 4 '-dimethoxy-biphenyl completes according to the following steps:
First using as 3 of reaction substrate, 4-methylene-dioxy bromobenzene and 3, the 4-dimethoxy phenylo boric acid in molar ratio ratio of 5:6 is put in reactor, then adds palladium/carbon and hexaoxacyclooctadecane-6-6 as composite catalyst, adds salt of wormwood, add again methanol aqueous solution, under nitrogen protection condition, room temperature reaction 24h, then obtain 3 through extraction → dry → filtration → vacuum concentration → chromatography → wash-out, 4-methylene-dioxy-3 ', 4 '-dimethoxy-biphenyl;
In described palladium/carbon, the palladium metal of load accounts for 10% of palladium/carbon total mass;
The described amount that adds palladium/carbon species is 5% of 3,4-methylene-dioxy bromobenzene amount of substance;
Described hexaoxacyclooctadecane-6-6 amount of substance that adds is 2.5 times of 3,4-methylene-dioxy bromobenzene amount of substance;
The described amount of substance that adds salt of wormwood is 3.5 times of 3,4-methylene-dioxy bromobenzene amount of substance;
Described methanol aqueous solution and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
9. adopt the method for the synthetic biphenyl compound of palladium/carbon and crown ether composite catalyzing, it is characterized in that adopting palladium/carbon and crown ether composite catalyzing synthetic, 4-methylene-dioxy-2 ', the method for 5 '-dimethyl diphenyl completes according to the following steps:
First using as 3 of reaction substrate, 4-methylene-dioxy bromobenzene and 2, the 5-dimethylphenyl boronic acid in molar ratio ratio of 5:6 is put in reactor, then adds palladium/carbon and hexaoxacyclooctadecane-6-6 as composite catalyst, adds salt of wormwood, add again methanol aqueous solution, under nitrogen protection condition, room temperature reaction 24h, then obtain 3 through extraction → dry → filtration → vacuum concentration → chromatography → wash-out, 4-methylene-dioxy-2 ', 5 '-dimethyl diphenyl;
In described palladium/carbon, the palladium metal of load accounts for 10% of palladium/carbon total mass;
The described amount that adds palladium/carbon species is 5% of 3,4-methylene-dioxy bromobenzene amount of substance;
Described hexaoxacyclooctadecane-6-6 amount of substance that adds is 2.5 times of 3,4-methylene-dioxy bromobenzene amount of substance;
The described amount of substance that adds salt of wormwood is 3.5 times of 3,4-methylene-dioxy bromobenzene amount of substance;
Described methanol aqueous solution and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
10. adopt the method for the synthetic biphenyl compound of palladium/carbon and crown ether composite catalyzing, it is characterized in that adopting palladium/carbon and crown ether composite catalyzing synthetic, the method for 3,4-methylene-dioxy-4 '-trifluoromethyl-biphenyl completes according to the following steps:
First using as 3 of reaction substrate, 4-methylene-dioxy bromobenzene and 4-trifluoromethyl the phenylo boric acid in molar ratio ratio of 5:6 are put in reactor, then add palladium/carbon and 15-crown ether-5 as composite catalyst, add salt of wormwood, add again methanol aqueous solution, under nitrogen protection condition, room temperature reaction 24h, then through extraction → dry → filtration → vacuum concentration → chromatography → wash-out to 3,4-methylene-dioxy-4 '-trifluoromethyl-biphenyl;
In described palladium/carbon, the palladium metal of load accounts for 10% of palladium/carbon total mass;
The described amount that adds palladium/carbon species is 5% of 3,4-methylene-dioxy bromobenzene amount of substance;
Described 15-crown ether-5 amount of substance that adds is 2.5 times of 3,4-methylene-dioxy bromobenzene amount of substance;
The described amount of substance that adds salt of wormwood is 3.5 times of 3,4-methylene-dioxy bromobenzene amount of substance;
Described methanol aqueous solution and the mass ratio of halogenated aryl hydrocarbon are 25:1, and methanol aqueous solution by anhydrous methanol and distilled water by volume 1:1 mix.
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