CN103880573A - Preparation method for biphenyl-type compound - Google Patents
Preparation method for biphenyl-type compound Download PDFInfo
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- CN103880573A CN103880573A CN201210560036.6A CN201210560036A CN103880573A CN 103880573 A CN103880573 A CN 103880573A CN 201210560036 A CN201210560036 A CN 201210560036A CN 103880573 A CN103880573 A CN 103880573A
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Abstract
The invention discloses a preparation method for a biphenyl-type compound. Aromatic boric acid is employed as a reaction substrate and palladium is employed as a catalyst. A catalytic amount of alkali is added. The mixture reacts in an amide-type solvent for three to eight hours at room temperature. The aromatic boric acid is subjected to a coupling reaction. The reacted mixture is processed and then the object product, namely, the biphenyl-type compound is obtained. The preparation method of the present invention is mild in reaction condition, small in catalyst using amount, high in atom economy, simple in operation and wide in suitable scope of the substrate. The preparation method has industrial practicality.
Description
Technical field
The present invention relates to the method that the coupling of a kind of catalysis fragrance boric acid self becomes biphenyl, be specifically related to a kind of method that palladium catalysis fragrance boric acid is prepared separate benzene nuclei compound.
Background technology
Biphenyl is important organic raw material, is widely used in the fields such as medicine, agricultural chemicals, dyestuff, liquid crystal material.Can be used for synthesizing softening agent, sanitas, can also be for the manufacture of fuel, engineering plastics and high energy fuels etc.
The synthetic method of biphenyl compound is mainly cross-coupling reaction.Ullmann reaction that the most representative is, issues raw reductive coupling reaction generation biphenyl compound by the situation that halogenated aryl hydrocarbon is made reductive agent at copper.These class methods need higher temperature, the reaction times, and also yield long, product is low, cost is high.
The Suzki-Miyaura linked reaction of the palladium catalysis extensively using in organic synthesis, reacts and obtains biphenyl compound with fragrant boric acid or fragrant boric acid ester with aromatic halides.The larger reaction of the common palladium catalyst amount ratio of these class methods generally need to be added some complicated parts, has increased cost, is not easy again to carry out aftertreatment.
Another method is under palladium complex catalyst, to carry out linked reaction with aryl halide and aryl grignard reagent, obtains target product.These class methods need to be prepared aryl grignard reagent, and Grignard reagent is unstable in air, also need the synthetic part that can improve reactive behavior, complicated operation, and cost is high.
The preparation of aryl boric acid compound is simple, its stable in the air depositing, and therefore, with respect to Ullmann, Suzki-Miyaura reaction, directly with fragrant boronic acid compounds self, linked reaction generation biphenyl compound occurring is also a good method.Simple to operate like this, reduce cost, environmental pollution is little, has more industrial application value.At present, the synthetic biphenyl compound of the fragrant boronic acid compounds of the use of bibliographical information self coupling is fewer:
Mao J.C etc., at Catalysis Communications2008, disclose the method for the synthetic biphenyl compound of a kind of fragrant boric acid self coupling on 9,97-100, the method is the Pd (OAc) with 3mol%
2as catalyzer, add the K of 2.5 equivalents
2cO
3as additive, acetone/water (v:v=1:1,4mL), as solvent, is reacted 24h under air at room temperature.The yield of product is at 25-91%.Although the method is reacted at ambient temperature, the consumption of catalyzer is large, and long reaction time also needs to add a large amount of K
2cO
3.
Yamamoto Y. etc. are at Eur.J.Org.Chem.2009,1864-1867 discloses self linked reaction of the fragrant boronic acid compounds of the CuOAc-Phen catalysis of 2-4mol%, does not add other additives, and 2-propyl alcohol is as solvent, under 28 ° of C air, react 2-24h, the yield of product is at 19-92%.Although the method does not add under other additive conditions and can carry out smoothly in room temperature, need to add part could realize the catalytic activity of Cu, and the yield of product is not high.
Mao J.C etc., at Eur.J.Org.Chem.2009, disclose the method for the synthetic biphenyl compound of a kind of fragrant boric acid self coupling on 2262-2266.The reaction conditions of the method is: the I of 1 equivalent
2, add the K of 5 equivalents
2cO
3as additive, PEG-400 is as solvent, and under air, 140 ° of C, react 48h, and the yield of product is 10-97%.Although the method non-metal catalyst, severe reaction conditions, is not suitable for large-scale production.
Summary of the invention
The present invention improves the method for the synthetic separate benzene nuclei compound of fragrant boric acid self coupling under a kind of mild conditions.
The technical solution used in the present invention is: in air atmosphere, palladium catalyst, substrate fragrance boronic acid compounds, taking the one in sodium-acetate, Potassium ethanoate, Lithium Acetate, sodium carbonate, salt of wormwood or cesium carbonate as alkaline additive, with N, N-N,N-DIMETHYLACETAMIDE (DMA), N, dinethylformamide (DMF), N, one in N-diethylformamide (DEF), N-Methyl pyrrolidone (NMP) is solvent, under room temperature, reaction 3-8h, reaction product aftertreatment obtains described separate benzene nuclei compound.
In technique scheme, described palladium catalyst is preferably PdCl
2.
In technique scheme, described alkaline additive is preferably sodium-acetate.
In technique scheme, described solvent is preferably N,N-dimethylacetamide (DMA).
In technique scheme, catalyst P dCl
2consumption and substrate fragrance boronic acid compounds mol ratio 0.5:100 ~ 2:100.
In technique scheme, the consumption of sodium-acetate and substrate fragrance boronic acid compounds mol ratio are 10:100.
In technique scheme, described fragrant boronic acid compounds, the substituting group on phenyl ring has hydrogen, methyl, methoxyl group, chlorine, fluorine, nitro, ethanoyl, and substituent position is in ortho position, contraposition, a position of boronate.
Because such scheme uses, the present invention has following advantages compared with prior art:
1. catalyst system reaction conditions gentleness of the present invention, does not need heating and heating installation, simple to operate: reaction, in room temperature, is carried out under air conditions; Reacted rear and reaction solution simply extracted with ether and water, collected ether layer, with anhydrous magnesium sulfate drying, filtered, steamed ether, last directly with sherwood oil as eluent, cross quick silicagel column separation and obtain target product.
2. catalyst system catalyst P dCl of the present invention
2consumption can be low to moderate 5/1000ths of amount of substrate, thereby reduced reaction cost, there is potential proper value.
3. the consumption of catalyst system additive basic of the present invention is few, only has 10 of amount of substrate, and the inorganic wastes finally producing is few, so environmentally friendly.
Embodiment
Below in conjunction with embodiment in detail the present invention is described in detail, but the scope of the invention is not limited to following embodiment.
Synthesizing of embodiment 1 biphenyl
By 4.425mgPdCl
2(0.5mol%), 41mgNaOAc (10mol%), 10mLDMA joins in the round-bottomed flask of 50mL successively, stir after 2min, add 609.6mg (5mmol) phenylo boric acid, then this system is reacted 3h under air at room temperature condition, 3 × 5mL ether/water for reaction solution (2:1) extraction, collect ether layer, with anhydrous magnesium sulfate drying, filter, boil off ether, column chromatography obtains product biphenyl 354.6mg, white solid, yield 92%.Fusing point 69-71 ° C.
1H?NMR(400MHz，CDCl
3)δppm：7.61(m,4H)，7.45(m,4H)，7.36(m,2H);
13CNMR(100MHz,CDCl
3)δppm：141.9,128.9,127.6,127.2.
Embodiment 24,4-dimethyl diphenyl synthetic
By 4.425mgPdCl
2(0.5mol%), 41mgNaOAc (10mol%), 10mLDMA joins in the round-bottomed flask of 50mL successively, stir after 2min, add 679.8mg (5mmol) 4-methylphenylboronic acid, then this system is reacted 3h under air at room temperature condition, 3 × 5mL ether/water for reaction solution (2:1) extraction, collects ether layer, with anhydrous magnesium sulfate drying, filter, boil off ether, column chromatography obtains product 4,4-dimethyl diphenyl 409.7mg, white solid, yield 90%.Fusing point 122-124 ° C.
1H?NMR(400MHz，CDCl
3)δppm：7.47(d,4H)，7.23(d,4H)，2.39(s,6H);
13CNMR(100MHz,CDCl
3)δppm：139.5,137.5,130.1,127.2,22.3.
Embodiment 33,3-dimethyl diphenyl synthetic
By 4.425mgPdCl
2(0.5mol%), 41mgNaOAc (10mol%), 10mLDMA joins in the round-bottomed flask of 50mL successively, stir after 2min, add 679.8mg (5mmol) 3-methylphenylboronic acid, then this system is reacted 3h under air at room temperature condition, 3 × 5mL ether/water for reaction solution (2:1) extraction, collects ether layer, with anhydrous magnesium sulfate drying, filter, boil off ether, column chromatography obtains product 3,3-dimethyl diphenyl 409.7mg, colourless liquid, yield 90%.
1H?NMR(400MHz，CDCl
3)δppm：7.41(s,2H)，7.40(d,2H)，7.32(t,2H)，7.17(d,2H)，2.43(s,6H);
13CNMR(100MHz,CDCl
3)δppm：141.6,138.2,128.6,128.2,128.1,124.2,21.5.
Embodiment 44,4-dimethoxy-biphenyl synthetic
By 4.425mgPdCl
2(0.5mol%), 41mgNaOAc (10mol%), 10mLDMA joins in the round-bottomed flask of 50mL successively, stir after 2min, add 760.3mg (5mmol) 4-methoxyphenylboronic acid, then this system is reacted 4h under air at room temperature condition, 3 × 5mL ether/water for reaction solution (2:1) extraction, collects ether layer, with anhydrous magnesium sulfate drying, filter, boil off ether, column chromatography obtains product 4,4-dimethoxy-biphenyl 454.9mg, white solid, yield 85%.Fusing point 173-175 ° C.
1H?NMR(400MHz，CDCl
3)δppm：7.47(d,4H)，6.96(d,4H)，3.85(s,6H);
13CNMR(100MHz,CDCl
3)δppm：158.9,133.8,127.6,114.6,55.4.
Embodiment 54,4-DCBP synthetic
By 8.85mgPdCl
2(1mol%), 41mgNaOAc (10mol%), 10mLDMA joins in the round-bottomed flask of 50mL successively, stir after 2min, add 780.0mg (5mmol) 4-chlorobenzene boric acid, then this system is reacted 6h under air at room temperature condition, 3 × 5mL ether/water for reaction solution (2:1) extraction, collects ether layer, with anhydrous magnesium sulfate drying, filter, boil off ether, column chromatography obtains product 4,4-DCBP 416.2mg, white solid, yield 75%.Fusing point 150-155 ° C.
1H?NMR(400MHz，CDCl
3)δppm：7.48(d,4H)，7.41(d,4H);
13CNMR(100MHz,CDCl
3)δppm：138.9,133.8,129.6,128.3.
Embodiment 63,3-dinitrobenzene biphenyl synthetic
By 17.7mgPdCl
2(2mol%), 41mgNaOAc (10mol%), 10mLDMA joins in the round-bottomed flask of 50mL successively, stir after 2min, add 835.0mg (5mmol) 4-chlorobenzene boric acid, then this system is reacted 6h under air at room temperature condition, 3 × 5mL ether/water for reaction solution (2:1) extraction, collects ether layer, with anhydrous magnesium sulfate drying, filter, boil off ether, column chromatography obtains product 3,3-dinitrobenzene biphenyl 396.5mg, yellow solid, yield 65%.Fusing point 201-203 ° C.
1H?NMR(400MHz，CDCl
3)δppm：8.50(t,2H)，8.32(dq,2H),7.98(dq,2H),7.77(t,2H);
13CNMR(100MHz,CDCl
3)δppm:148.9,140.8,133.6,130.3,123.3,122.5.
Embodiment 74,4-diformyl biphenyl synthetic
By 8.85mgPdCl
2(1mol%); 41mgNaOAc (10mol%); 10mL DMA joins in the round-bottomed flask of 50mL successively; stir after 2min; add 750.0mg (5mmol) 4-formylphenylboronic acid; then this system is reacted 8h under air at room temperature condition; 3 × 5mL ether/water for reaction solution (2:1) extraction, collects ether layer, with anhydrous magnesium sulfate drying; filter; boil off ether, column chromatography obtains product 4,4-diformyl biphenyl 315.0mg; white solid, yield 60%.Fusing point 148-150 ° C.
1H?NMR(400MHz，CDCl
3)δppm：10.2(s,2H)，8.01(d,4H),7.82(d,4H);
13C?NMR(100MHz,CDCl
3)δppm:191.6,145.8,133.6,130.3,123.3.
Embodiment 84,4-diacetyl biphenyl synthetic
By 8.85mg PdCl
2(1mol%); 41mg NaOAc (10mol%); 10mL DMA joins in the round-bottomed flask of 50mL successively; stir after 2min; add 820.0mg (5mmol) 4-acetylbenzene boric acid; then this system is reacted 8h under air at room temperature condition; 3 × 5mL ether/water for reaction solution (2:1) extraction, collects ether layer, with anhydrous magnesium sulfate drying; filter; boil off ether, column chromatography obtains product 4,4-diacetyl biphenyl 446.4mg; white solid, yield 75%.Fusing point 194-196 ° C.
1H?NMR(400MHz，CDCl
3)δppm：8.08(d,4H)，7.76(d,4H),2.68(s,6H);
13C?NMR(100MHz,CDCl
3)δppm:197.6,144.8,136.6,128.3,127.3,26.8.
Embodiment 92,2-naphthyl naphthalene synthetic
By 17.7mg PdCl
2(2mol%), 41mgNaOAc (10mol%), 10mL DMA joins in the round-bottomed flask of 50mL successively, stir after 2min, add 860.0mg (5mmol) 2-naphthalene boronic acids, then this system is reacted 8h under air at room temperature condition, 3 × 5mL ether/water for reaction solution (2:1) extraction, collects ether layer, with anhydrous magnesium sulfate drying, filter, boil off ether, column chromatography obtains product 2,2-naphthyl naphthalene 222.2mg, white solid, yield 35%.Fusing point 180-182 ° C.
1H?NMR(400MHz，CDCl
3)δppm：8.18(s,2H)，7.96(t,4H),7.88-7.94(m,4H),7.48-7.57(m,4H);
13CNMR(100MHz,CDCl
3)δppm:138.6,133.8,132.6,128.7,128.3,127.7,126.5,1260.125.8.
Embodiment 103,3-di-thiophene synthetic
By 17.7mg PdCl
2(2mol%), 41mg NaOAc (10mol%), 10mL DMA joins in the round-bottomed flask of 50mL successively, stir after 2min, add 640.0mg (5mmol) 3 thienylboronic acid, then this system is reacted 8h under air at room temperature condition, 3 × 5mL ether/water for reaction solution (2:1) extraction, collects ether layer, with anhydrous magnesium sulfate drying, filter, boil off ether, column chromatography obtains product 3,3-di-thiophene 290.5mg, white solid, yield 70%.Fusing point 130-132 ° C.
1H?NMR(400MHz，CDCl
3)δppm：7.39(d,2H),7.33(m,4H);
13CNMR(100MHz,CDCl
3)δppm:137.6,126.8,126.6,1205。
Claims (7)
1. the method for a synthetic separate benzene nuclei compound, it is characterized in that: in air atmosphere, palladium catalyst, substrate fragrance boronic acid compounds, taking the one in sodium-acetate, Potassium ethanoate, Lithium Acetate, sodium carbonate, salt of wormwood or cesium carbonate as alkaline additive, with N, N-N,N-DIMETHYLACETAMIDE (DMA), N, dinethylformamide (DMF), N, one in N-diethylformamide (DEF), N-Methyl pyrrolidone (NMP) is solvent, under room temperature, reaction 3-8h, reaction product aftertreatment obtains described separate benzene nuclei compound.
2. method according to claim 1, is characterized in that: described palladium catalyst is PdCl
2; Catalyst P dCl
2consumption and substrate fragrance boronic acid compounds mol ratio be 0.5:100 ~ 2:100.
3. method according to claim 1, is characterized in that: alkaline additive and substrate fragrance boronic acid compounds mol ratio are 5:100 ~ 10:100.
4. method according to claim 1, is characterized in that: during reaction is not, fragrant boronic acid compounds concentration is 2-10mol/L.
5. method according to claim 1, is characterized in that, described alkaline additive is sodium-acetate.
6. method according to claim 1, is characterized in that, described solvent is N,N-dimethylacetamide (DMA).
7. method according to claim 1; it is characterized in that: described fragrant boronic acid compounds be phenylo boric acid or on phenyl ring with boronate and except boronate other substituent aromatic compound; other substituting group on phenyl ring is the one in methyl, methoxyl group, chlorine, fluorine, nitro, ethanoyl; other substituting group quantity on phenyl ring is 1, and substituent position is in ortho position, contraposition or a position of boronate.
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| CN201210560036.6A CN103880573A (en) | 2012-12-20 | 2012-12-20 | Preparation method for biphenyl-type compound |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110683925A (en) * | 2019-10-23 | 2020-01-14 | 云南中医药大学 | Synthetic method of biphenyl compound |
| CN112939716A (en) * | 2021-02-01 | 2021-06-11 | 三峡大学 | Preparation method of biphenyl compound |
| CN114149298A (en) * | 2021-11-22 | 2022-03-08 | 江苏大学 | Method for preparing biaryl compound from arylboronic acid by using hydrazone catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1699312A (en) * | 2005-06-02 | 2005-11-23 | 上海交通大学 | Process for preparing biphenyl |
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2012
- 2012-12-20 CN CN201210560036.6A patent/CN103880573A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1699312A (en) * | 2005-06-02 | 2005-11-23 | 上海交通大学 | Process for preparing biphenyl |
Non-Patent Citations (2)
| Title |
|---|
| GEORGE W. KABALKA,ET AL.,: "Ligandless palladium chloride-catalyzed homo-coupling of arylboronic acids in aqueous media", 《TETRAHEDRON LETTERS》, vol. 43, 31 December 2002 (2002-12-31), pages 3067 - 3068 * |
| MAN SHING WONG,ET AL.,: "Ligand promoted palladium-catalyzed homo-coupling of arylboronic acids", 《TETRAHEDRON LETTERS》, vol. 42, 31 December 2001 (2001-12-31), pages 4087 - 4089, XP004240859, DOI: 10.1016/S0040-4039(01)00637-2 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110683925A (en) * | 2019-10-23 | 2020-01-14 | 云南中医药大学 | Synthetic method of biphenyl compound |
| CN110683925B (en) * | 2019-10-23 | 2022-09-23 | 云南中医药大学 | Synthetic method of biphenyl compound |
| CN112939716A (en) * | 2021-02-01 | 2021-06-11 | 三峡大学 | Preparation method of biphenyl compound |
| CN114149298A (en) * | 2021-11-22 | 2022-03-08 | 江苏大学 | Method for preparing biaryl compound from arylboronic acid by using hydrazone catalyst |
| CN114149298B (en) * | 2021-11-22 | 2023-11-24 | 江西麦豪化工科技有限公司 | Method for preparing biaryl compound from arylboronic acid by hydrazone catalyst |
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Application publication date: 20140625 |