CN112939715A - Synthesis method of 4-alkyl biphenyl acetylene - Google Patents

Synthesis method of 4-alkyl biphenyl acetylene Download PDF

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CN112939715A
CN112939715A CN202110138781.0A CN202110138781A CN112939715A CN 112939715 A CN112939715 A CN 112939715A CN 202110138781 A CN202110138781 A CN 202110138781A CN 112939715 A CN112939715 A CN 112939715A
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刘显伟
韩津
马青松
陈芳
王晓莹
马心旺
苏建
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Huize Chemical Technology Puyang Co ltd
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    • C07—ORGANIC CHEMISTRY
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    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
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    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
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    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
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    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
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Abstract

The invention discloses a method for synthesizing 4-alkyl biphenyl acetylene, which comprises the following steps: carrying out catalytic hydrogenation reaction on the 4-alkyl diketone to obtain 4-alkyl biphenyl; then 4-alkyl biphenyl reacts with halogen to obtain 4-halogeno-4' -alkyl biphenyl; 4-halogeno-4' -alkyl biphenyl and ethynylation reagent are subjected to coupling reaction, and then the compound of the formula (IV) is obtained under the action of alkali. The invention creatively adopts a catalytic system combining a palladium catalyst and Lewis acid to carry out deoxidation reaction on the 4-alkyl diketone, and has good selectivity and high yield; in addition, hydrogen is used as a hydrogen source, and the byproduct is only water, so that the method is environment-friendly.

Description

Synthesis method of 4-alkyl biphenyl acetylene
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for synthesizing 4-alkyl biphenyl acetylene.
Background
The biphenyl acetylene liquid crystal monomer is the basis for forming low-viscosity high-refractive index nematic liquid crystal, has smaller moment of inertia and a slender structure, has lower viscosity and quicker response time, and can be applied to three-dimensional stereoscopic display technology.
The current methods for synthesizing 4-alkyldiphenylacetylene are mainly three:
one is that biphenyl reacts with Grignard reagent to obtain 4-alkyl biphenyl, then reacts with iodine to obtain 4-iodine-4 '-alkyl biphenyl, and finally 4-iodine-4' -alkyl biphenyl reacts with isobutynol to obtain 4-alkyl biphenyl acetylene. The reaction formula is as follows:
Figure BDA0002927840260000011
one is to react 4-alkyl bromobenzene with phenylboronic acid to obtain 4-alkyl biphenyl, then react with iodine to obtain 4-iodine-4 '-alkyl biphenyl, and finally react 4-iodine-4' -alkyl biphenyl with isobutynol to obtain 4-alkyl biphenyl acetylene. The reaction formula is as follows:
Figure BDA0002927840260000012
one is that biphenyl-4-alkyl ketone reacts with hydrazine hydrate to obtain 4-alkyl biphenyl, then reacts with iodine to obtain 4-iodine-4 '-alkyl biphenyl, and finally the 4-iodine-4' -alkyl biphenyl reacts with isobutynol to obtain 4-alkyl biphenyl acetylene. The reaction formula is as follows:
Figure BDA0002927840260000021
the three methods for synthesizing the 4-alkyl biphenyl all involve harsh reaction conditions and complex post-treatment procedures, have low atom utilization rate, generate more three wastes and the like.
Disclosure of Invention
Aiming at the problems of harsh reaction conditions, complex post-treatment, low yield and the like in the prior art, the invention provides the method for synthesizing the 4-alkyl diphenyl acetylene, which has the advantages of mild reaction conditions, good selectivity, high yield, environmental friendliness and suitability for industrial production.
The method for synthesizing 4-alkyl biphenyl in the prior art has harsh reaction conditions, complex post-treatment and poor selectivity, and the inventor creatively finds that the biphenyl-4-alkyl ketone is subjected to catalytic hydrogenation reaction under a catalytic system of combination of a supported transition metal and Lewis acid, so that the selectivity and the yield are high, the method is environment-friendly and simple in post-treatment, and the yield of the whole reaction is further improved.
Accordingly, the present invention relates to a method for synthesizing 4-alkyldiphenylacetylene, comprising:
(1) carrying out catalytic hydrogenation reaction on the compound of the formula (I) in a catalytic system combining a supported transition metal and Lewis acid to obtain a compound of a formula (II);
(2) reacting the compound of the formula (II) with halogen to obtain a compound of a formula (III);
(3) the compound of the formula (III) and an ethynylation reagent are subjected to coupling reaction, and then the compound of the formula (IV) is obtained under the action of alkali.
The reaction formula is as follows:
Figure BDA0002927840260000022
r is CnH2n+1N is 1,2,3, 4; x is bromine or iodine.
The supported transition metal is selected from nickel/carbon, palladium/carbon, platinum/carbon, cobalt/carbon, rhodium/carbon, palladium/barium sulfate, palladium/ferroferric oxide, nickel/alumina, platinum/alumina, rhodium/alumina, ruthenium/alumina, cobalt/silica, rhodium/silica, ruthenium/silica, palladium/titania, ruthenium/titania or rhodium/titania; the Lewis acid is selected from aluminum trichloride, ferric trichloride, stannic chloride or zirconium tetrachloride.
The dosage of the supported transition metal is preferably 0.001-0.1 times of the molar weight of the compound of the formula (I) (calculated by active transition metal component in the catalyst); the amount of the Lewis acid used is preferably 0.05 to 0.2 times the molar amount of the compound of formula (I).
In the above-mentioned deoxidation reaction, it is preferable to carry out in an organic solvent selected from methanol, ethanol or isopropanol.
In the step (1), the reaction temperature is 20-80 ℃, and the reaction pressure is 1-10 MPa. The reaction time is generally 0.5 to 5 hours according to the actual reaction system.
Further, the step (2) is to react the compound of the formula (II) with halogen in a mixed solvent under the action of a catalyst to obtain the compound of the formula (III).
The halogen is bromine or iodine.
The mixed solvent is a solvent obtained by mixing acetic acid and alcohol; the alcohol is preferably methanol, ethanol or isopropanol. The volume ratio of the acetic acid to the alcohol is preferably 3: 1-5: 1.
The catalyst is concentrated sulfuric acid or phosphoric acid.
The molar ratio of the compound of the formula (II) to the halogen is preferably 1: 1.01-1.03.
Further, the compound of the formula (III) in the step (3) and an ethynylation reagent are subjected to a coupling reaction under the combined action of a palladium catalyst, a copper catalyst and a first base to generate an intermediate 4-alkyl biphenyl acetylene alcohol, and then the intermediate 4-alkyl biphenyl acetylene alcohol is reacted under the action of a second base to obtain the compound of the formula (IV).
The ethynylation reagent is selected from isobutynol, trimethylsilylacetylene, triethylsilylacetylene or triisopropylsilylacetylene.
The palladium catalyst is selected from palladium acetate, bis (triphenylphosphine) palladium chloride, 1' -bis (diphenylphosphino) ferrocene palladium dichloride or tris (dibenzylideneacetone) dipalladium; the copper catalyst is selected from cuprous chloride, cuprous bromide, cuprous iodide, copper acetate or copper acetylacetonate.
The first base is selected from triethylamine, triethylene diamine, tetrabutylammonium fluoride or N-methyl pyrrolidone.
In the above coupling reaction, it is preferable to carry out in a solvent selected from tetrahydrofuran, toluene and benzene.
The second base is selected from potassium hydroxide, sodium hydroxide or sodium carbonate.
The molar ratio of the compound of the formula (III) to the ethynylation reagent is preferably 1: 1-2.
The molar ratio of the compound of formula (III) to the palladium catalyst is preferably 1: 0.001-0.05.
Compared with the prior art, the invention has the beneficial effects that: the invention creatively adopts a catalytic system combining a palladium catalyst and Lewis acid to carry out catalytic hydrogenation on the 4-alkyl diketone, and has good selectivity and high yield; in addition, hydrogen is used as a hydrogen source, and the byproduct is only water, so that the method is environment-friendly.
Detailed Description
The invention is further illustrated, but not limited, by the following specific examples.
Example 1
Putting 4-acetylbiphenyl (1mol, 196.2g), palladium/titanium dioxide (containing 5g of palladium mass) and aluminum trichloride (0.1mol, 13.3g) into a high-pressure reaction kettle, adding 500mL of ethanol, introducing nitrogen into the high-pressure reaction kettle for three times, then introducing hydrogen (5MPa), stirring and heating to 50 ℃, reacting for 2 hours, filtering the reaction solution after the reaction is finished, washing filter residues with a small amount of ethanol for two times, combining the filtrate and washing solution, and then carrying out reduced pressure distillation to recover the solvent to obtain the 4-ethylbiphenyl with the content of 99% and the yield of 97%.
Dissolving iodine simple substance (1mol, 159.8g) and 4-ethyl biphenyl (1mol, 182.3g) in a mixed solvent of glacial acetic acid (300mL) and ethanol (100mL), adding 98% concentrated sulfuric acid (0.01mol, 1g), stirring, heating, refluxing and reacting for 5 hours, cooling to room temperature, washing with 20mL saturated sodium bisulfite solution, filtering, washing with water to neutrality, drying in the air, and recrystallizing with ethanol to obtain 4-ethyl-4' -bromobiphenyl with the content of 98% and the yield of 90%.
Dissolving 4-ethyl-4' -bromobiphenyl (1mol, 261.2g) in a mixed solution of tetrahydrofuran (250mL) and triethylamine (250mL), adding isobutynol (1.5mol, 126.2g), palladium dichloride bis (triphenylphosphine) (0.005mol, 3.5g) and cuprous iodide (0.01mol, 1.9g), heating under nitrogen protection, refluxing for 5 hours, cooling to room temperature, performing suction filtration, washing twice with 30mL triethylamine, stirring and washing once with 50mL saturated ammonium chloride, standing, separating, extracting an aqueous layer with ethyl acetate, combining organic phases, performing reduced pressure distillation to recover a solvent, and recrystallizing the residual solid with petroleum ether to obtain 4-ethylbiphenylethynylol with the content of 98% and the yield of 88%;
dissolving the 4-ethyl biphenyl acetylene alcohol (1mol, 264.4g) in 500mL of toluene, slowly adding sodium hydroxide (0.2mol, 8g), stirring for one hour at room temperature under the protection of nitrogen, then carrying out reflux reaction for 5 hours, cooling to room temperature, adding water into reaction liquid, stirring, standing for layering, extracting a water phase twice with toluene, combining organic phases, carrying out reduced pressure distillation to recover toluene, and carrying out freezing recrystallization twice on the residual product with ethanol to obtain a light yellow solid product, namely 4-ethyl biphenyl acetylene, wherein the content is 99% and the yield is 80%.
1H NMR(CDCl3,400MHz)：1.25(t，3H)，2.42～2.58(m，4H),4.06(s，1H)，7.30～7.40(m，4H)，7.60～7.65(m，4H)。
Example 2
Putting 4-propionyl biphenyl (1mol, 210.2g), platinum/titanium dioxide (containing 5g of platinum mass), ferric trichloride (0.05mol, 8.1g) into a high-pressure reaction kettle, adding 500mL of isopropanol, introducing nitrogen into the high-pressure reaction kettle for three times, then introducing hydrogen (1MPa), stirring and heating to 80 ℃, reacting for 2 hours, filtering the reaction solution after the reaction is finished, washing filter residues with a small amount of ethanol for two times, combining the filtrate and washing solution, and then carrying out reduced pressure distillation to recover the solvent to obtain the 4-propylbiphenyl with the content of 99% and the yield of 98%.
Dissolving bromine simple substance (1mol, 159.8g) and 4-propyl biphenyl (1mol, 196.3g) in a mixed solvent of glacial acetic acid (300mL) and ethanol (100mL), adding 98% concentrated sulfuric acid (0.01mol, 1g), stirring, heating, refluxing and reacting for 5 hours, cooling to room temperature, washing with 20mL saturated sodium bisulfite solution, filtering, washing with water to neutrality, drying in the air, and recrystallizing with ethanol to obtain 4-propyl-4' -bromobiphenyl with the content of 97% and the yield of 89%.
Dissolving 4-propyl-4 '-bromobiphenyl (1mol, 275.2g) in a mixed solution of toluene (250mL) and tetrabutylammonium fluoride (250mL), adding trimethylsilylacetylene (2mol, 196.4g), 1, 1' -bis (diphenylphosphino) ferrocene palladium dichloride (0.001mol, 0.71g) and cuprous bromide (0.1mol, 19g), heating under the protection of nitrogen, carrying out reflux reaction for 5 hours, cooling to room temperature, carrying out suction filtration, washing twice with 30mL triethylamine, fully stirring and washing once with 50mL saturated ammonium chloride, standing, separating liquid, extracting a water layer with ethyl acetate, combining organic phases, carrying out reduced pressure distillation to recover a solvent, recrystallizing the residual solid with petroleum ether to obtain 4-propyldiphenylacetylene trimethylsilane with the content of 98% and the yield of 88%;
dissolving the 4-propylbiphenyl acetylene trimethylsilane (1mol, 292.5g) in 500mL of toluene, slowly adding potassium hydroxide (0.2mol, 11.2g), stirring for one hour at room temperature under the protection of nitrogen, then refluxing for 5 hours, cooling to room temperature, adding water into the reaction solution, stirring, standing for layering, extracting the water phase twice with toluene, combining the organic phases, distilling under reduced pressure to recover toluene, freezing and recrystallizing the residual product twice with ethanol to obtain a light yellow solid product, namely 4-propylbiphenyl acetylene, wherein the content is 99%, and the yield is 82%.
1H NMR(CDCl3,400MHz)：0.90(t，3H)，1.31～1.35(m，2H)，2.62(t，2H)，4.05(s，1H)，7.30～7.35(m，4H),7.60～7.66(m，4H)。
Example 3
Putting 4-butyrylbiphenyl (1mol, 224.2g), rhodium/alumina (containing 5g of rhodium in mass) and stannic chloride (0.2mol, 52.1g) into a high-pressure reaction kettle, adding 500mL of methanol, introducing nitrogen into the high-pressure reaction kettle for three times of replacement, then introducing hydrogen (10MPa), stirring and heating at 20 ℃, reacting for 2 hours, filtering reaction liquid after the reaction is finished, washing filter residues with a small amount of ethanol twice, combining the filtrate and washing liquid, and then carrying out reduced pressure distillation to recover the solvent to obtain the 4-butylbiphenyl with the content of 99% and the yield of 98%.
Dissolving iodine simple substance (1mol, 253.8g) and 4-butyl biphenyl (1mol, 210.3g) in a mixed solvent of glacial acetic acid (300mL) and ethanol (100mL), adding 98% concentrated sulfuric acid (0.01mol, 1g), stirring, heating, refluxing and reacting for 5 hours, cooling to room temperature, washing with 20mL saturated sodium bisulfite solution, filtering, washing with water to neutrality, drying in the air, and recrystallizing with ethanol to obtain 4-butyl-4' -iodobiphenyl with the content of 98% and the yield of 91%.
Dissolving 4-butyl-4' -bromobiphenyl (1mol, 289.2g) in a mixed solution of acetonitrile (250mL) and triethylene diamine (250mL), adding triisopropylsilaacetylene (1mol, 182.4g), tris (dibenzylideneacetone) dipalladium (0.05mol, 35g) and cuprous chloride (0.1mol, 19g), heating under the protection of nitrogen, carrying out reflux reaction for 5 hours, cooling to room temperature, carrying out suction filtration and washing twice by using 30mL of triethylamine, fully stirring and washing once by using 50mL of saturated ammonium chloride, standing, carrying out liquid separation, extracting an aqueous layer by using ethyl acetate, combining organic phases, carrying out reduced pressure distillation to recover a solvent, and recrystallizing the residual solid by using petroleum ether to obtain 4-butylbiphenylacetylene alcohol, wherein the content is 99%, and the yield is 85%;
dissolving the 4-butyl biphenyl acetylene triisopropyl silane in toluene, adding anhydrous sodium carbonate (0.2mol, 21.2g), stirring for one hour at room temperature under the protection of nitrogen, then carrying out reflux reaction for 5 hours, cooling to room temperature, adding water into reaction liquid, stirring, standing for layering, extracting a water phase twice with toluene, combining organic phases, distilling under reduced pressure to recover toluene, freezing and recrystallizing the residual product twice with ethanol to obtain a light yellow solid product, namely 4-butyl biphenyl acetylene, wherein the content is 99%, and the yield is 85%.
1H NMR(CDCl3,400MHz)：0.85(t，3H)，1.31～1.35(m，2H)，1.51～1.60(m，2H)，2.54～2.60(t，2H)，4.01(s，1H),7.33～7.38(m，4H)，7.61～7.70(m，2H)。
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the invention is not limited to the embodiments described above, which are described in the specification only to illustrate the principles of the invention. The invention also includes various insubstantial changes and modifications within the spirit of the invention, as claimed by those skilled in the art.

Claims (7)

1. A method for synthesizing 4-alkyl diphenyl acetylene comprises the following steps:
(1) carrying out catalytic hydrogenation reaction on the compound of the formula (I) in a catalytic system combining a supported transition metal and Lewis acid to obtain a compound of a formula (II);
(2) reacting the compound of the formula (II) with halogen to obtain a compound of a formula (III);
(3) carrying out coupling reaction on the compound of the formula (III) and an ethynylation reagent, and then obtaining a compound of a formula (IV) under the action of alkali;
Figure FDA0002927840250000011
r is CnH2n +1, n is 1,2,3, 4; x is bromine or iodine.
2. The process according to claim 1, characterized by a combination of a supported transition metal and a lewis acid; the supported transition metal is selected from nickel/carbon, palladium/carbon, platinum/carbon, cobalt/carbon, rhodium/carbon, palladium/barium sulfate, palladium/ferroferric oxide, nickel/alumina, platinum/alumina, rhodium/alumina, ruthenium/alumina, cobalt/silica, rhodium/silica, ruthenium/silica, palladium/titania, ruthenium/titania or rhodium/titania; the Lewis acid is selected from aluminum trichloride, ferric trichloride, stannic chloride or zirconium tetrachloride.
3. The process according to claim 1 or 2, characterized in that the supported transition metal is preferably used in an amount of 0.001 to 0.1 times the molar amount of the compound of formula (i) (based on the active transition metal component of the catalyst); the amount of the Lewis acid used is preferably 0.05 to 0.2 times the molar amount of the compound of formula (I).
4. The method according to any one of claims 1 to 3, wherein the reaction temperature is 20 to 80 ℃ and the reaction pressure is 1 to 10 MPa; and/or the organic solvent is selected from methanol, ethanol or isopropanol.
5. The method according to any one of claims 1 to 3, wherein the compound of formula (II) is reacted with halogen in a mixed solvent to obtain the compound of formula (III) under the action of a catalyst in step (2).
6. The method according to claim 4, characterized in that the halogen is bromine or iodine; the molar ratio of the compound of the formula (II) to the halogen is preferably 1: 1.01-1.03.
7. The method according to any one of claims 1 to 3, wherein the compound of formula (III) in step (3) and an ethynylation reagent are subjected to a coupling reaction under the combined action of a palladium catalyst, a copper catalyst and a first base to generate an intermediate 4-alkyl biphenyl acetylene alcohol, and then the intermediate 4-alkyl biphenyl acetylene alcohol is subjected to a reaction under the action of a second base to obtain the compound of formula (IV).
The process according to claim 7, characterized in that the ethynylation agent is selected from the group consisting of isobutynol, trimethylsilylacetylene, triethylsilylacetylene or triisopropylsilylacetylene; the molar ratio of the compound of the formula (III) to the ethynylation reagent is preferably 1: 1-2.
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