CN116120172A - 1, 4-bis (2-phenylethynyl) benzene derivative and preparation method thereof - Google Patents

1, 4-bis (2-phenylethynyl) benzene derivative and preparation method thereof Download PDF

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CN116120172A
CN116120172A CN202211191041.4A CN202211191041A CN116120172A CN 116120172 A CN116120172 A CN 116120172A CN 202211191041 A CN202211191041 A CN 202211191041A CN 116120172 A CN116120172 A CN 116120172A
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phenylethynyl
bis
benzene derivative
tetrayne
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胡益民
董杰
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Anhui Normal University
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    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/753—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of polycyclic acids
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane

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Abstract

The invention provides a 1, 4-bis (2-phenylethynyl) benzene derivative and a preparation method thereof, wherein a tetrayne compound is used as a substrate, and the tetrayne compound, 1-phenyl-2- (trimethylsilyl) acetylene and cesium carbonate react in acetonitrile solvent in one step to synthesize the 1, 4-bis (2-phenylethynyl) benzene derivative with a complex structure, and the preparation method is simple and efficient. Compared with the prior art, the invention provides a brand new synthesis method of the 1, 4-bis (2-phenylethynyl) benzene derivatives, and a series of novel 1, 4-bis (2-phenylethynyl) benzene derivatives are generated. The synthesized 1, 4-bis (2-phenylethynyl) benzene derivative has higher atom economy and more complex and diversified structures, and provides a feasible scheme for synthesizing the more complex 1, 4-bis (2-phenylethynyl) benzene derivative under milder conditions.

Description

1, 4-bis (2-phenylethynyl) benzene derivative and preparation method thereof
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a 1, 4-bis (2-phenylethynyl) benzene derivative and a preparation method thereof.
Background
Phenylacetylene compounds are conjugated compounds, and have wide application in photoelectric fields such as molecular sensors, molecular wires, polarizers for liquid crystal display, energy transmission materials and the like. At present, the study on phenylacetylene compounds is mainly focused on high molecular polymers, and the study on phenylacetylene small molecules is relatively few. While highly symmetrical 1, 4-bis (2-phenylethynyl) benzene can serve as a good scintillator and laser dye.
Disclosure of Invention
The invention aims to provide a 1, 4-bis (2-phenylethynyl) benzene derivative and a preparation method thereof, wherein a tetrayne compound is used as a substrate, and the 1, 4-bis (2-phenylethynyl) benzene derivative with a complex structure can be synthesized by one-step reaction of the tetrayne compound, 1-phenyl-2- (trimethylsilyl) acetylene and cesium carbonate in an acetonitrile solvent, and the preparation method is simple and efficient.
The specific technical scheme of the invention is as follows:
a preparation method of a 1, 4-bis (2-phenylethynyl) benzene derivative comprises the following steps:
the tetrayne is reacted with 1-phenyl-2- (trimethylsilyl) acetylene and cesium carbonate in acetonitrile, and after the reaction is finished, the 1, 4-bis (2-phenylethynyl) benzene derivative is obtained by separation and purification.
The reaction is carried out at 100-110 ℃ for 12-14 hours, preferably 105 ℃ for 12 hours.
The ratio of the amounts of the substances of the tetrayne, the 1-phenyl-2- (trimethylsilyl) acetylene and the cesium carbonate is 1:1.2:1.5.
the concentration of the tetrayne in acetonitrile is 0.1-0.3M.
The separation and purification method comprises the following steps: adding saturated saline water and ethyl acetate into the system after the reaction is finished for extraction, collecting an organic phase, concentrating the organic phase, purifying by column chromatography, crystallizing and purifying, and washing the product after crystallizing and purifying by petroleum ether.
The eluent for column chromatography purification is ethyl acetate with the volume ratio: petroleum ether=1:80; the solvent used for crystallization and purification is petroleum ether.
The structural formula of the tetrayne is
Figure BDA0003869200150000021
Wherein R is a straight-chain alkyl or branched-chain alkyl within six carbons;
R 1 is hydrogen, halogen or straight chain alkyl or branched alkyl within six carbons; preferably, R is methyl or isopropyl; the R is 1 Is methyl or hydrogen.
The preparation method of the tetrayne comprises the following steps:
1) Adding malonate and propargyl bromide into anhydrous acetonitrile to react in an ice water bath by taking sodium hydride as alkali, and then purifying and separating to obtain a compound 1;
2) Mixing the compound 1 prepared in the step 1) with phenylethynyl bromide or substituted phenylethynyl bromide in a CuCl anhydrous oxygen-free catalytic system, adding n-butylamine aqueous solution and hydroxylamine hydrochloride, stirring for reaction in an ice bath, and separating and purifying the product to obtain the tetrayne compound.
Further, in step 1), the molar ratio of sodium hydride, malonate, propargyl bromide and anhydrous acetonitrile is 4-5:1:2.2-3:20-23.
The reaction temperature is 0-5 ℃ under the ice water bath condition in the step 1); the reaction time is more than or equal to 8 hours;
the purification and separation in the step 1) are specifically as follows: the product was washed with water, extracted with ethyl acetate, dried under reduced pressure, and ethyl acetate in the volume ratio: the mixed solvent of petroleum ether=1:80 is subjected to column chromatography to obtain a product, namely a compound 1.
The structural formula of the compound 1 in the step 1) is as follows:
Figure BDA0003869200150000031
wherein E is 1 And E is 2 The same is CO 2 R, R is a straight chain alkyl or branched alkyl within six carbons.
The molar ratio of the compound 1 to the phenylethynyl bromide or the substituted phenylethynyl bromide, cuCl and hydroxylamine hydrochloride in the step 2) is 1:2-2.5:0.15-0.16:0.1-0.2.
The substituted phenylethynyl bromide is p-phenylethynyl bromide.
The mass concentration of the n-butylamine aqueous solution used as the solvent in the step 2) is 30%.
In the step 2), the dosage ratio of the compound 1 to the n-butylamine aqueous solution is 0.4-0.5mol/L;
in step 2), stirring the reaction time for at least 12 hours;
in the step 2), the separation and purification means: the product was washed with saturated brine, extracted with ethyl acetate, and dried under reduced pressure in a volume ratio of ethyl acetate: carrying out column chromatography by using petroleum ether=1:80 as eluent, concentrating under reduced pressure, and drying to obtain the tetrayne compound;
the mechanism of the invention is as follows: the preparation method comprises the steps of taking tetrayne compounds, 1-phenyl-2- (trimethylsilyl) acetylene and cesium carbonate as raw materials, reacting in acetonitrile solvent, cyclizing the tetrayne compounds into a phenylacetylene intermediate through HDDA reaction, removing trimethylsilyl from the 1-phenyl-2- (trimethylsilyl) acetylene under the action of cesium carbonate to generate phenylethynyl anions, capturing the phenylethynyl anions generated by the phenylethynyl anions into a product a with carbanions, capturing methyl hydrogen on 1-phenyl-2- (trimethylsilyl) acetylene by the carbanions of a, and carrying out electron transfer to obtain a final product 1, 4-bis (2-phenylethynyl) benzene derivative b. Taking the example 2 as an example, a benzene derivative having 1, 4-bis (2-phenylethynyl) is obtained, and the reaction mechanism is shown in FIG. 10.
The structural formula of the 1, 4-bis (2-phenylethynyl) benzene derivative prepared by the preparation method is as follows:
Figure BDA0003869200150000041
/>
wherein E is CO 2 R is R; r is a straight-chain alkyl or branched-chain alkyl within six carbons;
R 1 is hydrogen, halogen or straight chain alkyl or branched alkyl within six carbons.
Further, the R is preferably methyl or isopropyl; the R is 1 Preferably methyl or hydrogen.
Further, the structural formula of the 1, 4-bis (2-phenylethynyl) benzene derivative is as follows:
Figure BDA0003869200150000042
compared with the prior art, the invention provides a brand new synthesis method of the 1, 4-bis (2-phenylethynyl) benzene derivatives, and a series of novel 1, 4-bis (2-phenylethynyl) benzene derivatives are generated. The synthesized 1, 4-bis (2-phenylethynyl) benzene derivative has higher atom economy and more complex and diversified structures, and provides a feasible scheme for synthesizing the more complex 1, 4-bis (2-phenylethynyl) benzene derivative under milder conditions.
Drawings
FIG. 1 is a structural formula of a 1, 4-bis (2-phenylethynyl) benzene derivative;
FIG. 2 is a structural formula of 1, 4-bis (2-phenylethynyl) benzene derivatives in example 1;
FIG. 3 is a structural formula of 1, 4-bis (2-phenylethynyl) benzene derivative in example 2;
FIG. 4 is a synthetic reaction scheme for the 1, 4-bis (2-phenylethynyl) benzene derivative of example 1;
FIG. 5 is a synthetic reaction scheme for the 1, 4-bis (2-phenylethynyl) benzene derivative of example 2;
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of a 1, 4-bis (2-phenylethynyl) benzene derivative synthesized in example 1;
FIG. 7 is a nuclear magnetic resonance carbon spectrum of a 1, 4-bis (2-phenylethynyl) benzene derivative synthesized in example 1;
FIG. 8 is a nuclear magnetic resonance hydrogen spectrum of a 1, 4-bis (2-phenylethynyl) benzene derivative synthesized in example 2;
FIG. 9 is a nuclear magnetic resonance carbon spectrum of a 1, 4-bis (2-phenylethynyl) benzene derivative synthesized in example 2;
FIG. 10 is a reaction scheme showing the synthesis of 1, 4-bis (2-phenylethynyl) benzene derivatives in example 2.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
A 1, 4-bis (2-phenylethynyl) benzene derivative having the structural formula:
Figure BDA0003869200150000051
the preparation method of the 1, 4-bis (2-phenylethynyl) benzene derivative comprises the following steps:
(1) With 830mmol of sodium hydride as a base, 200mmol of dimethyl malonate and 440mmol of propargyl bromide are added into 210mL of anhydrous acetonitrile for ice water bath, stirred and reacted for 8 hours, the product is washed with water, extracted with ethyl acetate, and dried under reduced pressure in a volume ratio of ethyl acetate: carrying out column chromatography by using petroleum ether=1:80 as eluent to obtain a white solid product, and concentrating and drying under reduced pressure to obtain a compound 1a; the structural formula is shown in figure 4;
(2) Mixing 40mmol of compound 1a with 100mmol of p-tolylethynyl bromide and NH 2 OH HCl/CuCl (4 mmol/6 mmol) in an oxygen-free system, molar ratio NH 2 OH HCl: cucl=2:3, 100ml of 30% aqueous n-butylamine solution was used as a solvent, the reaction was stirred at 0 ℃ for 12 hours, the product was washed with saturated brine, extracted with ethyl acetate, dried under reduced pressure, and the volume ratio was ethyl acetate: carrying out column chromatography by using petroleum ether=1:80 as eluent, concentrating under reduced pressure, and drying to obtain a pale yellow solid product, namely a precursor compound 2a; the structural formula is shown in figure 4;
(3) 1mmol of precursor compound 2a was reacted with 1.2mmol of 1-phenyl-2- (trimethylsilyl) acetylene and 1.5mmol of cesium carbonate in 5mL of acetonitrile at 105℃for 12 hours, and after the reaction was completed, cooled to room temperature;
(4) Adding saturated saline and ethyl acetate into the system after the reaction in the step (3) for extraction, collecting an organic phase, concentrating the organic phase, and adding ethyl acetate with the volume ratio of 1:80: and (3) carrying out column chromatography purification by using petroleum ether as an eluent, collecting and concentrating eluent containing a target product, then adding ethyl acetate until the concentrate is just dissolved, then adding petroleum ether with the volume of 10 times, standing and crystallizing for 12 hours at room temperature, carrying out suction filtration, and washing filter residues with petroleum ether to obtain a pale yellow solid, and drying to obtain the 1, 4-bis (2-phenylethynyl) benzene derivative, wherein the yield is 76%.
Product structure passage 1 H NMR、 13 C NMR was measured as shown in FIGS. 6 and 7.
1 H NMR(400MHz,CDCl 3 )δ7.51-7.43(m,4H),7.25-7.23(m,4H),7.22-7.20(m,2H),7.16(d,2H),7.08(d,2H),3.82(s,2H),3.79(s,6H),3.68(s,2H),2.44(s,3H),2.33(s,3H)；
13 C NMR(125MHz,CDCl 3 )δ171.96,144.93,143.16,138.61,138.50,137.08,135.92,131.38,130.40,129.02,128.20,128.02,127.46,123.48,122.05,120.19,119.75,96.70,92.09,89.44,86.20,59.70,52.81,41.14,40.70,21.54,21.45ppm。
Example 2
A 1, 4-bis (2-phenylethynyl) benzene derivative having the structural formula:
Figure BDA0003869200150000071
the preparation method of the 1, 4-bis (2-phenylethynyl) benzene derivative comprises the following steps:
(1) Adding 200mmol of diisopropyl malonate and 440mmol of propargyl bromide into anhydrous acetonitrile with 830mmol of sodium hydride as alkali, carrying out ice water bath, stirring and reacting for 8 hours, washing a product with water, extracting with ethyl acetate, and carrying out reduced pressure spin drying, wherein the volume ratio is ethyl acetate: carrying out column chromatography by using petroleum ether=1:80 as eluent, concentrating under reduced pressure, and drying to obtain a white solid product, namely a compound 1b;
(2) Mixing 40mmol of compound 1a with 100mmol of phenylethynyl bromide and NH 2 OH HCl/CuCl (4 mmol/6 mmol) in an oxygen-free system, molar ratio NH 2 OH HCl: cucl=2:3, 100ml of 30% aqueous n-butylamine solution was used as a solvent, the reaction was stirred at 0 ℃ for 12 hours, the product was washed with saturated brine, extracted with ethyl acetate, dried under reduced pressure, and the volume ratio was ethyl acetate: carrying out column chromatography by using petroleum ether=1:80 as an eluent, concentrating under reduced pressure, and drying to obtain a pale yellow solid product, namely a precursor compound 2b;
(3) Reacting 1mmol of precursor compound 2b with 1.2mmol of 1-phenyl-2- (trimethylsilyl) acetylene and 1.5mmol of cesium carbonate in 5mL of acetonitrile at 105 ℃ for 12 hours, and cooling to 0 ℃ after the reaction;
(4) Adding saturated saline and ethyl acetate into the system after the reaction in the step (3) for extraction, collecting an organic phase, concentrating the organic phase, and adding ethyl acetate with the volume ratio of 1:80: and (3) carrying out column chromatography purification by using petroleum ether as an eluent, collecting and concentrating eluent containing a target product, then adding ethyl acetate until the concentrate is just dissolved, then adding petroleum ether with the volume of 10 times, standing and crystallizing for 12 hours at room temperature, carrying out suction filtration, and washing filter residues with petroleum ether to obtain a pale yellow solid, and drying to obtain the 1, 4-bis (2-phenylethynyl) benzene derivative, wherein the yield is 63%.
The reaction mechanism diagram of the 1, 4-bis (2-phenylethynyl) benzene derivative is shown in fig. 10.
Product structure passage 1 H NMR； 13 C NMR was measured as shown in FIGS. 8 and 9.
1 H NMR(400MHz,CDCl 3 )：δ7.66-7.55(m,3H),7.50-7.41(m,4H),7.36(s,1H),7.30-7.26(m,2H),7.25-7.18(m,6H),5.14-5.06(m,2H),3.80(s,2H),3.67(s,2H),1.31-1.27(m,12H)；
13 C NMR(100MHz,CDCl 3 )：δ171.15,171.03,145.20,143.46,139.18,139.11,131.74,131.48,131.34,130.52,129.37,128.44,128.33,128.29,128.24,128.20,128.05,127.95,127.52,127.45,127.37,123.38,123.26,121.96,119.98,96.44,92.25,89.28,86.72,69.48,69.43,59.78,40.89,40.58,21.59ppm。
The foregoing detailed description of a 1, 4-bis (2-phenylethynyl) benzene derivative and a method for preparing the same, which are illustrative and not restrictive, can be exemplified by several examples within the scope of the invention without departing from the general inventive concept, and therefore, should be regarded as falling within the scope of the invention.

Claims (10)

1. A process for the preparation of a 1, 4-bis (2-phenylethynyl) benzene derivative, characterized in that the process comprises:
the tetrayne is reacted with 1-phenyl-2- (trimethylsilyl) acetylene and cesium carbonate in acetonitrile, and after the reaction is finished, the 1, 4-bis (2-phenylethynyl) benzene derivative is obtained by separation and purification.
2. The method according to claim 1, wherein the reaction is carried out at 100 to 110 ℃ for 12 to 14 hours.
3. The preparation method according to claim 1 or 2, wherein the ratio of the amounts of the substances of tetrayne, 1-phenyl-2- (trimethylsilyl) acetylene and cesium carbonate is 1:1.2:1.5.
4. the process according to claim 1, wherein the concentration of the tetrayne in acetonitrile is 0.1 to 0.3M.
5. The method according to claim 1, wherein the tetrayne has the formula
Figure FDA0003869200140000011
Wherein R is a straight-chain alkyl or branched-chain alkyl within six carbons;
R 1 is hydrogen, halogen or straight chain alkyl or branched alkyl within six carbons.
6. The preparation method according to claim 5, wherein the preparation method of the tetrayne comprises:
1) Adding malonate and propargyl bromide into anhydrous acetonitrile in an ice-water bath, taking sodium hydride as alkali, reacting, and then purifying and separating to obtain a compound 1;
2) Mixing the compound 1 prepared in the step 1) with phenylethynyl bromide or substituted phenylethynyl bromide in a CuCl anhydrous oxygen-free catalytic system, adding n-butylamine aqueous solution and hydroxylamine hydrochloride, stirring for reaction in an ice bath, and separating and purifying the product to obtain the tetrayne compound.
7. The process according to claim 6, wherein the molar ratio of sodium hydride, malonate, propargyl bromide to anhydrous acetonitrile in step 1) is 4 to 5:1:2.2-3:20-23.
8. The process according to claim 6, wherein the molar ratio of compound 1 to phenylethynyl bromide or substituted phenylethynyl bromide, cuCl, hydroxylamine hydrochloride in step 2) is 1:2-2.5:0.15-0.16:0.1-0.2.
9. A 1, 4-bis (2-phenylethynyl) benzene derivative prepared by the preparation method according to any one of claims 1 to 8, wherein the 1, 4-bis (2-phenylethynyl) benzene derivative has a structural formula:
Figure FDA0003869200140000021
wherein E is CO 2 R is R; r is a straight-chain alkyl or branched-chain alkyl within six carbons;
R 1 is hydrogen, halogen or straight chain alkyl or branched alkyl within six carbons.
10. The 1, 4-bis (2-phenylethynyl) benzene derivative according to claim 9, characterized in that the 1, 4-bis (2-phenylethynyl) benzene derivative has the structural formula:
Figure FDA0003869200140000022
/>
CN202211191041.4A 2022-09-28 2022-09-28 1, 4-bis (2-phenylethynyl) benzene derivative and preparation method thereof Pending CN116120172A (en)

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