CN112851494A - Preparation method of 1-pyrenebutyric acid - Google Patents
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- 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
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Abstract
The invention provides a preparation method of 1-pyrenebutyric acid, which comprises the following steps: step S1, carrying out F-C acylation reaction on pyrene and chloroformyl butyrate compounds to obtain an intermediate 4-oxo-4-pyrene butyrate; step S2, enabling the intermediate 4-oxo-4-pyrenebutyric acid ester and hydrazine hydrate to undergo Huang Minlon reduction and ester hydrolysis reaction to obtain the 1-pyrenebutyric acid. According to the preparation method of 1-pyrenebutyric acid provided by the embodiment of the invention, chloroformyl butyrate compounds are used for replacing succinic anhydride in the prior art to carry out F-C acylation to generate an intermediate 4-oxo-4-pyrenebutyrate, and the intermediate 4-oxo-4-pyrenebutyrate can be purified by ethanol or methanol recrystallization, so that the complex operation that repeated acid-base washing is needed in the F-C acylation reaction process by using succinic anhydride is avoided, and the purification difficulty of the product is greatly reduced.
Description
Technical Field
The invention relates to the technical field of organic synthesis, and particularly relates to a preparation method of 1-pyrenebutyric acid.
Background
1-pyrenebutyric acid is a lipophilic red fluorescent dye and is mainly used for a fluorescence probe. Aromatic pyrene molecules are highly symmetric, have 16 electrons and do not follow haake's 4n +2 rule, and the interesting electronic properties of pyrene are useful for studying the preparation of chemical sensors. In addition, the pyrene ring can be anchored to a lipid membrane and forms a double strand with a complementary single-stranded nucleic acid, and this property can be utilized in the fields of chip technology and diagnosis. Therefore, the 1-pyrenebutanoic acid has wide application prospect, for example, the 1-pyrenebutanoic acid can be applied to photoelectronic materials and can represent the detection nucleic acid and polyamine of the cyclodextrin-based polyrotaxane film in the biological field; protein can also be fixed, and human serum lysozyme is probed; polymerase activity, recombinase activity, topoisomerase activity were measured as substrates.
In the prior art, the synthesis of 1-pyrenebutyric acid mainly takes pyrene and derivatives thereof as raw materials, and mainly comprises the following three synthetic routes:
(1) route one: 1-pyrene acetaldehyde is used as a raw material and is mixed with ethyl acetate to generate 3-hydroxy-1-pyrene ethyl butyrate under the conditions of butyl lithium and-78 ℃; then reacting with bromine to generate 3-bromo-1-pyrenebutyric acid ethyl ester; then debrominating with tri-n-butyltin chloride; and finally, performing ester hydrolysis by using potassium hydroxide to obtain a target product 1-pyrenebutyric acid (reference: J.org.chem.1983, 48(23), 4361-4366).
The reaction route is shown as the following formula (1):
the disadvantages of this method include: the reaction in the first step has strict requirements on temperature, requires extremely low temperature and is difficult to operate; in the second step, the reaction system is a bromine/benzene/triphenylphosphine system, and the solvent is relatively toxic; and the third step is to reduce with tri-n-butyltin chloride, and finally hydrolyze, so that the whole process has many steps, and the operation is not easy to realize technologization. The yield is not high, and the method is not suitable for production.
(2) And a second route: the method comprises the steps of utilizing an iodine reagent to react pyrene serving as a raw material for 4 days to synthesize 1-iodinated pyrene, then carrying out a complex Willgetodt-Kindler reaction on the 1-iodinated pyrene and 3-hydroxy-1-butene to obtain 4-pyrene-2-butanone, and then carrying out a haloform reaction on methyl ketone to obtain a target product 1-pyrenebutyric acid (reference: Eur. J. Org. chem.2003, 16, 3167-3172).
The reaction route is shown as the following formula (2):
however, this method is long in step and requires 4 days for the iodination reaction, and a polysubstituted by-product cannot be avoided. And the yield of the second step is lower, and the operation is complicated. The total yield is not high, and the method is difficult to be suitable for industrialization.
(3) And a third route: the pyrene and succinic anhydride are subjected to an F-C acylation reaction under the action of titanium tetrachloride to obtain 4-oxo-4-pyrenebutyric acid. Then, the target product 1-pyrenebutyric acid is obtained by the reduction of the xantholone (reference: New J. chem.2008, 32(8), 1438-1448).
The reaction route is shown as the following formula (3):
however, in this method, impurities generated by F-C acylation with succinic anhydride are difficult to remove, and repeated acid-base washing is required many times; moreover, the solvent nitrobenzene is toxic and the filtration is blocked, so that the large-scale production is difficult to realize, and the method is not suitable for industrial production.
Disclosure of Invention
In view of the above, the invention aims to provide a novel preparation method of 1-pyrenebutanoic acid, which can reduce cost, simplify operation, reduce environmental pollution and is suitable for industrial production.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of 1-pyrenebutyric acid according to the embodiment of the invention comprises the following steps:
step S1, carrying out F-C acylation reaction on pyrene and chloroformyl butyrate compounds to obtain an intermediate 4-oxo-4-pyrene butyrate;
step S2, enabling the intermediate 4-oxo-4-pyrenebutyric acid ester and hydrazine hydrate to undergo Huang Minlon reduction and ester hydrolysis reaction to obtain the 1-pyrenebutyric acid.
Further, in the step S1, the F-C acylation reaction of pyrene and the chloroformyl butyrate compound is carried out in a first organic solvent in the presence of Lewis acid.
Further, the Lewis acid is one or more of aluminum trichloride, boron trifluoride, stannic chloride, ferric trichloride and zinc chloride.
Further, the first organic solvent is one or more of dichloromethane, dioxane and tetrahydrofuran.
Further, in the step S1, the chloroformyl butyrate compound is one or more selected from methyl chloroformyl butyrate, ethyl chloroformyl butyrate, diisopropyl chloroformyl butyrate and benzyl chloroformyl butyrate.
Further, the molar ratio of pyrene, chloroformyl butyrate compounds and Lewis acid is 1 (1-2) to 1-2, and the F-C acylation reaction is carried out for 4-24 hours at the temperature of 0-25 ℃.
Further, in the step S2, the intermediate 4-oxo-4-pyrene butyrate and hydrazine hydrate are subjected to the Huang Minlon reduction and ester hydrolysis reaction in a second organic solvent under the action of a base.
Further, the second organic solvent is one or more of diethylene glycol, triethylene glycol and polyethylene glycol.
Further, the base is an inorganic base, and the inorganic base is sodium hydroxide, potassium hydroxide, or a mixture thereof.
Further, the intermediate 4-oxo-4-pyrenebutyrate: hydrazine hydrate: the molar ratio of the alkali is 1 (1-4) to 1-4, and the reaction is performed at 150-200 ℃ for 3-10 h in the step S2.
The technical scheme of the invention at least has one of the following beneficial effects:
according to the preparation method of 1-pyrenebutyric acid provided by the embodiment of the invention, chloroformyl butyrate compounds are used for replacing succinic anhydride in the prior art to carry out F-C acylation to generate an intermediate 4-oxo-4-pyrenebutyrate, the intermediate 4-oxo-4-pyrenebutyrate can be purified by ethanol or methanol recrystallization, so that the complex operation that repeated acid-base washing is needed in the F-C acylation reaction process by using succinic anhydride is avoided, and the purification difficulty of the product is greatly reduced;
the operation is simple and convenient, and the production cost is reduced;
after the target product is obtained through the Huang Minlon reduction and ester hydrolysis reaction, the product can be purified through recrystallization, the purification process is simple, and the cost is low;
in addition, the whole reaction avoids the use of a highly toxic solvent nitrobenzene, has high yield, is suitable for industrial production, and has good application prospect.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention, are within the scope of the invention.
First, a method for preparing 1-pyrenebutanoic acid according to an embodiment of the present invention will be specifically described.
The preparation method of 1-pyrenebutyric acid according to the embodiment of the invention comprises the following steps:
step S1, carrying out F-C acylation reaction on pyrene and chloroformyl butyrate compounds to obtain an intermediate 4-oxo-4-pyrene butyrate.
That is, instead of succinic anhydride in the prior art, the preparation method of the invention uses chloroformyl butyrate compounds to perform F-C acylation reaction with pyrene to obtain an intermediate 4-oxo-4-pyrenebutyrate.
Specifically, the reaction is represented by the following formula (4):
in the reaction formula (4), (I) is a structural formula of pyrene, (II) is a structural formula of chloroformyl butyrate compounds used in the invention, and (III) is a structural formula of intermediate 4-oxo-4-pyrenebutyrate obtained after F-C acylation reaction in the invention.
Wherein, R can be methyl, ethyl, propyl, benzyl, etc. That is, in the step S1, the chloroformyl butyrate compound is one or more selected from the group consisting of methyl chloroformyl butyrate, ethyl chloroformyl butyrate, diisopropyl chloroformyl butyrate and benzyl chloroformyl butyrate. Correspondingly, the intermediate 4-oxo-4-pyrene butyrate can be one or more of 4-oxo-4-pyrene methyl butyrate, 4-oxo-4-pyrene ethyl butyrate, 4-oxo-4-pyrene propyl butyrate and 4-oxo-4-pyrene benzyl butyrate.
Specifically, in step S1, the F-C acylation reaction of pyrene with the chloroformyl butyrate based compound may occur in a first organic solvent in the presence of a Lewis acid. Under the action of Lewis acid, the method is favorable for promoting the reaction and improving the yield.
Wherein the Lewis acid can be one or more of aluminum trichloride, boron trifluoride, stannic chloride, ferric trichloride and zinc chloride.
The first organic solvent may be one or more of dichloromethane, dioxane, and tetrahydrofuran. The first organic solvent can fully dissolve the chloroformyl butyrate compounds, is beneficial to the purification of the intermediate 4-oxo-4-pyrenebutyrate, and has relatively low toxicity.
Furthermore, the molar ratio of the pyrene, the chloroformyl butyrate compounds and the Lewis acid is 1 (1-2) to (1-2), and preferably 1:1: 1.5. In addition, the F-C acylation reaction is carried out for 4-24 h at 0-25 ℃. By using a large amount of chloroformyl butyrate compounds and Lewis acid, the method is beneficial to promoting the reaction and improving the yield.
Specifically, the operation process may be, for example: fully dissolving chloroformyl butyrate compounds in any one of the first organic solvents, controlling the temperature of the solution to be 0-25 ℃, adding Lewis acid into the solution in batches until the solution is completely dissolved, further adding pyrene in batches, and reacting at room temperature until the pyrene is completely consumed after the pyrene is added to obtain an intermediate 4-oxo-4-pyrene butyrate.
Further, after the F-C acylation reaction is finished, the reaction liquid can be poured into ice water to separate out the intermediate 4-oxo-4-pyrene butyrate, after filtration, the filter cake is recrystallized by ethanol, and after filtration and drying, the purified intermediate 4-oxo-4-pyrene butyrate is obtained.
Step S2, enabling the intermediate 4-oxo-4-pyrenebutyric acid ester and hydrazine hydrate to undergo Huang Minlon reduction and ester hydrolysis reaction to obtain the 1-pyrenebutyric acid.
That is, after obtaining the intermediate 4-oxo-4-pyrenebutanoic acid ester, reduction and ester hydrolysis reaction should be carried out to obtain 1-pyrenebutanoic acid.
The reaction formula is shown as the following formula (5):
specifically, the intermediate 4-oxo-4-pyrenebutyrate and hydrazine hydrate can be subjected to the Huang Minlon reduction and ester hydrolysis reaction in a second organic solvent under the action of alkali.
The second organic solvent may be one or more of diethylene glycol, triethylene glycol, and polyethylene glycol, for example. The second organic solvent can well dissolve the intermediate 4-oxo-4-pyrenebutyrate and hydrazine hydrate, and has the advantages of low toxicity, good operability and simple product separation.
Preferably, the base is an inorganic base that is sodium hydroxide, potassium hydroxide, or a mixture thereof. The inorganic base has the advantages of low cost, easy obtaining and the like. In the present invention, the use of an inorganic base is advantageous in promoting the Huang Minlon reduction and the ester hydrolysis reaction by the action of the inorganic base.
Further, the intermediate 4-oxo-4-pyrenebutyrate: hydrazine hydrate: the molar ratio of the alkali is 1 (1-4) to (1-4), preferably 1:3: 3. In addition, in the step S2, the reaction is carried out for 3-10 h at 150-200 ℃ (preferably at 180 ℃).
Specifically, the reaction operation of step S2 may be, for example, as follows: dissolving the intermediate 4-oxo-4-pyrene butyrate, hydrazine hydrate and alkali in a second organic solvent, controlling the temperature of the solution to be about 150-200 ℃, stirring until the liquid phase monitors that the materials are completely consumed, and finishing the reaction.
Further, after the reaction is finished, the reaction solution can be introduced into a 25% glacial acetic acid aqueous solution under the ice-water bath condition, stirred, filtered, washed with water and drained, and then ethanol is recrystallized, filtered and dried to obtain the product.
The following examples are provided to further illustrate the preparation of 1-pyrenebutanoic acid in accordance with the present invention.
Example 1
(a) Synthesis of 4-oxo-4-pyrenebutanoic acid methyl ester
Methyl chloroformylbutyrate (22.6g, 0.15mol) and dichloromethane were added to a reaction flask, anhydrous aluminum trichloride (40g, 0.30mol) was added in portions at a controlled temperature of 0 ℃, then pyrene (30g, 0.15mol) was added in portions, and the reaction was carried out at room temperature until the pyrene was consumed. The reaction solution was poured into ice water to precipitate the product, and the filter cake was recrystallized from ethanol, filtered and dried to give a yellow powder (35g, yield 73%).
The results of nuclear magnetic testing of the product are as follows:
1H NMR(400MHz,DMSO):δ=2.44-2.50(m,2H,CH2),2.94-2.98(m,2H,CH2),3.67(s,4H,2CH2),7.71-8.45(m,9H,ArH)。
(b) synthesis of 1-pyrenebutanoic acid
4-oxo-4-pyrenebutyric acid methyl ester (31.6g, 0.1mol), diethylene glycol, hydrazine hydrate (18.9g, 0.3mol) and potassium hydroxide (17g, 0.3mol) were added to a reaction flask, and the reaction was terminated by heating and stirring at 180 ℃ until the liquid phase was monitored and the material was consumed. The reaction mixture was slowly poured into a 25% aqueous solution of glacial acetic acid in an ice-water bath, stirred, filtered, washed with water and drained, recrystallized from ethanol, filtered and dried to give a yellow powder (22g, yield 70%). The melting point was 184.9-185.6 deg.C, and the literature reference 184-186 deg.C.
The results of nuclear magnetic testing of the product are as follows:
1H NMR(400MHz,DMSO):δ=1.90-1.94(m,2H,CH2),2.22-2.26(m,2H,CH2),2.99-3.02(m,2H,CH2),7.68-8.12(m,9H,ArH),11.00(s,1H,COOH)。
example 2
(a) Synthesis of 4-oxo-4-pyrenebutanoic acid ethyl ester
Ethyl chloroformylbutyrate (24.7g, 0.15mol) and dichloroethane were charged into a reaction flask, anhydrous aluminum trichloride (40g, 0.30mol) was added in portions at a controlled temperature of 0 ℃, then pyrene (30g, 0.15mol) was added in portions, and the reaction was carried out at room temperature until the pyrene was consumed. The reaction solution was poured into ice water to precipitate the product, and the filter cake was recrystallized from ethanol, filtered and dried to give a yellow powder (34.7g, yield 70%).
The results of nuclear magnetic testing of the product are as follows:
1H NMR(400MHz,DMSO):δ=1.29-1.33(t,3H,CH3),2.44-2.50(m,2H,CH2),2.94-2.98(m,2H,CH2),4.10-4.14(q,2H,CH2),7.71-8.45(m,9H,ArH)。
(b) synthesis of 1-pyrenebutanoic acid
Adding 4-oxo-4-pyrenebutyric acid ethyl ester (33.1g, 0.1mol), diethylene glycol, hydrazine hydrate (18.9g, 0.3mol) and potassium hydroxide (17g, 0.3mol) into a reaction flask, heating and stirring at 180 ℃ until the liquid phase is monitored and the materials are completely consumed, and finishing the reaction. The reaction mixture was slowly poured into a 25% aqueous solution of glacial acetic acid in an ice-water bath, stirred, filtered, washed with water and drained, recrystallized from ethanol, filtered and dried to obtain a yellow powder (21.1g, yield 73%). The melting point is 185.3-185.7 ℃.
Example 3
(a) Synthesis of 4-oxo-4-pyrenebutyric acid benzyl ester
Benzyl chloroformylbutyrate (34g, 0.15mol) and dichloromethane were added to a reaction flask, anhydrous aluminum trichloride (40g, 0.30mol) was added in portions at a controlled temperature of 0 ℃, then pyrene (30g, 0.15mol) was added in portions, and the reaction was carried out at room temperature until pyrene was consumed. The reaction solution was poured into ice water to precipitate the product, and the filter cake was recrystallized from ethanol, filtered and dried to give a yellow powder (29.4g, yield 68%).
The results of nuclear magnetic testing of the product are as follows:
1H NMR(400MHz,DMSO):δ=2.42-2.46(m,2H,CH2),2.94-2.98(m,2H,CH2),5.32(s,2H,CH2),7.16-7.20(m,5H,ArH),7.71-8.45(m,9H,ArH)。
(b) synthesis of 1-pyrenebutanoic acid
To a reaction flask, 4-oxo-4-pyrenebutyric acid benzyl ester (39.2g, 0.1mol), diethylene glycol, hydrazine hydrate (18.9g, 0.3mol) and potassium hydroxide (17g, 0.3mol) were added, and the reaction was terminated by heating and stirring at 180 ℃ until the liquid phase was monitored and the material was consumed. The reaction mixture was slowly poured into a 25% aqueous solution of glacial acetic acid in an ice-water bath, stirred, filtered, washed with water and drained, recrystallized from ethanol, filtered and dried to give a yellow powder (17.9g, yield 62%). The melting point is 184.6-185.3 ℃.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of 1-pyrenebutyric acid is characterized by comprising the following steps:
step S1, carrying out F-C acylation reaction on pyrene and chloroformyl butyrate compounds to obtain an intermediate 4-oxo-4-pyrene butyrate;
step S2, enabling the intermediate 4-oxo-4-pyrenebutyric acid ester and hydrazine hydrate to undergo Huang Minlon reduction and ester hydrolysis reaction to obtain the 1-pyrenebutyric acid.
2. The method of claim 1, wherein in step S1, the F-C acylation reaction between pyrene and the chloroformyl butyrate compound is performed in a first organic solvent in the presence of a Lewis acid.
3. The method of claim 2, wherein the Lewis acid is one or more of aluminum trichloride, boron trifluoride, tin tetrachloride, ferric trichloride, and zinc chloride.
4. The method of claim 2, wherein the first organic solvent is one or more of dichloromethane, dioxane, and tetrahydrofuran.
5. The method according to claim 2, wherein in step S1, the chloroformylbutyrate compound is one or more selected from the group consisting of methyl chloroformylbutyrate, ethyl chloroformylbutyrate, diisopropyl chloroformylbutyrate and benzyl chloroformylbutyrate.
6. The method of claim 2, wherein the molar ratio of pyrene, chloroformyl butyrate and Lewis acid is 1 (1-2) to (1-2), and the F-C acylation reaction is carried out at 0-25 ℃ for 4-24 h.
7. The method of claim 1, wherein in step S2, the Huang Minlon reduction and ester hydrolysis reaction of the intermediate 4-oxo-4-pyrene butyrate ester and hydrazine hydrate are performed in a second organic solvent under the action of a base.
8. The method of claim 7, wherein the second organic solvent is one or more of diethylene glycol, triethylene glycol, and polyethylene glycol.
9. The method of claim 7, wherein the base is an inorganic base, and wherein the inorganic base is sodium hydroxide, potassium hydroxide, or a mixture thereof.
10. The method of claim 7, wherein the intermediate 4-oxo-4-pyrene butyrate: hydrazine hydrate: the molar ratio of the alkali is 1 (1-4) to 1-4, and the reaction is performed at 150-200 ℃ for 3-10 h in the step S2.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102070596A (en) * | 2011-01-22 | 2011-05-25 | 浙江大学 | Preparation method for dihydrosafrole |
CN104447376A (en) * | 2014-11-05 | 2015-03-25 | 平湖优康药物研发有限公司 | Synthesis process of antineoplastic drug chlorambucil |
CN105732331A (en) * | 2016-03-17 | 2016-07-06 | 宇瑞(上海)化学有限公司 | Synthesis method of 1-pyrenol and intermediates thereof |
CN106905175A (en) * | 2017-03-16 | 2017-06-30 | 厦门市瑞思医药科技有限公司 | A kind of preparation method of p-aminophenyl butyric acid |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102070596A (en) * | 2011-01-22 | 2011-05-25 | 浙江大学 | Preparation method for dihydrosafrole |
CN104447376A (en) * | 2014-11-05 | 2015-03-25 | 平湖优康药物研发有限公司 | Synthesis process of antineoplastic drug chlorambucil |
CN105732331A (en) * | 2016-03-17 | 2016-07-06 | 宇瑞(上海)化学有限公司 | Synthesis method of 1-pyrenol and intermediates thereof |
CN106905175A (en) * | 2017-03-16 | 2017-06-30 | 厦门市瑞思医药科技有限公司 | A kind of preparation method of p-aminophenyl butyric acid |
Non-Patent Citations (1)
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宁慧龙等: ""芘核心第一代树状聚合物的合成与性能研究"" * |
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