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Preparation method of 1-pyrene butyric acid

A technology of pyrene butyric acid and pyrene butyrate, which is applied in the field of preparation of 1-pyrene butyric acid, can solve the problems of difficult operation, solvent nitrobenzene toxicity, unsuitability for industrial production, etc., achieve simple purification process and reduce purification difficulty , the effect of good application prospects

Pending Publication Date: 2021-05-28
SUZHOU HIGHFINE BIOTECH
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Problems solved by technology

[0007] 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; the reaction system in the second step is a bromine / benzene / triphenylphosphine system, and the solvent is relatively toxic; the third step Reduction with tri-n-butyltin chloride, and finally hydrolysis, the whole process has many steps, and the operation is not easy to realize process
[0015] However, in this method, the impurities produced by F-C acylation with succinic anhydride are difficult to remove, and repeated acid-base washings are required many times; and the solvent nitrobenzene is relatively toxic, and the filtration is also very clogged, so it is difficult to achieve a scale-up production, making the method unsuitable for industrial production

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  • Preparation method of 1-pyrene butyric acid
  • Preparation method of 1-pyrene butyric acid
  • Preparation method of 1-pyrene butyric acid

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preparation example Construction

[0037] The preparation method of 1-pyrene butyric acid according to the embodiment of the present invention comprises the following steps:

[0038] Step S1, F-C acylation of pyrene with chloroformyl butyrate compounds to obtain intermediate 4-oxo-4-pyrene butyrate.

[0039] That is to say, instead of succinic anhydride in the prior art, the preparation method of the present invention uses chloroformyl butyrate compounds to undergo F-C acylation reaction with pyrene to obtain the intermediate 4-oxo-4-pyrene Ester.

[0040] Specifically, the reaction is shown in the following formula (4):

[0041]

[0042] In the above reaction formula (4), (I) is the structural formula of pyrene, (II) is the structural formula of the chloroformyl butyrate compound used in the present invention, and (III) is obtained after the F-C acylation reaction in the present invention The structural formula of the intermediate 4-oxo-4-pyrene butyrate.

[0043] Wherein, R may be methyl, ethyl, propyl,...

Embodiment 1

[0062] (a) Synthesis of 4-oxo-4-pyrene butyric acid methyl ester

[0063] Add methyl chloroformylbutyrate (22.6g, 0.15mol) and methylene chloride to the reaction flask, add anhydrous aluminum chloride (40g, 0.30mol) in batches under the condition of 0°C under temperature control, and then Pyrene (30 g, 0.15 mol) was added in batches and reacted 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 with ethanol, filtered and dried to obtain a yellow powder (35 g, yield 73%).

[0064] The nuclear magnetic test result of product is as follows:

[0065] 1 H NMR (400MHz, DMSO): δ=2.44-2.50(m, 2H, CH 2 ),2.94-2.98(m,2H,CH 2 ),3.67(s,4H,2CH 2 ), 7.71-8.45 (m, 9H, ArH).

[0066] (b) Synthesis of 1-pyrenebutyric acid

[0067] Add 4-oxo-4-pyrene butyric acid methyl ester (31.6g, 0.1mol), diethylene glycol, hydrazine hydrate (18.9g, 0.3mol) and potassium hydroxide (17g, ...

Embodiment 2

[0071] (a) Synthesis of ethyl 4-oxo-4-pyrene butyrate

[0072] Add ethyl chloroformylbutyrate (24.7g, 0.15mol) and ethylene dichloride in the reaction flask, control the temperature and add anhydrous aluminum trichloride (40g, 0.30mol) in batches under the condition of 0°C, and then Pyrene (30 g, 0.15 mol) was added in batches and reacted 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 with ethanol, filtered and dried to obtain a yellow powder (34.7 g, yield 70%).

[0073] The nuclear magnetic test result of product is as follows:

[0074] 1 H NMR (400MHz, DMSO): δ=1.29-1.33(t,3H,CH 3 ),2.44-2.50(m,2H,CH 2 ),2.94-2.98(m,2H,CH 2 ),4.10-4.14(q,2H,CH 2 ), 7.71-8.45 (m, 9H, ArH).

[0075] (b) Synthesis of 1-pyrenebutyric acid

[0076] Add ethyl 4-oxo-4-pyrenebutyrate (33.1 g, 0.1 mol), diethylene glycol, hydrazine hydrate (18.9 g, 0.3 mol) and potassium hyd...

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Abstract

The invention provides a preparation method of 1-pyrene butyric acid, which comprises the following steps: step S1, pyrene and a chloroformyl butyrate compound are subjected to F-C acylation reaction to obtain an intermediate 4-oxo-4-pyrene butyrate; step S2, the intermediate 4-oxo-4-pyrene butyrate and hydrazine hydrate are subjected to Huang Min-long reduction and ester hydrolysis reaction, so as to obtain the 1-pyrene butyric acid. According to the preparation method of the 1-pyrene butyric acid provided by the embodiment of the invention, the chloroformyl butyrate compound is used for replacing succinic anhydride in the prior art for F-C acylation to generate the intermediate 4-oxo-4-pyrene butyrate, and the intermediate 4-oxo-4-pyrene butyrate can be purified by recrystallization of ethanol or methanol, the tedious operation of repeatedly washing with acid and alkali for many times in the process of carrying out F-C acylation reaction by using succinic anhydride is avoided, and the purification difficulty of the product is greatly reduced.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to a preparation method of 1-pyrene butyric acid. Background technique [0002] 1-pyrenebutyric acid is a lipophilic red fluorescent dye, mainly used as a fluorescent probe. Aromatic pyrene molecules are highly symmetrical, have 16 electrons and do not follow Hacker's 4n+2 rule, and the interesting electronic properties of pyrene can be used to study the preparation of chemical sensors. In addition, because the pyrene ring can be anchored on the lipid membrane and form double strands with complementary single-stranded nucleotides, this property can be used in the field of chip technology and diagnosis. Therefore, 1-pyrenebutyric acid has a wide range of application prospects, such as in optoelectronic materials, in the biological field, it can characterize cyclodextrin-based polyrotaxane thin films to detect nucleic acids and polyamines; it can also immobilize proteins, a...

Claims

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Application Information

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IPC IPC(8): C07C51/09C07C51/43C07C57/40C07C67/343C07C69/738
CPCC07C51/09C07C51/43C07C67/343C07C2603/50C07C69/738C07C57/40Y02P20/55
Inventor 蒋兆芹杨晨
Owner SUZHOU HIGHFINE BIOTECH
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