CN109433260B - Application of catalyst in synthesis of cyanomethyl carboxylate - Google Patents

Application of catalyst in synthesis of cyanomethyl carboxylate Download PDF

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CN109433260B
CN109433260B CN201811420593.1A CN201811420593A CN109433260B CN 109433260 B CN109433260 B CN 109433260B CN 201811420593 A CN201811420593 A CN 201811420593A CN 109433260 B CN109433260 B CN 109433260B
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孙宏枚
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
    • B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/49—Esterification or transesterification
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron

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Abstract

The invention disclosesThe use of a catalyst of the formula [ ((II) [) ]tBuNCH2CH2NtBu)CH][FeBr4]The ionic iron (III) complex containing 1, 3-di-tert-butyl imidazoline cation is used as a catalyst, di-tert-butyl peroxide is used as an oxidant, and the cyanomethyl carboxylate is synthesized through the oxidative coupling reaction of carboxylic acid and acetonitrile. Suitable carboxylic acid substrates for use in the present invention relate to aliphatic, aromatic and heterocyclic carboxylic acids. This is the first example of the production of cyanomethyl carboxylate by oxidative coupling of carboxylic acid and acetonitrile in the presence of an iron-based catalyst.

Description

Application of catalyst in synthesis of cyanomethyl carboxylate
The invention relates to a method for synthesizing cyanomethyl carboxylate, a divisional application with application number of 2017103498421 and application date of 2017, 5 and 17, and belongs to the technical field of product application.
Technical Field
The invention belongs to the technical field of preparation of organic compounds, and particularly relates to a preparation method of cyanomethyl carboxylate, and further relates to application of a catalyst in synthesis of cyanomethyl carboxylate.
Background
The cyanomethyl carboxylate exists in a plurality of natural products and drug molecules and is widely applied to organic synthesis, the traditional method for synthesizing the compound needs to use a pre-functionalized halide, such as chloro-acetonitrile and the like, the method is not atom economical, and the halide with chemical pollution is often discharged, so that the development of a new method for synthesizing the cyanomethyl carboxylate has strong practical application value.
In recent years, direct esterification of carbon-hydrogen bonds has become a new method for synthesizing carboxylic esters. In the continuous report, direct esterification reaction of carbon-hydrogen bonds at ortho-position, benzyl-position and allyl-position of oxygen atom is reported, while no report is found on the synthesis of cyanomethyl carboxylate directly by esterification reaction of carbon-hydrogen bonds at ortho-position of nitrile group, and the report on novel method for synthesizing cyanomethyl carboxylate compound is less. The prior reaction realizes direct esterification by decarboxylation of alpha-cyanoacetic acid, but the method is not good in atom economy and has larger catalyst dosage. Therefore, the development of a relatively more efficient green synthetic method, namely the direct esterification reaction of carboxylic acid and acetonitrile, is extremely innovative and valuable in application.
In the past decade, iron-based catalysts have been rapidly developed due to the advantages of low price, easy availability, low toxicity or no toxicity, good biocompatibility and the like, but there are only two reports on the carbon-hydrogen bond functionalization reaction in acetonitrile catalyzed by iron-based catalysts, namely, a series of oxidative indole compounds, and the oxidative coupling reaction of acetonitrile and 1, 3-dicarbonyl compounds are constructed through the bifunctional reaction of acetonitrile and aryl acrylamide. So far, no literature report relating to the esterification reaction of carbon-hydrogen bonds of acetonitrile catalyzed by an iron-based catalyst is found. Therefore, the implementation of the esterification reaction of carboxylic acid and acetonitrile catalyzed by an iron-based catalyst to construct cyanomethyl carboxylate is a creative achievement with application prospect.
Disclosure of Invention
The object of the present invention is to provide a novel process for the synthesis of cyanomethyl carboxylates of the formula [ (II) ((III))tBuNCH2CH2NtBu)CH][FeBr4]The ionic iron (III) complex containing 1, 3-di-tert-butyl imidazoline cation is used as a catalyst, di-tert-butyl peroxide is used as an oxidant, and the corresponding cyanomethyl carboxylate is synthesized through the oxidative coupling reaction of carboxylic acid and acetonitrile. The catalyst is an iron (III) complex which is simple and easy to obtain, stable in air and has a definite structure.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a method for synthesizing carboxylic acid cyanomethyl ester takes carboxylic acid compound and acetonitrile as raw materials, and the carboxylic acid cyanomethyl ester is obtained by reaction in the presence of catalyst and organic oxidant;
the chemical structural formula of the catalyst is as follows:
Figure 230628DEST_PATH_IMAGE001
。
in the technical scheme, the molar ratio of the catalyst to the carboxylic acid compound to the organic oxidant is (0.08-0.12) to 1 to (2-3); preferably 0.10: 1: 2.5
In the technical scheme, the reaction temperature is 90-130 ℃, and the reaction time is 15-40 hours; the preferable reaction temperature is 100-120 ℃ and the time is 20-30 hours.
In the technical scheme, after the reaction is finished, the reaction product is cooled to room temperature, and the product is purified by column chromatography, for example, a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 20 is used as a developing solvent to obtain the cyanomethyl carboxylate.
In the above technical solution, the carboxylic acid compound includes aryl carboxylic acid compound, substituted aryl carboxylic acid compound, and heteroaryl carboxylic acid compound, such as benzoic acid, 4-methoxybenzoic acid, 4-methylbenzoic acid, 1-naphthoic acid, 2-thiophenecarboxylic acid, 4-chlorobenzoic acid, 4-bromobenzoic acid, 4-nitrobenzoic acid, 4-cyanobenzoic acid, cinnamic acid, phenylacetic acid, and phenylpropionic acid.
In the above technical solution, the organic oxidant is an organic peroxide, such as di-tert-butyl peroxide.
The invention also discloses an application of the catalyst in catalyzing the reaction of a carboxylic acid compound and acetonitrile and an application of the catalyst in synthesizing cyanomethyl carboxylate; the chemical structural formula of the catalyst is as follows:
Figure 521932DEST_PATH_IMAGE001
。
the reaction process of the present invention can be represented as follows:
Figure 523387DEST_PATH_IMAGE002
due to the application of the technical scheme, the invention has the following advantages:
1. the invention takes the iron (III) complex as the catalyst for the first time, and realizes the esterification reaction of carboxylic acid and acetonitrile. The method is the esterification reaction of carbon-hydrogen bonds in acetonitrile, and provides a new method for synthesizing carboxylic acid cyanomethyl ester compounds. Compared with the existing synthesis method, the method has better atom economy, reduces the chemical pollution of halide and the emission of carbon dioxide, and accords with the green chemical concept.
2. The iron (III) catalyst adopted by the invention has single component, definite structure, simple synthesis and stable existence in the air, shows good catalytic activity and is beneficial to large-scale industrial synthesis application.
Detailed Description
The invention is further described below with reference to the following examples:
the first embodiment is as follows: containing 1, 3-di-tert-butyl imidazoline cation (molecular formula [ () (tBuNCH2CH2NtBu)CH][FeBr4]) Synthesis of ionic iron complexes of
1, 3-di-tert-butylimidazoline chloride (0.22 g, 1.0 mmol) and NaBr (0.15 g, 1.5 mmol) were added to a tetrahydrofuran solution of iron tribromide (0.29 g, 1.0 mmol) in this order, reacted at 60 ℃ for 24 hours, the solvent was removed in vacuo, washed with hexane, drained, extracted with tetrahydrofuran, centrifuged to remove the supernatant, and recrystallized by adding hexane to the supernatant to precipitate reddish brown crystals at room temperature in 90% yield.
The chemical structural formula is as follows:
Figure 361767DEST_PATH_IMAGE001
elemental analysis of the product resulted in the following:
elemental analysis
C：（%） H：（%） N：（%）
Theoretical value 23.64 4.15 5.01
Actual value 23.88 4.31 5.34
The complex [ () ]tBuNCH2CH2NtBu)CH][FeBr4]In the form of ion pairs, in which [ FeBr ]4]-It was characterized by Raman spectroscopy and was found to be at 204 cm-1Has characteristic peaks, which are consistent with the reports in the literature.
Cationic moiety of the complex [ ((iii))tBuNCH2CH2NtBu)CH]+The compound is characterized by mass spectrum, a molecular ion peak is found at 183.1861, theoretically, the molecular ion peak is 183.1861, and the actual measurement is consistent with the theory, so that the obtained compound is proved to be the target compound.
Example two: [(tBuNCH2CH2NtBu)CH][FeBr4]Catalyzed esterification of benzoic acid with acetonitrile
Benzoic acid (61.1 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (232 μ l, 1.25 mmol), acetonitrile (10 ml) were added sequentially to a reaction flask, reacted at 110 ℃ for 24 hours, cooled to room temperature after the reaction was completed, and the product was purified by column chromatography (using a mixed solvent of ethyl acetate/petroleum ether in a volume ratio of 1: 20 as a developing solvent), with a yield of 80%.
Benzoic acid (61.1 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (186. mu.l, 1 mmol), acetonitrile (10 ml) were added sequentially to the reaction flask, reacted at 110 ℃ for 24 hours, cooled to room temperature after the reaction was completed, and the product was purified by column chromatography (using a mixed solvent of ethyl acetate/petroleum ether in a volume ratio of 1: 20 as a developing solvent), with a yield of 78%.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3, TMS): 8.13-8.07 (m, 2H), 7.67 (t, 1H), 7.52 (t, 2H), 5.01 (s, 2H)。
example three: [(tBuNCH2CH2NtBu)CH][FeBr4]Catalyzed esterification of 4-methoxybenzoic acid with acetonitrile
4-methoxybenzoic acid (76.1 mg, 0.5 mmol), a catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (232. mu.l, 1.25 mmol) and acetonitrile (10 ml) were sequentially added to a reaction flask, reacted at 100 ℃ for 30 hours, cooled to room temperature after the reaction was completed, and the product was purified by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 5 as a developing solvent), with a yield of 85%.
4-methoxybenzoic acid (76.1 mg, 0.5 mmol), a catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (278. mu.l, 1.5 mmol) and acetonitrile (10 ml) were sequentially added to a reaction flask, reacted at 100 ℃ for 30 hours, cooled to room temperature after the reaction was completed, and the product was purified by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 5 as a developing solvent), with a yield of 84%.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3, TMS): 8.02 (d, 2H), 6.96 (d, 2H), 4.96 (s, 2H), 3.89 (s, 3H)。
example four: [(tBuNCH2CH2NtBu)CH][FeBr4]Catalyzed esterification of 4-methylbenzoic acid with acetonitrile
4-methylbenzoic acid (68.1 mg, 0.5 mmol), a catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (232. mu.l, 1.25 mmol) and acetonitrile (10 ml) were sequentially added to a reaction flask, reacted at 120 ℃ for 20 hours, cooled to room temperature after the reaction was completed, and the product was purified by column chromatography (using a mixed solvent of ethyl acetate/petroleum ether in a volume ratio of 1: 20 as a developing solvent) at a yield of 83%.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3, TMS): 7.99 (d, 2H), 7.32 (d, 2H), 4.99 (s, 2H), 2.47 (s, 3H)。
example five: [(tBuNCH2CH2NtBu)CH][FeBr4]Catalyzed esterification of 1-naphthoic acid with acetonitrile
1-naphthoic acid (86.1 mg, 0.5 mmol), a catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (232. mu.l, 1.25 mmol), and acetonitrile (10 ml) were sequentially added to a reaction flask, reacted at 110 ℃ for 28 hours, cooled to room temperature after the reaction was completed, and the product was purified by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent), with a yield of 62%.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3, TMS): 8.97 (d, 1H), 8.30 (dd, 1H), 8.11 (t, 1H), 7.93 (d, 1H), 7.72-7.66 (m, 1H), 7.58 (ddd, 2H), 5.06 (s, 2H)。
example six: [(tBuNCH2CH2NtBu)CH][FeBr4]Catalyzed esterification of 2-thiophenecarboxylic acid with acetonitrile
2-thiophenecarboxylic acid (64.1 mg, 0.5 mmol), a catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (232. mu.l, 1.25 mmol) and acetonitrile (10 ml) were sequentially added to a reaction flask, reacted at 110 ℃ for 24 hours, cooled to room temperature after the reaction was completed, and the product was purified by column chromatography (using a mixed solvent of ethyl acetate/petroleum ether in a volume ratio of 1: 20 as a developing solvent) at a yield of 42%.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3, TMS): 7.94 (dd, 1H), 7.72 (dd, 1.2 Hz, 1H), 7.21 (dd, 1H), 4.99 (s, 2H)。
example seven: [(tBuNCH2CH2NtBu)CH][FeBr4]Catalyzed esterification of 4-chlorobenzoic acid with acetonitrile
4-chlorobenzoic acid (78.3 mg, 0.5 mmol), a catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (232. mu.l, 1.25 mmol) and acetonitrile (10 ml) are sequentially added into a reaction flask, the mixture is reacted at 110 ℃ for 20 hours, the reaction product is cooled to room temperature after the reaction is finished, and the product is purified by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent), and the yield is 80%.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3, TMS): 8.05-8.01 (m, 2H), 7.52-7.47 (m, 2H), 5.01 (s, 2H)。
example eight: [(tBuNCH2CH2NtBu)CH][FeBr4]Catalyzed esterification of 4-bromobenzoic acid with acetonitrile
4-bromobenzoic acid (100.5 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (232. mu.l, 1.25 mmol), acetonitrile (10 ml) were added in this order to a reaction flask, reacted at 110 ℃ for 24 hours, cooled to room temperature after the reaction was completed, and the product was purified by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent) at a yield of 76%.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3, TMS): 7.94 (d, 2H), 7.66 (d, 2H), 5.01 (s, 2H)。
example nine: [(tBuNCH2CH2NtBu)CH][FeBr4]Catalyzed esterification of 4-nitrobenzoic acid with acetonitrile
4-nitrobenzoic acid (83.6 mg, 0.5 mmol), a catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (232 microliters, 1.25 mmol) and acetonitrile (10 ml) are sequentially added into a reaction bottle, the reaction is carried out for 30 hours at 120 ℃, after the reaction is finished, the reaction is cooled to room temperature, and a product is purified by column chromatography (a mixed solvent with a volume ratio of ethyl acetate to petroleum ether of 1: 5 is used as a developing agent), so that the yield is 54%.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3, TMS): 8.36 (d, 2H), 8.27 (d,2H), 5.05 (s, 2H)。
example ten: [(tBuNCH2CH2NtBu)CH][FeBr4]Catalyzed esterification of 4-cyanobenzoic acid with acetonitrile
4-cyanobenzoic acid (73.6 mg, 0.5 mmol), a catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (232. mu.l, 1.25 mmol) and acetonitrile (10 ml) were sequentially added to a reaction flask, reacted at 110 ℃ for 28 hours, cooled to room temperature after the reaction was completed, and the product was purified by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent) at a yield of 55%.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3, TMS): 8.21 (d, J = 8.5 Hz, 2H), 7.84 (d, J = 8.5 Hz, 2H), 5.05 (d, J = 5.9 Hz, 2H)。
example eleven: [(tBuNCH2CH2NtBu)CH][FeBr4]Catalyzed esterification of cinnamic acid with acetonitrile
Cinnamic acid (74.1 mg, 0.5 mmol), catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (232. mu.l, 1.25 mmol), acetonitrile (10 ml) were added to the reaction flask in this order, reacted at 110 ℃ for 24 hours, cooled to room temperature after the reaction was complete, and the product was purified by column chromatography (using a mixed solvent of ethyl acetate/petroleum ether in a volume ratio of 1: 10 as a developing solvent) at a yield of 67%.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3, TMS): 7.78 (d, 1H), 7.54-7.50 (m, 2H), 7.45-7.37 (m, 3H), 6.44 (d, 1H), 4.84 (s, 2H)。
example twelve: [(tBuNCH2CH2NtBu)CH][FeBr4]Catalyzed esterification of phenylacetic acid with acetonitrile
Phenylacetic acid (68.0 mg, 0.5 mmol), a catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (232. mu.l, 1.25 mmol), and acetonitrile (10 ml) were sequentially added to a reaction flask, reacted at 110 ℃ for 24 hours, cooled to room temperature after the reaction was completed, and the product was purified by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent), with a yield of 60%.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3, TMS): 7.31-7.28 (m, 2H), 7.23-7.18 (m, 3H), 5.10 (s, 2H), 3.72 (t, 2H)。
example thirteen: [(tBuNCH2CH2NtBu)CH][FeBr4]Catalyzed esterification of phenylpropionic acid with acetonitrile
Phenylpropionic acid (75.1 mg, 0.5 mmol), a catalyst (28 mg, 0.05 mmol), di-tert-butyl peroxide (232 μ l, 1.25 mmol), and acetonitrile (10 ml) were sequentially added to a reaction flask, reacted at 110 ℃ for 24 hours, cooled to room temperature after the reaction was completed, and the product was purified by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent), with a yield of 60%.
The product was dissolved in CDCl3Medium (about 0.4 mL), seal tube, room temperatureCharacterization was determined on a Unity Inova-400 NMR instrument:1H NMR (400 MHz, CDCl3, TMS): 7.31-7.28 (m, 2H), 7.23-7.18 (m, 3H), 4.67 (s, 2H), 2.97 (t, 2H), 2.72 (t, 2H）。

Claims (2)

1. the use of a catalyst for the synthesis of cyanomethyl carboxylates; the chemical structural formula of the catalyst is as follows:
Figure 457039DEST_PATH_IMAGE001
when synthesizing the cyanomethyl carboxylate, taking a carboxylic acid compound and acetonitrile as raw materials, and carrying out the synthesis in the presence of an organic oxidant; the molar ratio of the catalyst to the carboxylic acid compound to the organic oxidant is (0.08-0.12) to 1 to (2-3);
the carboxylic acid compound is benzoic acid, 4-methoxybenzoic acid, 4-methylbenzoic acid, 1-naphthoic acid, 2-thiophenecarboxylic acid, 4-chlorobenzoic acid, 4-bromobenzoic acid, 4-nitrobenzoic acid, 4-cyanobenzoic acid, cinnamic acid, phenylacetic acid or phenylpropionic acid; the organic oxidant is di-tert-butyl peroxide;
when the cyanomethyl carboxylate is synthesized, the reaction temperature is 90-130 ℃, and the reaction time is 15-40 hours.
2. The use of the catalyst according to claim 1 for the synthesis of cyanomethyl carboxylate, wherein the cyanomethyl carboxylate is synthesized by cooling to room temperature after completion of the reaction and purifying the product by column chromatography to obtain cyanomethyl carboxylate.
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