CN116239461B - Synthesis process of a benzoic acid compound - Google Patents
Synthesis process of a benzoic acid compoundInfo
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- CN116239461B CN116239461B CN202310007344.4A CN202310007344A CN116239461B CN 116239461 B CN116239461 B CN 116239461B CN 202310007344 A CN202310007344 A CN 202310007344A CN 116239461 B CN116239461 B CN 116239461B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
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- C—CHEMISTRY; METALLURGY
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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Abstract
The application relates to the technical field of organic synthesis, in particular to a synthesis process of a benzoic acid compound. The synthesis process of benzoic acid compound includes the steps of adding hydrogen peroxide into mixed solution of compound of the formula I and water, adding povidone iodine at-5-0 deg.c to perform oxidation reaction to obtain compound of the formula II. Because the reaction system does not contain cobalt, manganese and other catalysts and contains heavy metals, the catalyst can be synthesized through one-step reaction. Therefore, the synthesis process of the application improves the environmental protection performance of synthesizing the benzoic acid compounds, and has the advantages of high efficiency, cleanness and wide applicability.
Description
Technical Field
The application relates to the technical field of organic synthesis, in particular to a synthesis process of a benzoic acid compound.
Background
Benzoic acid is an aromatic acid organic compound which can be used for synthesizing medicines, dyes, plasticizers, mordants, bactericides, fragrances and the like, so that the benzoic acid is also a common pharmaceutical and chemical intermediate.
At present, the synthesis method of benzoic acid is mainly prepared by adopting benzaldehyde, benzyl alcohol and toluene to perform oxidation reaction under the conditions of oxygen, cobalt, manganese and other catalysts. However, the cobalt, manganese and other catalysts contain heavy metals, which are not only toxic but also cause environmental pollution. Therefore, there is a need for an environment-friendly method for synthesizing benzoic acid.
Disclosure of Invention
In order to improve the environmental protection performance of synthesizing benzoic acid, the application provides a synthesis process of a benzoic acid compound.
The application provides a synthesis process of a benzoic acid compound, which adopts the following technical scheme:
A synthesis process of a benzoic acid compound comprises the following preparation steps:
Adding hydrogen peroxide into a mixed solution of a compound of the formula I and water, and adding povidone iodine at a temperature of between-5 and 0 ℃ to perform oxidation reaction to obtain a compound of the formula II;
the reaction formula of the preparation steps is as follows:
;
R is one or more of-H, -CH 3,-Br,-F,-Cl,-OCH3,-NO2,-CF3, -i-PrO, -t-Bu.
By adopting the technical scheme, the benzyl position of benzyl alcohol is a more active reaction site, water-soluble povidone iodine is adopted to slowly release iodine simple substance in a reaction system, the iodine simple substance reacts with hydrogen peroxide to form hydroxyl radical, the hydroxyl radical can react with the benzyl position of benzyl alcohol to obtain a benzyl radical intermediate, and the benzyl radical intermediate further reacts under the oxidizing effect of the hydrogen peroxide, so that hydroxyl is introduced to form carboxylic acid functional groups, and the benzoic acid compound of the formula II is rapidly synthesized. Because the reaction system does not contain cobalt, manganese and other catalysts and contains heavy metals, the catalyst can be synthesized through one-step reaction. Therefore, the synthesis process of the benzoic acid compound has the advantages of high efficiency, cleanliness and wide applicability.
Preferably, the feeding amount of the compound shown in the formula I, hydrogen peroxide and povidone-iodine is 0.1mol (0.4-0.6 mol) and 0.05-0.3 mol.
Preferably, the dosage of the compound of formula I, hydrogen peroxide and povidone-iodine is 0.1mol:0.5mol:0.1mol.
By adopting the technical scheme, the raw materials are fed according to the feeding ratio, the yield and purity of the obtained benzoic acid compound are higher, and the residual unreacted raw materials are less.
Preferably, the reaction temperature of the oxidation reaction is 70-100 ℃ and the reaction time is 6-12h.
Preferably, the reaction temperature of the oxidation reaction is 90 ℃ and the reaction time is 6h.
By adopting the technical scheme, the raw materials are subjected to oxidation reaction at the temperature and in the time, so that the reaction efficiency of each raw material is higher, and the yield of the obtained benzoic acid compounds is improved.
Preferably, the synthesis process of the benzoic acid compound comprises the following preparation steps:
adding hydrogen peroxide into a mixed solution of a compound of formula I and water, and adding povidone iodine at a temperature of between-5 and 0 ℃ for oxidation reaction, wherein the reaction temperature is between 70 and 100 ℃ and the reaction time is between 6 and 12 hours, so as to obtain a reaction solution containing the compound of formula II;
The reaction liquid is filtered by diatomite, a filtrate is collected, a saturated sodium bicarbonate aqueous solution is added into the filtrate to obtain a filtrate containing the saturated sodium bicarbonate aqueous solution, then the filtrate containing the saturated sodium bicarbonate aqueous solution is extracted by an organic solvent, a water phase is collected, the pH value of the water phase is regulated to be 4-6, a water phase with the pH value of 4-6 is obtained, and then the water phase with the pH value of 4-6 is extracted, dried and concentrated to obtain the compound shown in the formula II.
By adopting the technical scheme, the benzoic acid compound with higher purity can be obtained by adopting simple post-treatment modes such as filtration, extraction and the like, thereby being beneficial to improving the industrialized production efficiency of the benzoic acid compound.
Preferably, in the compound of formula I, R is any one of-CH 3,-OCH3, -I-PrO.
By adopting the technical scheme, the benzyl alcohol comprises the substituent groups, the benzyl activity of the obtained benzyl alcohol compound is higher, the reaction of hydroxyl free radicals and benzyl positions can be promoted, and the synthesis efficiency and yield of the benzoic acid compound are improved.
Preferably, the compound of formula II is 3-methylbenzoic acid or 4-methoxybenzoic acid or 4-methylbenzoic acid or 4-isopropoxybenzoic acid.
By adopting the technical scheme, the yield of the product synthesized by the synthesis process disclosed by the application is up to more than 80%, the purity is up to 95%, and the method is suitable for large-scale industrial production.
In summary, the application has the following beneficial effects:
According to the method, the benzyl alcohol compound is used as a reaction substrate, the povidone iodine is used as a catalyst, the povidone iodine is promoted to react under the oxidation action of the hydrogen peroxide to generate the hydroxyl radical which can react with the benzyl alcohol compound, and then the benzoic acid compound is obtained under the further oxidation action of the hydrogen peroxide, so that the direct conversion from the benzyl alcohol compound to the benzoic acid compound can be realized by the synthesis method of the benzoic acid compound, and the method has the advantages of high efficiency, cleanliness and wide applicability.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a compound of formula II-1 in example 1 of the present application;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the compound of formula II-2 in example 2 of the present application;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the compound of formula II-3 in example 3 of the present application;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the compound of formula II-4 in example 4 of the present application;
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the compound of formula II-5 in example 5 of the present application.
Detailed Description
The application is described in further detail below with reference to the drawings and examples.
Examples
Example 1
A benzoic acid compound has a specific structural formula:
Formula II-1;
The reaction equation of the synthesis process of the benzoic acid compound is as follows:
。
the synthesis process of the benzoic acid compound comprises the following steps:
S1, adding a compound (10.8 g,0.1 mol) of a formula I-1 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (56.7 g,0.5 mol) into the mixed solution, adding povidone iodine (36.5 g,0.1 mol) at-5-0 ℃, then carrying out oxidation reaction at 90 ℃ for 6h, and monitoring that the compound of the formula I is completely reacted by TLC (PE: EA=1:1, and a product Rf=0.2) to obtain a reaction solution;
S2 post-treatment, namely filtering reaction liquid by adopting diatomite, washing a filter cake by adopting ethyl acetate (300 mL), collecting filtrate, adding saturated sodium bicarbonate aqueous solution (300 mL) into the filtrate to obtain filtrate containing the saturated sodium bicarbonate aqueous solution, extracting the filtrate containing the saturated sodium bicarbonate aqueous solution by adopting ethyl acetate three times (300 mL 3), collecting aqueous phase, adjusting the pH value of the aqueous phase to 2-3 (2 in the embodiment), obtaining aqueous phase with the pH value of 2, extracting the aqueous phase with ethyl acetate three times (300 mL 3) with the pH value of 2, collecting organic phase, finally drying the organic phase, concentrating until no solvent residue exists, and obtaining the compound of the formula II-1 (9.2 g, purity 95%, yield 75%, HNMR (400 MHz, DMSO-d 6): delta=12.97 (br. S, 1H), 7.94 (m, 2H), 7.60 (m, 1H) and 7.48 (m, 2H)) by referring to FIG. 1.
Example 2
A benzoic acid compound has a specific structural formula:
formula II-2;
The reaction equation of the synthesis process of the benzoic acid compound is as follows:
。
the synthesis process of the benzoic acid compound comprises the following steps:
s1, adding a compound (12.3 g,0.1 mol) of a formula I-2 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (56.7 g,0.5 mol) into the mixed solution, adding povidone iodine (36.5 g,0.1 mol) at-5-0 ℃, then carrying out oxidation reaction at 90 ℃ for 6h, and monitoring that the compound of the formula I is completely reacted by TLC (PE: EA=1:1, and a product Rf=0.2) to obtain a reaction solution;
S2 working up in the same manner as in example 1 and referring to FIG. 2, a compound of formula II-2 (9.53 g, purity 95%, yield) 70%, HNMR(400 MHz, DMSO-d6): δ = 12.81(s,1 H), 7.80(d, 1H, t = 8.0 Hz), 7.41(t, 1H, t = 8.0 Hz), 7.26 (t, 2H, t = 8.0 Hz), 2.49(s, 3H)）.
Example 3
A benzoic acid compound has a specific structural formula:
Formula II-3;
The reaction equation of the synthesis process of the benzoic acid compound is as follows:
。
the synthesis process of the benzoic acid compound comprises the following steps:
S1, adding a compound (18.7 g,0.1 mol) of a formula I-3 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (56.7 g,0.5 mol) into the mixed solution, adding povidone iodine (36.5 g,0.1 mol) at-5-0 ℃, then carrying out oxidation reaction at 90 ℃ for 6h, and monitoring that the compound of the formula I is completely reacted by TLC (PE: EA=1:1, and a product Rf=0.2) to obtain a reaction solution;
S2 working up in the same manner as in example 1, see FIG. 3, a compound of formula II-3 (13.0 g, purity 95%, yield 65%, HNMR (400 MHz, DMSO-d 6): delta=13.41 (S, 1H), 7.71 (m, 2H), 7.40 (m, 2H)) was obtained.
Example 4
A benzoic acid compound has a specific structural formula:
formula II-4;
The reaction equation of the synthesis process of the benzoic acid compound is as follows:
。
the synthesis process of the benzoic acid compound comprises the following steps:
s1, adding a compound (17.7 g,0.1 mol) of a formula I-4 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (56.7 g,0.5 mol) into the mixed solution, adding povidone iodine (36.5 g,0.1 mol) at-5-0 ℃, then carrying out oxidation reaction at 90 ℃ for 6h, and monitoring that the compound of the formula I is completely reacted by TLC (PE: EA=1:1, and a product Rf=0.2) to obtain a reaction solution;
s2 working up in the same manner as in example 1, referring to FIG. 4, a compound of formula II-4 (11.46 g, purity 95%, yield 60%, HNMR (400 MHz, DMSO-d 6): delta=13.63 (S, 1H), 7.80 (m, 3H)) was obtained.
Example 5
A benzoic acid compound has a specific structural formula:
Formula II-5;
The reaction equation of the synthesis process of the benzoic acid compound is as follows:
。
the synthesis process of the benzoic acid compound comprises the following steps:
S1, adding a compound (12.6 g,0.1 mol) of a formula I-5 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (56.7 g,0.5 mol) into the mixed solution, adding povidone iodine (36.5 g,0.1 mol) at-5-0 ℃, then carrying out oxidation reaction at 90 ℃ for 6h, and monitoring that the compound of the formula I is completely reacted by TLC (PE: EA=1:1, and a product Rf=0.2) to obtain a reaction solution;
S2 post-treatment in the same manner as in example 1 and referring to FIG. 5, a compound of formula II-5 (9.8 g, purity 95%, yield) 70% ,HNMR(400 MHz, DMSO-d6): δ = 13.28(s,1 H), 7.76(d, 1H, t = 8.0 Hz), 7.62(d, 1H, t = 8.0 Hz), 7.53 (t, 1H, t = 8.0 Hz), 7.44 (t, 1H, t = 8.0 Hz)）.
Example 6
A benzoic acid compound has a specific structural formula:
Formula II-6;
The reaction equation of the synthesis process of the benzoic acid compound is as follows:
。
the synthesis process of the benzoic acid compound comprises the following steps:
s1, adding a compound (12.3 g,0.1 mol) of a formula I-6 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (56.7 g,0.5 mol) into the mixed solution, adding povidone iodine (36.5 g,0.1 mol) at-5-0 ℃, then carrying out oxidation reaction at 90 ℃ for 6h, and monitoring that the compound of the formula I is completely reacted by TLC (PE: EA=1:1, and a product Rf=0.2) to obtain a reaction solution;
S2 working up in the same manner as in example 1 gave a compound of formula II-6 (10.9 g, purity 95%, yield 80%, HNMR (400 MHz, DMSO-d 6): delta=12.84 (S, 1H), 7.72 (d, 2H, t=8.0 Hz), 7.36 (m, 2H), 2.32 (S, 3H)).
Example 7
A benzoic acid compound has a specific structural formula:
Formula II-7;
The reaction equation of the synthesis process of the benzoic acid compound is as follows:
。
the synthesis process of the benzoic acid compound comprises the following steps:
S1, adding a compound (17.6 g,0.1 mol) of a formula I-7 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (56.7 g,0.5 mol) into the mixed solution, adding povidone iodine (36.5 g,0.1 mol) at-5-0 ℃, then carrying out oxidation reaction at 90 ℃ for 6h, and monitoring that the compound of the formula I is completely reacted by TLC (PE: EA=1:1, and a product Rf=0.2) to obtain a reaction solution;
S2 working up in the same manner as in example 1, a compound of the formula II-7 (11.8 g, purity 95%, yield) 62%,HNMR (400 MHz, DMSO-d6): δ = 13.50(s,1 H), 8.24(d, 1H, t = 8.0 Hz), 8.18(s, 1H), 8.01 (d, 1H, t = 4.0 Hz), 7.77 (t, 1H, t = 8.0 Hz)）.
Example 8
A benzoic acid compound has a specific structural formula:
formula II-8;
The reaction equation of the synthesis process of the benzoic acid compound is as follows:
。
the synthesis process of the benzoic acid compound comprises the following steps:
S1, adding a compound (12.6 g,0.1 mol) of a formula I-8 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (56.7 g,0.5 mol) into the mixed solution, adding povidone iodine (36.5 g,0.1 mol) at-5-0 ℃, then carrying out oxidation reaction at 90 ℃ for 6h, and monitoring that the compound of the formula I is completely reacted by TLC (PE: EA=1:1, and a product Rf=0.2) to obtain a reaction solution;
S2 working up in the same manner as in example 1 gave a compound of formula II-8 (9.52 g, purity 95%, yield 68%, HNMR (400 MHz, DMSO-d 6): delta=13.00 (S, 1H), 7.98 (t, 2H, t=8.0 Hz), 7.29 (d, 2H, t=8.0 Hz)).
Example 9
A benzoic acid compound has a specific structural formula:
formula II-9;
The reaction equation of the synthesis process of the benzoic acid compound is as follows:
。
the synthesis process of the benzoic acid compound comprises the following steps:
S1, adding a compound (12.3 g,0.1 mol) of a formula I-9 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (56.7 g,0.5 mol) into the mixed solution, adding povidone iodine (36.5 g,0.1 mol) at-5-0 ℃, then carrying out oxidation reaction at 90 ℃ for 6h, and monitoring that the compound of the formula I is completely reacted by TLC (PE: EA=1:1, and a product Rf=0.2) to obtain a reaction solution;
S2 working up in the same manner as in example 1, a compound of the formula II-9 (11.1 g, purity 95%, yield) 82%,HNMR (400 MHz, DMSO-d6): δ = 12.79(s,1 H), 7.82(t, 2H, t = 8.0 Hz), 7.20(t, 2H, t= 8.0 Hz), 2.28(s, 3H)）.
Example 10
A benzoic acid compound has a specific structural formula:
Formula II-10;
The reaction equation of the synthesis process of the benzoic acid compound is as follows:
。
the synthesis process of the benzoic acid compound comprises the following steps:
S1, adding a compound (13.8 g,0.1 mol) of a formula I-10 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (56.7 g,0.5 mol) into the mixed solution, adding povidone iodine (36.5 g,0.1 mol) at-5-0 ℃, then carrying out oxidation reaction at 90 ℃ for 6h, and monitoring that the compound of the formula I is completely reacted by TLC (PE: EA=1:1, and a product Rf=0.2) to obtain a reaction solution;
s2 working up in the same manner as in example 1, a compound of the formula II-10 (12.9 g, purity 95%, yield) 85%,HNMR (400 MHz, DMSO-d6): δ = 12.62(s,1 H), 7.87(d, 2H, t = 8.0 Hz), 7.99(d, 2H, t= 8.0 Hz), 3.79(s, 3H) ）.
Example 11
A benzoic acid compound has a specific structural formula:
Formula II-11;
The reaction equation of the synthesis process of the benzoic acid compound is as follows:
。
the synthesis process of the benzoic acid compound comprises the following steps:
S1, adding a compound (17.6 g,0.1 mol) of a formula I-11 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (56.7 g,0.5 mol) into the mixed solution, adding povidone iodine (36.5 g,0.1 mol) at-5-0 ℃, then carrying out oxidation reaction at 90 ℃ for 6h, and monitoring that the compound of the formula I is completely reacted by TLC (PE: EA=1:1, and a product Rf=0.2) to obtain a reaction solution;
S2 working up in the same manner as in example 1 gave a compound of formula II-11 (12.3 g, purity 95%, yield 65%, HNMR (400 MHz, DMSO-d 6): delta=13.48 (S, 1H), 8.11 (d, 2H, t=8.0 Hz), 7.85 (d, 2H, t=8.0 Hz)).
Example 12
A benzoic acid compound has a specific structural formula:
formula II-12;
The reaction equation of the synthesis process of the benzoic acid compound is as follows:
。
the synthesis process of the benzoic acid compound comprises the following steps:
s1, adding a compound (16.4 g,0.1 mol) of a formula I-12 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (56.7 g,0.5 mol) into the mixed solution, adding povidone iodine (36.5 g,0.1 mol) at-5-0 ℃, then carrying out oxidation reaction at 90 ℃ for 6h, and monitoring that the compound of the formula I is completely reacted by TLC (PE: EA=1:1, and a product Rf=0.2) to obtain a reaction solution;
S2 working up in the same manner as in example 1, a compound of the formula II-12 (13.9 g, purity 95%, yield) 78%,HNMR (400 MHz, DMSO-d6): δ = 12.80(s,1 H), 7.84(d, 2H, t = 8.0 Hz), 7.47(d, 2H, t= 8.0 Hz), 1.26(s, 9H)）.
Example 13
A benzoic acid compound has a specific structural formula:
formula II-13;
The reaction equation of the synthesis process of the benzoic acid compound is as follows:
。
the synthesis process of the benzoic acid compound comprises the following steps:
s1, adding a compound (15.3 g,0.1 mol) of a formula I-13 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (56.7 g,0.5 mol) into the mixed solution, adding povidone iodine (36.5 g,0.1 mol) at-5-0 ℃, then carrying out oxidation reaction at 90 ℃ for 6h, and monitoring that the compound of the formula I is completely reacted by TLC (PE: EA=1:1, and a product Rf=0.2) to obtain a reaction solution;
s2 working up in the same manner as in example 1 gave a compound of formula II-13 (9.2 g, purity 95%, yield 55%, HNMR (400 MHz, DMSO-d 6): delta=13.66 (S, 1H), 8.28 (t, 2H, t=8.0 Hz), 8.13 (t, 2H, t=8.0 Hz)).
Example 14
A benzoic acid compound has a specific structural formula:
formula II-14;
The reaction equation of the synthesis process of the benzoic acid compound is as follows:
。
the synthesis process of the benzoic acid compound comprises the following steps:
S1, adding a compound (16.6 g,0.1 mol) of a formula I-14 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (56.7 g,0.5 mol) into the mixed solution, adding povidone iodine (36.5 g,0.1 mol) at-5-0 ℃, then carrying out oxidation reaction at 90 ℃ for 6h, and monitoring that the compound of the formula I is completely reacted by TLC (PE: EA=1:1, and a product Rf=0.2) to obtain a reaction solution;
S2 working up in the same manner as in example 1, a compound of the formula II-14 (14.4 g, purity 95%, yield) 80%,HNMR (400 MHz, DMSO-d6): δ = 12.58(s,1 H), 7.84(d, 2H, t = 8.0 Hz), 6.96(d, 2H, t= 8.0 Hz), 4.71(m, 1H), 1.25(d, 6H, t = 4.0 Hz ）.
Example 15
A benzoic acid compound, different from example 1 in the synthesis process of the benzoic acid compound, comprising the steps of:
S1, adding a compound (10.8 g,0.1 mol) of a formula I-1 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (45.3 g,0.4 mol) into the mixed solution, adding povidone iodine (18.2 g,0.05 mol) at a temperature of-5-0 ℃, and then carrying out oxidation reaction at 90 ℃ for 6h, wherein TLC (PE: EA=1:1, and a product Rf=0.2) monitors that the compound of the formula I is completely reacted to obtain a reaction solution;
S2 working up in the same manner as in example 1, a compound of the formula II-1 (8.0 g, purity 95%, yield) 65.2%,HNMR(400 MHz, CDCl3): δ = 12.08 (br. s, 1H), 8.16-8.13 (m, 2H), 7.65-7.61 (m, 1H), 7.52-7.47 (m, 2H)））.
Example 16
A benzoic acid compound, different from example 1 in the synthesis process of the benzoic acid compound, comprising the steps of:
s1, adding a compound (10.8 g,0.1 mol) of a formula I-1 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (68.0 g,0.6 mol) into the mixed solution, adding povidone iodine (109.5 g,0.3 mol) at-5-0 ℃, then carrying out oxidation reaction at 90 ℃ for 6h, and monitoring that the compound of the formula I is completely reacted by TLC (PE: EA=1:1, and a product Rf=0.2) to obtain a reaction solution;
S2 working up in the same manner as in example 1, a compound of the formula II-1 (9.2 g, purity 95%, yield) 75%,HNMR(400 MHz, CDCl3): δ = 12.08 (br. s, 1H), 8.16-8.13 (m, 2H), 7.65-7.61 (m, 1H), 7.52-7.47 (m, 2H)））.
Example 17
A benzoic acid compound, different from example 1 in the synthesis process of the benzoic acid compound, comprising the steps of:
S1, adding a compound (10.8 g,0.1 mol) of a formula I-1 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (56.7 g,0.5 mol) into the mixed solution, adding povidone iodine (36.5 g,0.1 mol) at-5-0 ℃, then carrying out oxidation reaction at 70 ℃ for 12h, and monitoring that the compound of the formula I is completely reacted by TLC (PE: EA=1:1, and a product Rf=0.2) to obtain a reaction solution;
S2 working up in the same manner as in example 1, a compound of the formula II-1 (7.5 g, purity 95%, yield) 61.1%,HNMR(400 MHz, CDCl3): δ = 12.08 (br. s, 1H), 8.16-8.13 (m, 2H), 7.65-7.61 (m, 1H), 7.52-7.47 (m, 2H)））.
Example 18
A benzoic acid compound, different from example 1 in the synthesis process of the benzoic acid compound, comprising the steps of:
S1, adding a compound (10.8 g,0.1 mol) of a formula I-1 into deionized water (200 mL) to obtain a mixed solution, adding 30% hydrogen peroxide (56.7 g,0.5 mol) into the mixed solution, adding povidone iodine (36.5 g,0.1 mol) at-5-0 ℃, and then carrying out oxidation reaction at 100 ℃ for 8 hours, wherein TLC (PE: EA=1:1, and product Rf=0.2) monitors that the compound of the formula I is completely reacted to obtain a reaction solution;
S2 working up in the same manner as in example 1, a compound of the formula II-1 (9.0 g, purity 95%, yield) 73.4%,HNMR(400 MHz, CDCl3): δ = 12.08 (br. s, 1H), 8.16-8.13 (m, 2H), 7.65-7.61 (m, 1H), 7.52-7.47 (m, 2H)））.
Comparative example
Comparative example 1
A benzoic acid compound has a specific structural formula:
Formula II-1;
The reaction equation of the synthesis process of the benzoic acid compound is as follows:
。
the synthesis process of the benzoic acid compound comprises the following steps:
Cobalt chloride hexahydrate (0.1 g) was added to toluene (30 g) to obtain a mixed solution, and the mixed solution was added to benzaldehyde (75 g), then 0.3L/min of oxygen was introduced, and the mixture was stirred and reacted at 75-80℃for 6 hours to obtain a reaction solution. The reaction solution was filtered and the filter cake was washed 2 times with clear water, then the filter cake was dried at 65℃for 5 hours, the filter cake was added to water (water and filter cake were mixed in a weight ratio of 10:1), heated to 100℃until the filter cake was dissolved, then naturally cooled to room temperature (20-25 ℃) and white crystals were precipitated, filtered, and the white crystals were collected to give a compound of formula II-1 (43.65 g, purity 93%, yield 51.2%, HNMR (400 MHz, DMSO-d 6): δ=12.97 (br. s, 1H), 7.94 (m, 2H), 7.60 (m, 1H), 7.48 (m, 2H))).
Comparative example 2
A benzoic acid compound has a specific structural formula:
Formula II-1;
The reaction equation of the synthesis process of the benzoic acid compound is as follows:
。
the synthesis process of the benzoic acid compound comprises the following steps:
Cobalt chloride hexahydrate (0.1 g) and an emulsifier Tween-8 (37.5 mg) were added to water (50 g) to obtain a mixed solution, the mixed solution was added to benzaldehyde (75 g), then oxygen of 0.3L/min was introduced, and the mixture was stirred and reacted at 75-80℃for 6 hours to obtain a reaction solution. The reaction solution was filtered and the filter cake was washed 2 times with clear water, then the filter cake was dried at 65 ℃ for 5 hours, the filter cake was added to water (water and filter cake were mixed in a weight ratio of 10:1), heated to 100 ℃ until the filter cake was dissolved, then naturally cooled to room temperature (20-25 ℃) and white crystals were precipitated, filtered, and the white crystals were collected to give a compound of formula II-1 (57.6 g, 92% purity, yield 68.1%, HNMR (400 MHz, DMSO-d 6): δ=12.97 (br. s, 1H), 7.94 (m, 2H), 7.60 (m, 1H), 7.48 (m, 2H))).
From analysis of example 1, comparative example 1 and comparative example 2, it is apparent that the products obtained in example 1, comparative example 1 and comparative example 2 are benzoic acid, wherein the purity and yield of benzoic acid are shown in the following table:
As can be seen from the analysis described above, the benzoic acid obtained in example 1 was higher in purity and yield than those obtained in comparative examples 1 and 2. Therefore, the benzoic acid synthesized by adopting the synthesis process of the benzoic acid compound can improve the purity and the yield of the benzoic acid. Meanwhile, hydrogen peroxide, water and povidone iodine are all green pollution-free raw materials in the synthesis process. However, in the synthesis process of comparative example 1 and comparative example 2, toxic cobalt chloride hexahydrate is used, and in the synthesis process of comparative example 1, toluene, which is an organic solvent, is also used, which causes environmental pollution. Therefore, the synthesis process of the benzoic acid compound is more environment-friendly and cleaner. Moreover, the synthesis process of the benzoic acid compound is simple and convenient to operate, the material is simple, oxygen is also required to be introduced into the comparative examples 1 and 2, and the dosage of the oxygen is controlled, so that the synthesis process of the benzoic acid compound is more efficient and has wider applicability.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
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| DE102012202885A1 (en) * | 2012-02-24 | 2012-05-10 | Symrise Ag | Producing menthane carbaldehyde, menthane carboxylic acid or its secondary product, comprises reacting an ester of menthane glycidic carbaldehyde with menthane |
| CN113307740A (en) * | 2021-05-27 | 2021-08-27 | 中瀚(齐河县)生物医药科技有限公司 | Preparation method of 2-amino-4-fluorobenzoic acid |
| CN114835574A (en) * | 2022-04-22 | 2022-08-02 | 苏州亚科科技股份有限公司 | Preparation process of 3-methyl sodium salicylate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102012202885A1 (en) * | 2012-02-24 | 2012-05-10 | Symrise Ag | Producing menthane carbaldehyde, menthane carboxylic acid or its secondary product, comprises reacting an ester of menthane glycidic carbaldehyde with menthane |
| CN113307740A (en) * | 2021-05-27 | 2021-08-27 | 中瀚(齐河县)生物医药科技有限公司 | Preparation method of 2-amino-4-fluorobenzoic acid |
| CN114835574A (en) * | 2022-04-22 | 2022-08-02 | 苏州亚科科技股份有限公司 | Preparation process of 3-methyl sodium salicylate |
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| "Metal-free one-pot oxidative conversion of benzylic alcohols and benzylic halides into aromatic amides with molecular iodine in aq ammonia, and hydrogen peroxide";Ryosuke Ohmura等;Tetrahedron Letters;20100616;第4378-4381页 * |
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