A catalyst composition, its use and a method for the synthesis of cyhalofop-butyl

Abstract

The application provides a catalyst composition, application thereof and a synthesis method of cyhalofop-butyl, which comprises the following steps: reacting a compound shown in formula (1) with hydroquinone and an alkaline substance under the action of a catalyst composition at 0-90 DEG C to obtain a compound shown in formula (2); and reacting the compound shown in formula (2) with 4-chloro-3-fluorobenzonitrile under the action of the catalyst composition at 80-100 DEG C to obtain a compound shown in formula (3). The catalyst composition provided by the application has the advantages of high catalytic efficiency and small product pollution when catalyzing aryl etherification. The synthesis method of the compound cyhalofop-butyl shown in formula (3) has the advantages of easy raw material, high yield, low cost, mild reaction condition, environmental friendliness and meeting the requirements of green chemistry; the compounds shown in formula (1)-(3) are shown in the following formula.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis, in particular to a catalyst composition, application thereof and a synthesis method of cyhalofop butyl. BACKGROUND

[0002] Cyhalofop butyl is a type of phenoxy propionic acid herbicide, which is a systemic herbicide for rice field and has a unique structure of aryloxyphenoxy propionate.

[0003] Cyhalofop butyl is developed by Dow Agro Sciences. As a systemic herbicide, the mechanism of action of cyhalofop butyl is to be absorbed by the leaves or leaf sheaths of plants, then conducted by the phloem, and finally enriched in the meristem area of plants. Cyhalofop butyl herbicide is widely used for controlling leafflower and also shows good herbicidal effect on low-age barnyard grass, double spike pigweed, crabgrass, dogtail grass, foxtail and other weeds in rice fields.

[0004] Since cyhalofop butyl has great potential for solving the problem of sulfonylurea herbicide-resistant weeds in rice fields, it is of great significance to develop a new synthesis process thereof.

[0005] In the prior art, the synthesis method of cyhalofop butyl mainly includes the following two methods:

[0006] The first method is as follows:

[0007]

[0008] The second method is as follows:

[0009]

[0010] However, in the prior art, the total yield of the method for synthesizing cyhalofop butyl is low, the cost is high, the reaction conditions are harsh and not friendly to the environment, and it does not meet the requirements of green chemistry. SUMMARY

[0011] To solve the above technical problems, the present application provides a catalyst composition, application thereof and a synthesis method of cyhalofop butyl.

[0012] The above-mentioned purposes of the present application are achieved by the following technical solutions:

[0013] In a first aspect, the present application provides a catalyst composition for catalyzing aryl etherification reaction, which comprises 50-70 parts of a first composite component, 20-40 parts of a second composite component and 5-15 parts of a third composite component by mole; wherein,

[0014] The first composite component comprises one or more of 4A molecular sieve, sodium sulfite and sodium hydrosulfite.

[0015] The second complex component comprises one or more of sodium bromide, potassium bromide, copper chloride, copper bromide, sodium iodide, potassium iodide, copper iodide, cuprous chloride, cuprous iodide and copper acetate;

[0016] The third complex component comprises one or more of bipyridine, 1,10-phenanthroline, triethylbenzylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, polyethylene glycol-400 (PEG-400), polyethylene glycol-600 (PEG-600) and 18-crown-6.

[0017] Preferably, the catalyst composition comprises 60 parts of the first complex component, 30 parts of the second complex component and 10 parts of the third complex component.

[0018] In a second aspect, the present application provides the use of the above catalyst composition in catalyzing aryl etherification reaction.

[0019] In a third aspect, the present application provides a method for synthesizing cyhalofop-butyl, which comprises the following steps:

[0020] Step one: reacting a compound represented by formula (1) (p-toluenesulfonyl butyl lactate), hydroquinone and an alkaline substance in a first solvent under the action of a first catalyst composition at 0-90℃, and obtaining a compound represented by formula (2) after the reaction is completed;

[0021] Step two: reacting the compound represented by formula (2) ((R)-2-(4-hydroxyphenoxy) butyl propionate) with 4-chloro-3-fluorobenzonitrile in a second solvent added with an alkaline substance under the action of a second catalyst composition at 80-100℃, and obtaining a compound represented by formula (3) ((R)-2-(4-(4-cyano-2-fluorophenoxy) phenoxypropionic acid butyl ester, i.e. cyhalofop-butyl) after the reaction is completed;

[0022] The first catalyst composition and the second catalyst composition are independently selected from the catalyst composition provided in the first aspect of the present application.

[0023] The compounds represented by formulae (1)-(3) are as shown in the following formulae:

[0024]

[0025] Further, in step one, the molar ratio of the compound represented by formula (1), hydroquinone, the alkaline substance and the first catalyst composition is 1:(1.5-2):(2-3):(0.1-0.3).

[0026] Further, in step one, the reaction time for the reaction of the compound of formula (1) with hydroquinone and the basic substance in the first solvent is 4-12 h; preferably, the reaction time is 8-9 h.

[0027] Further, in step one, the basic substance is selected from one or more of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate and sodium hydride.

[0028] Further, in step one, the first solvent is selected from one or more of water, methanol, ethanol, isopropanol and n-butanol.

[0029] Further, in step one, after the reaction is completed, the process further comprises the steps of suction filtration, drying of the filtrate and removing the solvent by distillation under reduced pressure.

[0030] Further, in step one, the method for preparing the compound of formula (1) comprises the following steps:

[0031] reacting the compound of formula (a), the compound of formula (b) and a basic compound under the catalysis of the first catalyst composition at 0-10°C, and after the reaction is completed, obtaining the compound of formula (1);

[0032] wherein the compounds of formula (a) and (b) are as shown in the following formula:

[0033]

[0034] Further, the basic compound is selected from one or more of triethylamine, pyridine, sodium hydroxide and potassium hydroxide.

[0035] Further, the molar ratio of the compound of formula (a), the compound of formula (b) and the basic compound is 1:(1.5-1.8):(1.6-1.9), preferably 1:1.68:1.72.

[0036] Further, in step two, the molar ratio of the compound of formula (2), 4-chloro-3-fluorobenzonitrile, the basic substance and the second catalyst composition is 1:(1.2-1.5):(0.5-1):(0.1-0.3).

[0037] Preferably, the reaction time of step two is 10-16 h.

[0038] Further, in step two, the basic substance is selected from one or more of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate and sodium hydride.

[0039] Further, in step two, the second solvent is selected from one or more of methanol, ethanol, tert-butanol, ethyl acetate, dichloromethane, tetrahydrofuran, acetone, toluene, N,N-dimethylformamide and dimethyl sulfoxide.

[0040] The inventors have found through in-depth research that by using a catalyst composition to catalyze the aromatic etherification reaction of 4-chloro-3-fluorocyanophenyl, (R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxyacetic acid] butyl ester (cyhalofop-butyl) can be synthesized with high efficiency. Without using a catalyst, the yield of cyhalofop-butyl is low (about 46%), while by using the self-made catalyst composition for catalytic reaction, the aromatic etherification reaction can proceed smoothly, no bis-etherification by-product is generated in the reaction process, and cyhalofop-butyl can be obtained with high yield.

[0041] The above technical scheme of the present application has the following beneficial effects:

[0042] 1. The catalyst composition provided by the present application has high catalytic efficiency and little pollution to the product when catalyzing the aromatic etherification reaction.

[0043] 2. The synthesis method of cyhalofop-butyl provided by the present application has the advantages of easy availability of raw materials, high yield, low cost, mild reaction conditions, environmental friendliness, and compliance with the requirements of green chemistry.

[0044] The above description is only a summary of the technical scheme of the present application. In order to better understand the technical means of the present application and to implement the content of the description, the following describes the preferred embodiments of the present application with detailed descriptions. DETAILED DESCRIPTION

[0045] The present application will be further described below with reference to specific examples, so that those skilled in the art can better understand the present application and implement it. However, the examples are not limiting to the present application.

[0046] In the following examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are commercially available unless otherwise specified.

[0047] Example 1

[0048] A catalyst composition, by mole, includes:

[0049] The first composite component is 60 parts, the second composite component is 30 parts, and the third composite component is 10 parts. The first composite component includes 4A molecular sieve and sodium sulfite (molar ratio 1:1); the second composite component includes sodium bromide and cuprous chloride (molar ratio 1:1); and the third composite component includes bipyridine, triethylbenzylammonium chloride and PEG-400 (molar ratio 1:1:1).

[0050] The catalyst composition is mixed uniformly after being weighed according to the formula.

[0051] Example 2

[0052] A catalyst composition, in terms of moles, includes:

[0053] The first composite component is 60 parts, the second composite component is 30 parts, and the third composite component is 10 parts; wherein the first composite component includes 4A molecular sieve and sodium hyposulfite (molar ratio 1:1); the second composite component includes potassium bromide and cuprous iodide (molar ratio 1:1); and the third composite component includes bipyridine, tetrabutylammonium iodide, and 18-crown-6 (molar ratio 1:1:1).

[0054] The catalyst composition is mixed uniformly after being weighed according to the formula.

[0055] Example 3

[0056] A catalyst composition, in terms of moles, includes:

[0057] The first composite component is 60 parts, the second composite component is 30 parts, and the third composite component is 10 parts; wherein the first composite component includes sodium sulfite and sodium hyposulfite (molar ratio 1:1); the second composite component includes copper chloride and copper acetate (molar ratio 1:1); and the third composite component includes 1,10-phenanthroline, tetrabutylammonium iodide, and PEG-600 (molar ratio 1:1:1).

[0058] The catalyst composition is mixed uniformly after being weighed according to the formula.

[0059] Example 4

[0060] A catalyst composition, in terms of moles, includes:

[0061] The first composite component is 60 parts, the second composite component is 30 parts, and the third composite component is 10 parts; wherein the first composite component includes sodium sulfite and sodium hyposulfite (molar ratio 1:1); the second composite component includes sodium iodide and cuprous iodide (molar ratio 1:1); and the third composite component includes 1,10-phenanthroline, tetrabutylammonium iodide, and PEG-600 (molar ratio 1:1:1).

[0062] The catalyst composition is mixed uniformly after being weighed according to the formula.

[0063] The catalyst compositions of Examples 1-4 are tested for catalytic aryl etherification reaction, and the catalyst composition provided in Example 4 is preferred according to the test results.

[0064] Example 5

[0065] A method for preparing p-toluenesulfonyl butyl lactate, comprising the following steps:

[0066] A mixture of 223.38 g (1.53 mol) of butyl lactate, 158.4 g (1.56 mol) of triethylamine, and 1000 mL of toluene was cooled to 0°C. A solution of 172.2 g (0.909 mol) of p-toluenesulfonyl chloride and 350 mL of toluene was added dropwise, and the reaction was allowed to proceed for 10 h. After the reaction was completed, the organic phase was washed with water, dried, and concentrated to obtain an oily product (1) 220.7 g. The yield of this reaction step was calculated to be 80.9%.

[0067] The reaction process in this example is shown in the following formula:

[0068]

[0069] The characterization data of product (1) are as follows: 1 H NMR (400 MHz, Chloroform-d) δ 7.82 (d, J = 8.4 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 4.92 (t, J = 6.9 Hz, 1H), 4.06 (td, J = 6.7, 1.4 Hz, 2H), 2.45 (s, 3H), 1.58 - 1.48 (m, 5H), 1.38 - 1.28 (m, 2H), 0.91 (t, J = 7.4 Hz, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 169.13, 145.03, 133.42, 129.79, 127.99, 74.17, 65.62, 30.35, 21.65, 18.91, 18.44, 13.62. HREMS (ESI-TOF): [M+H] + m / z calcd for C 14 H 21 O5S + :301.1005, found:230.1003.

[0070] The characterization data prove that p-toluenesulfonyl butyl lactate is prepared in Example 5.

[0071] Example 6

[0072] A method for preparing (R)-2-(4-hydroxyphenoxy)butyl lactate, comprising the following steps:

[0073] A mixture of 0.06 mol of hydroquinone 6.60 g, 0.09 mol of sodium hydroxide 3.60 g, 1.30 g of the catalyst composition provided in Example 4 and 100 mL of ethanol was prepared, and then added dropwise into a mixture of 0.038 mol of butyl p-toluenesulfonyl lactate 11.60 g provided in Example 5 and 70 mL of ethanol at 5°C. After 8 hours of reaction after the addition was completed, the pH was adjusted to 6-7 by adding an appropriate amount of hydrochloric acid, and then the ethanol was distilled off under reduced pressure. Then, 0.03 mol of potassium carbonate 4.15 g and 100 mL of n-butanol were added, and the mixture was reacted at 85°C for 8 hours. After the reaction was completed, the mixture was filtered, and the filtrate was distilled under reduced pressure to obtain 8.86 g of the product (2). The yield of this reaction step was calculated to be 98.0%.

[0074] The reaction process in this example is shown in the following formula:

[0075]

[0076] The characterization data of the product (2) are as follows: 1 H NMR (400 MHz, Chloroform-d) δ 6.77-6.56 (m, 4H), 5.12 (s, 1H), 4.58 (d, J = 6.8 Hz, 1H), 4.08 (q, J = 6.5 Hz, 2H), 1.57-1.48 (m, 5H), 1.30-1.17 (m, 2H), 0.82 (t, J = 7.4 Hz, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 172.90, 151.59, 150.43, 116.60, 116.08, 73.63, 65.18, 30.52, 18.96, 18.66, 13.61. HREMS (ESI-TOF): [M+H] + m / z calcd for C 13 H 19 O4 + : 239.1205, found: 239.1207.

[0077] The characterization data prove that (R)-butyl 2-(4-hydroxyphenoxy)propanoate is prepared in Example 6.

[0078] Example 7

[0079] A method for preparing cyhalofop-butyl, comprising the following steps:

[0080] A reaction solution was prepared by using 14 mmol of (R)-2-(4- hydroxyphenoxy)butyl butylate 3.30 g provided from Example 6, 11 mmol of 4-chloro-3-fluorobenzonitrile 1.71 g, 14 mmol of a basic substance (potassium carbonate 1.93 g), 0.46 g of the catalyst composition provided from Example 4 and 20 mL of DMF as a solvent, and the reaction was carried out at 90-100°C for 12 h. After the reaction was completed, the reaction solution was filtered, concentrated under reduced pressure, and the crude product was added to 50 mL of dichloromethane, washed with water twice, dried over anhydrous sodium sulfate, filtered, and concentrated to obtain the product 3.89 g. The product (3) 3.76 g was obtained after purification by column chromatography, and the yield of this reaction step was 95.7% by calculation.

[0081] The reaction process in this example is shown in the following formula:

[0082]

[0083] The characterization data of the product (3) are as follows: 1 H NMR (400 MHz, Chloroform-d) δ 7.57-7.25 (m, 2H), 7.04-6.81 (m, 5H), 4.74 (q, J = 6.8 Hz, 1H), 4.34-4.09 (m, 2H), 1.67-1.54 (m, 5H), 1.40-1.26 (m, 2H), 0.91 (t, J = 7.4 Hz, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 172.01, 155.08, 153.60, 151.09, 150.57, 150.47, 148.48, 129.36, 129.32, 121.04, 120.64, 120.43, 118.50, 118.48, 117.66, 117.64, 116.58, 106.02, 105.94, 73.11, 65.18, 30.51, 18.95, 18.59, 13.60. HREMS (ESI-TOF): [M+Na] + m / z calcd for C 20 H 21 O4FN + :358.1402, found:358.1404.

[0084] The characterization data prove that cyhalofop-butyl is prepared in Example 7.

[0085] Based on the above examples, it can be clear that the catalyst composition provided by the present application has higher catalytic efficiency when catalyzing the aryl etherification reaction; the synthesis method of cyhalofop-butyl provided by the present application has the advantages of easy raw material, higher yield, lower cost, mild reaction condition, environmental friendliness, meeting the requirements of green chemistry, the above process route is more feasible, and is suitable for industrialized scale production.

[0086] Obviously, the above examples of the present application are only examples for clearly illustrating the present application, and are not a limitation on the embodiments of the present application. Those skilled in the art should understand that other different forms of changes or variations can be made on the basis of the above description. Here, it is not necessary and also impossible to exhaust all the embodiments. Any modification, equivalent replacement and improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the claims of the present application.

Claims

1. A method for synthesizing cyhalofop-butyl, characterized by, The method comprises the following steps: Step one: reacting the compound shown in formula (1), hydroquinone and alkaline substance in a first solvent under the action of a first catalyst composition at 0-90 ℃, and obtaining the compound shown in formula (2) after the reaction; the molar ratio of the compound shown in formula (1), hydroquinone, alkaline substance and the first catalyst composition is 1:(1.5-2):(2-3):(0.1-0.3); Step two: reacting the compound shown in formula (2) and 4-chloro-3-fluorobenzonitrile in a second solvent added with alkaline substance under the action of a second catalyst composition at 80-100 ℃, and obtaining the compound shown in formula (3) after the reaction; the molar ratio of the compound shown in formula (2), 4-chloro-3-fluorobenzonitrile, alkaline substance and the second catalyst composition is 1:(1.2-1.5):(0.5-1):(0.1-0.3); The first catalyst composition and the second catalyst composition are respectively a catalyst composition for catalyzing aryl etherification reaction, and the catalyst composition comprises, in terms of molar number, 50-70 parts of a first composite component, 20-40 parts of a second composite component and 5-15 parts of a third composite component; wherein, The first composite component is selected from sodium sulfite and sodium dithionite; The second composite component is selected from A component and B component, the A component is selected from one or more of sodium bromide, potassium bromide, sodium iodide and potassium iodide, and the B component is selected from one or more of copper chloride, copper bromide, copper iodide, cuprous chloride and cuprous iodide; The third composite component is selected from C component and D component, the C component is selected from one or more of bipyridine and 1,10-phenanthroline, and the D component is selected from one or more of triethylbenzylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, polyethylene glycol-400, polyethylene glycol-600 and 18-crown-6; The compounds shown in formula (1)-(3) are shown in the following formula: 。 2. The method of synthesis of claim 1, wherein, In step one, the alkaline substance is selected from one or more of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate and sodium hydride.

3. The method of synthesis of claim 1, wherein, In step one, the first solvent is selected from one or more of water, methanol, ethanol, isopropanol and n-butanol.

4. The method of synthesis of claim 1, wherein, In step one, the preparation method of the compound shown in formula (1) comprises the following steps: reacting the compound shown in formula (a), the compound shown in formula (b) and an alkaline compound under the catalysis of a first catalyst composition at 0-10 ℃, and obtaining the compound shown in formula (1) after the reaction; The compounds shown in formula (a) and (b) are shown in the following formula: 。 5. The method of synthesis of claim 4, wherein, The alkaline compound is selected from one or more of triethylamine, pyridine, sodium hydroxide and potassium hydroxide.

6. The method of synthesis of claim 4, wherein, The molar ratio of the compound shown in formula (a), the compound shown in formula (b) and the alkaline compound is 1:(1.5-1.8):(1.6-1.9).

7. The method of synthesis of claim 1, wherein, In step two, the basic substance is selected from one or more of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate, and sodium hydride.

8. The method of synthesis of claim 1, wherein, In step two, the second solvent is selected from one or more of methanol, ethanol, tert-butanol, ethyl acetate, dichloromethane, tetrahydrofuran, acetone, toluene, N,N-dimethylformamide, and dimethylsulfoxide.

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