Catalyst composition, application thereof and cyhalofop-butyl synthesis method

Abstract

The invention provides a catalyst composition, application thereof and a cyhalofop-butyl synthesis method, and the method comprises the following steps: reacting a compound as shown in a formula (1) with hydroquinone and an alkaline substance at 0-90 DEG C under the action of the catalyst composition to obtain a compound as shown in a formula (2), the method comprises the following steps: reacting a compound as shown in a formula (2) with 4-chloro-3-fluorobenzonitrile at 80-100 DEG C under the action of a catalyst composition to obtain a compound as shown in a formula (3). The catalyst composition provided by the invention has the advantages of high catalytic efficiency and small pollution to products when catalyzing an aryl etherification reaction. According to the synthesis method of the compound cyhalofop-butyl as shown in the formula (3), the raw materials are easy to obtain, the yield is high, the cost is low, the reaction conditions are mild, the synthesis method is environmentally friendly, and the requirements of green chemistry are met; wherein compounds represented by formulae (1)-(3) are represented by formula # imgabs0 #

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a catalyst composition, application thereof and a method for synthesizing cyhalofop-butyl. Background Art

[0002] Cyhalofop butyl is a phenoxypropionic acid systemic herbicide for rice fields, which has a unique structure of aromatic phenoxypropionic acid esters.

[0003] Cyhalofop-butyl was developed by Dow AgroSciences. As a systemic herbicide, cyhalofop-butyl is absorbed by plant leaves or sheaths, then transmitted by the phloem, and finally enriched in the meristem of the plant. Cyhalofop-butyl herbicide is widely used to control Leptochloa chinensis, and also shows good weed control effects on weeds such as young barnyard grass, Paspalum distachyon, Digitaria, Setaria viridis, Alopecuroides australis and Goosegrass in rice fields.

[0004] Since cyhalofop-butyl is a herbicide variety with great potential for solving the problem of weeds in rice fields that are resistant to sulfonylurea herbicides, research on developing a new synthesis process for it is of great significance.

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

[0006] The first one:

[0007]

[0008] Second type:

[0009]

[0010] However, in the prior art, the methods for synthesizing cyfluthrin have low overall yield, high cost, harsh reaction conditions and are environmentally unfriendly, which do not meet the requirements of green chemistry. Summary of the invention

[0011] In order to solve the above technical problems, the present invention provides a catalyst composition, application thereof and a method for synthesizing cyhalofop-butyl.

[0012] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0013] In a first aspect, the present invention provides a catalyst composition for catalyzing an aryl etherification reaction, wherein the catalyst composition comprises, by mole, 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

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

[0015] The second composite component includes one or more of sodium bromide, potassium bromide, cupric chloride, cupric bromide, sodium iodide, potassium iodide, cupric iodide, cuprous chloride, cuprous iodide and cupric acetate;

[0016] The third composite component includes one or more of bipyridine, 1,10-phenanthroline, triethylbenzyl ammonium 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 composite component, 30 parts of the second composite component, and 10 parts of the third composite component.

[0018] In a second aspect, the present invention provides use of the catalyst composition in catalyzing aromatic etherification reactions.

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

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

[0021] Step 2: reacting the compound represented by formula (2) ((R)-2-(4-hydroxyphenoxy) butyl propionate) with 4-chloro-3-fluorobenzonitrile in a second solvent to which an alkaline substance is added at 80-100° C. in the presence of a second catalyst composition, to obtain a compound represented by formula (3) ((R)-2-(4-(4-cyano-2-fluorophenoxy) phenoxy butyl propionate, i.e., cyhalofop-butyl);

[0022] Wherein, the first catalyst composition and the second catalyst composition are independently selected from the catalyst composition provided in the first aspect of the present invention;

[0023] The compounds represented by formula (1)-(3) are shown below:

[0024]

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

[0026] Furthermore, in step 1, the reaction time of the compound represented by formula (1) with hydroquinone and alkaline substance in the first solvent is 4-12 hours; preferably, the reaction time is 8-9 hours.

[0027] Furthermore, in step 1, 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.

[0028] Furthermore, in step 1, the first solvent is selected from one or more of water, methanol, ethanol, isopropanol and n-butanol.

[0029] Furthermore, in step 1, after the reaction is completed, the steps of suction filtration, drying the filtrate and then distilling under reduced pressure to remove the solvent are also included.

[0030] Furthermore, in step 1, the preparation method of the compound represented by formula (1) comprises the following steps:

[0031] At 0-10° C., under the catalytic action of the first catalyst composition, reacting the compound represented by formula (a), the compound represented by formula (b) and a basic compound, after the reaction is completed, a compound represented by formula (1) is obtained;

[0032] Wherein, the compounds represented by formula (a) and (b) are as shown below:

[0033]

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

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

[0036] Furthermore, in step 2, the molar ratio of the compound represented by formula (2), 4-chloro-3-fluorobenzonitrile, the alkaline 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 2 is 10-16 hours.

[0038] Furthermore, in step 2, 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.

[0039] Furthermore, in step 2, 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 and detailed research that by using a catalyst composition in combination with 4-chloro-3-fluorobenzonitrile to catalyze the aromatic etherification reaction, (R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy acid] propionate butyl ester (cyhalofop-butyl) can be efficiently synthesized. In the case where the synthesis method of the present application does not use a catalyst, the yield of cyhalofop-butyl is low (about 46%), while by using a homemade catalyst composition for catalytic reaction, the aromatic etherification reaction can proceed smoothly, no dietherification byproducts are generated during the reaction, and cyhalofop-butyl can be obtained in high yield.

[0041] The above technical solution of the present invention has the following beneficial effects:

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

[0043] 2. The synthesis method of cyhalofop-butyl provided by the present invention has readily available raw materials, high yield, low cost, mild reaction conditions, is environmentally friendly, and meets the requirements of green chemistry.

[0044] The above description is only an overview of the technical solution of the present invention. In order to more clearly understand the technical means of the present invention and implement it according to the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention. DETAILED DESCRIPTION

[0045] The present invention is further described below in conjunction with specific embodiments so that those skilled in the art can better understand the present invention and implement it, but the embodiments are not intended to limit the present invention.

[0046] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods, and the materials, reagents, etc. used are all available from commercial sources unless otherwise specified.

[0047] Example 1

[0048] A catalyst composition, measured by mole, comprising:

[0049] 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 sulfite (molar ratio 1:1); the second composite component includes sodium bromide and cuprous chloride (molar ratio 1:1); the third composite component includes bipyridine, triethylbenzyl ammonium chloride and PEG-400 (molar ratio 1:1:1).

[0050] The above catalyst composition can be weighed according to the formula and mixed evenly.

[0051] Example 2

[0052] A catalyst composition, measured by mole, comprising:

[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 insurance powder (molar ratio 1:1); the second composite component includes potassium bromide and cuprous iodide (molar ratio 1:1); the third composite component includes bipyridine, tetrabutylammonium iodide and 18-crown-6 (molar ratio 1:1:1).

[0054] The above catalyst composition can be weighed according to the formula and mixed evenly.

[0055] Example 3

[0056] A catalyst composition, measured by mole, comprising:

[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 hydrosulfite (molar ratio 1:1); the second composite component includes copper chloride and copper acetate (molar ratio 1:1); the third composite component includes 1,10-phenanthroline, tetrabutylammonium iodide and PEG-600 (molar ratio 1:1:1).

[0058] The above catalyst composition can be weighed according to the formula and mixed evenly.

[0059] Example 4

[0060] A catalyst composition, measured by mole, comprising:

[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 hydrosulfite (molar ratio 1:1); the second composite component includes sodium iodide and cuprous iodide (molar ratio 1:1); the third composite component includes 1,10-phenanthroline, tetrabutylammonium iodide and PEG-600 (molar ratio 1:1:1).

[0062] The above catalyst composition can be weighed according to the formula and mixed evenly.

[0063] The catalyst compositions of Examples 1-4 were tested for catalytic aromatic etherification reaction, and the catalyst composition provided in Example 4 was preferred based on the test results.

[0064] Example 5

[0065] The preparation method of butyl p-toluenesulfonyl lactate comprises 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. 172.2 g (0.909 mol) of p-toluenesulfonyl chloride and 350 mL of toluene solution were added dropwise and reacted for 10 h. After the reaction was completed, the mixture was filtered and the organic phase was washed with water, dried and concentrated to obtain 220.7 g of an oily product (1). The yield of the reaction step was calculated to be 80.9%.

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

[0068]

[0069] The characterization data of product (1) are as follows: 1 H NMR(400MHz,Chloroform-d)δ7.82(d,J=8.4Hz,2H),7.34(d,J=8.0Hz,2H),4.92(t,J=6.9Hz,1H),4. 06(td,J=6.7,1.4Hz,2H),2.45(s,3H),1.58–1.48(m,5H),1.38–1.28(m,2H),0.91(t,J=7.4Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ169.13,145.03,133.42,129.79,127.99,74.17,65.62,30.35,21.65,18.91,18.44,13.62.HEMS(ESI-TOF):[M+H] + m / z calculation for C 14 H 21 O5S + :301.1005,found:230.1003.

[0070] Characterization data prove that Example 5 prepared butyl p-toluenesulfonyl lactate.

[0071] Example 6

[0072] The preparation method of (R)-2-(4-hydroxyphenoxy)butyl propionate comprises the following steps:

[0073] 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 were mixed, and then 0.038 mol of butyl p-toluenesulfonyl lactate 11.60 g and 70 mL of ethanol were added dropwise at 5°C, and the mixture was reacted for 8 hours. An appropriate amount of hydrochloric acid was added dropwise to adjust the pH to 6-7, and the ethanol was evaporated 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 solvent was evaporated under reduced pressure from the filtrate to obtain 8.86 g of product (2). The yield of this reaction step was calculated to be 98.0%.

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

[0075]

[0076] The characterization data of product (2) are as follows: 1 H NMR(400MHz,Chloroform-d)δ6.77–6.56(m,4H),5.12(s,1H),4.58(d,J=6.8Hz,1H) ,4.08(q,J=6.5Hz,2H),1.57–1.48(m,5H),1.30–1.17(m,2H),0.82(t,J=7.4Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ172.90,151.59,150.43,116.60,116.08,73.63,65.18,30.52,18.96,18.66,13.61.HEMS(ESI-TOF):[M+H] + m / zcalcd for C 13 H 19 O4 + :239.1205,found:239.1207.

[0077] Characterization data prove that Example 6 prepared (R)-butyl 2-(4-hydroxyphenoxy)propionate.

[0078] Example 7

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

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

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

[0082]

[0083] The characterization data of product (3) are as follows: 1 H NMR(400MHz,Chloroform-d)δ7.57–7.25(m,2H),7.04–6.81(m,5H),4.74(q,J=6.8Hz ,1H),4.34–4.09(m,2H),1.67–1.54(m,5H),1.40–1.26(m,2H),0.91(t,J=7.4Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ172.01,155.08,153.60,151.09,150.57,150.47,148.48,129.36,129.32,121.04,120.64,120.4 3,118.50,118.48,117.66,117.64,116.58,106.02,105.94,73.11,65.18,30.51,18.95,18.59,13.60.HEMS(ESI-TOF):[M+Na] + m / z calculation for C 20 H 21 O4F + :358.1402,found:358.1404.

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

[0085] Based on the above embodiments, it can be clearly seen that the catalyst composition provided by the present invention has a high catalytic efficiency when catalyzing the aromatic etherification reaction; the synthesis method of cyhalofop-butyl provided by the present invention has easy-to-obtain raw materials, high yield, low cost, mild reaction conditions, environmental friendliness, and meets the requirements of green chemistry. The above process route is relatively feasible and suitable for industrial-scale production.

[0086] Obviously, the above embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Those skilled in the art should understand that other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A method for synthesizing cyhalofop-butyl, characterized in that: The following steps are involved: Step 1: reacting the compound represented by formula (1), hydroquinone and an alkaline substance in a first solvent at 0-90° C. under the action of a first catalyst composition, and obtaining a compound represented by formula (2) after the reaction is completed; Step 2: reacting the compound represented by formula (2) with 4-chloro-3-fluorobenzonitrile in a second solvent to which a basic substance is added at 80-100° C. under the action of a second catalyst composition, to obtain a compound represented by formula (3) after the reaction is completed; Wherein, the first catalyst composition and the second catalyst composition are independently catalyst compositions for catalyzing aromatic etherification reaction, and the catalyst composition comprises 50-70 parts of the first composite component, 20-40 parts of the second composite component, and 5-15 parts of the third composite component by mole; wherein, The first composite component includes one or more of 4A molecular sieve, sodium sulfite and sodium hydrosulfite; The second composite component includes one or more of sodium bromide, potassium bromide, cupric chloride, cupric bromide, sodium iodide, potassium iodide, cupric iodide, cuprous chloride, cuprous iodide and cupric acetate; The third composite component includes one or more of bipyridine, 1,10-phenanthroline, triethylbenzyl ammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, polyethylene glycol-400, polyethylene glycol-600 and 18-crown-6; The compounds represented by formula (1)-(3) are shown below:

2. The synthesis method according to claim 1, characterized in that In step 1, the molar ratio of the compound represented by formula (1), hydroquinone, alkaline substance and the first catalyst composition is 1:(1.5-2):(2-3):(0.1-0.3).

3. The synthesis method according to claim 1, characterized in that In step 1, 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.

4. The synthesis method according to claim 1, characterized in that In step 1, the first solvent is selected from one or more of water, methanol, ethanol, isopropanol and n-butanol.

5. The synthesis method according to claim 1, characterized in that In step 1, the preparation method of the compound represented by formula (1) comprises the following steps: At 0-10° C., under the catalytic action of the first catalyst composition, reacting the compound represented by formula (a), the compound represented by formula (b) and a basic compound, after the reaction is completed, a compound represented by formula (1) is obtained; Wherein, the compounds represented by formula (a) and (b) are as shown below:

6. The synthesis method according to claim 5, characterized in that The alkaline compound is selected from one or more of triethylamine, pyridine, sodium hydroxide and potassium hydroxide.

7. The synthesis method according to claim 5, characterized in that The molar ratio of the compound represented by formula (a), the compound represented by formula (b) and the basic compound is 1:(1.5-1.8):(1.6-1.9).

8. The synthesis method according to claim 1, characterized in that In step 2, the molar ratio of the compound represented by formula (2), 4-chloro-3-fluorobenzonitrile, the alkaline substance and the second catalyst composition is 1:(1.2-1.5):(0.5-1):(0.1-0.3).

9. The synthesis method according to claim 1, characterized in that In step 2, 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.

10. The synthesis method according to claim 1, characterized in that In step 2, 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.

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