Synthesis method of 1-tribromomethylsulfonyl naphthalene and derivatives thereof

Abstract

The invention discloses a synthesis method of 1-tribromomethylsulfonyl naphthalene and derivatives thereof, and belongs to the technical field of chemical synthesis, the method comprises the following steps: S1, adding sodium methanesulfinate, a catalyst, a ligand and a solvent A into a compound 1, heating to 80-130 DEG C, stirring for 20-30 hours at 80-130 DEG C, cooling to room temperature, adding water and a solvent B, stirring for liquid separation, taking organic layer liquid, and evaporating out the solvent to obtain a compound 2; an intermediate compound 2 is obtained; s3, mixing the intermediate compound 2 and a solvent C, stirring until the intermediate compound 2 and the solvent C are dissolved, adding alkali and a sodium hypobromite aqueous solution, reacting at room temperature for 24-30 hours, then cleaning with water, filtering and drying in vacuum; the 1-tribromomethylsulfonyl naphthalene and the derivative thereof are synthesized by taking relatively cheap iodonaphthalene and the derivative thereof as raw materials through a two-step method, so that the total yield can be increased, the cost can be effectively reduced, the atom conversion rate can be increased, and the environmental pollution can be reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical synthesis, and particularly relates to a method for synthesizing 1-tribromomethylsulfonylnaphthalene and its derivatives. Background Art

[0002] Tribromomethylsulfonyl compounds often have biological activities and are commonly used in the preparation of pesticides, herbicides, fungicides, algaecides, etc. In organic synthesis, tribromomethylsulfonyl compounds are often used as reagents for introducing difluoromethyl or benzenesulfonyldifluoromethyl into different types of organic compounds. In addition, 1-tribromomethylsulfonylnaphthalene and its derivatives belong to tribromomethylsulfonyl compounds and have extensive applications in the preparation of pesticides, herbicides, fungicides, algaecides and the field of antifoggants.

[0003] When preparing tribromomethylsulfonyl compounds, generally, a mercapto compound is used as a raw material, which reacts with chloroacetic acid to obtain an intermediate carboxymethylthio compound, and then bromination is carried out. However, the raw material cost of the above process route is relatively high, the yield is low, the total yield of the two-step reaction is only 16.3%, the atomic conversion rate is low, and the environmental pollution is large. Summary of the Invention

[0004] Aiming at the deficiencies existing in the prior art, the present invention provides a method for synthesizing 1-tribromomethylsulfonylnaphthalene and its derivatives. Using cheaper iodonaphthalene and its derivatives as raw materials, 1-tribromomethylsulfonylnaphthalene and its derivatives are synthesized by a two-step method, which can improve the total yield, effectively reduce the cost, increase the atomic conversion rate, and reduce environmental pollution.

[0005] To solve the above technical problems, the technical solutions adopted by the present invention are as follows: A method for synthesizing 1-tribromomethylsulfonylnaphthalene and its derivatives, the synthesis route is as follows: ;

[0006] wherein, R 1 -R 7 is a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group, and R 1 -R 7 are the same or different groups.

[0007] A method for synthesizing 1-tribromomethylsulfonylnaphthalene and its derivatives, comprising the following steps: S1, adding sodium methylsulfinate, a catalyst, a ligand, and solvent A to compound 1, heating to 80-130 °C, stirring at 80-130 °C for 20-30 h, cooling to room temperature, adding water and solvent B, stirring and separating the liquid, taking the organic layer liquid, and evaporating the solvent to obtain intermediate compound 2; In S1, the compound 1 is 1-iodonaphthalene or its derivative, and the structural formula of the compound 1 is: ;

[0008] Among them, R 1 -R 7 is a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group, and R 1 -R 7 are the same or different groups; The catalyst is copper(I) trifluoromethanesulfonate tris(acetonitrile); The ligand is one of N,N-di-tert-butylethylenediamine or N,N-dimethylethylenediamine; The solvent A is one of DMF or DMSO; The solvent B is one of ethyl acetate, dichloromethane, or petroleum ether; The stirring time in the stirring and liquid separation is 20 - 40 min; The molar ratio of the compound 1 to sodium methylsulfinate is 1:1 - 1.5; The molar ratio of the compound 1 to the catalyst is 1:0.03 - 0.06; The molar ratio of the compound 1 to the ligand is 1:0.06 - 0.12; The dosage ratio of the compound 1 to the solvent A is 1 mol:0.8 - 1.2 L; The dosage ratio of the compound 1 to water is 1 mol:2 - 2.5 L; The dosage ratio of the compound 1 to the solvent B is 1 mol:1 - 1.5 L; The intermediate compound 2 is 1-methylsulfonylnaphthalene or its derivative, and the structural formula of the intermediate compound 2 is: ;

[0009] Among them, R 1 -R 7 is a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group, and R 1 -R 7 are the same or different groups; In S2, sodium hydroxide and deionized water are mixed, stirred until clear at -10°C to 0°C, bromine is added, and stirred for reaction to obtain an aqueous solution of sodium hypobromite; In S2, the molar ratio of sodium hydroxide to bromine is 3 - 6:1; The dosage ratio of sodium hydroxide to deionized water is 18 g:130 - 150 mL; The reaction time of stirring is 50 - 70 min; S3. Mix intermediate compound 2 and solvent C, stir until dissolved, add a base and an aqueous solution of sodium hypobromite, react at room temperature for 24 - 30 h to obtain a reaction mixture, wash the reaction mixture with water, filter, and dry under vacuum to obtain product 1 - tribromomethylsulfonylnaphthalene or its derivative; In S3, the solvent C is one of 1,4 - dioxane, DMSO, and DMF; The base is sodium hydroxide or potassium hydroxide; The dosage ratio of intermediate compound 2 to solvent C is 1 mol:0.5 - 1.5 L; The molar ratio of intermediate compound 2 to the base is 1:3 - 6.5; The molar ratio of intermediate compound 2 in S3 to bromine in S2 is 1:4 - 8; The structural general formula of the 1 - tribromomethylsulfonylnaphthalene and its derivative product is: ;

[0010] Among them, R 1 -R 7 is a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, or an amino group, and R 1 -R 7 are the same or different groups.

[0011] Compared with the prior art, the beneficial effects of the present invention are: (1) For the synthesis method of 1 - tribromomethylsulfonylnaphthalene and its derivative of the present invention, a relatively inexpensive catalyst is used. Through two - step reactions, the target product is obtained with high yield, less three - wastes, and simple equipment, which is suitable for industrial production.

[0012] (2) For the synthesis method of 1 - tribromomethylsulfonylnaphthalene and its derivative of the present invention, using relatively inexpensive iodonaphthalene and its derivative as raw materials, intermediate methylsulfonylnaphthalene or its derivative is obtained, and then brominated to obtain 1 - tribromomethylsulfonylnaphthalene. The raw material cost of this process route is relatively low, and the total yield of the two steps can reach 62.0 - 71.8%, which can greatly reduce the cost. Description of the Drawings

[0013] Figure 1 1H - NMR spectrum of intermediate 1 - methylsulfonylnaphthalene prepared in Example 1.

[0014] Figure 2 13C - NMR spectrum of intermediate 1 - methylsulfonylnaphthalene prepared in Example 1.

[0015] Figure 3 Mass spectrum of intermediate 1 - methylsulfonylnaphthalene prepared in Example 1.

[0016] Figure 4 1H NMR spectrum of product 1-(tribromomethylsulfonyl)naphthalene prepared in Example 1

[0017] Figure 5 13C NMR spectrum of product 1-(tribromomethylsulfonyl)naphthalene prepared in Example 1

[0018] Figure 6 Mass spectrum of product 1-(tribromomethylsulfonyl)naphthalene prepared in Example 1 Detailed implementation manners

[0019] For a clearer understanding of the technical features, objectives, and effects of the present invention, the detailed implementation manners of the present invention are now described.

[0020] The calculation formula for the total yield in Examples 1 - 5 = yield of the first step × yield of the second step.

[0021] Example 1 A synthesis method of 1-(tribromomethylsulfonyl)naphthalene, specifically as follows: 1. Add 49 g (0.48 mol) of sodium methylsulfinate, 7.5 g of copper(II) trifluoromethanesulfonate tetra(acetonitrile) (20 mmol), 6.9 g of N,N - di - tert - butylethylenediamine (40 mmol), and 320 mL of DMSO to 58.4 mL of 1 - iodonaphthalene (0.4 mol). Heat to 110 °C and stir at 110 °C for 30 h. Cool to room temperature, add 1000 mL of water and 450 mL of ethyl acetate, continue stirring for 30 min, separate the layers, take the organic layer liquid, evaporate the solvent to obtain 67.8 g of a white solid, which is intermediate 1 - methylsulfonylnaphthalene with a purity of 98.23% and a yield of 80.8%. The evaporated solvent is recycled; Perform 1H NMR analysis, 13C NMR analysis, and mass spectrometry on intermediate 1 - methylsulfonylnaphthalene. The obtained 1H NMR spectrum is shown in Figure 1 , the obtained 13C NMR spectrum is shown in Figure 2 , and the obtained mass spectrum is shown in Figure 3 ; Perform analysis on Figure 1 : 1 1H - NMR (400 MHz, DMSO - d 6 ) δ : 8.63 (d, J J = 8.4 Hz, 1H), 8.33(d, J J = 8.4 Hz, 1H), 8.24 (d, J J = 7.2 Hz, 1H), 8.16 (d, J= 8.0 Hz, 1H), 7.80 (t, J =7.2 Hz, 1H), 7.77–7.66 (m, 2H), 3.36 (s, 3H). Analysis of Figure 2 : 13 C-NMR (100 MHz, DMSO- d 6 ) δ : 135.8, 135.0, 133.8, 129.3, 129.0, 128.7, 127.8, 127.1, 124.8, 123.8, 43.9. Analysis of Figure 3 : The quasi-molecular ion peak is MS (ESI): 207.18 [M+H] + (calculated value is 207.05), 228.89 [M+Na] + (calculated value is 229.03); 2. After mixing 180 g of sodium hydroxide (4.5 mol) and 1400 mL of deionized water, stir at -10 °C until clear, slowly add dropwise 77 mL of bromine (1.5 mol), and continue stirring for 1 h after the addition is complete to obtain an aqueous sodium hypobromite solution; 3. After mixing 51.6 g (0.25 mol) of intermediate 1-methylsulfonylnaphthalene and 150 mL of 1,4-dioxane, stir until dissolved, then sequentially add 84.2 g of potassium hydroxide (1.5 mol) and all of the aqueous sodium hypobromite solution prepared in step 2, react at room temperature for 24 h to obtain a reaction mixture, wash the reaction mixture with 3 volumes of water, filter, and dry in vacuo at 60 °C to obtain 92.7 g of product 1-tribromomethylsulfonylnaphthalene, with a purity of 98.46% and a yield of 82.43%.

[0022] Perform nuclear magnetic resonance hydrogen spectrum analysis, nuclear magnetic resonance carbon spectrum analysis, and mass spectrometry analysis on the product 1-tribromomethylsulfonylnaphthalene. The nuclear magnetic resonance hydrogen spectrum obtained is shown in Figure 4 , and the nuclear magnetic resonance carbon spectrum obtained is shown in Figure 5 , and the mass spectrum obtained is shown in Figure 6 .

[0023] Analysis of Figure 4 : 1 H-NMR (400 MHz, DMSO- d 6 ) δ : 9.06 (d, J = 8.8 Hz, 1H), 8.59(d, J= 7.2 Hz, 1H), 8.54 (d, J = 8.0 Hz, 1H), 8.17 (d, J = 8.4 Hz, 1H), 7.88–7.79(m, 2H), 7.72 (t, J = 7.6 Hz, 1H). For Figure 5 analysis: 13 C-NMR (100 MHz, DMSO- d 6 ) δ : 138.34, 138.26, 133.9, 131.0, 129.2, 129.1, 127.3, 125.9, 124.4, 123.8, 51.5. For Figure 6 analysis: The quasi-molecular ion peak is MS (ESI): 465.08 [M+Na] + (the calculated value is 464.76).

[0024] In this example, the total yield of the product 1-tribromomethylsulfonylnaphthalene is 66.6%.

[0025] Example 2 A method for synthesizing 1-tribromomethylsulfonyl-6-methoxynaphthalene, specifically: 1. Add 49 g of sodium methylsulfinate, 6.8 g of copper(II) trifluoromethanesulfonate tetrakis(acetonitrile) (18 mmol), 6.2 g of N,N-di-tert-butylethylenediamine (36 mmol), and 400 mL of DMF to 113.6 g of 1-iodo-6-methoxynaphthalene (0.4 mol). Heat to 80 °C and stir at 80 °C for 30 h. Cool to room temperature, add 800 mL of water and 600 mL of ethyl acetate, continue to stir for 30 min, separate the layers, take the organic layer liquid, evaporate the solvent to obtain 80 g of a white solid, which is the intermediate 1-methylsulfonyl-6-methoxynaphthalene with a purity of 97.85% and a yield of 82.82%. The evaporated solvent is recycled; 2. Mix 90 g of sodium hydroxide (2.25 mol) and 700 mL of deionized water, stir until clear at 0 °C, slowly add 30 mL of bromine (0.58 mol), continue to stir for 1 h after the addition is complete to obtain an aqueous solution of sodium hypobromite; 3. Mix 27.5 g of intermediate 1-methylsulfonyl-6-methoxynaphthalene (0.117 mol) with 150 mL of DMSO, stir until dissolved, then successively add 30 g of sodium hydroxide (0.75 mol) and all of the sodium hypobromite aqueous solution prepared in Step 2, react at room temperature for 24 h to obtain a reaction mixture, wash the reaction mixture with 3 volumes of water, filter, and dry under vacuum at 80 °C to obtain 48.2 g of product 1-tribromomethylsulfonyl-6-methoxynaphthalene, with a purity of 98.16% and a yield of 85.49%.

[0026] In this example, the total yield of the product 1-tribromomethylsulfonyl-6-methoxynaphthalene is 70.8%.

[0027] Example 3 A method for synthesizing 1-(tribromomethyl)sulfonyl-2-methylnaphthalene, specifically: 1. Add 5.3 g of sodium methylsulfinate (0.052 mol), 0.60 g of copper(I) trifluoromethanesulfonate tetrakis(acetonitrile) (1.6 mmol), 0.55 g of N,N-di-tert-butylethylenediamine (3.2 mmol), and 36 mL of DMSO to 10.72 g of 1-iodo-2-methylnaphthalene (0.04 mol), heat to 100 °C, stir at 100 °C for 30 h, cool to room temperature, add 80 mL of water and 50 mL of dichloromethane, continue to stir for 30 min, separate the layers, take the organic layer liquid, evaporate the solvent to obtain 7.4 g of a white solid, which is the intermediate 1-methylsulfonyl-2-methylnaphthalene, with a purity of 98.27% and a yield of 82.52%. The evaporated solvent is recycled; 2. Mix 36.5 g of sodium hydroxide (0.9 mol) with 280 mL of deionized water, stir until clear at -5 °C, slowly add 11.7 mL of bromine (0.23 mol), continue to stir for 1 h after the addition is complete to obtain a sodium hypobromite aqueous solution; 3. Mix 6.7 g of intermediate 1-methylsulfonyl-2-methylnaphthalene (0.03 mol) with 30 mL of DMF, stir until dissolved, then successively add 6 g of sodium hydroxide (0.15 mol) and all of the sodium hypobromite aqueous solution prepared in Step 2, react at room temperature for 24 h to obtain a reaction mixture, wash the reaction mixture with 3 volumes of water, filter, and dry under vacuum at 60 °C to obtain 10.7 g of product 1-(tribromomethyl)sulfonyl-2-methylnaphthalene, with a purity of 97.82% and a yield of 76.3%.

[0028] In this example, the total yield of the product 1-(tribromomethyl)sulfonyl-2-methylnaphthalene is 63.0%.

[0029] Example 4 A method for synthesizing 4-(tribromomethylsulfonyl)naphthalen-1-amine, specifically as follows: 1. To 10.76 g (40 mmol) of 1-amino-4-iodonaphthalene, add 4.1 g (40 mmol) of sodium methylsulfinate, 0.45 g (1.2 mmol) of copper(II) trifluoromethanesulfonate tetrakis(acetonitrile), 0.21 g (2.4 mmol) of N,N-dimethylethylenediamine, and 32 mL of DMSO. Heat to 90 °C and continue stirring for 20 h. Cool to room temperature, add 80 mL of water and 60 mL of ethyl acetate, continue stirring for 30 min, separate the layers, take the organic layer liquid, evaporate the solvent to obtain 7.6 g of a white solid, which is the intermediate 4-(methylsulfonyl)naphthalen-1-amine with a purity of 98.36% and a yield of 84.56%. The evaporated solvent is recycled. 2. Mix 18 g of sodium hydroxide (450 mmol) and 140 mL of deionized water, stir until clear at -5 °C, slowly add 7.7 mL of bromine (150 mmol), and continue stirring for 1 h after the addition is complete to obtain an aqueous solution of sodium hypobromite. 3. Mix 5.5 g of the intermediate 4-(methylsulfonyl)naphthalen-1-amine (25 mmol) and 15 mL of DMF, stir until dissolved, then sequentially add 8.4 g of potassium hydroxide (150 mmol) and all of the sodium hypobromite prepared in step 2, react at room temperature for 24 h to obtain a reaction mixture. Wash the mixture with 3 volumes of water of the reaction mixture, filter, and dry under vacuum at 60 °C to obtain 9.9 g of the product 4-(tribromomethylsulfonyl)naphthalen-1-amine with a purity of 98.24% and a yield of 84.94%.

[0030] The total yield of the product 4-(tribromomethylsulfonyl)naphthalen-1-amine in this example is 71.8%.

[0031] Example 5 A method for synthesizing 1-(tribromomethylsulfonyl)-4-nitronaphthalene, specifically as follows: 1. To 12 g (40 mmol) of 1-iodo-4-nitronaphthalene, add 6.1 g (60 mmol) of sodium methylsulfinate, 0.9 g (2.4 mmol) of copper(II) trifluoromethanesulfonate tetrakis(acetonitrile), 0.42 g (4.8 mmol) of N,N-dimethylethylenediamine, and 48 mL of DMSO. Heat to 130 °C and continue stirring for 30 h. Cool to room temperature, add 100 mL of water and 60 mL of petroleum ether, continue stirring for 30 min, separate the layers, take the organic layer liquid, evaporate the solvent to obtain 8.1 g of a white solid, which is the intermediate 1-(methylsulfonyl)-4-nitronaphthalene with a purity of 97.66% and a yield of 78.79%. The evaporated solvent is recycled.

[0032] 2. After mixing 24 g of sodium hydroxide (600 mmol) and 185 mL of deionized water, stir at -5 °C until clear, slowly add 7.7 mL (150 mmol) of bromine, continue stirring for 1 h after the addition is complete to obtain an aqueous solution of sodium hypobromite; 3. Dissolve 6.3 g of intermediate 1-methylsulfonyl-4-nitronaphthalene (25 mmol) in 20 mL of 1,4-dioxane, stir until dissolved, then sequentially add 4.8 g of potassium hydroxide (86 mmol) and all of the aqueous sodium hypobromite solution prepared in step 2, react at room temperature for 30 h to obtain a reaction mixture, wash the mixture with 3 times the amount of water of the mixture, filter, and dry under vacuum at 60 °C to obtain 9.8 g of product 1-nitro-4-tribromomethylsulfonylnaphthalene, with a purity of 97.82% and a yield of 78.63%.

[0033] The total yield of the product 1-nitro-4-tribromomethylsulfonylnaphthalene in this example is 62.0%.

Claims

1. A method for synthesizing 1-tribromomethylsulfonylnaphthalene and its derivatives, characterized in that: The following steps are involved: S1, add sodium methanesulfinate, a catalyst, a ligand, and solvent A to compound 1, heat to 80-130°C, stir at 80-130°C for 20-30h, cool to room temperature, add water and solvent B, stir and separate, take the organic layer liquid, and evaporate the solvent to obtain intermediate compound 2; In S1, the compound 1 is 1-iodonaphthalene or its derivatives, and the structural formula of the compound 1 is: ； Wherein, R1-R7 are hydrogen atoms, alkyl groups, alkoxy groups, nitro groups, amine groups, and R1-R7 are the same or different groups; The catalyst is copper tetrakis(acetonitrile)trifluoromethanesulfonate; The ligand is one of N,N-di-tert-butylethylenediamine or N,N-dimethylethylenediamine; The solvent A is one of DMF or DMSO; The solvent B is one of ethyl acetate, dichloromethane and petroleum ether; The intermediate compound 2 is 1-methylsulfonylnaphthalene or a derivative thereof, and the structural formula of the intermediate compound 2 is: ； Wherein, R1-R7 are hydrogen atoms, alkyl groups, alkoxy groups, nitro groups, amine groups, and R1-R7 are the same or different groups; S2, mixing sodium hydroxide and deionized water, stirring at -10°C to 0°C until clear, adding bromine, stirring to react, and obtaining a sodium hypobromite aqueous solution; S3, mixing the intermediate compound 2 and the solvent C, stirring until dissolved, adding a base and an aqueous solution of sodium hypobromite, reacting at room temperature for 24-30 hours to obtain a reaction mixture, washing the reaction mixture with water, filtering, and vacuum drying to obtain a product 1-tribromomethylsulfonylnaphthalene or a derivative thereof; In S3, the solvent C is one of 1,4-dioxane, DMSO, and DMF; The alkali is sodium hydroxide or potassium hydroxide; The general structural formula of the 1-tribromomethylsulfonylnaphthalene and its derivative products is: ； Among them, R1-R7 are hydrogen atoms, alkyl groups, alkoxy groups, nitro groups, and amine groups, and R1-R7 are the same or different groups.

2. The method for synthesizing 1-tribromomethylsulfonylnaphthalene and its derivatives according to claim 1, characterized in that: In S1, the stirring time in the stirring and liquid separation is 20-40 min.

3. The method for synthesizing 1-tribromomethylsulfonylnaphthalene and its derivatives according to claim 1, characterized in that: In S1, the molar ratio of compound 1 to sodium methanesulfinate is 1:1-1.5; The molar ratio of compound 1 to the catalyst is 1:0.03-0.06; The molar ratio of compound 1 to the ligand is 1:0.06-0.

12.

4. The method for synthesizing 1-tribromomethylsulfonylnaphthalene and its derivatives according to claim 1, characterized in that: In S1, the ratio of compound 1 to solvent A is 1 mol:0.8-1.2 L; The dosage ratio of compound 1 to water is 1 mol:2-2.5 L; The usage ratio of compound 1 to solvent B is 1 mol:1-1.5L.

5. The method for synthesizing 1-tribromomethylsulfonylnaphthalene and its derivatives according to claim 1, characterized in that: In S2, the molar ratio of sodium hydroxide to bromine is 3-6:1; The dosage ratio of sodium hydroxide to deionized water is 18g:130-150mL; The stirring reaction time is 50-70 minutes.

6. The method for synthesizing 1-tribromomethylsulfonylnaphthalene and its derivatives according to claim 1, characterized in that: In S3, the ratio of the intermediate compound 2 to the solvent C is 1 mol:0.5-1.5 L; The molar ratio of the intermediate compound 2 to the base is 1:3-6.

5.

7. The method for synthesizing 1-tribromomethylsulfonylnaphthalene and its derivatives according to claim 1, characterized in that: The molar ratio of the intermediate compound 2 in S3 to the bromine in S2 is 1:4-8.

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