A method for synthesizing 1-trimethylsilylnaphthalene and derivatives thereof

Abstract

The application discloses a synthesis method of 1-trimethylsulfonylnaphthalene and derivatives thereof, and belongs to the technical field of chemical synthesis. The method comprises the following steps: S1, adding methylsulfinic acid sodium, a catalyst, a ligand and a solvent A into a compound 1, heating to 80-130 DEG C, stirring at 80-130 DEG C for 20-30 hours, reducing to room temperature, adding water and a solvent B, stirring and separating, taking organic layer liquid, evaporating the solvent, and obtaining an intermediate compound 2; and S3, mixing the intermediate compound 2 and a solvent C, stirring until dissolution, adding a base and a sodium hypobromite aqueous solution, reacting at room temperature for 24-30 hours, then washing with water, filtering and vacuum drying. The method uses iodine naphthalene and derivatives thereof as raw materials, synthesizes 1-trimethylsulfonylnaphthalene and derivatives thereof through a two-step method, can improve the total yield, effectively reduces the cost, improves the atomic conversion rate and reduces environmental pollution.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of chemical synthesis, in particular to a synthesis method of 1-trimethylsilyl naphthalene and its derivatives. BACKGROUND

[0002] The trimethylsilyl compound often has biological activity, and is often used in the preparation of insecticides, herbicides, fungicides, and algicides. In organic synthesis, the trimethylsilyl compound is often used as a reagent for introducing difluoromethyl or phenylsulfonyl difluoromethyl into different types of organic compounds. In addition, 1-trimethylsilyl naphthalene and its derivatives belong to trimethylsilyl compounds, and are widely used in the preparation of insecticides, herbicides, fungicides, and anti-fogging agents.

[0003] In the preparation of trimethylsilyl compounds, mercapto compounds are generally used as raw materials to react with chloroacetic acid to obtain intermediate carboxymethylthio compounds, and then bromination is performed. However, the above process route has relatively high raw material cost, low yield, and 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

[0004] In view of the deficiencies of the prior art, the present application provides a synthesis method of 1-trimethylsilyl naphthalene and its derivatives, which uses cheaper iodine naphthalene and its derivatives as raw materials, and synthesizes 1-trimethylsilyl naphthalene and its derivatives through a two-step method, which can improve the total yield, effectively reduce the cost, improve the atomic conversion rate, and reduce environmental pollution.

[0005] To solve the above technical problems, the technical scheme adopted by the present application is as follows:

[0006] A synthesis method of 1-trimethylsilyl naphthalene and its derivatives, the synthesis route is as follows:

[0007] ;

[0008] Among them, R1-R7 are hydrogen atoms, alkyl, alkoxy, nitro, amine group, and R1-R7 are the same or different groups.

[0009] A synthesis method of 1-trimethylsilyl naphthalene and its derivatives, comprising the following steps:

[0010] S1, sodium methylsulfinate, a catalyst, a ligand, and a solvent A are added to compound 1, heated to 80-130 DEG C, stirred at 80-130 DEG C for 20-30 h, cooled to room temperature, water and solvent B are added, stirred and separated, the organic layer liquid is taken out, and the solvent is distilled off to obtain intermediate compound 2;

[0011] In S1, the compound 1 is 1-iodonaphthalene or its derivative, and the structural formula of the compound 1 is:

[0012] ;

[0013] wherein, R1-R7 are hydrogen atoms, alkyl, alkoxy, nitro, amine groups, and R1-R7 are the same or different groups;

[0014] The catalyst is copper trifluoromethanesulfonate tetra(acetonitrile);

[0015] The ligand is one of N,N-di-tert-butyl ethylenediamine or N,N-dimethyl ethylenediamine;

[0016] The solvent A is one of DMF or DMSO;

[0017] The solvent B is one of ethyl acetate, dichloromethane, petroleum ether;

[0018] The stirring time in the stirring and separation is 20-40 min;

[0019] The molar ratio of compound 1 to sodium methylsulfinate is 1:1-1.5;

[0020] The molar ratio of compound 1 to the catalyst is 1:0.03-0.06;

[0021] The molar ratio of compound 1 to the ligand is 1:0.06-0.12;

[0022] The usage ratio of compound 1 to solvent A is 1 mol:0.8-1.2 L;

[0023] The usage ratio of compound 1 to water is 1 mol:2-2.5 L;

[0024] The usage ratio of compound 1 to solvent B is 1 mol:1-1.5 L;

[0025] In S2, the intermediate compound 2 is 1-methylsulfonylnaphthalene or its derivative, and the structural formula of the intermediate compound 2 is:

[0026] ;

[0027] wherein, R1-R7 are hydrogen atoms, alkyl, alkoxy, nitro, amine groups, and R1-R7 are the same or different groups;

[0028] In S2, sodium hydroxide and deionized water are mixed, stirred to be clear at-10℃ to 0℃, and then bromine is added, and the reaction is stirred to obtain a sodium hypobromite aqueous solution;

[0029] In S2, the molar ratio of sodium hydroxide to bromine is 3-6:1;

[0030] The ratio of the amount of sodium hydroxide to deionized water is 18g: 130-150mL;

[0031] The stirring time of the reaction is 50-70min;

[0032] S3, after mixing the intermediate compound 2 and the solvent C, stirring until dissolution, adding the base, the sodium hypobromite aqueous solution, reacting at room temperature for 24-30h, washing the reaction mixture with water, filtering, and vacuum drying to obtain the product 1-trimethylsulfonilnaphthalene or its derivative;

[0033] In S3, the solvent C is one of 1,4-dioxane, DMSO and DMF;

[0034] The base is sodium hydroxide or potassium hydroxide;

[0035] The ratio of the amount of the intermediate compound 2 to the solvent C is 1mol: 0.5-1.5L;

[0036] The molar ratio of the intermediate compound 2 to the base is 1: 3-6.5;

[0037] The molar ratio of the intermediate compound 2 in S3 to bromine in S2 is 1: 4-8;

[0038] The structural general formula of the product 1-trimethylsulfonilnaphthalene and its derivative is:

[0039] ;

[0040] Wherein, R1-R7 are hydrogen atoms, alkyl, alkoxy, nitro, amine group, and R1-R7 are the same or different groups.

[0041] Compared with the prior art, the present application has the following beneficial effects:

[0042] (1) The synthesis method of the 1-trimethylsulfonilnaphthalene and its derivative of the present application uses a relatively inexpensive catalyst, and the target product is obtained through two-step reaction, with high yield, less waste, simple equipment and suitable for industrial production.

[0043] (2) The synthesis method of the 1-trimethylsulfonilnaphthalene and its derivative of the present application uses relatively inexpensive iodine naphthalene and its derivative as raw material to obtain the intermediate product methylsulfonilnaphthalene or its derivative, and then bromination to obtain 1-trimethylsulfonilnaphthalene, the raw material cost of the 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. BRIEF DESCRIPTION OF DRAWINGS

[0044] Figure 1The nuclear magnetic resonance hydrogen spectrum of the intermediate 1-methylsulfonylnaphthalene prepared in Example 1.

[0045] Figure 2 The nuclear magnetic resonance carbon spectrum of the intermediate 1-methylsulfonylnaphthalene prepared in Example 1.

[0046] Figure 3 The mass spectrum of the product 1-tribromomethylsulfonylnaphthalene prepared in Example 1.

[0047] Figure 4 The nuclear magnetic resonance hydrogen spectrum of the product 1-tribromomethylsulfonylnaphthalene prepared in Example 1.

[0048] Figure 5 The nuclear magnetic resonance carbon spectrum of the product 1-tribromomethylsulfonylnaphthalene prepared in Example 1.

[0049] Figure 6 The mass spectrum of the product 1-tribromomethylsulfonylnaphthalene prepared in Example 1. DETAILED DESCRIPTION

[0050] In order to have a clearer understanding of the technical features, objectives and effects of the present application, the specific embodiments of the present application will now be described.

[0051] The calculation formula of the total yield in Examples 1-5 = the yield of the first step x the yield of the second step.

[0052] Example 1

[0053] A method for synthesizing 1-tribromomethylsulfonylnaphthalene, specifically comprising:

[0054] 1. Add 49 g (0.48 mol) of sodium methanesulfinate, 7.5 g of tetrakis(acetonitrile)copper (III) trifluoromethanesulfonate (20 mmol), 6.9 g of N,N-di-tert-butylethylenediamine (40 mmol) to 58.4 mL of 1-iodonaphthalene (0.4 mol), and add 320 mL of DMSO, heat to 110°C, stir at 110°C for 30 h, cool to room temperature, add 1000 mL of water and 450 mL of ethyl acetate, continue to stir for 30 min, separate the liquid, evaporate the solvent to obtain 67.8 g of white solid, which is the intermediate 1-methylsulfonylnaphthalene, with a purity of 98.23% and a yield of 80.8%, and the evaporated solvent is recycled;

[0055] The intermediate 1-methylsulfonylnaphthalene is subjected to nuclear magnetic resonance hydrogen spectrum analysis, nuclear magnetic resonance carbon spectrum analysis and mass spectrum analysis, the obtained nuclear magnetic resonance hydrogen spectrum is shown in Figure 1 , the obtained nuclear magnetic resonance carbon spectrum is shown in Figure 2 , and the obtained mass spectrum is shown in Figure 3 ;

[0056] TheFigure 1 Analysis: 1 H-NMR (400 MHz, DMSO- d 6) delta 8.63 (d, J = 8.4 Hz, 1H), 8.33(d, J = 8.4 Hz, 1H), 8.24 (d, 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).

[0057] right Figure 2 Analysis: 13 C-NMR (100 MHz, DMSO- d 6) delta : 135.8, 135.0, 133.8, 129.3, 129.0, 128.7, 127.8, 127.1, 124.8, 123.8, 43.9.

[0058] right Figure 3 Analysis revealed the quasi-molecular ion peak at MS (ESI): 207.18 [M+H]. + (Calculated value is 207.05), 228.89 [M+Na] + (The calculated value is 229.03);

[0059] 2. Mix 180g sodium hydroxide (4.5mol) and 1400mL deionized water, stir at -10℃ until clear, slowly add 77mL bromine (1.5mol), and continue stirring for 1h after the addition is complete to obtain sodium hypobromite aqueous solution;

[0060] 3. 51.6 g (0.25 mol) of intermediate 1-methylsulfonylnaphthalene and 150 mL of 1,4-dioxane were mixed and stirred until dissolved. Then, 84.2 g of potassium hydroxide (1.5 mol) and all of the sodium hypobromide aqueous solution prepared in step 2 were added sequentially. The mixture was reacted at room temperature for 24 h to obtain the reaction mixture. The reaction mixture was washed with 3 times its volume of water, filtered, and dried under vacuum at 60 °C to obtain 92.7 g of product 1-tribromomethylsulfonylnaphthalene with a purity of 98.46% and a yield of 82.43%.

[0061] The product 1-trimethylsilylnaphthalene was analyzed by H-NMR, C-NMR and MS. The obtained H-NMR spectrum is shown in Figure 4 , the obtained C-NMR spectrum is shown in Figure 5 , and the obtained MS spectrum is shown in Figure 6 .

[0062] The product Figure 4 was analyzed: 1 H-NMR (400 MHz, DMSO- d 6) delta : 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).

[0063] The product Figure 5 was analyzed: 13 C-NMR (100 MHz, DMSO- d 6) delta : 138.34, 138.26, 133.9,131.0, 129.2, 129.1, 127.3, 125.9, 124.4, 123.8, 51.5.

[0064] The product Figure 6 was analyzed: the quasi-molecular ion peak was MS (ESI): 465.08 [M+Na] + (calculated value was 464.76).

[0065] The total yield of the product 1-trimethylsilylnaphthalene in this embodiment was 66.6%.

[0066] Example 2

[0067] A method for synthesizing 1-trimethylsilylnaphthalene, specifically:

[0068] 1. To 113.6 g of 1-iodo-6-methoxynaphthalene (0.4 mol) was added 49 g of sodium methanesulfinate, 6.8 g of tetrakis(acetonitrile)copper (III) trifluoromethanesulfonate (18 mmol), 6.2 g of N,N-di-tert-butylethylenediamine (36 mmol), 400 mL of DMF, heated to 80 °C, stirred at 80 °C for 30 h, cooled to room temperature, added 800 mL of water, 600 mL of ethyl acetate, continued to stir for 30 min, separated the liquid, removed the solvent to obtain 80 g of white solid, which was intermediate 1-methylsulfonyl-6-methoxynaphthalene, purity 97.85%, yield 82.82%, and the removed solvent was recycled;

[0069] 2. After mixing 90 g of sodium hydroxide (2.25 mol) and 700 mL of deionized water, stirring at 0 °C until clear, slowly added 30 mL of bromine (0.58 mol), after dropwise addition, continued to stir for 1 h to obtain sodium hypobromite aqueous solution;

[0070] 3. After mixing 27.5 g of intermediate 1-methylsulfonyl-6-methoxynaphthalene (0.117 mol) and 150 mL of DMSO, stirred until dissolved, then added 30 g of sodium hydroxide (0.75 mol) and all the sodium hypobromite aqueous solution prepared in step 2, reacted at room temperature for 24 h to obtain a reaction mixture, after washing the reaction mixture with 3 times the volume of water, filtered, and dried at 80 °C under vacuum to obtain 48.2 g of product 1-tribromomethylsulfonyl-6-methoxynaphthalene, purity 98.16%, yield 85.49%.

[0071] The total yield of product 1-tribromomethylsulfonyl-6-methoxynaphthalene in this example was 70.8%.

[0072] Example 3

[0073] A method for synthesizing 1-(tribromomethyl)sulfonyl-2-methylnaphthalene, specifically:

[0074] 1. To 10.72 g of 1-iodo-2-methylnaphthalene (0.04 mol) was added 5.3 g of sodium methanesulfinate (0.052 mol), 0.60 g of tetrakis(acetonitrile)copper (III) trifluoromethanesulfonate (1.6 mmol), 0.55 g of N,N-di-tert-butylethylenediamine (3.2 mmol), 36 mL of DMSO, heated to 100 °C, stirred at 100 °C for 30 h, cooled to room temperature, added 80 mL of water, 50 mL of dichloromethane, continued to stir for 30 min, separated the liquid, removed the solvent to obtain 7.4 g of white solid, which was intermediate 1-methylsulfonyl-2-methylnaphthalene, purity 98.27%, yield 82.52%, and the removed solvent was recycled;

[0075] 2. Mix 36.5 g of sodium hydroxide (0.9 mol) and 280 mL of deionized water, stir until clear at -5°C, slowly add 11.7 mL of bromine (0.23 mol), continue stirring for 1 h after the dropwise addition is completed, to obtain an aqueous sodium hypobromite solution;

[0076] 3. Mix 6.7 g of intermediate 1-methylsulfonyl-2-methylnaphthalene (0.03 mol) and 30 mL of DMF, stir until dissolved, then add 6 g of sodium hydroxide (0.15 mol) and all 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 under vacuum at 60°C to obtain 10.7 g of product 1- (trifluoromethyl) sulfonyl-2-methylnaphthalene with a purity of 97.82% and a yield of 76.3%.

[0077] The total yield of product 1- (trifluoromethyl) sulfonyl-2-methylnaphthalene in this example is 63.0%.

[0078] Example 4

[0079] A method for synthesizing 4-trifluoromethylsulfonylnaphthalen-1-amine, specifically:

[0080] 1. To 10.76 g (40 mmol) of 1-amino-4-iodonaphthalene, add 4.1 g (40 mmol) of sodium methanesulfinate, 0.45 g (1.2 mmol) of copper (III) trifluoromethanesulfonate tetraacetonitrile, 0.21 g (2.4 mmol) of N,N-dimethylethylenediamine, and 32 mL of DMSO, heat to 90°C, 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 liquid organic layer, and evaporate the solvent to obtain 7.6 g of white solid, which is intermediate 4-methylsulfonylnaphthalen-1-amine with a purity of 98.36% and a yield of 84.56%, and the evaporated solvent is recycled;

[0081] 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), continue stirring for 1 h after the dropwise addition is completed, to obtain an aqueous sodium hypobromite solution;

[0082] 3. 5.5 g of intermediate 4-methylsulfonylnaphthalen-1-amine (25 mmol), 15 mL of DMF were mixed and stirred until dissolved, then 8.4 g of potassium hydroxide (150 mmol) and all the sodium hypobromite prepared in step 2 were added in turn, and the reaction was carried out at room temperature for 24 h to obtain a reaction mixture, which was washed with 3 times the volume of water, filtered, and dried at 60°C under vacuum to obtain 9.9 g of product 4-tribromomethylsulfonylnaphthalen-1-amine with a purity of 98.24% and a yield of 84.94%.

[0083] The total yield of product 4-tribromomethylsulfonylnaphthalen-1-amine in this example was 71.8%.

[0084] Example 5

[0085] A method for synthesizing 1-tribromomethylsulfonyl-4-nitronaphthalene, specifically:

[0086] 1. 12 g (40 mmol) of 1-iodo-4-nitronaphthalene was added to 6.1 g (60 mmol) of sodium methanesulfinate, 0.9 g (2.4 mmol) of tetrakis(acetonitrile)copper(III) trifluoromethanesulfonate, 0.42 g (4.8 mmol) of N,N-dimethylethylenediamine, 48 mL of DMSO, heated to 130°C, and stirred for 30 h, then cooled to room temperature, 100 mL of water and 60 mL of petroleum ether were added, and stirred for another 30 min, then the organic layer was separated and the solvent was evaporated to obtain 8.1 g of white solid, which was intermediate 1-methylsulfonyl-4-nitronaphthalene with a purity of 97.66% and a yield of 78.79%, and the evaporated solvent was recycled.

[0087] 2. 24 g of sodium hydroxide (600 mmol) and 185 mL of deionized water were mixed and stirred at -5°C until clear, then 7.7 mL (150 mmol) of bromine was slowly added, and after the addition was complete, the mixture was stirred for another 1 h to obtain an aqueous sodium hypobromite solution;

[0088] 3. 6.3 g of intermediate 1-methylsulfonyl-4-nitronaphthalene (25 mmol), 20 mL of 1,4-dioxane were mixed and stirred until dissolved, then 4.8 g of potassium hydroxide (86 mmol) and all the aqueous sodium hypobromite prepared in step 2 were added in turn, and the reaction was carried out at room temperature for 30 h to obtain a reaction mixture, which was washed with 3 times the volume of water, filtered, and dried at 60°C under vacuum to obtain 9.8 g of product 1-nitro-4-tribromomethylsulfonylnaphthalene with a purity of 97.82% and a yield of 78.63%.

[0089] The total yield of product 1-nitro-4-tribromomethylsulfonylnaphthalene in this example was 62.0%.

Claims

1. A process for the synthesis of 1-tribromomethylsulfonylnaphthalene and its derivatives, characterized by, The method comprises the following steps: S1, adding sodium methanesulfinate, a catalyst, a ligand, solvent A to compound 1, heating to 80-130 DEG C, stirring at 80-130 DEG C for 20-30 h, reducing to room temperature, adding water, solvent B, stirring, separating, taking the organic layer liquid, 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: ； Wherein, R1-R7 are hydrogen atoms, alkyl, alkoxy, nitro, amine groups, and R1-R7 are the same or different groups; The catalyst is copper trifluoromethanesulfonate tetra(acetonitrile); The ligand is one of N,N-di-tert-butyl ethylenediamine or N,N-dimethyl ethylenediamine; The solvent A is one of DMF or DMSO; The solvent B is one of ethyl acetate, dichloromethane, petroleum ether; The intermediate compound 2 is 1-methylsulfonylnaphthalene or its derivative, and the structural formula of the intermediate compound 2 is: ； Wherein, R1-R7 are hydrogen atoms, alkyl, alkoxy, nitro, amine groups, and R1-R7 are the same or different groups; The molar ratio of the compound 1 to the catalyst is 1:0.03-0.06; S2, mixing sodium hydroxide and deionized water, stirring to be clear at-10 DEG C to 0 DEG C, adding bromine, stirring to react, to obtain sodium hypobromite aqueous solution; S3, mixing the intermediate compound 2 and solvent C, stirring to dissolve, adding base and sodium hypobromite aqueous solution, reacting at room temperature for 24-30 h, washing the reaction mixture with water, filtering, vacuum drying, to obtain the product 1-trimethylsulfonylnaphthalene or its derivative; In S3, the solvent C is one of 1,4-dioxane, DMSO or DMF; The base is sodium hydroxide or potassium hydroxide; The molar ratio of the intermediate compound 2 to the base is 1:3-6.5; The structural general formula of the 1-trimethylsulfonylnaphthalene and its derivative product is: ； Wherein, R1-R7 are hydrogen atoms, alkyl, alkoxy, nitro, amine groups, and R1-R7 are the same or different groups.

2. The process for synthesis of 1-tribromomethylsulfonylnaphthalene and its derivatives as claimed in claim 1 wherein, In S1, the stirring time in the stirring separation is 20-40 min.

3. The process for synthesis of 1-tribromomethylsulfonylnaphthalene and its derivatives as claimed in claim 1, wherein, In S1, the molar ratio of the compound 1 to sodium methanesulfinate is 1:1-1.5; The molar ratio of the compound 1 to the ligand is 1:0.06-0.

12.

4. The process for synthesis of 1-tribromomethylsulfonylnaphthalene and its derivatives as claimed in claim 1, wherein, In S1, the usage ratio of the compound 1 to the solvent A is 1 mol:0.8-1.2 L; The usage ratio of the compound 1 to water is 1 mol:2-2.5 L; The usage ratio of the compound 1 to the solvent B is 1 mol:1-1.5 L.

5. The process for synthesis of 1-tribromomethylsulfonylnaphthalene and its derivatives as claimed in claim 1, wherein, In S2, the molar ratio of sodium hydroxide to bromine is 3-6:1; The usage ratio of sodium hydroxide to deionized water is 18 g:130-150 mL; The stirring reaction time is 50-70 min.

6. The process for synthesis of 1-tribromomethylsulfonylnaphthalene and its derivatives as claimed in claim 1, wherein, In S3, the usage ratio of the intermediate compound 2 to the solvent C is 1 mol:0.5-1.5 L.

7. The process for synthesis of 1-tribromomethylsulfonylnaphthalene and its derivatives as claimed in claim 1, wherein, The molar ratio of the intermediate compound 2 in S3 to bromine in S2 is 1:4-8.

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