CN1112355C - Difluore methane-sulfonic acid metal reagent, and its synthetic method and use - Google Patents
Difluore methane-sulfonic acid metal reagent, and its synthetic method and use Download PDFInfo
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- CN1112355C CN1112355C CN 01105780 CN01105780A CN1112355C CN 1112355 C CN1112355 C CN 1112355C CN 01105780 CN01105780 CN 01105780 CN 01105780 A CN01105780 A CN 01105780A CN 1112355 C CN1112355 C CN 1112355C
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Abstract
The present invention relates to a new difluore methane-sulfonic acid metal agent, a preparation method and functions thereof, namely that difluore methane-sulfonic acid and metallic oxides or metal hydroxides react so as to obtain the difluore methane-sulfonic acid metal agent, and the metals are zinc, cadmium, mercury, copper, silver, indium, tin, lead, antimony, bismuth, gold, thallium or yttrium, etc. The method has the advantages of moderate reaction condition, high yield and purity, easy operation, easy industrial production, etc.
Description
The invention relates to a novel difluoro methanesulfonic acid metal reagent, a synthetic method and application thereof.
The triflic acid metal reagent is a lewis acid commonly used to coordinate with chiral ligands to catalyze asymmetric chemical reactions. However, the metal triflate reagent is expensive, which limits its application in industrial production. Meanwhile, the cheap tetrafluoroethylene sultone is used as a raw material, and difluoro methanesulfonic acid (Chen, Qingyun; Wu Shengwen, J.Fluorine chem.1990, 47(3), 509-. The synthesis is described by the following reaction formula:
it is an object of the present invention to provide a novel metal difluoromethanesulfonate reagent.
The invention also aims to provide a synthesis method of the difluoro methanesulfonic acid metal reagent.
The invention also aims to provide the application of the difluoro methanesulfonic acid metal reagent.
The molecular general formula of the difluoro methanesulfonic acid metal reagent provided by the invention is M (OSO)2CF2H)nWherein, the metal M is zinc, cadmium, mercury, copper, silver, indium, tin, lead, antimony, bismuth, gold, thallium or ytterbium, etc., and n is 1-3. For example, zinc difluoromethanesulfonate, cadmium difluoromethanesulfonate, mercury difluoromethanesulfonate, copper difluoromethanesulfonate, silver difluoromethanesulfonate, indium difluoromethanesulfonate, tin difluoromethanesulfonate, lead difluoromethanesulfonate, antimony difluoromethanesulfonate, bismuth difluoromethanesulfonate, gold difluoromethanesulfonate, thallium difluoromethanesulfonate, ytterbium difluoromethanesulfonate, etc
The synthesis method of the invention is that difluoro methanesulfonic acid reacts with metal oxide or metal hydroxide to obtain difluoro methanesulfonic acid metal reagent in or without solvent at-10-100 ℃, and the reaction formula isFor example: wherein M, n is as previously described. The molar ratio of the difluoromethanesulfonic acid to the metal oxide or hydroxide is 1: 0.1-5, the recommended molar ratio is 1: 0.1-1, the more optimized molar ratio is 1: 0.16-0.5, the reaction is carried out for several minutes to 60 hours, and the reaction time can be prolonged, the reaction temperature can be increased or the dosage of reactants can be increased in the reaction. The solvent is H2O。
The difluoro methanesulfonic acid metal reagent can be used as a catalyst for organic synthesis reaction. For example, the compound can be used as a catalyst to replace a zinc trifluoromethanesulfonate reagent and is used for catalyzing the reaction of terminal alkyne and aldehyde to synthesize a secondary propargyl alcohol compound and the like.
The method has simple operation and the yield is more than 97 percent, and the obtained difluoromethanesulfonic acid metal reagent has similar chemical properties with trifluoromethanesulfonic acid metal reagent, but has lower price than trifluoromethanesulfonic acid metal reagent, can replace trifluoromethanesulfonic acid metal reagent for asymmetric chemical reaction, and is easy for industrial production.
The following examples are provided to aid understanding of the invention, but are not intended to limit the scope of the invention.
Example 1
FSO2CF2Preparation of COOH
670ml of petroleum ether and 800g (about 500ml, 4.44mol) of tetrafluoroethylene sultone were put into a 2000ml three-neck reaction flask, and H was dropped from a dropping funnel at a low temperature2O80 g (4.44mol), and after the addition, the mixture was stirred at room temperature overnight. Separating out the lower layer, distilling under reduced pressure, and collecting the boiling point: 80-83 deg.C/40 mmHg fraction, yield 69%.
Example 2
HCF2SO2Preparation of F
Mixing Na2SO4(28.4g, 0.2mol), 500mL acetonitrile and 500-1000mL distilled water were added with electromagnetic stirringA dropping funnel and a reflux condenser in a 1000mL three-necked flask. Slowly dropping FSO at 25 DEG C2CF2356g of COOH (2.0mol), stirred at room temperature overnight. The separatory funnel separated the organic and aqueous layers. The organic layer was washed twice with saturated brine: 100ml × 2. Obtaining HCF2SO2125.0g of crude F can be directly used for the next reaction.
Example 3
HCF2SO2And (4) preparing OH.
Mixing HCF2SO2250g of crude F, 200mL of Tetrahydrofuran (THF) and 200mL of distilled water were placed in a 2000mL single-neck reaction flask. Stirred at 80 ℃ overnight.19F NMR tracks the progress of the reaction, after the reaction is finished, a small amount of unreacted raw materials and THF are recovered by distillation, toluene with water is added, and the toluene is removed under reduced pressure. Vacuum distillation is carried out, and 240g of fraction at 110-112 ℃/10mmHg is collected. The compound is prepared by1H NMR，19F NMR confirmed. Based on fluorine-containing raw materials, the difluoromethanesulfonic acid is synthesized by three steps of reactions of rearrangement, decarboxylation and hydrolysis from tetrafluoroethylene sultone, and the total yield is 31%.
Example 4
Preparation of zinc difluoromethanesulfonate
To a 200ml beaker was added 4.1 g (0.05mol) zinc oxide followed by 50 ml water at room temperature. 13.2g (0.10mol) of difluoromethanesulfonic acid was slowly added dropwise to the beaker until the white powder was substantially dissolved. Stirring and standing to make it fully react. The reaction solution was filtered to remove a trace of solid residue. The filtrate was rotary evaporated to remove a large amount of water and dried under vacuum for 24 hours (110 ℃). Weighing 16.2g. yield: 98 percent. Zinc difluoromethanesulfonate:1H NMR(60MHz，CD3COCD3)，δ：6.1ppm(t，J＝52Hz)19F NMR(56.4MHz，CD3COCD3，CF3COOH as external standard, high field positive), δ: 77.0ppm (d, J ═ 52Hz) elemental analysis (fluorine) theoretical values: 23.20%, found: 23.31％Elemental analysis (fluorine) theoretical value: 23.20%, found: 23.31% moisture content:<0.1% (weight loss by heat method)
Example 5
Preparation of cadmium difluoromethanesulfonate
12.8 g (0.10mol) of cadmium oxide and 20 ml of water are added successively at room temperature to a 200ml beaker. 26.4g (0.20mol) of difluoromethanesulfonic acid was slowly added dropwise to the beaker until the solid was substantially dissolved, and the mixture was allowed to stand slightly hot to allow sufficient reaction. The reaction solution was filtered to remove a trace of solid residue. The above filtrate was rotary evaporated to remove a large amount of water. Dried under vacuum for 24 hours (110 ℃). 36.7g were weighed. The yield was 98%. Cadmium difluoromethanesulfonate:1H NMR(60MHz，CD3COCD3)，δ：6.1ppm(t，J＝52Hz)19F NMR(56.4MHz，CD3COCD3，CF3COOH as external standard, high field positive), δ: 77.2ppm (d, J ═ 52Hz) elemental analysis (fluorine) theoretical values: 20.29%, found: 20.27% moisture content:<0.1% (weight loss by heat method)
Example 6
Preparation of mercury difluoromethanesulfonate
To a 200ml beaker was added 21.7 g (0.10mol) of mercuric oxide and 100ml of water at 90 ℃. 26.4g (0.20mol) of difluoromethanesulfonic acid was slowly added dropwise to the beaker until the solid was substantially dissolved, and the reaction was allowed to proceed sufficiently. The reaction solution was filtered to remove a trace of solid residue. The above filtrate was rotary evaporated to remove a large amount of water. Dried under vacuum for 24 hours (110 ℃). Weigh 45.4g. yield 98%. Mercury difluoromethanesulfonate:1H NMR(60MHz，CD3COCD3)，δ：6.2ppm(t，J＝52Hz)19F NMR(56.4MHz，CD3COCD3，CF3COOH as external standard, high field positive) δ: 77.0ppm (d, J ═ 52Hz) elemental analysis (fluorine) theoretical values: 16.42%, found: 16.50% moisture content:<0.1% (weight loss by heat method)
Example 7
Preparation of copper difluoromethanesulfonate
8.0 g (0.10mol) of copper oxide and 50 ml of water were added in succession to a 200ml beaker at room temperature. 26.4g (0.20mol) of difluoromethanesulfonic acid was slowly added dropwise to the beaker until the solid was substantially dissolved. And (5) standing for slight heating to fully react. The reaction solution was filtered to remove a trace of solid residue. The above filtrate was rotary evaporated to remove a large amount of water. Dried under vacuum for 24 hours (110 ℃). 31.9g were weighed. The yield was 98%. Copper difluoromethanesulfonate:1H NMR(60MHz，CD3COCD3)，δ：6.0ppm(t，J＝52Hz)19F NMR(56.4MHz，CD3COCD3，CF3COOH as external standard, high field positive) δ: 77.5ppm (d, J ═ 52Hz) elemental analysis (fluorine) theoretical values: 23.33%, found: 23.31% moisture content:<0.1% (weight loss by heat method)
Example 8
Preparation of silver difluoromethanesulfonate
To a 200ml beaker was added 23.2g (0.10mol) of silver oxide followed by 50 ml of water at room temperature. 26.4g (0.20mol) of difluoromethanesulfonic acid was slowly added dropwise to the beaker until the solid was substantially dissolved, at which time the pH was 1-2. And (5) standing for slight heating to fully react. The reaction solution was filtered to remove a trace of solid residue. The above filtrate was rotary evaporated to remove a large amount of water. Dried under vacuum for 24 hours (110 ℃). Weight 46.8g. yield 97%. Silver difluoromethanesulfonate:1H NMR(60MHz，CD3COCD3)，δ：6.1ppm(t，J＝52Hz)19F NMR(56.4MHz，CD3COCD3，CF3COOH as external standard, high field positive) δ: 77.0ppm (d, J ═ 52Hz) elemental analysis (fluorine) theoretical values: 15.90%, found: 16.05% moisture content:<0.1% (weight loss by heat method)
Example 9
Preparation of indium difluoromethanesulfonate
16.6 g (0.10mol) of indium hydroxide and 50 ml of water are added in succession to a 200ml beaker at room temperature. 39.6g (0.30mol) of difluoromethanesulfonic acid was slowly added dropwise to the beaker until the solid was substantially dissolved, at which time the pH was 1-2. Standing slightly hot to make it filledAnd (4) carrying out reaction. The reaction solution was filtered to remove a trace of solid residue. The above filtrate was rotary evaporated to remove a large amount of water. Dried under vacuum for 24 hours (110 ℃). Weigh 49.8g. yield 98%. Indium difluoromethanesulfonate:1H NMR(60MHz，CD3COCD3)，δ：6.1ppm(t，J＝52Hz)19F NMR(56.4MHz，CD3COCD3，CF3COOH as external standard, high field positive) δ: 77.2ppm (d, J ═ 52Hz) elemental analysis (fluorine) theoretical values: 22.49%, found: 22.40% water content L<0.1% (thermal weight loss method)
Example 10
Preparation of tin difluoromethanesulfonate
13.5 g (0.10mol) of stannous oxide and 50 ml of water are added to a 200ml beaker at 0 ℃. 26.4g (0.20mol) of difluoromethanesulfonic acid was slowly added dropwise to the beaker until the solid was substantially dissolved, at which time the pH was 1-2. And (5) standing for slight heating to fully react. The reaction solution was filtered to remove a trace of solid residue. The above filtrate was rotary evaporated to remove a large amount of water. Dried under vacuum for 24 hours (110 ℃). Weigh 37.3g. yield 98%. Tin difluoromethanesulfonate:1H NMR(60MHz，CD3COCD3)，δ：6.1ppm(t，J＝52Hz)19F NMR(56.4MHz，CD3COCD3，CF3COOH as external standard, high field positive) δ: 77.0ppm (d, J ═ 52Hz) elemental analysis (fluorine) theoretical values: 19.95%, found: 19.91% moisture content:<0.1% (weight loss by heat method)
Example 11
Preparation of lead difluoromethanesulfonate
13.5 g or 108 g are added to a 200ml beaker at 0 DEG CLead (0.10mol or 0.8mmol) oxide and 50 ml water. 26.4g (0.20mol) of difluoromethanesulfonic acid was slowly added dropwise to the beaker until the solid was substantially dissolved, at which time the pH was 1-2. And (5) standing for slight heating to fully react. The reaction was filtered to remove excess solid residue. The above filtrate was rotary evaporated to remove a large amount of water. Dried under vacuum for 24 hours (110 ℃). Weight 46.0g. yield 98%. Lead difluoromethanesulfonate:1H NMR(60MHz，CD3COCD3)，δ：5.9ppm(t，J＝52Hz)19F NMR(56.4MHz，CD3COCD3，CF3COOH as external standard, high field positive) δ: 77.0ppm (d, J ═ 52Hz) elemental analysis (fluorine) theoretical values: 16.20%, found: 16.34% moisture content:<0.1% (weight loss by heat method)
Example 12
Preparation of antimony difluoromethanesulfonate
14.6 g (0.05mol) of antimony trioxide and 50 ml of water are added in succession to a 200ml beaker at 10 ℃. 39.6g (0.30mol) of difluoromethanesulfonic acid was slowly added dropwise to the beaker until the solid was substantially dissolved, at which time the pH was 1-2. And (5) standing for slight heating to fully react. The reaction solution was filtered to remove a trace of solid residue. The above filtrate was rotary evaporated to removea large amount of water. Dried under vacuum for 24 hours (110 ℃). 50.5g was weighed. The yield was 98%. Antimony difluoromethanesulfonate:1H NMR(60MHz，CD3COCD3)，δ：6.1ppm(t，J＝52Hz)19F NMR(56.4MHz，CD3COCD3，CF3COOH as external standard, high field positive) δ: 77.0ppm (d, J ═ 52Hz) elemental analysis (fluorine) theoretical values: 22.14%, found: 22.25% moisture content:<0.1% (weight loss by heat method)
Example 13
Preparation of bismuth difluoromethanesulfonate
To a 200ml beaker was added 26.0 g (0.10mol) bismuth hydroxide followed by 50 ml water at 10 ℃. To the beaker was slowly added dropwise 39.6g (0.30mol) of difluoromethanesulfonic acid to a solid baseThe solution is dissolved. So that the reaction is fully carried out. The reaction solution was filtered to remove a trace of solid residue. The above filtrate was rotary evaporated to remove a large amount of water. Dried under vacuum for 24 hours (110 ℃). 59.0g was weighed. The yield was 98%. Bismuth difluoromethanesulfonate:1H NMR(60MHz，CD3COCD3)，δ：6.2ppm(t，J＝52Hz)19F NMR(56.4MHz，CD3COCD3，CF3COOH as external standard, high field positive) δ: 77.2ppm (d, J52 Hz)Moisture content:<0.1% (weight loss by heat method)
Example 14
Preparation of ytterbium difluoromethanesulfonate
22.4 g (0.10mol) of ytterbium hydroxide and 50 ml of water were added in succession to a 200ml beaker at 10 ℃. Difluoromethanesulfonic acid (39.6 g, 0.30mol) was slowly added dropwise to the beaker until the solid was substantially dissolved. So that the reaction is fully carried out. The reaction solution was filtered to remove solid residue. The above filtrate was rotary evaporated to remove a large amount of water. Dried under vacuum for 24 hours (110 ℃). 55.5g was weighed. The yield was 98%. Ytterbium difluoromethanesulfonate:1H NMR(60MHz，CD3COCD3)，δ：6.0ppm(t，J＝52Hz)19F NMR(56.4MHz，CD3COCD3，CF3COOH as external standard, high field positive) δ: 77.0ppm (d, J ═ 52Hz) elemental analysis (fluorine) theoretical values: 20.14%, found: 20.23% moisture content:<0.1% (weight loss by heat method)
Example 15
Application of difluoromethane sulfonic acid metal reagent
Under nitrogen protection, zinc difluoromethanesulfonate (180mg, 0.55mmol, 1.1eq) and (-) -N, N-dimethylnorephedrine (108mg, 0.602mmol, 1.2eq) in toluene (2mL) were added triethylamine (61mg, 0.602mmol, 1.2eq), the mixture was stirred at room temperature for 2h, phenylacetylene (61mg, 0.6mmol, 1.2eq) was added, and after stirring at room temperature for 0.5h, cyclohexanal (58mg) was added, stirring was carried out for 12h, saturated aqueous ammonium chloride (3mL) was added, and ether extraction (3X 10mL) was carried out. Combined organic solventThe agent was washed with a saturated sodium chloride solution and dried over anhydrous sodium sulfate. The product was separated by silica gel column chromatography to give 96mg of (S) -1-cyclohexyl-3-phenyl-2-propyn-1-ol in a yield of 90%. 97% ee was determined using a chiral HPLC column.1H NMR(300MHz，CDCl3)δ 7.38-7.45(m，2H)，7.30-7.24(m，3H)，4.40-4.30(d，J＝6.0Hz，1H)，2.00-1.58(m，1H)，1.36-1.05(m，11H)。
Example 16
Application of difluoromethane sulfonic acid metal reagent
To a solution of bismuth difluoromethanesulfonate (51mg, 0.12mmol, 0.2eq) and (1S, 2S) - (+) -N, N-dimethylamino) -1- (4-nitrophenyl) -1, 3-propanediol (127mg, 0.602mmol, 1.2eq) in acetone (2mL) under nitrogen protection was added pyrimidine (1.8mmol, 3.6eq), the mixture was stirred at room temperature for 2h, phenylbutyne (61mg, 0.6mmol,1.2eq), after stirring at room temperature for 0.5h isobutyraldehyde (43mg) was added, stirring at 85 ℃ G for 5h saturated aqueous ammonium chloride (3mL) was added, and extraction was performed with ether (3X 10 mL). The combined organic solvents were washed with saturated sodium chloride solution and dried over anhydrous sodium sulfate. The product was separated by silica gel column chromatography to give 103mg of (S) -2-methyl-7-phenyl-4-heptyn-3-ol with a yield of 93%. The 71% ee was determined using a chiral HPLC column.1H NMR(300MHz，CDCl3)δ7.4(m，2H)，7.25(m.3H)，4.38(d，J＝6.0Hz，1H)，2.1-2.15(m，4H)2.04(d，J＝5.7Hz，1H)，1.97(m，1H)，1.05(dd，J＝6.7Hz，6H)。
Example 17
Application of difluoromethane sulfonic acid metal reagent
Cadmium difluoromethanesulfonate (224mg, 0.55mmol, 1.1eq) and (1S, 2S) - (+) -N, N-dimethylamino) -1- (4-nitrophenyl) -1, 3-propanediol (127mg, 0.602mmol, 1.2eq) in CH under nitrogen3CN (2mL), triethylamine (61mg, 0.602mmol, 1.2eq) was added to the solution, the mixture was stirred at room temperature for 2h, phenylacetylene (61mg, 0.6mmol, 1.2eq or 46mg, 0.45 m) was addedmol, 0.9eq), stirring at room temperature for 0.5h then cyclopropylaldehyde (58mg), stirring at 85 ℃ G for 8h, adding saturated aqueous ammonium chloride (3mL), and extracting with diethyl ether (3X 10 mL). The combined organic solvents were washed with saturated sodium chloride solution and dried over anhydrous sodium sulfate. The product was separated by silica gel column chromatography to give 96mg of (S) -1-cyclopropyl-3-phenyl-2-propyn-1-ol in 80% yield. The 76% ee was determined using a chiral HPLC column.1H NMR(300MHz，CDCl3)δ7.4(m，2H)，7.25(m.3H)，4.38(d，J＝6.0Hz，1H)，2.04(d，J＝5.7Hz，1H)，1.97(m，1H)，1.05(d，J＝6.7Hz，4H)。
Claims (6)
1. A difluoro methanesulfonic acid metal reagent with a molecular general formula of M (OSO)2CF2H)nWherein M is zinc, cadmium, mercury, copper, silver, indium, tin, lead, antimony, bismuth, gold, thallium or ytterbium, and n is 1-3.
2. The process for synthesizing difluoromethanesulfonic acid metal reagent as claimed in claim 1, wherein the molar ratio of difluoromethanesulfonic acid to metal M oxide or hydroxide is 1: 0.1-5 at-10 ℃ to 100 ℃ in solvent or not, the reaction is carried out for several minutes to 60 hours to obtain the corresponding difluoromethanesulfonic acid metal reagent M (OSO)2CF2H)nM, n is as claimed in claim 1.
3. The method of claim 2, wherein the molar ratio of difluoromethanesulfonic acid to metal oxide or hydroxide is 1: 0.1-1.
4. The method of claim 2, wherein the solvent is H2O。
5. Use of a difluoromethanesulfonic acid metal reagent according to claim 1, characterized by being useful as a catalyst for organic synthesis reactions.
6. Use of a metal difluoromethanesulfonate reagent according to claim 5, characterized in that it is used as a catalyst for the synthesis of secondary propargylic alcohols.
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