CN117903090A - Synthesis method of bis (2-methyl-3-furyl) disulfide - Google Patents
Synthesis method of bis (2-methyl-3-furyl) disulfide Download PDFInfo
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- OHDFENKFSKIFBJ-UHFFFAOYSA-N bis(2-methyl-3-furyl)disulfide Chemical compound O1C=CC(SSC2=C(OC=C2)C)=C1C OHDFENKFSKIFBJ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 24
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 238000004321 preservation Methods 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000012074 organic phase Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 13
- 230000002194 synthesizing effect Effects 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- RBBWNXJFTBCLKT-UHFFFAOYSA-M sodium;ethanethioate Chemical compound [Na+].CC([S-])=O RBBWNXJFTBCLKT-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 4
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- RUYNUXHHUVUINQ-UHFFFAOYSA-N 2-Methyl-3-furanthiol Chemical class CC=1OC=CC=1S RUYNUXHHUVUINQ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 26
- 239000012043 crude product Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000011534 incubation Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- OZQXEOSNFMMMRD-UHFFFAOYSA-M [Cl-].CC(C)[Mg+].C1CCOC1 Chemical compound [Cl-].CC(C)[Mg+].C1CCOC1 OZQXEOSNFMMMRD-UHFFFAOYSA-M 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005273 aeration Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 239000000686 essence Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 235000021168 barbecue Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of bis (2-methyl-3-furyl) disulfide. According to the method, simple raw material acetylene gas is introduced into isopropyl magnesium chloride to generate an intermediate 1, the intermediate 1 isopropyl magnesium chloride generates an intermediate 2, the intermediate 2 is formed into a ring to generate a derivative of 2-methyl-3-mercapto furan, and the derivative of 2-methyl-3-mercapto furan is oxidized to generate bis (2-methyl-3-furyl) disulfide.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of bis (2-methyl-3-furyl) disulfide.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Bis (2-methyl-3-furyl) disulfide, also known as bis disulfide, is a yellow liquid having the structural formula:
The bis (2-methyl-3-furyl) disulfide has good meat flavor and barbecue flavor, and can be used for preparing various food essences, especially flavoring essences.
In the prior art, the synthesis methods of the bis (2-methyl-3-furyl) disulfide are all 2-methyl-3-sulfhydryl furan oxidation methods proposed by U.S. Pat. No. 4020175, and the raw material 2-methyl-3-sulfhydryl furan is high in price and limited to be widely used although the method can be used for one-step oxidation. Chinese patent CN106749127a discloses a method for synthesizing bis (2-methyl-3-furyl) disulfide, but the steps are complicated, the yield is low, and the use of dangerous chemical bromine is unfavorable for mass production. Thus, there is a need for a method for synthesizing bis (2-methyl-3-furyl) disulfide that is simple in synthetic method, safe in operation and high in yield.
Disclosure of Invention
In order to overcome the problems, the invention provides a synthesis method of bis (2-methyl-3-furyl) disulfide, which has few reaction steps, mild reaction conditions and high product purity, and is suitable for industrial production.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a method for synthesizing bis (2-methyl-3-furanyl) disulfide, the method comprising the steps of:
(1) Introducing acetylene gas into tetrahydrofuran solution of isopropyl magnesium chloride at the temperature of 15-0 ℃ for a first heat preservation reaction, then dropwise adding N, N-Dimethylformamide (DMF), performing a second heat preservation reaction after the dropwise adding is finished, adding ethanol, heating, performing a third heat preservation reaction, adding saturated ammonium chloride solution, standing for layering, separating out an organic phase, and purifying to obtain an intermediate 1;
(2) Dropwise adding the intermediate 1 into tetrahydrofuran solution of isopropyl magnesium chloride at the temperature of 15-0 ℃, carrying out a fourth heat preservation reaction, dropwise adding acetaldehyde, carrying out a fifth heat preservation reaction after the dropwise adding is finished, adding saturated ammonium chloride solution, standing for layering, and separating out an organic phase to obtain an intermediate 2;
(3) Adding dichloromethane and sodium thioacetate into dilute sulfuric acid solution, uniformly mixing, adding an intermediate 2, heating, carrying out a sixth heat preservation reaction, standing for layering after the reaction is completed, separating an organic phase, and washing to obtain an intermediate 3;
(4) Adding the intermediate 3 into alkali liquor, performing a seventh heat preservation reaction, then dropwise adding hydrogen peroxide, extracting with an organic solvent after the reaction is finished, and then washing to obtain bis (2-methyl-3-furyl) disulfide;
In one or more embodiments, in step (1), the molar ratio of acetylene, isopropyl magnesium chloride and N, N-dimethylformamide is 1:1.2:1, preferably 1:1.03:1.
In one or more embodiments, in step (1), the concentration of isopropyl magnesium chloride in the tetrahydrofuran solution of isopropyl magnesium chloride is 1.5 to 2.5mol/L, preferably 2.0mol/L.
In one or more embodiments, in step (1), the temperature of the first incubation is from-20 to 0deg.C for a period of from 1.5 to 2.5 hours, preferably 2 hours.
In one or more embodiments, in step (1), the temperature of the second incubation is from-5 to 0deg.C for a period of from 1.5 to 2.5 hours, preferably 2 hours.
In one or more embodiments, in step (1), the temperature of the third incubation is from 35 to 40℃for a period of from 1.5 to 2.5 hours, preferably 2 hours.
In one or more embodiments, in step (2), the molar ratio of intermediate 1, isopropyl magnesium chloride and acetaldehyde is from 0.95 to 1:1:0.95 to 1, preferably 0.98:1:0.98.
In one or more embodiments, in step (2), the fourth incubation is carried out at a temperature of from-20 to 0deg.C for a period of from 2.5 to 3.5 hours, preferably 3 hours.
In one or more embodiments, in step (2), the temperature of the fifth incubation is from-20 to 0deg.C for a period of from 1.5 to 2.5 hours, preferably 2 hours.
In one or more embodiments, in step (3), the solute of the dilute sulfuric acid solution is present in a mass fraction of 8% to 12%, preferably 10%.
In one or more embodiments, in step (3), the mass ratio of sodium thioacetate to intermediate 2 is 1:1.5 to 2, preferably 1:1.7.
In one or more embodiments, in step (3), the temperature of the sixth incubation is 20-25 ℃ for 5-15 hours.
In one or more embodiments, in step (4), the lye is a potassium hydroxide solution or a sodium hydroxide solution, and the solute of the lye is 8% to 12% by mass, preferably 10% by mass.
In one or more embodiments, in step (4), the seventh incubation is performed at a temperature of 10 to 20℃for a period of 1.5 to 2.5 hours, preferably 2 hours.
In one or more embodiments, in step (4), the mass ratio of intermediate 3 to hydrogen peroxide in hydrogen peroxide is 1:0.15-0.3, preferably 1:0.22.
The invention has the beneficial effects that:
According to the method, simple raw material acetylene gas is introduced into isopropyl magnesium chloride to generate an intermediate 1, the intermediate 1 and the isopropyl magnesium chloride generate an intermediate 2, the intermediate 2 is formed into a ring to generate a derivative of 2-methyl-3-mercapto furan, and the derivative of 2-methyl-3-mercapto furan is oxidized to generate bis (2-methyl-3-furyl) disulfide.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of intermediate 1 prepared in example 1;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of intermediate 2 prepared in example 1;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of intermediate 3 prepared in example 1;
FIG. 4 is a nuclear magnetic resonance spectrum of bis (2-methyl-3-furyl) disulfide prepared in example 1.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Example 1
(1) Under the protection of nitrogen, adding 30L of isopropyl magnesium chloride tetrahydrofuran solution with the concentration of 2mol/L into a 100L reaction kettle, cooling to-5-0 ℃ under stirring, slowly introducing 1.6kg of acetylene into the system, controlling the aeration speed in the process, keeping the internal temperature between-5 and 0 ℃, continuing to carry out heat preservation reaction for 2h after the aeration, keeping the internal temperature between 0 and 5 ℃, dropwise adding 4.4kg of DMF, continuing to carry out heat preservation reaction for 2h after the dropwise adding, dropwise adding 10L of ethanol, dropwise adding the process, starting to increase the internal temperature, controlling the temperature not to exceed 40 ℃, carrying out heat preservation reaction for 2h at 35-40 ℃, adding 20L of saturated ammonium chloride solution, stirring for 30min, standing, separating out an organic phase, concentrating to obtain a crude product of the intermediate 1, decompressing and rectifying the crude product, collecting fractions with the air temperature of about 42-45 ℃ under the vacuum degree of about 10mm Hg, so as to obtain a product with the GC purity of more than 98%, wherein the yield is 90%, and the nuclear magnetic hydrogen spectrum of the intermediate 1 is shown in a graph of figure 1.
(2) Under the protection of nitrogen, adding 30L of isopropyl magnesium chloride tetrahydrofuran solution with the concentration of 2mol/L into a 100L reaction kettle, cooling to-5-0 ℃ under stirring, dropwise adding 7.5kg of mixed solution of intermediate 1 and 7.5kg of tetrahydrofuran, controlling the dropwise adding speed, keeping the internal temperature between-5-0 ℃, continuing to carry out heat preservation reaction for 3h, keeping the internal temperature between-5-0 ℃, dropwise adding 2.6kg of acetaldehyde, continuing to carry out heat preservation reaction for 2h, keeping the heat preservation, slowly dropwise adding the feed liquid into 5% hydrochloric acid solution (30L) which has been cooled to about 10 ℃, keeping the internal temperature between 10-15 ℃, standing for liquid separation, washing an organic phase once by using saturated sodium bicarbonate solution, concentrating to obtain 8.9kg of intermediate 2 crude product with the purity of 95%, and the crude product can be directly reacted with the next step, wherein the nuclear magnetic hydrogen spectrum of intermediate 2 is shown in figure 2.
(3) In a 100L enamel reaction kettle, 25kg of dilute sulfuric acid solution with the mass fraction of solute of 10 percent, 20L of dichloromethane and 2kg of sodium thioacetate are added under stirring at room temperature, stirring and dissolving are carried out, the system temperature is kept between 15 ℃ and 20 ℃, 3.4kg of mixed solution of intermediate 2 and 5kg of dichloromethane are dropwise added, the temperature is kept between 20 ℃ and 25 ℃ for reaction for 12 hours, standing is carried out, an organic phase is separated, the organic phase is washed once by saturated sodium bicarbonate solution, and the concentration is carried out, thus obtaining 2.5kg of crude intermediate 3 with the purity of 95 percent and the yield of 84 percent, and the crude product can be directly reacted with the next step. The nuclear magnetic hydrogen spectrum of intermediate 3 is shown in figure 3.
(4) Adding 30kg of solute into a 100L reaction kettle, dispersing into 10% KOH aqueous solution, adding 8.5kg of intermediate 3 crude product obtained by the reaction in the previous step into the system at room temperature, reacting for 4 hours at room temperature, cooling to about 10 ℃, dropwise adding 9.2kg of solute, dispersing into 20% hydrogen peroxide, dropwise adding the solution, controlling the temperature in the dropwise adding process to be between 10 and 20 ℃, continuously reacting for 2 hours, adding 20L of dichloromethane, extracting and separating liquid, washing an organic phase once by using 5% sodium bisulphite solution, concentrating to obtain a bis (2-methyl-3-furyl) disulfide crude product, rectifying the crude product by using an oil pump under reduced pressure, and collecting fractions with the air temperature of about 105 to 110 ℃ under the vacuum degree of about 1mm Hg to obtain 5.5kg of qualified product with the purity of 98% and the yield of 95%. (ms=226.1) 1H NMR(CDCl3-d6) δ=2.10 (s, 6H), 6.37 to 6.38 (d, 2H), 7.27 to 7.28 (d, 2H), and the nuclear magnetic resonance hydrogen spectrum of bis (2-methyl-3-furyl) disulfide obtained in this example is shown in fig. 4.
Example 2
(1) Under the protection of nitrogen, adding 30L of isopropyl magnesium chloride tetrahydrofuran solution with the concentration of 2mol/L into a 100L reaction kettle, cooling to-15 to-10 ℃ under stirring, slowly introducing 1.6kg of acetylene into the system, controlling the aeration speed in the process, keeping the internal temperature between-15 and-10 ℃, continuing to carry out heat preservation reaction for 2h after the introduction, keeping the internal temperature between 0 and 5 ℃, dropwise adding 4.4kg of DMF, continuing to carry out heat preservation reaction for 2h after the dropwise adding, dropwise adding 10L of ethanol, starting to increase the internal temperature in the dropwise adding process, controlling the temperature not to exceed 40 ℃, carrying out heat preservation reaction for 2h after the dropwise adding, adding 20L of saturated ammonium chloride solution, stirring for 30min, standing, separating out an organic phase, concentrating to obtain a crude product of an intermediate 1, decompressing and rectifying the crude product, and collecting a fraction with the temperature of about 42-45 ℃ under the vacuum degree of about 10mm Hg to obtain a product with the GC purity of more than 98 percent, wherein the yield is 85%.
(2) Under the protection of nitrogen, adding 30L of isopropyl magnesium chloride tetrahydrofuran solution with the concentration of 2mol/L into a 100L reaction kettle, cooling to-15 to-10 ℃ under stirring, dropwise adding 7.5kg of mixed solution of intermediate 1 and 7.5kg of tetrahydrofuran, controlling the dropwise adding speed, keeping the internal temperature between-5 and 0 ℃, continuing to carry out heat preservation reaction for 3 hours, keeping the internal temperature between-15 and-10 ℃, dropwise adding 2.6kg of acetaldehyde, continuing to carry out heat preservation reaction for 2 hours, keeping the heat preservation, slowly dropwise adding the feed liquid into 5% hydrochloric acid solution (30L) cooled to about 10 ℃ under the temperature, keeping the internal temperature between 10 and 15 ℃, standing for liquid separation, washing an organic phase once by saturated sodium bicarbonate solution, concentrating to obtain 9.3kg of crude intermediate 2, wherein the purity is 95%, and the yield is 90%.
(3) In a 100L enamel reaction kettle, 25kg of dilute sulfuric acid solution with the mass fraction of solute of 10 percent, 20L of dichloromethane and 2kg of sodium thioacetate are added under stirring at room temperature, stirring and dissolving are carried out, the system temperature is kept between 15 ℃ and 20 ℃, 3.4kg of mixed solution of intermediate 2 and 5kg of dichloromethane are dropwise added, the temperature is kept between 20 ℃ and 25 ℃ for reaction for 6 hours, standing is carried out, an organic phase is separated, the organic phase is washed once by saturated sodium bicarbonate solution, and the concentration is carried out, thus obtaining 2.14kg of crude intermediate 3 with the purity of 95 percent and the yield of 72 percent, and the crude product can be directly reacted with the next step.
(4) Adding 30kg of solute into a 100L reaction kettle, dispersing into 10% NaOH aqueous solution, adding 8.5kg of intermediate 3 crude product obtained by the reaction in the previous step into the system at room temperature, reacting for 4 hours at room temperature, cooling to about 10 ℃, dropwise adding 9.2kg of solute, dispersing into 20% hydrogen peroxide, dropwise adding the solution, controlling the temperature of the dropwise adding process between 10 and 20 ℃, continuously reacting for 2 hours, adding 20L of dichloromethane, extracting and separating liquid, washing an organic phase once by using 5% sodium bisulphite solution, concentrating to obtain a bis (2-methyl-3-furyl) disulfide crude product, rectifying the crude product by using an oil pump under reduced pressure, and collecting fractions with the air temperature of about 105 to 110 ℃ under the vacuum degree of about 1mm Hg to obtain 5.2kg of qualified product with the purity of 98% and the yield of 90%. Ms=226.1) 1H NMR(CDCl3-d6), δ=2.10 (s, 6H), 6.37-6.38 (d, 2H), 7.27-7.28 (d, 2H).
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for synthesizing bis (2-methyl-3-furyl) disulfide, which is characterized by comprising the following steps:
(1) Introducing acetylene gas into tetrahydrofuran solution of isopropyl magnesium chloride at the temperature of 15-0 ℃ for a first heat preservation reaction, then dropwise adding N, N-Dimethylformamide (DMF), performing a second heat preservation reaction after the dropwise adding is finished, adding ethanol, heating, performing a third heat preservation reaction, adding saturated ammonium chloride solution, standing for layering, separating out an organic phase, and purifying to obtain an intermediate 1;
(2) Dropwise adding the intermediate 1 into tetrahydrofuran solution of isopropyl magnesium chloride at the temperature of 15-0 ℃, carrying out a fourth heat preservation reaction, dropwise adding acetaldehyde, carrying out a fifth heat preservation reaction after the dropwise adding is finished, adding saturated ammonium chloride solution, standing for layering, and separating out an organic phase to obtain an intermediate 2;
(3) Adding dichloromethane and sodium thioacetate into dilute sulfuric acid solution, uniformly mixing, adding an intermediate 2, heating, carrying out a sixth heat preservation reaction, standing for layering after the reaction is completed, separating an organic phase, and washing to obtain an intermediate 3;
(4) Adding the intermediate 3 into alkali liquor, performing a seventh heat preservation reaction, then dropwise adding hydrogen peroxide, extracting with an organic solvent after the reaction is finished, and then washing to obtain bis (2-methyl-3-furyl) disulfide;
2. The method for synthesizing bis (2-methyl-3-furyl) disulfide according to claim 1, wherein in step (1), the molar ratio of acetylene, isopropyl magnesium chloride and N, N-dimethylformamide is 1:1.2:1, preferably 1:1.03:1;
Or in the step (1), the concentration of the isopropyl magnesium chloride in the tetrahydrofuran solution of the isopropyl magnesium chloride is 1.5-2.5 mol/L, preferably 2.0mol/L.
3. The method for synthesizing bis (2-methyl-3-furyl) disulfide according to claim 1, wherein in the step (1), the temperature of the first heat preservation reaction is-20-0 ℃ for 1.5-2.5 h, preferably 2h;
or in the step (1), the temperature of the second heat preservation reaction is-5-0 ℃ and the time is 1.5-2.5 h, preferably 2h;
Or in the step (1), the temperature of the third heat preservation reaction is 35-40 ℃ and the time is 1.5-2.5 h, preferably 2h.
4. The method for synthesizing bis (2-methyl-3-furyl) disulfide according to claim 1, wherein the molar ratio of intermediate 1, isopropyl magnesium chloride and acetaldehyde is 0.95-1:1:0.95-1, preferably 0.98:1:0.98.
5. The method for synthesizing bis (2-methyl-3-furyl) disulfide according to claim 1, wherein in the step (2), the temperature of the fourth heat preservation reaction is-20-0 ℃ for 2.5-3.5 h, preferably 3h;
or in the step (2), the temperature of the fifth heat preservation reaction is-20-0 ℃ and the time is 1.5-2.5 h, preferably 2h.
6. The method for synthesizing bis (2-methyl-3-furanyl) disulfide according to claim 1, wherein in step (3), the mass fraction of the solute of the dilute sulfuric acid solution is 8% to 12%, preferably 10%.
7. The method for synthesizing bis (2-methyl-3-furyl) disulfide according to claim 1, wherein in step (3), the mass ratio of sodium thioacetate to intermediate 2 is 1:1.5-2, preferably 1:1.7;
Or in the step (3), the temperature of the sixth heat preservation reaction is 20-25 ℃ and the time is 5-15 h.
8. The method for synthesizing bis (2-methyl-3-furyl) disulfide according to claim 1, wherein in the step (4), the alkali solution is potassium hydroxide solution or sodium hydroxide solution, and the solute of the alkali solution is 8% -12% by mass, preferably 10%.
9. The method for synthesizing bis (2-methyl-3-furyl) disulfide according to claim 1, wherein in the step (4), the seventh heat-preserving reaction is carried out at a temperature of 10 to 20 ℃ for a period of 1.5 to 2.5 hours, preferably 2 hours.
10. The method for synthesizing bis (2-methyl-3-furyl) disulfide according to claim 1, wherein in the step (4), the mass ratio of the intermediate 3 to hydrogen peroxide in hydrogen peroxide is 1:0.15-0.3, preferably 1:0.22.
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