CN111763163A - Preparation method of diphenyl disulfide compound - Google Patents
Preparation method of diphenyl disulfide compound Download PDFInfo
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- CN111763163A CN111763163A CN202010618777.XA CN202010618777A CN111763163A CN 111763163 A CN111763163 A CN 111763163A CN 202010618777 A CN202010618777 A CN 202010618777A CN 111763163 A CN111763163 A CN 111763163A
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- diphenyl disulfide
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- grignard reagent
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- GUUVPOWQJOLRAS-UHFFFAOYSA-N diphenyl disulphide Natural products C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- -1 diphenyl disulfide compound Chemical class 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012074 organic phase Substances 0.000 claims abstract description 16
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims abstract description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 6
- 238000010791 quenching Methods 0.000 claims abstract description 6
- 230000000171 quenching effect Effects 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 3
- 150000004768 bromobenzenes Chemical class 0.000 claims description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000008422 chlorobenzenes Chemical class 0.000 claims description 2
- 150000008424 iodobenzenes Chemical class 0.000 claims description 2
- LVKCSZQWLOVUGB-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].C[CH-]C LVKCSZQWLOVUGB-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- SYSZENVIJHPFNL-UHFFFAOYSA-N (alpha-D-mannosyl)7-beta-D-mannosyl-diacetylchitobiosyl-L-asparagine, isoform B (protein) Chemical compound COC1=CC=C(I)C=C1 SYSZENVIJHPFNL-UHFFFAOYSA-N 0.000 description 1
- UDHAWRUAECEBHC-UHFFFAOYSA-N 1-iodo-4-methylbenzene Chemical compound CC1=CC=C(I)C=C1 UDHAWRUAECEBHC-UHFFFAOYSA-N 0.000 description 1
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- GQDCUDAXOMFYFV-UHFFFAOYSA-N [Zn]C1=CC=CC=C1 Chemical compound [Zn]C1=CC=CC=C1 GQDCUDAXOMFYFV-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
- C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
- C07C323/20—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a diphenyl disulfide compound, which comprises the following steps: the isopropyl magnesium halide Grignard reagent and the substituted halogeno-benzene compound are stirred in an organic solvent at-78 to-20 ℃ for 30 to 90min to obtain the substituted phenyl Grignard reagent with thorough halogen-magnesium exchange. And then adding dichlorodisulfide into the reaction system, slowly heating to room temperature after the reaction is finished, quenching the reaction by using saturated ammonium chloride aqueous solution, extracting by using ethyl acetate or diethyl ether, drying by using anhydrous magnesium sulfate, and concentrating an organic phase to obtain the diphenyl disulfide compound. The method utilizes a one-pot method, takes the phenyl Grignard reagent as the raw material to prepare the diphenyl disulfide compound, has short synthetic route, simple preparation process, low cost, easy operation, excellent yield and easy industrial production.
Description
Technical Field
The invention relates to preparation of a high-purity organic intermediate, in particular to a preparation method for synthesizing a substituted diphenyl disulfide compound by taking substituted halogeno benzene, isopropyl magnesium halide and a disulfide dichloride compound as raw materials in two steps and one pot.
Background
Diphenyl disulfide is an important drug intermediate, and is widely applied to the fields of medicines, pesticides, dye intermediates, chemical engineering and the like. The prior preparation and synthesis methods of diphenyl disulfide all use thiophenol as a raw material, and the thiophenol is colorless liquid with foul smell at normal temperature, has active chemical properties, is extremely toxic and is easy to explode. The process using thiophenol as the starting material has long synthesis route, high requirement on reaction conditions and great environmental pollution.
Disclosure of Invention
Based on the defects of the prior art, the technical problem to be solved by the invention is to provide a method for preparing the diphenyl disulfide compound with low cost and easy operation, the diphenyl disulfide compound is prepared by using a one-pot method and a phenyl Grignard reagent as a raw material, the synthetic route is short, and the industrial production is easy.
In order to achieve the purpose, the invention adopts the following technical measures:
the structural general formula of the diphenyl disulfide compound is as follows:
in the formula (I), R1Alkyl, cyano or halogen sensitive to alkali, etc.
A preparation method of diphenyl disulfide compounds comprises the following steps:
the substituted halogenobenzene compound and isopropyl magnesium halide Grignard reagent are stirred and reacted for 30-90 min at-78 to-20 ℃ in an organic solvent, and then dichlorodisulfide is added into a reaction system (the concentration of reactants is maintained to be 0.5-1 mmol/mL). Slowly heating the reaction solution to room temperature, quenching the reaction solution by using a saturated ammonium chloride solution, extracting an organic phase by using diethyl ether or ethyl acetate, drying the organic phase by using anhydrous magnesium sulfate, and concentrating the organic phase to obtain the diphenyl disulfide compound (the yield is 80-91%).
Wherein, the structural general formula of the starting material substituted halogeno-benzene compound is as follows:
R1is alkyl, cyano or halogen, etc., X is I or Br or Cl;
the structural formula of the starting material isopropyl magnesium halide is as follows:
x is I or Br or Cl;
the structural formula of the dichloro disulfide is as follows:
as a preferred aspect of the above technical solution, the preparation method of the diphenyl disulfide compound provided by the present invention further includes a part or all of the following technical features:
as an improvement of the technical scheme, the substituted halogenobenzene compound is selected from substituted iodobenzene, substituted bromobenzene or substituted chlorobenzene.
As an improvement of the technical scheme, the organic solvent is tetrahydrofuran, diethyl ether or a mixed solvent of the tetrahydrofuran and the diethyl ether.
As an improvement of the technical scheme, the molar ratio of the substituted phenyl Grignard reagent compound to the dichloro disulfide compound is 1: 0.2-1;
preferably, the isopropyl magnesium halide is isopropyl magnesium chloride or isopropyl magnesium bromide.
Compared with the prior art, the technical scheme of the invention has the following obvious effects:
1. compared with the conventional process, the conversion rate is increased, no catalyst is needed, and the cost is reduced.
2. The preparation process of the diphenyl disulfide compound adopts the substituted phenyl Grignard reagent to replace the conventional thiophenol, and can greatly reduce the harm to the bodies of operators and the pollution to the environment.
3. The preparation process of the diphenyl disulfide compound adopts the dichloro disulfide compound to replace the conventional thiophenol, can quickly realize C-S bond coupling, and improves the reaction activity.
4. The preparation process of the diphenyl disulfide compound does not need to convert the obtained phenyl Grignard reagent into the phenyl zinc reagent, and has short synthetic route, thereby saving the necessary social labor time and the production cost.
5. The preparation process of the diphenyl disulfide compound can tolerate some groups sensitive to alkali or Grignard reagent, such as nitrile groups, and obtain higher yield.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the contents of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following detailed description is given in conjunction with the preferred embodiments.
Drawings
In order to more clearly illustrate the technical solution of the embodiment of the present invention, the following briefly introduces the drawings of the embodiment:
FIG. 1 shows diphenyl disulfide synthesized in example 1 of the present invention1HNMR characterization map;
FIG. 2 shows diphenyl disulfide synthesized in example 1 of the present invention13A CNMR characterization map;
FIG. 3 shows p-methyldiphenyldisulfide synthesized in example 2 of the present invention1HNMR characterization map;
FIG. 4 shows p-methyldiphenyldisulfide synthesized in example 2 of the present invention13A CNMR characterization map;
FIG. 5 shows p-methoxydiphenyl disulfide synthesized in example 3 of the present invention1HNMR characterization map;
FIG. 6 shows p-methoxydiphenyl disulfide synthesized in example 3 of the present invention13CNMR characterization profiles.
Detailed Description
Other aspects, features and advantages of the present invention will become apparent from the following detailed description, which, when taken in conjunction with the drawings, illustrate by way of example the principles of the invention.
Example 1. Synthesis of diphenyl disulfide
100mL of tetrahydrofuran was added to a reaction flask which had been previously dried and filled with nitrogen (or argon), the mixture was cooled to-78 ℃, iodobenzene (0.1mol) was then added, isopropyl magnesium chloride (0.11mol) was slowly added dropwise to the reaction solution, the reaction solution was stirred at-78 ℃ to-20 ℃ and the progress of the reaction was monitored by gas chromatography, and the halogen-magnesium exchange reaction was terminated after about 30 to 90 minutes. Then adding dichlorodisulfide (0.05mol) into the reaction system, slowly raising the reaction solution to room temperature, quenching the reaction by using saturated ammonium chloride solution, extracting an organic phase by using ether or ethyl acetate, drying the organic phase by using anhydrous magnesium sulfate, and concentrating the organic phase to obtain 9.7g of white solid diphenyl disulfide, wherein the yield is 89%, and the purity is more than or equal to 95%. FIG. 1 shows the preparation of diphenyl disulfide according to the invention in example 11HNMR characterization map; FIG. 2 shows the diphenyl disulfide synthesized in example 1 of the present invention13CNMR characterization profiles.
Mp:58-61℃.
1HNMR(400MHz,CDCl3,TMS):(ppm)7.40(d,4H,J＝8.0Hz),7.18(t,4H,J＝8.0Hz),7.11(t,2H,J＝4.0Hz).
13CNMR(100MHz,CDCl3,TMS):(ppm)137.1,129.2,127.6,127.2.HRMS(ESI)CalcdforC12H10S2(218.0224),found:218.0217.
Example 2. Synthesis of p-methyldiphenyldisulfide
100mL of tetrahydrofuran was added to a reaction flask which had been previously dried and filled with nitrogen (or argon), the mixture was cooled to-78 ℃, p-iodotoluene (0.1mol) was then added, isopropyl magnesium chloride (0.11mol) was slowly added dropwise to the reaction solution, the reaction solution was stirred at-78 ℃ to-20 ℃ and the progress of the reaction was monitored by gas chromatography, and after about 30 to 90 minutesThe halogen-magnesium exchange reaction is finished. Then adding dichlorodisulfide (0.05mol) into the reaction system, slowly raising the reaction solution to room temperature, quenching the reaction by using saturated ammonium chloride solution, extracting an organic phase by using ether or ethyl acetate, drying the organic phase by using anhydrous magnesium sulfate, and concentrating the organic phase to obtain yellow solid p-methyldiphenyldisulfide (10.8 g), wherein the yield is 88%, and the purity is more than or equal to 95%. FIG. 3 shows p-methyldiphenyldisulfide synthesized in example 2 of the present invention1HNMR characterization map; FIG. 4 shows p-methyldiphenyldisulfide synthesized in example 2 of the present invention13C NMR characterization spectrum.
Mp:43-46℃.
1HNMR(400MHz,CDCl3,TMS):(ppm)7.43(d,4H,J＝8.0Hz),7.15(d,4H,J＝8.0Hz),2.36(s,6H).
13CNMR(100MHz,CDCl3,TMS):(ppm)137.5,134.0,129.8,128.6,21.1.
HRMS(ESI):CalcdforC14H14S2(246.0537),found:246.0533.
Example 3. Synthesis of p-methoxydiphenyl disulfide
100mL of tetrahydrofuran was added to a reaction flask which had been previously dried and filled with nitrogen (or argon), the mixture was cooled to-78 ℃, p-methoxyiodobenzene (0.1mol) was then added, isopropyl magnesium chloride (0.11mol) was slowly added dropwise to the reaction solution, the reaction solution was stirred at-78 ℃ to-20 ℃ and the progress of the reaction was monitored by gas chromatography, and the halogen-magnesium exchange reaction was terminated after about 30 to 90 minutes. Then adding dichlorodisulfide (0.05mol) into the reaction system, slowly raising the reaction solution to room temperature, quenching the reaction by using saturated ammonium chloride solution, extracting an organic phase by using ether or ethyl acetate, drying the organic phase by using anhydrous magnesium sulfate, and concentrating the organic phase to obtain light yellow solid p-methoxydiphenyl disulfide (12.7 g), wherein the yield is 91 percent, and the purity is more than or equal to 95 percent. FIG. 5 shows p-methoxydiphenyl disulfide synthesized in example 3 of the present invention1H NMR characterization spectrum; FIG. 6 shows p-methoxybenzenedi-phenyl synthesized in example 3 of the present inventionProcess for preparing thioethers13CNMR characterization profiles.
Mp:41-45℃.
1HNMR(400MHz,CDCl3,TMS):(ppm)7.42(d,4H，J＝12.0Hz),6.86(d,4H，J＝8.0Hz)，3.82(s,6H).
13CNMR(100MHz,CDCl3,TMS):(ppm)159.9,132.7,128.5,114.6,55.4.
HRMS(ESI):CalcdforC14H14O2S2(278.0435),found:278.0428。
The raw materials listed in the invention, the upper and lower limits and interval values of the raw materials of the invention, and the upper and lower limits and interval values of the process parameters (such as temperature, time and the like) can all realize the invention, and the examples are not listed.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (6)
1. A compound of the formula:
in the formula (I), R1Is alkyl, halogen or cyano which is sensitive to bases;
2. a process for producing the diphenyl disulfide compound according to claim 1, which comprises the steps of:
isopropyl magnesium halide Grignard reagent and substituted halogeno-benzene compound are stirred in an organic solvent at-78 to-20 ℃ for 30 to 90min to obtain a substituted phenyl Grignard reagent with thorough halogen-magnesium exchange; then adding dichlorodisulfide into the reaction system, slowly heating to room temperature after the reaction is finished, quenching the reaction by using saturated ammonium chloride aqueous solution, extracting an organic phase by using ethyl acetate or diethyl ether, drying the organic phase by using anhydrous magnesium sulfate, and concentrating the organic phase to obtain the diphenyl disulfide compound;
wherein, the structural general formula of the starting material substituted halogeno-benzene compound is as follows:
R1is alkyl, cyano or halogen, etc., X is I or Br or Cl;
the structural formula of the starting material isopropyl magnesium halide is as follows:
x is I or Br or Cl;
the structural formula of the dichloro disulfide is as follows:
3. the method for preparing diphenyl disulfide compounds according to claim 2, wherein said substituted halogenobenzene compound is selected from substituted iodobenzene, substituted bromobenzene or substituted chlorobenzene.
4. The method for producing the diphenyl disulfide compound according to claim 2, wherein the organic solvent is tetrahydrofuran, diethyl ether or a mixed solvent of both.
5. The method for preparing diphenyl disulfide compounds according to claim 2, wherein the molar ratio of the substituted phenyl grignard reagent to the dichlorodisulfide is 1:0.2 to 1.
6. The process for producing diphenyl disulfide compounds according to claim 2, wherein said isopropyl magnesium halide is preferably isopropyl magnesium chloride or isopropyl magnesium bromide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114539113A (en) * | 2022-03-01 | 2022-05-27 | 苏州大学张家港工业技术研究院 | Method for preparing diphenyl disulfide compound by heterogeneous catalysis |
| WO2023278604A1 (en) * | 2021-06-29 | 2023-01-05 | Plex Pharmaceuticals, Inc. | Pharmacological agents for treating ophthalmic diseases |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023278604A1 (en) * | 2021-06-29 | 2023-01-05 | Plex Pharmaceuticals, Inc. | Pharmacological agents for treating ophthalmic diseases |
| CN114539113A (en) * | 2022-03-01 | 2022-05-27 | 苏州大学张家港工业技术研究院 | Method for preparing diphenyl disulfide compound by heterogeneous catalysis |
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