CN113717084A - Synthesis method of 2, 2' -dithiodiethylamine dihydrochloride - Google Patents
Synthesis method of 2, 2' -dithiodiethylamine dihydrochloride Download PDFInfo
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- CN113717084A CN113717084A CN202111079580.4A CN202111079580A CN113717084A CN 113717084 A CN113717084 A CN 113717084A CN 202111079580 A CN202111079580 A CN 202111079580A CN 113717084 A CN113717084 A CN 113717084A
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- dithiodiethylamine
- dihydrochloride
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- 238000001308 synthesis method Methods 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 16
- OGMADIBCHLQMIP-UHFFFAOYSA-N 2-aminoethanethiol;hydron;chloride Chemical compound Cl.NCCS OGMADIBCHLQMIP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 125000001741 organic sulfur group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000010977 unit operation Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 4
- 229940097265 cysteamine hydrochloride Drugs 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- NGDIAZZSCVVCEW-UHFFFAOYSA-M sodium;butyl sulfate Chemical compound [Na+].CCCCOS([O-])(=O)=O NGDIAZZSCVVCEW-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 150000002019 disulfides Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- -1 nitrogen-containing compound Chemical class 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000008127 vinyl sulfides Chemical class 0.000 description 1
Classifications
-
- 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
- C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of pharmaceutical chemicals, and particularly relates to a synthesis method of 2, 2' -dithiodiethylamine dihydrochloride, which comprises the steps of adding 2-aminoethanethiol hydrochloride, an oxidant and a catalyst into a reaction solvent; under the action of a catalyst, heating to 40-90 ℃ for oxidation reaction; with the progress of the oxidation reaction, gradually reducing the substrate, gradually increasing the product, gradually crystallizing the product in a reaction solvent, reacting for 4-10h, cooling to room temperature, continuously crystallizing for 2-3 h, filtering, washing and drying to obtain 2, 2' -dithiodiethylamine dihydrochloride; has little environmental pollution, can reuse the mother liquor for many times, has little three wastes and is suitable for large-scale production. The reaction condition is mild, the oxidant safety is high, the environment is friendly, and the method is economical and easy to treat. High production efficiency, high product quality, simple post-treatment and one unit operation.
Description
Technical Field
The invention belongs to the technical field of pharmaceutical chemicals, and particularly relates to a synthetic method of 2, 2' -dithiodiethylamine dihydrochloride.
Background
From a synthetic and biological point of view, symmetrical disulfides are one of the most important compounds, besides being industrially useful as vulcanizing agents for rubbers and elastomers, important starting materials for the synthesis of sulfinylated intermediates, sulfenyl intermediates, vinyl sulfides, disulfides.
In recent years, symmetrical disulfides have been studied more and more extensively, for example as photoinitiators for initiating photopolymerization of unsaturated olefins; the catalyst is used for catalyzing the isomerization reaction of the alpha, beta-unsaturated carbonyl compound; the selective deprotection reaction of aromatic acetate and aromatic benzoate formed by phenolic hydroxyl is combined with NMP.
Disulfide bond-containing compounds exist widely in nature and often show high biological activity, and therefore, how to effectively form disulfide becomes important.
The existing synthetic route of the symmetrical disulfide mainly comprises 8 methods of air direct oxidation coupling method, hydrogen peroxide oxidation coupling method, ammonium persulfate oxidation coupling method, halogen-containing oxidant oxidation coupling method, transition metal compound oxidation coupling method, nitrogen-containing compound oxidation coupling method, electrolytic oxidation coupling method and enzyme catalysis coupling method, wherein some methods need expensive reagents, some methods have great safety risk, some methods have troublesome treatment and are not suitable for industrial operation.
Disclosure of Invention
Aiming at the technical problems, the invention provides a synthesis method of 2, 2' -dithiodiethylamine dihydrochloride, which is simple and safe, has mild reaction conditions, is easy to operate, has high yield and good quality, and is suitable for industrial production.
In order to solve the technical problems, the invention adopts the technical scheme that:
a method for synthesizing 2, 2' -dithiodiethylamine dihydrochloride,
adding 2-aminoethanethiol hydrochloride, an oxidant and a catalyst into a reaction solvent; under the action of a catalyst, heating to 40-90 ℃ for oxidation reaction; with the progress of the oxidation reaction, gradually reducing the substrate, gradually increasing the product, gradually crystallizing the product in a reaction solvent, reacting for 4-10h, cooling to room temperature, continuously crystallizing for 2-3 h, filtering, washing and drying to obtain 2, 2' -dithiodiethylamine dihydrochloride; the reaction equation is:
adding 2-aminoethanethiol hydrochloride into a reaction solvent, and stirring for dissolving; and then adding a catalyst, heating to raise the temperature, adding an oxidant when the temperature is raised to 30-45 ℃, and preserving the heat to carry out an oxidation reaction when the temperature is raised to above 55 ℃.
The drying is vacuum drying, the drying temperature is 55-65 ℃, and the drying time is 6 hours.
The oxidant is dimethyl sulfoxide or other organic sulfur oxides.
The reaction solvent is one or more of methanol, ethanol, acetone, acetonitrile and chloroform.
The catalyst is one or more of formic acid, glacial acetic acid and hydrochloric acid.
After reacting for 5-6h, cooling to room temperature.
The mass ratio of the reaction solvent to the 2-aminoethanethiol hydrochloride is 2.5-3.5: 1; the mass ratio of the oxidant to the 2-aminoethanethiol hydrochloride is 0.8-1.2: 1, and the mass ratio of the catalyst to the 2-aminoethanethiol hydrochloride is 0.25-0.30: 1.
In the reaction formula, R is amino, alkali metal, halogen and phenyl.
Compared with the prior art, the invention has the following beneficial effects:
1. has little environmental pollution, can reuse the mother liquor for many times, has little three wastes and is suitable for large-scale production.
2. The reaction condition is mild, the oxidant safety is high, the environment is friendly, and the method is economical and easy to treat.
3. High production efficiency, high product quality, simple post-treatment and one unit operation.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding 50g of cysteamine hydrochloride and 125g of methanol into a 500ml four-neck flask, stirring to completely dissolve, then adding 1.2g of glacial acetic acid, starting heating, raising the temperature to 40 ℃, keeping the temperature at 40-45 ℃, slowly adding 50g of dimethyl sulfoxide into the system, continuing raising the temperature to 60 ℃, keeping the temperature to react for 5 hours, and separating out solids after reacting for 1 hour. And (3) cooling to about 25 ℃ for crystal growth for 2h after the reaction time is up, filtering, washing a filter cake with 20g of methanol, carrying out vacuum drying at 55-65 ℃ for 6h, and collecting to obtain 44.8g of cystamine dihydrochloride, wherein the mass yield is 89.6%, the liquid phase purity is 99.25%, and the content is 99.9%.
Example 2
Adding 500g of cysteamine hydrochloride and 1000g of methanol into a 2000ml four-neck flask, stirring to completely dissolve, then adding 15g of glacial acetic acid, starting heating, raising the temperature to 30 ℃, keeping the temperature at 30-35 ℃, slowly adding 450g of dimethyl sulfoxide into the system, continuing raising the temperature to 55 ℃, keeping the temperature to react for 6 hours, and separating out solids after reacting for 1.5 hours. And (3) cooling to room temperature for crystal growth for 2h after the reaction time is up, filtering, washing a filter cake with 180g of methanol (mother liquor is reserved for use) at 55-65 ℃, vacuum-drying for 6h, and collecting to obtain 455g of cystamine dihydrochloride, wherein the yield is 91%, the liquid phase purity is 99.55%, and the content is 99.7%.
Example 3
Adding 500g of cysteamine hydrochloride into a 2000ml four-neck flask, adding the filtered mother liquor of the embodiment 2 at room temperature, heating to 30 ℃, keeping the temperature at 30-35 ℃, slowly adding 45g of dimethyl sulfoxide and 0.75g of glacial acetic acid into the system, continuously heating to 55 ℃, keeping the temperature for reaction for 6 hours, and separating out solids after the reaction is carried out for 0.5 hour. And (3) when the reaction time is up, cooling to room temperature for crystal growth for 2h, filtering, washing a filter cake with 180g of methanol (mother liquor is reserved for use), carrying out vacuum drying for 6h at 55-65 ℃, and collecting to obtain 468g of cystamine dihydrochloride, wherein the yield is 93.6%, the liquid phase purity is 99.05%, and the content is 100%.
Example 4
Adding 500g of cysteamine hydrochloride into a 2000ml four-neck flask, adding the filtered mother liquor of the embodiment 3 at room temperature, heating to 30 ℃, keeping the temperature at 30-35 ℃, slowly adding 45g of dimethyl sulfoxide and 0.75g of glacial acetic acid into the system, continuously heating to 65 ℃, keeping the temperature for reaction for 6 hours, and separating out solids after the reaction is carried out for 0.5 hour. And (3) when the reaction time is up, cooling to room temperature for crystal growth for 2h, filtering, washing a filter cake with 180g of methanol, carrying out vacuum drying for 6h at 55-65 ℃, and collecting to obtain 463g of cystamine dihydrochloride, wherein the yield is 92.6%, the liquid phase purity is 98.95%, and the content is 99.4%.
Although only the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art, and all changes are encompassed in the scope of the present invention.
Claims (9)
1. A method for synthesizing 2, 2' -dithiodiethylamine dihydrochloride is characterized in that:
adding 2-aminoethanethiol hydrochloride, an oxidant and a catalyst into a reaction solvent; under the action of a catalyst, heating to 40-90 ℃ for oxidation reaction; with the progress of the oxidation reaction, gradually reducing the substrate, gradually increasing the product, gradually crystallizing the product in a reaction solvent, reacting for 4-10h, cooling to room temperature, continuously crystallizing for 2-3 h, filtering, washing and drying to obtain 2, 2' -dithiodiethylamine dihydrochloride; the reaction equation is:
2. the method for synthesizing 2, 2' -dithiodiethylamine dihydrochloride according to claim 1, characterized in that: adding 2-aminoethanethiol hydrochloride into a reaction solvent, and stirring for dissolving; and then adding a catalyst, heating to raise the temperature, adding an oxidant when the temperature is raised to 30-45 ℃, and preserving the heat to carry out an oxidation reaction when the temperature is raised to above 55 ℃.
3. The method for synthesizing 2, 2' -dithiodiethylamine dihydrochloride according to claim 1, characterized in that: the drying is vacuum drying, the drying temperature is 55-65 ℃, and the drying time is 6 hours.
4. The method for synthesizing 2, 2' -dithiodiethylamine dihydrochloride according to claim 1, characterized in that: the oxidant is dimethyl sulfoxide or other organic sulfur oxides.
5. The method for synthesizing 2, 2' -dithiodiethylamine dihydrochloride according to claim 1, characterized in that: the reaction solvent is one or more of methanol, ethanol, acetone, acetonitrile and chloroform.
6. The method for synthesizing 2, 2' -dithiodiethylamine dihydrochloride according to claim 1, characterized in that: the catalyst is one or more of formic acid, glacial acetic acid and hydrochloric acid.
7. The method for synthesizing 2, 2' -dithiodiethylamine dihydrochloride according to claim 1, characterized in that: after reacting for 5-6h, cooling to room temperature.
8. The method for synthesizing 2, 2' -dithiodiethylamine dihydrochloride according to claim 1, characterized in that: the mass ratio of the reaction solvent to the 2-aminoethanethiol hydrochloride is 2.5-3.5: 1; the mass ratio of the oxidant to the 2-aminoethanethiol hydrochloride is 0.8-1.2: 1, and the mass ratio of the catalyst to the 2-aminoethanethiol hydrochloride is 0.25-0.30: 1.
9. The method for synthesizing 2, 2' -dithiodiethylamine dihydrochloride according to claim 1, characterized in that: r in the reaction equation comprises amino, alkali metal, halogen and phenyl.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111079580.4A CN113717084A (en) | 2021-09-15 | 2021-09-15 | Synthesis method of 2, 2' -dithiodiethylamine dihydrochloride |
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| CN202111079580.4A CN113717084A (en) | 2021-09-15 | 2021-09-15 | Synthesis method of 2, 2' -dithiodiethylamine dihydrochloride |
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| CN202111079580.4A Pending CN113717084A (en) | 2021-09-15 | 2021-09-15 | Synthesis method of 2, 2' -dithiodiethylamine dihydrochloride |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1097748A (en) * | 1994-01-27 | 1995-01-25 | 北京轻工业学院 | A kind of preparation method of difurfuryl dithioether |
| CN109400510A (en) * | 2018-10-24 | 2019-03-01 | 科迈化工股份有限公司 | Thiuram-disulfide class compound and synthesis technology |
-
2021
- 2021-09-15 CN CN202111079580.4A patent/CN113717084A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1097748A (en) * | 1994-01-27 | 1995-01-25 | 北京轻工业学院 | A kind of preparation method of difurfuryl dithioether |
| CN109400510A (en) * | 2018-10-24 | 2019-03-01 | 科迈化工股份有限公司 | Thiuram-disulfide class compound and synthesis technology |
Non-Patent Citations (5)
| Title |
|---|
| LUANA BETTANIN，等: "Solven- and metal-free selective oxidation of thiols to disulfides using I2/DMSO catalytic system", 《TETRAHEDRON LETTERS》 * |
| RICARDO ACOSTA ORTIZ，等: "Synthesis of tetraallylated cystamine and the study of its performance as a curing agent for the epoxy/thiol-ene photopolymerization of biobased nopol epoxy resins", 《JOURNAL OF POLYMER RESEARCH》 * |
| Z. PAPANYAN，等: "DETECTION OF OXIDATION OF L-CYSTEINE BY DIMETHYL SULFOXIDE IN AQUEOUS SOLUTIONS BY IR SPECTROSCOPY", 《JOURNAL OF APPLIED SPECTROSCOPY》 * |
| ZOHREH MIRJAFARY，等: "A copper(II)–thioamide combination as a robust heterogeneous catalytic system for green synthesis of 1,4-disubstituted-1,2,3-triazoles under click conditions", 《RSC ADV.》 * |
| 景丽，等: "N-氟代双苯磺酰胺作为氧化剂制备二硫化合物的研究", 《有机化学》 * |
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