CN106631939A - Method for catalyzing molecular oxygen to oxidize into disulfides with S-S bonds in aqueous phase - Google Patents
Method for catalyzing molecular oxygen to oxidize into disulfides with S-S bonds in aqueous phase Download PDFInfo
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- CN106631939A CN106631939A CN201710054478.6A CN201710054478A CN106631939A CN 106631939 A CN106631939 A CN 106631939A CN 201710054478 A CN201710054478 A CN 201710054478A CN 106631939 A CN106631939 A CN 106631939A
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- disulfide
- molecular oxygen
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B45/00—Formation or introduction of functional groups containing sulfur
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
- C07D213/71—Sulfur atoms to which a second hetero atom is attached
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/34—Sulfur atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention provides a method for catalyzing molecular oxygen to oxidize into disulfides with S-S bonds in an aqueous phase. The method includes taking water-soluble transition metal phthalocyanine compounds as catalysts, and enabling sulfhydryl compounds to react for 1-30 hours in the aqueous phase at a pressure of 0.01-1.00 Mpa, at 40-100 DEG C and in the presence of oxygen or air so as to obtain the disulfides with the S-S bonds. The method has the advantages that reaction is conducted in the aqueous phase, so that addition of other organic solvents is unneeded; the catalysts are high in catalytic activity, high in reaction efficiency and reusable; the method is simple in synthetic process, high in product selectivity, fewer in byproducts and wastes and environment friendly, thereby being promising in industrial application prospect.
Description
Technical field
The invention belongs to organic sulfur-sulfide linkage synthesis technical field, and in particular to catalytic molecular oxygen oxidation life in a kind of water phase
Into the method for the disulfide with S -- S.
Background technology
Disulfide containing S -- S is many protein molecules and the key structure with biologically active, used as weight
The intermediate wanted, is widely deployed in the synthesis and preparation of numerous compounds, in organic synthesis, materia medica and life section
Occupy in very important status [F. D é nes, M. Pichowicz, G. Povie and P. Renaud,Chem. Rev., 2014, 114, 2587-2693.].Building the method for S -- S has various [L. Craine, M. Raban.Chem. Rev. 1989. 89(4), 659-712；B. Mandala, B. Basu.RSC Adv., 2014, 4, 13854-
13881], such as sulfenyl halides substitution reaction.But, the method that S -- S is built by the oxidation self-coupling reaction of sulfhydryl compound（Schema
1）.The most commonly used [Dariusz Witt,Synthesis. 2008, (16), 2491-2509], oxidative coupling reaction is commonly used
Oxidant include：Hydrogen peroxide [(a) Hatano, A.; Makita, S.; Kirihara, M.Bioorg. Med. Chem. Lett. 2004, 14, 2459. (b) Kesavan, V.; Bonnet-Delpon, D.; Begue, J. P.Synthesis 2000,223.], halogen [M. H. Ali, M. McDermott. Tetrahedron Letters 2002,43, 6271-6273], natrium nitrosum and burgess reagent etc..These methods belong to using the oxidative coupling of oxidant stoichiometry
Reaction, oxidizer have to be larger than or even be far longer than the equivalent required for oxidation reaction, therefore post-process difficult, it is difficult to real
Existing clean manufacturing, does not meet the production requirement of national environmental protection policy and energy-saving and emission-reduction.
The autoxidation coupling reaction of sulfhydryl compound
Use molecular oxygen（Oxygen or air）As the oxidant of oxidative coupling reaction, due to low cost, oxidant be easy to from
In system the advantages of separation, green non-pollution, high product purity, increasingly it is taken seriously.But the key of molecular oxygen oxidation reaction
It is the highly active catalyst of exploitation.Avelino Corma etc. [Chem. Sci., 2012, 3, 398-404] and report one
The method that solid supported gold catalytic air oxygen prepares disulfide kind under condition of no solvent, its product Jing course of dissolutions with
Catalyst is separated.Suman L. Jain etc. [Ind. Eng. Chem. Res. 2010, 49, 6674-6677] one is reported
The self-coupling reaction of the sulfhydryl compound of dioxygen oxidation is planted, catalyst is the Cobalt Phthalocyanine being immobilized on resin, and reaction medium is 1N
NaOH solution.
More than use molecular oxygen（Oxygen or air）The self-coupling reaction and cross-coupling reaction of oxidation, or in organic solvent
In carry out, or using heterogeneous catalyst, or needing exogenously added alkali, each of which increases product post processing purification difficulty and step
Suddenly, it is difficult to avoid the generation of brine waste, so as to limiting the use of these methods.
The content of the invention
The invention provides a kind of method that the oxidation of catalytic molecular oxygen generates the disulfide with S -- S in water phase,
The method method is reacted in water phase, without the need for being additionally supplemented with machine solvent, can just obtain intermediate S -- S, subsequent treatment letter
It is single.
The present invention is employed the following technical solutions：Catalytic molecular oxygen oxidation in a kind of water phase generates the curing with S -- S
The method of compound, with water-soluble transition metal phthalocyanine compound as catalyst, in oxygen or air ambient, makes sulfhydryl compound
1-30 hours are reacted under conditions of pressure 0.01-1.00MPa, temperature 40-100 DEG C in water phase, with S -- S two are generated
Sulphur compound.
The water-soluble transition metal phthalocyanine compound is made up of parent and metal center coordination, and parent phthalocyanine is tetracarboxylic
Phthalocyanine [Pc (COOH)4], Tetrasulphated phthalcyanine [Pc (SO3H)4], the sodium salt of tetracarboxylic phthalocyanine, in the sylvite of Tetrasulphated phthalcyanine
Any one；Metal center is any one in W, Ce, Cu, Fe, Co, Mn, Ni.
The catalyst is one or more any combination in water-soluble transition metal phthalocyanine compound.
The consumption of the catalyst is the 0.01-10% of sulfhydryl compound quality, and the consumption of the water is sulfhydryl compound matter
3-20 times of amount.
The sulfhydryl compound is any one in benzenethiol, thionaphthol, heterocycle thiophenol, alkyl thiophenol and alkyl thiophenol
Kind.
The reaction oxygen partial pressure is 0.03-0.4MPa, temperature is 50-80oC, the reaction time is 2-18 hours.
The consumption of the catalyst is the 0.03-5% of sulfhydryl compound quality, and the consumption of water is sulfhydryl compound quality
10-30 times.
Described to generate the method with sulphur-sulfide linkage compound, reaction is carried out in water phase, organic molten without the need for adding other
Agent.
It is described to generate the method with sulphur-sulfide linkage compound, the water-soluble transition metal phthalocyanine compound as catalyst
Can be a kind of；Can also be used in mixed way by two or more transition metal phthalocyanine compounds, between its metal phthalocyanine compound
Mass ratio there is no particular limitation, can be arbitrary proportion.
In the present invention, with one or two kinds of above water-soluble transition metal phthalocyanine compound as catalyst, direct plunge into
Use.Water-soluble transition metal phthalocyanine compound for catalyst can directly buy corresponding chemical products complex,
Use after can synthesizing.
In use, reaction effect increases and improves the present invention with catalyst amount, but catalyst amount increases life
Produce cost to be consequently increased, excessive catalyst can bring separation difficult.The consumption of catalyst is sulfhydryl compound quality
0.01-10 wt%, preferred 0.03-5 wt%.
The method of the present invention is carried out in water phase, and the consumption increase of water can dissolve more catalyst and improve reaction speed
Degree, can reduce reactant liquor viscosity and improve mixing effect, and then improve reaction effect, but the consumption of water crosses conference and reduces reaction
Efficiency, increases energy resource consumption.The consumption of water is 3-50 times, preferred 10-30 times of sulfhydryl compound quality.
After synthetic reaction terminates in the present invention, aftertreatment technology process is not particularly limited, and product separating-purifying can lead to
Crossing following methods is carried out：After oxidation reaction terminates, cooling is placed, by filtering by product and containing catalyst and unreacting material
Mother liquor separate, then it is scrubbed, drying or recrystallize, obtain product.
Oxidation reaction of the present invention terminates to isolate the later mother liquor of product can reuse the work for continuing to play catalyst
With more many using number of times more save production cost.But after repeatedly utilizing, due to the increase of the amount containing accessory substance etc., meeting in mother liquor
The carrying out of oxidation reaction, reaction rate and conversion ratio is affected to decline.Suitable mother liquor is 8-15 time using number of times.
Preparation method of the present invention has the advantage that compared with prior art：Reaction is carried out in water phase, without the need for adding other
Organic solvent；Catalyst activity is high, and reaction efficiency is high, can repeatedly utilize；Synthesis technique is simple and direct, and selectivity of product is high, secondary
Product is few；Waste is few, environmental friendliness, with stronger prospects for commercial application.
Description of the drawings
Fig. 1 is the sulphur of di-p-tolyl two prepared by embodiment 11HNMR spectrograms；
Fig. 2 is the sulphur of di-p-tolyl two prepared by embodiment 113HNMR spectrograms.
Specific embodiment
Embodiment 1：Synthesize the disulfide containing sulphur-sulfide linkage in oxygen atmosphere.
In the reactor of 100 mL, 6 g are to methylbenzene phenyl-sulfhydrate, 48 mg for input（0.8 wt%）The sodium of tetracarboxylic FePC four
[FePc(COONa)4] and 60 mL water；40 DEG C are heated under stirring, oxygen is passed through, keep pressure in reactor to be 0.15
MPa, reaction stops reaction after 15 hours, cooling is filtered, and 10 mL water washing filter cakes dry to obtain the g of white solid 5.88, product
Jing NMR（See accompanying drawing）, the method such as MS determine structure for the sulphur of di-p-tolyl two, yield is 98%, and liquid chromatograph assay products are pure
Spend for 99.5%.
The mother liquor for filtering to isolate the sulphur of di-p-tolyl two returns reactor, and 6 g are put into again to methylbenzene phenyl-sulfhydrate, without the need for
Catalyst is put into again, continues to press original conditioned response 15 hours, it is final to obtain 5.88 g products, liquid chromatograph assay products purity
For 99.5%.Mother liquor 10 times is so recycled under the same terms, each yield is more than 95%.Utilize for 10th time, yield is
95%, purity is 99%.
Embodiment 2：Synthesize the disulfide containing sulphur-sulfide linkage in air atmosphere.
In the reactor of 100 mL, 3 g 2- mercaptonaphthalenes of input, the potassium [WPc of 3 mg Tetrasulphated phthalcyanines tungsten four
(SO3K)4] and 12 mL water；60 DEG C are heated under stirring, air is pressed into, keep pressure in reactor to be 0.1 MPa, reacted
Stop reaction after 5.5 hours, cooling is filtered, 10 mL water washings, dry the g bis- of product 2.82-（2- naphthyls）Two sulphur, yield
For 94%, liquid chromatograph assay products purity is 99%.
Embodiment 3：Synthesize the disulfide containing sulphur-sulfide linkage in oxygen-enriched air atmosphere.
In the reactor of 100 mL, 2 g 2- mercapto-thiophenes of input, the potassium [WPc of 18 mg Tetrasulphated phthalcyanines tungsten four
(SO3K)4], the sodium [CePc (COONa) of 2 mg tetracarboxylic phthalocyanines cerium four4] and 36 mL water；75 DEG C are heated under stirring, press-in
Oxygen-enriched air [Yang Qi ︰ air（Wt ︰ wt）=2 ︰ 1], keep pressure in reactor to be 0.15 MPa, reaction stops after 18 hours
Reaction, cooling is filtered, and water washing dries to obtain the sulphur of 1.82 g Dithiophene -2- bases of product two, and yield is 91%, liquid chromatograph point
Analysis product purity is 98%.
Synthesize the organic matter containing sulphur-sulfide linkage by the identical method of embodiment 1, its various reaction condition and reaction result are shown in
Table 1.
Synthesize the various organic matters containing sulphur-sulfide linkage under the different condition of table 1
As seen from the above embodiment, using the preparation method of the present invention, yield has reached 90%, what the preparation method was adopted
Catalyst will not be high to environment, catalysis activity, and reaction efficiency is high.
Claims (10)
1. a kind of method that the oxidation of catalytic molecular oxygen generates the disulfide with S -- S in water phase, it is characterised in that：With mistake
It is catalyst to cross metal phthalocyanine compound, makes sulfhydryl compound that generation is reacted in water phase in oxygen or air ambient and has S-
The disulfide of S keys, the reaction time be 1-30 hours, reaction pressure be 0.01-1.00MPa, temperature be 40-100 DEG C.
2. the method that the oxidation of catalytic molecular oxygen generates the disulfide with S -- S in water phase as claimed in claim 1, its
It is characterised by：The transition metal phthalocyanine compound by parent and metal center coordination make, parent phthalocyanine be tetracarboxylic phthalocyanine,
Tetrasulphated phthalcyanine, the sodium salt of tetracarboxylic phthalocyanine, the sylvite of tetracarboxylic phthalocyanine, the sodium salt of Tetrasulphated phthalcyanine, tetrasulfonic acid base phthalein
The sylvite of cyanines；Metal center is any one in W, Ce, Cu, Fe, Co, Mn, Ni.
3. the method that the oxidation of catalytic molecular oxygen generates the disulfide with S -- S in water phase as claimed in claim 2, its
It is characterised by：Catalyst is one or more any combination in transition metal phthalocyanine compound.
4. the method that the oxidation of catalytic molecular oxygen generates the disulfide with S -- S in water phase as claimed in claim 1, its
It is characterised by：The sulfhydryl compound is any one in benzenethiol, thionaphthol, heterocycle thiophenol, alkyl thiophenol and alkyl thiophenol
Kind.
5. the oxidation of catalytic molecular oxygen generates the side of the disulfide with S -- S in the water phase as described in claim 1 or 3
Method, it is characterised in that：The consumption of the catalyst is the 0.01-10% of sulfhydryl compound quality.
6. the method that the oxidation of catalytic molecular oxygen generates the disulfide with S -- S in water phase as claimed in claim 5, its
It is characterised by：The consumption of the catalyst is the 0.03-5% of sulfhydryl compound quality.
7. the method that the oxidation of catalytic molecular oxygen generates the disulfide with S -- S in water phase as claimed in claim 1, its
It is characterised by：The consumption of the water is 3-50 times of sulfhydryl compound quality.
8. the method that the oxidation of catalytic molecular oxygen generates the disulfide with S -- S in water phase as claimed in claim 7, its
It is characterised by：The consumption of water is 10-30 times of sulfhydryl compound quality.
9. the method that the oxidation of catalytic molecular oxygen generates the disulfide with S -- S in the water phase as described in claim 1-,
It is characterized in that：In the water phase pressure be 0.03-0.4MPa, temperature be 50-80oC, the reaction time be 2-18 hours.
10. the method that the oxidation of catalytic molecular oxygen generates the disulfide with S -- S in water phase as claimed in claim 1,
It is characterized in that：After generating the disulfide with S -- S, the disulfide with S -- S is filtered out, mother liquor is made
For catalyst recycling, reuse 8-15 time.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180545A (en) * | 2018-09-19 | 2019-01-11 | 郑州大学 | The synthesis of phenyl phenol acid catalysis molecular oxygen oxidation has the method for the disulfide of S -- S in water phase |
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| US3654297A (en) * | 1969-02-10 | 1972-04-04 | American Cyanamid Co | Process for oxidizing 2-mercaptobenzothiazole |
| US4558135A (en) * | 1981-04-02 | 1985-12-10 | Akzona Incorporated | Process for the preparation of dithiazolyl disulfides |
| CN87101298A (en) * | 1986-12-16 | 1988-06-29 | 环球油品公司 | In the mercaptan extraction process, remove the method for the disulphide that returns |
| CN103880722A (en) * | 2014-03-31 | 2014-06-25 | 宁波中一石化科技股份有限公司 | Method for preparing high-purity diethyl disulfide |
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2017
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| US3654297A (en) * | 1969-02-10 | 1972-04-04 | American Cyanamid Co | Process for oxidizing 2-mercaptobenzothiazole |
| US4558135A (en) * | 1981-04-02 | 1985-12-10 | Akzona Incorporated | Process for the preparation of dithiazolyl disulfides |
| CN87101298A (en) * | 1986-12-16 | 1988-06-29 | 环球油品公司 | In the mercaptan extraction process, remove the method for the disulphide that returns |
| CN103880722A (en) * | 2014-03-31 | 2014-06-25 | 宁波中一石化科技股份有限公司 | Method for preparing high-purity diethyl disulfide |
| CN105562091A (en) * | 2014-10-17 | 2016-05-11 | 中国石油化工股份有限公司 | Catalytic promoter composition for catalytic oxidation of thiol and thiol catalytic oxidation method |
| CN105924372A (en) * | 2016-02-05 | 2016-09-07 | 宁夏紫光天化蛋氨酸有限责任公司 | Production method for dimethyl disulfide |
Non-Patent Citations (3)
| Title |
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| DEEPAK K. CHAUHAN 等: "A two in one approach: renewable support and enhanced catalysis for sweetening using chicken feather bound cobalt(II) phthalocyanine under alkali free environment", 《RSC ADVANCES》 * |
| GARIMA SINGH 等: "Magnetic silica beads functionalized with cobalt phthalocyanine for the oxidation of mercaptans in an alkali free aqueous medium", 《RSC ADVANCES》 * |
| SHAN-LI YI 等: "An efficient and convenient method for the preparation of disulfides from thiols using oxygen as oxidant catalyzed by tert-butyl nitrite", 《CHINESE CHEMICAL LETTERS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180545A (en) * | 2018-09-19 | 2019-01-11 | 郑州大学 | The synthesis of phenyl phenol acid catalysis molecular oxygen oxidation has the method for the disulfide of S -- S in water phase |
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Effective date of registration: 20191225 Address after: 100176 floor 8, building 1, No. 6, Taihe Road, Beijing Economic and Technological Development Zone, Daxing District, Beijing Patentee after: Kanglong (Beijing) new drug technology Limited by Share Ltd Address before: 450001 science and technology zone, Zhengzhou, Henan, No. 100 Patentee before: Zhengzhou University |
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