CN106631939B - The oxidation of catalytic molecular oxygen generates the method with the disulfide of S -- S in water phase - Google Patents
The oxidation of catalytic molecular oxygen generates the method with the disulfide of S -- S in water phase Download PDFInfo
- Publication number
- CN106631939B CN106631939B CN201710054478.6A CN201710054478A CN106631939B CN 106631939 B CN106631939 B CN 106631939B CN 201710054478 A CN201710054478 A CN 201710054478A CN 106631939 B CN106631939 B CN 106631939B
- Authority
- CN
- China
- Prior art keywords
- disulfide
- water phase
- oxidation
- catalyst
- molecular oxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 27
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 26
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 20
- 229910001882 dioxygen Inorganic materials 0.000 title claims abstract description 17
- 230000003647 oxidation Effects 0.000 title claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 14
- -1 transition metal phthalocyanine compound Chemical class 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 16
- 239000012452 mother liquor Substances 0.000 claims description 7
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- RFCQDOVPMUSZMN-UHFFFAOYSA-N 2-Naphthalenethiol Chemical compound C1=CC=CC2=CC(S)=CC=C21 RFCQDOVPMUSZMN-UHFFFAOYSA-N 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- 230000008901 benefit Effects 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 18
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- MAHNFPMIPQKPPI-UHFFFAOYSA-N disulfur Chemical compound S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005691 oxidative coupling reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- YSHOWEKUVWPFNR-UHFFFAOYSA-N burgess reagent Chemical compound CC[N+](CC)(CC)S(=O)(=O)N=C([O-])OC YSHOWEKUVWPFNR-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- SWEDAZLCYJDAGW-UHFFFAOYSA-N Thiophene-2-thiol Chemical class SC1=CC=CS1 SWEDAZLCYJDAGW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000002398 materia medica Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The present invention provides catalytic molecular oxygen oxidations in a kind of water phase to generate the method with the disulfide of S -- S, using water-soluble transition metal phthalocyanine compound as catalyst, in oxygen or air environment, it reacts sulfhydryl compound 1-30 hours under conditions of pressure 0.01-1.00MPa, 40-100 DEG C of temperature in water phase, generates the disulfide with S -- S.Reaction carries out in water phase, without adding other organic solvents；Catalyst activity is high, and reaction efficiency is high, can repeatedly utilize；Synthesis technology is simple and direct, and selectivity of product is high, and by-product is few；Waste is few, environmental-friendly, has stronger prospects for commercial application.
Description
Technical field
The invention belongs to organic sulfur-sulfide linkage synthesis technical fields, and in particular to catalytic molecular oxygen oxidation life in a kind of water phase
At the method for the disulfide with S -- S.
Background technique
Disulfide containing S -- S is many protein molecules and biologically active key structure, 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.].There are many ways to constructing S -- S [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 method (the schema of the oxidation self-coupling reaction building S -- S by sulfhydryl compound
1).The most commonly used [Dariusz Witt,Synthesis. 2008, (16), 2491-2509], oxidative coupling reaction is common
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], sodium nitrite and burgess reagent etc..These methods belong to the oxidative coupling using oxidant stoichiometry
Reaction, oxidizer have to be larger than or even are far longer than 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 at low cost, oxidant is easy
In separation, green non-pollution, the high product purity from system the advantages that, increasingly it is taken seriously.But molecular oxygen oxidation reaction
Key is to develop the catalyst of high activity.Avelino Corma etc. [Chem. Sci., 2012, 3, 398-404] and report
A kind of method that under solvent-free conditions solid supported gold catalytic air oxygen prepares disulfide, product was through dissolving
Journey is separated with catalyst.Suman L. Jain etc. [Ind. Eng. Chem. Res. 2010, 49, 6674-6677] it reports
A kind of self-coupling reaction of the sulfhydryl compound of dioxygen oxidation, catalyst are the Cobalt Phthalocyanine being immobilized on resin, reaction medium
For the NaOH solution of 1N.
Above with the self-coupling reaction and cross-coupling reaction of molecular oxygen (oxygen or air) oxidation or in organic solvent
Middle to carry out or using heterogeneous catalyst or need exogenously added alkali, each of which increases the difficulty and step of product post-processing purification
Suddenly, it is difficult to the generation of brine waste is avoided, to limit the use of these methods.
Summary of the invention
The present invention provides catalytic molecular oxygen oxidations in a kind of water phase to generate the method with the disulfide of S -- S,
This method method is reacted in water phase, without being additionally supplemented with solvent, can obtain intermediate S -- S, subsequent processing letter
It is single.
The invention adopts the following technical scheme: the oxidation of catalytic molecular oxygen generates the curing with S -- S in a kind of water phase
The method for closing object in oxygen or air environment, makes sulfhydryl compound using water-soluble transition metal phthalocyanine compound as catalyst
It is reacted 1-30 hours under conditions of pressure 0.01-1.00MPa, 40-100 DEG C of temperature in water phase, generating has the two of S -- S
Sulphur compound.
The water-soluble transition metal phthalocyanine compound is made 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, Tetrasulphated phthalcyanine sylvite in
Any one；Metal center is any one in W, Ce, Cu, Fe, Co, Mn, Ni.
The catalyst is one or more of water-soluble transition metal phthalocyanine compound any combination.
The dosage of the catalyst is the 0.01-10% of sulfhydryl compound quality, and the dosage 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 50-80oC, reaction time are 2-18 hours.
The dosage of the catalyst is the 0.03-5% of sulfhydryl compound quality, and the dosage of water is sulfhydryl compound quality
10-30 times.
Described generate has sulphur-sulfide linkage compound method, and reaction carries out in water phase, other organic molten without adding
Agent.
Described generate has sulphur-sulfide linkage compound method, the water-soluble transition metal phthalocyanine compound as catalyst
It can be one kind；It is also possible to be used in mixed way by two or more transition metal phthalocyanine compounds, between metal phthalocyanine compound
Mass ratio there is no particular limitation, can be arbitrary proportion.
In the present invention, using one or two kinds of above water-soluble transition metal phthalocyanine compound as catalyst, direct plunge into
It uses.Water-soluble transition metal phthalocyanine compound for catalyst can directly buy corresponding chemical products complex,
It is used after can synthesizing.
In use, reaction effect increases with catalyst amount and improves the present invention, but catalyst amount increases life
It produces cost to be consequently increased, excessive catalyst can bring separation difficult.The dosage of catalyst is sulfhydryl compound quality
0.01-10 wt%, preferably 0.03-5 wt%.
Method of the invention carries out in water phase, and the dosage increase of water can dissolve more catalyst and improve reaction speed
Degree, can reduce reaction solution viscosity and improve mixing effect, and then improve reaction effect, but the dosage of water is crossed conference and reduced and reacts
Efficiency increases energy consumption.The dosage of water is 3-50 times, preferably 10-30 times of sulfhydryl compound quality.
In the present invention after synthetic reaction, aftertreatment technology process is not particularly limited, and product separating-purifying can lead to
It crosses following methods progress: after oxidation reaction, placing cooling, catalyst and unreacting material by product and are contained by filtering
Mother liquor separation, then it is washed, drying or recrystallization, obtain product.
Oxidation reaction of the present invention, which terminates to isolate the later mother liquor of product, can reuse the work for continuing to play catalyst
With, using number it is more more save production cost.But after repeatedly utilizing, since the amount in mother liquor containing by-product etc. increases, meeting
Influence the progress of oxidation reaction, reaction rate and conversion ratio decline.Suitable mother liquor is 8-15 times using number.
Preparation method of the present invention has the advantage that reaction carries out in water phase compared with prior art, other without adding
Organic solvent；Catalyst activity is high, and reaction efficiency is high, can repeatedly utilize；Synthesis technology is simple and direct, and selectivity of product is high, secondary
Product is few；Waste is few, environmental-friendly, has stronger prospects for commercial application.
Detailed description of the invention
Fig. 1 is two sulphur of di-p-tolyl prepared by embodiment 11HNMR spectrogram；
Fig. 2 is two sulphur of di-p-tolyl prepared by embodiment 113HNMR spectrogram.
Specific embodiment
Embodiment 1: synthesis contains sulphur-sulfide linkage disulfide in oxygen atmosphere.
In the reaction kettle of 100 mL, 6 g are put into methylbenzene phenyl-sulfhydrate, 48 mg(0.8 wt%) four sodium of tetracarboxylic FePC
[FePc(COONa)4] and 60 mL water；It is heated to 40 DEG C under stirring, is passed through oxygen, keeping pressure in reaction kettle is 0.15
MPa stops reaction after reaction 15 hours, cooling, filtering, 10 mL water washing filter cakes dry to obtain 5.88 g of white solid, product
See attached drawing through NMR(), the methods of MS determine that structure is two sulphur of di-p-tolyl, yield 98%, it is pure that liquid chromatograph analyzes product
Degree is 99.5%.
The mother liquor for filtering to isolate two sulphur of di-p-tolyl returns to reaction kettle, puts into 6 g again to methylbenzene phenyl-sulfhydrate, is not necessarily to
Catalyst is put into again, is continued by original conditioned response 15 hours, it is final that 5.88 g products, liquid chromatograph analyze product purity
It is 99.5%.It is utilized mother liquor 10 times repeatedly under the same terms, each secondary yield is 95% or more.10th utilization, yield are
95%, purity 99%.
Embodiment 2: synthesis contains sulphur-sulfide linkage disulfide in air atmosphere.
In the reaction kettle of 100 mL, 3 g 2- mercaptonaphthalenes, 3 mg Tetrasulphated phthalcyanine tungsten, four potassium [WPc are put into
(SO3K)4] and 12 mL water；It is heated to 60 DEG C under stirring, is pressed into air, keeping pressure in reaction kettle is 0.1 MPa, reaction
Stop reaction after 5.5 hours, cooling, filtering, 10 mL water washings dry to obtain 2.82 g of product, bis--(2- naphthalene) two sulphur, yield
It is 94%, it is 99% that liquid chromatograph, which analyzes product purity,.
Embodiment 3: synthesis contains sulphur-sulfide linkage disulfide in oxygen-enriched air atmosphere.
In the reaction kettle of 100 mL, 2 g 2- mercapto-thiophenes, 18 mg Tetrasulphated phthalcyanine tungsten, four potassium [WPc are put into
(SO3K)4], 2 mg tetracarboxylic phthalocyanine cerium, four sodium [CePc (COONa)4] and 36 mL water；75 DEG C are heated under stirring, indentation
Oxygen-enriched air [oxygen gas ︰ air (wt ︰ wt)=2 ︰ 1], keeping pressure in reaction kettle is 0.15 MPa, and reaction stops after 18 hours
Reaction, cooling, filtering, water washing dry to obtain 1.82 g Dithiophene -2- base of product, two sulphur, yield 91%, liquid chromatograph point
Analysing product purity is 98%.
It synthesizes by the identical method of embodiment 1 containing sulphur-sulfide linkage organic matter, various reaction conditions and reaction result are shown in
Table 1.
It is synthesized under 1 different condition of table various containing sulphur-sulfide linkage organic matter
As seen from the above embodiment, using preparation method of the invention, yield has reached 90%, which is adopted
Catalyst not can cause environmental pollution, and catalytic activity is high, and reaction efficiency is high.
Claims (6)
1. the oxidation of catalytic molecular oxygen generates the method with the disulfide of S -- S in a kind of water phase, it is characterised in that: with mistake
Crossing metal phthalocyanine compound is catalyst, and so that sulfhydryl compound is reacted generation in water phase in oxygen or air environment has S-
The disulfide of S key, the reaction time is 1-30 hours, reaction pressure 0.01-1.00MPa, temperature are 40-100 DEG C；It generates
After disulfide with S -- S, the disulfide with S -- S is filtered out, mother liquor repeats benefit as catalyst
With recycling 8-15 times, the dosage of the catalyst is the 0.01-10% of sulfhydryl compound quality；The transition metal phthalocyanine
Compound is made of parent and metal center coordination, and parent phthalocyanine is tetracarboxylic phthalocyanine, Tetrasulphated phthalcyanine, tetracarboxylic phthalocyanine
Sodium salt, the sylvite of tetracarboxylic phthalocyanine, the sodium salt of Tetrasulphated phthalcyanine, Tetrasulphated phthalcyanine sylvite；Metal center be W, Ce,
Any one in Cu, Fe, Co, Mn, Ni；The dosage of the water is 3-50 times of sulfhydryl compound quality.
2. the oxidation of catalytic molecular oxygen generates the method with the disulfide of S -- S in water phase as described in claim 1,
Be characterized in that: catalyst is one or more of transition metal phthalocyanine compound any combination.
3. the oxidation of catalytic molecular oxygen generates the method with the disulfide of S -- S in water phase as described in claim 1,
Be characterized in that: the sulfhydryl compound is benzenethiol, thionaphthol, heterocycle thiophenol, any one in alkyl hydrosulfide.
4. the oxidation of catalytic molecular oxygen generates the method with the disulfide of S -- S in water phase as described in claim 1,
Be characterized in that: the dosage of the catalyst is the 0.03-5% of sulfhydryl compound quality.
5. the oxidation of catalytic molecular oxygen generates the method with the disulfide of S -- S in water phase as described in claim 1,
Be characterized in that: the dosage of water is 10-30 times of sulfhydryl compound quality.
6. the oxidation of catalytic molecular oxygen generates the method with the disulfide of S -- S in water phase as described in claim 1,
Be characterized in that: pressure is 0.03-0.4MPa in the water phase, temperature 50-80oC, reaction time are 2-18 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710054478.6A CN106631939B (en) | 2017-01-24 | 2017-01-24 | The oxidation of catalytic molecular oxygen generates the method with the disulfide of S -- S in water phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710054478.6A CN106631939B (en) | 2017-01-24 | 2017-01-24 | The oxidation of catalytic molecular oxygen generates the method with the disulfide of S -- S in water phase |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106631939A CN106631939A (en) | 2017-05-10 |
| CN106631939B true CN106631939B (en) | 2019-05-17 |
Family
ID=58841182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710054478.6A Active CN106631939B (en) | 2017-01-24 | 2017-01-24 | The oxidation of catalytic molecular oxygen generates the method with the disulfide of S -- S in water phase |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106631939B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180545B (en) * | 2018-09-19 | 2020-07-03 | 郑州大学 | Method for synthesizing disulfide with S-S bond by virtue of oxidation of phenyl phenolic acid catalytic molecular oxygen in aqueous phase |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4705620A (en) * | 1986-12-16 | 1987-11-10 | Uop Inc. | Mercaptan extraction process |
-
2017
- 2017-01-24 CN CN201710054478.6A patent/CN106631939B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
|---|
| A two in one approach: renewable support and enhanced catalysis for sweetening using chicken feather bound cobalt(II) phthalocyanine under alkali free environment;Deepak K. Chauhan 等;《RSC Advances》;20160523;第6卷;第51983-51988页 * |
| Magnetic silica beads functionalized with cobalt phthalocyanine for the oxidation of mercaptans in an alkali free aqueous medium;Garima Singh 等;《RSC Advances》;20140620;第4卷;第29127页Table 1 * |
| 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》.2016,第27卷第1505-1508页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106631939A (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106866577B (en) | The method of catalytic molecular oxygen oxidation preparation sulfenamide thiofide in water phase | |
| CN108772103A (en) | Bimetallic MOF catalyst, preparation method and application | |
| CN101139338B (en) | Preparation of 2,2'-disulfo-dibenzopyrene by oxygen process based on 2-mercaptan benzothiazole ammonia salt | |
| CN102876462B (en) | Method for preparing high-quality epoxidized soybean oil | |
| CN106349126B (en) | The method for preparing 4,4 '-dichloro diphenyl sulfone | |
| CN103382168B (en) | Synthetic method for N,N'-diisopropyl carbodiimide | |
| CN102816045B (en) | Method for synthesizing chloromethane by tail gas generated during chloroacetic acid production | |
| CN106831750B (en) | The oxidation of catalytic molecular oxygen generates the method with the sulfenamide compound of S-N key in water phase | |
| CN106866466A (en) | A kind of method for synthesizing N-acetylsulfanilyl chloride as sulfonating agent with sulfur trioxide | |
| CN106631939B (en) | The oxidation of catalytic molecular oxygen generates the method with the disulfide of S -- S in water phase | |
| CN106831644B (en) | The method of catalytic molecular oxygen oxidation 2,2 '-two sulphur union II benzothiazoles of preparation in water phase | |
| CN105585541A (en) | Preparation method of cyclohexene oxide | |
| CN107501059B (en) | Green and environment-friendly synthesis method of 4- (4' -alkylcyclohexyl) cyclohexanone | |
| CN102936297A (en) | Porous chitosan metal porphyrin composite and preparation method and application thereof | |
| CN107082892A (en) | A kind of preparation method of bimetallic organic framework material and its application in cyclohexylhydroperoxdecomposition decomposition reaction | |
| CN101885712B (en) | Method for producing propylene oxide | |
| CN109772326A (en) | A kind of catalyst and its preparation method and application synthesizing Fluorenone | |
| CN107233921A (en) | The methods and applications that SalenMX prepares catalyst are loaded with modified cellulose | |
| CN107266393B (en) | A kind of application of Cu base non-noble metal composite oxide catalyst | |
| CN105524022B (en) | A kind of method for preparing expoxy propane | |
| CN108276261A (en) | Catalytic molecular oxygen aoxidizes the method for preparing 2- bromine Fluorenones in a kind of water phase | |
| CN108003031A (en) | A kind of method for preparing nitro compound using graphene catalysis nitrogen dioxide | |
| CN111100214B (en) | Preparation method of oxidized starch with high carboxyl content | |
| CN103864575A (en) | Method for preparing 1,2-pentanediol | |
| CN103450028B (en) | Method for preparing cyclohexylamine and dicyclohexylamine from nitrobenzene through one-step catalytic hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
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 |
|
| TR01 | Transfer of patent right |