CN113860982A - Green disulfide synthesis method - Google Patents
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- CN113860982A CN113860982A CN202111391256.6A CN202111391256A CN113860982A CN 113860982 A CN113860982 A CN 113860982A CN 202111391256 A CN202111391256 A CN 202111391256A CN 113860982 A CN113860982 A CN 113860982A
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- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000001308 synthesis method Methods 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 14
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims abstract description 11
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims abstract description 11
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 11
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 11
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 229910004755 Cerium(III) bromide Inorganic materials 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 66
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 150000002019 disulfides Chemical class 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021576 Iron(III) bromide Inorganic materials 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims 2
- 238000010791 quenching Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 4
- 239000000575 pesticide Substances 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- 239000012074 organic phase Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 13
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000011734 sodium Substances 0.000 description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 239000008346 aqueous phase Substances 0.000 description 10
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 10
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 olefine Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- 208000023275 Autoimmune disease Diseases 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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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
-
- 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles 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 in position 2
- C07D277/70—Sulfur atoms
- C07D277/76—Sulfur atoms attached to a second hetero atom
- C07D277/78—Sulfur atoms attached to a second hetero atom to a second sulphur atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Cephalosporin Compounds (AREA)
Abstract
The invention discloses a green disulfide synthesis method, and belongs to the technical field of green chemistry and organic synthesis. Under the conditions of room temperature, open and neutral, the symmetric disulfide with parent nucleus of alkane, olefin, arene, oxazole, thiazole, pyrazole, imidazole and other derivatives is rapidly prepared, and the catalyst is MBrx(M is Fe)2+、Fe3+、Ce3+Etc., x is 2-3), the only oxidizing agent is H2O2. The present invention uses commercially available and relatively low cost reagents (e.g., FeBr)2、CeBr3And H2O2Etc.) and common organic solvent, simple steps, convenient operation, rapid reaction, mild reaction conditions, and open mouth at room temperature, and can obtain pure disulfide without further purification, has more advantages than all the previous methods, and is expected to be widely applied in the industries of organic synthesis, medicine, pesticide, electronic products, etc.
Description
Technical Field
The invention relates to the technical field of green chemistry and organic synthesis, in particular to a novel green synthesis method of symmetrical disulfide containing alkane, olefin, aromatic hydrocarbon, oxazole, thiazole, pyrazole, imidazole and the like and derivatives thereof.
Background
Organic sulfides are a class of compounds with wide application, and play a vital role in material chemistry, organic synthesis, biosynthesis and pharmaceutical chemistry. Disulfides are present in many biologically active natural products and have found wide application at various industrial levels. The formation of S-S bonds is a fundamental step in obtaining structurally diverse organic molecules that are widely used in the pharmaceutical and agrochemical industries. Disulfide bonds are key fragments for stabilizing protein structure, play a crucial role in biological activity, and are widely applied to the field of medicinal chemistry, and the excellent redox sensitivity of the disulfide bonds becomes a key step in a drug delivery procedure and is also a key pharmacophore for treating cancers and autoimmune diseases. In addition, disulfides are widely used in organic synthesis, and their reversible nature has recently become an important tool in the study of kinetic and dynamic combinatorial chemistry, and in addition, disulfides are also useful as sulfurizing agents and agricultural pesticides. Thus, it is becoming increasingly important to prepare disulfides of different parent nuclei in an economical, green, simple manner.
Currently, there are many documents on the preparation of disulfides, and strong oxidants such as iodine, potassium permanganate, halogens, etc. are commonly used for the synthesis of disulfides. However, most of the methods have disadvantages, such as excessive oxidation of raw materials, generation of more byproducts such as sulfoxide, sulfone and the like, and low recovery rate; the catalyst is expensive, and the production cost is increased; the purification process is complicated, and a large amount of waste harmful to the environment is generated, so that the environment is not green. Therefore, there is a need to develop a new method for oxidizing mercaptans to form disulfides, which comprises an inexpensive green catalyst, simple reaction conditions, simple purification steps and high yields.
Disclosure of Invention
The invention aims to develop a green and efficient method for synthesizing disulfide bonds, which is used for preparing symmetric disulfides with parent nuclei of alkane, alkene, arene, oxazole, thiazole, pyrazole, imidazole and the like and derivatives thereof.
The technical scheme adopted by the invention is as follows:
a green disulfide preparation process:
under the conditions of room temperature, open and neutral, the reaction raw material is mercaptan whose mother nucleus is alkane, olefine, arene, oxazole, thiazole, pyrazole, imidazole and their derivatives, and the catalyst is MBrx(M is Fe)2+、Fe3+、Ce3+Etc., x is 2-3), the oxidizing agent is H2O2Symmetric disulfides are rapidly formed.
The reaction takes the parent nucleus containing mercaptan of alkane, alkene, arene, oxazole, thiazole, pyrazole, imidazole and the like and derivatives thereof as raw materials, for example, R can be different functional groups of alkane, alkene, alkyne, alicyclic hydrocarbon, arene, oxazole, thiazole, thiophene, thiazine, pyrazole, imidazole, pyridine and the like, and common protective groups comprise TIPS, TBS, Bn, Ac, Bz, Piv, Boc and the like.
The catalyst is FeBr2、CeBr3、FeBr3And FeCl2-KBr、Fe(NO3)3-KBr、Ce(NO3)3-KBr、CeCl3-KBr、Ce2(C2O4)3-KBr、Ce(SO4)2-KBr、Ce(OTf)3KBr, etc., metal (Fe)2+、Fe3+、Ce3+、Ce4+) And bromide.
The solvent used in the reaction is water, ethanol, methanol, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, acetonitrile, tert-butanol, 1, 4-dioxane, ethylene glycol dimethyl ether and other solvents.
In the specific operation, a scheme is provided: dissolving mercaptan containing alkane, olefin, arene, oxazole, thiazole, pyrazole, imidazole, etc. and their derivatives in reaction solvent such as THF, etc., sequentially adding catalyst such as FeBr2、CeBr3Etc. (0.02-0.1eq) and H2O2Aqueous solution (30 wt%, 0.5-3 eq). The mixture was stirred at room temperature for 0.1-1.5h, after which diluted Na was used2S2O3The solution (0.1M) quenches the finished reaction, and is extracted for a plurality of times by organic solvents such as ethyl acetate, etc., filtered and concentrated under reduced pressure, thus obtaining the pure target product.
The invention has the beneficial effects that:
compared with the prior art, the method has the following advantages and effects:
the invention realizes the first time that2O2Being the sole oxidizing agent, FeBr2、CeBr3Equal MBrxThe compound is a reaction for green synthesis of the symmetric disulfide by the metal catalyst, has rapid reaction, does not need further purification, and can be applied to the production of synthesizing the symmetric disulfide in large quantity. Under neutral condition by MBrx-H2O2The generated HOBr is used as an oxidant, the catalytic reaction is green and sustainable, and byproducts are hardly generated, so that the problems of environmental damage, low yield and the like caused by catalytic reaction of other strong oxidants are solved. The present invention uses commercially available and relatively low cost reagents (e.g., FeBr)2、CeBr3And H2O2And the like) and common organic solvents, has simple steps, convenient operation, mild reaction conditions and open mouth at room temperature, does not need to further extract and separate products, has more advantages than all the prior methods, and is expected to be widely applied to the industries of organic synthesis, medicines, pesticides, electronic products and the like.
Drawings
FIGS. 1 and 2 are those of example 11H-NMR and13C-NMR spectrum
FIGS. 3 and 4 show the embodiment 2Is/are as follows1H-NMR and13C-NMR spectrum
FIGS. 5 and 6 are those of embodiment 31H-NMR and13C-NMR spectrum
FIGS. 7 and 8 are those of embodiment 41H-NMR and13C-NMR spectrum
FIGS. 9 and 10 are those of example 51H-NMR and13C-NMR spectrum
FIGS. 11 and 12 are those of example 61H-NMR and13C-NMR spectrum
FIGS. 13 and 14 are those of example 71H-NMR and13C-NMR spectrum
FIGS. 15 and 16 are those of example 81H-NMR and13C-NMR spectrum
FIGS. 17 and 18 are those of example 91H-NMR and13C-NMR spectrum
FIGS. 19 and 20 are those of example 101H-NMR and13C-NMR spectrum
Detailed Description
In the following examples1H-NMR and13the C-NMR spectra were measured at room temperature and recorded on a 400MHz spectrometer,1the H-NMR was 400MHz, and the molecular weight,13C-NMR was 100MHz and the spectrometer was from Bruker.
The invention will now be described in more detail by way of specific embodiments, but the practice of the invention is not limited to these examples:
example 1
1a (1mmol, 124.2mg) was dissolved in THF (1.5ml) and CeBr was added to the mixture successively3(0.02mmol，7.6mg)，H2O2The reaction mixture was stirred at room temperature for 0.1-1.5h in an aqueous solution (30 wt%, 0.6mmol, 61.3. mu.l). After the reaction is finished, Na is used2S2O3The reaction was quenched with a solution (0.1M, 1.5ml) and extracted with ethyl acetate (30 ml). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (3X 10 ml). The organic phases are combined and washed by water in turn,drying with anhydrous sodium sulfate, filtering, and concentrating under reduced pressure to obtain the target product 2a (yield:%). The characterization data for this compound are as follows:1H-NMR(400MHz，Chloroform-d)δ7.40-7.37(m，4H)，7.11(d，J＝8.0Hz，4H)，2.32(s，6H).13C-NMR(101MHz，Chloroform-d)δ137.6，134.0，129.9，128.6，21.2
example 2
1b (1mmol, 125.2mg) was dissolved in THF (1.5ml) and CeBr was added to the mixture successively3(0.02mmol，7.6mg)，H2O2The reaction mixture was stirred at room temperature for 0.1-1.5h in an aqueous solution (30 wt%, 0.6mmol, 61.3. mu.l). After the reaction is finished, Na is used2S2O3The reaction was quenched with a solution (0.1M, 1.5ml) and extracted with ethyl acetate (30 ml). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (3X 10 ml). The organic phases are combined and washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the target product 2b (yield: 92%). The characterization data for this compound are as follows:1H-NMR(400MHz，Chloroform-d)δ7.15(ddd，J＝7.6，6.4，1.7Hz，4H)，6.71(dd，J＝8.5，1.3Hz，2H)，6.59(td，J＝7.5，1.3Hz，2H).13C-NMR(100MHz，Chloroform-d)δ148.8，137.0，131.7，118.9，118.4，115.4
example 3
1c (1mmol, 246.2mg) was dissolved in THF (2.5ml) and to the mixture was added CeBr successively3(0.02mmol，7.6mg)，H2O2The reaction mixture was stirred at room temperature for 0.1-1.5h in an aqueous solution (30 wt%, 0.6mmol, 61.3. mu.l). After the reaction is finished, Na is used2S2O3The reaction was quenched with a solution (0.1M, 1.5ml) and extracted with ethyl acetate (30 ml). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (3X 10 ml). Is combined withThe organic phase was washed with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the objective product 2c (yield: 92%). The characterization data for this compound are as follows: H-NMR (400MHz, CDCl)3)δ：7.55(s，4H)，7.78-7.77(s，2H).13C-NMR(101MHz，Chloroform-d)δ139.1，132.6(s，J＝34.3Hz)，122.0(s，J＝4.0Hz)，118.8(s，J＝274.7Hz)
Example 4
1d (1mmol, 170.2mg) was dissolved in THF (2ml) and CeBr was added to the mixture successively3(0.02mmol，7.6mg)，H2O2The reaction mixture was stirred at room temperature for 0.1-1.5h in an aqueous solution (30 wt%, 0.6mmol, 61.3. mu.l). After the reaction is finished, Na is used2S2O3The reaction was quenched with a solution (0.1M, 1.5ml) and extracted with ethyl acetate (30 ml). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (3X 10 ml). The organic phases are combined and washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the target product 2d (yield: 92%). The characterization data for this compound are as follows:1H-NMR(400MHz，Chloroform-d)δ7.05(d，J＝2.1Hz，1H)，7.03(d，J＝2.1Hz，1H)，7.01(d，J＝2.1Hz，2H)，6.79(s，1H)，6.77(s，1H)，3.86(s，6H)，3.82(s，6H).13C-NMR(100MHz，CDCl3)δ：149.6，149.3，128.8，124.0，114.2，111.4，56.1，56.0
example 5
1e (1mmol, 160.2mg) was dissolved in THF (2ml) and CeBr was added to the mixture successively3(0.02mmol，7.6mg)，H2O2The reaction mixture was stirred at room temperature for 0.1-1.5h in an aqueous solution (30 wt%, 0.6mmol, 61.3. mu.l). After the reaction is finished, Na is used2S2O3The reaction was quenched with solution (0.1M, 1.5ml) and quenched with ethyl acetateExtraction with ethyl acetate (30 ml). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (3X 10 ml). The organic phases are combined and washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the target product 2e (yield: 92%). The characterization data for this compound are as follows:1H-NMR(400MHz，Chloroform-d)δ8.00(d，J＝1.9Hz，2H)，7.80(dd，J＝9.0，3.0Hz，4H)，7.75-7.73(m，2H)，7.64(dd，J＝8.7，2.0Hz，2H)，7.49-7.44(m，4H).13C-NMR(101MHz，Chloroform-d)δ134.4，133.6，132.6，129.1，127.9，127.6，126.9，126.7，126.4，125.8
example 6
1f (1mmol, 168.3mg) was dissolved in THF (2ml) and CeBr was added to the mixture successively3(0.02mmol，7.6mg)，H2O2The reaction mixture was stirred at room temperature for 0.1-1.5h in an aqueous solution (30 wt%, 0.6mmol, 61.3. mu.l). After the reaction is finished, Na is used2S2O3The reaction was quenched with a solution (0.1M, 1.5ml) and extracted with ethyl acetate (30 ml). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (3X 10 ml). The organic phases are combined and washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the target product 2f (yield: 92%). The characterization data for this compound are as follows:1H-NMR(400MHz，Chloroform-d)δ2.07-2.05(m，10H)，1.82(s，10H)，1.66(s，10H).13C-NMR(100MHz，CDCl3)δ：47.5，43.2，36.3，30.2
example 7
1g (1mmol, 118.2mg) was dissolved in THF (1.5ml), and CeBr was added to the mixture successively3(0.02mmol，7.6mg)，H2O2The reaction mixture was stirred at room temperature for 0.1-1.5h in an aqueous solution (30 wt%, 0.6mmol, 61.3. mu.l). After the reaction is finished, Na is used2S2O3The reaction was quenched with a solution (0.1M, 1.5ml) and extracted with ethyl acetate (30 ml). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (3X 10 ml). After the organic phases were combined, the mixture was washed with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain 2g of the objective product (yield: 92%). The characterization data for this compound are as follows:1H-NMR(400MHz，Chloroform-d)δ2.68(t，J＝7.4Hz，4H)，1.67(t，J＝7.3Hz，4H)，1.45-1.21(m，12H)，0.89(t，J＝6.7Hz，6H).13C-NMR(101MHz，Chloroform-d)δ39.3，31.6，29.3，28.3，22.7，14.2.
example 8
1h (1mmol, 78.1mg) was dissolved in THF (1ml) and CeBr was added to the mixture successively3(0.02mmol，7.6mg)，H2O2The reaction mixture was stirred at room temperature for 0.1-1.5h in an aqueous solution (30 wt%, 0.6mmol, 61.3. mu.l). After the reaction is finished, Na is used2S2O3The reaction was quenched with a solution (0.1M, 1.5ml) and extracted with ethyl acetate (30 ml). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (3X 10 ml). And combining organic phases, washing with water, drying with anhydrous sodium sulfate, filtering, and concentrating under reduced pressure to obtain the target product for 2h (yield: 92%). The characterization data for this compound are as follows:1H-NMR(400MHz，Chloroform-d)δ3.93-3.90(m，1H)，2.90-2.87(m，1H).13C-NMR(101MHz，Chloroform-d)δ60.51，41.37.
example 9
1i (1mmol, 171.7mg) was dissolved in THF (2ml), and CeBr was added to the mixture successively3(0.02mmol，7.6mg)，H2O2The reaction mixture was stirred at room temperature for 0.1-1.5h in an aqueous solution (30 wt%, 0.6mmol, 61.3. mu.l). After the reaction is finished, Na is used2S2O3The reaction was quenched with a solution (0.1M, 1.5ml) and extracted with ethyl acetate (30 ml). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (3X 10 ml). The organic phases are combined and washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the target product 2i (yield: 92%). The characterization data for this compound are as follows:1H-NMR(400MHz，Chloroform-d)δ5.39(d，J＝8.2Hz，2H)，4.58(d，J＝6.7Hz，2H)，3.75(s，6H)，3.14(d，J＝5.4Hz，4H)，1.43(s，18H).13C-NMR(100MHz，CDCl3)δ：171.3，155.2，80.4，52.9，52.7，41.4，28.4.
example 10
1j (1mmol, 167.3mg) was dissolved in THF (2ml), and CeBr was added to the mixture successively3(0.02mmol，7.6mg)，H2O2The reaction mixture was stirred at room temperature for 0.1-1.5h in an aqueous solution (30 wt%, 0.6mmol, 61.3. mu.l). After the reaction is finished, Na is used2S2O3The reaction was quenched with a solution (0.1M, 1.5ml) and extracted with ethyl acetate (30 ml). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (3X 10 ml). The organic phases are combined and washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the target product 2j (yield: 92%). The characterization data for this compound are as follows:1H-NMR(400MHz，DMSO-d6)δ8.08(d，J＝8.0Hz，2H)，7.96(d，J＝8.2Hz，2H)，7.54(t，J＝7.7Hz，2H)，7.45(t，J＝7.6Hz，2H).13C-NMR(101MHz，DMSO-d6)δ167.3，153.9，135.6，126.9，125.6，122.4，122.2.
Claims (7)
1. a method for synthesizing a green disulfide bond. It is characterized in that under the conditions of room temperature, openness and neutrality, the reaction raw material is mercaptan containing alkane, alkene, arene, oxazole, thiazole, pyrazole, imidazole and the like and derivatives thereof, and the catalyst is MBrx(M is Fe)2+、Fe3+、Ce3+Etc., x is 2-3), the oxidizing agent is H2O2Symmetric disulfides are rapidly formed.
2. The method of claim 1, wherein: the catalyst used is FeBr2、CeBr3、FeBr3、CeBr4And FeSO4-KBr、FeCl2-KBr、FeCl3-KBr、Fe(NO3)3-KBr、Ce(NO3)3-KBr、CeCl3-KBr、Ce2(C2O4)3-KBr、Ce(SO4)2-KBr, etc. Metal (Fe)2+、Fe3+) And bromide, wherein the molar ratio of the bromide to mercaptan with alkane, alkene, arene, oxazole, thiazole, pyrazole, imidazole, etc. and derivatives thereof as parent nucleus is 0.02-0.1: 1.
3. The method of claim 1, wherein: the reaction is carried out in a solvent, wherein the solvent is water, ethanol, methanol, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, acetonitrile, tert-butanol, 1, 4-dioxane, ethylene glycol dimethyl ether and other solvents.
4. The method of claim 1, wherein: h2O2Being the sole oxidizing agent, H2O2The mol ratio of the thiol to the thiol with the parent nucleus of alkane, alkene, arene, oxazole, thiazole, pyrazole, imidazole and the like and derivatives thereof is 0.5-3: 1.
5. The method of claim 1, wherein: the reaction temperature is room temperature; the reaction is carried out under an open condition; the reaction is carried out under the condition that the pH value is neutral; the reaction time is 0.1-1.5 h.
6. The method of claim 1, wherein: during the specific operation, the mercaptan with the mother nucleus of alkane, olefin, arene, oxazole, thiazole, pyrazole, imidazole, etc. and their derivatives is dissolved in the reaction solvent, and metal is added successivelyBromide catalyst and H2O2The aqueous solution (30 wt%) is stirred at room temperature for 0.1-1.5h to generate symmetrical disulfide.
7. The method of claim 1, wherein: after the reaction is completed, diluted Na is used2S2O3Quenching the solution (0.1M), extracting with ethyl acetate or other organic solvent for several times, filtering, and concentrating under reduced pressure to obtain the target product.
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| CN101475517A (en) * | 2009-01-15 | 2009-07-08 | 河南大学 | Preparation of symmetrical disulfide bond-bearing compound |
| CN112778257A (en) * | 2021-01-21 | 2021-05-11 | 香港科技大学 | Green method for oxidizing furfuryl alcohol into dihydropyrone derivative |
| CN112939749A (en) * | 2021-02-22 | 2021-06-11 | 香港科技大学 | Green bromination method |
| CN113024438A (en) * | 2021-02-22 | 2021-06-25 | 香港科技大学 | Green method for preparing oxindole derivative |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101475517A (en) * | 2009-01-15 | 2009-07-08 | 河南大学 | Preparation of symmetrical disulfide bond-bearing compound |
| CN112778257A (en) * | 2021-01-21 | 2021-05-11 | 香港科技大学 | Green method for oxidizing furfuryl alcohol into dihydropyrone derivative |
| CN112939749A (en) * | 2021-02-22 | 2021-06-11 | 香港科技大学 | Green bromination method |
| CN113024438A (en) * | 2021-02-22 | 2021-06-25 | 香港科技大学 | Green method for preparing oxindole derivative |
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