CN104761477B - A kind of method preparing adjacent diphenyl disulfide phenol - Google Patents
A kind of method preparing adjacent diphenyl disulfide phenol Download PDFInfo
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- CN104761477B CN104761477B CN201510212276.0A CN201510212276A CN104761477B CN 104761477 B CN104761477 B CN 104761477B CN 201510212276 A CN201510212276 A CN 201510212276A CN 104761477 B CN104761477 B CN 104761477B
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- QIFGGIHWYKYFGH-UHFFFAOYSA-N C1(=CC=CC=C1)O.C1(=CC=CC=C1)SSC1=CC=CC=C1 Chemical group C1(=CC=CC=C1)O.C1(=CC=CC=C1)SSC1=CC=CC=C1 QIFGGIHWYKYFGH-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 11
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims abstract description 20
- QPUSANCBJDDXSA-UHFFFAOYSA-N ethanethiol;sodium Chemical compound [Na].CCS QPUSANCBJDDXSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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 claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZQNAGCUHNSMONH-UHFFFAOYSA-N 1,2-bis(ethylsulfanyl)benzene Chemical compound CCSC1=CC=CC=C1SCC ZQNAGCUHNSMONH-UHFFFAOYSA-N 0.000 claims abstract description 13
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000005171 halobenzenes Chemical class 0.000 claims abstract description 6
- 238000010511 deprotection reaction Methods 0.000 claims abstract description 3
- 238000006073 displacement reaction Methods 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 239000011737 fluorine Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 3
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 18
- 235000015424 sodium Nutrition 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 14
- 230000006837 decompression Effects 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract description 12
- 239000003814 drug Substances 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 239000002798 polar solvent Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- -1 sulfenyl benzene Chemical compound 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 208000035126 Facies Diseases 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 239000003480 eluent Substances 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- 229960001866 silicon dioxide Drugs 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012263 liquid product Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 241001249696 Senna alexandrina Species 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000000481 breast Anatomy 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000004662 dithiols Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 230000003257 anti-anginal effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 208000029078 coronary artery disease Diseases 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of method preparing adjacent diphenyl disulfide phenol.With metallic sodium, ethyl mercaptan and adjacent two halobenzenes as initiation material; by controlling the molar ratio of reactant; utilize the nucleophilic displacement of fluorine ability that ethyl mercaptan sodium is stronger; at polar solvent N; replacing two halogen atoms of adjacent two halobenzenes in N dimethylformamide completely, high productivity obtains 1,2 diethyl sulfenyl benzene; then the reduction at metallic sodium Yu naphthalene carries out the deprotection of sulphur atom, generation target product neighbour's diphenyl disulfide phenol the most quantitative after hydrochloric acid is acidified.The preparation method of the present invention is simple, easy to operate, low price, and productivity is high, is with a wide range of applications in fine chemistry industry and pharmaceuticals industry.
Description
Technical field
The present invention relates to technical field of medical chemistry, be specifically related to a kind of method preparing adjacent diphenyl disulfide phenol.
Background technology
Adjacent diphenyl disulfide phenol is a kind of broad-spectrum chemical intermediate, all has important application in terms of medicine with Chemical Manufacture.Such as,
Adjacent diphenyl disulfide phenol can be used for the synthesis of the medicines such as resisting coronary heart disease, antianginal, anti-digestive system ill symptoms it can also be used to multiple
The study on the synthesis of functional dye and engineering plastics, rubber chemicals, developer, sequestration phenolic resin etc..Meanwhile, as a class tool
There is the organic ligand of good coordination property, also function as important role building of functional complexes in research and development.Although adjacent benzene
The simple in construction of dithiol, but its synthetic method is not easy to.The method of the adjacent diphenyl disulfide phenol of multiple production of report at present, or former
Material cost is high, operation complexity, or by-product is many, low yield, and these shortcomings hinder the further research to this production technology,
Its industrial applicability is received limit significantly, cause the price of adjacent diphenyl disulfide phenol on the market to remain high always.Cause
This, the method generating adjacent diphenyl disulfide phenol explored with develop low cost, simple to operate, conversion ratio is high, either in basic research
Aspect, or in terms of actual production application, it is respectively provided with important researching value.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of method preparing adjacent diphenyl disulfide phenol.
The present invention provides a kind of method preparing adjacent diphenyl disulfide phenol, and the method is using metallic sodium, ethyl mercaptan and adjacent two halobenzenes as initial
Raw material, through nucleophilic displacement of fluorine, reduction deprotection and hydrochloric acid acidifying, obtains adjacent diphenyl disulfide phenol.
Further, under absolute ether and inert gas shielding, the mol ratio controlling described metallic sodium and described ethyl mercaptan is 1:
1～1:3, it is stirred at room temperature 3～4 hours forming white suspended thing to the reaction of all described sodium, decompression extracts solvent and excess
Described ethyl mercaptan, obtains white powder ethyl mercaptan sodium.
Further, the mol ratio controlling described adjacent two halobenzenes and described ethyl mercaptan sodium is 1:4～1:6, with N, N-dimethyl methyl
Amide (DMF) is as solvent, and reaction temperature is 130 DEG C, and the response time is 12 hours, prepares 1,2-diethyl sulfenyl benzene.
Further, described 1,2-diethyl sulfenyl benzene using more than four times excess metallic sodiums and naphthalene as reduction deprotecting regent, four
Hydrogen furan is solvent, and under room temperature, stirring reaction 12 hours, are subsequently adding hydrochloric acid and are acidified, and prepares described adjacent diphenyl disulfide phenol.
The beneficial effects of the present invention is, the raw material used in the present invention and reagent low price, be easy to get, reaction condition is gentle,
Easy to operate, product yield is high, is with a wide range of applications in fine chemistry industry and pharmaceuticals industry.
Accompanying drawing explanation
Fig. 1 schematically shows the chemical formula of the adjacent diphenyl disulfide phenol of preparation；
Fig. 2 schematically shows the chemical formula preparing ethyl mercaptan sodium；
Fig. 3 schematically shows and prepares 1 with ethyl mercaptan sodium and the o-dichlorohenzene prepared shown in Fig. 2 for raw material, 2-diethyl sulfenyl benzene
Chemical formula；
Fig. 4 schematically shows and prepares 1 with ethyl mercaptan sodium and the o-dibromobenzene prepared shown in Fig. 2 for raw material, 2-diethyl sulfenyl benzene
Chemical formula；
Fig. 5 schematically show with prepare shown in Fig. 3 Yu Fig. 41,2-diethyl sulfenyl benzene is the change of the raw material adjacent diphenyl disulfide phenol of preparation
Formula；
Fig. 6 is the present invention 1, the hydrogen spectrogram of 2-diethyl sulfenyl benzene；
Fig. 7 is the present invention 1, the carbon spectrogram of 2-diethyl sulfenyl benzene；
Fig. 8 is the hydrogen spectrogram of neighbour's diphenyl disulfide phenol of the present invention；
Fig. 9 is the carbon spectrogram of neighbour's diphenyl disulfide phenol of the present invention.
Detailed description of the invention
The present invention is described in detail below in conjunction with specific embodiment.It should be noted that, the technical characteristic described in following embodiment
Or the combination of technical characteristic is not construed as isolating, and they can be mutually combined thus reach superior technique effect.
As it is shown in figure 1, the step of the adjacent diphenyl disulfide phenol of preparation is as follows:
(1) preparation of ethyl mercaptan sodium is described in detail below in conjunction with Fig. 2
Example 1:
Under the conditions of argon shield, in 100mL tool mouth reaction bulb, add the ether of 40mL fresh dried and 1.15g
Metallic sodium (50mmol).The lower ethyl mercaptan (55mmol) being added dropwise over 4.07mL toward reactant liquor of stirring, stirs reaction 4 under room temperature
Hour, until metallic sodium is wholly absent and generates a large amount of white casse thing.Then decompression extracts ether and the second sulfur of small part excess
Alcohol, gained white powder is ethyl mercaptan sodium (yield: 3.88g, productivity: 92.4%), and is directly used in next step reaction.
Example 2:
Under the conditions of argon shield, in 100mL tool mouth reaction bulb, add the ether of 40mL fresh dried and 1.15g
Metallic sodium (50mmol).The lower ethyl mercaptan (100mmol) being added dropwise over 7.4mL toward reactant liquor of stirring, stirs reaction 4 under room temperature
Hour, until metallic sodium is wholly absent and generates a large amount of white casse thing.Then decompression extracts ether and the second sulfur of small part excess
Alcohol, gained white powder is ethyl mercaptan sodium (yield: 4.07g, productivity: 96.9%), and is directly used in next step reaction.
Example 3:
Under the conditions of argon shield, in 100mL tool mouth reaction bulb, add the ether of 40mL fresh dried and 1.15g
Metallic sodium (50mmol).The lower ethyl mercaptan (150mmol) being added dropwise over 11.1mL toward reactant liquor of stirring, stirring reaction under room temperature
3 hours, until metallic sodium is wholly absent and generates a large amount of white casse thing.Then decompression extracts ether and the second of small part excess
Mercaptan, gained white powder is ethyl mercaptan sodium (yield: 4.18g, productivity: 99.5%), and is directly used in next step reaction.
(2) describing, below with reference to Fig. 3 Yu Fig. 4, the ethyl mercaptan sodium prepared with step (1) in detail is that raw material prepares 1,2-diethyl
The step of sulfenyl benzene.
1. 1 is prepared with o-dichlorohenzene for raw material, 2-diethyl sulfenyl benzene (seeing Fig. 3)
Example 1:
The ethyl mercaptan sodium weighing 1.68g (20mmol) above-mentioned preparation is placed in 100mL tool mouth reaction bulb, adds under argon shield
Enter the chromatographically pure DMF of 40mL.Then in reactant liquor, add 0.57mL (5mmol) o-dichlorohenzene, be heated to 130 DEG C and stir
Mix reaction 12 hours.Stopped reaction is also cooled to room temperature, adds 60mL distilled water, n-hexane extraction (4 × 50 toward reactant liquor
ML), collecting and merge organic facies, concentrating dry solvent, head product separates (eluent: petroleum ether) through silicagel column, obtains colourless liquid
Product 1,2-diethyl sulfenyl benzene, yield: 878mg, productivity: 88.7%.
Example 2:
The ethyl mercaptan sodium weighing 2.10g (25mmol) above-mentioned preparation is placed in 100mL tool mouth reaction bulb, adds under argon shield
Enter the chromatographically pure DMF of 40mL.Then in reactant liquor, add 0.57mL (5mmol) o-dichlorohenzene, be heated to 130 DEG C and stir
Mix reaction 12 hours.Stopped reaction is also cooled to room temperature, adds 60mL distilled water, n-hexane extraction (4 × 50 toward reactant liquor
ML), collecting and merge organic facies, concentrating dry solvent, head product separates (eluent: petroleum ether) through silicagel column, obtains colourless liquid
Product 1,2-diethyl sulfenyl benzene, yield: 892mg, productivity: 90.1%.
Example 3:
The ethyl mercaptan sodium weighing 2.52g (30mmol) above-mentioned preparation is placed in 100mL tool mouth reaction bulb, adds under argon shield
Enter the chromatographically pure DMF of 40mL.Then in reactant liquor, add 0.57mL (5mmol) o-dichlorohenzene, be heated to 130 DEG C and stir
Mix reaction 12 hours.Stopped reaction is also cooled to room temperature, adds 60mL distilled water, n-hexane extraction (4 × 50 toward reactant liquor
ML), collecting and merge organic facies, concentrating dry solvent, head product separates (eluent: petroleum ether) through silicagel column, obtains colourless liquid
Product 1,2-diethyl sulfenyl benzene, yield: 906mg, productivity: 91.5%.
2. 1 is prepared with o-dibromobenzene for raw material, 2-diethyl sulfenyl benzene (seeing Fig. 4)
Example 1:
The ethyl mercaptan sodium weighing 1.68g (20mmol) above-mentioned preparation is placed in 100mL tool mouth reaction bulb, adds under argon shield
Enter the chromatographically pure DMF of 40mL.Then in reactant liquor, add 0.60mL (5mmol) o-dibromobenzene, be heated to 130 DEG C and stir
Mix reaction 12 hours.Stopped reaction is also cooled to room temperature, adds 60mL distilled water, n-hexane extraction (4 × 50 toward reactant liquor
ML), collecting and merge organic facies, concentrating dry solvent, head product separates (eluent: petroleum ether) through silicagel column, obtains colourless liquid
Product 1,2-diethyl sulfenyl benzene, yield: 902mg, productivity: 91.1%.
Example 2:
The ethyl mercaptan sodium weighing 2.10g (25mmol) above-mentioned preparation is placed in 100mL tool mouth reaction bulb, adds under argon shield
Enter the chromatographically pure DMF of 40mL.Then in reactant liquor, add 0.60mL (5mmol) o-dibromobenzene, be heated to 130 DEG C and stir
Mix reaction 12 hours.Stopped reaction is also cooled to room temperature, adds 60mL distilled water, n-hexane extraction (4 × 50 toward reactant liquor
ML), collecting and merge organic facies, concentrating dry solvent, head product separates (eluent: petroleum ether) through silicagel column, obtains colourless liquid
Product 1,2-diethyl sulfenyl benzene, yield: 928mg, productivity: 93.7%.
Example 3:
The ethyl mercaptan sodium weighing 2.52g (30mmol) above-mentioned preparation is placed in 100mL tool mouth reaction bulb, adds under argon shield
Enter the chromatographically pure DMF of 40mL.Then in reactant liquor, add 0.60mL (5mmol) o-dibromobenzene, be heated to 130 DEG C and stir
Mix reaction 12 hours.Stopped reaction is also cooled to room temperature, adds 60mL distilled water, n-hexane extraction (4 × 50 toward reactant liquor
ML), collecting and merge organic facies, concentrating dry solvent, head product separates (eluent: petroleum ether) through silicagel column, obtains colourless liquid
Product 1,2-diethyl sulfenyl benzene, yield: 953mg, productivity: 96.3%.
The nuclear magnetic spectrum of 1,2-diethyl sulfenyl benzene is as shown in Fig. 6 Yu Fig. 7, and its result is:
1H NMR (400MHz, CDCl3): δ 7.29 (d, J=8.0Hz, Ph, 2H), 7.15 (d, J=8.0Hz, Ph, 2H),
2.95 (m, 2 × CH2,4H), 1.35 (t, J=8.0Hz, 2 × CH3,6H)；13C NMR(100MHz,CDCl3):δ
136.93,128.65,126.02,27.19,13.92.
(3) describing, below with reference to Fig. 5,1 prepared with above-mentioned steps (2) in detail, 2-diethyl sulfenyl benzene is the adjacent benzene of raw material preparation
The step of dithiol.
Example 1:
Weigh 1.15g naphthalene (9mmol) join 0.594g1,2-diethyl sulfenyl benzene (3mmol) oxolane (fresh dried,
60mL) in solution.Then 0.276g metallic sodium (12mmol) is added toward reactant liquor, stirring reaction 12 hours, reaction under room temperature
Liquid is gradually become bottle green by colourless.Being slowly added dropwise 10mL methanol cancellation reaction, continue stirring 15 minutes, reactant liquor becomes breast
White.It is subsequently adding 10mL hydrochloric acid (37%, aq), acidification hydrolization 30 minutes, adds 40mL distilled water, ether extraction (4
× 50mL), collect and merge organic facies, concentrating dry solvent, head product through silicagel column sharp separation (eluent: petroleum ether),
Obtain faint yellow oil product neighbour's diphenyl disulfide phenol, yield: 395mg, productivity: 92.7%.
Example 2:
Weigh 1.92g naphthalene (15mmol) join 0.594g 1,2-diethyl sulfenyl benzene (3mmol) oxolane (fresh dried,
60mL) in solution.Then 0.345g metallic sodium (15mmol) is added toward reactant liquor, stirring reaction 12 hours, reaction under room temperature
Liquid is gradually become bottle green by colourless.Being slowly added dropwise 10mL methanol cancellation reaction, continue stirring 15 minutes, reactant liquor becomes breast
White.It is subsequently adding 10mL hydrochloric acid (37%, aq), acidification hydrolization 30 minutes, adds 40mL distilled water, ether extraction (4
× 50mL), collect and merge organic facies, concentrating dry solvent, head product through silicagel column sharp separation (eluent: petroleum ether),
Obtain faint yellow oil product neighbour's diphenyl disulfide phenol, yield: 409mg, productivity: 96.0%.
The nuclear magnetic spectrum of adjacent diphenyl disulfide phenol is as shown in Fig. 8 Yu Fig. 9, and its result is:1H NMR(400MHz,CDCl3):δ
7.37(m,Ph,2H),7.07(m,Ph,2H),3.72(s,SH,2H)；13C NMR(100MHz,CDCl3):δ131.16,
131.12,126.77；IR(KBr,cm-1):2548.2(νSH).
Raw material used in the present invention and reagent low price, be easy to get, and reaction condition is gentle, easy to operate, and product yield is high.
Although have been presented for some embodiments of the present invention herein, it will be appreciated by those of skill in the art that without departing from this
In the case of bright spirit, the embodiments herein can be changed.Above-described embodiment is exemplary, should be with this paper's
Embodiment is as the restriction of interest field of the present invention.
Claims (1)
1. the method preparing adjacent diphenyl disulfide phenol, it is characterised in that using metallic sodium, ethyl mercaptan and adjacent two halobenzenes as initial former
Material, through nucleophilic displacement of fluorine, reduction deprotection and hydrochloric acid acidifying, obtains adjacent diphenyl disulfide phenol, specifically includes following steps:
Under absolute ether and inert gas shielding, the mol ratio controlling metallic sodium and ethyl mercaptan is 1:1～1:3, is stirred at room temperature
3～4 hours form white suspended thing to the reaction of all sodium, decompression extracts solvent and the ethyl mercaptan of excess, obtains white powder second
Sodium mercaptides；
The mol ratio controlling adjacent two halobenzenes and ethyl mercaptan sodium is 1:4～1:6, using DMF as solvent, reaction
Temperature is 130 DEG C, and the response time is 12 hours, prepares 1,2-diethyl sulfenyl benzene；
1,2-diethyl sulfenyl benzene using more than four times excess metallic sodiums and naphthalene as reduction deprotecting regent, oxolane is solvent,
Under room temperature, stirring reaction 12 hours, are subsequently adding hydrochloric acid and are acidified, and prepare described adjacent diphenyl disulfide phenol.
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