CN107814756B - A kind of synthetic method of methyl phenyl sulfoxide - Google Patents
A kind of synthetic method of methyl phenyl sulfoxide Download PDFInfo
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- CN107814756B CN107814756B CN201610819042.7A CN201610819042A CN107814756B CN 107814756 B CN107814756 B CN 107814756B CN 201610819042 A CN201610819042 A CN 201610819042A CN 107814756 B CN107814756 B CN 107814756B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
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Abstract
The invention discloses a kind of synthetic methods of methyl phenyl sulfoxide.Using aminomethyl phenyl sulfide derivative as raw material, under nitrogen atmosphere, using acetonitrile as solvent, SelectFluor is usedTMFor oxidising agent, after reacting 10-20min at room temperature, triethylamine is added and continues to be catalyzed 10-20min, after reaction, reaction solution is through isolating and purifying to obtain methyl sulfoxide compound.Synthetic method craft mild condition of the invention, easy to operate, the reaction time is extremely short, conversion ratio yield stable, and substrate spectrum is broad, using SelectFluorTMFor oxidising agent, it is not necessarily to metallic catalyst, is a kind of method of efficient synthesizing methyl sulfoxide compound.
Description
Technical field
The invention belongs to technical field of organic synthesis, are related to a kind of synthetic method of methyl sulfoxide compound, more specifically,
It is related to a kind of method by phenyl methyl sulfide derivative for Material synthesis methyl sulfoxide compound.
Background technique
Sulfoxide is not only in organic synthetic experiment common solvent and extractant, is also widely used for various pharmaceutical synthesis
In, it is important the intermediate of medicine, pesticide and expensive material.Select which kind of catalyst that can efficiently be oxidized to thioether
Sulfoxide is always the hot spot in synthesis field, and currently used catalyst mainly has a hydrogen peroxide, metallic compound and halogenated
Close object.
(Zhou, Wenjie et al.Preparation and application of heterogeneous of document 1.
glutamic acid catalyst for aqueous oxidation of sulfide.Faming Zhuanli
Shenqing, 105498836,20Apr 2016) one kind is reported using ethyl alcohol as solvent, hydrogen peroxide as oxidant prepares methyl
The method of sulfoxide compound, although the method most only needs 4h fastly, and yield is up to 90% or more, needs early-stage preparations DSA@MNPs
(a kind of acid-functionalized magnetic nano-particle), the cumbersome time-consuming of process, be not suitable for reaction step it is more, mass production or it is high in short-term
The scientific research demand of effect；
(Carmen M R, Jesus M O, the Jose M P.Simple and efficient oxidation of of document 2
sulfides to sulfone using catalytic ruthenium tetroxide[J].Tetrahedron,1992,
48 (17): 3571.) using this strong oxidizer, a series of sulfoxide compounds prepared in acetonitrile and carbon tetrachloride solvent, however
Ruthenium tetroxide property is very unstable, and being heated to 100 DEG C or more will explode；
(Wang, Fang et al.Selective oxidation of sulfides the to sulfoxides of document 3
using hydrogen peroxide over Au/CTN-silica catalyst.Catalysis Communications,
72,142146；2015) a kind of novel nano metal catalysis method is reported, gold/poly glucosamine-nanometer titanium dioxide is used
Silicon core-shell material is as catalyst, although this method is smaller to environmental hazard, the preparation condition of nanogold and the core-shell material
Harshness, increases additional cost and efficiency is very low；
(Hajjami, Maryam and Kolivand, Somaye.New the metal complexes of document 4
supported on Fe3O4magnetic nanoparticles as recoverable catalysts for
selective oxidation of sulfides to sulfoxides[J].Applied Organometallic
Chemistry,30(5),282-288；2016) using the compound Metals composite obtained of chromium or copper and magnetic Fe_3O_4 nanoparticle
Material is used as catalyst, although the material has circular regeneration, transition metal toxicity is big, all into the slight residual after human body
Very major injury can be generated；
(Yoshiaki K, George R, the PettitM T.Synthesis ofalkyl-substituted of document 5
Thiirene dioxides [J] .J Org Chem, 1974,39:2320) report it is a kind of with NaOBr sodium hypobromite by thioether
The method for being oxidized to sulfoxide, but there are many process side reaction, and yield is lower, is not suitable for being used to prepare sulfoxide compound.
Above method covers the synthetic method and current research of methyl sulfoxide compound.Methyl Asia is prepared with hydrogen peroxide
Sulphones less pollution, meets the theory of " Green Chemistry ", but needs to prepare in advance cocatalyst, such as DSA@MNPs,
Increase additional cost and inefficient, using the strong metallic compound of oxidisability and halogen compounds although directly, efficiently,
However its existing genotoxic potential and risk limit their extensive use.Therefore, seek a kind of efficient, convenient, safe
The method of synthesizing methyl sulfoxide compound have important practical significance.
Summary of the invention
A kind of the purpose of the present invention is to provide simple processes reasonable, low in cost, highly effective and safe methyl sulfoxide chemical combination
The synthetic method of object, using SelectFluorTMOxidizing process, in acetonitrile solvent and under the assistance of triethylamine, with
SelectFluorTMFor oxidising agent, benzyl thioethers derivative is Material synthesis methyl sulfoxide compound.
Realize that the technical solution of the object of the invention is as follows:
A kind of synthetic method of methyl sulfoxide compound, using phenyl methyl sulfide derivative shown in formula (I) as raw material,
Under nitrogen atmosphere, using acetonitrile as solvent, with SelectFluorTM(F-TEDA-BFI) it is oxidising agent, reacts at room temperature
After 10min, triethylamine (TEA) is added and reacts 10min again, after reaction, reaction solution is isolated and purified to obtain such as formula (II) institute
The methyl sulfoxide compound shown.
Wherein, in formula (I) and formula (II), R is selected from hydrogen, methyl or halogen.
A kind of synthetic method of methyl sulfoxide compound of the invention, reaction equation are as follows:
Preferably, SelectFluorTM(F-TEDA-BFI) mole is aminomethyl phenyl sulfide derivative mole
1.2~1.3 times
Preferably, the mole of triethylamine is 1.2~1.3 times of phenyl methyl sulfide derivative mole
Preferably, the mole of acetonitrile is 83~85 times of phenyl methyl sulfide derivative mole
Preferably, triethylamine should phenyl methyl sulfide derivative and SelectFluor under nitrogen atmosphere and in acetonitrileTM
It is added after being stirred to react 10min at room temperature, and continues to be stirred to react 10min at room temperature.
After reaction, method of the reaction solution through isolating and purifying are as follows: water and methylene chloride extraction are added in reaction solution
It takes, uses Na2CO3Solution dries, filters, and obtains methyl sulfoxide compound.
Compared with prior art, remarkable result of the invention is as follows:
(1) process conditions advantages of simple, reaction speed very rapidly (only 20min) and conversion ratio it is good, be especially suitable for nothing
The multistep reaction experiment that can directly carry out next-step operation need to be purified；
(2) using it is relatively inexpensive, be easy to get and safety SelectFluorTMFor oxidising agent；
(3) it uses triethylamine as catalyst, is not necessarily to transition metal, greatly reduces residual in drug by transition metal
It stays and human body bring is endangered；
(4) using thioether as skeleton, raw material is common, can expand a variety of substrates, provides one kind for design medicine synthetic route
Method.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic spectrogram that methyl phenyl sulfoxide is made in embodiment 1.
Fig. 2 is the carbon nuclear magnetic spectrogram that methyl phenyl sulfoxide is made in embodiment 1.
Fig. 3 is the gas chromatography mass spectrometry spectrogram that methyl phenyl sulfoxide is made in embodiment 1.
Specific embodiment
Below with reference to embodiment, invention is further described in detail.
Embodiment 1
(10ml) acetonitrile is added in 25ml anhydrous and oxygen-free bottle, 885mg (2.50mmol) F-TEDA-BFI solution is being full of
Under nitrogen atmosphere, the pre- phenyl methyl sulfide (2.0mmol) for being first dissolved in 1.0ml acetonitrile is added dropwise, then stirs at room temperature
10min is mixed, 347uL (2.5mmol) triethylamine is added followed by, continues to stir 10min.After reaction, reaction solution is poured into
In water, 15ml methylene chloride is added and is extracted, Na is then used2CO3Solution dries, filters to obtain methyl phenyl sulfoxide, yield
54%
NMR 1H(CDCl3,300MHz):δ2.72(s,3H),7.49-7.55(3H),7.63-7.66(2H)
NMR 13C(CDCl3,100MHz):δ145.4(Cq),130.8(CH),129.2(CH),123.3(CH),43.7
(CH3)
GCMS(EI)Calcd.for C7H8OS 140.20,found 140.04。
Embodiment 2
(12ml) acetonitrile is added in 25ml anhydrous and oxygen-free bottle, 885mg (2.50mmol) F-TEDA-BFI solution is being full of
Under nitrogen atmosphere, the pre- methyl for being first dissolved in 1.1ml acetonitrile is added dropwise to ditolyl suifide (2.0mmol), then at room temperature
10min is stirred, 347uL (2.5mmol) triethylamine is added followed by, continues to stir 10min.After reaction, reaction solution is fallen
Enter in water, 15ml methylene chloride is added and is extracted, Na is then used2CO3Solution dries, filters to obtain methyl to toluene sulfoxide, produces
Rate 61%.
NMR 1H (CDCl3,400MHz): δ 2.41 (s, 3H), 2.70 (s, 3H), 7.32 (d, J=8.1Hz, 2H), 7.53
(d, J=8.1Hz, 2H)
NMR 13C(CDCl3,100MHz):δ142.3(Cq),141.5(Cq),130.0(CH),123.5(CH),43.8
(CH3),21.3(CH3)
GCMS(EI)Calcd.for C8H10OS 154.23,found 154.05。
Embodiment 3
(10ml) acetonitrile is added in 25ml anhydrous and oxygen-free bottle, 886mg (2.50mmol) F-TEDA-BFI solution is being full of
Under nitrogen atmosphere, the pre- 4- Chlorophenylmethyl thioether for being first dissolved in 1.0ml acetonitrile is added dropwise (i.e. to chlorine thioanisole)
(2.0mmol), is then stirred at room temperature 10min, is added followed by 350uL (2.5mmol) triethylamine, continues to stir 10min.
After reaction, reaction solution is poured into water, 15ml methylene chloride is added and is extracted, Na is then used2CO3Solution dries, filters
Obtain rubigan methyl sulfoxide, yield 68%.
1HNMR(500MHz,CDCl3)δ(ppm):7.63-7.60(m,2H),7.55-7.52(m,2H),2.74(s,3H)；
13C NMR(126MHz,CDCl3)δ(ppm):144.2,137.3,131.1,129.7,128.9,125.0,44.0.
GCMS(EI)Calcd.for C7H7ClOS 174.64, found 173.99.
Claims (6)
1. a kind of synthetic method of methyl sulfoxide compound, which is characterized in that with aminomethyl phenyl sulfide derivative (I)
Under nitrogen atmosphere for raw material, using acetonitrile as solvent, SelectFluorTMFor oxidising agent, 10- is reacted at room temperature
After 20min, triethylamine is added and reacts 10-20min again, after reaction, reaction solution is through isolating and purifying to obtain methyl sulfoxide chemical combination
Object (II)；
Wherein, in (I) and (II), R is selected from hydrogen, methyl or halogen.
2. a kind of synthetic method of methyl sulfoxide compound according to claim 1, which is characterized in that described
SelectFluorTMMole be 1.2~1.3 times of aminomethyl phenyl sulfide derivative mole.
3. a kind of synthetic method of methyl sulfoxide compound according to claim 1, which is characterized in that the triethylamine
Obtain 1.2~1.3 times that mole is phenyl methyl sulfide derivative mole.
4. a kind of synthetic method of methyl sulfoxide compound according to claim 1, which is characterized in that the acetonitrile
Mole is 83~85 times of phenyl methyl sulfide derivative mole.
5. a kind of synthetic method of methyl sulfoxide compound according to claim 1, which is characterized in that three are added in reaction
Ethamine should be under nitrogen atmosphere and in acetonitrile solvent, and phenyl methyl sulfide derivative and SelectFluorTMAfter reacting 10min
It adds, and continues to stir 10min.
6. a kind of synthetic method of methyl sulfoxide compound according to claim 1, which is characterized in that after reaction,
Method of the reaction solution through isolating and purifying are as follows: water, methylene chloride extraction are added in reaction solution, uses Na2CO3Solution is dry,
Filtering, obtains methyl sulfoxide compound.
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| CN104418837A (en) * | 2013-08-19 | 2015-03-18 | 长沙市如虹医药科技有限公司 | Method for oxidizing thioether into sulfoxide |
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| CN104418837A (en) * | 2013-08-19 | 2015-03-18 | 长沙市如虹医药科技有限公司 | Method for oxidizing thioether into sulfoxide |
Non-Patent Citations (2)
| Title |
|---|
| Masayuki Kirihara，等.Oxidation of disulfides with Selectfluor™: concise syntheses of thiosulfonates and sulfonyl fluorides.《Tetrahedron Letters》.2011,第52卷3086-3089. * |
| Mild and efficient oxidation of phosphorus(III) compounds with Selectfluor;Qian Chen，等;《Tetrahedron Letters》;20160618;第57卷;3379–3381 * |
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Inventor after: Yi Wenbin Inventor after: Xiong Jiayu Inventor after: Liang Shuaishuai Inventor after: Chu Ling Inventor before: Xiong Jiayu Inventor before: Liang Shuaishuai Inventor before: Yi Wenbin Inventor before: Chu Ling |