CN102127038A

CN102127038A - Method for synthetizing mono-thioether compound

Info

Publication number: CN102127038A
Application number: CN 201110022751
Authority: CN
Inventors: 刘晓智; 龙慎杰; 毛颖; 刁海倩; 孔庆文; 王月娇; 郭福顺
Original assignee: Liaoning University
Current assignee: Liaoning University
Priority date: 2011-01-20
Filing date: 2011-01-20
Publication date: 2011-07-20
Anticipated expiration: 2031-01-20
Also published as: CN102127038B

Abstract

The invention relates to a method for synthetizing mono-thioether compound. The technical scheme adopted by the invention is as follows: in the presence of carbon monoxide and water, disulfide compound and halogenated hydrocarbon compound are used as raw materials, selenium is used as catalyst, organic base or inorganic base is used as cocatalyst or any cocatalyst is not added, the raw materials react in organic solvent at 20-100 DEG C under atmospheric pressure for 1-24 hours, the product is cooled to the room temperature, then carbon monoxide is displaced by air, stirring is performed for 0.2-2 hours, filtration is performed, distilled water and cyclohexane are used to extract the filtrate, and the solvent in the extract liquor is distilled out through reduced pressure distillation to obtain the target product. The method is convenient and safe to operate, adopts one-pot reaction, has common raw materials, no pollution, high selectivity and high yield; and the catalyst can be separated and recycled after the reaction.

Description

A kind of method of synthetic single thio-ether type compounds

Technical field

The invention belongs to the field of chemical synthesis, relating to disulfide compound and halohydrocarbon particularly is raw material, utilizes carbon monoxide and water, by the method for the synthetic single thio-ether type compounds of selenium catalyzed reaction.

Background technology

Single thio-ether type compounds is important fine chemical material and organic synthesis intermediate.Thioether is the raw material of organic synthesis, is again good solvent and extraction agent, is used for extracting rare metal and precious metal (as Au, Pd, Ag etc.).Thioether is widely used in organic synthesis, medicine, agricultural chemicals, dyestuff and the foodstuff additive field, thioether still is the important spices of a class simultaneously, furfuryl sulfide has coffee or sesame oil fragrance, and furfuryl group amyl group thioether has fruital, and furfuryl group benzyl thioether has burnt coffee perfume (or spice).Thioether can be synthetic by several different methods: the synthetic method of more early stage classics is for being that solvent reaction gets by potassium sulphide (or sodium) with the dehydrated alcohol with halohydrocarbon or sulfuric ester, but this method long reaction time, preparation condition is harshness; The method that grew up afterwards also has: phase-transfer catalysis synthesis method, the microwave radiation synthesis method of dipping reagent method, use phase-transfer catalyst.Above synthetic method general operation method is comparatively complicated, and reaction conditions requires comparatively strict.

Summary of the invention

The object of the present invention is to provide the method for the synthetic single thio-ether type compounds of a kind of selenium catalysis that reaction conditions gentleness, cost are low under normal pressure.

For achieving the above object, the technical solution used in the present invention is as follows: in the presence of carbon monoxide and water, disulfide compound and halogenated hydrocarbon compound are raw material, selenium is catalyzer, organic bases or mineral alkali are promotor, or do not add any promotor, under normal pressure, 20 ~ 100 ℃ were reacted 1 ~ 24 hour, and were cooled to room temperature in organic solvent, carbon monoxide is switched to air, stirred 0.2 ~ 2 hour, and filtered, filtrate is respectively with distilled water and hexanaphthene extraction, underpressure distillation steams the solvent in the extraction liquid, obtains target product.Reaction formula is as follows:

R, R ' are aromatic group, heterocyclic group or alkyl; X is Cl, Br, I or OTs(tosic acid base);

Wherein: the mol ratio of disulfide compound and halogenated hydrocarbon compound is 1:2 ~ 1:3; The mole dosage of selenium is 1 ~ 20% of a disulfide compound; The mol ratio of disulfide compound and water is 1:1 ~ 1:100; The mole dosage of organic bases or mineral alkali is 0 ~ 200% of a disulfide compound.

Above-mentioned mineral alkali is one or more a mixture of sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate; Above-mentioned organic bases is sodium acetate, potassium acetate, triethylamine, aniline, pyridine, 4-picoline, 1, the mixture of one or more in 5-diaza-bicyclo [5.4.0]-5-undecylene (DBU) and the N-crassitude.

Carbon monoxide also can use the industrial carbon monoxide tail gas that contains air, nitrogen, carbonic acid gas, water vapour, and wherein the content sum of nitrogen, carbonic acid gas, water vapour is smaller or equal to 95% of cumulative volume, and air content is less than 30%.

Described organic solvent is one or more polarity or nonpolar inert solvent; described polar solvent is tetrahydrofuran (THF), methylene dichloride, N; dinethylformamide (DMF), N; N-N,N-DIMETHYLACETAMIDE (DMAC), dimethyl sulfoxide (DMSO) (DMSO), glycol ether, ethylene glycol diethyl ether, N-formyl piperidine (FP), dioxane, crown ether or acetone, non-polar solvent is toluene, dimethylbenzene, normal hexane or benzene.

The present invention has following advantage:

1. the present invention is a synthesis under normal pressure, one pot reaction, and facility investment is few, and is easy to operate and safe.

2. cost is low.Raw material is simple, be easy to get, and only uses the lower nonmetal selenium of price to be catalyzer.

3. environmentally friendly.It is green reaction that the present invention does not have the three wastes, has reached the requirement of cleaner production, helps large-scale industrial production.

4. the reaction process difficulty is low.The present invention is easy and simple to handle, and product separates with the postorder of catalyzer easily.

5. good economy performance.The present invention reacts and selects row high, and adopting nonmetal selenium is catalyzer, and catalytic selectivity can reach more than 99%.

6. has phase transfer function.In catalyzed reaction of the present invention, solid selenium powder catalyzer is insoluble in the reaction system before the reaction beginning, the selenium of solid phase changes the active specy that is dissolved in reaction system into and carries out the homogeneous catalyzed reaction in reaction process, after reaction ends, catalyzer is separated out with the solid phase selenium powder again, very easily separates with product.Therefore, the present invention combines the advantage of homogeneous catalysis and heterogeneous catalyst.

Embodiment

Following example is to detailed description of the present invention, rather than limitation of the present invention.

Embodiment 1

Be equipped with one and add furfuryl disulfide ether (2mmol), bromo pentane (4.2mmol), selenium powder (0.2mmol), H in the 100ml there-necked flask of stirrer, prolong ₂NaOAC(1.25mmol) and solvent DMF (20ml) O(50 mmol),, continue to feed carbon monoxide, under the normal pressure, be heated to the 90oC stirring reaction 5 hours, after being cooled to room temperature, carbon monoxide is switched to air, stir after 0.5-1 hour, filter out selenium powder, filtrate is respectively with distilled water and hexanaphthene extraction, underpressure distillation steams the solvent in the extraction liquid, obtains target product, yield 80.9%.

Embodiment 2

Method is with embodiment 1, and is as follows for the yield of different substrates, and product verifies that through nuclear-magnetism structural formula is as follows

Embodiment 3

Method only changes the consumption of catalyzer selenium with embodiment 1, and yield is as follows:

The consumption of selenium (mmol)	0.02	0.10	0.16	0.20	0.24	0.30	0.40
								Hundred parts of the relative furfuryl disulfide ether of selenium are compared %	1	5	8	10	12	15	20
Yield %	74	85	90	80.9	89	87	90

Embodiment 4

Method only changes the consumption of water with embodiment 1, and yield is as follows:

The consumption of water (mmol)	2.0	10	20	40	50	100	200
								The mol ratio of furfuryl disulfide ether and water	1:1	1:5	1:10	1:20	1:25	1:50	1:100
Yield %	67.1	74.5	78.4	79.9	80.9	80.4	80.3

Embodiment 5

Method only changes the consumption of sodium acetate with embodiment 1, and yield is as follows:

The consumption of sodium acetate (mmol)	0	0.8	1.6	2.0	2.8	3.6	4.0
								The sodium acetate consumption is that hundred parts of disulfide compound compare %	0	40	80	100	140	180	200
Yield %	53	79	80	80	80	80	80

Embodiment 6

The consumption of promotor and organic solvent is as follows, and experimental technique and other condition are with embodiment 1, and yield is as follows:

Embodiment 7

Method is with embodiment 1, and is as follows for the yield in differing temps and reaction times:

Temperature of reaction ( ^oC）	20	50	70	90	100
						Reaction times (hr)	24	5	5	5	3
Yield %	45	66	81	80.9	80

Embodiment 8

One be equipped with add in the 100ml there-necked flask of stirrer, prolong to nitro phenylbenzene disulfide (2mmol),

Bromo pentane (4.2mmol), selenium powder (0.2mmol), H ₂NaOAC(1.25mmol) and solvent DMF (20ml) O(50mmol),, continue to feed carbon monoxide, then be heated to the 90oC stirring reaction 5 hours, be cooled to room temperature after, carbon monoxide is switched to-air, stir after 0.5-1 hour, filter out selenium powder, with distilled water and hexanaphthene extraction, underpressure distillation steams the solvent in the extraction liquid to filtrate respectively, obtain target product, yield 82.9%.

Product is as follows through nuclear-magnetism checking structural formula:

Claims

1. the method for a synthetic single thio-ether type compounds, it is characterized in that: in the presence of carbon monoxide and water, with disulfide compound and halogenated hydrocarbon compound is raw material, selenium is catalyzer, organic bases or mineral alkali are promotor, or do not add any promotor, in organic solvent, under normal pressure, 20 ~ 100 ℃ were reacted 1 ~ 24 hour, be cooled to room temperature, carbon monoxide is switched to air, stirred 0.2 ~ 2 hour, filter, with distilled water and hexanaphthene extraction, underpressure distillation steams the solvent in the extraction liquid to filtrate, obtains target product respectively; Wherein:

The mol ratio of disulfide compound and halogenated hydrocarbon compound is 1:2 ~ 1:3;

The mole dosage of selenium is 1 ~ 20% of a disulfide compound;

The mol ratio of disulfide compound and water is 1:1 ~ 1:100;

The mole dosage of organic bases or mineral alkali is 0 ~ 200% of a disulfide compound.

2. according to the method for the described synthetic single thio-ether type compounds of claim 1, it is characterized in that: described mineral alkali is one or more a mixture of sodium hydroxide, potassium hydroxide, yellow soda ash and sodium bicarbonate; Described organic bases is sodium acetate, potassium acetate, triethylamine, aniline, pyridine, 4-picoline, 1, the mixture of one or more in 5-diaza-bicyclo [5.4.0]-5-undecylene and the N-crassitude.

3. according to the method for the described synthetic single thio-ether type compounds of claim 1, it is characterized in that: described organic solvent is polar solvent and/or non-polar solvent.

4. according to the method for the described synthetic single thio-ether type compounds of claim 1, it is characterized in that: described polar solvent is tetrahydrofuran (THF), methylene dichloride, N, one or more mixing of dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), glycol ether, ethylene glycol diethyl ether, N-formyl piperidine, dioxane, crown ether or acetone; Described non-polar solvent is one or more mixing of toluene, dimethylbenzene, normal hexane or benzene.