CN106008295B - A kind of preparation method of the alkylthio group toluene of 2 halo 6 - Google Patents
A kind of preparation method of the alkylthio group toluene of 2 halo 6 Download PDFInfo
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- CN106008295B CN106008295B CN201610390644.5A CN201610390644A CN106008295B CN 106008295 B CN106008295 B CN 106008295B CN 201610390644 A CN201610390644 A CN 201610390644A CN 106008295 B CN106008295 B CN 106008295B
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- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
Abstract
The present invention relates to field of compound preparation, discloses a kind of preparation method of the alkylthio group toluene of 2 halo 6, and this method includes：Mixed the aqueous solution of alkyl hydrosulfide sodium compound with the dimethyl sulfoxide (DMSO) as solvent, obtained mixture is dehydrated, the material obtained after dehydration and substrate compounds are subjected to haptoreaction.This method is simple to operate, cost is low, high income, suitable for large-scale industrial production.
Description
Technical field
The present invention relates to field of compound preparation, in particular it relates to a kind of preparation side of 2- halos -6- alkylthio group toluene
Method.
Background technology
The present invention relates to field of compound preparation, 2- halo -6- alkylthio group toluene prepares pesticide herbicide ring sulphur ketone
Intermediate.
WO2000021924 and Tetrohedron Letters (1980, volume 21,3099-3100 pages) disclose one kind
The preparation method of benzoylcyclohexanedione, this method carry out reacting the chloro- 6- of obtained 2- with anhydrous solid sodium methyl mercaptide and hempa
(methylthiomethyl).The high income of this method, and react fast, still, because hempa price is high, anhydrous solid sodium methyl mercaptide is more difficult
Obtain, and price is high, causes the method cost high.
WO2008066033 discloses a kind of preparation method of the benzene derivative of alkylthio group substitution, and this method uses 1,3- bis-
Methyl -2- imidazolidinones carry out reflux water-dividing with toluene, the sodium methyl mercaptide aqueous solution are added dropwise and is reacted as solvent.The method
Advantage is can to use the relatively low sodium methyl mercaptide aqueous solution of price, still, because solvent for use price is high, causes cost high, simultaneously
Reaction temperature is higher, causes the product facile hydrolysis of generation.Although hydrolysate is converted into product, first by the later stage by esterification
Mercaptan sodium utilization is low.
In addition, CN200510030163 discloses a kind of preparation method of 3- chloro-2-methyl thiobenzoxides, with 2- methyl-
3- chloroanilines first carry out diazotising, then carry out reaction with the sodium methyl mercaptide aqueous solution and be prepared target product, the advantages of this method
It is that sodium methyl mercaptide used is the aqueous solution, and reaction does not have to solvent, mild condition, still, shortcoming are that yield is relatively low, and instead
Answer wastewater flow rate big.
The content of the invention
The purpose of the present invention is to overcome prior art to prepare 2- halo -6- alkylthio group toluene complex operation, cost height, yield
A kind of the defects of low, there is provided preparation method of 2- halos -6- alkylthio group toluene.
To achieve these goals, the present invention provides a kind of preparation of the 2- halo -6- alkylthio group toluene as shown in formula (1)
Method, wherein, this method includes：The aqueous solution of compound shown in formula (3) is mixed with the dimethyl sulfoxide (DMSO) as solvent, will
Obtained mixture is dehydrated, by the compound haptoreaction shown in the material obtained after dehydration and formula (2)；
Wherein, two R1Respectively F, Cl or Br；R2For C1-C6Straight or branched alkyl.
Method provided by the invention uses dimethyl sulfoxide (DMSO) as solvent, and sodium methyl mercaptide is the aqueous solution, can it is low into
The target product of (yield is more than 85%, and more than 93% is can reach under the conditions of more excellent) in high yield, therefore, the party are obtained under this
Method has the advantages that step is simple, synthesis condition is gentle, cost is low and high income, suitable for large-scale industrial production.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The invention provides the preparation method of 2- halo -6- alkylthio group toluene of the one kind as shown in formula (1), its feature exists
In this method includes：The aqueous solution of compound shown in formula (3) is mixed with the dimethyl sulfoxide (DMSO) as solvent, by what is obtained
Mixture is dehydrated, by the compound haptoreaction shown in the material obtained after dehydration and formula (2)；
In formula (2), two R1Respectively F, Cl or Br；Preferably, two R1Respectively Cl or Br；It is further preferred that
Two R1It is Cl.
In formula (3), R2For C1-C6Straight or branched alkyl, such as can be methyl, ethyl, n-propyl, isopropyl,
Normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, sec-amyl, 1- ethyl propyls, 2- methyl butyls, tertiary pentyl, 1,2- bis-
Methyl-propyl, isopentyl, neopentyl, n-hexyl, Sec-Hexyl, tertiary hexyl, isohesyl or new hexyl；Preferably, R2For C1-C3's
Straight chained alkyl, such as can be methyl, ethyl, n-propyl；It is further preferred that R2For methyl.
In the present invention, the solvent is dimethyl sulfoxide (DMSO), stability, price and the boiling point of dimethyl sulfoxide (DMSO) all appropriate
Invention.Other solvents or because activity it is relatively low, such as acetonitrile；Or because that can be decomposed with the compound mixed dehydration shown in formula (3), such as DMF；
Or because price is higher, such as hempa, these are unsuitable for as solvent.It is not special to the dosage of dimethyl sulfoxide (DMSO) in the present invention
Restriction.Under preferable case, the weight ratio of the dosage and the dosage of the compound shown in formula (2) of the dimethyl sulfoxide (DMSO) is 1-
20：1, more preferably 2-15：1, more preferably 2-6：1.
If due to being directly dehydrated to the aqueous solution of the compound shown in formula (3), the compound shown in formula (3) can be sent out
Solution estranged, and being dissolved in the dimethyl sulfoxide (DMSO), the stability of compound that can be shown in freeze mode (3), therefore, this hair
In bright, the aqueous solution of the compound shown in formula (3) first mixes with the dimethyl sulfoxide (DMSO), is then dehydrated.
In the present invention, the compound shown in formula (3) adds in form of an aqueous solutions, it is preferable that the change shown in formula (3)
The concentration of the aqueous solution of compound is 10-40 weight %, more preferably more preferably 15-25 weight %, 15-20 weight %.
In the present invention, the process of the dehydration can be implemented by way of this area is conventional, such as can be that centrifugation is de-
Water or vacuum distillation are dehydrated, and under preferable case, the process of the dehydration is that vacuum distillation is dehydrated.In the present invention, to the dehydration
Condition there is no particular limitation, still, in order to ensure dehydrating effect, under preferable case, the condition of the dehydration includes：Vacuum
Spend for 0.1-5000Pa, preferably 500-2000Pa；Temperature is 20-130 DEG C, preferably 60-110 DEG C.It is heretofore described true
Reciprocal of duty cycle refers to absolute pressure, and the process of the dehydration carries out to a small amount of dimethyl sulfoxide (DMSO) being distilled out of.
It is not special to the dosage of the dosage and the compound shown in formula (3) of the compound shown in formula (2) in the present invention
Limit.But in order to make full use of the compound shown in the compound and formula (3) shown in formula (2), cost is reduced, yield is improved,
Under preferable case, the mol ratio of the dosage and the dosage of the compound shown in formula (2) of the compound shown in formula (3) is 0.5-3：1,
More preferably 0.8-1.5：1.In order to improve the utilization rate of the compound shown in formula (3), kept during the haptoreaction
The dosage of compound shown in formula (2) is excessive.
In the present invention, to the catalytic condition, there is no particular limitation, described catalytic under preferable case
Condition includes：Temperature is 60-150 DEG C, preferably 80-120 DEG C；Reaction time is 0.5-8 hours, preferably 1-3 hours.
In the present invention, methods described is additionally included in after the haptoreaction terminates, and formula (4) institute is added into reaction system
The compound shown；
R2Cl formulas (4)；
Wherein, R2With the R in the formula (3)2It is identical.
There is no particular limitation for dosage of the present invention to the compound shown in formula (4), under preferable case, shown in formula (4)
The mol ratio of the dosage of compound and the dosage of the compound shown in formula (2) is 0.02-0.4：1, preferably 0.05-0.2：1.
In a kind of preferred embodiment of the method for the invention, methods described also includes：In the haptoreaction
After end and before the compound shown in the formula of addition (4), reaction system is cooled to 20-30 DEG C.
The present invention will be described in detail by way of examples below.
In following examples, pass through the amount of target product in liquid chromatography for measuring product；
In following examples, yield is calculated by following formula：
In following examples, dimethyl sulfoxide (DMSO) is purchased from Beijing chemical reagents corporation；Sodium methyl mercaptide, ethyl mercaptan sodium are purchased from Beijing
Even summation Science and Technology Ltd.；2,6- dichlorotoleune is purchased from Beijing even summation Science and Technology Ltd..
Embodiment 1
The present embodiment is used for the preparation method for illustrating the chloro- 6- (methylthiomethyl)s of 2-.
It is anti-by four mouthfuls of 600g dimethyl sulfoxide (DMSO)s and 633g (1.81mol) the 20% sodium methyl mercaptide aqueous solution addition 2000mL
Answer in bottle, water pump vacuum distillation is carried out under the conditions of being 2000Pa in 90 DEG C, vacuum, until there is a small amount of dimethyl sulfoxide (DMSO) to be steamed
Go out, then 300g (1.81mol) 2,6-DCT is added in 2000mL four mouthfuls of reaction bulbs, react 3h at 100 DEG C.Instead
After should terminating, 30 DEG C are cooled to, then 0.18mol chloromethanes is passed through reaction system, stirring reaction is filtered after 0.5 hour,
Filter obtained solid and elute secondary, merging filtrate with dimethyl sulfoxide (DMSO), carry out negative pressure rectifying, obtain the chloro- 6- methyl mercaptos first of 2-
Benzene 220.6g (1.27mol), yield 92.5%.
Embodiment 2
The present embodiment is used for the preparation method for illustrating the chloro- 6- (methylthiomethyl)s of 2-.
1800g dimethyl sulfoxide (DMSO)s and 1269g (2.72mol) the 15% sodium methyl mercaptide aqueous solution are added four mouthfuls of 2000mL
In reaction bulb, water pump vacuum distillation is carried out under the conditions of being 500Pa in 60 DEG C, vacuum, until there is a small amount of dimethyl sulfoxide (DMSO) to be steamed
Go out, then 300g (1.81mol) 2,6-DCT is added in 2000mL four mouthfuls of reaction bulbs, react 1h at 80 DEG C.Instead
After should terminating, 20 DEG C are cooled to, then 0.091mol chloromethanes is passed through reaction system, stirring reaction is taken out after 0.5 hour
Filter, the solid for filtering to obtain elute secondary, merging filtrate with dimethyl sulfoxide (DMSO), carry out negative pressure rectifying, obtain the chloro- 6- methyl mercaptos of 2-
Toluene 184.9g (1.05mol), yield 93.7%.
Embodiment 3
The present embodiment is used for the preparation method for illustrating the chloro- 6- (methylthiomethyl)s of 2-.
1500g dimethyl sulfoxide (DMSO)s and 564g (1.45mol) the 18% sodium methyl mercaptide aqueous solution are added four mouthfuls of 2000mL
In reaction bulb, water pump vacuum distillation is carried out under the conditions of being 1300Pa in 110 DEG C, vacuum, until there is a small amount of dimethyl sulfoxide (DMSO) quilt
Steam, then 300g (1.81mol) 2,6-DCT is added in 2000mL four mouthfuls of reaction bulbs, react 1h at 120 DEG C.
After reaction terminates, 25 DEG C are cooled to, then 0.362mol chloromethanes is passed through reaction system, stirring reaction is taken out after 0.5 hour
Filter, the solid for filtering to obtain elute secondary, merging filtrate with dimethyl sulfoxide (DMSO), carry out negative pressure rectifying, obtain the chloro- 6- methyl mercaptos of 2-
Toluene 164.3g (0.993mol), yield 93.3%.
Embodiment 4
The present embodiment is used for the preparation method for illustrating the chloro- 6- ethylmercapto groups toluene of 2-.
The chloro- 6- ethylmercapto groups toluene of 2- is prepared according to the method for embodiment 1, unlike, the reactant sodium methyl mercaptide aqueous solution
It is changed to ethyl mercaptan sodium water solution.The yield of the chloro- 6- ethylmercapto groups toluene of 2- is 87.2%.
Embodiment 5
The present embodiment is used for the preparation method for illustrating the chloro- 6- (methylthiomethyl)s of 2-.
The chloro- 6- (methylthiomethyl)s of 2- are prepared according to the method for embodiment 1, unlike, dimethyl sulfoxide (DMSO) and 2,6- dichloro
The weight ratio of toluene is 1：1.The yield of the chloro- 6- (methylthiomethyl)s of 2- is 85.5%.
Embodiment 6
The present embodiment is used for the preparation method for illustrating the chloro- 6- (methylthiomethyl)s of 2-.
The chloro- 6- (methylthiomethyl)s of 2- are prepared according to the method for embodiment 1, unlike, 2,6-DCT and methyl mercaptan
The mol ratio of sodium is 0.5：1.The yield of the chloro- 6- (methylthiomethyl)s of 2- is 85%.
Comparative example 1
Hydrochloric acid and 250g (1.77mol) 3- chloro-2-methyl anilines that 720g (4.07mol) concentration is 20% are added
In tetra- mouthfuls of reaction bulbs of 2000mL, stirring reaction 0.5h, then at 5 DEG C, 40% sodium nitrite in aqueous solution 321g is added dropwise
(1.86mol), 0.5h is stirred after dripping off, diazonium salt solution is made, puts standby at 5 DEG C.Will be in 928g (2.65mol) concentration
Added for the 20% sodium methyl mercaptide aqueous solution in another 3000mL four mouthfuls of reaction bulbs, be cooled to 10 DEG C, above-mentioned system is slowly added dropwise
Standby diazonium salt solution, 2h are added dropwise.Room temperature is slowly increased to after dripping off, stirring reaction 2 hours, stratification, separates lower floor
Yellow oil, water layer add the extraction of 200mL toluene once, merge organic phase, be washed with water once, then negative pressure rectifying, obtain
258g colorless oil products, content 98%, the yield of the chloro- 6- (methylthiomethyl)s of 2- is 82.9%.
2- halo -6- alkylthio group first is prepared using the method for the invention it can be seen from above example and comparative example
Benzene it is higher, yield can reach more than 85%, and more than 93% is can reach under the conditions of more excellent, also, in the method, using two
Methyl sulfoxide is solvent, and sodium methyl mercaptide used is the aqueous solution, and synthesis cost is low, suitable for large-scale industrial production.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (19)
1. the preparation method of a kind of 2- halo -6- alkylthio group toluene as shown in formula (1), it is characterised in that this method includes：Will
The aqueous solution of compound shown in formula (3) is mixed with the dimethyl sulfoxide (DMSO) as solvent, and obtained mixture is dehydrated, will
The material obtained after dehydration and the compound haptoreaction shown in formula (2)；
R2NaS formulas (3)；
Wherein, two R1Respectively F, Cl or Br；R2For C1-C6Straight or branched alkyl.
2. the method according to claim 11, wherein, two R1Respectively Cl or Br；R2For C1-C3Straight chained alkyl.
3. the method according to claim 11, wherein, two R1For Cl；R2For methyl.
4. according to the method described in any one in claim 1-3, wherein, dosage and formula (2) institute of the dimethyl sulfoxide (DMSO)
The weight ratio of the dosage for the compound shown is 1-20：1.
5. the method according to claim 11, wherein, dosage and the compound shown in formula (2) of the dimethyl sulfoxide (DMSO)
The weight ratio of dosage is 2-15：1.
6. the method according to claim 11, wherein, dosage and the compound shown in formula (2) of the dimethyl sulfoxide (DMSO)
The weight ratio of dosage is 2-6：1.
7. according to the method described in any one in claim 1-3, wherein, dosage and the formula (2) of the compound shown in formula (3)
The mol ratio of the dosage of shown compound is 0.5-3：1.
8. the method according to claim 11, wherein, dosage and the compound shown in formula (2) of the compound shown in formula (3)
The mol ratio of dosage be 0.8-1.5：1.
9. according to the method for claim 1, wherein, the concentration of the aqueous solution of the compound shown in formula (3) is 10-40 weights
Measure %.
10. according to the method for claim 9, wherein, the concentration of the aqueous solution of the compound shown in formula (3) is 15-25 weights
Measure %.
11. the method according to claim 1 or 9, wherein, the process of the dehydration is dehydrated for vacuum distillation.
12. according to the method for claim 11, wherein, the condition of the dehydration includes：Vacuum is 0.1-5000Pa；Temperature
Spend for 20-130 DEG C.
13. according to the method for claim 12, wherein, the condition of the dehydration includes：Vacuum is 500-2000Pa；Temperature
Spend for 60-110 DEG C.
14. according to the method for claim 1, wherein, the catalytic condition includes：Temperature is 60-150 DEG C；Instead
It it is 0.5-8 hours between seasonable.
15. according to the method for claim 14, wherein, the catalytic condition includes：Temperature is 80-120 DEG C；Instead
It it is 1-3 hours between seasonable.
16. according to the method for claim 1, wherein, methods described is additionally included in after the haptoreaction terminates, to anti-
Answer the compound shown in addition formula (4) in system；
R2Cl formulas (4)；
Wherein, R2With the R in the formula (3)2It is identical.
17. the method according to claim 11, wherein, shown in the dosage and formula (2) of the compound shown in the formula (4)
The mol ratio of the dosage of compound is 0.02-0.4：1.
18. the method according to claim 11, wherein, shown in the dosage and formula (2) of the compound shown in the formula (4)
The mol ratio of the dosage of compound is 0.05-0.2：1.
19. according to the method described in any one in claim 16-18, wherein, methods described also includes：It is anti-in the contact
After should terminating and before the compound shown in addition formula (4), reaction system is cooled to 20-30 DEG C.
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| CN106631941B (en) * | 2016-12-30 | 2018-09-28 | 青岛瀚生生物科技股份有限公司 | A kind of preparation method of -3 chlorphenyl methyl sulfide of 2- methyl |
| CN108947878B (en) * | 2018-07-24 | 2020-07-03 | 浙江中山化工集团股份有限公司 | Preparation method of 2-chloro-6-methylthiotoluene |
| CN109053511A (en) * | 2018-08-10 | 2018-12-21 | 安徽久易农业股份有限公司 | A kind of preparation method of the chloro- 6- (methylthiomethyl) of 2- |
| CN111233721B (en) * | 2018-11-28 | 2022-12-13 | 沈阳科创化学品有限公司 | Synthesis method of 2-alkylthio-6-halogenated alkylbenzene |
| CN115806515A (en) * | 2022-12-16 | 2023-03-17 | 启农生物科技(北京)有限公司 | Synthesis process of intermediate 2-methyl-3-methylthio-chlorobenzene |
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