CN109734639A - A kind of preparation method of edible essence fragrance - Google Patents
A kind of preparation method of edible essence fragrance Download PDFInfo
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- CN109734639A CN109734639A CN201910174190.1A CN201910174190A CN109734639A CN 109734639 A CN109734639 A CN 109734639A CN 201910174190 A CN201910174190 A CN 201910174190A CN 109734639 A CN109734639 A CN 109734639A
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- chloride
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- dimethyl benzene
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- methyl sulfide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
Abstract
The present invention provides a kind of preparation method of edible essence fragrance, the edible essence fragrance is 2,3- dimethyl benzene methyl sulfide, the method comprises the following steps: using 3- nitro ortho-xylene and methyl mercaptan potassium as raw material, under compound lewis acidic catalytic action, reaction obtains 2,3- dimethyl benzene methyl sulfide in organic solvent.The present invention uses under the action of composite catalyst, and the reaction time significantly shortens, and the yield of reaction has obtained promotion by a relatively large margin, and reaction yield can achieve 96% or more, and the purity of product 2,3- dimethyl benzene methyl sulfide can achieve 99% or more.
Description
Technical field
The invention belongs to a kind of synthesis technical fields of edible essence fragrance, more particularly to one kind 2,3- dimethyl benzene first sulphur
The preparation method of ether.
Background technique
ManojitP etc. [W02001090097,2001-11-29] is disclosed with 2,3- dimethylaniline for raw material, in acid
Property under the conditions of with sodium nitrite diazotising, diazo-group convertion, which occurs, with ehtyl potassium xanthate later reacts, then alkaline hydrolysis in ethanol,
Methylation reaction occurs with iodomethane in acetone and generates 2,3- dimethyl benzene methyl sulfide, yield 78%.This method raw material is easy to get, but
Be it is cumbersome, generate that " three wastes " are more, and post-processing difficulty is big, industrialized production difficulty, product yield is low.
Yuan Yunlong etc. is disclosed in CN1793118A patent with the preparation method of 3- chloro-2-methyl thiobenzoxide, with 3-
Chloro-2-methyl aniline is added diazo reagent and is prepared diazonium salt I in an acidic solution as raw material, above-mentioned diazonium salt I with
Sodium methyl mercaptide aqueous solution.
However reactions steps of this method is cumbersome, the reaction reagent used is more, and at high cost, reaction yield is low.
AkazomeMotohiro etc. [Journal of Organic Chemistry, 2010,75 (3): 660-665] report
2,3- dimethyl bromobenzene is prepared grignard reagent by road, then reacts to obtain 2,3- dimethyl benzene methyl sulfide with dimethyl disulfide, is received
Rate 96%.This method high income, but this method raw material is not easy to obtain, uses Grignard Reagent in reaction process, severe reaction conditions,
Reaction process is dangerous, and post-processing difficulty is big, and industrialized production is difficult.
Rheinheimer J etc. [US20030216580,2003-11-20] is disclosed with 2,3- dimethylaniline as original
Material, dimethyl disulfide be solvent and reaction reagent, with nitrite tert-butyl diazotising after under the action of copper powder with dimethyl two
Sulphur is coupled to obtain 2,3- dimethyl benzene methyl sulfide, yield 83%.This method yield is higher, easy to operate, but at " three wastes " generated
Reason difficulty is big, and the prices of raw materials are higher, and also there are many side reactions other than participating in main reaction for solvent, and recycling is difficult, and industrialization is comprehensive
Close high production cost.
Luo Xianfu et al. discloses the preparation method of one kind 2,3- dimethyl benzene methyl sulfide in patent 107162944A,
It is characterized in that, under inert atmosphere protection, using 3- nitro ortho-xylene as raw material, is acted on through nickel salt and co-catalyst, organic
It is reacted in solvent with sodium methyl mercaptide heating, reaction solution is post-processed, 2,3- dimethyl benzene methyl sulfide, chemical equation are obtained
Are as follows:
However, the preparation method reaction time is long, reaction yield is low.
Summary of the invention
Technical problems to be solved by the inivention
An object of the present invention is to solve the above problem in the prior art, especially solves to prepare 2 in the prior art,
In the method for 3- dimethyl benzene methyl sulfide, reaction system is complicated, reaction yield is low, and reaction time length, severe reaction conditions etc. are asked
Topic.
The solution to the problem
In order to solve the above technical problem, the present invention provides technical solution are as follows:
The preparation method of one kind 2,3- dimethyl benzene methyl sulfide, the method comprises the following steps: with 3- nitro neighbour's diformazan
Benzene and methyl mercaptan potassium are raw material, and under compound lewis acidic catalytic action, reaction obtains 2,3- dimethyl in organic solvent
Thioanisole.
Preferably, the compound lewis acid catalyst is copper chloride, calcium chloride, magnesium chloride, frerrous chloride, nickel chloride
With one of aluminium chloride or a variety of and BF3·Et2The compound of O.
Preferably, the copper chloride, calcium chloride, one of magnesium chloride, frerrous chloride, nickel chloride and aluminium chloride or a variety of
With BF3·Et2O molar ratio is 0.1-1:1, preferably 0.2-0.5:1, the compound lewis acid catalyst and 3- nitro neighbour two
The molar ratio of toluene is 0.5-10%:1, preferably 1-5%:1.
Preferably, the molar ratio of the methyl mercaptan potassium and 3- nitro ortho-xylene is 1.1-2:1, preferably 1.2-1.5:1.
Preferably, the organic solvent is the mixture of any one or more in benzene, toluene, DMF or acetone.
Preferably, the temperature of the reaction is 25-120 DEG C, and preferably 25-80 DEG C, the reaction time is 0.5-3 hours, excellent
It is selected as 1-2 hours.
The effect of invention
1. preparation 2 of the invention, the method for 3- dimethyl benzene methyl sulfide is reacted using under the action of composite catalyst
Time significantly shortens, and the yield of reaction has obtained promotion by a relatively large margin, and reaction yield can achieve 96% or more, product 2,3-
The purity of dimethyl benzene methyl sulfide can achieve 99% or more.And it also needs that co-catalyst is added in compared with the existing technology,
Reaction system of the invention is further simplified, and post-reaction treatment process is simpler.
2. in preparation method of the invention, since methyl mercaptan potassium is molten in benzene, toluene, DMF or acetone and other organic solvent
Solution property is better than sodium methyl mercaptide, therefore, when using reaction raw materials methyl mercaptan potassium, does not need using phase transfer catalyst, reaction is former
Material 3- nitro ortho-xylene can be mixed more fully hereinafter with methyl mercaptan potassium, therefore reaction condition is milder, and reaction rate is big
Big to be promoted, the reaction time only needs 1-2 hours.
Specific embodiment
Firstly, the present invention provides one kind 2,3- dimethyl benzene methyl sulfide preparation method, the method include it is as follows
Step: using 3- nitro ortho-xylene and methyl mercaptan potassium as raw material, under compound lewis acidic catalytic action, in organic solvent
Reaction obtains 2,3- dimethyl benzene methyl sulfide.
In a preferred embodiment, the molar ratio of the methyl mercaptan potassium and 3- nitro ortho-xylene is 1.1-2:
1, preferably 1.2-1.5:1.
In a preferred embodiment, the compound lewis acid catalyst refers to two or more road
The mixture of Lewis acid, in a further preferred embodiment, the compound lewis acid catalyst is copper chloride, chlorination
Calcium, one of magnesium chloride, frerrous chloride, nickel chloride and aluminium chloride or a variety of and BF3·Et2The compound of O, most preferably chlorine
Change copper and BF3·Et2The compound of O, wherein copper chloride, calcium chloride, one in magnesium chloride, frerrous chloride, nickel chloride and aluminium chloride
Kind or a variety of and BF3·Et2O molar ratio is 0.1-1:1, preferably 0.2-0.5:1.The compound lewis acid catalyst and 3-
The molar ratio of nitro ortho-xylene is 0.5-10%:1, preferably 1-5%:1.
In a preferred embodiment, the organic solvent can be any common Solvents Solvent in this field, excellent
The mixture of any one or more being selected as in benzene, toluene, DMF or acetone.
Following specific embodiments are only used for explaining the present invention, can not be used to limit protection model of the invention
It encloses.
Embodiment 1
200ml toluene, 0.3mol 3- nitro ortho-xylene, 0.36mol methyl mercaptan are sequentially added in 1000ml there-necked flask
Potassium, 0.003mol copper chloride and BF3·Et2Mixture (copper chloride and the BF of O3·Et2The molar ratio of O is 2:8), it is heated to 60
DEG C reaction 2 hours, after reaction be not added 40ml, stir 5 minutes, organic phase is separated after stratification.Water phase uses 30ml again
Toluene extraction is primary, merges organic phase, and after anhydrous magnesium sulfate drying, filtering is added, rectifying obtains product 43.79g, yield
96%, purity 99.2%.GC-MS(m/z):152.1(M+),138,105.1,77,45。
Embodiment 2
200ml toluene, 0.3mol 3- nitro ortho-xylene, 0.36mol methyl mercaptan are sequentially added in 1000ml there-necked flask
Potassium, 0.003mol magnesium chloride and BF3·Et2The mixture (molar ratio 2:8) of O is heated to 60 DEG C and reacts 2 hours, and reaction terminates
40ml is not added afterwards, stirs 5 minutes, organic phase is separated after stratification.Water phase uses the extraction of 30ml toluene primary again, merges organic
Phase, after anhydrous magnesium sulfate drying, filtering is added, rectifying obtains product 38.79g, yield 85%, purity 99.2%.
Embodiment 3
200ml toluene, 0.3mol 3- nitro ortho-xylene, 0.36mol methyl mercaptan are sequentially added in 1000ml there-necked flask
Potassium, 0.003mol nickel chloride and BF3·Et2The mixture (molar ratio 2:8) of O is heated to 60 DEG C and reacts 2 hours, and reaction terminates
40ml is not added afterwards, stirs 5 minutes, organic phase is separated after stratification.Water phase uses the extraction of 30ml toluene primary again, merges organic
Phase, after anhydrous magnesium sulfate drying, filtering is added, rectifying obtains product 40.14g, yield 88%, purity 99.0%.
Embodiment 4
200ml toluene, 0.3mol 3- nitro ortho-xylene, 0.36mol methyl mercaptan are sequentially added in 1000ml there-necked flask
Potassium, 0.003mol aluminium chloride and BF3·Et2The mixture (molar ratio 2:8) of O is heated to 60 DEG C and reacts 2 hours, and reaction terminates
40ml is not added afterwards, stirs 5 minutes, organic phase is separated after stratification.Water phase uses the extraction of 30ml toluene primary again, merges organic
Phase, after anhydrous magnesium sulfate drying, filtering is added, rectifying obtains product 42.45g, yield 93%, purity 99.4%.
Embodiment 5
200ml toluene, 0.3mol 3- nitro ortho-xylene, 0.36mol methyl mercaptan are sequentially added in 1000ml there-necked flask
Sodium, 0.003mol copper chloride and BF3·Et2The mixture (molar ratio 2:8) of O is heated to 60 DEG C and reacts 8 hours, and reaction terminates
40ml is not added afterwards, stirs 5 minutes, organic phase is separated after stratification.Water phase uses the extraction of 30ml toluene primary again, merges organic
Phase, after anhydrous magnesium sulfate drying, filtering is added, rectifying obtains product 41.12g, yield 90%, purity 99.1%.
Embodiment 6
200ml toluene, 0.3mol 3- nitro ortho-xylene, 0.36mol methyl mercaptan are sequentially added in 1000ml there-necked flask
Potassium, 0.003mol copper chloride are heated to 60 DEG C and react 16 hours, 40ml is not added after reaction, stirs 5 minutes, standing point
Organic phase is separated after layer.Water phase uses the extraction of 30ml toluene primary again, merges organic phase, after anhydrous magnesium sulfate drying, filtering is added,
Rectifying obtains product 25.56g, yield 56%, purity 99.1%.
Embodiment 7
200ml toluene, 0.3mol 3- nitro ortho-xylene, 0.36mol methyl mercaptan are sequentially added in 1000ml there-necked flask
Potassium, 0.003mol BF3·Et2O is heated to 60 DEG C and reacts 20 hours, 40ml is not added after reaction, stirs 5 minutes, stands
Organic phase is separated after layering.Water phase uses the extraction of 30ml toluene primary again, merges organic phase, and anhydrous magnesium sulfate drying, filtering is added
Afterwards, rectifying obtains product 11.89g, yield 27%, purity 99.1%.
It can be seen that copper chloride and BF from embodiment 1-4 in summary3·Et2The composite catalyst of the mixture of O compared with
The catalytic effect of other catalyst is best, reaction yield highest, and the reaction time is also shorter.
By the comparison of embodiment 1 and 5 it can be found that dissolubility of the methyl mercaptan potassium than sodium methyl mercaptide in toluene solvant
More, faster, reaction yield is also higher for the rate of reaction.
By embodiment 1 and 6-7 comparison it can be found that using composite catalyst than being received using the reaction of single catalyst
Rate and reaction time are obviously improved.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to restrict the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent substitution, improvement and etc. done be should all be included in the protection scope of the present invention.
Claims (6)
1. one kind 2, the preparation method of 3- dimethyl benzene methyl sulfide, which is characterized in that the method comprises the following steps: with 3- nitre
Base ortho-xylene and methyl mercaptan potassium are raw material, and under compound lewis acidic catalytic action, reaction obtains 2 in organic solvent,
3- dimethyl benzene methyl sulfide.
2. the preparation method of one kind 2,3- dimethyl benzene methyl sulfide as described in claim 1, which is characterized in that described is compound
Lewis acid catalyst be copper chloride, calcium chloride, one of magnesium chloride, frerrous chloride, nickel chloride and aluminium chloride or it is a variety of with
BF3·Et2The compound of O.
3. the preparation method of one kind 2,3- dimethyl benzene methyl sulfide as claimed in claim 2, which is characterized in that the wherein chlorine
Change copper, calcium chloride, one of magnesium chloride, frerrous chloride, nickel chloride and aluminium chloride or a variety of and BF3·Et2O molar ratio is
The molar ratio of 0.1-1:1, preferably 0.2-0.5:1, the compound lewis acid catalyst and 3- nitro ortho-xylene is 0.5-
10%:1, preferably 1-5%:1.
4. the preparation method of one kind 2,3- dimethyl benzene methyl sulfide as described in claim 1, which is characterized in that the methyl mercaptan
The molar ratio of potassium and 3- nitro ortho-xylene is 1.1-2:1, preferably 1.2-1.5:1.
5. the preparation method of one kind 2,3- dimethyl benzene methyl sulfide as described in claim 1, which is characterized in that described organic molten
Agent is the mixture of any one or more in benzene, toluene, DMF or acetone.
6. the preparation method of one kind 2,3- dimethyl benzene methyl sulfide as described in claim 1, which is characterized in that the reaction
Temperature is 25-120 DEG C, and preferably 25-80 DEG C, the reaction time is 0.5-3 hours, preferably 1-2 hours.
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|---|---|---|---|
| CN202010809003.5A CN111848466A (en) | 2019-03-08 | 2019-03-08 | Preparation method of edible essence and spice |
| CN201910174190.1A CN109734639B (en) | 2019-03-08 | 2019-03-08 | Preparation method of edible essence and spice |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910174190.1A CN109734639B (en) | 2019-03-08 | 2019-03-08 | Preparation method of edible essence and spice |
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| CN202010809003.5A Division CN111848466A (en) | 2019-03-08 | 2019-03-08 | Preparation method of edible essence and spice |
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| CN109734639B CN109734639B (en) | 2020-10-09 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1044965A1 (en) * | 1998-09-09 | 2000-10-18 | Nippon Finechemical Co., Ltd. | Process for the preparation of aromatic sulfur compounds |
| CN100516030C (en) * | 1998-05-11 | 2009-07-22 | 巴斯福股份公司 | Intermidiate for preparing 1,2-oxygen nitrogen heterocyclic-2-alkene acylbenzene and its preparation |
| CN107162944A (en) * | 2017-04-27 | 2017-09-15 | 湖南化工研究院有限公司 | The preparation method of 2,3 dimethyl benzene methyl sulfides |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2915833T3 (en) * | 2014-01-31 | 2022-06-27 | Cognition Therapeutics Inc | Isoindoline compositions and methods for treating neurodegenerative disease and macular degeneration |
-
2019
- 2019-03-08 CN CN201910174190.1A patent/CN109734639B/en active Active
- 2019-03-08 CN CN202010809003.5A patent/CN111848466A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100516030C (en) * | 1998-05-11 | 2009-07-22 | 巴斯福股份公司 | Intermidiate for preparing 1,2-oxygen nitrogen heterocyclic-2-alkene acylbenzene and its preparation |
| EP1044965A1 (en) * | 1998-09-09 | 2000-10-18 | Nippon Finechemical Co., Ltd. | Process for the preparation of aromatic sulfur compounds |
| CN107162944A (en) * | 2017-04-27 | 2017-09-15 | 湖南化工研究院有限公司 | The preparation method of 2,3 dimethyl benzene methyl sulfides |
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| CN111848466A (en) | 2020-10-30 |
| CN109734639B (en) | 2020-10-09 |
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Effective date of registration: 20200911 Address after: 462000 No.1, west side of Zhongshan Road, south of Dongfanghong Road, Luohe economic and Technological Development Zone, Luohe City, Henan Province Applicant after: Luohe Weilong Biotechnology Co., Ltd Address before: 312599 No. 35 Shizhuwan Village, Qixing Street, Xinchang County, Shaoxing City, Zhejiang Province Applicant before: XINCHANG DACHUANFAN BIOTECHNOLOGY Co.,Ltd. |
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