CN103539643A - Method for preparing 2-ethoxy-6-chloro-toluene - Google Patents
Method for preparing 2-ethoxy-6-chloro-toluene Download PDFInfo
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- CN103539643A CN103539643A CN201210244232.2A CN201210244232A CN103539643A CN 103539643 A CN103539643 A CN 103539643A CN 201210244232 A CN201210244232 A CN 201210244232A CN 103539643 A CN103539643 A CN 103539643A
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- toluene
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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Abstract
The invention relates to a preparation method of an intermediate 2-ethoxy-6-chloro-toluene capable of synthesizing some phenols and ethers which can not be easily prepared.2,6-dichlorotoluene is used as a raw material, and caustic alkali-ethanol and dimethyl sulfoxide are used as solvents to obtain the target substance. The preparation method can avoid using the ethanol solution of sodium ethylate, has the advantages of lower production cost and higher safety, is simple to operate and has industrial production value.
Description
Technical field
The present invention relates to the preparation method of the chloro-toluene of a kind of chemical intermediate 2-oxyethyl group-6-.
Background technology
The chloro-toluene of 2-oxyethyl group-6-be a kind of important organic synthesis intermediate, can be by phenolic compound and the ether compound of its synthetic a series of difficult preparation.
About synthesizing of the chloro-toluene of 2-oxyethyl group-6-, document EP1044980; (2000); (A1) in English, have been reported.In document, take 2,6-DCT as raw material, through reacting and obtain target product with sodium ethylate, its reaction process is shown below:
The chloro-toluene of I 2,6-DCT II 2-oxyethyl group-6-
In the method, the ethanolic soln generation substitution reaction of 2,6-DCT (formula I) and sodium ethylate, obtains 2-oxyethyl group-6-toluene(mono)chloride (formula II).Then, reaction mass is added to acid treatment, obtain containing target product 52%, hydroxyl replaces the crude product of the by product 45% of chlorine, crude product is carried out to separation and obtain target product.This preparation method has used has larger dangerous alcohol sodium solution, and when producing enforcement, operation easier is larger, and security risk is larger.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of the chloro-toluene of a kind of 2-oxyethyl group-6-.This preparation method can avoid using the ethanolic soln of sodium ethylate, and is that a kind of production cost is lower and simple to operate, safer, has the preparation method that industrial production is worth.
The present invention is prepared in the method for the chloro-toluene of 2-oxyethyl group-6-for take 2,6-DCT as raw material, and concrete technology comprises the following steps:
(1) in reaction flask, add 2,6-DCT, reaction solvent, add caustic alkali and ethanol at 25 ℃, heat to 100～150 ℃, insulation reaction 10～30h stops heating when 2,6-DCT has reacted, and stirs cooling;
(2) aftertreatment obtains the chloro-toluene of 2-oxyethyl group-6-, i.e. structure II compound.
Ⅰ Ⅱ
Reaction solvent in above-mentioned steps (1) is dimethyl sulfoxide (DMSO).
Caustic alkali in above-mentioned steps (1) is potassium hydroxide or sodium hydroxide.
Caustic alkali molar weight in above-mentioned steps (1) is 2,6-DCT 1～2 times, ethanol molar weight is 2,6-DCT 2～4 times.
Post processing mode in above-mentioned steps (2), for adding concentrated hydrochloric acid solution to regulate reaction solution pH=7, adds extraction solvent, stirs after 1 hour, gets after organic phase decompression steams extraction solvent and carries out rectifying.
Aftertreatment extraction solvent in above-mentioned steps (2) is methylene dichloride, 1,2-ethylene dichloride, 1,2-propylene dichloride or 1,3-propylene dichloride.
The inventor finds in research process, uses the ethanolic soln of sodium ethylate can prepare the chloro-toluene of 2-oxyethyl group-6-, and still, the ethanolic soln price of sodium ethylate is more expensive, and operation easier is also relatively larger, and security risk is also larger.
The inventor finds under study for action, adopt low-cost caustic alkali-ethanol to react, reaction process adopts methyl-sulphoxide to make solvent, the security risk of reaction reduces greatly, and reaction is carried out smoothly, and reaction finishes, concentrated hydrochloric acid solution neutralizing treatment, solvent extraction, gets organic phase decompression and steams and carry out rectifying after extraction solvent and obtain 2-oxyethyl group-6-toluene(mono)chloride, and yield can reach 75.0%.
In the inventive method, in reaction process, use low-cost caustic alkali-ethanolic soln, not only make product ultimate yield higher, and there is feature simple to operate, cost is low.
In the inventive method, in post-reaction treatment process, adopted solvent extraction, by the material to after neutralization, extracted, reduced the impurity in the front material of rectifying, reduced the difficulty of rectifying, made product ultimate yield higher.
Outstanding feature of the present invention is: (1) has been used cheap caustic alkali-ethanolic soln as reaction reagent, post-reaction treatment, and solubilizing agent extraction after neutralization, reaction yield is higher, and cost is low; (2) simple to operate, be easy to industrializing implementation.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1:
In 2000ml reaction flask, add 161.0g(1.0mol) 2, the chloro-toluene of 6-bis-, dimethyl sulfoxide (DMSO) 700ml, at 25 ℃, add potassium hydroxide 84.2g(1.5mol) and ethanol 138.2g(3.0mol), heat to 130 ℃, insulation reaction 10h, to 2, the chloro-toluene of 6-bis-stops heating while having reacted, stir cooling; With concentrated hydrochloric acid solution, regulate reaction solution pH=7, add methylene dichloride 500ml, stir after 1 hour, get organic phase decompression and steam and carry out rectifying after extraction solvent and obtain the chloro-toluene of 2-oxyethyl group-6-, be i.e. compound ii, 119.4g (0.700mol), GC content 98.6%, yield 70.0%;
1hNMR(CDCl
3, 400MHz) characterize: δ 1.44(t, 3H), δ 2.29(s, 3H), δ 4.03(m, 2H) and, δ 6.74(d, J=8.0Hz, 1H), δ 6.97(d, J=8.0Hz, 1H) and, δ 7.06(m, J=16.0Hz, 1H).
Embodiment 2:
In 2000ml reaction flask, add 161.0g(1.0mol) 2, the chloro-toluene of 6-bis-, dimethyl sulfoxide (DMSO) 700ml,, add sodium hydroxide 40.0g(1.0mol at 25 ℃) and ethanol 92.1g(2.0mol), heat to 100 ℃, insulation reaction 16h, when the chloro-toluene of 2,6-bis-has reacted, stop heating, stir cooling; With concentrated hydrochloric acid solution, regulate reaction solution pH=7, add 1,2-propylene dichloride 500ml, stir after 1 hour, get organic phase decompression and steam and carry out rectifying after extraction solvent and obtain the chloro-toluene of 2-oxyethyl group-6-, i.e. compound ii, 115.4g (0.676mol), GC content 98.5%, yield 67.6%;
1hNMR(CDCl
3, 400MHz) characterize: δ 1.44(t, 3H), δ 2.29(s, 3H), δ 4.03(m, 2H) and, δ 6.74(d, J=8.0Hz, 1H), δ 6.97(d, J=8.0Hz, 1H) and, δ 7.06(m, J=16.0Hz, 1H).
Embodiment 3:
In 2000ml reaction flask, add 161.0g(1.0mol) 2, the chloro-toluene of 6-bis-, dimethyl sulfoxide (DMSO) 700ml, at 25 ℃, add potassium hydroxide 112.2g(2.0mol) and ethanol 138.2g(3.0mol), heat to 140 ℃, insulation reaction 30h, to 2, the chloro-toluene of 6-bis-stops heating while having reacted, stir cooling; With concentrated hydrochloric acid solution, regulate reaction solution pH=7, add 1,3-propylene dichloride 500ml, stir after 1 hour, get organic phase decompression and steam and carry out rectifying after extraction solvent and obtain the chloro-toluene of 2-oxyethyl group-6-, i.e. compound ii, 123.9g (0.726mol), GC content 98.5%, yield 72.6%;
1hNMR(CDCl
3, 400MHz) characterize: δ 1.44(t, 3H), δ 2.29(s, 3H), δ 4.03(m, 2H) and, δ 6.74(d, J=8.0Hz, 1H), δ 6.97(d, J=8.0Hz, 1H) and, δ 7.06(m, J=16.0Hz, 1H).
Embodiment 4:
In 2000ml reaction flask, add 161.0g(1.0mol) 2, the chloro-toluene of 6-bis-, dimethyl sulfoxide (DMSO) 700ml, at 25 ℃, add sodium hydroxide 80.0g(2.0mol) and ethanol 184.3g(4.0mol), heat to 150 ℃, insulation reaction 20h, to 2, the chloro-toluene of 6-bis-stops heating while having reacted, stir cooling; With concentrated hydrochloric acid solution, regulate reaction solution pH=7, add 1,2-ethylene dichloride 500ml, stir after 1 hour, get organic phase decompression and steam and carry out rectifying after extraction solvent and obtain the chloro-toluene of 2-oxyethyl group-6-, i.e. compound ii, 128.0g (0.750mol), GC content 98.7%, yield 75.0%;
1hNMR(CDCl
3, 400MHz) characterize: δ 1.44(t, 3H), δ 2.29(s, 3H), δ 4.03(m, 2H) and, δ 6.74(d, J=8.0Hz, 1H), δ 6.97(d, J=8.0Hz, 1H) and, δ 7.06(m, J=16.0Hz, 1H).
The above is only the preferred embodiments of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some optimization and improvement, these optimizations and improvement also should be considered as protection scope of the present invention.
Claims (7)
- The preparation method of the chloro-toluene of 1.2-oxyethyl group-6-, is characterized in that comprising the following steps:In reaction flask, add 2,6-DCT, reaction solvent, add caustic alkali and ethanol at 25 ℃, heat to 100～150 ℃, insulation reaction 10～30h stops heating when 2,6-DCT has reacted, and stirs cooling; Aftertreatment obtains the chloro-toluene of 2-oxyethyl group-6-.
- 2. the preparation method of the chloro-toluene of 2-oxyethyl group-6-according to claim 1, is characterized in that: said reaction solvent is dimethyl sulfoxide (DMSO).
- 3. the preparation method of the chloro-toluene of 2-oxyethyl group-6-according to claim 1, is characterized in that: said caustic alkali is sodium hydroxide or potassium hydroxide, preferably sodium hydroxide.
- 4. the preparation method of the chloro-toluene of 2-oxyethyl group-6-according to claim 1, is characterized in that: said caustic alkali molar weight is 2,6-DCT 1～2 times, ethanol molar weight is 2,6-DCT 2～4 times.
- 5. the preparation method of the chloro-toluene of 2-oxyethyl group-6-according to claim 1, it is characterized in that: said aftertreatment is for adding concentrated hydrochloric acid solution to regulate reaction solution pH=7, add extraction solvent, stir after 1 hour, get after organic phase decompression steams extraction solvent and carry out rectifying.
- 6. post-treating method according to claim 5, is characterized in that: said extraction solvent is methylene dichloride, 1,2-ethylene dichloride, 1,2-propylene dichloride or 1,3-propylene dichloride, preferably 1,2-ethylene dichloride.
- 7. the preparation method of the chloro-toluene of 2-oxyethyl group-6-according to claim 1, is characterized in that: said temperature of reaction is 100～150 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068106A (en) * | 1991-06-21 | 1993-01-20 | 上海市农药研究所 | The new method synthetic herbicide of monoetherization oxyfluorfen |
| EP1044980A1 (en) * | 1997-12-09 | 2000-10-18 | Ihara Chemical Industry Co., Ltd. | Process for producing toluene derivatives |
| CN101121647A (en) * | 2007-08-11 | 2008-02-13 | 姜堰市菲娜英胶粘剂有限公司 | Preparation method of p-fluoroanisole |
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2012
- 2012-07-16 CN CN201210244232.2A patent/CN103539643B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068106A (en) * | 1991-06-21 | 1993-01-20 | 上海市农药研究所 | The new method synthetic herbicide of monoetherization oxyfluorfen |
| EP1044980A1 (en) * | 1997-12-09 | 2000-10-18 | Ihara Chemical Industry Co., Ltd. | Process for producing toluene derivatives |
| CN101121647A (en) * | 2007-08-11 | 2008-02-13 | 姜堰市菲娜英胶粘剂有限公司 | Preparation method of p-fluoroanisole |
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