CN107673949A - A kind of preparation method of the butylene of 1 chlorine, 3 methyl 2 - Google Patents
A kind of preparation method of the butylene of 1 chlorine, 3 methyl 2 Download PDFInfo
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- CN107673949A CN107673949A CN201711006829.2A CN201711006829A CN107673949A CN 107673949 A CN107673949 A CN 107673949A CN 201711006829 A CN201711006829 A CN 201711006829A CN 107673949 A CN107673949 A CN 107673949A
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- China
- Prior art keywords
- methyl
- hydrogen chloride
- preparation
- cmb
- butylene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title abstract 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 title abstract 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title abstract 3
- 239000000460 chlorine Substances 0.000 title abstract 3
- 229910052801 chlorine Inorganic materials 0.000 title abstract 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 23
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 abstract 2
- 238000003756 stirring Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- MXVSJNLRVLKAOG-UHFFFAOYSA-N 1-chloro-3-methylbut-1-ene Chemical class CC(C)C=CCl MXVSJNLRVLKAOG-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000009423 ventilation Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- OCUAPVNNQFAQSM-UHFFFAOYSA-N 3-Methyl-3-butenyl acetate Chemical compound CC(=C)CCOC(C)=O OCUAPVNNQFAQSM-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- JPTOCTSNXXKSSN-UHFFFAOYSA-N methylheptenone Chemical compound CCCC=CC(=O)CC JPTOCTSNXXKSSN-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical compound CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006273 synthetic pesticide Substances 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of the butylene of 1 chlorine, 3 methyl 2, it is characterized in that, comprise the following steps, the alcohol of 3 methyl, 2 butylene 1 is added in closed reaction unit, hydrogen chloride gas is passed through under the conditions of 30~25 DEG C to be reacted, reaction is finished, and branch vibration layer, obtains the butylene of 1 chlorine of product, 3 methyl 2.The present invention, as raw material, without using organic solvent and catalyst in preparation process, simplifies aftertreatment technology, reduces environmental pollution, improve production efficiency and security using the alcohol of 3 methyl, 2 butylene 1 and with hydrogen chloride.
Description
Technical field
The present invention relates to chemical field, and in particular to a kind of preparation method of 1,3,2-CMB.
Background technology
1,3,2-CMB (1,3,2-CMB) is a kind of important intermediate, and it is used for synthetic pesticide, beast
Medicine, spices, food additives and medicine, it prepares pesticide intermediate acetic acid isopentenyl ester with anhydrous sodium acetate reaction, is sent out with ketone
Raw dehydrochlorination reaction obtains methyl heptenone.
It by isoprene and hydrogen chloride or hydrochloric acid is main that existing literature and patent report 1,3,2-CMB, which are,
Raw material, using dichloromethane as solvent, catalyst reaction is made with stannous chloride, triethylamine hydrochloride or acetic acid and obtains the chloro- 3- of 1-
Methyl-2-butene.The preparation method needs to use raw material isoprene and methylene chloride, because both chemical substances are boiled
Point is low, and production and transport process hazard is big, and solvent recovery loss is big, the shortcomings of easily causing environmental pollution.
The content of the invention
The invention provides a kind of preparation method of 1,3,2-CMB, without solvent and catalyst, simplify
Production technology, reduce environmental pollution, improve production efficiency and security.
In order to solve the above problems, the technical solution adopted in the present invention is a kind of such, chloro- 3- methyl -2- fourths of 1-
The preparation method of alkene, comprises the following steps, and 3-M2BOL is added in closed reaction unit, -30~25
It is passed through hydrogen chloride gas under the conditions of DEG C to be reacted, reaction is finished, and branch vibration layer, obtains product 1,3,2-CMB.
Reaction principle is：
Described 3-M2BOL and the amount ratio of the material of hydrogen chloride are 1：1~1.5, preferably 1：1.25.
Preferably, hydrogen chloride gas is passed through under the conditions of -10~-5 DEG C to be reacted, and control reaction temperature in course of reaction
Spend for -10~-5 DEG C.
Beneficial effect：The present invention, as raw material, need not make using 3-M2BOL and with hydrogen chloride in preparation process
With organic solvent and catalyst, aftertreatment technology is simplified, reduces environmental pollution, improves production efficiency and security.
Embodiment
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, the embodiment
It is only used for explaining the present invention, is not intended to limit the scope of the present invention..
Embodiment 1：
Into the 1L four-hole boiling flasks equipped with agitator, thermometer and gas introduction tube, 430g (5mol) 3- methyl -2- is added
Butene-1-ol, stirring is opened, cools to -10~-5 DEG C, be passed through hydrogen chloride gas 228.1g (6.25mol), control logical hydrogen chloride
During reacting liquid temperature be -10~-5 DEG C, ventilation finishes, stirring be warming up to room temperature, stand, branch vibration layer, obtain about 520g
Product, gas chromatographic analysis：1,3,2-CMB 91.2%；The chloro- 3-methyl-1-butenes 8.1% of 3-；Dichloride
0.2%；3-M2BOL 0.4%；Impurity：0.1%.
Embodiment 2：
Into the 1L four-hole boiling flasks equipped with agitator, thermometer and gas introduction tube, 430g (5mol) 3- methyl -2- is added
Butene-1-ol, stirring is opened, cools to -10~-5 DEG C, be passed through hydrogen chloride gas 182.5g (5mol), control logical hydrogen chloride mistake
Reacting liquid temperature is -10~-5 DEG C in journey, and ventilation finishes, and stirring is warming up to room temperature, is stood, branch vibration layer, obtains about 504g productions
Product, gas chromatographic analysis：1,3,2-CMB 77.7%；The chloro- 3-methyl-1-butenes 6.9% of 3-；Dichloride
0.1%；3-M2BOL 15.2%；Impurity：0.1%.
Embodiment 3：
Into the 1L four-hole boiling flasks equipped with agitator, thermometer and gas introduction tube, 430g (5mol) 3- methyl -2- is added
Butene-1-ol, stirring is opened, cools to -10~-5 DEG C, be passed through hydrogen chloride gas 273.8g (7.5mol), control logical hydrogen chloride
During reacting liquid temperature be -10~-5 DEG C, ventilation finishes, stirring be warming up to room temperature, stand, branch vibration layer, obtain about 550g
Product, gas chromatographic analysis：1,3,2-CMB 66.9%；The chloro- 3-methyl-1-butenes 6.5% of 3-；Dichloride
21.6%；3-M2BOL 0.5%；Impurity：4.5%.
Embodiment 4：
Into the 1L four-hole boiling flasks equipped with agitator, thermometer and gas introduction tube, 430g (5mol) 3- methyl -2- is added
Butene-1-ol, stirring is opened, cools to -10~-5 DEG C, be passed through hydrogen chloride gas 219g (6mol), control logical hydrogen chloride process
Middle reacting liquid temperature is -10~-5 DEG C, and ventilation finishes, and stirring is warming up to room temperature, stands, branch vibration layer, obtains about 512g products,
Gas chromatographic analysis：1,3,2-CMB 88.44%；The chloro- 3-methyl-1-butenes 7.8% of 3-；Dichloride
0.16%；3-M2BOL 3.5%；Impurity：0.1%.
Embodiment 5：
Into the 1L four-hole boiling flasks equipped with agitator, thermometer and gas introduction tube, 430g (5mol) 3- methyl -2- is added
Butene-1-ol, stirring is opened, cools to -10~-5 DEG C, be passed through hydrogen chloride gas 237.3g (6.5mol), control logical hydrogen chloride
During reacting liquid temperature be -10~-5 DEG C, ventilation finishes, stirring be warming up to room temperature, stand, branch vibration layer, obtain about 550g
Product, gas chromatographic analysis：1,3,2-CMB 81.1%；The chloro- 3-methyl-1-butenes 7.5% of 3-；Dichloride
8.6%；3-M2BOL 1.3%；Impurity：1.5%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (5)
1. a kind of preparation method of 1,3,2-CMB, it is characterised in that comprise the following steps, filled in closed reaction
Middle addition 3-M2BOL is put, being passed through hydrogen chloride gas under the conditions of -30~25 DEG C is reacted, and reaction is finished, point
Water layer is removed, obtains product 1,3,2-CMB.
2. the preparation method of 1,3,2-CMB according to claim 1, it is characterised in that described 3- first
Base -2- butene-1-ols：The amount ratio of the material of hydrogen chloride is 1：1~1.5.
3. the preparation method of 1,3,2-CMB according to claim 2, it is characterised in that described 3- first
The amount ratio of the material of base -2- butene-1-ols and hydrogen chloride is 1：1.25.
4. the preparation method of 1,3,2-CMB according to claim 1, it is characterised in that at -10~-5 DEG C
Under the conditions of be passed through hydrogen chloride gas and reacted.
5. the preparation method of the 1,3,2-CMB according to claim 1 or 4, it is characterised in that course of reaction
Middle controlling reaction temperature is -10~-5 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711006829.2A CN107673949B (en) | 2017-10-25 | 2017-10-25 | Preparation method of 1-chloro-3-methyl-2-butene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711006829.2A CN107673949B (en) | 2017-10-25 | 2017-10-25 | Preparation method of 1-chloro-3-methyl-2-butene |
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| Publication Number | Publication Date |
|---|---|
| CN107673949A true CN107673949A (en) | 2018-02-09 |
| CN107673949B CN107673949B (en) | 2021-02-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711006829.2A Active CN107673949B (en) | 2017-10-25 | 2017-10-25 | Preparation method of 1-chloro-3-methyl-2-butene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232212A (en) * | 2018-09-28 | 2019-01-18 | 万华化学集团股份有限公司 | A method of by prenol synthesizing methyl heptenone |
| CN110746282A (en) * | 2019-11-04 | 2020-02-04 | 天津市安凯特科技发展有限公司 | Synthetic method of 4-chloro-2-butanone |
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| JP4196669B2 (en) * | 2002-12-25 | 2008-12-17 | 住友化学株式会社 | Method for producing allyl halide derivative |
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2017
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232212A (en) * | 2018-09-28 | 2019-01-18 | 万华化学集团股份有限公司 | A method of by prenol synthesizing methyl heptenone |
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| CN110746282A (en) * | 2019-11-04 | 2020-02-04 | 天津市安凯特科技发展有限公司 | Synthetic method of 4-chloro-2-butanone |
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| CN107673949B (en) | 2021-02-23 |
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Effective date of registration: 20240110 Address after: Room 811, Strategic Emerging Industry Incubation Base, Qinchuan Park, Lanzhou New Area, Lanzhou City, Gansu Province, 730207 Patentee after: Gansu Taixinlong New Material Co.,Ltd. Address before: 210047 room 521, building a, 606 ningliu Road, Nanjing Chemical Industrial Park, Jiangsu Province Patentee before: NANJING HENGWANG BIOLOGICAL PHARMACEUTICAL CO.,LTD. |