CN105461550A - Preparation method of p-anisoyl chloride - Google Patents
Preparation method of p-anisoyl chloride Download PDFInfo
- Publication number
- CN105461550A CN105461550A CN201510953274.7A CN201510953274A CN105461550A CN 105461550 A CN105461550 A CN 105461550A CN 201510953274 A CN201510953274 A CN 201510953274A CN 105461550 A CN105461550 A CN 105461550A
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- CN
- China
- Prior art keywords
- anisoyl chloride
- preparation
- anisic acid
- btc
- initiator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- MXMOTZIXVICDSD-UHFFFAOYSA-N anisoyl chloride Chemical compound COC1=CC=C(C(Cl)=O)C=C1 MXMOTZIXVICDSD-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 16
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 208000011580 syndromic disease Diseases 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000001722 carbon compounds Chemical class 0.000 abstract 1
- 238000005660 chlorination reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001263 acyl chlorides Chemical class 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 240000007232 Illicium verum Species 0.000 description 1
- 235000008227 Illicium verum Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- IYIKLHRQXLHMJQ-UHFFFAOYSA-N amiodarone Chemical compound CCCCC=1OC2=CC=CC=C2C=1C(=O)C1=CC(I)=C(OCCN(CC)CC)C(I)=C1 IYIKLHRQXLHMJQ-UHFFFAOYSA-N 0.000 description 1
- 229960005260 amiodarone Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WHQCHUCQKNIQEC-UHFFFAOYSA-N benzbromarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC(Br)=C(O)C(Br)=C1 WHQCHUCQKNIQEC-UHFFFAOYSA-N 0.000 description 1
- 229960002529 benzbromarone Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229960004121 encainide hydrochloride Drugs 0.000 description 1
- OJIIZIWOLTYOBS-UHFFFAOYSA-N encainide hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1C(=O)NC1=CC=CC=C1CCC1N(C)CCCC1 OJIIZIWOLTYOBS-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- -1 methoxyl group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of p-anisoyl chloride, and belongs to the technical field of carbon compounds. The method comprises the steps that p-anisic acid serves as the raw material, BTC/C2H4Cl2 serves as a reagent of sulfonyl chlorination, an initiator is added, a reaction is conducted at the reflux temperature, and the p-anisoyl chloride is prepared. According to the preparation method of the p-anisoyl chloride, the reaction condition is mild, the technology is simple, operation is easy, the purity and yield of obtained products are high, and the preparation method of the p-anisoyl chloride is suitable for industrial production.
Description
Technical field
The invention belongs to technical field of organic synthesis, particularly relate to a kind of preparation method of anisoyl chloride.
Background technology
Anisoyl chloride (4-Methoxybenzoylchloride), has another name called star anise acyl chlorides, 4-methoxy benzoyl chloride.Its structural formula is as follows:
Anisoyl chloride is dissolved in acetone, methylene dichloride and benzene, meets water or ethanol and then decomposes, and is the intermediate for producing the medicines such as pull-up western smooth, amiodarone, encainide hydrochloride, A Nisitan, lamp-dish flower acetic and benzbromarone.
The technique producing anisoyl chloride known at present general is: with anisic acid and sulfur oxychloride back flow reaction 6 hours, recovery protochloride is soughed, underpressure distillation obtains pure anisoyl chloride, produces a large amount of byproduct hydrogen chloride and sulfurous gas in simultaneous reactions process.The method long reaction time, productive rate is also undesirable, and is unfavorable for environmental protection, makes troubles to suitability for industrialized production.
Chinese patent ZL201210073143.6 with trichlorotoluene zotrichloride and to methoxyl group formic acid for raw material, under the lewis acidic effect of catalyzer, acyl chloride reaction is there is after 5-10 hour in 100-150 DEG C, reaction mass is cooled to 20 ± 5 DEG C, then add Resorcinol purify obtain anisoyl chloride.Reaction conditions of the present invention is high, and the reaction times is longer, is not suitable for suitability for industrialized production.
Summary of the invention
In order to solve Problems existing in existing anisoyl chloride building-up process, the invention provides a kind of preparation method of anisoyl chloride, the method reaction conditions is gentle, technique is simple, easy handling, the product purity obtained is high, yield is high, is applicable to suitability for industrialized production.
The technical scheme that technical solution problem of the present invention adopts is:
A preparation method for anisoyl chloride, described preparation method is as follows:
In with the reaction vessel of device for absorbing tail gas, add anisic acid, solvent ethylene dichloride, initiator, be warming up to 40-45 DEG C, slowly drip BTC-C
2h
4cl
2solution, dropwises back flow reaction 1-2 hour, and after vacuum distillation recovered solvent, residuum is anisoyl chloride.
As preferably, described anisoyl chloride preparation method, is characterized in that, described BTC-C
2h
4cl
2the substance withdrawl syndrome of solution is 2mol/L, and the molar ratio of described anisic acid, initiator and solid phosgene is 1:0.04-0.06:0.31, and the mass ratio of described solvent ethylene dichloride and anisic acid is 2-4:1.
As preferably, described anisoyl chloride preparation method, is characterized in that, described initiator is DMF or pyridine.
As preferably, described tail gas absorption adopts water to absorb.
Beneficial effect of the present invention is:
1, BTC-C is adopted
2h
4cl
2make acyl chlorides reagent, reaction temperature and, environmental protection, adopt drip mode add BTC-C
2h
4cl
2solution, is conducive to the absorption process controlling speed of response and hydrogenchloride.
2, preparation method's reaction conditions of the present invention is gentle, and technique is simple, easy handling, and the product purity obtained is high, yield is high, is applicable to suitability for industrialized production.
Embodiment
Explain the present invention further below in conjunction with embodiment, but embodiment does not limit in any form to the present invention.
Embodiment 1
Anisic acid 15.23g (0.1mol), solvent ethylene dichloride 30.5g, DMF0.3g (0.004mol) is added in the reaction vessel of device for absorbing tail gas that water is housed, be warming up to 40 DEG C, slowly dripping concentration is the BTC-C of 2mol/L
2h
4cl
2solution 15.5ml, dropwises back flow reaction 1 hour, after vacuum distillation recovered solvent, obtains anisoyl chloride 16.88g, content 99.62% (gas-chromatography), yield 98.57%.
Embodiment 2
Anisic acid 15.23g (0.1mol), solvent ethylene dichloride 45.7g, pyridine 0.48g (0.006mol) is added in the reaction vessel of device for absorbing tail gas that water is housed, be warming up to 42 DEG C, slowly dripping concentration is the BTC/C of 2mol/L
2h
4cl
2solution 15.5ml, dropwises back flow reaction 1.5 hours, after vacuum distillation recovered solvent, obtains anisoyl chloride 16.86g, content 99.68% (gas-chromatography), yield 98.28%.
Embodiment 3
Anisic acid 15.23g (0.1mol), solvent ethylene dichloride 60.9g, DMF0.38g (0.005mol) is added in the reaction vessel of device for absorbing tail gas that water is housed, be warming up to 45 DEG C, slowly dripping concentration is the BTC/C of 2mol/L
2h
4cl
2solution 15.5ml, dropwises back flow reaction 2 hours, after vacuum distillation recovered solvent, obtains anisoyl chloride 16.92g, content 99.87% (gas-chromatography), yield 98.82%.
Embodiment 4
Anisic acid 15.23g (0.1mol), solvent ethylene dichloride 31g, pyridine 0.32g (0.004mol) is added in the reaction vessel of device for absorbing tail gas that water is housed, be warming up to 40 DEG C, slowly dripping concentration is the BTC-C of 2mol/L
2h
4cl
2solution 15.5ml, dropwises back flow reaction 2 hours, after vacuum distillation recovered solvent, obtains anisoyl chloride 16.91g, content 99.77% (gas-chromatography), yield 98.66%.
Embodiment 5
In the reaction vessel of device for absorbing tail gas that water is housed, add anisic acid 15.23g (0.1mol), solvent ethylene dichloride 60g, DMF0.3g (0.004mol), be warming up to 45 DEG C, slowly dripping concentration is the BTC-C of 2mol/L
2h
4cl
2solution 15.5ml, dropwises back flow reaction 2 hours, after vacuum distillation recovered solvent, obtains anisoyl chloride 16.98g, content 99.91% (gas-chromatography), yield 99.21%.
Below only list the preferred embodiments of the invention, protection scope of the present invention is not restricted to this, and any change that those skilled in the art do within the scope of the claims in the present invention all falls in scope.
Claims (4)
1. a preparation method for anisoyl chloride, is characterized in that, described preparation method is as follows:
In with the reaction vessel of device for absorbing tail gas, add anisic acid, solvent ethylene dichloride, initiator, be warming up to 40-45 DEG C, slowly drip BTC-C
2h
4cl
2solution, dropwises back flow reaction 1-2 hour, and after vacuum distillation recovered solvent, residuum is anisoyl chloride.
2. anisoyl chloride preparation method as claimed in claim 1, is characterized in that, described BTC-C
2h
4cl
2the substance withdrawl syndrome of solution is 2mol/L, and the molar ratio of described anisic acid, initiator and solid phosgene is 1:0.04-0.06:0.31, and the mass ratio of described solvent ethylene dichloride and anisic acid is 2-4:1.
3. anisoyl chloride preparation method as claimed in claim 1, it is characterized in that, described initiator is DMF or pyridine.
4. anisoyl chloride preparation method as claimed in claim 1, is characterized in that, described tail gas absorption adopts water to absorb.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510953274.7A CN105461550A (en) | 2015-12-17 | 2015-12-17 | Preparation method of p-anisoyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510953274.7A CN105461550A (en) | 2015-12-17 | 2015-12-17 | Preparation method of p-anisoyl chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105461550A true CN105461550A (en) | 2016-04-06 |
Family
ID=55599773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510953274.7A Pending CN105461550A (en) | 2015-12-17 | 2015-12-17 | Preparation method of p-anisoyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105461550A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409558A (en) * | 2018-04-12 | 2018-08-17 | 杭州金仕源医药化工有限公司 | A method of preparing oxalyl chloride |
| CN111548263A (en) * | 2020-05-26 | 2020-08-18 | 江苏巨莱生物医药有限公司 | Process method for preparing o-ethoxy benzoyl chloride |
| CN115043774A (en) * | 2022-06-15 | 2022-09-13 | 山东省农药检定所 | Synthesis method of fluoride ether bacteria amide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531888A (en) * | 2011-12-12 | 2012-07-04 | 温州大学 | Chemical synthesis method of 3,4,5-trimethoxy benzoyl chloride |
| CN102627555A (en) * | 2012-03-19 | 2012-08-08 | 丹阳市万隆化工有限公司 | Preparation method of p-anisoyl chloride |
-
2015
- 2015-12-17 CN CN201510953274.7A patent/CN105461550A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531888A (en) * | 2011-12-12 | 2012-07-04 | 温州大学 | Chemical synthesis method of 3,4,5-trimethoxy benzoyl chloride |
| CN102627555A (en) * | 2012-03-19 | 2012-08-08 | 丹阳市万隆化工有限公司 | Preparation method of p-anisoyl chloride |
Non-Patent Citations (4)
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|---|
| 李俊波: "三光气在酰氯化反应中的应用", 《化工中间体》 * |
| 李志成等: "L-（-）二对甲氧基苯甲酰酒石酸的合成", 《应用化工》 * |
| 杨雪艳等: "含海因环二当量黄成色剂的合成", 《华东理工大学学报》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409558A (en) * | 2018-04-12 | 2018-08-17 | 杭州金仕源医药化工有限公司 | A method of preparing oxalyl chloride |
| CN111548263A (en) * | 2020-05-26 | 2020-08-18 | 江苏巨莱生物医药有限公司 | Process method for preparing o-ethoxy benzoyl chloride |
| CN115043774A (en) * | 2022-06-15 | 2022-09-13 | 山东省农药检定所 | Synthesis method of fluoride ether bacteria amide |
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| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160406 |
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