CN102557895A - Method for preparing trichlorine metoxybenzene - Google Patents
Method for preparing trichlorine metoxybenzene Download PDFInfo
- Publication number
- CN102557895A CN102557895A CN2010106093228A CN201010609322A CN102557895A CN 102557895 A CN102557895 A CN 102557895A CN 2010106093228 A CN2010106093228 A CN 2010106093228A CN 201010609322 A CN201010609322 A CN 201010609322A CN 102557895 A CN102557895 A CN 102557895A
- Authority
- CN
- China
- Prior art keywords
- anisole
- trichlorine
- preparing
- chlorination reagent
- hour
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 62
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 31
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical group ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- RWNKSTSCBHKHTB-UHFFFAOYSA-N Hexachloro-1,3-butadiene Chemical compound ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl RWNKSTSCBHKHTB-UHFFFAOYSA-N 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- GQHWSLKNULCZGI-UHFFFAOYSA-N trifluoromethoxybenzene Chemical compound FC(F)(F)OC1=CC=CC=C1 GQHWSLKNULCZGI-UHFFFAOYSA-N 0.000 description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical group C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- RINWGRJHXCCLOV-UHFFFAOYSA-N BPO Chemical compound BPO RINWGRJHXCCLOV-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing trichlorine metoxybenzene. The preparation method comprises the following step of: introducing chlorine gas into metoxybenzene serving as a reactant and a chlorination reagent under the actions of heating and an initiator to obtain a product finally. The method has a simple, stable and reliable process and high production efficiency.
Description
Technical field
The present invention relates to a kind of method for preparing the trichlorine anisole.
Background technology
The trichlorine anisole is the important source material of producing Trifluoromethyl phenyl ether.Trifluoromethyl phenyl ether is the important intermediate of synthesizing new medicine, agricultural chemicals and dyestuff, especially on agricultural chemicals, can be used for the production of weedicide and sterilant, has the advantages that consumption is little, toxicity is low, drug effect is high.It simultaneously also is the midbody of functional material such as liquid crystal.The preparation method of trichlorine anisole is starting raw material with the anisole mainly, the chlorine radical generation substitution reaction that under illumination, produces, production trichlorine anisole.Concrete working method is to be raw material with the anisole, and under the illumination condition, in carbon tetrachloride solvent, logical chlorine carries out chlorination, production trichlorine anisole.The shortcoming of this method is to use tetracol phenixin to make solvent.Because tetracol phenixin is a kind of ODS; Be one of reagent of international convention Montreal Protocol on Substances that Deplete the Ozone Layer limit production and use; Require developed country to 1996 year superseded fully, developing country to 2010 year all stops using; Simultaneously HUMAN HEALTH there is harm.China has forbidden the tetracol phenixin clean-out system at present fully, simultaneously in the use that progressively replaces and forbid tetracol phenixin.Therefore the novel method of developing a kind of alternative tetracol phenixin production trichlorine anisole is extremely urgent.
The present invention mainly adopts chloride compound such as tetrachloroethane, pentaline, Sesquichloratum, two (trichloromethyl) carbonic ether, HEXACHLOROBUTADIENE to replace the present tetracol phenixin that uses as solvent and chlorination reagent; Can reduce the destruction of tetracol phenixin, reduce the healthy infringement of the person to ozonosphere.Because the boiling point substance of these alternative tetracol phenixin is higher than tetracol phenixin, can reduce the loss through volatilization in the reaction process, has reduced raw materials cost.Can satisfy simultaneously the needs of chemical reaction.
Summary of the invention
The object of the present invention is to provide a kind of method of production trichlorine anisole.The method of production trichlorine anisole is among the present invention, and anisole, an amount of initiator are added in the reaction kettle, adds chlorination reagent then, feeds chlorine, and reacting by heating under the normal pressure makes product trichlorine anisole.
Said chlorination reagent is tetrachloroethane, pentaline, Sesquichloratum, two (trichloromethyl) carbonic ether, HEXACHLOROBUTADIENE, is preferably two (trichloromethyl) carbonic ether.
Said initiator is cyclohexanone peroxide, BPO, tertbutyl peroxide, Diisopropyl azodicarboxylate, ABVN, is preferably Diisopropyl azodicarboxylate.
The mol ratio of chlorination reagent and anisole is 3-6:1, is preferably 3-5:1, more preferably 3.5-4:1.
The consumption of initiator is 0.01-0.08%, is preferably 0.01-0.06%, more preferably 0.02-0.03%.
Temperature of reaction is 85-180 ℃, is preferably 85-150 ℃, more preferably 90-100 ℃.
Reaction times is 2-15 hour, is preferably 2-8 hour, more preferably 2-3 hour.
The chlorination reagent that the present invention adopts mainly is in order to substitute tetracol phenixin; Reduce environmental pollution and to the injury of HUMAN HEALTH, the chlorination reagent that the present invention adopts obtains mainly due to its Industrial products easily; It is solid about 81-83 ℃ simultaneously; Be convenient to production operation, shortened the reaction times, reduced production cost and labour intensity.
Embodiment
Embodiment 1
With anisole 1mol, Diisopropyl azodicarboxylate 0.003mol, two (trichloromethyl) carbonic ether 4mol is heated to 85 ℃ under the normal pressure, feed excessive chlorine then, reacts 8 hours down at 85 ℃, obtains the trichlorine anisole.Productive rate 98%.
1HNMR(CCl
3D)δ6.77?ppm?(2H,d)，6.87ppm(1H,t)，7.05?ppm?(2H,t)。
Embodiment 2
With anisole 1mol, Diisopropyl azodicarboxylate 0.003mol, two (trichloromethyl) carbonic ether 4mol is heated to 120 ℃ under the normal pressure, feed excessive chlorine then, reacts 3 hours down at 120 ℃, obtains the trichlorine anisole.Productive rate 95%.
1HNMR(CCl
3D)δ6.75?ppm?(2H,d)，6.86ppm(1H,t)，7.04?ppm?(2H,t)。
Embodiment 3
With anisole 1mol, Diisopropyl azodicarboxylate 0.00135mol is heated to 85 ℃ under the tetrachloroethane 3.5mol, normal pressure, feed excessive chlorine then, reacts 5 hours down at 85 ℃, obtains the trichlorine anisole.Productive rate 96%.
1HNMR(CCl
3D)δ6.78?ppm?(2H,d)，6.88ppm(1H,t)，7.05?ppm?(2H,t)。
Embodiment 4
With anisole 1mol, BPO 0.0022mol is heated to 95 ℃ under the HEXACHLOROBUTADIENE 4.5mol, normal pressure, feed excessive chlorine then, reacts 4 hours down at 95 ℃, obtains the trichlorine anisole.Productive rate 95%.
1HNMR(CCl
3D)δ6.785ppm?(2H,d)，6.87ppm(1H,t)，7.06?ppm?(2H,t)。
Claims (6)
1. method for preparing the trichlorine anisole is characterized in that: anisole, an amount of initiator are added in the reaction kettle, add chlorination reagent then, feed chlorine, reacting by heating under the normal pressure makes product trichlorine anisole.
2. the method for preparing the trichlorine anisole according to claim 1 is characterized in that: the mol ratio of chlorination reagent and anisole is 3-6:1, is preferably 3-5:1, more preferably 3.5-4:1.
3. the method for preparing the trichlorine anisole according to claim 1 is characterized in that: temperature of reaction is 85-180 ℃, is preferably 85-150 ℃, more preferably 90-100 ℃.
4. the method for preparing the trichlorine anisole according to claim 1 is characterized in that: reaction times 2-15 hour, be preferably 2-8 hour, more preferably 2-3 hour.
5. according to the method for preparing the trichlorine anisole described in the claim 1 and 2, it is characterized in that: chlorination reagent is tetrachloroethane, pentaline, Sesquichloratum, two (trichloromethyl) carbonic ether, HEXACHLOROBUTADIENE, is preferably two (trichloromethyl) carbonic ether.
6. the method for preparing the trichlorine anisole according to claim 1 is characterized in that: the consumption of initiator is 0.01-0.08%, is preferably 0.01-0.06%, more preferably 0.02-0.03%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106093228A CN102557895A (en) | 2010-12-28 | 2010-12-28 | Method for preparing trichlorine metoxybenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106093228A CN102557895A (en) | 2010-12-28 | 2010-12-28 | Method for preparing trichlorine metoxybenzene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102557895A true CN102557895A (en) | 2012-07-11 |
Family
ID=46404676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010106093228A Pending CN102557895A (en) | 2010-12-28 | 2010-12-28 | Method for preparing trichlorine metoxybenzene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102557895A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085202A (en) * | 2014-05-22 | 2015-11-25 | 刘世伟 | Synthetic method for trichloromethoxybenzene |
| WO2016125185A2 (en) | 2015-02-02 | 2016-08-11 | Srf Limited | Process for the preparation of 4-substituted-1-(trifluoromethoxy)benzene compounds |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1390820A (en) * | 2001-06-07 | 2003-01-15 | 刘影 | Process for preparing trifluomethoxybenzene |
| CN102531421A (en) * | 2010-12-13 | 2012-07-04 | 北京金源化学集团有限公司 | Cement with low carbon dioxide emission and preparation method thereof |
-
2010
- 2010-12-28 CN CN2010106093228A patent/CN102557895A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1390820A (en) * | 2001-06-07 | 2003-01-15 | 刘影 | Process for preparing trifluomethoxybenzene |
| CN102531421A (en) * | 2010-12-13 | 2012-07-04 | 北京金源化学集团有限公司 | Cement with low carbon dioxide emission and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085202A (en) * | 2014-05-22 | 2015-11-25 | 刘世伟 | Synthetic method for trichloromethoxybenzene |
| WO2016125185A2 (en) | 2015-02-02 | 2016-08-11 | Srf Limited | Process for the preparation of 4-substituted-1-(trifluoromethoxy)benzene compounds |
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| C06 | Publication | ||
| PB01 | Publication | ||
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| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120711 |