CN1978429A - Method for treating 4 chloro pyridine in solvent - Google Patents
Method for treating 4 chloro pyridine in solvent Download PDFInfo
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- CN1978429A CN1978429A CN 200510045501 CN200510045501A CN1978429A CN 1978429 A CN1978429 A CN 1978429A CN 200510045501 CN200510045501 CN 200510045501 CN 200510045501 A CN200510045501 A CN 200510045501A CN 1978429 A CN1978429 A CN 1978429A
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- solvent
- treatment process
- process according
- salt
- chloro pyridine
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- 239000002904 solvent Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 25
- PVMNPAUTCMBOMO-UHFFFAOYSA-N 4-chloropyridine Chemical compound ClC1=CC=NC=C1 PVMNPAUTCMBOMO-UHFFFAOYSA-N 0.000 title claims description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 239000006227 byproduct Substances 0.000 claims abstract description 11
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 10
- 239000005944 Chlorpyrifos Substances 0.000 claims abstract description 8
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical group CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 claims abstract description 8
- MFTSCJIEOYYRPN-UHFFFAOYSA-N ClC=1C(=C(C(=NC1)[Na])Cl)Cl Chemical compound ClC=1C(=C(C(=NC1)[Na])Cl)Cl MFTSCJIEOYYRPN-UHFFFAOYSA-N 0.000 claims description 17
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000001103 potassium chloride Substances 0.000 claims description 17
- 235000011164 potassium chloride Nutrition 0.000 claims description 17
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 2
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 3
- WLARTYCFUUGKSW-UHFFFAOYSA-N ClC1=C(C(=NC=C1)Cl)Cl.[Na] Chemical compound ClC1=C(C(=NC=C1)Cl)Cl.[Na] WLARTYCFUUGKSW-UHFFFAOYSA-N 0.000 abstract 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract 4
- DLOOKZXVYJHDIY-UHFFFAOYSA-N 2,3,4,5-tetrachloropyridine Chemical compound ClC1=CN=C(Cl)C(Cl)=C1Cl DLOOKZXVYJHDIY-UHFFFAOYSA-N 0.000 abstract 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract 1
- 229920001223 polyethylene glycol Polymers 0.000 abstract 1
- 235000011118 potassium hydroxide Nutrition 0.000 abstract 1
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- -1 polyoxyethylene Polymers 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VMHZXXPDUOVTHD-UHFFFAOYSA-N 2,3,4-trichloropyridine Chemical compound ClC1=CC=NC(Cl)=C1Cl VMHZXXPDUOVTHD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000007883 cyanide addition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000005461 organic phosphorous group Chemical group 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
This invention relates to a treatment method of tetrachloro pyridine in solvent. The stated solvent is chlorpyrifos intermediate for producing trichloro pyridine sodium alcoholate salt or kalium salt. Its characteristic is including that under effect of the phase-transfer catalyst, solvent containing by-product tetrachloro pyridine is transformed into trichloro pyridine sodium alcoholate salt or kalium salt by using water solution of natrium hydroxydatum or caustic potash. The mentioned phase-transfer catalyst utilizes carbowax of low molecular. In this invention, there is no need to separate and purify the by-product tetrachloro pyridine existing in solvent in the technology of using trichloroacetyl chloride route to synthesize trichloro pyridine sodium alcoholate salt or kalium salt as intermediate, but directly using lye to process to transform it into trichloro pyridine sodium alcoholate salt or kalium salt. The method reduces the procedure of separation and purification in present technique. Technology is simple and reliable, yield is near theoretical value.
Description
Technical field
The present invention relates to the treatment process of the contained by product of solvent in the production of agricultural chemicals Chlorpyrifos 94 intermediate.
Background technology
Chlorpyrifos 94 (chlorpyrifos), chemistry O by name, O-diethyl-O-(3,5, the 6-trichloro-2-pyridyl) thiophosphatephosphorothioate are the organic phosphorous insecticides of a kind of efficient, wide spectrum, middle low toxicity, are the regeneration products that the present pesticide structure of China is adjusted.Because the restriction of raw material, technology and equipment, China adopts trichoroacetic chloride route synthetic intermediate trichloro pyridyl sodium alcoholate salt or sylvite more, and trichloro pyridyl sodium alcoholate salt or sylvite make Chlorpyrifos 94 with the diethylaluminum monochloride condensation more then.The synthetic method of trichloro pyridyl sodium alcoholate salt or sylvite is, is catalyzer with the cuprous chloride, makes trichoroacetic chloride and vinyl cyanide addition cyclisation in solvent (orthodichlorobenzene, oil of mirbane, dimethylbenzene, tetramethylene sulfone etc.), generates pyridone and by-product 4 chloro pyridine.Through aromizing salify art breading, pyridone changes trichloro pyridyl sodium alcoholate (potassium) salt into, and 4 chloro pyridine still is dissolved in the solvent.When the content of 4 chloro pyridine in solvent reaches certain value, it must be removed, otherwise solvent can not recycled.Purify out many at present 4 chloro pyridine the separation with physics or chemical process, uses the potassium hydroxide alkaline hydrolysis then, makes it to be converted into trichloropyridine alcohol sylvite.Separate purification process cost height, the time is long.The solid 4 chloro pyridine is time-consuming equally with the potassium hydroxide alkaline hydrolysis, and yield is not ideal enough, and potassium hydroxide is relatively costly.
Summary of the invention
Technical problem to be solved by this invention provides the treatment process that is dissolved in the by product 4 chloro pyridine in the solvent in a kind of trichloro pyridyl sodium alcoholate salt or the sylvite production, must not separate purification, the 4 chloro pyridine in the solvent is converted into trichloro pyridyl sodium alcoholate salt or sylvite.
The treatment process of 4 chloro pyridine in the solvent of the present invention, described solvent is Chlorpyrifos 94 intermediate trichloro pyridyl sodium alcoholate salt or sylvite production solvent, it is characterized in that the solvent that contains the by product 4 chloro pyridine is converted into trichloro pyridyl sodium alcoholate salt or sylvite with sodium hydroxide or potassium hydroxide aqueous solution under the effect of phase-transfer catalyst, described phase-transfer catalyst adopts low molecular poly.
The solvent that contains the by product 4 chloro pyridine is an oil phase, sodium hydroxide or potassium hydroxide aqueous solution are water, under the phase-transfer catalyst effect, sodium hydroxide or potassium hydroxide are converted into trichloro pyridyl sodium alcoholate salt or sylvite with 4 chloro pyridine, reaction end can be determined with vapor-phase chromatography, filter layering then, trichloro pyridyl sodium alcoholate salt or sylvite enter the refining step of former technology (production technique of trichloro pyridyl sodium alcoholate salt or sylvite), oil phase recycled after the washing dehydration enters the original production process flow process, and water is applied mechanically at this treatment process internal recycle after treatment.
The phase transfer reaction temperature can be controlled at 20～140 ℃.Reaction is under agitation carried out, and mixing speed can be 20～200 rev/mins.
Phase-transfer catalyst employing molecular weight is 200～1000 low molecular poly, the product of PEG (polyoxyethylene glycol)-200, PEG-400, PEG-600 or the PEG-800 trade mark as is known.The usage quantity of catalyzer is 0.1～2% of a material gross weight (oil phase and water weight sum).
The mass concentration of sodium hydroxide or potassium hydroxide aqueous solution is 10～50%.
The phase-transfer-catalyzed reactions that oil phase and water carry out, best charging capacity are that the volume ratio that feeds intake in oil phase and the water is 1: 0.1～10, and when feeding intake, the mole number of sodium hydroxide or potassium hydroxide should be more than or equal to 1 with the ratio of the mole number of 4 chloro pyridine.
Solvent of the present invention can be an employed all kinds of SOLVENTS in existing Chlorpyrifos 94 intermediate trichloro pyridyl sodium alcoholate salt or the sylvite production technology, as orthodichlorobenzene, oil of mirbane, dimethylbenzene, tetramethylene sulfone etc.The solvent species of dissolving 4 chloro pyridine is to the not influence of treatment process of this technology.Whenever 4 chloro pyridine content in solvent involves is enough to obviously reduce before the pyridone yield, all can use treatment process of the present invention that solvent is handled.Only from 4 chloro pyridine the solvent is transformed, the content of 4 chloro pyridine can be the solubleness that reaches capacity.
Advantage of the present invention:
1, with trichoroacetic chloride route synthetic intermediate trichloro pyridyl sodium alcoholate salt or sylvite, the by product 4 chloro pyridine that exists in the solvent must not separate purification, is converted into trichloro pyridyl sodium alcoholate salt or sylvite but directly handle with alkali lye, and is identical with the target product of technology.Saved the separation purification process, simple and reliable process, yield is near theoretical value.
2, both can be converted into trichloropyridine alcohol sylvite to 4 chloro pyridine, and also can use cheap sodium hydroxide that 4 chloro pyridine is converted into trichloro pyridyl sodium alcoholate salt with traditional potassium hydroxide.
3, phase-transfer catalyst has used the low molecular poly of relative low price.
Embodiment
The present invention will be described below in conjunction with embodiment.
Embodiment 1:
Contain 2% and (account for the per-cent of oil phase total mass, down with) orthodichlorobenzene of 4 chloro pyridine and 40% sodium hydroxide solution and molecular weight be that 600 polyoxyethylene glycol adds in the same reactor, oil phase and water volume ratio were controlled at 1: 1, catalyst levels is 1% of oil phase and a water gross weight, 80 ℃ of reactions down, and stir with 100 rev/mins, determine terminal point with the gas-chromatography tracking reaction process.
Embodiment 2:
Containing the orthodichlorobenzene of 5% 4 chloro pyridine and 20% sodium hydroxide solution and molecular weight and be 200 polyoxyethylene glycol adds in the same reactor, oil phase and water volume ratio were controlled at 1: 5, catalyst levels is 2% of oil phase and a water gross weight, 120 ℃ of reactions down, and stir with 200 rev/mins, determine terminal point with the gas-chromatography tracking reaction process.
Embodiment 3:
Containing the oil of mirbane of 1% 4 chloro pyridine and 10% sodium hydroxide solution and molecular weight and be 800 polyoxyethylene glycol adds in the same reactor, oil phase and water volume ratio were controlled at 1: 0.5, catalyst levels is 0.3% of oil phase and a water gross weight, 40 ℃ of reactions down, and stir with 40 rev/mins, determine terminal point with the gas-chromatography tracking reaction process.
Embodiment 4:
Containing the orthodichlorobenzene of 10% 4 chloro pyridine and 50% potassium hydroxide solution and molecular weight and be 400 polyoxyethylene glycol adds in the same reactor, oil phase and water volume ratio were controlled at 1: 2, catalyst levels is 1% of oil phase and a water gross weight, 60 ℃ of reactions down, and stir with 100 rev/mins, determine terminal point with the gas-chromatography tracking reaction process.
Embodiment 5:
Containing the dimethylbenzene of 7% 4 chloro pyridine and 30% potassium hydroxide solution and molecular weight and be 600 polyoxyethylene glycol adds in the same reactor, oil phase and water volume ratio were controlled at 1: 0.5, catalyst levels is 0.8% of oil phase and a water gross weight, 70 ℃ of reactions down, and stir with 150 rev/mins, determine terminal point with the gas-chromatography tracking reaction process.
Embodiment 6:
Containing the orthodichlorobenzene of 20% 4 chloro pyridine and 10% potassium hydroxide solution and molecular weight and be 800 polyoxyethylene glycol adds in the same reactor, oil phase and water volume ratio were controlled at 1: 10, catalyst levels is 0.1% of oil phase and a water gross weight, 140 ℃ of reactions down, and stir with 80 rev/mins, determine terminal point with the gas-chromatography tracking reaction process.
Embodiment 7:
Containing the tetramethylene sulfone of 6% 4 chloro pyridine and 40% sodium hydroxide solution and molecular weight and be 1000 polyoxyethylene glycol adds in the same reactor, oil phase and water volume ratio were controlled at 1: 1, catalyst levels is 1.2% of oil phase and a water gross weight, 80 ℃ of reactions down, and stir with 200 rev/mins, determine terminal point with the gas-chromatography tracking reaction process.
Claims (9)
1, the treatment process of 4 chloro pyridine in the solvent, described solvent is Chlorpyrifos 94 intermediate trichloro pyridyl sodium alcoholate salt or sylvite production solvent, the solvent that it is characterized in that containing the by product 4 chloro pyridine reacts under the effect of phase-transfer catalyst with sodium hydroxide or potassium hydroxide aqueous solution and is converted into trichloro pyridyl sodium alcoholate salt or sylvite, and described phase-transfer catalyst adopts low molecular poly.
2, treatment process according to claim 1, the molecular weight that it is characterized in that described low molecular poly is 200～1000.
3, treatment process according to claim 2 is characterized in that described phase-transfer catalyst is PEG-200, PEG-400, PEG-600 or PEG-800.
4, treatment process according to claim 2, the usage quantity that it is characterized in that described catalyzer is 0.1～2% of a material gross weight.
5, treatment process according to claim 1, the mass concentration that it is characterized in that described sodium hydroxide or potassium hydroxide aqueous solution is 10～50%.
6, treatment process according to claim 1 is characterized in that describedly containing the solvent of by product 4 chloro pyridine and the volume ratio that feeds intake of sodium hydroxide or potassium hydroxide aqueous solution is 1: 0.1～10.
7, treatment process according to claim 1 is characterized in that temperature of reaction is 20～140 ℃.
8, treatment process according to claim 1 is characterized in that reacting and under agitation carries out, and mixing speed is 20～200 rev/mins.
9, treatment process according to claim 1 is characterized in that the described solvent that contains the by product 4 chloro pyridine, and solvent wherein is orthodichlorobenzene, oil of mirbane, dimethylbenzene or tetramethylene sulfone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100455012A CN100532360C (en) | 2005-12-03 | 2005-12-03 | Method for treating 4 chloro pyridine in solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100455012A CN100532360C (en) | 2005-12-03 | 2005-12-03 | Method for treating 4 chloro pyridine in solvent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1978429A true CN1978429A (en) | 2007-06-13 |
| CN100532360C CN100532360C (en) | 2009-08-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100455012A Active CN100532360C (en) | 2005-12-03 | 2005-12-03 | Method for treating 4 chloro pyridine in solvent |
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| Country | Link |
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| CN (1) | CN100532360C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941940A (en) * | 2010-07-27 | 2011-01-12 | 山西康得利精细化工有限公司 | 3,5,6-trichloropyridin-2-ol sodium high-boiling solid waste conversion method |
| CN106279005A (en) * | 2016-08-17 | 2017-01-04 | 重庆华歌生物化学有限公司 | A kind of method reclaiming trichloro pyridyl sodium alcoholate from trichloro pyridyl sodium alcoholate production waste material |
| CN107216351A (en) * | 2017-08-09 | 2017-09-29 | 重庆华歌生物化学有限公司 | Chlopyrifos and preparation method thereof |
| CN108409645A (en) * | 2018-06-20 | 2018-08-17 | 德州绿霸精细化工有限公司 | A kind of preparation method of high-purity 3,5,6- trichloropyridines -2- sodium alkoxides |
-
2005
- 2005-12-03 CN CNB2005100455012A patent/CN100532360C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941940A (en) * | 2010-07-27 | 2011-01-12 | 山西康得利精细化工有限公司 | 3,5,6-trichloropyridin-2-ol sodium high-boiling solid waste conversion method |
| CN101941940B (en) * | 2010-07-27 | 2012-07-04 | 山西康得利精细化工有限公司 | 3,5,6-trichloropyridin-2-ol sodium high-boiling solid waste conversion method |
| CN106279005A (en) * | 2016-08-17 | 2017-01-04 | 重庆华歌生物化学有限公司 | A kind of method reclaiming trichloro pyridyl sodium alcoholate from trichloro pyridyl sodium alcoholate production waste material |
| CN107216351A (en) * | 2017-08-09 | 2017-09-29 | 重庆华歌生物化学有限公司 | Chlopyrifos and preparation method thereof |
| CN108409645A (en) * | 2018-06-20 | 2018-08-17 | 德州绿霸精细化工有限公司 | A kind of preparation method of high-purity 3,5,6- trichloropyridines -2- sodium alkoxides |
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| Publication number | Publication date |
|---|---|
| CN100532360C (en) | 2009-08-26 |
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