CN110372581A - A method of preparing 2-(3- 4-trifluoromethylphenopendant) -6- trichloromethyl pyridine - Google Patents
A method of preparing 2-(3- 4-trifluoromethylphenopendant) -6- trichloromethyl pyridine Download PDFInfo
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- CN110372581A CN110372581A CN201910762221.5A CN201910762221A CN110372581A CN 110372581 A CN110372581 A CN 110372581A CN 201910762221 A CN201910762221 A CN 201910762221A CN 110372581 A CN110372581 A CN 110372581A
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- tower
- toluene
- trifluoromethylphenopendant
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- trichloromethyl pyridine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives thereof
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Abstract
A method of preparing 2-(3- 4-trifluoromethylphenopendant) -6- trichloromethyl pyridine, include the following steps: 1) successively to put into m-trifluoromethyl phenol, N-serve, alkali, dimethyl sulfoxide and toluene into dissolution kettle, agitating and heating dissolution, material is discharged from bottom, preheats into preheater;2) thermal material continuously enters reaction dehydrating tower, and by the packed tower rectifying and dewatering of upper end, the plate column of m-trifluoromethyl phenol metal salt and N-serve in lower part reacts;3) reaction product enters distillation still from tower bottom and continues to react, and until the reaction is complete, reaction system is then continuously discharged;4) after the mixture precipitation that distillation still comes out, toluene is added, alkali cleaning, washing is successively carried out, evaporates toluene, obtain target product.Present invention continuous operation, production capacity are big;The moisture that dereaction generates can be removed with highly efficient distilling, conversion ratio is higher, and yield is higher.
Description
Technical field
The present invention relates to technical field of chemistry, specifically a kind of preparation 2-(3- 4-trifluoromethylphenopendant) -6- trichloromethyl
The continuous reaction apparatus and method of pyridine.
Background technique
2-(3- 4-trifluoromethylphenopendant) -6- trichloromethyl pyridine is to prepare herbicide fluorine pyrrole acyl grass amine
(picolinafen) important intermediate.Fluorine metazachlor is the acetamide-group herbicides of BASF AG's exploitation, belongs to carotenoid
Biosynthesis inhibitor, adopted name picolinafen, CAS accession number are [137641-05-5].
2-(3- 4-trifluoromethylphenopendant is prepared by m-trifluoromethyl phenol and N-serve) -6- trichlorine
The reaction equation of picoline is as follows:
Document CN107382847A carries out azeotropic dehydration using toluene: by m-trifluoromethyl phenol, sodium hydroxide, dimethyl sulfoxide
Azeotropic dehydration is carried out using Dean and Stark water segregator with toluene, dehydration finishes, distills toluene, be warming up to 150 DEG C,
Insulation reaction, DMSO is fallen in vacuum distillation after reaction;Be dissolved in water inorganic salts, is extracted with toluene, is washed with water;Vacuum distillation
Fall toluene, obtain 2-(3- 4-trifluoromethylphenopendant) -6- trichloromethyl pyridine;
The defects of above method only rests on lab scale level, there are no industrialization report, and there are also reaction time length, intermittently operated.
Summary of the invention
To solve the above-mentioned problems, 2-(3- 4-trifluoromethylphenopendant is prepared the invention discloses a kind of) -6- trichloromethyl
The method of pyridine.
The technical solution of the present invention is as follows: a kind of prepare 2-(3- 4-trifluoromethylphenopendant) method of -6- trichloromethyl pyridine,
Include the following steps:
1) m-trifluoromethyl phenol, N-serve, alkali, dimethyl sulfoxide and first are successively put into dissolution kettle
Benzene, agitating and heating dissolution, keeps the temperature at 60~80 DEG C, and material is discharged from bottom, by delivery pump, is preheated to 100 into preheater
~120 DEG C;
2) thermal material continuously enters reaction dehydrating tower, and by the packed tower rectifying and dewatering of upper end, the azeotropic mixture of toluene and water is from tower
Top comes out, and condenses by condenser, and into the water segregator below condenser, lower water separates discharge reaction system in water segregator
System, upper toluene enter tower from overhead reflux, and tower top temperature is 85~105 DEG C, m-trifluoromethyl phenol metal salt and the chloro- 6- tri- of 2-
Plate column of the chloromethylpyridine in lower part reacts;
3) m-trifluoromethyl phenol metal salt and N-serve enter distillation still from tower bottom and continue to occur instead
It answers, controls 140~160 DEG C of pot temperature, material stop was at distillation still 2~5 hours, until the reaction is complete, then continuous to arrange
Reaction system out;
4) after the mixture precipitation that distillation still comes out, toluene is added, alkali cleaning, washing is successively carried out, evaporates toluene, obtain 2-
(3- 4-trifluoromethylphenopendant) -6- trichloromethyl pyridine.
Further, alkali is potassium hydroxide, sodium hydroxide, potassium carbonate or sodium carbonate, m-trifluoromethyl phenol: the chloro- 6- of 2-
Trichloromethyl pyridine: alkali: dimethyl sulfoxide: toluene=1:1~3:1~1.2:12~15:2~5.
Further, the filler for reacting the packed tower on dehydrating tower top includes: dumped packing, structured packing, packed height
For 6~11 pieces of theoretical plates.
Preferably High Efficient Standard Packing.
Further, the plate column for reacting dehydrating tower lower part includes: valve tower, bubble column, ligulate tower, sieve-plate tower, column plate
Number is 3~6 pieces of theoretical plates.
Preferably valve tower.
Usefulness of the present invention: it can operate continuously, production capacity is big.The water that dereaction generates can be removed with highly efficient distilling
Point, conversion ratio is higher, and yield is higher.
Detailed description of the invention
Fig. 1 is the structural diagram of the present invention;
Wherein: 1, dissolution kettle, 2, delivery pump, 3, preheater, 4, reaction dehydrating tower, 5, condenser, 6, water segregator, 7, distillation still.
Specific embodiment
As shown in Figure 1, a kind of prepare 2-(3- 4-trifluoromethylphenopendant) continuous reaction apparatus of -6- trichloromethyl pyridine,
Including dissolution kettle 1, delivery pump 2, preheater 3, reaction dehydrating tower 4, condenser 5, water segregator 6 and distillation still 7, dissolution kettle 1 is successively
It is connected by delivery pump 2, preheater 3 with reaction dehydrating tower 4, reacts and pass through 6 one end of condenser 5 and water segregator at the top of dehydrating tower 4
It is connected, 6 other end of water segregator is connected with reaction 4 top of dehydrating tower, and reaction 4 bottom of dehydrating tower is connected with 7 one end of destilling tower, distills
7 other end of tower is connected with reaction 4 lower part of dehydrating tower.
Reaction 4 upper part of dehydrating tower is packed tower, and packed tower is used for rectifying and dewatering;Reaction dehydrating tower end portion be
Plate column, plate column are used for reactor.
Embodiment 1
The top for reacting dehydrating tower uses stainless steel wire corrugated wire gauze packing, and packed height is 8 pieces of theoretical plates;It reacts under dehydrating tower
Portion is valve plate, the number of plates 5.
Into dissolution kettle according to m-trifluoromethyl phenol: N-serve: sodium hydroxide: dimethyl sulfoxide:
Toluene=1:2:1:15:4 ratio successively puts into m-trifluoromethyl phenol, N-serve, sodium hydroxide, diformazan
Base sulfoxide and toluene, agitating and heating dissolution, keep the temperature at 70 DEG C, and material is discharged from bottom, by delivery pump, preheat into preheater
To 106 DEG C;Thermal material continuously enters reaction dehydrating tower, by the packed tower rectifying and dewatering of upper end, the azeotropic mixture of toluene and water from
Top of tower comes out, and condenses by condenser, and into the water segregator below condenser, lower water separates discharge reaction system, upper layer
Toluene enters tower from overhead reflux, and tower top temperature is 105 DEG C, and m-trifluoromethyl phenol sodium salt and N-serve exist
The plate column of lower part reacts;M-trifluoromethyl phenol sodium salt and N-serve enter distillation from tower bottom
Kettle continues to react, and controls 145 DEG C of pot temperature, material stop until the reaction is complete, then connected at distillation still 2 hours
Continuous discharge reaction system.
After the mixture precipitation that distillation still comes out, toluene is added, alkali cleaning, washing is successively carried out, evaporates toluene, obtain
2-(3- 4-trifluoromethylphenopendant) -6- trichloromethyl pyridine, yield 95%.
Embodiment 2
The top for reacting dehydrating tower uses stainless steel wire corrugated wire gauze packing, and packed height is 7 pieces of theoretical plates;It reacts under dehydrating tower
Portion is valve plate, the number of plates 5.
Into dissolution kettle according to m-trifluoromethyl phenol: N-serve: sodium hydroxide: dimethyl sulfoxide:
Toluene=1:1.5:1:13:3 ratio successively puts into m-trifluoromethyl phenol, N-serve, sodium hydroxide, two
Methyl sulfoxide and toluene, agitating and heating dissolution, keep the temperature at 65 DEG C, and material is discharged from bottom, pre- into preheater by delivery pump
Heat is to 100 DEG C;Thermal material continuously enters reaction dehydrating tower, passes through the packed tower rectifying and dewatering of upper end, the azeotropic mixture of toluene and water
It comes out from top of tower, is condensed by condenser, into the water segregator below condenser, lower water separates discharge reaction system, on
Layer toluene enters tower from overhead reflux, and tower top temperature is 98 DEG C, and m-trifluoromethyl phenol sodium salt and N-serve exist
The plate column of lower part reacts;M-trifluoromethyl phenol sodium salt and N-serve enter distillation from tower bottom
Kettle continues to react, and controls 148 DEG C of pot temperature, material stop until the reaction is complete, then connected at distillation still 4 hours
Continuous discharge reaction system.
After the mixture precipitation that distillation still comes out, toluene is added, alkali cleaning, washing is successively carried out, evaporates toluene, obtain
2-(3- 4-trifluoromethylphenopendant) -6- trichloromethyl pyridine, yield 96%.
Embodiment 3
The top for reacting dehydrating tower uses stainless steel wire corrugated wire gauze packing, and packed height is 8 pieces of theoretical plates;It reacts under dehydrating tower
Portion is sieve plate column plate, the number of plates 5.
Into dissolution kettle according to m-trifluoromethyl phenol: N-serve: sodium hydroxide: dimethyl sulfoxide:
Toluene=1:2.5:1:14:5 ratio successively puts into m-trifluoromethyl phenol, N-serve, sodium hydroxide, two
Methyl sulfoxide and toluene, agitating and heating dissolution, keep the temperature at 78 DEG C, and material is discharged from bottom, pre- into preheater by delivery pump
Heat is to 108 DEG C;Thermal material continuously enters reaction dehydrating tower, passes through the packed tower rectifying and dewatering of upper end, the azeotropic mixture of toluene and water
It comes out from top of tower, is condensed by condenser, into the water segregator below condenser, lower water separates discharge reaction system, on
Layer toluene enters tower from overhead reflux, and tower top temperature is 99 DEG C, and m-trifluoromethyl phenol sodium salt and N-serve exist
The plate column of lower part reacts;M-trifluoromethyl phenol sodium salt and N-serve enter distillation from tower bottom
Kettle continues to react, and controls 150 DEG C of pot temperature, material stop until the reaction is complete, then connected at distillation still 5 hours
Continuous discharge reaction system.
After the mixture precipitation that distillation still comes out, toluene is added, alkali cleaning, washing is successively carried out, evaporates toluene, obtain
2-(3- 4-trifluoromethylphenopendant) -6- trichloromethyl pyridine, yield 93%.
Embodiment 4
The top for reacting dehydrating tower uses stainless steel wire corrugated wire gauze packing, and packed height is 10 pieces of theoretical plates;React dehydrating tower
Lower part is valve plate, the number of plates 5.
Into dissolution kettle according to m-trifluoromethyl phenol: N-serve: sodium hydroxide: dimethyl sulfoxide:
Toluene=1:2:1:13:4 ratio successively puts into m-trifluoromethyl phenol, N-serve, sodium hydroxide, diformazan
Base sulfoxide and toluene, agitating and heating dissolution, keep the temperature at 78 DEG C, and material is discharged from bottom, by delivery pump, preheat into preheater
To 108 DEG C;Thermal material continuously enters reaction dehydrating tower, by the packed tower rectifying and dewatering of upper end, the azeotropic mixture of toluene and water from
Top of tower comes out, and condenses by condenser, and into the water segregator below condenser, lower water separates discharge reaction system, upper layer
Toluene enters tower from overhead reflux, and tower top temperature is 88 DEG C, and m-trifluoromethyl phenol sodium salt and N-serve are under
The plate column in portion reacts;M-trifluoromethyl phenol sodium salt and N-serve enter distillation still from tower bottom
Continue to react, controls 152 DEG C of pot temperature, material stop was at distillation still 5 hours, until the reaction is complete, then continuously
Reaction system is discharged.
After the mixture precipitation that distillation still comes out, toluene is added, alkali cleaning, washing is successively carried out, evaporates toluene, obtain
2-(3- 4-trifluoromethylphenopendant) -6- trichloromethyl pyridine, yield 94%.
Embodiment 5
The top for reacting dehydrating tower uses stainless steel wire corrugated wire gauze packing, and packed height is 9 pieces of theoretical plates;It reacts under dehydrating tower
Portion is valve plate, the number of plates 5.
Into dissolution kettle according to m-trifluoromethyl phenol: N-serve: sodium hydroxide: dimethyl sulfoxide:
Toluene=1:2.5:1.05:15:4 ratio successively puts into m-trifluoromethyl phenol, N-serve, hydroxide
Sodium, dimethyl sulfoxide and toluene, agitating and heating dissolution, keep the temperature at 68 DEG C, and material is discharged from bottom, by delivery pump, into pre-
Hot device is preheated to 100 DEG C;Thermal material continuously enters reaction dehydrating tower, by the packed tower rectifying and dewatering of upper end, toluene and water
Azeotropic mixture comes out from top of tower, condenses by condenser, and into the water segregator below condenser, lower water separates discharge reaction system
System, upper toluene enter tower from overhead reflux, and tower top temperature is 105 DEG C, m-trifluoromethyl phenol sodium salt and the chloro- 6- trichloromethyl of 2-
Plate column of the pyridine in lower part reacts;M-trifluoromethyl phenol sodium salt and N-serve from tower bottom into
Entering distillation still to continue to react, controls 150 DEG C of pot temperature, material stop was at distillation still 5 hours, until the reaction is complete,
Then reaction system is continuously discharged.
After the mixture precipitation that distillation still comes out, toluene is added, alkali cleaning, washing is successively carried out, evaporates toluene, obtain
2-(3- 4-trifluoromethylphenopendant) -6- trichloromethyl pyridine, yield 96%.
Claims (6)
1. a kind of prepare 2-(3- 4-trifluoromethylphenopendant) method of -6- trichloromethyl pyridine, which is characterized in that including following step
It is rapid:
1) m-trifluoromethyl phenol, N-serve, alkali, dimethyl sulfoxide and first are successively put into dissolution kettle
Benzene, agitating and heating dissolution, keeps the temperature at 60~80 DEG C, and material is discharged from bottom, by delivery pump, is preheated to 100 into preheater
~120 DEG C;
2) thermal material continuously enters reaction dehydrating tower, and by the packed tower rectifying and dewatering of upper end, the azeotropic mixture of toluene and water is from tower
Top comes out, and condenses by condenser, and into the water segregator below condenser, lower water separates discharge reaction system in water segregator
System, upper toluene enter tower from overhead reflux, and tower top temperature is 85~105 DEG C, m-trifluoromethyl phenol metal salt and the chloro- 6- tri- of 2-
Plate column of the chloromethylpyridine in lower part reacts;
3) m-trifluoromethyl phenol metal salt and N-serve enter distillation still from tower bottom and continue to occur instead
It answers, controls 140~160 DEG C of pot temperature, material stop was at distillation still 2~5 hours, until the reaction is complete, then continuous to arrange
Reaction system out;
4) after the mixture precipitation that distillation still comes out, toluene is added, alkali cleaning, washing is successively carried out, evaporates toluene, obtain 2-
(3- 4-trifluoromethylphenopendant) -6- trichloromethyl pyridine.
2. a kind of 2-(3- 4-trifluoromethylphenopendant is prepared according to claim 1) method of -6- trichloromethyl pyridine,
Be characterized in that: the alkali is potassium hydroxide, sodium hydroxide, potassium carbonate or sodium carbonate, m-trifluoromethyl phenol: the chloro- 6- trichlorine of 2-
Picoline: alkali: dimethyl sulfoxide: toluene=1:1~3:1~1.2:12~15:2~5.
3. a kind of 2-(3- 4-trifluoromethylphenopendant is prepared according to claim 1) method of -6- trichloromethyl pyridine,
It is characterized in that: the plate column of the reaction dehydrating tower lower part are as follows: valve tower, bubble column, ligulate tower, sieve-plate tower, preferably float valve
Tower;The number of plates is 3~6 pieces of theoretical plates.
4. a kind of 2-(3- 4-trifluoromethylphenopendant is prepared according to claim 5) method of -6- trichloromethyl pyridine,
Be characterized in that: the plate column is preferably valve tower.
5. a kind of 2-(3- 4-trifluoromethylphenopendant is prepared according to claim 1) method of -6- trichloromethyl pyridine,
Be characterized in that: the filler of the packed tower on the reaction dehydrating tower top includes: dumped packing, structured packing, and packed height is 6~
11 pieces of theoretical plates.
6. a kind of 2-(3- 4-trifluoromethylphenopendant is prepared according to claim 3) method of -6- trichloromethyl pyridine,
Be characterized in that: the filler is preferably High Efficient Standard Packing.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102993091A (en) * | 2012-11-28 | 2013-03-27 | 张家港市大伟助剂有限公司 | Preparation method of 5-amino-2-(4-amino phenoxy)-pyridine |
CN105085388A (en) * | 2015-09-06 | 2015-11-25 | 合肥华方医药科技有限公司 | Synthesis method for sorafenib intermediate |
CN107266358A (en) * | 2017-06-21 | 2017-10-20 | 南通施壮化工有限公司 | A kind of Nylar active compound synthetic method |
CN107382847A (en) * | 2017-07-21 | 2017-11-24 | 南通嘉禾化工有限公司 | A kind of synthetic method of fluorine metazachlor |
-
2019
- 2019-08-19 CN CN201910762221.5A patent/CN110372581A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102993091A (en) * | 2012-11-28 | 2013-03-27 | 张家港市大伟助剂有限公司 | Preparation method of 5-amino-2-(4-amino phenoxy)-pyridine |
CN105085388A (en) * | 2015-09-06 | 2015-11-25 | 合肥华方医药科技有限公司 | Synthesis method for sorafenib intermediate |
CN107266358A (en) * | 2017-06-21 | 2017-10-20 | 南通施壮化工有限公司 | A kind of Nylar active compound synthetic method |
CN107382847A (en) * | 2017-07-21 | 2017-11-24 | 南通嘉禾化工有限公司 | A kind of synthetic method of fluorine metazachlor |
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Application publication date: 20191025 |