CN106146393A - Prepare 3,4,6-trichloropyridine-2-formic acid and the method for corresponding esters thereof - Google Patents
Prepare 3,4,6-trichloropyridine-2-formic acid and the method for corresponding esters thereof Download PDFInfo
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- CN106146393A CN106146393A CN201510176326.4A CN201510176326A CN106146393A CN 106146393 A CN106146393 A CN 106146393A CN 201510176326 A CN201510176326 A CN 201510176326A CN 106146393 A CN106146393 A CN 106146393A
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- formic acid
- trichloropyridine
- bis
- aminopyridine
- chlorine
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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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
-
- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
Abstract
The invention belongs to chemical production field, be specifically related to prepare 3,4,6-trichloropyridine-2-formic acid and the methods of corresponding esters thereof.The technical problem to be solved in the present invention is the most methodical synthetic route length, yield difficulty low, isolated and purified, cost height, it is difficult to meet the needs of industrialized great production.The present invention solves the scheme of above-mentioned technical problem and is to provide one and prepares 3,4,6-trichloropyridine-2-formic acid and the method for corresponding esters thereof, the method is: with 2, and 6-bis-chlorine-3-aminopyridine-2-formic acid is initiation material, react under the effect of catalyst Cu-lyt. with hydrochloric acid, sodium nitrite and obtain 3,4,6-trichloropyridine-2-formic acid, obtain 3 with alcohol esterification the most again, 4,6-trichloropyridine-2-formic acid esters.Preparation 3,4, the 6-trichloropyridine-2-formic acid of present invention offer and the method for corresponding esters thereof, easy and simple to handle, reactions steps is short, and yield is high, is suitable to industrialized production.
Description
Technical field
The invention belongs to chemical production field, be specifically related to prepare 3,4,6-trichloropyridine-2-formic acid and the methods of corresponding esters thereof.
Background technology
3,4,6-trichloropyridine-2-formic acid and corresponding ester thereof are a kind of useful fine-chemical intermediates, and it is in terms of synthetic herbicide
Purposes by disclosed in patent WO2010149956.This patent is also disclosed following synthetic route simultaneously:
The method shortcoming is that synthetic route is long, yield low (document report not higher than 30%), and isolated and purified difficulty also to use
The reagent that trifluoroacetic anhydride etc. are expensive, it is difficult to meet the needs of industrialized great production.
Summary of the invention
The technical problem to be solved in the present invention is the most methodical synthetic route length, yield difficulty low, isolated and purified, cost height,
It is difficult to meet the needs of industrialized great production.
The present invention solves the scheme of above-mentioned technical problem and is to provide a kind of method preparing 3,4,6-trichloropyridine-2-formic acid.
The method of above-mentioned preparation 3,4,6-trichloropyridine-2-formic acid, comprises the following steps: with 2,6-bis-chlorine-3-aminopyridine-2-formic acid
For initiation material, react under the effect of catalyst Cu-lyt. with hydrochloric acid, sodium nitrite and obtain 3,4,6-trichloropyridine-2-formic acid.
The operating procedure of the method for the above-mentioned 3,4,6-of preparation trichloropyridine-2-formic acid is: add 2,6-bis-chloro-3-amino pyrrole in hydrochloric acid
Pyridine-2-formic acid and Cu-lyt., then drip the saturated aqueous solution of sodium nitrite, reacts 1～3h after dropping, then filter,
After drying, obtain 3,4,6-trichloropyridine-2-formic acid.
Wherein, in the method for above-mentioned preparation 3,4,6-trichloropyridine-2-formic acid, described hydrochloric acid and 2,6-bis-chlorine-3-aminopyridine-2-first
The mol ratio of acid is 2～4 1.
Wherein, in the method for above-mentioned preparation 3,4,6-trichloropyridine-2-formic acid, described sodium nitrite and 2,6-bis-chlorine-3-aminopyridine-2-
The mol ratio of formic acid is 1.5～4 1.
Wherein, in the method for above-mentioned preparation 3,4,6-trichloropyridine-2-formic acid, described Cu-lyt. and 2,6-bis-chlorine-3-aminopyridine-2-
The mol ratio of formic acid is 0.15～0.2 1.
Wherein, in the method for above-mentioned preparation 3,4,6-trichloropyridine-2-formic acid, described sodium nitrite dropping temperature and reaction temperature are equal
For-10 DEG C～10 DEG C.
The method that present invention also offers preparation 3,4,6-trichloropyridine-2-formic acid esters, comprises the following steps:
A, in hydrochloric acid add 2,6-bis-chlorine-3-aminopyridine-2-formic acid and Cu-lyt., then drip the saturated water-soluble of sodium nitrite
Liquid, reacts 1～3h, after then filtering, drying, obtains 3,4,6-trichloropyridine-2-formic acid after dropping；
B, by 3,4,6-trichloropyridine-2-formic acid and alcohol, catalyst back flow reaction 4～18h, after completion of the reaction, remove alcohol, obtain
Crude product；
C, crude product are heated to reflux in the alcohol identical with step b that its triploid is long-pending, are cooled to 0 DEG C, are filtrated to get 3,4,6-
Trichloropyridine-2-formic acid esters.
Wherein, in the method for above-mentioned preparation 3,4,6-trichloropyridine-2-formic acid and corresponding esters thereof, hydrochloric acid described in step a and 2,6-dichloro
The mol ratio of-3-aminopyridine-2-formic acid is 2～4 1.
Wherein, in step a of said method, described sodium nitrite and 2, the mol ratio of 6-bis-chlorine-3-aminopyridine-2-formic acid be 1.5～
41.
Wherein, in step a of said method, described Cu-lyt. and 2, the mol ratio of 6-bis-chlorine-3-aminopyridine-2-formic acid is
0.15～0.2 1.
Wherein, in step a of said method, described sodium nitrite dropping temperature and reaction temperature are-10 DEG C～10 DEG C.
Wherein, in step b of said method, described alcohol be ROH, R be C1～C4 alkyl.
Wherein, in step b of said method, described catalyst is concentrated sulphuric acid or thionyl chloride.
Wherein, in step b of said method, described 3,4,6-trichloropyridine-2-formic acid, the mol ratio of alcohol are 0.05～0.2 1.
Wherein, in step b of said method, the consumption of described catalyst be 3,4,6-trichloropyridine-2-formic acid quality 25%～
30%.
The synthetic route of the method for the above-mentioned 3,4,6-of preparation trichloropyridine-2-formic acid esters is:
Wherein, R is C1～C4 alkyl.
Preparation 3,4, the 6-trichloropyridine-2-formic acid of present invention offer and the method for corresponding esters thereof, easy and simple to handle, reactions steps is short,
And yield is high, be suitable to industrialized production.
Detailed description of the invention
The operating procedure of the method preparing 3,4,6-trichloropyridine-2-formic acid and corresponding esters thereof is:
A, in hydrochloric acid add 2,6-bis-chlorine-3-aminopyridine-2-formic acid and Cu-lyt., then drip the saturated water-soluble of sodium nitrite
Liquid, reacts 1～3h, after then filtering, drying, obtains 3,4,6-trichloropyridine-2-formic acid after dropping；
B, by 3,4,6-trichloropyridine-2-formic acid and alcohol, catalyst back flow reaction 4～18h, after completion of the reaction, remove alcohol, obtain
Crude product；
C, crude product are heated to reflux in the alcohol identical with step b that its triploid is long-pending, are cooled to 0 DEG C, are filtrated to get 3,4,6-
Trichloropyridine-2-formic acid esters.
Wherein, in the method for above-mentioned preparation 3,4,6-trichloropyridine-2-formic acid and corresponding esters thereof, hydrochloric acid described in step a and 2,6-dichloro
The mol ratio of-3-aminopyridine-2-formic acid is 2～4 1.
Wherein, in step a of said method, described sodium nitrite and 2, the mol ratio of 6-bis-chlorine-3-aminopyridine-2-formic acid be 1.5～
41.
Wherein, in step a of said method, described Cu-lyt. and 2, the mol ratio of 6-bis-chlorine-3-aminopyridine-2-formic acid is
0.15～0.2 1.
Wherein, in step a of said method, the temperature of described dropping sodium nitrite and reaction is-10 DEG C～10 DEG C.
Wherein, in step b of said method, described alcohol be ROH, R be C1～C4 alkyl.
Wherein, in step b of said method, described catalyst is concentrated sulphuric acid or thionyl chloride.
Wherein, in step b of said method, described 3,4,6-trichloropyridine-2-formic acid, the mol ratio of alcohol are 0.05～0.2 1.
Wherein, in step b of said method, the consumption of described catalyst be 3,4,6-trichloropyridine-2-formic acid weight 25%～
30%.
According to sandmeyer principle, inventor's original adoption following route synthesis 3,4,6-trichloropyridine-2-formic acid:
But the method is when synthesizing 3,4,6-trichloropyridine-2-formic acid, and yield is the lowest, and by-product is many.
Later by substantial amounts of experimentation, inventor creatively by 2,6-bis-chlorine-3-aminopyridine-2-formic acid and hydrochloric acid, nitrous
Acid sodium and catalyst Cu-lyt. react simultaneously, and the receipts of 3,4,6-trichloropyridine-2-formic acid are unexpectedly greatly improved
Rate (can improve to more than 90%).
The preparation of embodiment 1 3,4,6-trichloropyridine-2-formic acid
500mL four-hole bottle adds hydrochloric acid 90g (36% concentrated hydrochloric acid 60g+ water 30g), then adds 2,6-bis-chloro-3-amino pyrrole
Pyridine-2-formic acid 10g (0.0485mol), drips the saturated aqueous solution of sodium nitrite 4.0g (0.0580mol), drips under ice bath
Stirring reaction 2h after Biing；It is subsequently adding Cu-lyt. 0.5g (0.0078mol), is slowly heated to 80 DEG C, after insulation reaction 3h,
It is down to room temperature, extracts by ethyl acetate (120mL × 3), concentrating under reduced pressure solvent, after recrystallization, obtain 3,4,6-trichloropyridines
-2-formic acid, yield 33%.
The preparation of embodiment 2 3,4,6-trichloropyridine-2-formic acid
500mL four-hole bottle adds hydrochloric acid 90g (36% concentrated hydrochloric acid 60g+ water 30g), then adds 2,6-bis-chloro-3-amino pyrrole
Pyridine-2-formic acid 10g (0.0485mol) and Cu-lyt. 0.5g (0.0078mol), drip sodium nitrite 4.0g (0.0580mol) under ice bath
Saturated aqueous solution, after dropping stirring reaction 2h, be then filtrated to get wet product, purity 96%, after drying, obtain 3,4,6-
Trichloropyridine-2-formic acid 10g, yield 91.7%.
The screening experiment of embodiment 3 Cu-lyt. consumption
Use reaction condition same as in Example 2, the selection result of Cu-lyt. consumption is shown in Table 1.
The selection result of table 1 Cu-lyt. consumption
| Experiment sequence number | Cu-lyt. consumption/eq | Yield/% |
| 1 | 0 | 30 |
| 2 | 0.05 | 50 |
| 3 | 0.10 | 75 |
| 4 | 0.15 | 90 |
| 5 | 0.20 | 91 |
Data according to table 1 can be seen that, when the consumption of catalyst Cu-lyt. is increased to 0.15 equivalent by 0, yield significantly improves,
After being further added by catalyst amount, yield does not significantly improve, therefore screening optimum catalyst consumption is 0.15 equivalent.
The preparation of embodiment 4 3,4,6-trichloropyridine-2-methyl formate
100mL reaction bulb adds 3,4,6-trichloropyridines-2-formic acid 10g (0.0444mol), adds methanol 20g and dense sulfur the most again
Acid (catalyst) 1g, temperature rising reflux reaction 16h, the most first decompression steams methanol, then regathers 155-160 DEG C
/-0.098MPa fraction.Above-mentioned fraction is heated to reflux with three times of methanol, is cooled to 0 DEG C, and decompression sucking filtration obtains white solid 3,4,6-
Trichloropyridine-2-methyl formate.After sucking filtration mother solution is spin-dried for, again with methanol is heated to reflux, and then cools down, and sucking filtration obtains white solid,
Merge white solid, be 9.5g after drying, yield 90%.mp 60-63℃；1H NMR (400MHz, CDCl3) δ 7.58 (s, 1H),
4.01(s,3H)ppm。
The embodiment 5 screening experiment to catalyst amount
Use reaction condition the same as in Example 4, to catalyst amount (with 3, the mass ratio of 4,6-trichloropyridine-2-formic acid)
Screening be shown in Table 2.
The screening of table 2 catalyst amount (with the mass ratio of 3,4,6-trichloropyridine-2-formic acid)
| Experiment sequence number | Catalyst amount/% | Yield/% |
| 1 | 5.0 | 30 |
| 2 | 10.0 | 35 |
| 3 | 15.0 | 60 |
| 4 | 20.0 | 85 |
| 5 | 25.0 | 90 |
| 6 | 30.0 | 90 |
Data according to table 2 can be seen that, along with the increase of catalyst amount, yield significantly improves, and when catalyst amount arrives
The when of 25%, yield reaches peak value.But after improving catalyst amount again, yield does not significantly improve, therefore the optimal catalysis of screening
Agent consumption is 25%.
The preparation of embodiment 6 3,4,6-trichloropyridine-2-methyl formate
100mL reaction bulb adds 3,4,6-trichloropyridines-2-formic acid 10g (0.0444mol), adds methanol 20g the most again, then
Dropping thionyl chloride 5.5g, temperature rising reflux reaction 5h after dropping, the most first decompression steams methanol and the chlorination of excess
Sulfoxide, then regathers 155-160 DEG C/-0.098MPa fraction.Above-mentioned fraction is heated to reflux with three times of methanol, is cooled to 0 DEG C,
Decompression sucking filtration obtains white solid 3,4,6-trichloropyridine-2-methyl formate.After sucking filtration mother solution is spin-dried for, again with methanol is heated to reflux,
Then cooling down, sucking filtration obtains white solid, and merging white solid is 9.5g, yield 90%.
The preparation of embodiment 7 3,4,6-trichloropyridine-2-Ethyl formate
Operating procedure is with embodiment 4, and difference is: changed by methanol after making ethanol, and collection condition during decompression distillation is 170-175 DEG C
/-0.098MPa.The fraction collected, with three times of alcohol heating reflux, is cooled to 0 DEG C, and the sucking filtration that reduces pressure obtains white solid 3, and 4,6-tri-
Chloropyridine-2-Ethyl formate.After sucking filtration mother solution is spin-dried for, then with alcohol heating reflux, then cooling down, sucking filtration obtains white solid,
Merge white solid, yield 90%.
The preparation of embodiment 8 3,4,6-trichloropyridine-2-propyl formate
Methanol, with embodiment 4, is changed after doing propanol by operating procedure, and collection condition during decompression distillation is 179-185 DEG C
/-0.098MPa.Being heated to reflux with three times of propanol, be cooled to 0 DEG C, decompression sucking filtration obtains white solid 3,4,6-trichloropyridine-2-first
Propyl propionate.After sucking filtration mother solution is spin-dried for, then being heated to reflux with propanol, then cool down, sucking filtration obtains white solid, merges white solid
Body, yield 90%.
Preparation 3,4, the 6-trichloropyridine-2-formic acid of present invention offer and the method for corresponding esters thereof, easy and simple to handle, reactions steps is short,
And 3, the yield of 4,6-trichloropyridine-2-formic acid is up to 91.7%, and the yield of 3,4,6-trichloropyridine-2-formic acid esters is up to 90%.
Claims (9)
1. the method preparing 3,4,6-trichloropyridine-2-formic acid, comprises the following steps: with 2, and 6-bis-chlorine-3-aminopyridine-2-formic acid is
Initiation material, reacts under the effect of catalyst Cu-lyt. with hydrochloric acid, sodium nitrite and obtains 3,4,6-trichloropyridine-2-formic acid.
The method of preparation 3,4,6-trichloropyridine-2-formic acid the most according to claim 1, it is characterised in that: operating procedure is:
In hydrochloric acid, addition 2,6-bis-chlorine-3-aminopyridine-2-formic acid and Cu-lyt., then drip the saturated aqueous solution of sodium nitrite, drips
React 1～3h after adding, after then filtering, drying, obtain 3,4,6-trichloropyridine-2-formic acid.
The method of preparation 3,4,6-trichloropyridine-2-formic acid the most according to claim 2, it is characterised in that: described hydrochloric acid with
The mol ratio of 2,6-bis-chlorine-3-aminopyridine-2-formic acid is 2～4 1.
The method of preparation 3,4,6-trichloropyridine-2-formic acid the most according to claim 2, it is characterised in that: described nitrous acid
Sodium is 1.5～4 1 with the mol ratio of 2,6-bis-chlorine-3-aminopyridine-2-formic acid.
The method of preparation 3,4,6-trichloropyridine-2-formic acid the most according to claim 2, it is characterised in that: described protochloride
Copper is 0.15～0.2 1 with the mol ratio of 2,6-bis-chlorine-3-aminopyridine-2-formic acid.
The method of preparation 3,4,6-trichloropyridine-2-formic acid the most according to claim 2, it is characterised in that: described nitrous acid
Sodium dropping temperature and reaction temperature are-10 DEG C～10 DEG C.
7. the method preparing 3,4,6-trichloropyridine-2-formic acid esters, comprises the following steps:
A, in hydrochloric acid add 2,6-bis-chlorine-3-aminopyridine-2-formic acid and Cu-lyt., then drip the saturated water-soluble of sodium nitrite
Liquid, reacts 1～3h, after then filtering, drying, obtains 3,4,6-trichloropyridine-2-formic acid after dropping；
B, by 3,4,6-trichloropyridine-2-formic acid and alcohol, catalyst back flow reaction 4～18h, after completion of the reaction, remove alcohol, obtain
Crude product；
C, crude product are heated to reflux in the alcohol identical with step b that its triploid is long-pending, are cooled to 0 DEG C, are filtrated to get 3,4,6-
Trichloropyridine-2-formic acid esters.
The method of preparation 3,4,6-trichloropyridine-2-formic acid esters the most according to claim 7, it is characterised in that: step a institute
The mol ratio stating hydrochloric acid and 2,6-bis-chlorine-3-aminopyridine-2-formic acid is 2～4 1；
Described sodium nitrite is 1.5～4 1 with the mol ratio of 2,6-bis-chlorine-3-aminopyridine-2-formic acid；
Described Cu-lyt. is 0.15～0.2 1 with the mol ratio of 2,6-bis-chlorine-3-aminopyridine-2-formic acid；
Described sodium nitrite dropping temperature and reaction temperature are-10 DEG C～10 DEG C.
The method of preparation 3,4,6-trichloropyridine-2-formic acid esters the most according to claim 7, it is characterised in that: step b institute
The alcohol stated be ROH, R be C1～C4 alkyl；
Described catalyst is any one in concentrated sulphuric acid or thionyl chloride；
Described 3,4,6-trichloropyridine-2-formic acid, the mol ratio of alcohol are 0.05～0.2 1；
The consumption of described catalyst is the 25%～30% of 3,4,6-trichloropyridine-2-formic acid quality.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1416419A (en) * | 2000-01-14 | 2003-05-07 | 美国陶氏益农公司 | 4-aminopicolinates and their use as herbicides |
| CN1923810A (en) * | 2006-09-22 | 2007-03-07 | 四川绵阳利尔化工有限公司 | Chemical synthesis method of 4-amino-3,5,6-trichloropyridine-2-formic acid |
| CN103140466A (en) * | 2010-08-04 | 2013-06-05 | 第一三共株式会社 | Process for preparing compound by novel sandmeyer-like reaction using nitroxide radical compound as reaction catalyst |
| CN103570609A (en) * | 2013-10-28 | 2014-02-12 | 南通天泽化工有限公司 | Preparation method for 2,3-dichloropyridine |
-
2015
- 2015-04-14 CN CN201510176326.4A patent/CN106146393A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1416419A (en) * | 2000-01-14 | 2003-05-07 | 美国陶氏益农公司 | 4-aminopicolinates and their use as herbicides |
| CN1923810A (en) * | 2006-09-22 | 2007-03-07 | 四川绵阳利尔化工有限公司 | Chemical synthesis method of 4-amino-3,5,6-trichloropyridine-2-formic acid |
| CN103140466A (en) * | 2010-08-04 | 2013-06-05 | 第一三共株式会社 | Process for preparing compound by novel sandmeyer-like reaction using nitroxide radical compound as reaction catalyst |
| CN103570609A (en) * | 2013-10-28 | 2014-02-12 | 南通天泽化工有限公司 | Preparation method for 2,3-dichloropyridine |
Non-Patent Citations (2)
| Title |
|---|
| 何敬文主编: "《药物合成反应》", 31 December 1995, 中国医药科技出版社 * |
| 卢新生、张志国、贾鑫: "《现代有机合成反应技术与应用研究》", 31 October 2014, 中国水利水电出版社 * |
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Application publication date: 20161123 |