CN109748865A - A kind of preparation method of the chloro- 4-aminopyridine of 2- - Google Patents
A kind of preparation method of the chloro- 4-aminopyridine of 2- Download PDFInfo
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- CN109748865A CN109748865A CN201711085778.7A CN201711085778A CN109748865A CN 109748865 A CN109748865 A CN 109748865A CN 201711085778 A CN201711085778 A CN 201711085778A CN 109748865 A CN109748865 A CN 109748865A
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- aminopyridine
- chloropyridine
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Abstract
The invention belongs to organic synthesis fields, and in particular to a kind of preparation method of the chloro- 4-aminopyridine of 2-, comprising the following steps: (1) using 2- chloropyridine as raw material, chloroform is solvent, and 2- chloropyridine oxide is generated under the action of metachloroperbenzoic acid；(2) 2- chloropyridine oxide is reacted with the nitration mixture being made of the concentrated nitric acid concentrated sulfuric acid generates the chloro- 4- nitropyridine nitrogen oxides of 2-；(3) the chloro- 4- nitropyridine nitrogen oxides of 2- is reduced to the chloro- 4-aminopyridine of 2-.Using the beneficial effects of the present invention are: reaction condition is mild, easily operated, post-processing is simple, is easy amplification production, is very suitable to industrialized production；Excellent catalytic effect, high income；Cost of material is cheap, and production cost is low.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of preparation method of the chloro- 4-aminopyridine of 2-.
Background technique
The chloro- 4-aminopyridine of 2- is a kind of important organic synthesis intermediate, can synthesize N- (the chloro- 4- pyridine of 2- with it
Base) ureas new plant growth regulator, this is to belong to cytohormone activity class to plant adjustment, has and promotes cell growth, differentiation is made
With can prevent plant aging, promote slender formation and fruit mast.Also there is effect to tuberous plants such as potatoes, potato can be made
Harvest improves, and to its toxicity very little, has very big purposes, the existing commodity listing of foreign countries to agricultural production, the chloro- 4-aminopyridine of 2- is
Synthesize this kind of key intermediate planted and adjusted.
The synthesising method reacting condition harshness, complex process of the chloro- 4-aminopyridine of the 2- of document announcement, at high cost at present.
Summary of the invention
It is an object of the invention to: overcome the at high cost, technical deficiencies such as yield is low in the prior art, a kind of cost is provided
The preparation method of the chloro- 4-aminopyridine of low, high income the 2- suitable for industrialized production.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
A kind of preparation method of the chloro- 4-aminopyridine of 2-, comprising the following steps:
(1) using 2- chloropyridine as raw material, chloroform is solvent, and 2- chloropyridine nitrogen is generated under the action of metachloroperbenzoic acid
Oxide；
(2) 2- chloropyridine nitrogen oxides is reacted with the nitration mixture being made of the concentrated nitric acid concentrated sulfuric acid generates the chloro- 4- nitropyridine of 2-
Nitrogen oxides；
(3) the chloro- 4- nitropyridine nitrogen oxides of 2- is reduced to the chloro- 4-aminopyridine of 2-.
Further, the molar ratio of 2- chloropyridine and metachloroperbenzoic acid is 1:2-3 in the step (1).
Further, the volume ratio of concentrated nitric acid and the concentrated sulfuric acid is 1:1.6-2 in nitration mixture described in the step (2).
Further, the reduction reaction in the step (3) is catalyzed by iron powder and concentrated hydrochloric acid, by ethyl alcohol and water as solvent.
Further, the molar ratio of the chloro- 4- nitropyridine nitrogen oxides of the 2- and iron powder is 1:5.
Further, the volume ratio of the second alcohol and water is 3:1.
Reaction equation of the invention is as follows:
Using the beneficial effects of the present invention are: reaction condition is mild, easily operated, post-processing is simple, is easy amplification production,
It is very suitable to industrialized production；Excellent catalytic effect, high income；Cost of material is cheap, and production cost is low.
Specific embodiment
The present invention is further elaborated below according to specific embodiment, right of the invention is not intended to limit and wants
Seek range.
Embodiment 1
(1) 2- chloropyridine (11.3g, 0.1mol), chloroform (100ml), m-chloro peroxide benzene are added in 250ml three-necked flask
Formic acid (34.5g, 0.2mol), 25 DEG C of reaction 10h, TLC monitoring reactions, after complete reaction, pours into ice-water bath for reaction solution
In saturated aqueous sodium thiosulfate, stirring will be anti-after being destroyed completely with starch potassium iodide paper detection metachloroperbenzoic acid
It answers liquid pH to be adjusted to alkalinity, is extracted with DCM, merge organic layer, dry, concentration obtains 2- chloropyridine nitrogen oxides, molar yield is
68%；
(2) dense H is added in 250ml there-necked flask2SO4(16ml), ice water are cooled to 0 DEG C, instill concentrated nitric acid (10ml) and are formed
2- chloropyridine nitrogen oxides (6.4g, 0.05mol) is added portionwise under the conditions of 0 DEG C in nitration mixture, adds 0-10 DEG C of stirring 20min,
It is warming up to 100 DEG C again to be stirred to react, TLC is monitored to fully reacting, and ice water is quenched after reaction, is filtered, is obtained the chloro- 4- nitro of 2-
Pyridine nitric oxide, molar yield 65%；
(3) the addition chloro- 4- nitropyridine nitrogen oxides (7.9g, 0.05mol) of 2- in 500ml there-necked flask, iron powder (14g,
0.25mol), ethyl alcohol 150ml, water 50ml, concentrated hydrochloric acid 5ml are warming up to reflux, and TLC is monitored to fully reacting, to fully reacting plus
Ethyl acetate 30ml, stirring, which is stood, to be filtered, and layering, anhydrous sodium sulfate is dry, and concentration obtains the chloro- 4-aminopyridine of product 2-, mole
Yield 85%.
Embodiment 2
(1) 2- chloropyridine (11.3g, 0.1mol), chloroform (100ml), m-chloro peroxide benzene are added in 250ml three-necked flask
Formic acid (43.1g, 0.25mol), 25 DEG C of reaction 10h, TLC monitoring reactions, after complete reaction, pours into ice-water bath for reaction solution
In saturated aqueous sodium thiosulfate, stirring will be anti-after being destroyed completely with starch potassium iodide paper detection metachloroperbenzoic acid
It answers liquid pH to be adjusted to alkalinity, is extracted with DCM, merge organic layer, dry, concentration obtains 2- chloropyridine nitrogen oxides, molar yield is
72%；
(2) dense H is added in 250ml there-necked flask2SO4(18ml), ice water are cooled to 0 DEG C, instill concentrated nitric acid (10ml) and are formed
2- chloropyridine nitrogen oxides (6.4g, 0.05mol) is added portionwise under the conditions of 0 DEG C in nitration mixture, adds 0-10 DEG C of stirring 20min,
It is warming up to 100 DEG C again to be stirred to react, TLC is monitored to fully reacting, and ice water is quenched after reaction, is filtered, is obtained the chloro- 4- nitro of 2-
Pyridine nitric oxide, molar yield 70%；
(3) step reaction is the same as embodiment 1.
The present embodiment is preferred forms.
Embodiment 3
(1) 2- chloropyridine (11.3g, 0.1mol), chloroform (100ml), m-chloro peroxide benzene are added in 250ml three-necked flask
Formic acid (51.8g, 0.3mol), 25 DEG C of reaction 10h, TLC monitoring reactions, after complete reaction, pours into ice-water bath for reaction solution
In saturated aqueous sodium thiosulfate, stirring will be anti-after being destroyed completely with starch potassium iodide paper detection metachloroperbenzoic acid
It answers liquid pH to be adjusted to alkalinity, is extracted with DCM, merge organic layer, dry, concentration obtains 2- chloropyridine nitrogen oxides, molar yield is
70%；
(2) dense H is added in 250ml there-necked flask2SO4(20ml), ice water are cooled to 0 DEG C, instill concentrated nitric acid (10ml) and are formed
2- chloropyridine nitrogen oxides (6.4g, 0.05mol) is added portionwise under the conditions of 0 DEG C in nitration mixture, adds 0-10 DEG C of stirring 20min,
It is warming up to 100 DEG C again to be stirred to react, TLC is monitored to fully reacting, and ice water is quenched after reaction, is filtered, is obtained the chloro- 4- nitro of 2-
Pyridine nitric oxide, molar yield 68%；
(3) step reaction is the same as embodiment 1.
Claims (6)
1. a kind of preparation method of the chloro- 4-aminopyridine of 2-, it is characterised in that the following steps are included:
(1) using 2- chloropyridine as raw material, chloroform is solvent, and 2- chloropyridine nitrogen oxidation is generated under the action of metachloroperbenzoic acid
Object；
(2) 2- chloropyridine nitrogen oxides is reacted with the nitration mixture being made of the concentrated nitric acid concentrated sulfuric acid generates the chloro- 4- nitropyridine nitrogen oxygen of 2-
Compound；
(3) the chloro- 4- nitropyridine nitrogen oxides of 2- is reduced to the chloro- 4-aminopyridine of 2-.
2. a kind of preparation method of the chloro- 4-aminopyridine of 2- according to claim 1, it is characterised in that the step (1)
The molar ratio of middle 2- chloropyridine and metachloroperbenzoic acid is 1:2-3.
3. a kind of preparation method of the chloro- 4-aminopyridine of 2- according to claim 1, it is characterised in that the step (2)
Described in nitration mixture the volume ratio of concentrated nitric acid and the concentrated sulfuric acid be 1:1.6-2.
4. a kind of preparation method of the chloro- 4-aminopyridine of 2- according to claim 1, it is characterised in that the step (3)
In reduction reaction be catalyzed by iron powder and concentrated hydrochloric acid, by ethyl alcohol and water as solvent.
5. a kind of preparation method of the chloro- 4-aminopyridine of 2- according to claim 1, it is characterised in that the chloro- 4- of 2-
The molar ratio of nitropyridine nitrogen oxides and iron powder is 1:5.
6. a kind of preparation method of the chloro- 4-aminopyridine of 2- according to claim 1, it is characterised in that the second alcohol and water
Volume ratio be 3:1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711085778.7A CN109748865A (en) | 2017-11-07 | 2017-11-07 | A kind of preparation method of the chloro- 4-aminopyridine of 2- |
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| CN201711085778.7A CN109748865A (en) | 2017-11-07 | 2017-11-07 | A kind of preparation method of the chloro- 4-aminopyridine of 2- |
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| CN201711085778.7A Withdrawn CN109748865A (en) | 2017-11-07 | 2017-11-07 | A kind of preparation method of the chloro- 4-aminopyridine of 2- |
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2017
- 2017-11-07 CN CN201711085778.7A patent/CN109748865A/en not_active Withdrawn
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Application publication date: 20190514 |
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