CN106748992A - A kind of synthetic method of the trichloromethyl pyridine of 3 chlorine, 2 diazanyl 5 - Google Patents
A kind of synthetic method of the trichloromethyl pyridine of 3 chlorine, 2 diazanyl 5 Download PDFInfo
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- CN106748992A CN106748992A CN201710005106.4A CN201710005106A CN106748992A CN 106748992 A CN106748992 A CN 106748992A CN 201710005106 A CN201710005106 A CN 201710005106A CN 106748992 A CN106748992 A CN 106748992A
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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
- C07D213/72—Nitrogen atoms
- C07D213/76—Nitrogen atoms to which a second hetero atom is attached
- C07D213/77—Hydrazine radicals
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Abstract
The present invention provides a kind of synthetic method of the trichloromethyl pyridine of 3 chlorine, 2 diazanyl 5, and step is as follows：By 2, the trichloromethyl pyridine of 3 dichloro 5 and hydrazine hydrate are added separately in reaction vessel, are subsequently adding polar organic solvent, after 4~7h of stirring reaction, suction filtration, you can obtain the trichloromethyl pyridine of 3 chlorine, 2 diazanyl 5.Present invention process is simple, and cost of material is relatively low, and reaction condition is gentle, low production cost, the purity and high income of products obtained therefrom, and, up to 95%, product purity is up to more than 99% for yield, it is possible to achieve industrialized production, there is good promotional value.
Description
Technical field
The present invention relates to organic synthesis field, and in particular to a kind of synthesis side of the chloro- 2- diazanyls -5- trichloromethyl pyridines of 3-
Method.
Background technology
Nowadays, chlorination hydrazino pyridine class compound, is one in the synthesis of agricultural chemicals and field of medicaments nitrogen-containing heterocycle compound
Important direction, it often shows wide variety of bioactivity.Some report display chlorination hydrazino pyridine derivatives lead to
The advantages of often showing activity of weeding, antifungal activity, bactericidal activity, antitumor activity, makes it have extremely extensive purposes.
Wherein schiff base structure is considered as an important core in terms of drug discovery, particularly hydrazone class.It is reported that hydrazone class derives
Such as thing has shown various bioactivity, anti-amoeba activity, urease inhibiting activity, antitumor activity, insecticidal activity,
Antifungal activity etc..The new chlorination hydrazino pyridine class compound with bactericidal activity of exploitation is significant.
The content of the invention
It is an object of the invention to provide a kind of chloro- chloromethanes of 2- diazanyls -5- three of the new compound 3- with bactericidal activity
The synthetic method of yl pyridines.
To realize object above, the present invention is achieved by the following technical programs：
A kind of synthetic method of the chloro- 2- diazanyls -5- trichloromethyl pyridines of 3-, step is as follows：By the chloro- chloromethanes of 5- tri- of 2,3- bis-
Yl pyridines and hydrazine hydrate are added separately in reaction vessel, are subsequently adding polar organic solvent, after 4~7h of stirring reaction, suction filtration,
Can obtain the chloro- 2 diazanyl -5- trichloromethyl pyridines of 3-.
Preferably, the mol ratio of the chloro-5-trichloromethylpyridines of 2, the 3- bis- and hydrazine hydrate is 1：1~5.
Preferably, the mol ratio of the chloro-5-trichloromethylpyridines of 2, the 3- bis- and hydrazine hydrate is 1：4.
Preferably, the mass fraction of described hydrazine hydrate is 60%~80%.
Preferably, the consumption of described polar organic solvent is with the amount of the material of the chloro- 2 diazanyl -5- trichloromethyl pyridines of 3-
It is calculated as 5-15mL/mmol.
Preferably, the polar organic solvent is selected from methyl alcohol, ethanol, tetrahydrofuran, one kind of DMF
Or it is various.
Preferably, the reaction temperature of the reaction is 20~40 DEG C.
Beneficial effect of the present invention：The invention provides a kind of preparation method of the chloro- 2- diazanyls -5- trichloromethyl pyridines of 3-,
The preparation method process is simple, cost of material is relatively low, and reaction condition is gentle, low production cost, the purity and yield of products obtained therefrom
Height, up to 95%, product purity is up to more than 99% for yield, it is possible to achieve industrialized production, there is good promotional value.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under the premise of creative work, belongs to the scope of protection of the invention.
Embodiment 1：
To the addition chloro-5-trichloromethylpyridine 26.5g (0.1mol) of 2,3- bis- and 80% hydrazine hydrate 16g in reactor
(0.4mol), adds absolute ethyl alcohol 1000ml, and after reacting 5h at 30 DEG C, sampling after middle control is qualified, is steamed molten using HPLC analyses
Agent, cooling suction filtration obtains product 2, the chloro-5-trichloromethylpyridines of 3- bis-, and product yield is 95%, and purity is 99.15%.
Embodiment 2：
To the addition chloro-5-trichloromethylpyridine 26.5g (0.1mol) of 2,3- bis- and 80% hydrazine hydrate 16g in reactor
(0.4mol), adds methyl alcohol 1000ml, and after reacting 5h at 30 DEG C, sampling after middle control is qualified, steams solvent using HPLC analyses,
Cooling suction filtration obtains product 2, the chloro-5-trichloromethylpyridines of 3- bis-, and product yield is 87%, and purity is 99.21%.
Embodiment 3：
To the addition chloro-5-trichloromethylpyridine 26.5g (0.1mol) of 2,3- bis- and 80% hydrazine hydrate 16g in reactor
(0.4mol), adds tetrahydrofuran 1000ml, and after reacting 5h at 30 DEG C, sampling after middle control is qualified, is steamed molten using HPLC analyses
Agent, cooling suction filtration obtains product 2, the chloro-5-trichloromethylpyridines of 3- bis-, and product yield is 82%, and purity is 99.08%.
Embodiment 4：
To the addition chloro-5-trichloromethylpyridine 26.5g (0.1mol) of 2,3- bis- and 80% hydrazine hydrate 6g in reactor
(0.4mol), adds absolute ethyl alcohol 1000ml, and after reacting 4h at 20 DEG C, sampling after middle control is qualified, is steamed molten using HPLC analyses
Agent, cooling suction filtration obtains product 2, the chloro-5-trichloromethylpyridines of 3- bis-, and product yield is 84%, and purity is 99.13%.
Embodiment 5：
To the addition chloro-5-trichloromethylpyridine 26.5g (0.1mol) of 2,3- bis- and 80% hydrazine hydrate 16g in reactor
(0.4mol), adds absolute ethyl alcohol 1000ml, and after reacting 6h at 40 DEG C, sampling after middle control is qualified, is steamed molten using HPLC analyses
Agent, cooling suction filtration obtains product 2, the chloro-5-trichloromethylpyridines of 3- bis-, and product yield is 94%, and purity is 99.1%.
Embodiment 6：
To the addition chloro-5-trichloromethylpyridine 26.5g (0.1mol) of 2,3- bis- and 60% hydrazine hydrate 4g in reactor
(0.1mol), adds absolute ethyl alcohol 1000ml, and after reacting 4h at 20 DEG C, sampling after middle control is qualified, is steamed molten using HPLC analyses
Agent, cooling suction filtration obtains product 2, the chloro-5-trichloromethylpyridines of 3- bis-, and product yield is 68%, and purity is 99.21%.
Embodiment 7：
To the addition chloro-5-trichloromethylpyridine 26.5g (0.1mol) of 2,3- bis- and 70% hydrazine hydrate 8g in reactor
(0.2mol), adds absolute ethyl alcohol 1000ml, and after reacting 7h at 40 DEG C, sampling after middle control is qualified, is steamed molten using HPLC analyses
Agent, cooling suction filtration obtains product 2, the chloro-5-trichloromethylpyridines of 3- bis-, and product yield is 77%, and purity is 99.23%.
Embodiment 8：
To the addition chloro-5-trichloromethylpyridine 26.5g (0.1mol) of 2,3- bis- and 80% hydrazine hydrate 12g in reactor
(0.3mol), adds absolute ethyl alcohol 1000ml, and after reacting 5h at 30 DEG C, sampling after middle control is qualified, is steamed molten using HPLC analyses
Agent, cooling suction filtration obtains product 2, the chloro-5-trichloromethylpyridines of 3- bis-, and product yield is 86%, and purity is 99.11%.
Embodiment 9：
To the addition chloro-5-trichloromethylpyridine 26.5g (0.1mol) of 2,3- bis- and 80% hydrazine hydrate 16g in reactor
(0.4mol), adds absolute ethyl alcohol 500ml, and after reacting 5h at 30 DEG C, sampling after middle control is qualified, is steamed molten using HPLC analyses
Agent, cooling suction filtration obtains product 2, the chloro-5-trichloromethylpyridines of 3- bis-, and product yield is 75%, and purity is 98.1%.
Embodiment 10：
To the addition chloro-5-trichloromethylpyridine 26.5g (0.1mol) of 2,3- bis- and 80% hydrazine hydrate 16g in reactor
(0.4mol), adds absolute ethyl alcohol 1500ml, and after reacting 4h at 30 DEG C, sampling after middle control is qualified, is steamed molten using HPLC analyses
Agent, cooling suction filtration obtains product 2, the chloro-5-trichloromethylpyridines of 3- bis-, and product yield is 92%, and purity is 99.01%.
It should be noted that herein, such as first and second or the like relational terms are used merely to a reality
Body or operation make a distinction with another entity or operation, and not necessarily require or imply these entities or deposited between operating
In any this actual relation or order.And, term " including ", "comprising" or its any other variant be intended to
Nonexcludability is included, so that process, method, article or equipment including a series of key elements not only will including those
Element, but also other key elements including being not expressly set out, or also include being this process, method, article or equipment
Intrinsic key element.In the absence of more restrictions, the key element limited by sentence "including a ...", it is not excluded that
Also there is other identical element in process, method, article or equipment including the key element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
The present invention has been described in detail, it will be understood by those within the art that：It still can be to foregoing each implementation
Technical scheme described in example is modified, or carries out equivalent to which part technical characteristic；And these modification or
Replace, do not make the spirit and scope of the essence disengaging various embodiments of the present invention technical scheme of appropriate technical solution.
Claims (7)
1. the synthetic method of the chloro- 2- diazanyls -5- trichloromethyl pyridines of a kind of 3-, it is characterised in that step is as follows：By 2,3- bis-
Chloro-5-trichloromethylpyridine and hydrazine hydrate are added separately in reaction vessel, are subsequently adding polar organic solvent, stirring reaction 4
After~7h, suction filtration, you can obtain the chloro- 2 diazanyl -5- trichloromethyl pyridines of 3-.
2. the synthetic method of the chloro- 2- diazanyls -5- trichloromethyl pyridines of 3- as claimed in claim 1, it is characterised in that described 2,
The mol ratio of the chloro-5-trichloromethylpyridines of 3- bis- and hydrazine hydrate is 1：1~5.
3. the synthetic method of the chloro- 2- diazanyls -5- trichloromethyl pyridines of 3- as claimed in claim 2, it is characterised in that described 2,
The mol ratio of the chloro-5-trichloromethylpyridines of 3- bis- and hydrazine hydrate is 1：4.
4. the synthetic method of the chloro- 2- diazanyls -5- trichloromethyl pyridines of 3- as claimed in claim 2, it is characterised in that described
The mass fraction of hydrazine hydrate is 60%~80%.
5. the synthetic method of the chloro- 2- diazanyls -5- trichloromethyl pyridines of 3- as claimed in claim 1, it is characterised in that described
The consumption of polar organic solvent is calculated as 5-15mL/mmol with the amount of the material of the chloro- 2 diazanyl -5- trichloromethyl pyridines of 3-.
6. the synthetic method of the chloro- 2- diazanyls -5- trichloromethyl pyridines of 3- as claimed in claim 5, it is characterised in that the pole
Property organic solvent be selected from methyl alcohol, ethanol, tetrahydrofuran, one or more of DMF.
7. the synthetic method of the chloro- 2- diazanyls -5- trichloromethyl pyridines of 3- as claimed in claim 1, it is characterised in that described anti-
The reaction temperature answered is 20~40 DEG C.
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| CN201710005106.4A CN106748992A (en) | 2017-01-04 | 2017-01-04 | A kind of synthetic method of the trichloromethyl pyridine of 3 chlorine, 2 diazanyl 5 |
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| CN101333213A (en) * | 2008-07-07 | 2008-12-31 | 中国中化集团公司 | 1-substituted pyridyl-pyrazol acid amide compounds and use thereof |
| WO2009117421A2 (en) * | 2008-03-17 | 2009-09-24 | Kalypsys, Inc. | Heterocyclic modulators of gpr119 for treatment of disease |
| CN102249991A (en) * | 2011-06-01 | 2011-11-23 | 河南中医学院 | Method for high-yield synthesis of 3-chloride-2-hydrazinopyridine |
| CN103237800A (en) * | 2010-10-14 | 2013-08-07 | 田边三菱制药株式会社 | Amide derivative and use thereof |
| CN103588705A (en) * | 2013-10-11 | 2014-02-19 | 青岛文创科技有限公司 | Synthetic method of 3-chlorine-2-hydrazinopyridine |
| EP2927229A1 (en) * | 2012-10-16 | 2015-10-07 | Takeda Pharmaceutical Company Limited | Heterocyclic compound |
| CN105541706A (en) * | 2015-09-23 | 2016-05-04 | 浙江工业大学 | 3-Chloro-2-hydrazino-5-trifluoromethylpyridine derivative, and preparation method and application thereof |
| WO2016113155A1 (en) * | 2015-01-13 | 2016-07-21 | Syngenta Participations Ag | Pesticidally active heterocyclic derivatives with sulphur containing substituents |
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| WO2009117421A2 (en) * | 2008-03-17 | 2009-09-24 | Kalypsys, Inc. | Heterocyclic modulators of gpr119 for treatment of disease |
| CN101333213A (en) * | 2008-07-07 | 2008-12-31 | 中国中化集团公司 | 1-substituted pyridyl-pyrazol acid amide compounds and use thereof |
| CN103237800A (en) * | 2010-10-14 | 2013-08-07 | 田边三菱制药株式会社 | Amide derivative and use thereof |
| CN102249991A (en) * | 2011-06-01 | 2011-11-23 | 河南中医学院 | Method for high-yield synthesis of 3-chloride-2-hydrazinopyridine |
| EP2927229A1 (en) * | 2012-10-16 | 2015-10-07 | Takeda Pharmaceutical Company Limited | Heterocyclic compound |
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| WO2016113155A1 (en) * | 2015-01-13 | 2016-07-21 | Syngenta Participations Ag | Pesticidally active heterocyclic derivatives with sulphur containing substituents |
| CN105541706A (en) * | 2015-09-23 | 2016-05-04 | 浙江工业大学 | 3-Chloro-2-hydrazino-5-trifluoromethylpyridine derivative, and preparation method and application thereof |
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