WO2020026259A1 - Ethyl 2-bromo-4-[2-(3-halopyridin-2-yl)-hydrazinyl]-4-oxobutanoate hbr salt, method of preparation and use thereof - Google Patents
Ethyl 2-bromo-4-[2-(3-halopyridin-2-yl)-hydrazinyl]-4-oxobutanoate hbr salt, method of preparation and use thereof Download PDFInfo
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- WO2020026259A1 WO2020026259A1 PCT/IN2019/000020 IN2019000020W WO2020026259A1 WO 2020026259 A1 WO2020026259 A1 WO 2020026259A1 IN 2019000020 W IN2019000020 W IN 2019000020W WO 2020026259 A1 WO2020026259 A1 WO 2020026259A1
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- ethyl
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- compound
- hbr
- halopyridin
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- 0 CCOC(C(C1)*(c2ncccc2*)NC1=O)=O Chemical compound CCOC(C(C1)*(c2ncccc2*)NC1=O)=O 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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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
Definitions
- This invention relates to ethyl 2-bromo-4-[2-(3-halopyridin-2-yl)- hydrazinyl]-4-oxobutanoate HBr salt, method of preparation and use thereof. More particularly, the invention relates to the title compound, preparation thereof from ethyl 4-[2-(3-halopyridin-2- yl)hydrazinyl]-4-oxobut-2-enoate and use of the title compound in preparation of ethyl 2-(3-halopyridin-2-yl)-5-oxopyrazolidine-3- carboxylate, which is a useful intermediate for preparation of pesticides.
- ethyl 2-(3-halopyridin-2-yl)-5-xopyrazolidine-3- carboxylate is an intermediate for preparation of pesticides.
- Present invention discloses Ethyl 2-bromo-4-[2-(3-halopyridin-2-yl)- hydrazinyl]-4-oxobutanoate HBr salt i.e., compound of Formula I, preparation thereof from compound of Formula II and use of compound of Formula I for the preparation of ethyl 2-(3-halopyridin- 2-yl)-5-oxopyra2olidine-3-carboxylate i.e., compound of Formula III.
- R 1 is a halogen in compounds of Formula I, II & III.
- Present invention thus provides a new route for preparation of compound of Formula III, via compound of Formula I which is prepared from compound of Formula II.
- Compounds of Formula II & III are known compounds. However, preparation of compound of Formula III from the compound of Formula I is not reported in the literature.
- Another object of invention is to provide a process for preparation of compound of Formula I from compound of Formula II.
- Another object of invention is to provide a process for preparation of compound of Formula III (which is an intermediate for preparation of pesticides) from the invented compound of Formula I.
- Ethyl 2-bromo-4-[2-(3- halopyridin - 2 -yl) -hydrazinyl] - 4 - oxobu tano ate HBr salt is prepared by reaction of ethyl 4-[2-(3-halopyridin-2- yl)hydrazinyl]-4-oxobut-2-enoate with HBr as follows:
- R 1 is a halogen
- the reaction can be carried out from 0-30°C. However, preferred temperature is 8-12°C.
- Reaction can be carried out using HBr. It is preferable to use HBr in acetic acid. When HBr in acetic acid is used, excess thereof is removed by distillation under reduced pressure. A solvent in which the desired product does not have significant solubility is added to the reaction mass. The resultant product is filtered and dried.
- the invented product thus obtained is taken in a solvent such as acetonitrile and treated with a base such as aqueous NaHC03 to produce ethyl 2-(3-halopyridin-2-yl)-5-oxopyrazolidine-3-carboxylate as follows:
- R 1 is a halogen. HBr is neutralized and the compound undergoes cyclization as shown in the above reaction.
- the resultant compound i.e., ethyl 2-(3-halopyridin-2-yl)-5-oxopyrazolidine-3-carboxylate is an intermediate in the preparation of pesticides.
- a 100 ml reaction flask equipped with a magnetic stirrer was charged with 60 ml of 33% HBr in acetic acid. It was cooled to about 5°C. 4 .0 gm ethyl 4 -[2-(3-chloropyridin-2-yl)hydrazinyl]-4-oxobut-2-enoate was added. The mixture was stirred for 7 hrs. at 8-12°C. Excess HBr in acetic acid was removed by distillation under reduced pressure. 25 ml Ethyl acetate was added to the reaction mass to obtain precipitate which was filtered and dried to get the compound with 94% yield and 85.3% purity.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Present invention provides novel Ethyl 2-bromo-4-[2-(3-halopyridin-2-yl)-hydrazinyl]-4-oxobutanoate HBr salt, method of preparation and use thereof. The compound is prepared by reaction of ethyl (2Z)-4-[2-(3-chloropyridin-2-yl) hydrazinyl]-4-oxobut-2-enoate with HBr. Invented compound can be used in the preparation of ethyl 2-(3-halopyridin-2-yl)-5-oxopyrazolidine-3-carboxylate which is an intermediate for preparation of pesticides.
Description
Ethyl 2-bromo-4-[2-(3 - halopyridin- 2 -yl) - hy draziny 1] - 4 - oxobutanoate HBr salt, method of preparation
and use thereof
FIELD OF INVENTION
This invention relates to ethyl 2-bromo-4-[2-(3-halopyridin-2-yl)- hydrazinyl]-4-oxobutanoate HBr salt, method of preparation and use thereof. More particularly, the invention relates to the title compound, preparation thereof from ethyl 4-[2-(3-halopyridin-2- yl)hydrazinyl]-4-oxobut-2-enoate and use of the title compound in preparation of ethyl 2-(3-halopyridin-2-yl)-5-oxopyrazolidine-3- carboxylate, which is a useful intermediate for preparation of pesticides.
BACKGROUND AND PRIOR ART
As mentioned above, ethyl 2-(3-halopyridin-2-yl)-5-xopyrazolidine-3- carboxylate (Formula III) is an intermediate for preparation of pesticides.
Present invention discloses Ethyl 2-bromo-4-[2-(3-halopyridin-2-yl)- hydrazinyl]-4-oxobutanoate HBr salt i.e., compound of Formula I, preparation thereof from compound of Formula II and use of compound of Formula I for the preparation of ethyl 2-(3-halopyridin- 2-yl)-5-oxopyra2olidine-3-carboxylate i.e., compound of Formula III.
R1 is a halogen in compounds of Formula I, II & III.
Present invention thus provides a new route for preparation of compound of Formula III, via compound of Formula I which is prepared from compound of Formula II. Compounds of Formula II & III are known compounds. However, preparation of compound of Formula III from the compound of Formula I is not reported in the literature.
OBJECTS OF INVENTION
It is an object of invention to provide compound of Formula I.
Another object of invention is to provide a process for preparation of compound of Formula I from compound of Formula II.
Another object of invention is to provide a process for preparation of compound of Formula III (which is an intermediate for preparation of pesticides) from the invented compound of Formula I.
DETAILED DESCRIPTION OF INVENTION
Ethyl 2-bromo-4-[2-(3- halopyridin - 2 -yl) -hydrazinyl] - 4 - oxobu tano ate HBr salt is prepared by reaction of ethyl 4-[2-(3-halopyridin-2- yl)hydrazinyl]-4-oxobut-2-enoate with HBr as follows:
R1 is a halogen.
The reaction can be carried out from 0-30°C. However, preferred temperature is 8-12°C.
Reaction can be carried out using HBr. It is preferable to use HBr in acetic acid. When HBr in acetic acid is used, excess thereof is removed by distillation under reduced pressure. A solvent in which the desired product does not have significant solubility is added to the reaction mass. The resultant product is filtered and dried.
The invented product thus obtained is taken in a solvent such as acetonitrile and treated with a base such as aqueous NaHC03 to produce ethyl 2-(3-halopyridin-2-yl)-5-oxopyrazolidine-3-carboxylate as follows:
R1 is a halogen.
HBr is neutralized and the compound undergoes cyclization as shown in the above reaction. The resultant compound i.e., ethyl 2-(3-halopyridin-2-yl)-5-oxopyrazolidine-3-carboxylate is an intermediate in the preparation of pesticides.
The reagents used in the following examples are for illustration purpose and they are not limitative to the scope of the invention.
Example -1
Preparation of Ethyl 2-bromo-4-[2-(3-chloropyridin-2-yl)-hydrazinyl]- 4-oxobutar.oate HBr salt:
A 100 ml reaction flask equipped with a magnetic stirrer was charged with 60 ml of 33% HBr in acetic acid. It was cooled to about 5°C. 4.0 gm ethyl 4-[2-(3-chloropyridin-2-yl)hydrazinyl]-4-oxobut-2-enoate was added. The mixture was stirred for 7 hrs. at 8-12°C. Excess HBr in acetic acid was removed by distillation under reduced pressure. 25 ml Ethyl acetate was added to the reaction mass to obtain precipitate which was filtered and dried to get the compound with 94% yield and 85.3% purity.
1H NMR (MeOD, 400 MHz) 6: 8.199-8.177 (dd, J1 = 7.6 Hz, J2 = 1.2 Hz, 1H, pyridyl-H); 7.933-7.914 (dd, J = 6.4 Hz, J2 = 1.2 Hz, 1H, pyridyl-H); 7.076 - 7.041 (dd, J = 7.6 Hz, J2 - 6.4 Hz, 1H, pyridyl-H); 4.61-4.55 (m, 1H, CH-Br), 4.15-4.10 (q, 7.2 Hz, 2H, OCH2); 3.31-3.25 (dd, J = 8.8 Hz, J2 = 6.4 Hz, 1H,); 3.09-3.03 (dd, J = 16.8 Hz, J2 = 6 Hz, 1H,): 1.18 (t, J = 7.2 Hz, 3H, CH3) m/z = 349 (DI)
IR spectra: 3303.92 cra-'-NH amide stretch, 3119.34 cm-1 = -NH stretch, 2935.55 = aromatic -CH stretch, 2746.84 cm 1 = aliphatic - CH stretch, 1708.29 cm 1 -C=0 stretch ester, 1629.51 cm 1 -C=0 stretch amide, 779.78 cm 1 = C-Cl stretch.
Example -2
Preparation of ethyl 2-{3-chloropyridin-2-yl)-5-oxopyrazolidine-3- carboxylate from compound obtained in Example- 1 :
100 ml reaction flask was charged with 6.0 gm ethyl 2-bromo-4-[2-(3- chloropyridin-2-yl)hydrazinyl]-4-oxobutanoate HBr salt as obtained in Example- 1 and 100 ml acetonitrile. The mixture was cooled to 5°C. 10% NaHC03 solution was added drop wise with stirring and the temperature was allowed to raise to room temperature during which HBr was neutralized and the compound underwent cyclization. The reaction mixture was washed with brine and the organic layer was separated & dried over anhydrous Na2S04. Solvent was removed by distillation under reduced pressure and the residue was washed with 2.5-5% ethanol in water and dried under reduced pressure to get the product with 84.6% yield and 96% purity.
Claims
1. Compound of Formula (1)
wherein R1 is a halogen.
2. A process for preparation of compound of Formula (I) as claimed in claim 1 by reaction of ethyl 4-[2-(3-halopyridin-2-yl)hydrazinyl]-4- oxobut-2-enoate with HBr.
3. A process as claimed in claim 2, wherein the reaction is carried out at 0-30°C.
4. A process as claimed in claim 2, wherein HBr is taken in acetic acid, and after completion of the reaction, excess HBr in acetic acid is removed by distillation under reduced pressure.
5. A process as claimed in claim 2, wherein HBr is taken in acetic acid, and after completion of the reaction, excess HBr in acetic acid is removed by distillation under reduced pressure and thereafter the product is separated from reaction mass by adding to the reaction mass a solvent in which the product does not have significant solubility, followed by filtration and drying.
6. A process for preparation of ethyl 2-(3-halo-pyridin-2-yl)-5- oxopyrazolidine-3-carboxylate from the compound of Formula (I) as claimed in claim 1 by neutralization with a base.
7. A process as claimed in claim 6, wherein said base is NaHCOs.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN201821028730 | 2018-07-31 | ||
| IN201821028730 | 2018-07-31 |
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| Publication Number | Publication Date |
|---|---|
| WO2020026259A1 true WO2020026259A1 (en) | 2020-02-06 |
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| PCT/IN2019/000020 WO2020026259A1 (en) | 2018-07-31 | 2019-07-18 | Ethyl 2-bromo-4-[2-(3-halopyridin-2-yl)-hydrazinyl]-4-oxobutanoate hbr salt, method of preparation and use thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2100889B1 (en) * | 2002-07-31 | 2011-04-20 | E. I. du Pont de Nemours and Company | Method for preparing 3-halo-4, 5-dihydro-1h-pyrazoles |
| US8217179B2 (en) * | 2008-04-01 | 2012-07-10 | Sinochem Corporation | Preparation method of phenylcarboxamides |
| US8492409B2 (en) * | 2008-07-07 | 2013-07-23 | Sinochem Corporation | 1-substituted pyridyl-pyrazolyl amide compounds and uses thereof |
| EP1417175B1 (en) * | 2001-08-13 | 2013-07-24 | E.I. Du Pont De Nemours And Company | Substituted dihydro 3-halo-1h-pyrazole-5-carboxylates, their preparation and use |
| EP2093223B1 (en) * | 2006-12-15 | 2013-08-21 | Ishihara Sangyo Kaisha, Ltd. | Process and intermediates for production of an anthranilamide compound |
-
2019
- 2019-07-18 WO PCT/IN2019/000020 patent/WO2020026259A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1417175B1 (en) * | 2001-08-13 | 2013-07-24 | E.I. Du Pont De Nemours And Company | Substituted dihydro 3-halo-1h-pyrazole-5-carboxylates, their preparation and use |
| EP2100889B1 (en) * | 2002-07-31 | 2011-04-20 | E. I. du Pont de Nemours and Company | Method for preparing 3-halo-4, 5-dihydro-1h-pyrazoles |
| EP2093223B1 (en) * | 2006-12-15 | 2013-08-21 | Ishihara Sangyo Kaisha, Ltd. | Process and intermediates for production of an anthranilamide compound |
| US8217179B2 (en) * | 2008-04-01 | 2012-07-10 | Sinochem Corporation | Preparation method of phenylcarboxamides |
| US8492409B2 (en) * | 2008-07-07 | 2013-07-23 | Sinochem Corporation | 1-substituted pyridyl-pyrazolyl amide compounds and uses thereof |
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