US20060100217A9 - Preparation of 4-haloalkylnicotinamides - Google Patents

Preparation of 4-haloalkylnicotinamides Download PDF

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US20060100217A9
US20060100217A9 US10/515,507 US51550704A US2006100217A9 US 20060100217 A9 US20060100217 A9 US 20060100217A9 US 51550704 A US51550704 A US 51550704A US 2006100217 A9 US2006100217 A9 US 2006100217A9
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Sergiy Pazenok
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Bayer CropScience AG
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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
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3

Definitions

  • the present invention relates to a process for preparing 4-haloalkyinicotinamides.
  • 4-Haloalkylnicotinamides are useful starting materials for preparing pesticides, as described, for example, in WO-A 98/57 969, EP-A 0 580 374 and WO-A 01/70692.
  • These compounds can be prepared in two stages from 4-haloalkylnicotinic acids whose synthesis is described, for example, in EP-A 0 744 400, or by hydrolysis of 4-haloalkylnicotinonitriles, see, for example, WO-A 02/048111.
  • the invention therefore provides a process for preparing 4-haloalkylnicotinamides of the formula (I) where
  • the process according to the invention enables the preparation of the nicotinamide derivatives (I) from the nitrile derivatives (II-IV) in only one step and is additionally particularly simple to carry out. This is particularly surprising because it is known that the hydrolysis of 4-trifluoromethylnicotinonitrile to the amide is only achieved by heating to 120-140° C. for 8 h in concentrated H 2 SO 4 .
  • (C 1 -C 4 )-Haloalkyl is an alkyl group in which one or more hydrogen atoms are replaced by the same number of identical or different halogen atoms, preferably chlorine or fluorine, such as the trifluoromethyl, the 1-fluoroethyl, the 2,2,2-trifluoroethyl, the chloromethyl, the fluoromethyl, the difluoromethyl and the 1,1,2,2-tetrafluoroethyl group.
  • the cyclization to the 4-haloalkylnicotinamides (I) takes place in the presence of a strong acid, preferably having a pK a value of below 0.5. During the cyclization in the strongly acidic medium, the transformation of the nitrile group also takes place.
  • Particularly preferred acids are H 2 SO 4 , SO 3 , oleum, phosphoric acid, polyphosphoric acids, perfluoroalkanesulfonic acids, such as trifluoromethylsulfonic acid, methanesulfonic acid and p-toluenesulfonic acid, and very particular preference is given to H 2 SO 4 and polyphosphoric acid, special preference to H 2 SO 4 .
  • the ratio of the compound(s) (II), (III) and/or (IV) to acid can vary within a wide range.
  • the amount of acid used is from 4 to 30 parts by weight, preferably from 6 to 15 parts by weight, per part by weight of compound (II)-(IV).
  • the reaction temperature can vary within wide limits. In general, it is in the range from 0° C. to +40° C., and the reaction time is typically from 0.1 to 6 h, preferably from 3 to 5 h.
  • reaction conditions also vary in a manner familiar to those skilled in the art, depending on whether a compound of the formula (II), (III) or (IV) is used.
  • the reaction can be carried out in a solvent.
  • the components (II-IV) and the acid can be initially charged separately in the solvent and these solutions/suspensions reacted together, or one of the components is initially charged in the solvent and the other component is added.
  • Preferred solvents are halogenated hydrocarbons such as methylene chloride or chloroform, ethers such as diethyl ether or diisopropyl ether, and SO 2 .
  • the amount of solvent used can vary within wide limits and depends, for example, on which starting material is used. It is generally up to 30 parts by weight, preferably from 6 to 15 parts by weight, per part by weight of compound (II)-(IV).
  • the workup can be effected by known methods familiar to those skilled in the art, for example by dilution with water and filtration or extraction of the product.
  • aqueous workup is strictly necessary to release the amide from its precursor, if necessary, and to isolate it.
  • the compound (I), in particular 4-trifluoromethylnicotinamide finds use, for example, as an intermediate in the preparation of crop protection agents, in particular pesticides, such as insecticides.
  • the invention also provides a process for preparing insecticidally active 4-haloalkylnicotinic acid derivatives, in particular 4-trifluoromethylnicotinic acid derivatives, according to WO-A 98/57969, EP-A 0 580 374 and/or WO-A 01/70692, by preparing the above-described compounds of the formula (I), subjecting these to a ring-closing reaction, optionally hydrolyzing them and further reacting them by processes described in the documents cited to give the insecticidally active end compounds.
  • example 1 The procedure of example 1 was repeated, except using polyphosphoric acid instead of H 2 SO 4 .
  • the reaction mixture was heated to 40° C. for 4 h and 24 g (80%) of the product having a melting point of 165° C. were obtained.

Abstract

A process for preparing 4-haloalkylnicotinamides of the formula (I)
Figure US20060100217A9-20060511-C00001
 where
R1 is (C1-C4-haloalkyl, which comprises subjecting
one or more 3-((C1-C4)-haloalkyl-3-oxo-1-alkenylamino)nitriles of the formula (II), (III) and/or (IV)
R1—C(O)—CH=CH—NH—CH=CH—CN  (II)
R1—C(O)—CH=CH—NH—CH(ZR2)—CH2—CN  (III)
R1—C(O)—CH=CH—NH—CH(Hal)—CH2—CN  (IV) where
    • R1 is as defined above;
    • R2 is the same or different and is (C1-C6)-alkyl and
    • Z is the same or different and is O, S or NR1, to a ring-closing reaction and simultaneous hydrolysis in the presence of a strong acid. The compounds of the formula (I) are useful as intermediates for preparing pesticides.

Description

  • The present invention relates to a process for preparing 4-haloalkyinicotinamides.
  • 4-Haloalkylnicotinamides are useful starting materials for preparing pesticides, as described, for example, in WO-A 98/57 969, EP-A 0 580 374 and WO-A 01/70692.
  • These compounds can be prepared in two stages from 4-haloalkylnicotinic acids whose synthesis is described, for example, in EP-A 0 744 400, or by hydrolysis of 4-haloalkylnicotinonitriles, see, for example, WO-A 02/048111.
  • Surprisingly, a simple process has now been found for preparing 4-haloalkylnicotinamides, especially trifluoromethyinicotinamide, by cyclization and hydrolysis of 3-(haloalkyl-3-oxo-1-butenylamino)acrylonitriles in the presence of a strong acid.
  • The invention therefore provides a process for preparing 4-haloalkylnicotinamides of the formula (I)
    Figure US20060100217A9-20060511-C00002
    where
      • R1 is (C1-C4)-haloalkyl,
        which comprises subjecting
      • one or more 3-((C1-C4)-haloalkyl-3-oxo-1-alkenylamino)nitriles of the formula (II), (III) and/or (IV)
        R1—C(O)—CH=CH—NH—CH=CH—CN  (II)
        R1—C(O)—CH=CH—NH—CH(ZR2)—CH2—CN  (III)
        R1—C(O)—CH=CH—NH—CH(Hal)—CH2—CN  (IV)
        where
      • R1 is as defined above;
      • R2 is the same or different and is (C1-C6)-alkyl and
      • Z is the same or different and is O, S or NR1,
        to a ring-closing reaction and simultaneous hydrolysis in the presence of a strong acid.
  • The process according to the invention enables the preparation of the nicotinamide derivatives (I) from the nitrile derivatives (II-IV) in only one step and is additionally particularly simple to carry out. This is particularly surprising because it is known that the hydrolysis of 4-trifluoromethylnicotinonitrile to the amide is only achieved by heating to 120-140° C. for 8 h in concentrated H2SO4.
  • “(C1-C4)-Haloalkyl” is an alkyl group in which one or more hydrogen atoms are replaced by the same number of identical or different halogen atoms, preferably chlorine or fluorine, such as the trifluoromethyl, the 1-fluoroethyl, the 2,2,2-trifluoroethyl, the chloromethyl, the fluoromethyl, the difluoromethyl and the 1,1,2,2-tetrafluoroethyl group.
  • The symbols in the formulae (I) to (IV) are preferably defined as follows:
      • R1 is preferably CF2H, CFCl2, CF2Cl, CF3, C2F5 or C3F7, more preferably CF3.
      • R2 is preferably (C1-C4)-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, more preferably methyl or ethyl, most preferably methyl.
      • Z is preferably O or NR1.
      • Hal is F, Cl, Br or I, preferably Cl or Br.
  • The starting materials, 3-(haloalkyl-3-oxo-1-alkenylamino)acrylonitrile derivatives (II) or enamines of the formulae (III) and (IV), are known and can be prepared, for example, as described in WO-A 02/048111.
  • The cyclization to the 4-haloalkylnicotinamides (I) takes place in the presence of a strong acid, preferably having a pKa value of below 0.5. During the cyclization in the strongly acidic medium, the transformation of the nitrile group also takes place.
  • Particularly preferred acids are H2SO4, SO3, oleum, phosphoric acid, polyphosphoric acids, perfluoroalkanesulfonic acids, such as trifluoromethylsulfonic acid, methanesulfonic acid and p-toluenesulfonic acid, and very particular preference is given to H2SO4 and polyphosphoric acid, special preference to H2SO4.
  • It is also possible to use acid mixtures.
  • Depending on the compound, acid and further reaction conditions used, the ratio of the compound(s) (II), (III) and/or (IV) to acid can vary within a wide range.
  • In general, the amount of acid used is from 4 to 30 parts by weight, preferably from 6 to 15 parts by weight, per part by weight of compound (II)-(IV).
  • Depending on the compound used and other reaction conditions, the reaction temperature can vary within wide limits. In general, it is in the range from 0° C. to +40° C., and the reaction time is typically from 0.1 to 6 h, preferably from 3 to 5 h.
  • The reaction conditions also vary in a manner familiar to those skilled in the art, depending on whether a compound of the formula (II), (III) or (IV) is used.
  • The reaction can be carried out in a solvent. The components (II-IV) and the acid can be initially charged separately in the solvent and these solutions/suspensions reacted together, or one of the components is initially charged in the solvent and the other component is added.
  • Preferred solvents are halogenated hydrocarbons such as methylene chloride or chloroform, ethers such as diethyl ether or diisopropyl ether, and SO2. The amount of solvent used can vary within wide limits and depends, for example, on which starting material is used. It is generally up to 30 parts by weight, preferably from 6 to 15 parts by weight, per part by weight of compound (II)-(IV).
  • The workup can be effected by known methods familiar to those skilled in the art, for example by dilution with water and filtration or extraction of the product.
  • Depending on the nature of the cyclization reagent (e.g. SO3, oleum, concentrated H2SO4), aqueous workup is strictly necessary to release the amide from its precursor, if necessary, and to isolate it.
  • The compound (I), in particular 4-trifluoromethylnicotinamide, finds use, for example, as an intermediate in the preparation of crop protection agents, in particular pesticides, such as insecticides.
  • It is particularly suitable for further conversion to compounds, as described in WO-A 98/57969, EP-A 0 580 374 and WO-A 01/07692. These documents, in particular the compounds of the formula (I) in each case and the exemplary embodiments, are explicitly incorporated herein by reference.
  • The invention also provides a process for preparing insecticidally active 4-haloalkylnicotinic acid derivatives, in particular 4-trifluoromethylnicotinic acid derivatives, according to WO-A 98/57969, EP-A 0 580 374 and/or WO-A 01/70692, by preparing the above-described compounds of the formula (I), subjecting these to a ring-closing reaction, optionally hydrolyzing them and further reacting them by processes described in the documents cited to give the insecticidally active end compounds.
  • The content of German patent application 102 23 274.1, from which this application claims priority, and of the enclosed abstract is hereby incorporated by reference.
  • The invention is illustrated by the examples which follow, without being limited by them.
    • EXAMPLE NO. 1
  • 4-Trifluoromethylnicotinamide
  • A three-neck flask was initially charged under N2 with 100 ml of H2SO4 (d 1.8) and the solution was cooled to 10° C.
  • 30 g (0.5 mol) of N-(2-cyanovinyl)-4,4,4-trifluoro-3-keto-1-butenylamine were added at this temperature within 1 h.
  • Subsequently, the mixture was stirred at room temperature (RT) for 3-5 h. The reaction mixture was added to 300 g of ice, the pH adjusted to 3-4 using 40% by weight NaOH and the product extracted using ethyl acetate. The solvent was removed under reduced pressure.
  • 27 g (90%) of the amide were obtained, m.p.: 166-167° C.
  • 19F NMR δ: −60.0 (singlet) ppm.
    • EXAMPLE NO. 2
  • 4-Trifluoromethylnicotinamide
  • The procedure of example 1 was repeated, except using polyphosphoric acid instead of H2SO4. The reaction mixture was heated to 40° C. for 4 h and 24 g (80%) of the product having a melting point of 165° C. were obtained.
    • EXAMPLE NO. 3
  • 4-Difluoromethylnicotinamide
  • The procedure of example 1 was repeated, except that N-(2-cyanovinyl)-4,4-difluoro-3-keto-1-butenylamine was used instead of N-(2-cyanovinyl)-4,4,4-trifluoro-3-keto-1-butenylamine.
  • Yield 65%. m.p.: 124-125° C.

Claims (18)

1. A process for preparing 4-haloalkylnicotinamides of the formula (I)
Figure US20060100217A9-20060511-C00003
where
R1 is (C1-C4)-haloalkyl,
which comprises subjecting
one or more 3-((C1-C4)-haloalkyl-3-oxo-1-alkenylamino)nitriles of the formula (II), (III) and/or (IV)
R1—C(O)—CH=CH—NH—CH=CH—CN (II)
R1—C(O)—CH=CH—NH—CH(ZR2)—CH2—CN (III)
R1—C(O)—CH=CH—NH—CH(Hal)-CH2—CN (IV)
where
R1 is as defined above;
R2 is the same or different and is (C1-C6)-alkyl and
Z is the same or different and is O, S or NR1,
to a ring-closing reaction and simultaneous hydrolysis in the presence of a strong acid having a pKa value of below 0.5.
2. The process as claimed in claim 1, wherein R1 in the formula (I) is CF2H, CFCl2, CF2Cl, CF3, C2F5 or C3F7.
3. The process as claimed in claim 2, wherein R1 in the formula (I) is CF3.
4. The process as claimed in claim 1, carried out in the presence of one or more acids selected from the group consisting of H2SO4, SO3, oleum, phosphoric acid, polyphosphoric acids, perfluoroalkanesulfonic acids, methanesulfonic acid and p-toluenesulfonic acid is used.
5. The process as claimed in claim 4, carried out in the presence of H2SO4.
6. The process as claimed in claim 1, carried out in a solvent.
7. The process as claimed in claim 2, carried out in the presence of one or more acids selected from the group consisting of H2SO4, SO3, oleum, phosphoric acid, polyphosphoric acids, perfluoroalkanesulfonic acids, methanesulfonic acid and p-toluenesulfonic acid.
8. The process as claimed in claim 3, carried out in the presence of one or more acids selected from the group consisting of H2SO4, SO3, oleum, phosphoric acid, polyphosphoric acids, perfluoroalkanesulfonic acids, methanesulfonic acid and p-toluenesulfonic acid.
9. The process as claimed in claim 7, carried out in the presence of H2SO4.
10. The process as claimed in claim 8, carried out in the presence of H2SO4.
11. The process as claimed in claim 2, wherein the reaction is carried out in a solvent.
12. The process as claimed in claim 3, wherein the reaction is carried out in a solvent.
13. The process as claimed in claim 4, wherein the reaction is carried out in a solvent.
14. The process as claimed in claim 5, wherein the reaction is carried out in a solvent.
15. The process as claimed in claim 7, wherein the reaction is carried out in a solvent.
16. The process as claimed in claim 8, wherein the reaction is carried out in a solvent.
17. The process as claimed in claim 9, wherein the reaction is carried out in a solvent.
18. the process as claimed in claim 10, wherein the reaction is carried out in a solvent.
US10/515,507 2002-05-24 2003-05-09 Preparation of 4-haloalkylnicotinamides Expired - Fee Related US7317105B2 (en)

Applications Claiming Priority (3)

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DE10223274A DE10223274A1 (en) 2002-05-24 2002-05-24 Process for the preparation of 4-haloalkyl nicotinic acid amides
DE10223274.1 2002-05-24
PCT/EP2003/004869 WO2003099791A1 (en) 2002-05-24 2003-05-09 Method for producing 4-haloalkyl nicotinic acid amides

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KR (1) KR20050004218A (en)
CN (1) CN1310888C (en)
AU (1) AU2003242532A1 (en)
BR (1) BR0311246A (en)
DE (1) DE10223274A1 (en)
IL (1) IL165356A0 (en)
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CN113816901B (en) * 2021-08-27 2023-08-15 淮北龙溪生物科技有限公司 Synthesis method of 4-trifluoromethyl nicotinamide

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6239160B1 (en) * 1997-06-16 2001-05-29 Hoechst Schering Agrevo Gmbh 4-haloalkyl-3-heterocyclylpyridines and 4-haloalkyl-5-heterocyclylpyrimidines, processes for their preparation, compositions comprising them, and their use as pesticides
US6541640B2 (en) * 2000-12-13 2003-04-01 Aventis Cropscience Gmbh Process for the preparation of 4-haloalkylnicotinonitriles
US20040167334A1 (en) * 2000-03-22 2004-08-26 Shermolovich Yuriy Grigorievich Heterocyclic acylsulfimides, processes for their preparation, compositions comprising them and their use as pesticides

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Publication number Priority date Publication date Assignee Title
JP2994182B2 (en) 1992-07-23 1999-12-27 石原産業株式会社 Amide compounds or salts thereof, methods for producing them and pest control agents containing them
DE69623532T2 (en) 1995-05-26 2003-03-20 Ishihara Sangyo Kaisha Process for the preparation of 4-trifluoromethylnicotinic acid
BR0214448B1 (en) 2001-11-21 2013-11-26 N-HETEROARYL-4- (HALOALKYL) NICOTINAMIDE DERIVATIVE, PESTICIDE CONTAINING THE SAME AND METHOD FOR PRODUCTION OF SUCH DERIVATIVE

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6239160B1 (en) * 1997-06-16 2001-05-29 Hoechst Schering Agrevo Gmbh 4-haloalkyl-3-heterocyclylpyridines and 4-haloalkyl-5-heterocyclylpyrimidines, processes for their preparation, compositions comprising them, and their use as pesticides
US20040167334A1 (en) * 2000-03-22 2004-08-26 Shermolovich Yuriy Grigorievich Heterocyclic acylsulfimides, processes for their preparation, compositions comprising them and their use as pesticides
US6541640B2 (en) * 2000-12-13 2003-04-01 Aventis Cropscience Gmbh Process for the preparation of 4-haloalkylnicotinonitriles

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CN1656074A (en) 2005-08-17
US20050176734A1 (en) 2005-08-11
IL165356A0 (en) 2006-01-15
EP1511731A1 (en) 2005-03-09
ZA200408769B (en) 2005-12-28
US7317105B2 (en) 2008-01-08
MXPA04011622A (en) 2005-03-07
DE10223274A1 (en) 2003-12-04
TW200306977A (en) 2003-12-01
JP2005535595A (en) 2005-11-24
WO2003099791A1 (en) 2003-12-04
BR0311246A (en) 2005-03-15
AU2003242532A1 (en) 2003-12-12
CN1310888C (en) 2007-04-18

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