EP1345906A2 - Verfahren zur herstellung von 4-haloalkylnicotinnitrilen - Google Patents

Verfahren zur herstellung von 4-haloalkylnicotinnitrilen

Info

Publication number
EP1345906A2
EP1345906A2 EP01985871A EP01985871A EP1345906A2 EP 1345906 A2 EP1345906 A2 EP 1345906A2 EP 01985871 A EP01985871 A EP 01985871A EP 01985871 A EP01985871 A EP 01985871A EP 1345906 A2 EP1345906 A2 EP 1345906A2
Authority
EP
European Patent Office
Prior art keywords
formula
compound
viii
reaction
haloalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01985871A
Other languages
German (de)
English (en)
French (fr)
Inventor
Sergiy Pazenok
Henricus Maria Martinus Bastiaans
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
Original Assignee
Bayer CropScience AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE2000161967 external-priority patent/DE10061967A1/de
Priority claimed from DE2001120819 external-priority patent/DE10120819A1/de
Priority claimed from DE2001144411 external-priority patent/DE10144411A1/de
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Publication of EP1345906A2 publication Critical patent/EP1345906A2/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
    • C07C255/27—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton containing cyano groups, amino groups and doubly-bound oxygen atoms bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/30—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same unsaturated acyclic carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D211/78—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/80—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D211/84—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen directly attached to ring carbon atoms
    • C07D211/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • 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
    • C07D213/84—Nitriles
    • C07D213/85—Nitriles in position 3

Definitions

  • the invention relates to a process for the preparation of 4-haloalkyl-3-pyridinecarbonitriles (4-haloalkylnicotin nitriles) and their further conversion to insecticidally active 4-haloalkylnicotinic acid derivatives.
  • 4-Haloalkylnicotin yarn are useful starting materials for the production of pesticides, as described for example in WO-A 98/57969, EP-A 0 580 374 and DE-A 100 14 006.
  • the invention therefore relates to a process for the preparation of 4-haloalkylnicotin nitrites (I),
  • R F means (C 1 -C 4 ) haloalkyl, preferably CF 3 , where an a) 3-amino-1-haloalkyl-2-propen-1-one
  • R F -C (O) -CH CH-NH 2 (II) in a condensation reaction with a compound of the formula (III) to (VII),
  • Hal-CH CH-CN (V) Hal 2 CH-CH 2 CN (VI)
  • R F -C (O) -CH CH-NH-CH (ZR 1 ) -CH 2 -CN (IX)
  • R F -C (O) -CH CH-NH-CH (Hal) -CH 2 -CN (X), where R F R 1 , Z and Hai have the meanings given above, and the reaction product
  • R F is preferably CH 2 F, CFCI 2> CF 2 CI, CF 3 or C 2 F 5 , particularly preferably CF 3 .
  • R 1 is preferably (-C 4 ) alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-
  • Z is preferably O or NR 1 .
  • Shark preferably means F or CI.
  • the invention also relates to the use of 4-haloalkylnicotin nitriles as intermediates for the production of crop protection agents, in particular pesticides, such as insecticides.
  • the invention furthermore relates to a process for the preparation of 4-haloalkylnicotinamides (XI),
  • a particular economic advantage over the known synthesis from the acid is that no activated acid derivative, such as e.g. an acid chloride is required and no reaction with ammonia is required.
  • the invention furthermore relates to compounds of the formulas (VIII), (IX) and (X) and their salts,
  • R F -C (O) -CH CH-NH-CH (OR 2 ) -CH 2 -CN (IX)
  • R F -C (O) -CH CH-NH-CH (Hal) -CH 2 -CN (X) where R F , Z and Hai have the meanings given above and R 2 denotes an alkyl group.
  • the formulas (VIII), (XI) and (X) include all stereoisomers of the compounds, such as (Z) and (E) isomers on the double bonds, e.g. the (Z, Z), (Z, E), (E, Z) and (E, E) isomers of the compound (VIII) and in each case the (Z) and (E) isomers of the compounds (IX) and ( X).
  • R 2 is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, methyl and ethyl are preferred, methyl is particularly preferred.
  • the invention likewise relates to the use of compounds of the formula (VIII), (IX) and / or (X) as intermediates for the production of crop protection agents, in particular pesticides, such as insecticides.
  • 4-Amino-1,1, 1-trifluoro-3-buten-2-one (II) is known and can be prepared, for example, as described in EP-A 0744400 by using an acid halide of the formula (XII ) wherein X represents a halogen atom with a compound of the formula (XIII)
  • R F -C (O) -CH CH (OR) (XIV) from which compound (II) is obtained by reaction with ammonia.
  • R 3 is preferably a linear or branched alkyl group having 1 to 6, preferably 1 to 4, carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, methyl and ethyl are particularly preferred, are particularly preferred is methyl.
  • compound (II) is reacted in a condensation reaction with one or more compounds of the formulas (III) and (VII) to give compound (VIII), (IX) and / or (X).
  • the condensation of (II) with (III) - (VII) is preferably carried out under reduced pressure (particularly preferably at a pressure in the range from 5-150 mbar, very particularly preferably 10-100 mbar).
  • the preferably low-boiling components are distilled off from the reaction mixture, thereby allowing the two starting materials to be converted completely.
  • the vacuum is advantageously chosen so that the boiling point of the compound R 1 ZH, such as CH 3 OH, EtOH, BuOH, is below, preferably 50 to 10 ° C. below the reaction temperature and the boiling point of the solvent is above, preferably 50 to 150 ° C is above the reaction temperature.
  • the formation of by-products is largely suppressed and the reaction rate increases.
  • the ratio of the two components (II) and (III) to (VII) can in the
  • the reaction temperature can vary depending on the compound used and the others
  • Reaction temperature in the range from -20 ° C - + 10 ° C, preferably 0 ° C - + 30 ° C and the reaction time is usually 0.5 to 12 h, preferably from 1 to 6 h.
  • the reaction temperature is preferably from -10 to +75 ° C.
  • Suitable bases are, for example, alkali metal hydrides such as NaH or KH, alkyl lithium compounds such as n-butyllithium or t-butyllithium, alkali metals such as sodium or potassium, alkali metal hydroxides such as NaOH or KOH, alcoholates such as Na methanolate, Na ethanolate, K -Methanolat or Kt-Butanolat, or basic heterocycles, such as pyridine or quinoline.
  • Alkali metal hydrides are preferred, NaH and K-t-butoxide are particularly preferred.
  • the bases can be used individually or in a mixture.
  • the amount of base used can vary within wide limits, depending on what compound of formula (III) or (V) is used, whether and in which solvent the process is carried out and the further reaction conditions. In general, 1.0 to 1.2 weight equivalents of base, preferably 1.05 to 1.1 weight equivalents of base, are used per mole of compound of the formula (II).
  • the reaction is preferably carried out in a solvent.
  • Components (II) can be placed in the solvent and these solutions can be reacted with base to react with (III) or (V).
  • Preferred solvents are polar aprotic solvents such as N, N-dimethylformamide or acetonitrile, halogenated hydrocarbons such as methylene chloride or chloroform, ethers such as diethyl ether, dimethoxyethane or tetrahydrofuran, alcohols such as methanol or ethanol, or basic heterocycles such as pyridine or quinoline.
  • Polar aprotic solvents are preferred, particularly preferred are N, N-dimethylformamide (DMF) and dimethoxyethane (DME).
  • the amount of solvent used can vary within wide limits and depends, for example, on whether and which base is added. In general, the amount of the solvent used is 1 to 30, preferably 4 to 15 parts by weight per part by weight of the compound (III) or (V).
  • the salts can be used instead of the pure compounds or can be obtained depending on the reaction.
  • Base RF_C-CH : CH-NH 2 + (R1Z) 2 CHCH 2 CN ⁇
  • Condensation reaction advantageously carried out at low temperatures, preferably from -10 to 0 ° C, the reaction time is then preferably 0.2 to 4 h.
  • the reaction must be carried out at higher temperatures, preferably 20 to + 25 ° C, the
  • Reaction time for this second stage is preferably 3 to 10 hours.
  • the condensation reaction is carried out in the presence of a base which contains an alkali metal, the compounds (VIII), (IX) and / or (X) form alkali metal salts which, under certain circumstances, can be present in the reaction product.
  • the condensation reaction is followed by a neutralization step, the reaction product being treated, for example, with a mineral acid, such as hydrochloric acid or sulfuric acid.
  • the isolated compound (VIII) may contain a compound of formula (VIII):
  • R F -C-CH CH-N-CH-CH 2 -CN
  • the formulas (VIII), (IX) and (X) encompass all of these tautomers and salts of the compounds.
  • the ring closure reaction of the compounds (VIII), (XI) and / or (X) to give the compound (I) is advantageously carried out in a solvent.
  • Alcohols are preferred, particularly preferred primary (CrC6) alcohols, very particularly preferred are methanol and ethanol, in particular methanol. Mixtures of the solvents mentioned can also be used.
  • the compounds (VIII), (IX) and / or (X) can be initially introduced into the solvent, or the solvent is added to the reaction mixture.
  • the amount of solvent used for the ring closure reaction can vary within wide limits depending on the starting compound and reaction conditions. In general, it is 1 to 30, preferably 4 to 15 parts by weight per part by weight of compound (VIII) or (IX) and / or (X).
  • R F is (C 1 -C 4) -haloalkyl, preferably CF 3
  • R 1 is a, preferably straight-chain (Ci-C ⁇ ), preferably (CC 4 ) - in particular (C1-C2) -, alkyl radical and MH + or a monovalent cation such as Na + , K + , Li + , 1 / 2Ca 2+ , 1 / 2Mg 2+ , HN ((CrC 4 ) -alkyl) 3 + .
  • Suitable bases are, for example, alkali metal carbonates, hydrogen carbonates and acetates, such as the corresponding Li, Na, K and Cs salts, alkaline earth metal carbonates and hydrogen carbonates, such as the corresponding Mg and Ca salts, alkali metal hydrides such as NaH and KH, alkyl lithium compounds, such as n-butyllithium, alkali metals such as Na and K, alkali metal hydroxides such as NaOH and KOH, alkali metal alcoholates such as NaOMe, NaOEt, KOMe and KOtBu, basic hetrocycles such as pyridine, 4-NN-dimethylaminopyridine and quinoline, or ammonia.
  • alkali metal carbonates such as the corresponding Li, Na, K and Cs salts
  • alkaline earth metal carbonates and hydrogen carbonates such as the corresponding Mg and Ca salts
  • alkali metal hydrides such as NaH and KH
  • alkyl lithium compounds such as n
  • Alkali and alkaline earth carbonates, bicarbonates and acetates such as Li 2 CO 3) Na 2 CO 3 , NaHCO 3 , K 2 CO 3 , CaCO 3 and MgCO 3 , are preferred.
  • Particularly preferred are Li 2 C03, Na2 C03 and K2CO3, very particularly preferably Li 2 CO 3 and K 2 CO 3. the selectivity of the reaction in the direction of the desired end product (I) can in particular be increased by the two latter bases.
  • the bases can be used individually or in a mixture. In general, 0.05 to 1 equivalent, preferably 0.1 to 0.8 equivalent, of base are used per mole of compound of the formula (VIII), (IX) and / or (X). The base can optionally be filtered off after the reaction and used again.
  • the activity and selectivity of the base can be controlled by phase transfer catalysts (PTK). Crown ethers, cryptands, quaternary ammonium, phosphonium and onium compounds are typically suitable as PTK. Examples include 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown-6, tetrabutylammonium chloride and bromide, tetrabutylphosphonium chloride and bromide. 18-crown-6 is preferred.
  • the PTK is usually used in an amount of 1 to 10, preferably 1 to 5 mol%, based on the compound (VIII), (IX) and / or (X).
  • the pH of the reaction mixture is generally adjusted to 1 to 2, which is usually achieved by using 0.1 to 1 equivalent of acid, based on the theoretical amount of compound (I).
  • the saponification of the nitrile (I) to the acid amide (XI) can be carried out by known methods known to the person skilled in the art, as described, for example, in Houben Weyl, Methods of Organic Chemistry.
  • the synthesis of the compounds (I) and (XI) is carried out in a one-pot reaction, i.e. without isolating intermediates of formulas (VIII) to (X) and / or (XII).
  • Compounds (I) and (XI) find e.g. as intermediates in the production of crop protection agents, in particular pesticides, such as insecticides.
  • the invention also relates to a process for the preparation of insecticidally active 4-trifluoromethylnicotinic acid derivatives according to WO-A 98/57969, EP-A 0 580 374 and / or DE 100 14006.8, 4-trifluoromethylnicotinitrile being prepared as described above, optionally saponified and after in the quoted Processes described documents further implemented to the insecticidally active end compounds of the respective formula (I).
  • the invention furthermore relates to a process for the preparation of compounds of the formula (XVIII), amide (XI) obtained according to the invention being reacted with a halogenating agent to give (XIX), optionally as a salt, from which reaction with R 4 R 5 S / base and optionally subsequent oxidation, the compounds (XVIII) are obtained,
  • R 4 and R 5 together with the sulfur to which they are attached form a three- to eight-membered, saturated or unsaturated, optionally mono- or polysubstituted, preferably substituted by radicals R 8 , preferably carbocyclic ring system which optionally has 1 to 4 contains further heteroatoms, two or more of the substituents optionally forming one or more further ring systems;
  • W is O or S;
  • R 6 is the same or different (CrC 20 ) alkyl, (C 2 -C 2 o) alkenyl, (C 2 -C 2 o) alkynyl, (C 3 -C 8 ) cycloalkyl, (C 4 -C 8 ) -cycloalkenyl, (C 8 -C 10 ) -cycloalkynyl, aryl or heterocyclyl; where the radicals mentioned can be substituted one or more times, preferably by radicals R 8 ;
  • R 7 is the same or different H or R 6 .
  • the invention furthermore relates to a process for the preparation of the formulas (XX) and (XXI)
  • the invention furthermore relates to a process for the preparation of compounds of the formula (XXV),
  • R F has the meanings given above and
  • R 6 R 7 H or optionally substituted alkyl, alkenyl, alkynyl or
  • Cycloalkyl groups are or together form a ring system, optionally containing one or more N, S or O atoms; where (XXII) obtained according to the invention,
  • reaction mixture was poured onto ice and acidified to pH 3-4 with HCl.
  • Tube reactor 60 cm glass tube with an inner diameter of 4 cm, with a heated jacket, half filled with glass balls, cooled template and vacuum connection with
  • NMP N-Methylpyrrolidone
  • Dimethoxypropionitrile was slowly added in succession at this temperature. This mixture was transferred to the template.
  • the tube reactor was filled with NMP, the jacket was heated to 80-85 ° C and a vacuum of 30 -35 mbar was applied. From the template, the reaction mixture was uniformly added to the tubular reactor within 1 h. The reaction time was 7-8 min at 80-85 C, with methanol being condensed in the cold trap. After the addition had ended, a further 120 ml of NMP were added dropwise in order to completely displace the reaction mixture from the reactor. The reaction mixture was poured onto ice water and HCI added and, if necessary, adjusted to pH 2-3 with HCI. The fancy
  • the product was filtered off and washed with water.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogenated Pyridines (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Plural Heterocyclic Compounds (AREA)
EP01985871A 2000-12-13 2001-12-12 Verfahren zur herstellung von 4-haloalkylnicotinnitrilen Withdrawn EP1345906A2 (de)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE10061967 2000-12-13
DE2000161967 DE10061967A1 (de) 2000-12-13 2000-12-13 Verfahren zur Herstellung von 4-Trifluormethylnicotinnitril
DE2001120819 DE10120819A1 (de) 2001-04-27 2001-04-27 Verfahren zur Herstellung von 4-Trifluormethylnicotinnitril
DE10120819 2001-04-27
DE2001144411 DE10144411A1 (de) 2001-09-11 2001-09-11 Verfahren zur Herstellung von 3-(Haloalkyl-3-oxo-1-butenylamino)acrylnitrilen
DE10144411 2001-09-11
PCT/EP2001/014584 WO2002048111A2 (de) 2000-12-13 2001-12-12 Verfahren zur herstellung von 4-haloalkylnicotinnitrilen

Publications (1)

Publication Number Publication Date
EP1345906A2 true EP1345906A2 (de) 2003-09-24

Family

ID=27214195

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01985871A Withdrawn EP1345906A2 (de) 2000-12-13 2001-12-12 Verfahren zur herstellung von 4-haloalkylnicotinnitrilen

Country Status (14)

Country Link
US (2) US6541640B2 (cs)
EP (1) EP1345906A2 (cs)
JP (1) JP2004525091A (cs)
KR (1) KR100845376B1 (cs)
CN (1) CN1244560C (cs)
AR (1) AR031658A1 (cs)
AU (1) AU2002235770A1 (cs)
BR (1) BR0116124A (cs)
CZ (1) CZ20031662A3 (cs)
HU (1) HUP0401099A3 (cs)
IL (3) IL156359A0 (cs)
MX (1) MXPA03005258A (cs)
TW (1) TWI222442B (cs)
WO (1) WO2002048111A2 (cs)

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DE10223274A1 (de) * 2002-05-24 2003-12-04 Bayer Cropscience Gmbh Verfahren zur Herstellung von 4-Haloalkylnicotinsäureamiden
WO2010113175A2 (en) 2009-04-01 2010-10-07 Matrix Laboratories Ltd Enzymatic process for the preparation of (s)-5-(4-fluoro-phenyl)-5-hydroxy- 1morpholin-4-yl-pentan-1-one, an intermediate of ezetimibe and further conversion to ezetimibe
FR2985857B1 (fr) 2012-01-17 2014-01-03 Hutchinson Cathode pour cellule de batterie lithium-ion, son procede de fabrication et cette batterie l'incorporant.
JP2017509433A (ja) 2014-04-01 2017-04-06 クロックス テクノロジーズ インコーポレイテッドＫｌｏｘ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｉｎｃ． 組織充填剤組成物および使用方法
JP2022036351A (ja) * 2018-10-30 2022-03-08 日本曹達株式会社 ３－シアノ－４－トリフルオロメチルピリジン若しくはその塩を含有する、土壌処理剤、水田処理剤又は種子処理剤
CN109851552A (zh) * 2018-12-28 2019-06-07 京博农化科技有限公司 一种n-氰甲基-4-（三氟甲基）烟酰胺的合成方法
CN113816901B (zh) * 2021-08-27 2023-08-15 淮北龙溪生物科技有限公司 一种4－三氟甲基烟酰胺的合成方法

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CZ20031662A3 (cs) 2003-09-17
JP2004525091A (ja) 2004-08-19
IL187126A (en) 2009-08-03
HUP0401099A2 (hu) 2004-09-28
WO2002048111A3 (de) 2003-03-27
AU2002235770A1 (en) 2002-06-24
AR031658A1 (es) 2003-09-24
KR100845376B1 (ko) 2008-07-09
BR0116124A (pt) 2003-12-09
US20030109711A1 (en) 2003-06-12
HUP0401099A3 (en) 2007-02-28
MXPA03005258A (es) 2003-09-25
WO2002048111A2 (de) 2002-06-20
US6864385B2 (en) 2005-03-08
US6541640B2 (en) 2003-04-01
CN1244560C (zh) 2006-03-08
IL156359A (en) 2009-05-04
US20020087004A1 (en) 2002-07-04
CN1479723A (zh) 2004-03-03
TWI222442B (en) 2004-10-21
IL187126A0 (en) 2008-02-09
IL156359A0 (en) 2004-01-04
KR20030060116A (ko) 2003-07-12

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