WO2018202677A1 - Procédé de production d'acides carboxyliques ou de dérivés d'acide carboxylique - Google Patents

Procédé de production d'acides carboxyliques ou de dérivés d'acide carboxylique Download PDF

Info

Publication number
WO2018202677A1
WO2018202677A1 PCT/EP2018/061139 EP2018061139W WO2018202677A1 WO 2018202677 A1 WO2018202677 A1 WO 2018202677A1 EP 2018061139 W EP2018061139 W EP 2018061139W WO 2018202677 A1 WO2018202677 A1 WO 2018202677A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
alkyl
process according
optionally substituted
Prior art date
Application number
PCT/EP2018/061139
Other languages
English (en)
Inventor
Qingyi Li
Mingchun WANG
Janis Jaunzems
Original Assignee
Solvay Sa
Changzhou Keylab Biochemical Co., Ltd.
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
Application filed by Solvay Sa, Changzhou Keylab Biochemical Co., Ltd. filed Critical Solvay Sa
Publication of WO2018202677A1 publication Critical patent/WO2018202677A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms

Definitions

  • This invention concerns a process for the manufacture of carboxylic acids or carboxylic acid derivatives and a process for the manufacture of
  • agrochemically and pharmaceutically active compounds comprising the process for the manufacture of carboxylic acids or their derivatives.
  • Carboxylic acid and their derivatives, in particular 3-halomethylpyrazol-4- yl carboxylic acids and esters, are valuable intermediates in the synthesis of agrochemical and pharmaceutical active ingredients.
  • Agrochemical active ingredients which contain 3-halomethylpyrazol-4-yl building blocks are, for example, 2'-[l,l'-bicycloprop-2-yl]-3-(difluoromethyl)-l-methylpyrazole-4- carboxanilide (Sedaxane), as described, for example, in WO2006015866, 3- (difluoromethyl)- 1 -methyl-N- [2-(3 ' ,4' ,5 ' -trifluorophenyl)phenyl]pyrazole-4- carboxamide (Fluxapyroxad), as described, for example, in WO2006087343, N- (3',4'-Dichloro-5-fluorobiphenyl-2-yl)-3-(difluoromethyl
  • WO2016/152886 discloses oxidation of pyrazolyl ketone derivatives with hypohalite solutions.
  • hypohalites When hypohalites are used for oxidation of the keto function, a large amount, at least three equivalents, of hypohalite is necessary to convert the keto group into a carboxylate salt. This results in a large volume of salt waste per mole carboxylate produced, which is often also difficult to treat because of its organic impurities.
  • hypohalite solutions are often restricted in their upper concentration limit due to stability concerns, the waste volume is even higher per mole carboxylate produced.
  • the process according to the present invention allows for the manufacture of a carboxylic acid or its derivative while avoiding a large amount of salt waste.
  • the process shows good yields, lower waste and can be processed on a large scale.
  • the invention thus concerns a process for the manufacture of a compound of formula (II) comprising a step of catalytic oxidation in the presence of at least one catalyst and at least one oxidant, of compound number (I),
  • the invention further concerns a process as shown above wherein the process for the manufacture of a compound of formula (II) further comprises a step of reacting a compound of formula (III) with a compound selected from the group consisting of co
  • the invention also concerns a process for the manufacture of an agrochemical or pharmaceutical compound, preferably a carboxamide SDHI fungicide, which comprises the processes as shown above for the manufacture of compound (II).
  • designations in singular are in intended to include the plural; for example, "a solvent” is intended to denote also "more than one solvent” or "a plurality of solvents”.
  • catalytic oxidation is intended to denote an oxidation wherein the oxidation is carried out in the presence of at least one oxidant and at least one catalyst. Oxidants and catalysts will be defined as below.
  • the invention concerns a process for the manufacture of a compound of formula (II) comprising a step of catalytic oxidation in the presence of at least one catalyst and at least one oxidant, of compound number (I),
  • R 1 is selected from the group consisting of Ci-C4-alkyl groups which is substituted by at least one halogen atom independently selected from the group consisting of F, CI and Br or by a CF 3 group,
  • R is selected from the group consisting of an optionally substituted Q-Cg alkyl group, an optionally substituted C 3 -Cg cycloalkyl group, an optionally substituted aryl group and an optionally substituted heteroaryl group,
  • R is selected from the group consisting of H, X, COOR, OR, SR,
  • R is selected from the group consisting of hydrogen, a Cp Ci 2 -alkyl, CN, C 2 -C 6 alkenyl, aryl, C 3 -Cg cycloalkyl, aralkyl or heteroaryl group, each of which is optionally substituted, with the proviso that both R in C(0)NR 2 may be the same or different, wherein X is a halogen atom and is selected from the group consisting of F, CI, Br and I, and R is independently selected from the group consisting of hydrogen or a Ci-Ci 2 -alkyl, C 2 -C 6 alkenyl, aryl, cycloalkyl, aralkyl, heteroaryl,
  • R 4 is selected from the group consisting of H, Ci-Ci 2 -alkyl, C 2 -C 6 alkenyl, C 3 -C 8 cycloalkyl, aryl, heteroaryl or aralkyl group, each of which is optionally substituted,
  • R 5 is a -OH group or a -O " group, wherein, when R 5 is a -O " group, at least one countercation is present in (II), such as an alkali or earth alkali cation.
  • Ci-C4-alkyl groups is intended to denote straight or branched alkyl groups having one to four carbon atoms. This group comprises methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec- and t-butyl. "Ci-Cg alkyl group” intends to denote straight or branched alkyl groups having one to eight carbon atoms.
  • This group comprises methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec- and t-butyl, n-pentyl and its isomers, n-hexyl and its isomers, 1,3-dimethylbutyl, 3,3-dimethylbutyl, n-heptyl and its isomers and n- octyl and its isomers.
  • the Q to C 4 alkyl groups are the most preferred groups of the Q-Cg alkyl group.
  • the term "Ci-Ci 2 -alkyl groups" is intended to denote straight or branched alkyl groups having one to twelve carbon atoms.
  • the group comprises, for example, n-nonyl and its isomers, n-decyl and its isomers, n-undecyl and its isomers and n-dodecyl and its isomers.
  • the Q to C 4 alkyl groups are the most preferred groups of the C 1 -C 12 alkyl group.
  • C 3 -C 8 cycloalkyl group intends to denote mono-, bi- or tricyclic hydrocarbon groups comprising 3 to 10 carbon atoms, especially 3 to 6 carbon atoms.
  • monocyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • bicyclic groups include bicyclo[2.2.1]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl.
  • tricyclic groups are adamantyl and
  • aryl group intends to denote C 5 -C 18 monocyclic and polycyclic aromatic hydrocarbons with 5 to 18 carbon atoms in the cyclic system.
  • this definition comprises, for example, the meanings
  • cyclopentadienyl phenyl, cycloheptatrienyl, cyclooctatetraenyl, naphthyl and anthracenyl.
  • this definition comprises, for example, the meanings 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2- pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4- isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4- oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4- imidazolyl, l,2,4-oxadiazol-3-yl, l,2,4-oxadiazol-5-yl, l,2,4-thiadiazol-3-yl, l,2,4-thiadiazol-5-yl, l,2,4-triazol-3-yl, l,3,4-oxadiazol-2-yl, l
  • C 2 -C6 alkenyl intends to denote a group comprising a carbon chain and at least one double bond.
  • Alkenyl group are, for example, ethenyl, propenyl, butenyl, pentenyl or hexenyl.
  • aralkyl intends to denote alkyl groups which are substituted by aryl groups, which have a Ci-Cg-alkylene chain and which may be substituted in the aryl skeleton or the alkylene chain by one or more heteroatoms selected from the group consisting of O, N, P and S.
  • a C1-C4 alkyl group, Q-Cg alkyl group, Ci-Ci 2 alkyl group, aryl group, heteroaryl group, Ci-Ci 2 -alkyl group, C 2 -C 6 alkenyl group, aryl group, aralkyl group or heteroaryl group each can be optionally substituted by one or more substituents of the following group consisting of R', -X', -OR', - SR', -NR' 2 , -SiR' 3 , -COOR', -(C-O)R', -CN and -CONR' 2 , wherein R' is selected independently, from the group consisting of hydrogen or Ci-Ci 2 -alkyl group and X' is selected from the group consisting of F, CI, Br, or I.
  • R 1 is a group selected from the group consisting of Ci-C 4 -alkyl groups, which is substituted by at least one halogen atom independently selected from the group consisting of F, CI and Br or by a CF 3 group.
  • Ri is selected from the group consisting of CF 2 H, CF 3 , CC1F 2 , CC1 2 H and CC1 3 , wherein CF 2 H and CF 3 are most preferred.
  • R is selected from the group consisting of an optionally substituted Q-Cg alkyl group, an optionally substituted C 3 -Cg cycloalkyl group, an optionally substituted aryl group and an optionally substituted heteroaryl group.
  • R are ethyl, methyl and phenyl, wherein a methyl group is most preferred as R .
  • R 3 is selected from the group consisting of H, X, COOR, OR, SR, C(0)NR 2 , wherein R is selected from the group consisting of hydrogen, a Ci-Ci 2 -alkyl, C 2 - C alkenyl, aryl, C 3 -C 8 cycloalkyl, aralkyl or heteroaryl group, each of which is optionally substituted, with the proviso that both R in C(0)NR 2 may be the same or different, wherein X is a halogen atom and is selected from the group consisting of F, CI, Br and I, and R is independently selected from the group consisting of hydrogen or a Ci-Ci 2 -alkyl, C 2 -C 6 alkenyl, aryl, cycloalkyl, aralkyl, heteroaryl, each of which can be optionally substituted.
  • R 4 is selected from the group consisting of H, Ci-Ci 2 -alkyl, C 2 -C 6 alkenyl,
  • R 4 is preferably selected from the group consisting of Q to C 4 alkyl groups, H, optionally substituted phenyl and optionally substituted benzyl, wherein a methyl group is the most preferred R 4 .
  • R 5 is a -OH group or a -O " group, wherein, when R 5 is a -O " group, at least one countercation is present in (II), such as an alkali or earth alkali cation, wherein alkali cations such as sodium or potassium are preferred.
  • the process can comprise a step in which a compound (II) in which R 5 is -O " is treated with an aqueous acidic solution, for example an aq. HC1 solution, such that the compound (II) is protonated and R 5 is -OH.
  • compound (I) is submitted to a step of catalytic oxidation, wherein the at least one oxidant present often is selected from the group consisting of oxygen, a gas comprising oxygen, a peroxide, KMn0 4 and ozone.
  • a gas comprising oxygen is intended to denote a gas mixture in which from 1 vol to 99% oxygen is present; for example, such a gas is air.
  • Peroxides can be organic and inorganic peroxides, such as tert-Butylhydroperoxid and hydrogen peroxide, wherein the peroxides and the reaction conditions must be chosen such that they are compatible with the compound (I), in particular with the pyrazole ring system.
  • oxygen and a gas comprising oxygen, in particular air are the most preferred oxidants. Oxygen and a gas comprising oxygen can be applied at elevated pressure or ambient pressure, or can be bubbled through the reaction mixture.
  • the at least one catalyst often is selected from the group consisting of a metal salt comprising at least one metal species and a metal complex comprising at least one metal species.
  • metal species intends to denote a metal atom with charge zero or a positive charge of one, two, three or up to seven, depending on the valency in the respective catalyst compound. In some catalyst compounds, more than one metal species can be present, but generally, the catalyst is preferred to have one metal species present.
  • the catalyst compound is a metal salt
  • the at least one metal species often is a cation with a positive charge of one, two, three, four, five, six or seven.
  • the at least one metal salt or metal complex can comprise at least one metal species selected from the group consisting from the groups 3 to 12 of the periodic system. This includes the groups of the lanthanides and actinides (atomic numbers 57 to 71 and 89 to 103).
  • the at least one metal species is selected from Ti, Co, Y, Ce, Yb, La, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd and Hg. This is in particular applicable for metal salt catalysts.
  • Co, Y, Ce, Yb, La, Cr, Mo, Mn, Fe, Ni, Cu, Zn and Hg are preferred metal species, in particular in metal salt catalysts.
  • Metal salt catalysts comprising Co, Y, Ce, Yb, La, Fe and Mn are more particularly preferred.
  • the at least one metal salt can be selected from the group consisting of oxides, halide, nitrates, acetates, or hydrates of any of the foregoing.
  • the at least one metal salt may be a mixed salt, wherein any of the anions oxide, hydroxide, carbonate, halide, nitrate, acetate are mixed, such that a mixed salt of two or more anions exist.
  • the at least one catalyst is selected from the group consisting of Fe(N0 3 ) 3 or its hydrate, Co(N0 3 ) 3 or its hydrate, Ni(N0 3 ) 3 or its hydrate, Co(N0 3 ) 3 or its hydrate, Mn(N0 3 ) 3 or its hydrate, Zn(N0 3 ) 3 or its hydrate, Mn(OAc 2 ) or its hydrate, Co(OAc 2 ), Cu(OAc 2 ), CuCl 2 or its hydrate, CuO, CuBr 2 , CuCl, CuBr, Cul and Re 2 0 7 . Nitrates and acetates are particularly preferred metal salts.
  • two or more catalysts can be present in the process for the manufacture of a compound of formula (II).
  • catalytic systems which comprise Mn(N0 3 ) 3 or its hydrate, Mn(N0 3 ) 3 4H 2 0, and one additional metal salt which preferably is a nitrate or its hydrate or an acetate or its hydrate.
  • the additional metal salt preferably comprises as metal species Co, Y, Ce, Yb, La or Fe.
  • the at least one catalyst in the process of the present invention often is present in an amount of from 0.01 to 30 mol calculated on the amount of compound (I). Generally, the at least one catalyst in the process of the present invention is present in an amount of equal to or more than 0.01 mol , preferably equal to or more than 1 mol calculated on the amount of compound (I). In some systems, an amount of equal to or more than 5 mol calculated on the amount of compound (I) gives good results. Often, the at least one catalyst in the process of the present invention is present in an amount of equal to or less than 30 mol , preferably equal to or less than 20 mol calculated on the amount of compound (I). In some systems, an amount of equal to or less than 15 mol calculated on the amount of compound (I) gives good results.
  • At least one additional reagent can be present in the reaction, wherein the at least one additional reagent is a co-oxidant or an auxiliary.
  • Co-oxidants can be, for example, TEMPO (2,2,6,6- Tetramethylpiperidinyloxyl), 4-hydroxy-TEMPO, 4-acetamido-TEMPO, 2- Azaadamantane N-Oxyl (AZADO), 9-Azabicyclo[3.3.1]nonane N-Oxyl (ABNO) and 9-Azanoradamantane N-oxyl (Nor- AZADO).
  • Auxiliary agents can be, for example, KC1, ⁇ , ⁇ ', ⁇ ' '-trihydroxyisocyanuric acid (THICA) and N- hydroxyphthalimide (NHPI), tetra-n-butylammonium bromide or even NaCl.
  • THICA ⁇ , ⁇ ', ⁇ ' '-trihydroxyisocyanuric acid
  • NHPI N- hydroxyphthalimide
  • Particularly suitable catalytic systems employing a co-oxidant and/or auxiliary are, for example, THICA/Mn(OAc) 2 , NHPI/Mn(OAc)2,
  • the oxidation often is carried out in a suitable solvent, such as
  • dichloromethane dichloroethane, methanol, ethanol, DMSO, DMF, acetonitrile or aliphatic ethers such as diethylether, or aromatic hydrocarbons such as toluene.
  • Other very suitable solvents often are optionally substituted carboxylic acids, in particular acetic acid, trichloroacetic acid, dichloro acetic acid, propionic acid and butyric acid.
  • the oxidation often is carried out at temperatures of from 0°C to 120°C.
  • a temperature of from 60°C to 110°C can be particularly preferred.
  • the invention also concerns a process as described for the manufacture of a compound of formula (II) which further comprises a step of reacting a compound of formula (III) with a compound selected from the group consisting of compound (IV), (V) and (VI) to obtain the compound of
  • R 6 independently is selected from the group consisting of an Cp Ci 2 -alkyl, C 2 -C 6 alkenyl or C 3 -Cg-cycloalkyl group, each of which is optionally substituted
  • R 7 and R 7' independently from each other are selected from the group consisting of H, Ci-Ci 2 -alkyl, C 2 -C 6 alkenyl, cycloalkyl, aryl, heteroaryl or aralkyl group, each of which is optionally substituted,
  • R 8 is selected from the group consisting of Ci-Ci 2 -alkyl, OR 9 and NR 9 R 9 , wherein R 9 and R 9 independently are selected from the group consisting of Cp Ci 2 -alkyl and H.
  • Y is O and R 6 is ethyl, or Y is NR 6 and both R 6 are methyl, R 3 is H, R 4 and R 2 are methyl, and R 1 is CF 2 H or CF 3 .
  • R 7 in (V) is H
  • R 7' is phenyl, benzyl or C 3 to C 6 cycloalkyl, each of which can be optionally substituted.
  • both R 6 in (III) with the N to which they are attached can form a heterocyclic compound, such as piperidinyl.
  • All embodiments of the present invention are particularly preferred when (I) is l-(3-(difluoromethyl)-l-methyl-lH-pyrazol-4-yl)ethanone and (II) is 3- (difluoromethyl)-l-methyl-lH-pyrazole-4-carboxylic acid, and when (I) is l-(3- (trifluoromethyl)-l-methyl-lH-pyrazol-4-yl)ethanone and (II) is 3- (trifluoromethyl)-l-methyl-lH-pyrazole-4-carboxylic acid.
  • the invention also concerns a process for the manufacture of an agrochemical or pharmaceutical compound, preferably a carboxamide SDHI fungicide, which comprises the process for manufacturing a compound of formula (II) as described above.
  • SDHI fungicides are SDH inhibitors which target succinate dehydrogenase (SDH, so-called complex II in the mitochondrial respiration chain), and generally contain a carboxamide moiety, wherein the carbonyl carbon atom is attached to a pyrazole ring identical to the pyrazole system of formula (II).
  • An agrochemically or pharmaceutically active compound can, for example, be obtained by converting a compound of formula (II) obtained by the process according to the present invention into a carboxylic acid halide or anhydride, and reacting the carboxylic acid halide or anhydride with a primary or secondary amine to obtain a carboxamide which is an agrochemically or pharmaceutically active compound.
  • Such reactions are known, for example, from
  • an agrochemical compound for example compounds such as N- (3',4'-Dichlor-5-fluorbiphenyl-2-yl)-3-(difluormethyl)-l-methylpyrazol-4- carboxamid, 3-(difluoromethyl)-l-methyl-N-[2-(3',4',5'- trifluorophenyl)phenyl]pyrazole-4-carboxamide, N-(2-Bicyclopropyl-2- ylphenyl)-3-difluoromethyl-l-methyl-lH-pyrazol-4-carboxylic acid amide, 3- (Difluormethyl)- 1 -methyl-N- [ 1 ,2,3,4-tetrahydro-9-( 1 -methylethyl)- 1 ,4- methanonaphthalen-5-yl]-lH-pyrazol-4-carboxamid or N-[(lRS,4SR)-9- (dichlor
  • the new process according to the present invention allows for efficient syntheses of carboxylic acids or a carboxylic acid derivatives, which are useful intermediates for, e.g., agrochemical and pharmaceutical compounds. Departing from easily accessible starting materials, such as methyl ketones, the carboxylic acids or a carboxylic acid derivatives can be obtained while avoiding a high amount of salt waste which often also is difficult to dispose of and/or recycle due to organic impurities. Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.
  • Example 1 The catalytic reaction is performed in a 15-mL autoclave reactor with an internal Teflon insert.0.5 mmol of l-(3-(difluoromethyl)-l-methyl-lH-pyrazol-4- yl)ethanone, 0.1 mmol of Cu(N0 3 ) 3 3H 2 0 and 2 mL of acetonitrile are added into the reactor. Then, the reactor is charged with 0.6 MPa Air and heated to 120 °C under magnetic stirring for approximately 12 hours. After cooling to room temperature, the reaction mixture is diluted with 4 mL methanol and 5 mL IN HC1 before analysis with HPLC.
  • Run 1 10 kg of l-(3-(difluoromethyl)-l-methyl-lH-pyrazol-4-yl)ethanone was mixed with 60 kg acetic acid, 0.28 kg Co(N0 3 )26H 2 0 and 1.03 kg of a 50 wt% aqueous solution of Mn(N03) 2 were added. The mixture was heated to 75- 80°C, and oxygen was bubbled through. After conversion was stable (GC), the mixture was cooled to room temperature, and crude 3-(difluoromethyl)-l- methyl-lH-pyrazole-4-carboxylic acid precipitated. The precipitate was filtered off, and the mother liquor was used as solvent in run 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'acides carboxyliques ou de dérivés d'acide carboxylique et un procédé de fabrication de composés actifs sur les plans agrochimique et pharmaceutique comprenant le procédé de fabrication d'acides carboxyliques ou de leurs dérivés. Le procédé de fabrication d'acides carboxyliques ou de dérivés d'acide carboxylique comprend une étape d'oxydation catalytique en présence d'au moins un catalyseur et d'au moins un oxydant, du composé numéro (I) pour obtenir un composé de formule (II).
PCT/EP2018/061139 2017-05-02 2018-05-02 Procédé de production d'acides carboxyliques ou de dérivés d'acide carboxylique WO2018202677A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/CN2017/082689 WO2018201272A1 (fr) 2017-05-02 2017-05-02 Procédé de production d'acides carboxyliques ou de dérivés d'acide carboxylique
CNPCT/CN2017/082689 2017-05-02

Publications (1)

Publication Number Publication Date
WO2018202677A1 true WO2018202677A1 (fr) 2018-11-08

Family

ID=62143131

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/CN2017/082689 WO2018201272A1 (fr) 2017-05-02 2017-05-02 Procédé de production d'acides carboxyliques ou de dérivés d'acide carboxylique
PCT/EP2018/061139 WO2018202677A1 (fr) 2017-05-02 2018-05-02 Procédé de production d'acides carboxyliques ou de dérivés d'acide carboxylique

Family Applications Before (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/082689 WO2018201272A1 (fr) 2017-05-02 2017-05-02 Procédé de production d'acides carboxyliques ou de dérivés d'acide carboxylique

Country Status (1)

Country Link
WO (2) WO2018201272A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020210094A1 (fr) * 2019-04-08 2020-10-15 Amgen Inc. Dispositif automatisé de délivrance de médicaments et conteneur
CN117384096A (zh) * 2023-12-13 2024-01-12 山东国邦药业有限公司 一种二氟吡唑酸的制备方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003070705A1 (fr) 2002-02-19 2003-08-28 Bayer Cropscience Aktiengesellschaft Carboxanilides de pyrazolyle disubstitues
WO2004035589A1 (fr) 2002-10-18 2004-04-29 Syngenta Participations Ag Derives d'heterocyclocarboxamide
WO2006015866A1 (fr) 2004-08-12 2006-02-16 Syngenta Participations Ag Procédé servant à protéger des plantes utiles ou une matière de propagation de plante
WO2006087343A1 (fr) 2005-02-16 2006-08-24 Basf Aktiengesellschaft Anilides d'acide carboxylique pyrazole, procedes de production associes et agents les contenant pour la lutte antifongique
WO2007031323A1 (fr) 2005-09-16 2007-03-22 Syngenta Participations Ag. Procédé de production d'amides
WO2007048556A1 (fr) 2005-10-25 2007-05-03 Syngenta Participations Ag Dérivés d'amides hétérocycliques utiles en tant que microbiocides
WO2012055864A1 (fr) 2010-10-27 2012-05-03 Solvay Sa Procédé de préparation de pyrazole-4-carboxamides
WO2016152886A1 (fr) 2015-03-26 2016-09-29 旭硝子株式会社 Procédé de fabrication d'un dérivé pyrazole
CN106554310A (zh) * 2015-09-25 2017-04-05 陈旭 一种3-二氟甲基-1-甲基吡唑-4-甲酸的合成方法
WO2017054112A1 (fr) 2015-09-28 2017-04-06 常州市卜弋科研化工有限公司 Procédé de préparation d'acide 3-fluoroalkyl-1-méthylpyrazole-4-carboxylique

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104945325B (zh) * 2015-06-19 2017-04-05 浙江永太科技股份有限公司 一种吡唑甲酸衍生物的制备方法
KR101730393B1 (ko) * 2015-08-06 2017-05-11 (주)부흥산업사 피라졸 카르복실산 유도체의 제조방법

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003070705A1 (fr) 2002-02-19 2003-08-28 Bayer Cropscience Aktiengesellschaft Carboxanilides de pyrazolyle disubstitues
WO2004035589A1 (fr) 2002-10-18 2004-04-29 Syngenta Participations Ag Derives d'heterocyclocarboxamide
WO2006015866A1 (fr) 2004-08-12 2006-02-16 Syngenta Participations Ag Procédé servant à protéger des plantes utiles ou une matière de propagation de plante
WO2006087343A1 (fr) 2005-02-16 2006-08-24 Basf Aktiengesellschaft Anilides d'acide carboxylique pyrazole, procedes de production associes et agents les contenant pour la lutte antifongique
WO2007031323A1 (fr) 2005-09-16 2007-03-22 Syngenta Participations Ag. Procédé de production d'amides
WO2007048556A1 (fr) 2005-10-25 2007-05-03 Syngenta Participations Ag Dérivés d'amides hétérocycliques utiles en tant que microbiocides
WO2012055864A1 (fr) 2010-10-27 2012-05-03 Solvay Sa Procédé de préparation de pyrazole-4-carboxamides
WO2016152886A1 (fr) 2015-03-26 2016-09-29 旭硝子株式会社 Procédé de fabrication d'un dérivé pyrazole
EP3275868A1 (fr) * 2015-03-26 2018-01-31 Asahi Glass Company, Limited Procédé de fabrication d'un dérivé pyrazole
CN106554310A (zh) * 2015-09-25 2017-04-05 陈旭 一种3-二氟甲基-1-甲基吡唑-4-甲酸的合成方法
WO2017054112A1 (fr) 2015-09-28 2017-04-06 常州市卜弋科研化工有限公司 Procédé de préparation d'acide 3-fluoroalkyl-1-méthylpyrazole-4-carboxylique

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
"Bioactive Heterocyclic Compound Classes", 2012, WILEY, pages: 175 - 193
"Modern Crop Protection Compounds", 2012, WILEY, pages: 627 - 639
FRANCESCO MINISCI ET AL: "Highly Selective and Efficient Conversion of Alkyl Aryl and Alkyl Cyclopropyl Ketones to Aromatic and Cyclopropane Carboxylic Acids by Aerobic Catalytic Oxidation: A Free-radical Redox Chain Mechanism", SYNLETT, no. 4, 1 January 2002 (2002-01-01), DE, pages 610 - 612, XP055470008, ISSN: 0936-5214 *
K. ARAVINDA KUMAR ET AL: "A Metal-Free Approach to Carboxylic Acids by Oxidation of Alkyl, Aryl, or Heteroaryl Alkyl Ketones or Arylalkynes", SYNTHESIS, vol. 47, no. 20, 15 July 2015 (2015-07-15), STUTTGART, DE., pages 3161 - 3168, XP055470016, ISSN: 0039-7881, DOI: 10.1055/s-0034-1381026 *
S. GURUNATH ET AL: "Re2O7-Catalyzed Carbon-Carbon Bond Cleavage of Ketones into Carboxylic Acids with aq. TBHP", SYNLETT, vol. 1999, no. 5, 1 May 1999 (1999-05-01), DE, pages 559 - 560, XP055495948, ISSN: 0936-5214, DOI: 10.1055/s-1999-2669 *
TACHIKAWA YUMA ET AL: "Aerobic photooxidative cleavage of 1,3-diketones to carboxylic acids using 2-chloroanthraquinone", TETRAHEDRON LETTERS, vol. 54, no. 46, 10 September 2013 (2013-09-10), pages 6218 - 6221, XP028735833, ISSN: 0040-4039, DOI: 10.1016/J.TETLET.2013.09.015 *
WANG MIN ET AL: "Oxidative C(OH)C bond cleavage of secondary alcohols to acids over a copper catalyst with molecular oxygen as the oxidant", JOURNAL OF CATALYSIS, ACADEMIC PRESS, DULUTH, MN, US, vol. 348, 16 March 2017 (2017-03-16), pages 160 - 167, XP029963543, ISSN: 0021-9517, DOI: 10.1016/J.JCAT.2017.02.017 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020210094A1 (fr) * 2019-04-08 2020-10-15 Amgen Inc. Dispositif automatisé de délivrance de médicaments et conteneur
US11464706B2 (en) 2019-04-08 2022-10-11 Amgen Inc. Automated drug delivery device and container
CN117384096A (zh) * 2023-12-13 2024-01-12 山东国邦药业有限公司 一种二氟吡唑酸的制备方法

Also Published As

Publication number Publication date
WO2018201272A1 (fr) 2018-11-08

Similar Documents

Publication Publication Date Title
RU2498977C9 (ru) Способ региоселективного синтеза производных 1-алкил-3-галогеналкилпиразол-4-карбоновой кислоты
WO2018024644A1 (fr) Fabrication de composés hydrazinyle utiles dans la fabrication d'acide pyrazole carboxylique et de dérivés, composés hydrazinyle et leur utilisation
JP7080407B2 (ja) ハロゲン置換化合物およびその調製方法と適用
US20210040043A1 (en) Halogen substituted diketones, pyrazole compounds and processes for the manufacture of pyrazole compounds
WO2018202677A1 (fr) Procédé de production d'acides carboxyliques ou de dérivés d'acide carboxylique
WO2017194517A1 (fr) Composition comprenant des acides ou des esters 3-(halogénoalkyle ou formyle)-1h-pyrazole-4-carboxyliques, sa fabrication et son utilisation pour la préparation de carboxamides
EP3495351A1 (fr) Oxydation d'un composé pyrazolyl cétone en l' acide carboxylique correspondant
CN111587241A (zh) 亚胺鎓化合物的制造方法及其在制造吡唑衍生物中的应用
CN111372908A (zh) 用于制造二氟乙酰氯的方法和中间体
EP3415507A1 (fr) Procédé de fabrication de composés d'acétamides aryl-thiadiazole
WO2019122204A1 (fr) Procédé de fabrication de composés pyrazoles
JPH0361664B2 (fr)
HU204792B (en) Process for producing 1-aryl-5-aminopyrazole derivatives
US20210171468A1 (en) Process for the manufacture of pyrazole carboxylic derivatives and precursors thereof
EP1368298B1 (fr) Procede de preparation d'esters d'acide 2 - hydroxy-benzoique substitues en 5 et/ou 6
CN114149370A (zh) 1-(4-卤苯基)-吡唑烷-3-酮的制备方法
ZA200305638B (en) Process for the preparation of 5- and/or 6-substituted-2-hydroxy-benzoic acid esthers.
BR112017002773B1 (pt) Processos para a preparação de 5-fluoro-1h-pirazóis e derivados e uso do intermediário 3-perfluoroetil-4-perfluorometil-5-fluoro-pirazol

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18723447

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18723447

Country of ref document: EP

Kind code of ref document: A1