WO2013127441A1 - Process for the preparation of substituted phenylpropanones - Google Patents

Process for the preparation of substituted phenylpropanones Download PDF

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Publication number
WO2013127441A1
WO2013127441A1 PCT/EP2012/053371 EP2012053371W WO2013127441A1 WO 2013127441 A1 WO2013127441 A1 WO 2013127441A1 EP 2012053371 W EP2012053371 W EP 2012053371W WO 2013127441 A1 WO2013127441 A1 WO 2013127441A1
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Prior art keywords
formula
compound
preparation
crc
alkyl
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PCT/EP2012/053371
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French (fr)
Inventor
Daniel Stierli
Harald Walter
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Syngenta Participations AG
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Syngenta Participations AG
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Priority to CA2863420A priority Critical patent/CA2863420C/en
Priority to EP12708105.7A priority patent/EP2819983B1/en
Priority to MX2014009829A priority patent/MX349740B/en
Priority to PL12708105T priority patent/PL2819983T3/en
Priority to PCT/EP2012/053371 priority patent/WO2013127441A1/en
Priority to KR1020147024525A priority patent/KR101902373B1/en
Priority to ES12708105.7T priority patent/ES2652365T3/en
Priority to JP2014558015A priority patent/JP6251197B2/en
Priority to BR112014021063-2A priority patent/BR112014021063B1/en
Priority to HUE12708105A priority patent/HUE037597T2/en
Priority to PT127081057T priority patent/PT2819983T/en
Priority to CN201280070805.2A priority patent/CN104136409B/en
Application filed by Syngenta Participations AG filed Critical Syngenta Participations AG
Priority to US14/379,013 priority patent/US9073839B2/en
Priority to DK12708105.7T priority patent/DK2819983T3/en
Priority to AU2012371236A priority patent/AU2012371236B2/en
Publication of WO2013127441A1 publication Critical patent/WO2013127441A1/en
Priority to IL233938A priority patent/IL233938A/en
Priority to ZA2014/05824A priority patent/ZA201405824B/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/516—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of nitrogen-containing compounds to >C = O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives

Definitions

  • the present invention relates to a process for the preparation of propane-2-one-substituted phenyls, in particular to the preparation of 1-(2,4,6-trihalo-phenyl)-propan-2-ones.
  • Propane-2-one-substituted phenyls are valuable intermediates for the preparation of fungicidally active pyrazole carboxamides, as described for example in
  • Rn is hydrogen, halogen or d-C 6 alkyl
  • R 12 is hydrogen, halogen, CrC 6 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkinyl, C3-C 6 cycloalkyl-C 3 - C 6 alkinyl, halophenoxy, halophenyl-C 3 -C 6 alkinyl, C
  • R 13 is hydrogen, halogen or CrC 6 alkyl
  • a disadvantage of this prior art process is the high production costs caused by the significant number of reaction steps which makes this process uneconomical and especially unsuitable for a large-scale production.
  • WO 00/34229 describes a process for the preparation of a ketone of formula V
  • Diazonium salts in general are sensitive to physical agents such as heat, light, shock, static electricity and dehydration that can lead to rapid, uncontrollable decompositions and explosions.
  • a further disadvantage is that 2 different equipments are needed to perform the reactions.
  • the aim of the present invention is therefore to provide a novel process for the production of
  • propane-2-one-substituted phenyls that avoids the disadvantages of the known process and makes it possible to prepare propane-2-one-substituted phenyls in high yields and good quality in an economically advantageous way with less reaction steps.
  • R is hydrogen, halogen or CrC 6 alkyl
  • R 2 is hydrogen, halogen, CrC 6 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkinyl, C 3 -C 6 cycloalkyl-C 3 -C 6 alkinyl, halophenoxy, halophenyl-C 3 -C 6 alkinyl, CrC 6 haloalkyl, CrC 6 haloalkoxy, C 2 -C 6 haloalkenyl or C 2 -C 6 haloalkenyloxy; and R 3 is hydrogen, halogen or d-C 6 alkyl;
  • R 2 and R 3 have the meanings as described under formula I, in the presence of an inert organic solvent, to a mixture comprising an organic nitrite of formula III
  • R 4 -0-N 0 (III), wherein R 4 is CrC 8 alkyl, a compound of formula IV
  • the process according to the invention uses easily accessible and nontoxic starting material, without the need of isolation or accumulation of diazonium salt and is therefore especially suitable for the large-scale preparation of a compound of formula I.
  • the process according to the invention is especially suitable for the production of compounds of formula I, wherein at least one of R ⁇ R 2 and R 3 is different from hydrogen.
  • the process according to the invention is especially suitable for the preparation of compounds of formula I, wherein at least one of R ⁇ R 2 and R 3 is halogen.
  • the compound of formula V can be prepared preferably by a one pot reaction adding the aniline of formula II to a mixture of isoprenylacetate of formula IV, an organic nitrite of formula III and a solvent.
  • R 4 is C 4 -C 7 alkyl.
  • a preferred nitrite is tert-butyl nitrite.
  • the mixture of isoprenylacetate of formula IV, an organic nitrite of formula III and a solvent can additionally contain a copper compound which can be advantageous to increase yield and/or quality of the product.
  • Preferred copper compounds are CuO, CuCI 2 or CuSCv
  • the amount of the copper compounds is preferably is 1-20 mol% in the relation to the aniline of formula II.
  • the reaction is a temperature of -10°C to 50°C. No isolation or accumulation of the diazonium salt is required for this process step.
  • the same solvent is used for the aniline of formula II and the mixture of isoprenylacetate of formula IV, and the organic nitrite of formula III.
  • Suitable inert organic solvents are for example ketones, for example acetone, methylethylketone (MEK) or nitriles, for example acetonitrile.
  • Preferred solvents are acetone and acetonitrile.
  • the compounds of formula II and III are either known or can be prepared according to methods well known in the art. Some compounds of formula II are commercially available, e.g. the compound of formula II, wherein R 2 and R 3 is chloro. Isoprenylacetate of formula IV is commercially available.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a process for the preparation of a compound of formula (I) wherein the substituents are defined as in claim 1, which process comprises adding a compound of formula (II), wherein R1, R2 and R3 have the meanings as described under formula (I), in the presence of an inert organic solvent, to a mixture comprising an organic nitrite of formula (III) R4-O-N=O, wherein R4 is C1-C8alkyl, a compound of formula (IV), and an inert organic solvent.

Description

PROCES S FOR THE PREPARATION OF SUBSTITUTED PHENYL PRO PANONES
The present invention relates to a process for the preparation of propane-2-one-substituted phenyls, in particular to the preparation of 1-(2,4,6-trihalo-phenyl)-propan-2-ones. Propane-2-one-substituted phenyls are valuable intermediates for the preparation of fungicidally active pyrazole carboxamides, as described for example in
WO 2010/063700.
It is known from scheme 3 on page 1 1 of WO 2010/063700 to prepare propane-2-one- substituted phenyls by
a) reducing a compound of formula XIX to a compound of formula XX,
Figure imgf000002_0001
wherein Rn is hydrogen, halogen or d-C6alkyl;
R12 is hydrogen, halogen, CrC6alkyl, C2-C6alkenyl, C3-C6alkinyl, C3-C6cycloalkyl-C3- C6alkinyl, halophenoxy, halophenyl-C3-C6alkinyl,
Figure imgf000002_0002
C
C6haloalkyl,
CrC6haloalkoxy, C2-C6haloalkenyl, or C2-C6haloalkenyloxy; and
R13 is hydrogen, halogen or CrC6alkyl;
b) reacting the compound of formula XX to an activated benzylic derivative of formula XXI,
Figure imgf000002_0003
(XX) wherein Y represents a leaving group, such as halogen, mesylate or tosylate, la XXII
Figure imgf000003_0001
(XXI) and
d) reacting the compound of formula XXII with a Grignard reagent of the formula R5-MgBr, wherein R5 is for example methyl, to the propane-2-one-substituted phenyl of formula Xa (wherein R5 is methyl).
Figure imgf000003_0002
A disadvantage of this prior art process is the high production costs caused by the significant number of reaction steps which makes this process uneconomical and especially unsuitable for a large-scale production.
WO 00/34229 describes a process for the preparation of a ketone of formula V
Figure imgf000003_0003
by diazotizing an aniline of formula VI
Figure imgf000003_0004
and reacting the resulting diazonium salt with isopropenylacetate of formula X and re
Figure imgf000004_0001
with an organic nitrite in the presence of hydrogen chloride.
A disadvantage of this process is the accumulation of the very reactive diazonium salt in the reaction mixture. Diazonium salts in general are sensitive to physical agents such as heat, light, shock, static electricity and dehydration that can lead to rapid, uncontrollable decompositions and explosions.
A further disadvantage is that 2 different equipments are needed to perform the reactions. The aim of the present invention is therefore to provide a novel process for the production of
propane-2-one-substituted phenyls that avoids the disadvantages of the known process and makes it possible to prepare propane-2-one-substituted phenyls in high yields and good quality in an economically advantageous way with less reaction steps.
Thus, according to the present invention, there is provided a process for the preparation of the compound of formula I
Figure imgf000004_0002
wherein
R is hydrogen, halogen or CrC6alkyl;
R2 is hydrogen, halogen, CrC6alkyl, C2-C6alkenyl, C3-C6alkinyl, C3-C6cycloalkyl-C3-C6alkinyl, halophenoxy, halophenyl-C3-C6alkinyl,
Figure imgf000004_0003
CrC6haloalkyl, CrC6haloalkoxy, C2-C6haloalkenyl or C2-C6haloalkenyloxy; and R3 is hydrogen, halogen or d-C6alkyl;
which process comprises
adding a compound of formula II
Figure imgf000005_0001
wherein R2 and R3 have the meanings as described under formula I, in the presence of an inert organic solvent, to a mixture comprising an organic nitrite of formula III
R4-0-N=0 (III), wherein R4 is CrC8alkyl, a compound of formula IV
Figure imgf000005_0002
and an inert organic solvent.
The process according to the invention uses easily accessible and nontoxic starting material, without the need of isolation or accumulation of diazonium salt and is therefore especially suitable for the large-scale preparation of a compound of formula I.
The process according to the invention is especially suitable for the production of compounds of formula I, wherein at least one of R^ R2 and R3 is different from hydrogen. The process according to the invention is especially suitable for the preparation of compounds of formula I, wherein at least one of R^ R2 and R3 is halogen.
Further compounds of formula I can be advantageously prepared, wherein R^ R2 and R3 are all halogen, especially chloro. Compounds of formula I which can be advantageously prepared according to the process of this invention are described in Table 1.
Table 1 : Preferred compounds of formula I
Figure imgf000006_0001
Figure imgf000006_0002
The compound of formula V can be prepared preferably by a one pot reaction adding the aniline of formula II to a mixture of isoprenylacetate of formula IV, an organic nitrite of formula III and a solvent. In preferred compounds of formula III, R4 is C4-C7alkyl. A preferred nitrite is tert-butyl nitrite. The mixture of isoprenylacetate of formula IV, an organic nitrite of formula III and a solvent can additionally contain a copper compound which can be advantageous to increase yield and/or quality of the product. Preferred copper compounds are CuO, CuCI2 or CuSCv The amount of the copper compounds is preferably is 1-20 mol% in the relation to the aniline of formula II. Advantageous for the reaction is a temperature of -10°C to 50°C. No isolation or accumulation of the diazonium salt is required for this process step. Preferably, the same solvent is used for the aniline of formula II and the mixture of isoprenylacetate of formula IV, and the organic nitrite of formula III. Suitable inert organic solvents are for example ketones, for example acetone, methylethylketone (MEK) or nitriles, for example acetonitrile. Preferred solvents are acetone and acetonitrile.
The compounds of formula II and III are either known or can be prepared according to methods well known in the art. Some compounds of formula II are commercially available, e.g. the compound of formula II, wherein R2 and R3 is chloro. Isoprenylacetate of formula IV is commercially available.
Preparatory examples:
Example P1 : Preparation of 1-(2,4,6-trichloro-phenyl)-propan-2-one (compound
CAS1228284-86-3):
Figure imgf000007_0001
In a 1.51 sulfonation flask equipped with mechanical stirring, cooling funnel, dropping funnel and thermometer under nitrogen at ambient temperature filled with acetone (240 ml), were added isopropenyl acetate (66 ml, 0.60 mol), tert-butyl nitrite (40 ml, 0.30 mol) and cupric sulfate pentahydrate (2.5 g, 0.001 mol) . The resulting light green-blue suspension is stirred for 15min at ambient temperature. A solution of 2,4,6-trichloroaniline (40 g, 0.20 mol), dissolved in acetone (320 ml) was added dropwise over a period of 2 hours. During the addition, bubbling observed, temperature rose to 30°C and the mixture turned green. 1 Hour after the addition, an amber solution was obtained. The mixture was stirred for 6 hours. Completion of the reaction was confirmed by GC-MS. The crude mixture was concentrated under reduce pressure to remove most of the acetone and the residue was dissolved in ethyl acetate (300 ml) and wash with 1 M hydrochloric acid (2x300 ml), water (2x300 ml) potassium carbonate solution (300 ml) followed by water (300 ml). Combined basic aqueous were re-extracted with of ethyl acetate (150 ml). Combined organics were dried over sodium sulfate, and the organics were concentrated under reduced pressure to give crude 1-(2,4,6-trichloro-phenyl)-propan-2-one (53g) as a dark brown oil. The crude was dissolved again in ethyl acetate (200 ml) and washed with 1 M sodium hydroxide (300 ml) 1 M hydrochloric acid (100 ml) and water (200 ml). The organic layers were dried and evaporated to give crude 1-(2,4,6-trichloro-phenyl)-propan-2-one 49 g dark brown oil which crystallized.
1 H NMR (400MHz, CDCI3): δ 2.26 (s,3H,CH3 ), 4.05(s,2H,CH2), 7.34 (s,2H, Ar-H) Example P2: Preparation of 1-(4-bromo-2,6-dichloro-phenyl)-propan-2-one:
Figure imgf000008_0001
In a 50ml three-neck flask equipped with mechanical stirring, cooling funnel, dropping funnel and thermometer under nitrogen at ambient temperature filled with acetonitrile (10 ml), were added cuprous oxide (1.5 g, 0.018 mol), isopropenyl acetate (13.6 ml, 0.125 mol) and tert-butyl nitrite (1.7 ml, 0.0125 mol). The resulting red suspension is stirred for 15min at ambient temperature. A solution of 4-bromo-2,6-dichloroaniline (2.0 g, 0.0083 mol), dissolved in acetonitrile (15 ml) was added dropwise over a period of 20 minutes. During the addition, bubbling was observed. The mixture was stirred at 40°C for 20 hours. The red crude mixture was passed through celite to remove solid particles and concentrated under reduce pressure to give a brown solid. The residue was dissolved in dichloromethane (120 ml) and washed with water (2 x 50 ml) and brine (40 ml). Organics were dried over sodium sulfate and concentrated under reduced pressure to give crude 1-(4-bromo-2,6-dichloro- phenyl)-propan-2-one (2.3g) as a dark brown oil.
1 H NMR (400MHz, CDCI3): δ 2.25 (s,3H,CH3 ), 4.06(s,2H,CH2), 7.50 (s,2H, Ar-H)
Example P3: Preparation of 1-(2,4,6-trichloro-phenyl)-propan-2-one:
Figure imgf000008_0002
A mixture of isopropenyl acetate (12.2 g, 122 mmol), 2,4,6-trichloroaniline (16.0 g, 81.4 mmol), potassium carbonate (100 mg, 0.7 mmol), and acetone (100 g) was cooled to 10 °C. tert-Butyl nitrite (90%, 10 g, 87.3 mmol) was dosed over 30 minutes. The reaction was stirred for further 90 minutes, and it was concentrated to a black oil. The residue was triturated with water, and the pH was adjusted to 10.5 with sodium hydroxide solution. The precipitate was filtered and recrystallized from methanol-water 1 : 1. The solid was filtered, washed with methanol-water 1 : 1 , and dried. The product was obtained as dark-brown crystalline material (15.9 g, 70.7% purity, 47.3 mmol, 58% yield). Further purification was achieved by recrystallization from hexanes. 1 H NMR (400 MHz, CDCI3): δ 2.23 (s, 3H, CH3), 4.02 (s, 2H, CH2), 7.31 (s, 2H, CH).

Claims

What is claimed is:
1. A process for the preparation ula I
Figure imgf000009_0001
wherein
is hydrogen, halogen or CrC6alkyl;
R2 is hydrogen, halogen, CrC6alkyl, C2-C6alkenyl, C3-C6alkinyl, C3-C6cycloalkyl-C3-C6alkinyl, halophenoxy, halophenyl-C3-C6alkinyl,
Figure imgf000009_0002
CrC6haloalkyl, CrC6haloalkoxy, C2-C6haloalkenyl, or C2-C6haloalkenyloxy;
R3 is hydrogen, halogen, CrC6alkyl;
which process comprises
adding a compound of formula II
Figure imgf000009_0003
wherein R2 and R3 have the meanings as described under formula I, in the presence of an inert organic solvent to a mixture comprising an organic nitrite of formula III
R4-0-N=0 (III), wherein R4 is CrC8alkyl, a compound of formula IV
Figure imgf000009_0004
and an inert organic solvent.
2. A process according to claim 1 for the preparation of a compound of formula I, wherein at least one of R^ R2 and R3 is different from hydrogen.
3. A process according to claim 1 for the preparation of a compound of formula I, wherein at least one of R2 and R3 is halogen.
4. A process according to claim 1 for the preparation of a compound of formula I, wherein Ri , R2 and R3 are chloro.
5. A process according to claim 1 for the preparation of a compound of formula I, wherein R is C4-C7alkyl.
PCT/EP2012/053371 2012-02-28 2012-02-28 Process for the preparation of substituted phenylpropanones Ceased WO2013127441A1 (en)

Priority Applications (17)

Application Number Priority Date Filing Date Title
PT127081057T PT2819983T (en) 2012-02-28 2012-02-28 Process for the preparation of substituted phenylpropanones
MX2014009829A MX349740B (en) 2012-02-28 2012-02-28 Process for the preparation of substituted phenylpropanones.
PL12708105T PL2819983T3 (en) 2012-02-28 2012-02-28 Process for the preparation of substituted phenylpropanones
PCT/EP2012/053371 WO2013127441A1 (en) 2012-02-28 2012-02-28 Process for the preparation of substituted phenylpropanones
KR1020147024525A KR101902373B1 (en) 2012-02-28 2012-02-28 Process for the preparation of substituted phenylpropanones
ES12708105.7T ES2652365T3 (en) 2012-02-28 2012-02-28 Process for the preparation of substituted phenylpropanones
JP2014558015A JP6251197B2 (en) 2012-02-28 2012-02-28 Process for preparing substituted phenylpropanones
BR112014021063-2A BR112014021063B1 (en) 2012-02-28 2012-02-28 PROCESS FOR THE PREPARATION OF REPLACED PHENYLPROPANONES
HUE12708105A HUE037597T2 (en) 2012-02-28 2012-02-28 Process for the preparation of substituted phenylpropanones
CA2863420A CA2863420C (en) 2012-02-28 2012-02-28 Process for the preparation of substituted phenylpropanones
EP12708105.7A EP2819983B1 (en) 2012-02-28 2012-02-28 Process for the preparation of substituted phenylpropanones
CN201280070805.2A CN104136409B (en) 2012-02-28 2012-02-28 Process for the preparation of substituted propiophenones
US14/379,013 US9073839B2 (en) 2012-02-28 2012-02-28 Process for the preparation of substituted phenylpropanones
DK12708105.7T DK2819983T3 (en) 2012-02-28 2012-02-28 Process for preparing substituted phenylpropanones
AU2012371236A AU2012371236B2 (en) 2012-02-28 2012-02-28 Process for the preparation of substituted phenylpropanones
IL233938A IL233938A (en) 2012-02-28 2014-08-04 Process for the preparation of substituted phenylpropanones
ZA2014/05824A ZA201405824B (en) 2012-02-28 2014-08-07 Process for the preparation of substituted phenylpropanones

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AU (1) AU2012371236B2 (en)
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CA (1) CA2863420C (en)
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ES (1) ES2652365T3 (en)
HU (1) HUE037597T2 (en)
IL (1) IL233938A (en)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024056863A (en) * 2018-09-06 2024-04-23 エフ エム シー コーポレーション Fungicidal nitroanilino-substituted pyrazoles.
WO2026131414A1 (en) * 2024-12-18 2026-06-25 Syngenta Crop Protection Ag Chemical process for the production of pydiflumetofen

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108610290B (en) * 2018-06-11 2020-04-24 武汉工程大学 Preparation method of fluxapyroxad
CN113004131B (en) * 2021-02-01 2022-05-13 江苏先导药业有限公司 Preparation method of 2,4, 6-trichlorophenyl substituted acetone
CN115703701B (en) * 2021-08-16 2024-06-25 上海晓明检测技术服务有限公司 Method for continuously synthesizing 1- (2, 4, 6-trichloro-phenyl) -propan-2-one by micro-channel

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000034229A1 (en) 1998-12-10 2000-06-15 Bayer Aktiengesellschaft Process for the preparation of strobilurin intermediates
US20080221198A1 (en) * 2005-03-10 2008-09-11 Dalian Zhao Novel Crystalline Forms of Antidiabetic Compounds
WO2010063700A2 (en) 2008-12-05 2010-06-10 Syngenta Participations Ag Novel microbiocides

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013100235A (en) * 2010-03-08 2013-05-23 Dainippon Sumitomo Pharma Co Ltd Novel indole derivative

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000034229A1 (en) 1998-12-10 2000-06-15 Bayer Aktiengesellschaft Process for the preparation of strobilurin intermediates
US20080221198A1 (en) * 2005-03-10 2008-09-11 Dalian Zhao Novel Crystalline Forms of Antidiabetic Compounds
WO2010063700A2 (en) 2008-12-05 2010-06-10 Syngenta Participations Ag Novel microbiocides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LI LIA ET AL: "Facile Synthesis of 1-Aryl-2-propanones from Aromatic Amine", SYNTHETIC COMMUNICATIONS,, vol. 37, no. 6, 31 December 2007 (2007-12-31), pages 985 - 991, XP002666726, ISSN: 0039-7911, [retrieved on 20070224], DOI: 10.1080/00397910601163950 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024056863A (en) * 2018-09-06 2024-04-23 エフ エム シー コーポレーション Fungicidal nitroanilino-substituted pyrazoles.
EP4388876A3 (en) * 2018-09-06 2025-05-14 FMC Corporation Fungicidal nitroanilino substituted pyrazoles
JP7695421B2 (en) 2018-09-06 2025-06-18 エフ エム シー コーポレーション Fungicidal nitroanilino-substituted pyrazoles.
WO2026131414A1 (en) * 2024-12-18 2026-06-25 Syngenta Crop Protection Ag Chemical process for the production of pydiflumetofen

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BR112014021063B1 (en) 2019-08-20
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US20150031919A1 (en) 2015-01-29
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