Method for production of 3-hydroxypropan-1-one compound for production of 2- propen-1-one compound and method for production of isoxazline compound

A method for producing an isoxazoline compound represented by Formula (1):

• (where R1, R2, X, A1, A2, A3, A4, A5, A6 and A7 represent the same meaning as described below), the method comprising reacting a 1,3-bis(substituted phenyl)-3-substituted-2-propen-1-one compound represented by Formula (2):
• (where R1 represents a C1-C6 haloalkyl or C3-C8 halocycloalkyl;
• each of A1, A2, A3 and A4 independently represents N or C—Y;
• each of A5, A6 and A7 independently represents N or C—X;
• X represents a hydrogen atom, halogen atom, cyano, nitro, —SF5, C1-C6 alkyl, C1-C6 haloalkyl, hydroxy (C1-C6) haloalkyl, C1-C6 alkoxy (C1-C6) haloalkyl, C1-C6 haloalkoxy (C1-C6) haloalkyl, C3-C8 halocycloalkyl, —OR3, —OSO2R3 or —S(O)rR3;
• and each X is optionally the same as or different from each other;
• R3 represents a C1-C6 alkyl, C1-C4 alkoxy (C1-C4) alkyl, C1-C6 haloalkyl or C1-C3 haloalkoxy (C1-C3) haloalkyl;
• R2 represents a C1-C6 alkyl, halogen atom, cyano, nitro, —NH2, —N(R5)R4, —OH, —OR3, benzyloxy, —OSO2R3, phenylsulfonyloxy, phenylsulfonyloxy substituted by (Z)p1, —C(O)OH, —C(O)OR3, —C(O)NH2, —C(O)N(R1b)R1a, —C(S)N(R1b)R1a, -L-Q, -L-N(R1c)R1d, —S(O)r-L2-Q2 and substituent selected from D-1 to D-50;
• Y represents a hydrogen atom, halogen atom, cyano, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-Co alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, —NH2, or —N(R5)R4, and each Y is optionally the same as or different from each other;
• two adjacent Ys optionally form A8=A9-A10=A11 together;
• each of A8, A9, A10 and A11 independently represents N or C—Y1;
• Y1 represents a hydrogen atom, halogen atom, cyano, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, —NH2, or —N(R5)R4, and each Y1 is optionally the same as or different from each other;
• R4 represents a C1-C6 alkyl, —CHO, C1-C6 alkylcarbonyl, C1-C6 haloalkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthiocarbonyl, C1-C6 alkoxythiocarbonyl, C1-C6 alkyldithiocarbonyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl;
• R5 represents a hydrogen atom or C1-C6 alkyl;
• R1a represents a C1-C6 alkyl, C1-C6 alkyl optionally substituted by R8, C3-C6 cycloalkyl which is optionally ring-condensed by benzene ring, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, —N(R11)R10, —C(O)OR9, —C(O)NH2, —C(O)NHR9, —C(R7)═NOR6, phenyl, phenyl substituted by (Z)p1, D-5, D-7, D-10, D-11, D-12, D-14, D-15, D-18, D-31, D-32, D-42, D-43, D-45, D-46, D-48, E-1, E-2, E-3, E-4 or E-7;
• R1b represents a hydrogen atom, C1-C6 alkyl, C1-C4 alkoxy (C1-C4) alkyl, cyano (C1-C6) alkyl, C3-C6 alkynyl, —C(O)R9 or —C(O)OR9,
• or represents that R1b optionally forms a 3-7 membered ring with a nitrogen atom to be bonded, by forming a C2-C6 alkylene chain together with R1a, and this alkylene chain optionally contains one oxygen atom, sulfur atom or nitrogen atom in this case;
• L represents —C(R2a)(R2b)—, —C(R2a)(R2b)CH2—, —CH2C(R2a)(R2b)— or —N(R2c)—;
• Q represents a hydrogen atom, halogen atom, cyano or nitro;
• R1c represents a hydrogen atom, —C(O)R3a, —C(O)OR3a, —C(O)SR3a, —C(O)N(R3b)R3a, —C(S)N(R3b)R3a or —S(O)2R3a;
• R1d represents a hydrogen atom, C1-C6 alkyl, C1-C6 haloalkyl, C1-Ca alkoxy (C1-C4) alkyl, C1-Ca haloalkoxy (C1-C4) alkyl, C1-Ca alkylthio (C1-C4) alkyl, C1-C4 alkylsulfonyl (C1-C4) alkyl, cyano (C1-C6) alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl (C1-C4) alkyl, C3-C6 alkenyl, C3-C6 alkynyl, —C(O)R3c, —C(O)OR3c, —C(O)SR3c, C1-C6 haloalkylthio or C1-C6 alkylsulfonyl,
• or represents that R1c optionally forms a 5-7 membered ring with a nitrogen atom to be bonded, by forming a C4-C6 alkylene chain together with R1d, and this alkylene chain optionally contains one oxygen atom, sulfur atom or nitrogen atom in this case and is optionally substituted by a C1-C6 alkyl group, —CHO group, C1-C6 alkylcarbonyl group, C1-C6 haloalkylcarbonyl group, C1-C6 alkoxycarbonyl group, C1-C6 haloalkoxycarbonyl group, C1-C6 alkylaminocarbonyl group, C1-C6 haloalkylaminocarbonyl group, oxo group or thioxo group;
• R2a represents a hydrogen atom, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxycarbonyl, —C(O)NH2 or —C(S)NH2;
• R2b represents a hydrogen atom or C1-C6 alkyl, or represents that R2b optionally forms a 3-6 membered ring with a carbon atom to be bonded, by forming a C2-C5 alkylene chain together with R2a, and this alkylene chain optionally contains one to three oxygen atom(s), sulfur atom(s) or nitrogen atom(s) in this case;
• R2c represents a hydrogen atom, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkylcarbonyl, C1-C6 haloalkylcarbonyl or C1-C6 alkoxycarbonyl;
• R3a represents a C1-C6 alkyl, C1-C6 haloalkyl, (C1-C4) alkyl optionally substituted by R4a, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, E-1, E-2, E-4, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, phenyl, phenyl substituted by (V)p1, D-3, D-4, D-12 to D-14, D-42 or D-43;
• R3b represents a hydrogen atom or C1-C6 alkyl;
• R3c represents a hydrogen atom, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl (C1-C4) alkyl, C3-C6 cycloalkyl, C3-C6 alkenyl or C3-C6 alkynyl, or represents that R3 optionally forms a 5-7 membered ring with a nitrogen atom, carbon atom, oxygen atom or sulfur atom to be bonded, by forming an ethylene chain or benzene ring bonded at an ortho-position together with R3a;
• R4a represents a halogen atom, cyano, nitro, C3-C6 cycloalkyl, C1-C4 alkoxy, C1-C6 alkoxycarbonyl, S(O)rR5a, D-42 or D-43;
• R5a represents a C1-C4 alkyl;
• V represents a halogen atom, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, —OH, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfonyloxy, C1-C6 haloalkylsulfonyloxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, —NH2, C1-C6 alkylamino, di(C1-C6 alkyl)amino, C1-C6 alkoxycarbonyl, —C(O)NH2, C1-C6 alkylaminocarbonyl, C1-C6 haloalkylaminocarbonyl, di(C1-C6 alkyl)aminocarbonyl, —C(S)NH2, —S(O)2NH2, C1-C6 alkylaminosulfonyl or di(C1-C6 alkyl)aminosulfonyl, and each V is optionally the same as or different from each other when p1 represents an integer of 2 or more;
• moreover, when two Vs are adjacent, the two adjacent Vs optionally form a 5-membered ring or a 6-membered ring with carbon atoms bonding to each of the two Vs by forming —OCH2O— or —OCH2CH2O—, and hydrogen atoms bonding to each carbon atom forming the ring are optionally substituted by halogen atoms in this case;
• R6 represents a C1-C6 alkyl or C1-C6 haloalkyl;
• R7 represents a hydrogen atom or C1-C6 alkyl;
• R8 represents a halogen atom, cyano, amino, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, —C(O)R14, —C(O)OR14, —C(O)NH2, —C(O)N(R15)R14, —C(S)NH2, —C(S)N(R15)R14, —C(R7)═NOH, —C(R7)═NOR6, phenyl, phenyl substituted by (Z)p1, D-1 to D-50 or E-1 to E-8;
• D-1 to D-50 represent aromatic heterocyclic rings represented by the following structural formulae:
• Z represents a halogen atom, cyano, nitro, amino, C1-C6 alkyl, (C1-C6) alkyl optionally substituted by R16, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C1-C6 alkoxycarbonyl, —C(O)NH2, —C(S)NH2, —S(O)2NH2, —C(O)N(R18)R17, —C(S)N(R18)R17, C1-C6 alkylaminosulfonyl or di(C1-C6 alkyl)aminosulfonyl, and each Z is optionally the same as or different from each other when p1, p2, p3 or p4 represents an integer of 2 or more;
• E-1 to E-8 represent saturated heterocycles represented by the following structural formulae:
• R9 represents a C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy (C1-C4) alkyl, C1-C6 alkylthio (C1-C4) alkyl, C3-C8 cycloalkyl, C3-C6 alkenyl or C3-C6 alkynyl;
• R10 represents a C1-C6 haloalkyl, —C(O)R14, —C(O)OR14, phenyl, phenyl substituted by (Z)p1, D-3, D-4, D-18, D-42, D-45, D-46, D-48 or D-49;
• R11 represents a hydrogen atom, C1-C6 alkyl or C3-C6 alkynyl;
• R12 represents a C1-C6 alkyl, phenyl or phenyl substituted by (Z)p1;
• R13 represents a C1-C4 alkyl, and each R13 is optionally the same as or different from each other when q1, q2, q3 or q4 represents an integer of 2 or more, and moreover represents that two R13s optionally form oxo together when the two R13s are bonded to the same carbon atom;
• R14 represents a C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl (C1-C4) alkyl, C3-C6 cycloalkyl, C3-C6 alkenyl or C3-C6 alkynyl;
• R15 represents a hydrogen atom or C1-C6 alkyl;
• R16 represents a —OH, C1-C4 alkoxy or C1-C4 alkylthio;
• R17 represents a hydrogen atom, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, —C(R5)═NOR19, —C(O)OR19, —C(O)NH2, —C(O)N(R5)R19, —C(O)NHC(O)R19, —C(O)N(R5)C(O)OR19, —N(R21)R20, K phenyl substituted by (Z)p1, D9 to D11, D18 to D20, D42 to D47 or D48;
• R18 represents a hydrogen atom, C1-C6 alkyl, C3-C6 alkynyl, —C(O)R19a, —C(O)OR19a or C1-C6 haloalkylthio;
• R19 represents a C1-C6 alkyl, C1-C6 haloalkyl or C2-C6 alkenyl;
• R19a represents a C1-C6 alkyl, C1-C6 haloalkyl, C1-C4 alkoxy (C1-C4) alkyl, C1-C4 alkylthio (C1-C4) alkyl, C1-C4 alkylsulfinyl (C1-C4) alkyl, C1-C4 alkylsulfonyl (C1-C4) alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, C1-C6 alkoxycarbonyl, phenyl, phenyl substituted by (Z)p1, D42, D43 or D44;
• R20 represents a C1-C6 haloalkyl, C1-C6 alkoxycarbonyl, phenyl, phenyl substituted by (Z)p1, D42 to D46 or D47;
• R21 represents a hydrogen atom, C1-C6 alkyl, C3-C6 alkenyl or C3-C6 alkynyl;
• L2 represents a single bond or C1-C6 alkylene chain;
• Q2 represents a hydrogen atom, C1-C6 haloalkyl, C2-C6 alkynyl, —N(R23)R22, —C(O)N(R23)R22, phenyl, phenyl substituted by (Z)p1, D18 to D20, D42 to D46 or D47;
• R22 represents a C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 alkenyl, C3-C6 alkynyl, phenyl or phenyl substituted by (Z)p1;
• R23 represents a hydrogen atom or C1-C6 alkyl;
• p1 represents an integer of 1 to 5;
• p2 represents an integer of 0 to 4;
• p3 represents an integer of 0 to 3;
• p4 represents an integer of 0 to 2;
• p5 represents an integer of 0 or 1;
• q2 represents an integer of 0 to 5;
• q3 represents an integer of 0 to 7;
• q4 represents an integer of 0 to 9;
• r represents an integer of 0 to 2;
• t represents an integer of 0 or 1) and a hydroxylamine in an aliphatic or an aromatic hydrocarbon solvent which is optionally substituted by a halogen atom by adding an additive selected from a phase-transfer catalyst, a C1-C6 alcohol and an aprotic polar solvent in the presence of a base and water.