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

Patent metadata

Field	Value
Publication number	US-9676692-B2
Application number	US-201414584642-A
Country	US
Kind code	B2
Filing date	Dec 29, 2014
Priority date	Jun 27, 2007
Publication date	Jun 13, 2017
Grant date	Jun 13, 2017

Abstract

There is provided a novel intermediate for producing pesticides. A method for producing the compound of Formula (3) comprises reacting an aromatic ketone compound of Formula (4) and a substituted acetophenone compound of Formula (5) as starting raw materials in an organic solvent or water in the presence or absence of an additive in the presence of a base in a suspended state. A method may comprise dehydrating the compound of Formula (3). A method for producing compound (2) in one step comprises reacting compound (4) and compound (5) to obtain compound (3). Further, a method for producing an isoxazoline compound of Formula (1) comprises reacting compound (2) 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 C 1 -C 6 alcohol and an aprotic polar solvent in the presence of a base and water.

First claim

The invention claimed is:

1. A method for producing a 1,3-bis(substituted phenyl)-3-substituted-3-hydroxypropan-1-one compound represented by Formula (3):

wherein R 1 represents a trifluoromethyl group;
each of A 1 , A 2 , A 3 and A 4 independently represents C—Y;
each of A 5 , A 6 and A 7 independently represents C—X;
X represents a hydrogen atom or a halogen atom, and each X is optionally the same as or different from each other;
R 2 represents a halogen atom, cyano, —C(O)OH, —C(O)OR 3 , —C(O)NH 2 , —C(O)N(R 1b )R 1a , or a substituent selected from D-21 to D-36;
R 3 represents a C 1 -C 6 alkyl, C 1 -C 4 alkoxy (C 1 -C 4 ) alkyl, or C 1 -C 6 haloalkyl;
Y represents a hydrogen atom, cyano, or C 1 -C 4 alkyl, and each Y is optionally the same as or different from each other;
two adjacent Ys optionally form A 8 =A 9 -A 10 =A 11 together;
each of A 8 , A 9 , A 10 and A 11 independently represents C—Y 1 ;
Y 1 represents a hydrogen atom;
R 1a represents a C 1 -C 6 alkyl optionally substituted by R 8 , —N(R 11 )R 10 , —C(O)OR 9 , —C(O)NH 2 , —C(O)NHR 9 , —C(R 7 )═NOR 6 , 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, or E-7;
R 1b represents a hydrogen atom, C 1 -C 6 alkyl, C 1 -C 4 alkoxy (C 1 -C 4 ) alkyl, cyano (C 1 -C 6 ) alkyl, C 3 -C 6 alkynyl, —C(O)R 9 or —C(O)OR 9 ,
or represents that R 1b optionally forms a 3-7 membered ring with a nitrogen atom to be bonded, by forming a C 2 -C 6 alkylene chain together with R 1a , and this alkylene chain optionally contains one oxygen atom, sulfur atom or nitrogen atom in this case;
R 6 represents a C 1 -C 6 alkyl;
R 7 represents a hydrogen atom or C 1 -C 6 alkyl;
R 8 represents a halogen atom, cyano, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, —C(O)N(R 15 )R 14 , —C(R 7 )═NOR 6 , phenyl, phenyl substituted by (Z) p1 ; D-11 to D-14, D-18, D-19, D-25, D-26, D-31, D-32, D-36, D-42, D-45, D-48, D-49, E-1, E-2, or E-5;
D-3 to D-5, D-7, D-9 to D-15, D-18 to D-36, and D-42 to D-49 represent aromatic heterocyclic rings represented by the following structural formulae:

Z represents a halogen atom, cyano, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkoxy, 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, E-2, E-5, and E-7 represent saturated heterocycles represented by the following structural formulae:

R 9 represents a C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 6 alkylthio (C 1 -C 4 ) alkyl, C 3 -C 8 cycloalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl;
R 10 represents a C 1 -C 6 haloalkyl, —C(O)R 14 , —C(O)OR 14 , phenyl, phenyl substituted by (Z) p1 , D-3, D-4, D-18, D-42, D-45, D-46, D-48 or D-49;
R 11 represents a hydrogen atom, C 1 -C 6 alkyl or C 3 -C 6 alkynyl;
R 12 represents a C 1 -C 6 alkyl;
R 13 represents a C 1 -C 4 alkyl, and each R 13 is optionally the same as or different from each other when q1, q2, q3 or q4 represents an integer of 2 or more, wherein two R 13 s optionally form oxo together when two R 13 s are bonded to the same carbon atom;
R 14 represents a C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl (C 1 -C 4 ) alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl;
R 15 represents a hydrogen atom or C 1 -C 6 alkyl;
R 16 represents a —OH, C 1 -C 4 alkoxy or C 1 -C 4 alkylthio;
R 17 represents a hydrogen atom, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, —C(R 5 )═NOR 19 , —C(O)OR 19 , —C(O)NH 2 , —C(O)N(R 5 )R 19 , —C(O)NHC(O)R 19 , —C(O)N(R 5 )C(O)OR 19 , —N(R 21 )R 20 , phenyl substituted by (Z) p1 , D-9 to D-11, D-18 to D-20, D-42 to D-47 or D-48;
R 18 represents a hydrogen atom, C 1 -C 6 alkyl, C 3 -C 6 alkynyl, —C(O)R 19a , —C(O)OR 19a or C 1 -C 6 haloalkylthio;
R 19 represents a C 1 -C 6 alkyl, C 1 -C 6 haloalkyl or C 2 -C 6 alkenyl;
R 19a represents a C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 4 alkoxy (C 1 -C 4 ) alkyl, C 1 -C 4 alkylthio (C 1 -C 4 ) alkyl, C 1 -C 4 alkylsulfinyl (C 1 -C 4 ) alkyl, C 1 -C 4 alkylsulfonyl (C 1 -C 4 ) alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxycarbonyl, phenyl, phenyl substituted by (Z) p1 , D42, D43 or D44;
R 20 represents a C 1 -C 6 haloalkyl, C 1 -C 6 alkoxycarbonyl, phenyl, phenyl substituted by (Z) p1 , D42 to D46 or D47;
R 21 represents a hydrogen atom, C 1 -C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl;
p1 represents an integer of 1 to 2;
p2 represents an integer of 0 to 1;
p3 represents an integer of 0 to 1;
p4 represents an integer of 0 to 1;
p5 represents an integer of 0 or 1;
q2 represents an integer of 0 to 2;
q3 represents an integer of 0 to 2;
q4 represents an integer of 0 to 2;
r represents an integer of 0 to 2;
t represents an integer of 0 or 1,
the method consisting of
reacting an aromatic ketone compound represented by Formula (4)

wherein R 1 , X, A 5 , A 6 and A 7 represent the same meaning as described above, and a substituted acetophenone compound represented by Formula (5)

wherein R 2 , A 1 , A 2 , A 3 and A 4 represent the same meaning as described above, in a suspended state in the presence or absence of an additive and in the presence of a base in a solvent, wherein
the base is selected from the group consisting of sodium acetate, potassium acetate, methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, t-butylamine, n-pentylamine, i-pentylamine, benzylamine, aniline, dimethylamine, diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-n-pentylamine, di-i-pentylamine, pyrrolidine, piperidine, piperazine, morpholine, dibenzylamine, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tripentylamine, tribenzylamine, diisopropylethylamine, N-methylmorpholine, and combinations thereof, and
the additive is selected from the group consisting of a C 1 -C 6 alcohol, an aprotic polar solvent, a surfactant, a water soluble organic solvent, and combinations thereof.

2. The method according to claim 1 , wherein the solvent is an organic solvent and the reaction is conducted in the absence of the additive.

3. The method according to claim 1 , wherein the solvent is water and the reaction is conducted in the presence of a water-soluble organic solvent as the additive.

4. The method according to claim 1 , wherein the solvent is water and the reaction is con

Assignees

• Nissan Chemical Ind Ltd

Inventors

• Yaosaka Manabu
• Utsunomiya Tomohisa
• Moriyama Yuji
• Matsumoto Tomohiro
• Matoba Kazutaka

Classifications

• C07D213/04

  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 · CPC title

• C07C51/367

  by introduction of functional groups containing oxygen only in singly bound form · CPC title

• C07D413/14

  containing three or more hetero rings · CPC title

• C07D233/60

  with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms · CPC title

• C07C51/377

  by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups {(C07C51/36 - C07C51/373 take precedence)} · CPC title