Oxy-cope rearrangement for the manufacture of insecticidal cyclopentene compounds

Patent metadata

Field	Value
Publication number	US-10526264-B2
Application number	US-201716315417-A
Country	US
Kind code	B2
Filing date	Jun 23, 2017
Priority date	Jul 7, 2016
Publication date	Jan 7, 2020
Grant date	Jan 7, 2020

Abstract

Compounds of formula I

a process for preparation of compounds of formula I; precursor compounds of formula II

a process for preparation of precursor compounds of formula II; compounds of formula III

a process for the preparation of compounds of formula IV from compounds of formula III

and the use of compounds of formula I for the preparation of compounds of formula IV.

First claim

The invention claimed is:

1. A compound of formula I

wherein
R 1 is halomethyl;
R 2 is halogen, halomethyl, or halomethoxy;
R 3 , R 4 are independently H, or as defined for R 2 ;
R 5a is H, C 1 -C 4 -alkyl, or C 1 -C 4 -haloalkyl;
R 5b is CN, halogen, C 1 -C 2 -alkyl, C 1 -C 2 -haloalkyl, C 1 -C 2 -alkoxy, C 1 -C 2 -haloalkoxy; or
R 5a and R 5b form together with the C-atoms they are bound to a 5-, or 6-membered saturated, partially, or fully unsaturated ring containing none, or one heteroatom O, N(O) n or S(O) m as ring members;
A is halogen, CN, C 1 -C 6 -alkoxy, C 6 -C 10 -aryloxy, C 1 -C 6 -haloalkoxy, C 6 -C 10 -arylalkoxy, C 6 -C 10 -aryl-C 1 -C 6 -alkoxy, OS(O) 2 R 6 ; or
a group A 1 , or A 2 ; wherein
A 1 is a group of following formula:

wherein
# denotes the attachment point to the remainder of the molecule;
Y OR 7 , or N(R 8 )R 9 ; and
A 2 is a group of following formula:

wherein
# denotes the attachment point to the remainder of the molecule;

R 6 halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl;
phenyl, which is unsubstituted, or substituted by halogen, OH, CN, NO 2 , C 1 -C 6 -alkyl, or C 1 -C 6 -haloalkyl;

R 7 a) H;
b) C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkenyl, C 1 -C 6 -alkynyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl; or
c) phenyl, or benzyl, which are unsubstituted, or substituted by halogen, C 1 -C 2 -alkyl, C 1 -C 2 -haloalkyl, or C 1 -C 2 -alkoxy;

R 8 H, CN;
C 1 -C 6 -alkyl-C(═O), C 1 -C 6 -haloalkyl-C(═O), C 1 -C 6 -alkyl-OC(═O), C 1 -C 6 -alkenyl-OC(═O), or C 6 -C 12 -aryl-C 1 -C 6 -alkyl-OC(═O);
C 1 -C 10 -alkyl, C 3 -C 8 -cycloalkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -alkynyl, which are unsubstituted or substituted by R 81 ;
R 81 halogen, CN, N 3 , NO 2 , SCN, SF 5 , C 3 -C 8 -cycloalkyl, C 3 -C 8 halocycloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 3 -C 8 -cycloalkoxy, or C 3 -C 8 -halocycloalkoxy;

R 9 H;
C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, which are unsubstituted, or substituted by R 91 ;
C 3 -C 6 -cycloalkyl, C 3 -C 6 -halocycloalkyl, which are unsubstituted, or substituted by R 92 ;
N(R 93 )R 94 ;
phenyl, heterocyclyl, or hetaryl, which are unsubstituted, or substituted by R D ; or
C 1 -C 6 -alkyl-C(═O), C 1 -C 6 -haloalkyl-C(═O), C 1 -C 6 -alkyl-OC(═O), C 1 -C 6 -alkenyl-OC(═O), or C 6 -C 12 -aryl-C 1 -C 6 -alkyl-OC(═O);
R 91 halogen, OH, CN, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkyl-S(O) m , C 1 -C 4 -haloalkyl-S(O) m , C(═O)N(R A )R B ;
C 3 -C 6 -cycloalkyl, C 3 -C 6 -halocycloalkyl, which are unsubstituted, or substituted by R C ;
phenyl, heterocyclyl, or hetaryl which are unsubstituted, or substituted by R D ;
R A , R 93 H, C 1 -C 3 -alkyl, or C 1 -C 3 -haloalkyl;
R B H, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 2 -C 3 -alkenyl, C 2 -C 3 -haloalkenyl, C 2 -C 3 -alkynyl, C 2 -C 3 -haloalkynyl, C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkoxy, C 3 -C 4 -halocycloalkyl; or
C 3 -C 4 -cycloalkyl, C 3 -C 4 -halocycloalkyl, C 3 -C 4 -cycloalkylmethyl, C 3 -C 4 -halocycloalkylmethyl, wherein the cyclic groups are unsubstituted, or substituted by CN;
R C OH, CN, C 1 -C 2 -alkyl, or C 1 -C 2 -haloalkyl;
R D halogen, CN, NO 2 , C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -alkynyl, C 2 -C 4 -haloalkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -halocycloalkyl, C 3 -C 4 -cycloalkylmethyl, or C 3 -C 4 -halocycloalkylmethyl; or
two R D present on the same carbon atom of a saturated, or partially saturated ring form together a carbonyl group (═O);

R 92 C 1 -C 2 -alkyl, C 1 -C 2 -haloalkyl, or a group as defined for R 91 ;
R 94 C(═O)N(R A )R B , C(═O)OR A ; or
phenyl, heterocyclyl, or hetaryl which rings are unsubstituted, or substituted by R D ;

R 10 H, CN, methyl, or halomethyl;
R 11 H, C 1 -C 6 -alkyl-C(═O), C 1 -C 6 -haloalkyl-C(═O), C 1 -C 6 -alkyl-OC(═O), C 1 -C 6 -alkenyl-OC(═O), or C 6 -C 12 -aryl-C 1 -C 6 -alkyl-OC(═O);
R 12 H, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, which are unsubstituted, or substituted by R 91 ;
C 3 -C 6 -cycloalkyl, C 3 -C 6 -halocycloalkyl, which are unsubstituted, or substituted by R 92 ; or
phenyl, heterocycyl, or hetaryl which rings are unsubstituted, or substituted by R D ;

n is 0, or 1;
m is 0, 1, or 2;
and the N-oxides, stereoisomers and agriculturally or veterinarily acceptable salts thereof.

2. The compound of claim 1 , wherein
R 1 is CF 3 ;
R 2 is F, Cl, Br, CF 3 , or OCF 3 ;
R 3 , R 4 are independently H, or as defined for R 2 ;
R 5a is H; and
R 5b is F, Cl, Br, CH 3 , or CF 3 ; or
R 5a and R 5b form together with the C-atoms they are bound to a bridging group selected from —CH═CH—CH═CH—, —CH═CH—CH═N—, —CH═CH—N═CH—, —CH═N—CH═CH—, —N═CH—CH═CH—, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 O—, —OCH 2 CH 2 —, —CH 2 CH 2 CH 2 O—, —OCH 2 CH 2 CH 2 —, —CH 2 CH 2 S(O) p —, —S(O) p CH 2 CH 2 —;
and wherein p is 0, 1, or 2.

3. The compound of claim 1 , wherein
A is A 1 ;
Y is OR 7 ; and
R 7 is as defined in claim 1 .

4. The compound of claim 3 , wherein R 7 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkenyl, C 1 -C 6 -alkynyl, phenyl, or benzyl.

5. The compound of claim 2 , wherein
A is A 1 ;
Y is N(H)R 9 .

6. The compound of claim 1 , wherein A is Cl, Br, I, or CN.

7. The compound of claim 1 , wherein
A is A 2 ;
R 10 H; and
R 12 C 1 -C 4 -alkyl, and C 1 -C 4 -haloalkyl, which are unsubstituted, or substituted by R 91 ;
C 3 -C 5 -cycloalkyl, C 3 -C 5 -halocycloalkyl, which are unsubstituted, or substituted by R 92 ;
R 91 is independently OH, CN, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkyl-S(O) m , C 1 -C 4 -haloalkyl-S(O) m ;
C 3 -C 5 -cycloalkyl, C 3 -C 5 -halocycloalkyl, which are unsubstituted, or substituted by R C ;
R C is independently OH, CN, C 1 -C 2 -alkyl, or C 1 -C 2 -haloalkyl;

R 92 is independently C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, or a group as defined for R 91 ; and

m is 0, 1, or 2.

8. A process for preparing the compound of claim 1 comprising reacting a compound of formula II

with a base at a temperature from −100 to 50° C., followed by rearrangement at a temperature from −50 to 150° C.

9. The process of claim 8 , wherein the reaction of the compound of formula (II) with the base is carried out in a solvent selected from the selected from an aliphatic C 5 -C 16 -hydrocarbon, aromatic C 6 -C 10 -hydrocarbon, halogenated aliphatic C 1 -C 6 -hydrocarbon, halogenated aromatic C 6 -C 10 -hydrocarbon, a C 1 -C 6 -cycloalkyl ether, a C 1 -C 6 -alkyl-C 1 -C 6 -alkyl ether, and a C 1 -C 6 -alkyl-C 6 -C 10 -aryl ether, or a mixture thereof.

10. The process of claim 8 , wherein the rearrangement is carried out at a temperature from −10 to 40° C.

11. The process of claim 8 , wherein compound of formula I are subsequently reacted with an olefinating agent to compound of formula III

wherein all substituents have

Assignees

• Basf Se

Inventors

• Mclaughlin Martin John
• Koerber Karsten
• Gockel Birgit
• Bindschaedler Pascal
• Soergel Sebastian
• Vyas Devendra
• Roeckl Johannes

Classifications

• C07C67/343

  by increase in the number of carbon atoms · CPC title

• C07C33/486 Primary

  Polycyclic · CPC title

• C07C69/76

  Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring · CPC title

• C07C63/74

  having unsaturation outside the aromatic rings · CPC title

• C07C49/813

  polycyclic · CPC title