Dioxolane and dioxane derivatives and a process for their preparation
View Patent ↗The present invention relates to novel acylmethylene-1,3-dioxolanes and acylmethylene-1,4-dioxanes of the general formula (I) in which R 1 , R 2 , R 3 and n have the meanings given in the description, and also a novel process for their preparation. Acylmethylene-1,3-dioxolanes and acylmethylene-1,4-dioxanes are important intermediates for the preparation of pyrazoles and anthranilamides, which can be used as insecticides.
1. A compound of general formula (I)
in which
R 1 and R 2 , independently of one another, are hydrogen, alkyl, haloalkyl, aryl or alkylaryl,
n is 0 or 1,
R 3 is CX 3 , (C═O)Oalkyl or (C═O)Oaryl, and
X is halogen.
2. The compound according to claim 1 , wherein
R 1 and R 2 , independently of one another, are hydrogen or methyl,
n is 0,
R 3 is CX 3 or (C═O)Oalkyl, and
X is chlorine.
3. The compound according to claim 1 , wherein
R 1 and R 2 , independently of one another, are hydrogen or methyl,
n is 0, and
R 3 is (C═O)Omethyl.
4. A process for preparing a compound of formula (I) according to claim 1 , comprising, reacting a compound of formula (II),
in which
R 1 and R 2 , independently of one another, are hydrogen, alkyl, haloalkyl, aryl or alkylaryl, and
n is 0 or 1,
with a compound of general formula (III),
in which
R 3 is CX 3 , (C═O)Oalkyl or (C═O)Oaryl,
X is halogen, and
R 4 is X, O(C═O)R 3 or (CH 3 ) 3 COO,
to give a compound of the general formula (I).
5. The process of claim 4 , wherein R 4 is X.
6. The process of claim 4 , further comprising carrying out said process in a temperature range from −20° C. to 100° C.
7. The process of claim 4 , wherein 1 mol of said compound of the formula (II) is reacted with 0.8 to 1.5 mol of said compound of the formula (III).
8. A process for the preparation of a compound of Formula (V):
wherein
R 3 is CX 3 , (C═O)Oalkyl, or (C═O)Oaryl;
R 5 is halogen, cyano, nitro, alkyl, cycloalkyl, haloalkyl, halocycloalkyl, alkoxy, haloalkoxy, alkylamino, dialkylamino, or cycloalkylamino;
R 6 is halogen, OSO 2 Me, or O(C═O)CH 3 , and
Z is CH or N;
comprising, reacting a compound of Formula (I):
wherein
R 1 and R 2 , independently of one another, are hydrogen, alkyl, haloalkyl, aryl, or alkylaryl;
n is 0 or 1; and
R 3 is CX 3 , (C═O)Oalkyl, or (C═O)Oaryl;
with a compound of the formula:
wherein R 5 and Z have the meaning given above.
to give a compound of Formula (V).
9. The compound of claim 1 , wherein the compound of formula (I) is selected from the group consisting of:
1,1,1-Trichloro-3-(2,2,-dimethyl-1,3-dioxolan-4-ylidene)acetone;
Methyl 3-(2,2-dimethyl-1,3-dioxolan-4-ylidene)-2-oxopropanoate;
Methyl 3-(1,3-dioxolan-4-ylidene)-2-oxopropanoate;
Ethyl 3-(2,2-dimethyl-1,3-dioxolan-4-ylidene)-2-oxopropanoate; and
Ethyl 3-(5,5-dimethyl-1,4-dioxan-2-ylidene)-2-oxopropanoate.
10. The process of claim 8 , wherein the compound of Formula (V) is selected from the group consisting of:
Methyl 1-(3-chloropyridin-2-yl)-5-hydroxy-3-(hydroxymethyl)-4,5-dihydro-1H-pyrazole-5-carboxylate;
Ethyl 1-(3-chloropyridin-2-yl)-5-hydroxy-3-(hydroxymethyl)-4,5-dihydro-1H-pyrazole-5-carboxylate;
Methyl 1-(3-chloropyridin-2-yl)-3-{[(methylsulphonyl)oxy]methyl}-1H-pyrazole-5-carboxylate; and
Methyl 3-(chloromethyl)-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylate.