2,6-dihalo-5-alkoxy-4-substituted-pyrimidines, pyrimidine-carbaldehydes, and methods of formation and use
View Patent ↗2,6-Dihalo-5-alkoxy-4-substituted-pyrimidines, 2,6-dihalo-5-alkoxy-4-pyrimdine carbaldehydes, and derivatives of each are useful intermediates in forming potent herbicides that demonstrate a broad spectrum of weed control. These compounds are disclosed, as are methods of forming and using these compounds.
1. A method of forming a 2,6-dihalo-5-alkoxy-pyrimdine-4-carbaldehyde comprising reacting a 2,6-dihalo-5-alkoxy-4-substituted pyrimidine with an oxidant.
2. The method of claim 1 wherein reacting a 2,6-dihalo-5-alkoxy-4-substituted pyrimidine with an oxidant comprises reacting the 2,6-dihalo-5-alkoxy-4-substituted pyrimidine with ozone.
3. The method of claim 1 wherein reacting a 2,6-dihalo-5-alkoxy-4-substituted pyrimidine with an oxidant comprises reacting a 2,6-dichloro-5-methoxy-4-vinylic pyrimidine with ozone to form a 2,6-dichloro-5-methoxy-pyrimidine-4-carbaldehyde.
4. A method of forming a 2,6-dihalo-5-alkoxy-4-substituted pyrimidine comprising:
reacting a 2,6-dihalo-5-alkoxy pyrimidine with an organometallic halide reagent to form a 2,6-dihalo-5-alkoxy-4-substituted-3-(metal-halo or metal) pyrimidine; and
oxidizing the 2,6-dihalo-5-alkoxy-4-substituted-3-(metal-halo or metal) pyrimidine to form the 2,6-dihalo-5-alkoxy-4-substituted pyrimidine.
5. The method of claim 4 , wherein reacting a 2,6-dihalo-5-alkoxy pyrimidine with an organometallic halide reagent comprises reacting a 2,6-dihalo-5-alkoxy pyrimidine with a Grignard reagent.
6. The method of claim 5 , wherein reacting a 2,6-dihalo-5-alkoxy pyrimidine with a Grignard reagent comprises reacting a 2,6-dihalo-5-alkoxy pyrimidine with a vinyl magnesium bromide.
7. The method of claim 4 , wherein reacting a 2,6-dihalo-5-alkoxy pyrimidine with an organometallic halide reagent comprises reacting a 2,6-dihalo-5-alkoxy pyrimidine with an organolithium reagent.
8. The method of claim 4 , wherein oxidizing the 2,6-dihalo-5-alkoxy-4-substituted-3-(metal-halo or metal) pyrimidine comprises reacting the 2,6-dihalo-5-alkoxy-4-substituted-3-(metal-halo or metal) pyrimidine with 2,3-dichloro-5,6-dicyano-p-benzoquinone.
9. A method of using a 2,6-dihalo-5-alkoxy-4-substituted pyrimidine to form an herbicide, the 2,6-dihalo-5-alkoxy-4-substituted pyrimidine comprising a pyrimidine ring having a 4 position and a 6 position, the pyrimidine ring further comprising a hydrocarbon chain at the 4 position and a halogen at the 6 position, the method comprising:
contacting the hydrocarbon chain at the 4 position with an oxidant to form a carbonyl group at the 4 position;
contacting the carbonyl group at the 4 position with bromine in an alcohol to form a carboalkoxy group at the 4 position; and
contacting the halogen at the 6 position with an amine to form an amino group at the 6 position.
10. The method of claim 9 , wherein contacting the hydrocarbon chain at the 4 position with an oxidant comprises contacting the hydrocarbon chain at the 4 position of the pyrimidine ring of the 2,6-dihalo-5-alkoxy-4-substituted pyrimidine with ozone to form 2,6-dihalo-5-alkoxy-pyrimidine-4-carbaldehyde comprising the pyrimidine ring comprising the carbonyl group at the 4 position.
11. The method of claim 10 , wherein contacting the carbonyl group at the 4 position with bromine in an alcohol comprises contacting the carbonyl group at the 4 position of the pyrimidine ring of the 2,6-dihalo-5-alkoxy-pyrimidine-4-carbaldehyde with bromine in the alcohol to form alkyl 2,6-dihalo-5-alkoxy-pyrimidine-4-carboxylate comprising the pyrimidine ring comprising the carboalkoxy group at the 4 position and the halogen at the 6 position.
12. The method of claim 11 , wherein contacting the halogen at the 6 position with an amine comprises contacting the halogen at the 6 position of the pyrimidine ring of the alkyl 2,6-dihalo-5-alkoxy-pyrimidine-4-carboxylate with amine to form an alkyl 6-amino-2-halo-5-alkoxy-pyrimidine-4-carboxylate comprising the pyrimidine ring comprising the amino group at the 6 position.
13. The method of claim 9 , wherein contacting the halogen at the 6 position with an amine comprises contacting the halogen at the 6 position of the pyrimidine ring of the 2,6-dihalo-5-alkoxy-4-substituted pyrimidine with the amine to form a 6-amino-2-halo-5-alkoxy-4-substituted pyrimidine comprising the pyrimidine ring comprising the amino group at the 6 position and the hydrocarbon chain at the 4 position.
14. The method of claim 13 , wherein contacting the hydrocarbon chain at the 4 position with an oxidant comprises contacting the hydrocarbon chain of the 6-amino-2-halo-5-alkoxy-4-substituted pyrimidine with an oxidant to form a 6-amino-2-halo-5-alkoxy-pyrimidine-4-carbaldehyde comprising the pyrimidine ring comprising the carbonyl group at the 4 position.
15. The method of claim 14 , wherein contacting the carbonyl group at the 4 position with bromine in an alcohol comprises contacting the carbonyl group at the 4 position of the 6-amino-2-halo-5-alkoxy-pyrimidine-4-carbaldehyde with bromine in an alcohol to form alkyl 6-amino-2-halo-5-alkoxy-pyrimidine-4-carboxylate comprising the pyrimidine ring comprising the carboalkoxy group at the 4 position.
16. A method of using 2,6-dihalo-5-alkoxy-4-substituted pyrimidine to form a 2,6-dihalo-5-alkoxy-pyrimidine-4-carboxylic acid, the 2,6 dihalo-5-alkoxy-4-substituted pyrimidine comprising a pyrimidine ring comprising a 4 position, the pyrimidine ring comprising a hydrocarbon chain at the 4 position, the method comprising contacting the hydrocarbon chain at the 4 position with an oxidant to form a carboxyl group at the 4 position.