Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2003-03-24
2004-10-26
Solola, Taofiq (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C549S023000, C568S023000
Reexamination Certificate
active
06809206
ABSTRACT:
BACKGROUND OF THE INVENTION
Acylated cyclic 1,3-dicarbonyl compounds and salt derivatives represented by the triketone tautomer of Formula i:
wherein linking group A
0
completes a 5-, 6- or 7-membered, optionally substituted carbocyclic or heterocyclic ring, and J
0
is an aliphatic or aromatic group, are well known in the literature. Examples of such compounds are disclosed in European Patent Application Publication EP-666254-A1, PCT Patent Application Publications WO96/22958 and WO97/01550, and U.S. Pat. Nos. 2,672,483, 4,560,403, 4,678,496 and 5,480,858.
Cyclic 1,3-dicarbonyl compounds of Formula i are known to equilibrate with enolic tautomer forms, such as Formula ia:
As equilibration between the triketone of Formula i and its enolic tautomers is facile, they are chemical and biological equivalents. Through this equilibration the 1,3-dione moiety is equivalent to its enolic 3-hydroxy-2-en-1-one tautomers. These compounds are acidic and easily form salts on treatment with bases. As the free acid and salt forms of these compounds rapidly equilibrate in the environment and under physiological conditions, they can be considered biological equivalents.
Many of the acylated 1,3-dicarbonyl compounds of Formula i are known to be biologically active. Examples of such compounds are disclosed in PCT Patent Application Publication WO97/01550 as valuable for controlling undesired vegetation in such important crops as rice, soybeans, sugar beets, corn (maize), potato, wheat, barley, tomato and plantation crops. U.S. Pat. Nos. 4,560,403 and 4,678,496 indicate compounds in this class are also plant growth regulants, both for crop and non-crop uses such as for lawns. In
Chemical Reviews
1999, 99(4), pages 1047-1065, D. B. Rubinov et al. published “Chemistry of 2-Acylcycloalkane-1,3-diones” in which he reviews the chemistry of this class of compounds as well as their usefulness. Rubinov indicates that these compounds exhibit antibiotic, antibacterial, antihelmintic, antimalarial, antidiabetic, anticancer and other useful therapeutic properties. Plants and fruits used as folk medicines may be extracted to yield flavanoids with this basic structure.
Examples of specific compounds represented by Formula i with commercial significance are shown in Table 1.
TABLE 1
Commercially Useful Triketones
STRUCTURE
IDENTITY
USE
Sulcotrione CAS 99105-77-8
Pre and post emergence control in maize of annual and broadleaf grasses.
2-isovalerylindane- 1,3-dione CAS 83-28-3
Insecticide. Rodenticide.
Pindone CAS 83-26-1
Anticoagulant, Rodenticide
Chlorophacinone CAS 3691-35-8
Anticoagulent, Rodenticide
Difenadione CAS 82-66-6
Anticoagulant Rodenticide
Dehydroacetic acid CAS 520-45-6
Sodium salt as dip- fungicide, Bacteriacide in toothpastes. Plasticizer.
Pyratrione CAS 51089-21-5
Anti-hypertensive.
Prohexadione CAS 88805-35-0
Plant growth regulator.
2,5-dihydroxy-3- methoxy-6-[(2E)-1- oxo-3-phenyl-2- propenyl]-2,5- cyclohexadiene-1,4- dione
Extract from
Didymocarpus
leucocalyx
(M. Fujii, Natural Medicines 1996, V50, p404)
4,5-dimethoxy-2- [(2E)-1-oxo-3- phenyl-2-propenyl]- 4-cyclopentene-1,3- dione
Flavanoids from the fruits of
Lindera erythrocarpa
, used as a folk medicine. (Sheng-Yien Liu, Yukio Ogihara, Yakugaku Zasshi 1975, 95(9), 1114-18)
Apiosporamide
Antifungal extract from mycelium of the coprophilous fungus. (Ali A. Alfatafta et al. J. Nat. Prod. 1994, 57(12), 1696-702)
Compound 79 Table II Page 36 of EP 0 283 261 B1
EP 0 283 261 B1 “Herbicidal Substituted Cyclic Diones”
Compound 74 Table I Page 34 of EP 0 283 261 B1
EP 0 283 261 B1 “Herbicidal Substituted Cyclic Diones”
Scheme i shows preparation of acylated cyclic 1,3-dicarbonyl compounds of Formula i, via rearrangement of the corresponding enol ethers of Formula ii, wherein linking group A
0
and J
0
are as already described. Such a rearrangement is disclosed in a number of references including PCT Patent Application Publications WO99/28282 and WO96/22958, and U.S. Pat. Nos. 4,695,673 and 4,678,496.
The reaction requires a catalyst to proceed in satisfactory rate and yield. Known catalysts include azoles such as 1,2,4-triazole as described in PCT Patent Application Publication WO99/28282, 4-(dimethylamino)pyridine as described in PCT Patent Application Publication WO93/08153, cyanide as described in U.S. Pat. No. 4,695,673 and aluminum trichloride as described in
Synthesis
1978, pages 925-6.
As described in PCT Patent Application Publication WO99/28282 and shown in Scheme ii, some enol ethers of Formula ii can be prepared by treating a 1,3-dicarbonyl compound of Formula iii with an acylating reagent of Formula iv in the presence of a base.
wherein linking group A
0
completes a 5-, 6- or 7-membered optionally substituted carbocyclic or heterocyclic ring. J
0
is an aliphatic or aromatic group, and X
0
is a halogen leaving group, usually chlorine.
PCT Patent Application Publications WO99/28282, WO96/22958 and WO96/22957, and U.S. Pat. Nos. 5,559,218, and 5,480,858 describe acyl halides as suitable acylating agents. The enol ether may be isolated, or the crude reaction mass may be treated with a catalyst, as indicated above to give the desired acylated cyclic 1,3-dicarbonyl compounds of general Formula i. A limitation of the method of Scheme ii is that acyl halides are produced under acidic conditions that can decompose acid-sensitive chemical substituents on the acyl halide itself causing reduced yield and purity. Also, substituents that would react with the highly reactive acyl halide group cannot be included. Additional methods to prepare acylated cyclic 1,3-dicarbonyl compounds are therefore needed.
SUMMARY OF THE INVENTION
This invention pertains to a method for preparing an acylated product of Formula 1:
wherein
A is a linking group comprising an optionally substituted backbone segment consisting of 2 to 4 atoms selected from carbon atoms and 0 to 2 nitrogen, 0 to 2 oxygen and 0 to 2 sulfur atoms;
J is an optionally substituted, carbon-linked hydrocarbyl group; and
Y is H or a salt cation;
the process comprising contacting a phenyl ester of Formula 2:
wherein
y is 0, 1, 2 or 3;
each R is independently selected from electron-withdrawing groups; and
J is as defined for Formula 1
with a cyclic compound of Formula 3:
wherein
A and Y are as defined for Formula 1;
in the presence of a source of cyanide or fluoride ion.
REFERENCES:
patent: 2672483 (1954-03-01), Thomas
patent: 4560403 (1985-12-01), Motojima et al.
patent: 4678496 (1987-07-01), Motojima et al.
patent: 4695673 (1987-09-01), Heather et al.
patent: 5480858 (1996-01-01), Sakamoto et al.
patent: 5523462 (1996-06-01), Kast et al.
patent: 5559218 (1996-09-01), Kast et al.
patent: 0283261 (1998-09-01), None
patent: 0666254 (1999-04-01), None
patent: WO 9308153 (1993-04-01), None
patent: WO 9622957 (1996-08-01), None
patent: WO 9622958 (1996-08-01), None
patent: WO 9701550 (1997-01-01), None
patent: WO 9928282 (1999-06-01), None
Chemical Reviews 1999, 99(4), p. 1047-1065, D. B. Rubinov et al. “Chemistry of 2-Acylcycloalkane-1,3-diones”.
Sheny-Yien Liu, Yukio Ogihara, Yakugaku Zasshi 1975, 95(9), 1114-1118.
Ali A. Alfatafta et al., J. Nat. Prod. 1994, 57(12), 1696-1702.
Synthesis 1978, pp. 925-926.
M. Fuji, Natural Medicines (1996), V50,P404.
E. I. du Pont de Nemours and Company
Solola Taofiq
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