Claims
- 1. A process for producing 3-phenyl-2,4(1H,3H)-pyrimidinediones having the general formula (I) and their salts whereinA1 is hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cyloalkynyl, cycloalkylalkyl, each being optionally substituted, A2 is hydrogen, —Q1—A3 wherein Q1 is O, S, SO, or SO2; A3 is hydrogen or A4 (A4 is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cyloalkynyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl, heterocyclicalkyl, each being optionally substituted), —Q1—CQ2—A3 wherein Q2 is O or S, —Q1—CQ2—Q2—A3, —Q1—CQ2—N(A3)2, —CQ2—A3, —CQ2—Q2—A3, —CQ2—N(A3)2, —N(A3)2, —N(Q1—A3)2, —N(CQ2—A3)2, —N(Q1—A3)(CQ2—A3), —N(CQ2—Q2—A3)2, —N(A3)—CQ2—N(A3)2, or —SO2—N(A3)2, each A3 group of (A3)2 being independently same or different, any two of (A1)l and (A2)m groups being optionally combined through a saturated or unsaturated carbon, —CQ2—, and/or hetero O, N, S, SO, or SO2 linkage to form a cyclic ring having up to 12 membered ring, each being optionally substituted,l is an integer of 1 to 5, m is an integer of 1 to 3, l+m is an integer of 2 to 5, R1 is A4, —Q1—A3, —Q1—CQ2—A3, —Q1—CQ2—Q2—A3, —Q1—CQ2—N(A3)2, —CQ2—A3, —CQ2—Q2—A3, —CQ2—N(A3)2, —N(A3)2, —N(Q1—A3)2, —N(CQ2—A3)2, —N(Q1—A3)(CQ2—A3), —N(CQ2—Q2—A3)2, —N(A3)—CQ2—N(A3)2, or —SO2—N(A3)2, each A3 group of (A3)2 being independently same or different, R2 is hydrogen or R1, R1 and R2 groups being optionally combined together with N of N(R1)(R2) through a saturated or unsaturated carbon, —CQ2—, and/or hetero O, N, S, SO, or SO2 linkage to form a cyclic ring having up to 12 membered ring, each being optionally substituted, which comprises reacting an isocyanate represented by the general formula (II) wherein A1, A2, l and m are as defined above, and a substituted hydrazono ester represented by the general formula (III) wherein R5 is A4, R1 and R2 are as defined above, with the presence of a Grignard reagent.
- 2. The process according to claim 1 for producing a 3-(3-substituted phenyl)-2,4(1H,3H)-pyrimidinedione having the formula (I-a) or its salt whereinX, Y are hydrogen, halogen, cyano, nitro, alkyl, alkoxy, cycloalkyl, cycloalkylalkyl or thiocarbamoyl, each being optionally substituted, Z is O, S, SO, SO2 or NR wherein R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, each being optionally substituted, Ar is a substituted or unsubstituted 3 to 12 membered cyclic ring, it having optionally one or more saturated or unsaturated carbon, —CQ2—, and/or hetero O, N, S, SO, or SO2 linkage, R1 is A4, —Q1—A3, —Q1—CQ2—A3, —Q1—CQ2—Q2—A3, —Q1—CQ2—N(A3)2, —CQ2—A3, —CQ2—Q2—A3, —CQ2—N(A3)2, —N(A3)2, —N(Q1—A3)2, —N(CQ2—A3)2, —N(Q1—A3)(CQ2—A3), —N(CQ2—Q2—A3)2, —N(A3)—CQ2—N(A3)2, or —SO2—N(A3)2, each A3 group of (A3)2 being independently same or different, R2 is hydrogen or R1, R1 and R2 groups being optionally combined together with N of N(R1)(R2) through a saturated or unsaturated carbon, —CQ2—, and/or hetero O, N, S, SO, or SO2 linkage to form a cyclic ring having up to 12 membered ring, each being optionally substituted, which comprises reacting an isocyanate represented by the general formula (II-a) wherein Ar, X, Y, and Z are as defined above, and a substituted hydrazono ester represented by the formula (III-a) wherein R5 is A4.
- 3. A process according to claim 1 for producing a compound or its salt represented by the formula (I-c) whereinX, Y are hydrogen, halogen, cyano, nitro, alkyl, alkoxy, cycloalkyl, cycloalkylalkyl or thiocarbamoyl, each being optionally substituted, Z is O, S, SO, SO2 or NR wherein R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, each being optionally substituted, Ar is a substituted or unsubstituted 3 to 12 membered cyclic ring, it having optionally one or more saturated or unsaturated carbon, —CQ2—, and/or hetero O, N, S, SO, or SO2 linkage, R3 is A4, —Q1—A3, —Q1—CQ2—A3, —Q1—CQ2—Q2—A3, —Q1—CQ2—N(A3)2, —CQ2—A3, —CQ2—Q2—A3, —CQ2—N(A3)2, —N(A3)2, —N(Q1—A3)2, —N(CQ2—A3)2, —N(Q1—A3)(CQ2—A3), —N(CQ2—Q2—A3)2, —N(A3)—CQ2—N(A3)2, or —SO2—N(A3)2, each A3 of (A3)2 being independently same or different, R4 is hydrogen or R3, R3 and R4 groups being optionally combined together with C of ═C(R3)(R4) through a saturated or unsaturated carbon, —CQ2—, and/or hetero O, N, S, SO, or SO2 linkage to form a cyclic ring having up to 12 membered ring, each being optionally substituted, which comprises reacting an isocyanate represented by the formula (II-c) with a hydrazono-ester represented by the formula (III-c) wherein R5 is A4.
- 4. The process according to claim 1, wherein the reaction is carried out in the presence of tetrahydrofuran as the solvent.
- 5. The process according to claim 1, wherein the hydrazono-ester is alkyl 4,4,4-trifluoro-(3Z)-3-[(1-methylethylidene)hydrazono]-butanoate and the Grignard reagent is methyl magnesium bromide.
- 6. A compound or its salt represented by the formula (I-c) whereinX, Y are hydrogen, halogen, cyano, nitro, alkyl, alkoxy, cycloalkyl, cycloalkylalkyl or thiocarbamoyl, Z is O, S, SO, SO2 or NR wherein R is alkyl, alkenyl, alkynyl, cycloalkyl, or cycloalkylalkyl, Ar is pyridyl, pyrimidyl, triazolyl, thiazolyl, isothiazolyl, or phenyl, or pyridyl, pyrimidyl, triazolyl, thiazolyl, isothiazolyl, or phenyl substituted with up to five substituents independently selected the from group consisting of bromo, chloro, fluoro, iodo, (C1-C4)alkyl, halo(C1-4)alkyl C1-4)alkoxy, (C1-4)alkylthio, halo(C1-4)alkoxy, (C1-4)alkylsulfonyl, (C1-C3)alkylsulfinyl, di(C1-4)alkylaminocarbonyl, cyano, nitro, (C1-4)alkylsulfonylamino, (C1-4)alkoxycarbony(C1-4)alkoxy, and (C1-4)alkoxycarbonylamino, R3 is A4, —Q1—A3, —Q1—CQ2—A3, —Q1—CQ2—Q2—A3, —Q1—CQ2—N(A3)2, —CQ2—A3, —CQ2—Q2—A3, —CQ2—N(A3)2, —N(A3)2, —N(Q1—A3)2, —N(CQ2—A3)2, —N(Q1—A3)(CQ2—A3), —N(CQ2—Q2—A3)2, —N(A3)—CQ2—N(A3)2, or —SO2—N(A3)2, each A3 of (A3)2 being independently same or different, R4 is hydrogen or R3, R3 and R4 groups being optionally combined together with C of ═C(R3)(R4) to form a cyclopentylidene.
- 7. The compound or its salt according to claim 6,whereinX is fluorine, and Y is chlorine, and Z is oxygen or sulfur, and Ar is 2-pyridyl, 3-pyridyl , 4-pyridyl , 3-bromo-2-pyridyl, 5-bromo-2-pyridyl, 6-bromo-2-pyridyl, 3-chloro-2-pyridyl, 5-chloro-2-pyridyl, 6-chloro-2-pyridyl, 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 6-fluoro-2-pyridyl, 3-cyano-2-pyridyl, 5-cyano-2-pyridyl, 6-cyano-2-pyridyl, 3-nitro-2-pyridyl, 5-nitro-2-pyridyl, 6-nitro-2-pyridyl, 3-trifluoromethyl-2-pyridyl, 4-trifluoromethyl-2-pyridyl, 5-trifluoromethyl-2-pyridyl, 6-trifluoromethyl-2-pyridyl, 3-dimethylaminocarbonyl-2-pyridyl, 3-methylsulfonyl-2-pyridyl, 3-isopropylsulfonyl-2-pyridyl, 6-chloro-3-trifluoromethyl-2-pyridyl, 3,5,6-trifluoropyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-bromo-2-pyrimidyl, 4-chloro-2-pyrimidyl, 4-trifluoromethyl-2-pyrimidyl, 4,6-dimethoxy-2-pyrimidyl, 2,6-dimethoxy-4-pyrimidyl, 4,6-dimethoxy-2-triazinyl, phenyl, 2-iodophenyl, 2-trifluoromethoxyphenyl, 2-nitrophenyl, 4-nitrophenyl, 4-methylsulfonylaminophenyl, 4-(1-ethoxycarbonylethoxy)phenyl, 2-cyanophenyl, 2-cyano-3-fluorophenyl, 2-cyano-4-fluorophenyl, 2-cyano-4-nitrophenyl, 4-nitro-2-trifluoromethylphenyl, 4-acetylamino-2-trifluoromethylphenyl, 4-(1-ethoxycarbonylethoxy)-2-nitrophenyl, 5-chloro-4-(1-ethoxycarbonylethoxy)-2-nitrophenyl, 3-methyl-4-nitro-5-isothiazolyl, or 5-nitro-2-thiazolyl.
- 8. A herbicidal composition comprising an effective amount of one or more compounds selected from claim 6 in combination with an inert carrier.
Parent Case Info
This is a Continuation-in-Part of Application No. 09/888,426 filed Jun. 26, 2001, now abandoned.
Foreign Referenced Citations (3)
Number |
Date |
Country |
WO 9607323 |
Mar 1996 |
WO |
WO 9608151 |
Mar 1996 |
WO |
WO 9841093 |
Sep 1998 |
WO |
Continuation in Parts (1)
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Number |
Date |
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Parent |
09/888426 |
Jun 2001 |
US |
Child |
09/962081 |
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US |