ZA200007286B - Method for producing isoxazoline-3-yl-acyl benzene. - Google Patents
Method for producing isoxazoline-3-yl-acyl benzene. Download PDFInfo
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- ZA200007286B ZA200007286B ZA200007286A ZA200007286A ZA200007286B ZA 200007286 B ZA200007286 B ZA 200007286B ZA 200007286 A ZA200007286 A ZA 200007286A ZA 200007286 A ZA200007286 A ZA 200007286A ZA 200007286 B ZA200007286 B ZA 200007286B
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- 238000004519 manufacturing process Methods 0.000 title claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title 2
- 150000001875 compounds Chemical class 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- -1 nitro-o-methylphenyl compound Chemical class 0.000 claims description 4
- 150000002923 oximes Chemical class 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 238000007363 ring formation reaction Methods 0.000 claims description 2
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 2
- XXWVVIRTHDRMEY-UHFFFAOYSA-N bromo thiohypobromite Chemical compound BrSBr XXWVVIRTHDRMEY-UHFFFAOYSA-N 0.000 claims 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 2
- 230000021523 carboxylation Effects 0.000 claims 2
- 238000006473 carboxylation reaction Methods 0.000 claims 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- 150000002545 isoxazoles Chemical class 0.000 claims 2
- 150000002825 nitriles Chemical class 0.000 claims 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims 2
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical compound OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 claims 1
- WEQPBCSPRXFQQS-UHFFFAOYSA-N 4,5-dihydro-1,2-oxazole Chemical compound C1CC=NO1 WEQPBCSPRXFQQS-UHFFFAOYSA-N 0.000 claims 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 239000003513 alkali Chemical group 0.000 claims 1
- 125000004414 alkyl thio group Chemical group 0.000 claims 1
- 239000000010 aprotic solvent Substances 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 150000002391 heterocyclic compounds Chemical class 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 125000001624 naphthyl group Chemical group 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 125000003544 oxime group Chemical group 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical class [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims 1
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 150000003217 pyrazoles Chemical class 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000000543 intermediate Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 7
- YVEMRSAMGFGCFA-UHFFFAOYSA-N 3-(4,5-dihydro-1,2-oxazol-3-yl)benzoic acid Chemical class OC(=O)C1=CC=CC(C=2CCON=2)=C1 YVEMRSAMGFGCFA-UHFFFAOYSA-N 0.000 description 3
- 125000003236 benzoyl group Chemical class [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- XBYRMPXUBGMOJC-UHFFFAOYSA-N 1,2-dihydropyrazol-3-one Chemical compound OC=1C=CNN=1 XBYRMPXUBGMOJC-UHFFFAOYSA-N 0.000 description 1
- FDUDOXAXTYOKLB-UHFFFAOYSA-N 3-(2-bromophenyl)-4,5-dihydro-1,2-oxazole Chemical compound BrC1=CC=CC=C1C1=NOCC1 FDUDOXAXTYOKLB-UHFFFAOYSA-N 0.000 description 1
- QWKJJRPLMQHLTK-UHFFFAOYSA-N 3-(3-bromophenyl)-4,5-dihydro-1,2-oxazole Chemical class BrC1=CC=CC(C=2CCON=2)=C1 QWKJJRPLMQHLTK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004768 bromobenzenes Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
- C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
g 0050749012 AMENDED SHEET
Preparation of isoxazolin-3-ylacylbenzenes
The present invention provides a process for .preparing isoxazolin-3-ylacylbenzenes, novel intermediates and novel processes for preparing these intermediates.
Isoxazolin-3-ylacylbenzenes are useful compounds which can be used in the field of crop protection. WO 98/31681, for example, describes 2-alkyl-3-(4,5-dihydroisoxazol-3-yl)acylbenzenes as herbicidally active compounds.
A need exists to provide an alternative process for preparing 3- heterocyclyl-substituted benzoyl derivatives. The preparation process described in WO 98/31681 for 2-alkyl-3-(4,5- dihydroisoxazol-3-yl)acylbenzenes or precursors thereof (2-alkyl- 3-(4,5-dihydroisoxazol-3-yl) bromobenzene derivatives) is not particularly suitable for the industrial preparation of these compounds, since the synthesis involves a plurality of steps and the yield of the end product in question, based on the starting materials employed in the first step of the synthesis, is relatively low.
The preparation of compounds or intermediates with a structure similar to that of the compounds of the formula I is known from the literature:
WO 96/26206 discloses a process for preparing 4-[3~(4,5-dihydroisoxazol-3-~yl)benzoyl]-5-hydroxypyrazoles where, in the last step, a 5-hydroxypyrazole is reacted with a 3-(4,5-dihydroisoxazol-3-yl)benzoic acid derivative. The 3-(4,5-dihydroisoxazol-3-yl)benzoic acid derivative required for this process can only be obtained with difficulty, via a large number of steps. Accordingly, the process is relatively expensive - and not optimal economically.
DE 197 09 118 describes a process for preparing 3-(4,5-dihydroisoxazol-3-yl)benzoic acids starting from 40 3-bromo-(4,5-dihydroisoxazol-3-yl)benzene, Grignard reagents and carbon dioxide.
Surprisingly, we have found that the number of process steps in the preparation of the 3-heterocyclyl-substituted benzoyl 45 derivatives can be reduced compared to the process described in
WO 98/31681 if the synthesis is carried out via selected intermediates. Moreover, the process according to the invention
. 0050/49012 AMENDED SHEET © @ 2 ) has the advantage that the overall yield of the end products of the formula I and also that of the intermediates X, based on the starting materials employed, is higher than the yield of the processes described in WO 98/31681. Furthermore, the respective ] 5 intermediates of the individual process steps can be obtained in good yield. Moreover, some of the individual process steps are advantageous for the industrial preparation of the intermediates, since they allow a cost-effective and economic preparation of the latter. Furthermore, it is advantageous that the starting materials used are basic chemicals which are easy to prepare and which can be obtained from several independent suppliers of raw materials, even in relatively large amounts. Overall, the process according to the invention provides a more cost-effective, economical and safe industrial process for preparing herbicidally active compounds of the formula I.
The present invention provides a process for preparing compounds of the formula I
R® 4 o R 4 S
R! S(0) R? I . R®
Oo where the substituents are as defined below:
R! is hydrogen, C,-Cg~alkyl,
R2 is C;-Cg-alkyl,
R3, R4, RS are hydrogen, C;-Cg-alkyl, or R? and RS together form a bond,
R6 is a heterocyclic ring, n is 0, 1 or 2; 40 which comprises preparing an intermediate of the formula VI
0050/49012
Rr? 4 0 R /
N NN R®
VI
R: NH, in which R! and R3 - R35 are as defined above.
In subsequent reaction steps, compounds of the formula VI are converted into the corresponding 3-bromo-substituted compounds : (bromobenzene derivatives), and the amino group on the phenyl ring is transformed into a sulfonyl group, giving compounds of the formula X:
Rr? 4 o R / 5
R! S(0) R® X
Br
The compounds of the formula X (3-(4,5-dihydroisoxazol-3- yl)bromobenzenes) are useful intermediates for preparing active compounds of the formula I. In particular, the process according to the invention affords the compounds I in the last reaction step in good yield. The compounds I are suitable, for example, for use as crop protection agents, in particular as herbicides, as described in WO 96/26206 and WO 97/35850.
According to the invention, the compounds of the formula I and the required intermediates, in particular compounds of the 40 formula VI or X, can be prepared advantageously by combining one or more of the following process steps a) - g):
’ 0050/49012 07 ® 20007286 ) a) reaction of a nitro-o-methylphenyl compound of the formula II
CH, 1
Or - in which the radical R! is as defined above with an organic nitrite R-ONO in the presence of a base to give an oxime of the formula III
OH
N
NX
R? NO, 111 in which the radical Rl! is as defined above; b) cyclization of the oxime of the formula III with an alkene of the formula IV
RY R°®
N=/ Iv
R* in which R3 to R5 are as defined in claim 1 in the presence of a base to give the isoxazole of the formula V
R® 4 o R / 5
NNR
\Y
R? NO, 40
0050/49012 ® 20007286 i 5 : in which R! and R3 to R5 are as defined in claim 1; c) reduction of the nitro group in the presence of a catalyst to give the aniline of the formula VI
Rr? 4 0 R
N .
NN R
VI
R' NH, in which R! and R3 to R5 are as defined in claim 1; : d) reaction of the aniline of the formula VI with a dialkyl disulfide of the formula VII
RZ—Ss—Ss—R’ VII in the presence of an organic nitrite R-ONO and, if appropriate, a catalyst to give the thioether of the formula
VIII
R®
R* 0 /
N NN R®
VIII
R! SR’ in which R! to R5 are as defined in claim 1; 40
Claims (1)
- . . 0050/49012 AMENDED SHEET @® 52 CLAIMS1. A process for preparing isoxazoles of the formula I5 . Rr? e 0 R / 5 NNR R S(0),R’® : R® 0) where the substituents are as defined below: Rl is hydrogen, C;-Cg-alkyl, . R2 is C;-Cg-alkyl, To 20 R3, R4, R5 are hydrogen, C;-Cg-alkyl, or R? and R5 together form a bond, RE is a heterocyclic ring, n is 0, 1 or 2; which comprises preparing an intermediate of the formula VI R® 4 o R / C NR vI RY NH, where R!, R3, RY and R53 are as defined above, and subsequent reaction to give compounds of the formula I.2. A process as claimed in claim 1, comprising one or more of 40 the following process steps: a) reaction of a nitro-o-methylphenyl compound of the formula II; 0050/49012 AMENDED SHEET CH, R" om II5 . . in which the radical R! is as defined above with an organic nitrite R-ONO in the presence of a base to give an oxime of the formula III OH Na R' NO, III in which the radical R! is as defined above; b) cyclization of the oxime of the formula III with an . alkene of the formula IV RR R® N=’ Iv 4 R in which R3 to RS are as defined in claim 1 in the presence of a base to give the 4,5-dihydroisoxazole of the formula VR® . 0 R / S Vv t R NO, 40 in which R! and R3 to R35 are as defined in claim 1; Cc) reduction of the nitro group in the presence of a catalyst to give the aniline of the formula VI] 0050/4%012 AMENDED SHEETRr? 4 o R / 5 N \N = R VI R NH,in which R! and R3 to RS are as defined in claim 1; d) reaction of the aniline of the formula VI with a dialkyl disulfide of the formula VIIRiX—Ss—s-R* VII in the presence of an organic nitrite and, if appropriate, a catalyst to give the thioether of the formula VIII Rr 4 o R / NN R® .25% VIII R: SR?in which R! to R53 are as defined in claim 1; ] e) bromination of the thioether of the formula VIII with a brominating agent to give the bromothioether of the ° formula IX : Rr? ( 3 o R / 5 R! SR? Br 45 in which R! to RS are as defined in claim 1;. . 0050749012 AMENDED SHEET . f) oxidation of the bromothioether of the formula IX with an oxidizing agent to give the isoxazoles of the formula X Rr® 4 ) o R ’ / S$ NR RY S(0),R* X 8 where n is the numbers 1 or 2, g) carboxylation of the isoxazole of the formula X in the presence of a compound R6-0H (XI) and carbon monoxide and a catalyst giving compounds of the formula IX.3. A process as claimed in claim 2, wherein the carboxylation in process step g) is carried out in the presence of carbon monoxide, a palladium catalyst, if appropriate at least one molar equivalent of a potassium salt and if appropriate at least one molar equivalent of a tertiairy amine of the formula XIII N(Ra), XIII in which one of the radicals R3 can be phenyl or naphthyl and the other radicals R2 are C;-Cg-alkyl, are reacted with one another at 100-140°C and at a pressure of 1-40 kg/cm2.4. A process is claimed in claim 3, wherein the reaction is carried out at a pressure of 5-8 kg/cm2.5. A process as claimed in claim 3 or 4, wherein the reaction is carried out at 110-130°C.6. A process as claimed in any of claims 3 to 5, wherein the catalyst used is a palladium(II) salt. 40 7. A process as claimed in claim 6, wherein the catalyst used is bis(triphenylphosphane)palladium(II) chloride.8. A process as claimed in any of claims 3 to 5, wherein the catalyst used is tetrakistriphenylphosphanepalladium(0). 459. A process as claimed in any of claims 3 to 8, wherein the potassium salt used is potassium carbonate, and an amine of.- 0050/49012 AMENDED SHEET ® 56 the formula XIII (N(R2)3) is additionally used.10. A process as claimed in any of claims 2 to 9, wherein the compound XI and the compound X are employed in a molar ratio of from 1 to 2.11. A process as claimed in any of claims 2 to 10, wherein, in process step g), the heterocyclic compound XI used is a pyrazole derivative of the formula XI.aR? . . 15 : and R7 is C;-C4-alkyl and M is hydrogen or an alkali : metal atom.12. A process as claimed in any of claims 1 to 11, wherein the substituents are as defined below: Rl is C-Cg-alkyl; R2 is C;-Cs-alkyl; R3,R4,R5 are hydrogen or C;-Cs-alkyl; . RS is pyrazol-4-yl which may be substituted by alkyl groups and/or a hydroxyl group.13. A compound of the formula III OH NN “Or IIx where R! is C;-Cg-alkyl. 40. \ 0050/49G12 AMENDED SHEET14. A compound of the formula XII Rr: : 4 0 ~R : 5 . N NL Rr? XII R' A where the radicals are as defined below: A is nitro, amino or the group S~R2; RL is hydrogen, C,-Cg-alkyl; R2 is C;-Cg-alkyl; R3, R¢, R5 are hydrogen, C;-Cg-alkyl, or R? and RS together form a bond.15. A compound of the formula X R’ 4 o RN . Nn R R! S(0),R® X Br where the radicals are as defined below: Rl is hydrogen, C,-Cg-alkyl; R2 is C;-Cg¢-alkyl; R3, RY, R5 are hydrogen, C;-Cg-alkyl, or R? and RS together form a bond; n is the number 0, 1 or 2.16. A process for preparing compounds as claimed in claim 15, 40 comprising one or more of the process steps a)-f) set forth in claim 2.17. The use of compounds as claimed in any of claims 13, 14 or 15 for preparing compounds of the formula I. 4518. A process for preparing compounds of the formula XV® 58 (Rx), xv C=NOH H ) X ’ in which the radicals are as defined below: X is NO;, S(O)qRY, : Rx, Ry are in each case any inert radical; m is 0, 1, 2, 3 or 4; n is 2; which comprises reacting compounds of the formula XVI y 15 (Rx), XVI CH, X in which the substituents are as defined above with an organic nitrite of the formula R-O-NO, where R is an aliphatic or aromatic radical, in the presence of a base, the reaction being carried out at a temperature below -20°C in the presence of a dipolar aprotic solvent followed, if appropriate, by conversion of the oxime group -CH=NOH in formula XV into the corresponding aldehydes ~CHO, nitriles (-CN) or nitrile oxides (-CNO).19. A process as claimed in claim 18, wherein the solvent used isDMF.20. A process for preparing thioethers of the formula XIX (RX), i 40 R? in which the substituents are as defined below: Rx 1s an inert radical, 45 m is a number from 0 to 5, RZ is C;-Cg-alkyl,. 0050/49012 AMENDED SHEET © @ 59 which comprises reacting an aniline of the formula XX (Rx), Oo, NH, with a dialkyl disulfide of the formula VII R*Y—S—s-R* VII in the presence of a catalyst.21. A process as claimed in claim 20, wherein the catalyst used is copper powder or elemental copper.22. A compound of the formula XV R' C=NOH H : X in which the radicals are as defined below: X is S(0)qaRy, Rl! is hydrogen, C;-Cg-alkyl, halogen, C,;-Cg-alkoxy, C;-Cg~alkylthio, Rx is an inert radical, Ry is any radical selected from the group consisting of hydrogen, chlorine and bromine and located on the phenyl ring in the position para to group X, m is 1, n is 0, 1 or 2.35 .23. A process for preparing compounds IX or X using one of the processes as claimed in claim 18 and 20.24. A process according to the invention for preparing a compound 40 of the formula I, XV, XIX, IX or X substantially as hereinbefore described or exemplified.25. A process for preparing a compound of the formula I, XV, XIX, IX or X including any new inventive integer or combination of 45 integers, substantially as herein described.« © 0050/29012 AMENDED SHEET ‘@26. A compound of the formula III, XII, X or XV as claimed in any one of claims 13 to 15 and 22, specifically as hereinbefore described or exemplified. :27. A compound of the formula III, XII, X or XV including any new inventive integer or combination of integers, substantially as herein described.28. The use of compounds of the formula III, XII or X as claimed in claim 17, substantially as hereinbefore described or exemplified.29. The use of compounds of the formula III, XII or X including any new inventive integer or combination of integers, substantially as herein described. 40
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19820722A DE19820722C1 (en) | 1998-05-11 | 1998-05-11 | Preparation of benzoyl pyrazole derivative herbicides, in single stage from hydroxypyrazole, bromobenzene and carbon monoxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ZA200007286B true ZA200007286B (en) | 2001-12-10 |
Family
ID=7867165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ZA200007286A ZA200007286B (en) | 1998-05-11 | 2000-12-08 | Method for producing isoxazoline-3-yl-acyl benzene. |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN100516030C (en) |
| DE (1) | DE19820722C1 (en) |
| ZA (1) | ZA200007286B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4818511B2 (en) * | 1998-11-18 | 2011-11-16 | ビーエーエスエフ ソシエタス・ヨーロピア | Process for producing 2-alkyl-3- (4,5-dihydroisoxazol-3-yl) halobenzenes |
| GB201117019D0 (en) | 2011-10-04 | 2011-11-16 | Syngenta Ltd | Herbicidal compounds |
| GB201121317D0 (en) | 2011-12-09 | 2012-01-25 | Syngenta Ltd | Herbicidal compounds |
| CN110526844B (en) * | 2018-05-25 | 2021-11-12 | 江苏中旗科技股份有限公司 | Synthetic method of topramezone intermediate 2, 3-dimethyl benzylthio-ether |
| CN111848466A (en) * | 2019-03-08 | 2020-10-30 | 新昌县大船畈生物科技有限公司 | Preparation method of edible essence and spice |
| CN112321466A (en) * | 2020-11-23 | 2021-02-05 | 华东师范大学 | Synthetic method of topramezone key intermediate |
| CN115385832B (en) * | 2022-09-13 | 2024-04-30 | 江苏七洲绿色科技研究院有限公司 | Preparation method of 2, 3-dimethyl 4-methylsulfonyl bromobenzene |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2699549B2 (en) * | 1988-06-03 | 1998-01-19 | 日産化学工業株式会社 | Method for producing 4-benzoyl-5-hydroxypyrazoles |
| US5486521A (en) * | 1994-03-21 | 1996-01-23 | Uniroyal Chemical Company, Inc. | Pyrimidinyl aryl ketone oximes |
| TR199700844T1 (en) * | 1995-02-24 | 1998-01-21 | Basf Aktiengesellschaft | Pyrazolyl-Benzoil T�revleri. |
| EP0891972A4 (en) * | 1996-03-26 | 2000-12-13 | Nippon Soda Co | 3-(isoxazol-5-yl)-substituted benzoic acid derivatives and process for producing the same |
-
1998
- 1998-05-11 DE DE19820722A patent/DE19820722C1/en not_active Expired - Lifetime
-
1999
- 1999-05-04 CN CNB2005100558786A patent/CN100516030C/en not_active Expired - Lifetime
-
2000
- 2000-12-08 ZA ZA200007286A patent/ZA200007286B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE19820722C1 (en) | 1999-11-04 |
| CN100516030C (en) | 2009-07-22 |
| CN1757634A (en) | 2006-04-12 |
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