NO172641B - 2,6-SUBSTITUTED-3,5-PYRIDE INDICARBOXYL ACID DERIVATIVES USED AS INTERMEDIATES IN THE PREPARATION OF OTHER 2,6-SUBSTITUTED-3,5-PYRIDINE DICARBOXYL ACID DERIVATIVES WITH HERBICIDE EFFECT - Google Patents
2,6-SUBSTITUTED-3,5-PYRIDE INDICARBOXYL ACID DERIVATIVES USED AS INTERMEDIATES IN THE PREPARATION OF OTHER 2,6-SUBSTITUTED-3,5-PYRIDINE DICARBOXYL ACID DERIVATIVES WITH HERBICIDE EFFECTInfo
- Publication number
- NO172641B NO172641B NO910057A NO910057A NO172641B NO 172641 B NO172641 B NO 172641B NO 910057 A NO910057 A NO 910057A NO 910057 A NO910057 A NO 910057A NO 172641 B NO172641 B NO 172641B
- Authority
- NO
- Norway
- Prior art keywords
- alkyl
- substituted
- acid derivatives
- methyl
- hydrogen
- Prior art date
Links
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 5
- 239000000543 intermediate Substances 0.000 title claims abstract description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000002253 acid Substances 0.000 title 2
- 230000000694 effects Effects 0.000 title 1
- 239000004009 herbicide Substances 0.000 title 1
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 28
- -1 benzyloxymethyl Chemical group 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical class [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000004069 aziridinyl group Chemical group 0.000 claims abstract description 8
- 125000004966 cyanoalkyl group Chemical group 0.000 claims abstract description 8
- 125000000466 oxiranyl group Chemical group 0.000 claims abstract description 8
- 125000004076 pyridyl group Chemical group 0.000 claims abstract description 8
- 125000001544 thienyl group Chemical group 0.000 claims abstract description 8
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 7
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 7
- 125000002541 furyl group Chemical group 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 125000001730 thiiranyl group Chemical group 0.000 claims abstract description 7
- 150000003254 radicals Chemical class 0.000 claims abstract description 6
- 125000004946 alkenylalkyl group Chemical group 0.000 claims abstract description 5
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 5
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims abstract description 4
- 125000000278 alkyl amino alkyl group Chemical group 0.000 claims abstract description 4
- 125000004687 alkyl sulfinyl alkyl group Chemical group 0.000 claims abstract description 4
- 125000004688 alkyl sulfonyl alkyl group Chemical group 0.000 claims abstract description 4
- 125000006350 alkyl thio alkyl group Chemical group 0.000 claims abstract description 4
- 125000004103 aminoalkyl group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000005002 aryl methyl group Chemical group 0.000 claims abstract description 4
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 claims abstract description 4
- 125000000262 haloalkenyl group Chemical group 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 150000002431 hydrogen Chemical class 0.000 claims abstract 3
- 150000001875 compounds Chemical class 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000005242 carbamoyl alkyl group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 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
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000006272 (C3-C7) cycloalkyl group Chemical group 0.000 claims 1
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 abstract description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 125000004983 dialkoxyalkyl group Chemical group 0.000 abstract 1
- 238000010992 reflux Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 125000005038 alkynylalkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- JSYGRUBHOCKMGQ-UHFFFAOYSA-N dichloramine Chemical compound ClNCl JSYGRUBHOCKMGQ-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006018 1-methyl-ethenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- PEOGRCGQVFDFSO-UHFFFAOYSA-N 2-(difluoromethyl)-5-ethoxycarbonyl-4-propan-2-yl-6-(trifluoromethyl)pyridine-3-carboxylic acid Chemical compound C(C)OC(=O)C=1C(=C(C(=NC1C(F)(F)F)C(F)F)C(=O)O)C(C)C PEOGRCGQVFDFSO-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 description 1
- 125000006022 2-methyl-2-propenyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000012988 Dithioester Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical class OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 0.000 description 1
- 125000005022 dithioester group Chemical group 0.000 description 1
- KUINZHZKLVGIGV-UHFFFAOYSA-N ethyl 5-carbonochloridoyl-6-(difluoromethyl)-4-propan-2-yl-2-(trifluoromethyl)pyridine-3-carboxylate Chemical compound CCOC(=O)C1=C(C(F)(F)F)N=C(C(F)F)C(C(Cl)=O)=C1C(C)C KUINZHZKLVGIGV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002463 imidates Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000007970 thio esters Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
2,6-substituert-3,5-pyridin- dicarboxylsyrederivater som er anvendelige som mellomprodukter ved fremstilling av andre 2,6-substi- tuert-3,5-pyridindicarboxylsyrederi- vater med herbicid virkning. De har den generelle formel: hvor R er valgt blant lavere alkyl, lavere alkenyl, lavere alkynyl, lavere alkenylalkyl, halogenalkyl, halogenalkenyl, C^.v-cycloalkyl, Cj.^-cycloalkanylalkyl, aryl,arylme- thyl, alkoxyalkyl, benzyloxymethyl, alkylthioalkyl, dialkoxyalkyl, (l-alkoxy-l-alkylthio)-alkyl, amino- alkyl, alkylaminoalkyl, dialkylamino- alkyl, alkylsulfonylalkyl, alkylsul- finylalkyl, alkyl substituert med et dialkylsulfoniumsalt, cyanoalkyl, carbalkoxyalkyl, carbalkoxyalkenyl, et heterocyclisk radikal valgt blant furyl, pyridyl, thienyl, thiiranyl, oxiranyl og aziridinyl bundet til pyridinringen gjennom en C-C-binding, og lavere alkyl substituert med furyl, pyridyl, thienyl, thiiranyl, oxiranyl eller aziridinyl, Rj og Rj uavhengig av hverandre er valgt blant alkyl, fluorert methyl og klorfluorerte methylradikaler, forutsatt at ett av radikalene Rj og Rj må være et fluorert methyl-radikal eller et klorfluorert methylradikal, og X og/eller Y er en gruppe hvor R^ er halogen, og den eventuelt gjenværende X eller Y er valgt blant grup- pene: ^Z,R, hvor Z er valgt blant 0 og NR,, hvor R, er hydrogen eller lavere alkyl, og hvor Z, er valgt blant 0 og S, mens R, fritt er valgt blant hydrogen, Cj.^-alkyl, Cj.^-alkenylalkyl, C,.<-halogenalkyl, cyclo- alkanylalkyl, cyanoalkyl eller2,6-substituted-3,5-pyridinedicarboxylic acid derivatives useful as intermediates in the preparation of other 2,6-substituted-3,5-pyridinedicarboxylic acid derivatives with herbicidal activity. They have the general formula: wherein R is selected from lower alkyl, lower alkenyl, lower alkynyl, lower alkenylalkyl, haloalkyl, halogenalkenyl, C1-5 cycloalkyl, C1-6 cycloalkanylalkyl, aryl, arylmethyl, alkoxyalkyl, benzyloxymethyl, alkylthioalkyl, dialkoxyalkyl, (1-alkoxy-1-alkylthio) -alkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl, alkyl substituted with a dialkylsulfonium salt, cyanoalkyl, carbalkoxyalkyl, carbalkoxyalkyl, carbalkoxyalkyl, carbalkoxyalkyl , pyridyl, thienyl, thiriranyl, oxiranyl and aziridinyl bonded to the pyridine ring through a CC bond, and lower alkyl substituted with furyl, pyridyl, thienyl, thiiranyl, oxiranyl or aziridinyl, R 1 and R 2 are independently selected from alkyl, fluorinated methyl and chlorofluorinated methyl radicals, provided that one of the radicals R 1 and R 2 must be a fluorinated methyl radical or a chlorofluorinated methyl radical, and X and / or Y is a group wherein R 1 is halogen and the n optionally the remaining X or Y is selected from the groups: ^ Z, R, where Z is selected from 0 and NR1, where R, is hydrogen or lower alkyl and where Z is selected from 0 and S, while R is freely selected from hydrogen, C1-6 alkyl, C1-6 alkenylalkyl, C1-6 haloalkyl, cycloalkanylalkyl, cyanoalkyl or
Description
Denne oppfinnelse angår 2,6-substituert-3,5-pyridindicarboxylsyrederivater som er anvendelige som mellomprodukter ved fremstilling av andre 2,6-substituert-3,5-pyridindicarboxylsyrederivater med herbicid virkning. This invention relates to 2,6-substituted-3,5-pyridinedicarboxylic acid derivatives which are useful as intermediates in the production of other 2,6-substituted-3,5-pyridinedicarboxylic acid derivatives with herbicidal action.
De sistnevnte 2,6-substituert-3,5-pyridindikarboxyl-syrederivater med herbicid virkning er gjenstand for norsk patent nr. 168.801 (søknad nr. 843205) og har den generelle formel I: The latter 2,6-substituted-3,5-pyridinedicarboxylic acid derivatives with herbicidal action are the subject of Norwegian patent no. 168,801 (application no. 843205) and have the general formula I:
hvor where
R er valgt blant lavere alkyl, lavere alkenyl, lavere alkynyl, lavere alkenylalkyl, halogenalkyl, halogenalkenyl, C3.7-cycloalkyl, C3.6-cycloalkanylalkyl, aryl, arylmethyl, alkoxyalkyl, benzyloxymethyl, alkylthioalkyl, dialkoxyalkyl, (1-alkoxy-l-alkylthio)-alkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl, alkyl substituert med et dialkylsulfoniumsalt, cyanoalkyl, carbamoylalkyl, carbalkoxyalkyl, carbalkoxyalkenyl, et heterocyclisk radikal valgt blant furyl, pyridyl, thienyl, thiiranyl, oxiranyl og aziridinyl bundet til pyridinringen gjennom en C-C-binding, og lavere alkyl substituert med furyl, pyridyl, thienyl, thiiranyl, oxiranyl eller aziridinyl, R is selected from lower alkyl, lower alkenyl, lower alkynyl, lower alkenylalkyl, haloalkyl, haloalkenyl, C3.7-cycloalkyl, C3.6-cycloalkanylalkyl, aryl, arylmethyl, alkyloxyalkyl, benzyloxymethyl, alkylthioalkyl, dialkylalkyl, (1-alkyloxy-l -alkylthio)-alkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl, alkyl substituted with a dialkylsulfonium salt, cyanoalkyl, carbamoylalkyl, carbalkoxyalkyl, carbalkoxyalkenyl, a heterocyclic radical selected from furyl, pyridyl, thienyl, thiiranyl, oxiranyl and aziridinyl attached to the pyridine ring through a C-C bond, and lower alkyl substituted with furyl, pyridyl, thienyl, thiiranyl, oxiranyl or aziridinyl,
Rx og R2uavhengig av hverandre er valgt blant alkyl, fluorert methyl og klorfluorerte methylradikaler, forutsatt at ett av radikalene Rx og R2må være et fluorert methyl-radikal eller et klorfluorert methylradikal, og Rx and R2 are independently selected from alkyl, fluorinated methyl and chlorofluorinated methyl radicals, provided that one of the radicals Rx and R2 must be a fluorinated methyl radical or a chlorofluorinated methyl radical, and
X og Y uavhengig av hverandre er valgt blant gruppene: X and Y are independently selected from the groups:
hvor Z er valgt blant where Z is chosen from
0 og NR7, hvor R7er hydrogen eller lavere alkyl, og hvor Z2er valgt blant 0 og S, mens R3fritt er valgt 0 and NR7, where R7 is hydrogen or lower alkyl, and where Z2 is selected from 0 and S, while R3 is freely selected
blant hydrogen, C^-alkyl, C3_4-alkenylalkyl, C1.4-halogenalkyl, cycloalkanylalkyl, cyanoalkyl eller C3.4. alkynylalkyl; med det forbehold at når Z2er S i begge tilfeller, må R3være C1.2-alkyl; hvor R5og R6uavhengig av hverandre er valgt blant hydrogen, lavere alkyl og fenyl; among hydrogen, C 1 -alkyl, C 3-4 -alkenylalkyl, C 1-4 -haloalkyl, cycloalkanylalkyl, cyanoalkyl or C 3-4 . alkynylalkyl; with the proviso that when Z 2 is S in either case, R 3 must be C 1-2 alkyl; wherein R 5 and R 6 are independently selected from hydrogen, lower alkyl and phenyl;
Den foreliggende oppfinnelse er avdelt fra ovennevnte patentsøknad nr. 843205 (patent nr. 168.801). De nye 2,6-substituert-3,5-pyridindikarboksylsyrederivater som er anvendelige som mellomprodukter for fremstilling av forbindelsene ifølge patent nr. 168.801, har den generelle formel 1: The present invention is separated from the above-mentioned patent application no. 843205 (patent no. 168,801). The new 2,6-substituted-3,5-pyridinedicarboxylic acid derivatives which are useful as intermediates for the preparation of the compounds according to patent no. 168,801 have the general formula 1:
hvor where
R er lavere alkyl, lavere alkenyl, lavere alkynyl, lavere alkenylalkyl, halogenalkyl, halogenalkenyl, C3.7-cycloalkyl, C3.6-cycloalkanylalkyl, aryl, arylmethyl, alkoxyalkyl, benzyloxymethyl, alkylthioalkyl, dialkoxyalkyl, (1-alkoxy-l-alkylthio)-alkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl, alkyl substituert med et dialkylsulfoniumsalt, cyanoalkyl, carbamoylalkyl, carbalkoxyålkyl, carbalkoxyalkenyl; furyl, pyridyl, thienyl, thiiranyl, oxiranyl og aziridinyl bundet til pyridinringen gjennom en C-C-binding; eller lavere alkyl substituert med furyl, pyridyl, thienyl, thiiranyl, oxiranyl eller aziridinyl, R is lower alkyl, lower alkenyl, lower alkynyl, lower alkenylalkyl, haloalkyl, haloalkenyl, C3.7-cycloalkyl, C3.6-cycloalkanylalkyl, aryl, arylmethyl, alkyloxyalkyl, benzyloxymethyl, alkylthioalkyl, dialkylalkyl, (1-alkylthio-1-alkylthio )-alkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl, alkyl substituted with a dialkylsulfonium salt, cyanoalkyl, carbamoylalkyl, carbalkoxyalkyl, carbalkoxyalkenyl; furyl, pyridyl, thienyl, thiiranyl, oxiranyl and aziridinyl attached to the pyridine ring through a C-C bond; or lower alkyl substituted with furyl, pyridyl, thienyl, thiiranyl, oxiranyl or aziridinyl,
Rx og R2uavhengig av hverandre er valgt blant alkyl, fluorert methyl og klorfluorerte methylradikaler, forutsatt at ett av radikalene Rx og R2må være et fluorert methyl-radikal eller et klorfluorert methylradikal, og Rx and R2 are independently selected from alkyl, fluorinated methyl and chlorofluorinated methyl radicals, provided that one of the radicals Rx and R2 must be a fluorinated methyl radical or a chlorofluorinated methyl radical, and
X og/eller Y er en gruppe X and/or Y is a group
hvor R4er halogen, og where R 4 is halogen, and
den eventuelt gjenværende X eller Y er valgt blant gruppene: the possibly remaining X or Y is selected from the groups:
hvor Z er valgt blant 0 og NR7, hvor R7er hydrogen eller lavere alkyl, og hvor Z2er valgt blant 0 og S, mens R3fritt er valgt blant hydrogen, C1.4-alkyl, C3_4-alkenylalkyl, C1.4-halogenalkyl, cycloalkanylalkyl, cyanoalkyl eller C3.4. alkynylalkyl; med det forbehold at når Z2er S i begge tilfeller, må R3være C1.2-alkyl; hvor R5og R6uavhengig av hverandre er valgt blant hydrogen, lavere alkyl og fenyl; where Z is selected from 0 and NR7, where R7 is hydrogen or lower alkyl, and where Z2 is selected from 0 and S, while R3 is freely selected from hydrogen, C1.4-alkyl, C3_4-alkenylalkyl, C1.4-haloalkyl, cycloalkanylalkyl, cyanoalkyl or C3.4. alkynylalkyl; with the proviso that when Z 2 is S in either case, R 3 must be C 1-2 alkyl; wherein R 5 and R 6 are independently selected from hydrogen, lower alkyl and phenyl;
Med betegnelsen "alkyl" menes her både rettkjedede og forgrenede radikaler som innbefatter, men ikke er begrenset til, ethyl, methyl, n-propyl, 1-ethylpropyl, 1-methylpropyl, n-butyl, 2,2-dimethylpropyl, pentyl, isobutyl og isopropyl. Med betegnelsen "cycloalkyl" menes cycloalkylradikaler såsom cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl og cyclohep-tyl. By the term "alkyl" is meant here both straight-chain and branched radicals which include, but are not limited to, ethyl, methyl, n-propyl, 1-ethylpropyl, 1-methylpropyl, n-butyl, 2,2-dimethylpropyl, pentyl, isobutyl and isopropyl. The term "cycloalkyl" refers to cycloalkyl radicals such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
Med betegnelsen "lavere alkyl" menes et alkylradikal med fra 1 til 7 carbonatomer. Betegnelsen "lavere alkenyl" og "lavere alkynyl" er ment å skulle dekke alkenyl- og alkynyl-grupper med fra 2 til 7 carbonatomer. Eksempler på slike alke-nylgrupper er ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-methylethenyl og lignende. Eksempler på de nevnte alkynyl-grupper er ethynyl, 1-propynyl, 2-propynyl, osv. The term "lower alkyl" means an alkyl radical with from 1 to 7 carbon atoms. The terms "lower alkenyl" and "lower alkynyl" are intended to cover alkenyl and alkynyl groups of from 2 to 7 carbon atoms. Examples of such alkenyl groups are ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-methylethenyl and the like . Examples of the aforementioned alkynyl groups are ethynyl, 1-propynyl, 2-propynyl, etc.
Med betegnelsen "cycloalkanylalkyl" menes alkylradikaler som er substituert med et cycloalkylradikal med 3-6 carbonatomer. Betegnelsen "halogenalkyl" er ment å skulle dekke alkylradikaler som er substituert med ett eller flere halogen-atomer. The term "cycloalkanylalkyl" refers to alkyl radicals which are substituted by a cycloalkyl radical with 3-6 carbon atoms. The term "haloalkyl" is intended to cover alkyl radicals which are substituted with one or more halogen atoms.
Med betegnelsen "fluorert methyl" menes her methylradikaler som har ett eller flere fluoratomer tilbundet. Betegnelsen innbefatter radikaler i hvilke samtlige hydrogen-atomer er erstattet med fluor. The term "fluorinated methyl" refers here to methyl radicals which have one or more fluorine atoms attached. The term includes radicals in which all hydrogen atoms have been replaced by fluorine.
Med betegnelsen "klorfluorert methyl" menes her et methylradikal hvor minst ett hydrogenatom er erstattet med fluor og minst ett annet hydrogenatom er erstattet med klor. The term "chlorofluorinated methyl" here means a methyl radical where at least one hydrogen atom has been replaced by fluorine and at least one other hydrogen atom has been replaced by chlorine.
De av forbindelsene med den generelle formel 1 hvor den ene av gruppene X' og Y' er Those of the compounds of the general formula 1 where one of the groups X' and Y' is
hvor Hal betegner halogen valgt blant klor, brom og fluor, og den andre er nemlig forbindelsene med den generelle formel 1A: where Hal denotes halogen selected from chlorine, bromine and fluorine, and the other is namely the compounds with the general formula 1A:
hvor R, RltR2, R3og Hal har de ovenfor angitte betydninger, kan fremstilles ved at en forbindelse med den generelle formel where R, RltR2, R3 and Hal have the meanings given above, can be prepared by a compound of the general formula
III: III:
hvor R, RlrR2, og R3har de ovenfor angitte betydninger, blan-des med et overskudd av thionylhalogenid eller et annet egnet middel og blandingen kokes under tilbakeløpsbetingelser i noen timer. De av forbindelsene med den generelle formel 1 hvor begge grupper X' og Y<1>er hvor Hal er som ovenfor angitt, nemlig forbindelsene med den generelle formel 1B: hvor R, RlfR2og Hal har de ovenfor angitte betydninger, kan fremstilles ved at en forbindelse med den generelle formel V: where R, R1rR2, and R3 have the meanings given above, is mixed with an excess of thionyl halide or another suitable agent and the mixture is boiled under reflux conditions for a few hours. Those of the compounds with the general formula 1 where both groups X' and Y<1> are where Hal is as indicated above, namely the compounds with the general formula 1B: where R, R 1 R 2 and Hal have the meanings indicated above, can be prepared by a connection with the general formula V:
hvor R, RlrR2og Hal har de ovenfor angitte betydninger, om-settes med et overskudd av thionylhalogenid eller fosforhalo-genid under tilbakeløpsbetingelser i noen timer. Produktet inndampes deretter og tørres. where R, R1rR2 and Hal have the meanings indicated above, is reacted with an excess of thionyl halide or phosphorus halide under reflux conditions for a few hours. The product is then evaporated and dried.
Med hensyn til fremstillingen av forbindelsene med de ovenstående generelle formler III og V kan det vises f.eks. til ovennevnte norske patentskrift nr. 168.801. With regard to the preparation of the compounds with the above general formulas III and V, it can be shown e.g. to the above-mentioned Norwegian patent document no. 168,801.
De nye 2,6-substituert, 3,5-pyridindikarboxylsyrede-rivater ifølge oppfinnelsen er som nevnt anvendelige for fremstilling av 2,6-substituert-3,5-pyridindicarboxylsyrederivater som er gjenstand for norsk patent nr. 168.801, hvilke forbindelser er virksomme ved ugressbekjempelse. The new 2,6-substituted, 3,5-pyridinedicarboxylic acid derivatives according to the invention are, as mentioned, applicable for the production of 2,6-substituted-3,5-pyridinedicarboxylic acid derivatives which are the subject of Norwegian patent no. 168,801, which compounds are effective at weed control.
For fremstilling av en sluttforbindelse med den ovenstående generelle formel I hvor 3,5-estergruppene er ulike, blir en forbindelse med den ovenstående generelle formel la kokt med tilbakeløpskjøling med den passende alkohol i noen timer. Det ønskede produkt utvinnes etter i og for seg kjente metoder, hvorved man får den ønskede forbindelse med formel I ovenfor, i hvilken X og Y er ulike estere. For the preparation of a final compound of the above general formula I in which the 3,5-ester groups are different, a compound of the above general formula I is refluxed with the appropriate alcohol for a few hours. The desired product is extracted according to methods known per se, whereby the desired compound with formula I above is obtained, in which X and Y are different esters.
De symmetriske diesterforbindelser med den generelle formel I fremstilles ved omsetning av en forbindelse med den generelle formel 1B med den passende alkohol ved tilbakeløpsbe-tingelser i tilstrekkelig lang tid, f.eks. i 15-20 timer. Al-ternativt kan en blanding av én ekvivalent av en forbindelse med formel 1B, et overskudd av et egnet alkylhalogenid og to ekvivalenter kaliumcarbonat omrøres i et egnet oppløsningsmid-del, såsom N,N-dimethylformamid, i flere timer, hvoretter blandingen helles over i vann. Det ønskede produkt utvinnes ved hjelp av kjente oppløsningsmiddelekstraksjonsmetoder og rensemetoder. The symmetrical diester compounds of the general formula I are prepared by reacting a compound of the general formula 1B with the appropriate alcohol under reflux conditions for a sufficiently long time, e.g. for 15-20 hours. Alternatively, a mixture of one equivalent of a compound of formula 1B, an excess of a suitable alkyl halide and two equivalents of potassium carbonate can be stirred in a suitable solvent, such as N,N-dimethylformamide, for several hours, after which the mixture is poured into water. The desired product is recovered using known solvent extraction methods and purification methods.
Forbindelser ifølge norsk patentskrift nr. 168.801 som er representert ved den generelle formel VII: Compounds according to Norwegian patent document no. 168,801 which are represented by the general formula VII:
hvor R, RlfR2, R3, R5og R6har de betydninger som ovenfor er angitt for formel I, fremstilles ved omsetning av en forbindelse med formel 1B med en passende mengde amin eller ammoniakk. where R, R 1 R 2 , R 3 , R 5 and R 6 have the meanings given above for formula I, is prepared by reacting a compound of formula 1B with a suitable amount of amine or ammonia.
Forbindelser ifølge norsk patentskrift nr. 168.801 som kan representeres ved den generelle formel VIII: Compounds according to Norwegian patent document no. 168,801 which can be represented by the general formula VIII:
hvor R, RlfR2, R3, R5og R6har de samme betydninger som i formel I, fremstilles ved omsetning av et overskudd av det passende amin eller ammoniakk med en forbindelse med formel 1B. where R, R 1 R 2 , R 3 , R 5 and R 6 have the same meanings as in formula I, is prepared by reacting an excess of the appropriate amine or ammonia with a compound of formula 1B.
Forbindelser ifølge norsk patentskrift nr. 168.801 som kan representeres ved den generelle formel IX: Compounds according to Norwegian patent document no. 168,801 which can be represented by the general formula IX:
hvor R, RlrR2, og R3har de samme betydninger som i formel I, kan fremstilles ved omsetning av en forbindelse med den ovenstående formel VII, hvor R5og R6begge er hydrogen, med et overskudd av et dehydratiseringsmiddel, såsom fosforoxyklorid, ved tilbakeløpsbetingelser. where R, R1rR2, and R3 have the same meanings as in formula I, can be prepared by reacting a compound of the above formula VII, where R5 and R6 are both hydrogen, with an excess of a dehydrating agent, such as phosphorus oxychloride, under reflux conditions.
Thioesterforbindelser ifølge norsk patentskrift nr. 168.801, svarende til den generelle formel XV: Thioester compounds according to Norwegian patent document no. 168,801, corresponding to the general formula XV:
fremstilles ved omsetning av en passende thiol med en forbindelse med den generelle formel 1A ovenfor, på samme måte som ved fremstilling av en vanlig ester. is prepared by reacting an appropriate thiol with a compound of the general formula 1A above, in the same manner as in the preparation of a common ester.
På tilsvarende måte kan dithioestere representert ved den generelle formel XVI: Similarly, dithioesters can be represented by the general formula XVI:
fremstilles ved omsetning av en forbindelse med den generelle formel 1B ovenfor med en passende thiol. Vanligvis foretas fremstillingen av de forskjellige thioestergrupper på samme måte som den ovenfor beskrevne fremstilling av esterne. is prepared by reacting a compound of general formula 1B above with an appropriate thiol. Usually, the preparation of the various thioester groups is carried out in the same way as the preparation of the esters described above.
Imidatforbindelser ifølge norsk patentskrift nr. 168.801, som er representert ved den generelle formel XVII: Imidate compounds according to Norwegian patent document no. 168,801, which are represented by the general formula XVII:
fremstilles fra det tilsvarende amid med den generelle formel VIII ved omsetning av amidet med thionylklorid for dannelse av et klorimid og påfølgende omsetning av klorimidet med en alkohol. is prepared from the corresponding amide of the general formula VIII by reaction of the amide with thionyl chloride to form a chlorimide and subsequent reaction of the chlorimide with an alcohol.
Ytterligere opplysninger om fremstillingen av sluttforbindelsene med den generelle formel I fra forbindelsene med den generelle formel 1 ifølge oppfinnelsen vil finnes i norsk patentskrift nr. 168.801. Further information on the preparation of the final compounds with the general formula I from the compounds with the general formula 1 according to the invention can be found in Norwegian Patent Document No. 168,801.
De nedenstående eksempler illustrerer fremstillingen av de nye 2, 6-substituert-3, 5-pyridindicarboxylsyrederivater med den generelle formel 1 som er anvendelige som mellomprodukter ved fremstilling av sluttforbindelsene ifølge norsk patentskrift nr. 168.801. The following examples illustrate the preparation of the new 2,6-substituted-3,5-pyridinedicarboxylic acid derivatives with the general formula 1 which are usable as intermediate products in the preparation of the final compounds according to Norwegian patent document no. 168,801.
Eksempel 1 Example 1
Fremstilling av ethyl- 5- klorcarbonyl- 6-( difluormethyl)- 4-isopropyl- 2-( trif luormethyl )- pyridin- 3- carboxylat. Preparation of ethyl-5-chlorocarbonyl-6-(difluoromethyl)-4-isopropyl-2-(trifluoromethyl)-pyridine-3-carboxylate.
En blanding av 3,72 g (0,105 mol) 2-(difluormethyl)-4-isopropyl-6-( trif luormethyl )-3, 5-pyridindicarboxylsyre-5-ethyl-ester fremstilt ifølge eksempel 31 i norsk patentskrift nr. 168.801 og 50 ml thionylklorid kokes med tilbakeløpskjø-ling i 18 timer og inndampes i vakuum, hvorved det fås 3,8 g (97%) av det ønskede produkt i form av en olje, med nD<25>1,4570. A mixture of 3.72 g (0.105 mol) 2-(difluoromethyl)-4-isopropyl-6-(trifluoromethyl)-3,5-pyridinedicarboxylic acid-5-ethyl ester prepared according to example 31 in Norwegian patent document no. 168,801 and 50 ml of thionyl chloride are boiled with reflux for 18 hours and evaporated in vacuo, whereby 3.8 g (97%) of the desired product is obtained in the form of an oil, with nD<25>1.4570.
Analyse: Beregnet for C14H13C11F5N03: Analysis: Calculated for C14H13C11F5N03:
På tilsvarende måte som beskrevet i eksempel 1 fremstilles andre, i den nedenstående tabell oppførte monosyre-klorider og disyreklorider ifølge oppfinnelsen fra de angitte utgangsmaterialer. In a similar manner to that described in example 1, other monoacid chlorides and diacid chlorides listed in the table below are prepared according to the invention from the indicated starting materials.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO910057A NO172641C (en) | 1983-08-11 | 1991-01-07 | 2,6-SUBSTITUTED-3,5-PYRIDE INDICARBOXYL ACID DERIVATIVES USED AS INTERMEDIATE PRODUCTS BY THE PREPARATION OF OTHER 2,6-SUBSTITUTED-3,5-PYRIDINE DICARBOXYL ACID DERIVATIVES WITH HERBICIDE EFFECT |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US52243083A | 1983-08-11 | 1983-08-11 | |
| US06/602,021 US4692184A (en) | 1984-04-24 | 1984-04-24 | 2,6-substituted pyridine compounds |
| NO843205A NO168801C (en) | 1983-08-11 | 1984-08-10 | NEW 2,6-SUBSTITUTED-3,5-PYRIDINE INDICARBOXYLIC ACID DERIVATIVES, HERBICIDE PREPARATIONS CONTAINING SAME AS ACTIVE COMPOUNDS, AND USE OF THE DERIVATIVES FOR ANTI-CONGRESSION |
| NO910057A NO172641C (en) | 1983-08-11 | 1991-01-07 | 2,6-SUBSTITUTED-3,5-PYRIDE INDICARBOXYL ACID DERIVATIVES USED AS INTERMEDIATE PRODUCTS BY THE PREPARATION OF OTHER 2,6-SUBSTITUTED-3,5-PYRIDINE DICARBOXYL ACID DERIVATIVES WITH HERBICIDE EFFECT |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| NO910057L NO910057L (en) | 1985-02-12 |
| NO910057D0 NO910057D0 (en) | 1991-01-07 |
| NO172641B true NO172641B (en) | 1993-05-10 |
| NO172641C NO172641C (en) | 1993-08-18 |
Family
ID=27484098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO910057A NO172641C (en) | 1983-08-11 | 1991-01-07 | 2,6-SUBSTITUTED-3,5-PYRIDE INDICARBOXYL ACID DERIVATIVES USED AS INTERMEDIATE PRODUCTS BY THE PREPARATION OF OTHER 2,6-SUBSTITUTED-3,5-PYRIDINE DICARBOXYL ACID DERIVATIVES WITH HERBICIDE EFFECT |
Country Status (1)
| Country | Link |
|---|---|
| NO (1) | NO172641C (en) |
-
1991
- 1991-01-07 NO NO910057A patent/NO172641C/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO172641C (en) | 1993-08-18 |
| NO910057L (en) | 1985-02-12 |
| NO910057D0 (en) | 1991-01-07 |
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