EP3356336A1 - Verfahren zur herstellung von n-(1,3,4-oxadiazol-2-yl)arylcarboxamiden - Google Patents
Verfahren zur herstellung von n-(1,3,4-oxadiazol-2-yl)arylcarboxamidenInfo
- Publication number
- EP3356336A1 EP3356336A1 EP16777581.6A EP16777581A EP3356336A1 EP 3356336 A1 EP3356336 A1 EP 3356336A1 EP 16777581 A EP16777581 A EP 16777581A EP 3356336 A1 EP3356336 A1 EP 3356336A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- methyl
- formula
- alkyl
- iii
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 29
- -1 aryl carboxamides Chemical class 0.000 title claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000001424 substituent group Chemical group 0.000 claims abstract description 3
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 18
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 8
- 125000004509 1,3,4-oxadiazol-2-yl group Chemical group O1C(=NN=C1)* 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- APKZPKINPXTSNL-UHFFFAOYSA-N 1,3,4-oxadiazol-2-amine Chemical class NC1=NN=CO1 APKZPKINPXTSNL-UHFFFAOYSA-N 0.000 claims description 6
- NTSLROIKFLNUIJ-UHFFFAOYSA-N 5-Ethyl-2-methylpyridine Chemical compound CCC1=CC=C(C)N=C1 NTSLROIKFLNUIJ-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- 150000001559 benzoic acids Chemical class 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 claims description 4
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012359 Methanesulfonyl chloride Substances 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims description 2
- 125000006216 methylsulfinyl group Chemical group [H]C([H])([H])S(*)=O 0.000 claims description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims 2
- 229910019213 POCl3 Inorganic materials 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 125000001188 haloalkyl group Chemical group 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- DDSDJJJQHOSXTM-UHFFFAOYSA-N 2-methyl-n-(5-methyl-1,3,4-oxadiazol-2-yl)-3-methylsulfonyl-4-(trifluoromethyl)benzamide Chemical compound O1C(C)=NN=C1NC(=O)C1=CC=C(C(F)(F)F)C(S(C)(=O)=O)=C1C DDSDJJJQHOSXTM-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 2
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- NUHFJFXYAKTQLZ-UHFFFAOYSA-N 2-methyl-3-methylsulfonyl-4-(trifluoromethyl)benzoic acid Chemical compound CC1=C(C(O)=O)C=CC(C(F)(F)F)=C1S(C)(=O)=O NUHFJFXYAKTQLZ-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- NURQLCJSMXZBPC-UHFFFAOYSA-N 3,4-dimethylpyridine Chemical compound CC1=CC=NC=C1C NURQLCJSMXZBPC-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- XPXWYVCQCNFIIJ-UHFFFAOYSA-N 5-methyl-1,3,4-oxadiazol-2-amine Chemical compound CC1=NN=C(N)O1 XPXWYVCQCNFIIJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical group 0.000 description 2
- HSZDSMXLTKOBRO-UHFFFAOYSA-N (5-imino-2H-1,3,4-oxadiazol-2-yl)-phenylmethanone Chemical class C(C1=CC=CC=C1)(=O)C1N=NC(O1)=N HSZDSMXLTKOBRO-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PLVXZFMZGNGIPO-UHFFFAOYSA-N O=C(NC1=NN=CO1)C1=CC=CC=C1 Chemical class O=C(NC1=NN=CO1)C1=CC=CC=C1 PLVXZFMZGNGIPO-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical class ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-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
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- LFKYBJLFJOOKAE-UHFFFAOYSA-N imidazol-2-ylidenemethanone Chemical compound O=C=C1N=CC=N1 LFKYBJLFJOOKAE-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010667 large scale reaction Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 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
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
- C07D271/113—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the invention relates to a process for the preparation of herbicidally active N- (1, 3,4-oxadiazol-2-yl) arylcarboxamiden.
- WO 2012/126932 A1 discloses herbicidally active N- (1, 3,4-oxadiazol-2-yl) arylcarboxamides. There is also described a process for their preparation. In this process, substituted benzoic acids are substituted with 2-amino-1, 3,4-oxadiazoles which are substituted in the 5-position in the presence of activating
- Reagents such as carbonyl imidazole (CDI), dicyclohexylcarbodiimide or 2,4,6-
- such reagents are unsuitable for large scale reactions because they are very expensive and are not recyclable.
- 2216 is known that substituted benzoic acid chlorides react with 2-amino-1, 3,4-oxadiazole not only to the desired 2-Benzoylamino1, 3,4-oxadiazoles but also to the isomers.
- 3 Benzoyl-2-imino-1,3,4-oxadiazolines are known that substituted benzoic acid chlorides react with 2-amino-1, 3,4-oxadiazole not only to the desired 2-Benzoylamino1, 3,4-oxadiazoles but also to the isomers.
- the object of the present invention is to provide a method for
- An object of the present invention is thus a process for the preparation of N- (1, 3,4-oxadiazol-2-yl) aryl-carboxamides of the general formula (I) by reaction of 2-amino-1, 3,4-oxadiazoles of the general formula (II) with benzoic acids of the general formula (III),
- R 1 is hydrogen, C 3 -C 2 cycloalkyl, Ci-C 8 -alkyl, C 5 alkoxy,
- R 2 is hydrogen, C 1 -C 8 -alkyl or halogen
- R 3 is hydrogen, C 1 -C 8 -alkyl, C 1 -C 8 -alkyl sulfenyl, C 1 -C 8 -alkylsulfinyl or C 1 -C 8 -alkylsulfonyl,
- R 4 is C 1 -C 5 -alkyl or C 1 -C 3 -haloalkyl
- R 5 is Ci-Ci 2 alkyl or phenyl.
- Alkyl radicals mean e.g. Methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl and 1, 3-dimethylbutyl.
- alkoxy and cycloalkyl radicals mean e.g. Methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl and 1, 3-dimethylbutyl.
- alkoxy and cycloalkyl radicals mean e.g. Methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls,
- Halogen is fluorine, chlorine is bromine or iodine, preferably fluorine or chlorine.
- the activator and the compounds of the formula (III) are usually employed in a molar ratio of from 0.5 to 3, preferably from 1 to 2, particularly preferably from 1.2 to 1.9.
- the activator used is preferably thionyl chloride, phosgene or diphosgene, particularly preferably thionyl chloride.
- the base of the formula (IV) and the compounds of the formula (III) are usually employed in a molar ratio of from 0.5 to 10, preferably from 1 to 3, particularly preferably from 1 to 2.5.
- the process according to the invention is generally carried out in a solvent.
- Suitable solvents are inert organic solvents, preferably aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene and decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, tetrachloromethane, dichloroethane and trichloroethane; Esters such as ethyl acetate and isopropyl acetate; Ethers such as diethyl ether, diisopropyl ether, methyl
- the inventive method in a temperature range of -5 ° to 50 ° C, preferably 0 ° to 25 ° C is performed.
- the process according to the invention is usually carried out in such a way that the compounds of the formulas (II), (III) and (IV) are initially charged in a solvent and the activator is slowly added dropwise with stirring or introduced in the case of phosgene.
- the progress of the reaction can be monitored by HPLC control. Full implementation is usually done after 10 to 20 hours. After complete reaction, the reaction mixture is cooled and the product usually precipitates almost quantitatively. Alternatively, the
- reaction mixture with a polar solvent such as water or alcohols such as isopropanol diluted.
- the reaction product of formula (I) is highly pure and can be further purified if necessary. Especially advantageous is to allow the reaction mixture at a temperature between 20 and 35 ° C within 3 to 6 hours with water.
- the product is obtained in a quickly filterable form.
- the base of the formula (IV) can be recovered by distillation to about 95%.
- R 1 is hydrogen, methyl, ethyl, n-propyl, i-propyl or phenyl,
- R 2 is methyl or chlorine
- R 3 is methylsulfenyl, methylsulfinyl or methylsulfonyl
- R 4 is trifluoromethyl
- R 5 is methyl or n-butyl.
- R 1 is methyl
- R 2 is methyl or chlorine
- R 3 is methylsulfonyl
- R 4 is trifluoromethyl
- R 5 is methyl
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- Agronomy & Crop Science (AREA)
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- Plant Pathology (AREA)
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- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP15187023 | 2015-09-28 | ||
| PCT/EP2016/072629 WO2017055175A1 (de) | 2015-09-28 | 2016-09-23 | Verfahren zur herstellung von n-(1,3,4-oxadiazol-2-yl)arylcarboxamiden |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3356336A1 true EP3356336A1 (de) | 2018-08-08 |
Family
ID=54207378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP16777581.6A Withdrawn EP3356336A1 (de) | 2015-09-28 | 2016-09-23 | Verfahren zur herstellung von n-(1,3,4-oxadiazol-2-yl)arylcarboxamiden |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US10189800B2 (enExample) |
| EP (1) | EP3356336A1 (enExample) |
| JP (1) | JP2018529703A (enExample) |
| KR (1) | KR20180059456A (enExample) |
| CN (1) | CN108137519A (enExample) |
| BR (1) | BR112018006202A2 (enExample) |
| IL (1) | IL258320B (enExample) |
| MX (1) | MX2018003963A (enExample) |
| TW (1) | TW201711566A (enExample) |
| WO (1) | WO2017055175A1 (enExample) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018202535A1 (de) * | 2017-05-04 | 2018-11-08 | Bayer Cropscience Aktiengesellschaft | Herbizid wirksame 4-difluormethylbenzoylamide |
| KR102868734B1 (ko) * | 2020-12-17 | 2025-10-02 | 주식회사 팜한농 | N-(1-메틸-1h-테트라졸-5-일)-2-(((2-메틸-2h-테트라졸-5-일)메톡시)메틸)-6-(트리플루오로메틸)니코틴아마이드의 제조 방법 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040077690A1 (en) * | 2000-09-29 | 2004-04-22 | Bing-Yan Zhu | Quaternary amidino based inhibitors of factor xa |
| US20080090834A1 (en) * | 2006-07-06 | 2008-04-17 | Pfizer Inc | Selective azole pde10a inhibitor compounds |
| JP2009091267A (ja) * | 2007-10-04 | 2009-04-30 | Kyorin Pharmaceut Co Ltd | アミド誘導体及びそれらを有効成分とするスフィンゴシン−１−リン酸−１（ｓ１ｐ１）受容体選択的アゴニスト |
| EP3556367A1 (en) * | 2009-07-06 | 2019-10-23 | Aerpio Therapeutics, Inc. | Benzosulfonamide derivatives, compositions thereof, and their use in the treatment of cancer or metastasis |
| JP5805767B2 (ja) * | 2010-09-01 | 2015-11-10 | バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＢａｙｅｒ Ｉｎｔｅｌｌｅｃｔｕａｌ Ｐｒｏｐｅｒｔｙ ＧｍｂＨ | Ｎ−（テトラゾール−５−イル）アリールカルボキサミド類及びｎ−（トリアゾール−５−イル）アリールカルボキサミド類並びに除草剤としてのそれらの使用 |
| BR112013023911B1 (pt) * | 2011-03-22 | 2018-07-10 | Bayer Intellectual Property Gmbh | Amidas de ácido n-(1,3,4-oxadiazol-2-il)- arilcarboxílico, seu uso, composições herbicidas, e processo para combate de plantas indesejadas |
| CN103443107B (zh) * | 2011-03-28 | 2016-04-20 | 弗·哈夫曼-拉罗切有限公司 | 噻唑并嘧啶化合物 |
| JP6001048B2 (ja) * | 2011-03-28 | 2016-10-05 | エフ．ホフマン−ラ ロシュ アーゲーＦ． Ｈｏｆｆｍａｎｎ−Ｌａ Ｒｏｃｈｅ Ａｋｔｉｅｎｇｅｓｅｌｌｓｃｈａｆｔ | チアゾロピリミジン化合物 |
| AU2012331283A1 (en) * | 2011-11-03 | 2014-05-22 | Bayer Intellectual Property Gmbh | Herbicidally active oxime-ether-substituted benzoylamides |
| CN102491971B (zh) * | 2011-12-19 | 2017-03-01 | 北京理工大学 | 手性[(4-甲基-2-丙基-1h-苯并咪唑-6-酰胺)-1-基]甲基联苯类化合物及其制备方法和用途 |
| EP2817296B1 (de) | 2012-02-21 | 2016-08-31 | Bayer Intellectual Property GmbH | Herbizid wirksame 3-(sulfin-/sulfonimidoyl)-benzamide |
| US9682967B2 (en) | 2013-01-28 | 2017-06-20 | H. Lundbeck A/S | N-substituted-5-substituted phthalamic acids as sortilin inhibitors |
| JP6398124B2 (ja) * | 2014-03-10 | 2018-10-03 | Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社 | ２−アシルイミノピリジン誘導体の製造法 |
-
2016
- 2016-09-10 TW TW105129443A patent/TW201711566A/zh unknown
- 2016-09-23 US US15/763,181 patent/US10189800B2/en not_active Expired - Fee Related
- 2016-09-23 JP JP2018515819A patent/JP2018529703A/ja active Pending
- 2016-09-23 MX MX2018003963A patent/MX2018003963A/es unknown
- 2016-09-23 EP EP16777581.6A patent/EP3356336A1/de not_active Withdrawn
- 2016-09-23 KR KR1020187009051A patent/KR20180059456A/ko not_active Withdrawn
- 2016-09-23 WO PCT/EP2016/072629 patent/WO2017055175A1/de not_active Ceased
- 2016-09-23 CN CN201680056686.3A patent/CN108137519A/zh active Pending
- 2016-09-23 BR BR112018006202A patent/BR112018006202A2/pt not_active Application Discontinuation
-
2018
- 2018-03-22 IL IL258320A patent/IL258320B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TW201711566A (zh) | 2017-04-01 |
| US20180273496A1 (en) | 2018-09-27 |
| BR112018006202A2 (pt) | 2018-10-09 |
| US10189800B2 (en) | 2019-01-29 |
| KR20180059456A (ko) | 2018-06-04 |
| IL258320B (en) | 2019-09-26 |
| CN108137519A (zh) | 2018-06-08 |
| WO2017055175A1 (de) | 2017-04-06 |
| IL258320A (en) | 2018-05-31 |
| MX2018003963A (es) | 2018-06-08 |
| JP2018529703A (ja) | 2018-10-11 |
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