EP0000542B1 - Verfahren zur Herstellung von Trifluormethylphenolen - Google Patents
Verfahren zur Herstellung von Trifluormethylphenolen Download PDFInfo
- Publication number
- EP0000542B1 EP0000542B1 EP78100436A EP78100436A EP0000542B1 EP 0000542 B1 EP0000542 B1 EP 0000542B1 EP 78100436 A EP78100436 A EP 78100436A EP 78100436 A EP78100436 A EP 78100436A EP 0000542 B1 EP0000542 B1 EP 0000542B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- nitro
- employed
- formula
- alkali metal
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 36
- ZOQOPXVJANRGJZ-UHFFFAOYSA-N 2-(trifluoromethyl)phenol Chemical class OC1=CC=CC=C1C(F)(F)F ZOQOPXVJANRGJZ-UHFFFAOYSA-N 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 14
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 150000004714 phosphonium salts Chemical class 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- -1 Äthyl Chemical group 0.000 description 20
- 150000003254 radicals Chemical class 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- TZGFQIXRVUHDLE-UHFFFAOYSA-N 1-chloro-2-nitro-4-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=CC=C1Cl TZGFQIXRVUHDLE-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XZEDEVRSUANQEM-UHFFFAOYSA-N 2-nitro-4-(trifluoromethyl)phenol Chemical compound OC1=CC=C(C(F)(F)F)C=C1[N+]([O-])=O XZEDEVRSUANQEM-UHFFFAOYSA-N 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 5
- HQROXDLWVGFPDE-UHFFFAOYSA-N 1-chloro-4-nitro-2-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(C(F)(F)F)=C1 HQROXDLWVGFPDE-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- FZHCKUHPOZBPHB-UHFFFAOYSA-N 1,2-dichloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=CC(Cl)=C1Cl FZHCKUHPOZBPHB-UHFFFAOYSA-N 0.000 description 3
- DPOBIBPWXIPEHF-UHFFFAOYSA-N 1,2-dichloro-5-nitro-3-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=C(Cl)C(C(F)(F)F)=C1 DPOBIBPWXIPEHF-UHFFFAOYSA-N 0.000 description 3
- VLVNHMVSVDVAOA-UHFFFAOYSA-N 1,5-dichloro-2-nitro-4-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=C(Cl)C=C1Cl VLVNHMVSVDVAOA-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- PSRPKTROFCUEOD-UHFFFAOYSA-N 2-chloro-3-nitro-5-(trifluoromethyl)benzoic acid Chemical compound OC(=O)C1=CC(C(F)(F)F)=CC([N+]([O-])=O)=C1Cl PSRPKTROFCUEOD-UHFFFAOYSA-N 0.000 description 3
- HVGBLBWQDJLOQT-UHFFFAOYSA-N 2-chloro-4-nitro-6-(trifluoromethyl)phenol Chemical compound OC1=C(Cl)C=C([N+]([O-])=O)C=C1C(F)(F)F HVGBLBWQDJLOQT-UHFFFAOYSA-N 0.000 description 3
- IPYLMZRACSULIH-UHFFFAOYSA-N 2-chloro-5-nitro-3-(trifluoromethyl)benzoic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC(C(F)(F)F)=C1Cl IPYLMZRACSULIH-UHFFFAOYSA-N 0.000 description 3
- GAZOASPEAVAGAU-UHFFFAOYSA-N 2-chloro-6-nitro-4-(trifluoromethyl)phenol Chemical compound OC1=C(Cl)C=C(C(F)(F)F)C=C1[N+]([O-])=O GAZOASPEAVAGAU-UHFFFAOYSA-N 0.000 description 3
- BEFJANXIJAXYRJ-UHFFFAOYSA-N 2-hydroxy-5-nitro-3-(trifluoromethyl)benzoic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC(C(F)(F)F)=C1O BEFJANXIJAXYRJ-UHFFFAOYSA-N 0.000 description 3
- CQYPDXUWXKXLSD-UHFFFAOYSA-N 5-methoxy-2-nitro-4-(trifluoromethyl)phenol Chemical compound COC1=CC(O)=C([N+]([O-])=O)C=C1C(F)(F)F CQYPDXUWXKXLSD-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 150000005840 aryl radicals Chemical class 0.000 description 3
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- PESPBNYBZVIGRO-UHFFFAOYSA-N 1-bromo-2-nitro-4-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=CC=C1Br PESPBNYBZVIGRO-UHFFFAOYSA-N 0.000 description 2
- SXEQQBBOAMHOID-UHFFFAOYSA-N 1-bromo-4-nitro-2-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C(C(F)(F)F)=C1 SXEQQBBOAMHOID-UHFFFAOYSA-N 0.000 description 2
- IQINJIIPYDIFFF-UHFFFAOYSA-N 1-chloro-5-methoxy-2-nitro-4-(trifluoromethyl)benzene Chemical compound COC1=CC(Cl)=C([N+]([O-])=O)C=C1C(F)(F)F IQINJIIPYDIFFF-UHFFFAOYSA-N 0.000 description 2
- KGFADEJSZXEVMC-UHFFFAOYSA-N 1-methoxy-4-nitro-2-(trifluoromethyl)benzene Chemical compound COC1=CC=C([N+]([O-])=O)C=C1C(F)(F)F KGFADEJSZXEVMC-UHFFFAOYSA-N 0.000 description 2
- ZDGMUMYTECMUEP-UHFFFAOYSA-N 2-chloro-1-methoxy-5-nitro-3-(trifluoromethyl)benzene Chemical compound COC1=CC([N+]([O-])=O)=CC(C(F)(F)F)=C1Cl ZDGMUMYTECMUEP-UHFFFAOYSA-N 0.000 description 2
- IDLIMVJATJRKPZ-UHFFFAOYSA-N 4-chloro-2-nitro-6-(trifluoromethyl)phenol Chemical compound OC1=C([N+]([O-])=O)C=C(Cl)C=C1C(F)(F)F IDLIMVJATJRKPZ-UHFFFAOYSA-N 0.000 description 2
- GWGZFNRFNIXCGH-UHFFFAOYSA-N 4-nitro-2-(trifluoromethyl)benzenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1C(F)(F)F GWGZFNRFNIXCGH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000005362 aryl sulfone group Chemical group 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 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 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 2
- HVZWVEKIQMJYIK-UHFFFAOYSA-N nitryl chloride Chemical compound [O-][N+](Cl)=O HVZWVEKIQMJYIK-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- DGRVQOKCSKDWIH-UHFFFAOYSA-N 1-chloro-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1Cl DGRVQOKCSKDWIH-UHFFFAOYSA-N 0.000 description 1
- ZECBOHAXBNGMSP-UHFFFAOYSA-N 1-chloro-2-nitro-3-(trifluoromethyl)benzene Chemical class [O-][N+](=O)C1=C(Cl)C=CC=C1C(F)(F)F ZECBOHAXBNGMSP-UHFFFAOYSA-N 0.000 description 1
- RPMVCORTTKCGQU-UHFFFAOYSA-M 1-ethyl-1-methylpiperidin-1-ium;bromide Chemical compound [Br-].CC[N+]1(C)CCCCC1 RPMVCORTTKCGQU-UHFFFAOYSA-M 0.000 description 1
- NDZJSUCUYPZXPR-UHFFFAOYSA-N 1-nitro-2-(trifluoromethyl)benzene Chemical class [O-][N+](=O)C1=CC=CC=C1C(F)(F)F NDZJSUCUYPZXPR-UHFFFAOYSA-N 0.000 description 1
- CQHBGTPDLFACRC-UHFFFAOYSA-N 12-cyclohexyldodecyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CCCCCCCCCCCCC1CCCCC1 CQHBGTPDLFACRC-UHFFFAOYSA-N 0.000 description 1
- FYELSNVLZVIGTI-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1CC)CC(=O)N1CC2=C(CC1)NN=N2 FYELSNVLZVIGTI-UHFFFAOYSA-N 0.000 description 1
- RUASQOAEBVHEHE-UHFFFAOYSA-N 2-hydroxy-3-nitro-5-(trifluoromethyl)benzoic acid Chemical compound OC(=O)C1=CC(C(F)(F)F)=CC([N+]([O-])=O)=C1O RUASQOAEBVHEHE-UHFFFAOYSA-N 0.000 description 1
- IIVWHGMLFGNMOW-UHFFFAOYSA-N 2-methylpropane Chemical compound C[C](C)C IIVWHGMLFGNMOW-UHFFFAOYSA-N 0.000 description 1
- KLWSGZHZNIOCPO-UHFFFAOYSA-N 2-nitro-3-(trifluoromethyl)phenol Chemical class OC1=CC=CC(C(F)(F)F)=C1[N+]([O-])=O KLWSGZHZNIOCPO-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940027983 antiseptic and disinfectant quaternary ammonium compound Drugs 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960001716 benzalkonium Drugs 0.000 description 1
- WCHPXAFAEZGCMB-UHFFFAOYSA-M benzyl(tributyl)phosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CC1=CC=CC=C1 WCHPXAFAEZGCMB-UHFFFAOYSA-M 0.000 description 1
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 1
- FKPSBYZGRQJIMO-UHFFFAOYSA-M benzyl(triethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC1=CC=CC=C1 FKPSBYZGRQJIMO-UHFFFAOYSA-M 0.000 description 1
- WTEPWWCRWNCUNA-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 WTEPWWCRWNCUNA-UHFFFAOYSA-M 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 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
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JVQOASIPRRGMOS-UHFFFAOYSA-M dodecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCC[N+](C)(C)C JVQOASIPRRGMOS-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical class CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 150000004010 onium ions Chemical group 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- XMVJITFPVVRMHC-UHFFFAOYSA-N roxarsone Chemical compound OC1=CC=C([As](O)(O)=O)C=C1[N+]([O-])=O XMVJITFPVVRMHC-UHFFFAOYSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ICTMDIORIDZWQN-UHFFFAOYSA-M triethyl(phenyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)C1=CC=CC=C1 ICTMDIORIDZWQN-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
Definitions
- the invention relates to a process for the preparation of phenols having a trifluoromethyl group.
- trifluoromethylphenols are obtained by cleaving the corresponding methoxy compounds with pyridine hydrochloride at 210 ° C. (J. org. Chem. 27, 4660 (1962): in this process, the methoxy compounds are prepared from chloronitrobenzotrifluorides in a preceding process step.
- Halogens (X) can be fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
- Halogen atom (Y) may be, for example, fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.
- the alkoxy group (Y) preferably contains alkyl radicals having 1 to 4 carbon atoms, for example the methyl, ethyl, propyl, isopropyl, butyl or tert-butyl radical.
- Alkonols with a lower unbranched or branched alkyl radical can be used as solvents for the process according to the invention.
- Alcohols whose unbranched or branched alkyl radical has 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, the various isomeric butanols, glycol and glycol monomethyl ether, are preferred.
- the amount of solvent can vary within wide limits, for example 1 to 20 parts by weight, preferably 2 to 8 parts by weight, of solvent can be used per 1 part by weight of a compound of the formula (I).
- Sodium or potassium hydroxide are preferably used as alkali metal hydroxides for the process according to the invention. They are generally used in the form of their aqueous solutions which contain, for example, 30-50% by weight of alkali metal hydroxide. However, the sodium or potassium hydroxide can also be added in solid form to the aqueous alcoholic solution.
- the alkali metal hydroxides are generally used in excess, the use of about three times the molar amount based on the conversion of the halogen atom to the phenolic hydroxyl group is particularly advantageous.
- the water content of the reaction solution can vary within wide limits. In general, it can be about 20 to 25% by weight.
- the radicals R 4 to R 7 can be low-molecular or high-molecular organic radicals.
- Optionally substituted alkyl radicals, cycloalkyl radicals, aralkyl radicals or aryl radicals may be mentioned as low molecular weight organic radicals.
- Two of the radicals R 4 to R 7 can also form a heterocycle together with the central atom Z and optionally further heteroatoms.
- the optionally substituted or branched alkyl radicals can especially those with 1-18 Carbon atoms, preferably having 1-12 carbon atoms, such as the methyl, ethyl, isomeric propyl, butyl, octyl, decyl or dodecyl radicals.
- the cycloalkyl radicals can be cyclopentyl and in particular cyclohexyl radicals which are optionally substituted by C 1 -C 4 -alkyl radicals.
- the aralkyl radicals can optionally be benzyl radicals substituted by C i -c 4- alkyl radicals, methoxy groups or halogen atoms.
- the aryl radicals can be phenyl radicals which are optionally substituted by C 1 -C 4 -alkyl radicals, methoxy groups, ethoxy groups or halogen atoms.
- the 5- and 6-membered heterocycles may be mentioned, for example the pyrrolidine ring, the piperidine ring or the morpholine ring.
- polystyrene which may be crosslinked by divinylbenzene.
- the total number of carbon atoms of all radicals R 4 to R 7 is at least six for the process according to the invention.
- the maximum number of all carbon atoms in a polymeric organic radical can be very large.
- the preferred total number of carbon atoms of all low-molecular radicals R 4 to R 7 is 8 to 25.
- Preferred anions A are the chloride, bromide and hydroxide anion.
- Examples of the preferred quaternary ammonium or phosphonium salts are: tetraethylammonium chloride, tetrabutylammonium bromide, triethylbenzylammonium hydroxide, benzyldimethyldodecylammonium chloride, dibutylpiperidiniumbromide, methyltrioctylammoniumchloride, dimethylbenzylpidylphenyl-methyldylylphenyl-methylphenyl-methyl-phenyl methyl-piperdinium hydroxide, triethyl-phenyl-ammonium chloride, dodecyl-trimethyl-ammonium hydroxide, cyclohexyldodecyl-dimethyl-ammonium chloride, methyl-ethyl-piperidinium bromide, triphenyl-benzyl-phosphonium bromide, tetrabutyl-phosphonium chloride,
- Quaternary ammonium compounds in which one of the radicals R 4 to R 7 is a polymeric radical can be, for example, ion exchangers based on styrene and generally 2 mol% of divinylbenzene as crosslinking agents which carry quaternary ammonium groups.
- the amounts of the quaternary onium salt used can vary from 1 to 20% by weight and are generally about 5 to 10% by weight, based on the starting compound.
- phase transition catalysts in multiphase systems and can be prepared by known processes (Houben-Weyl, 4th ed. Stuttgart 1958, volume XI, 2, p. 587 and volume XIV, 2nd p. 750).
- the process according to the invention can be carried out in the temperature range from about 0 to about 80 ° C., preferably from about 50 to 75 ° C.
- the alkyl radicals R 12 of these alkoxy compounds are determined by the alcohol used as solvent; when using methanol, a methoxy compound is obtained.
- alkoxy compounds are known (J. Org. Chem. 26, 2707 (1961)) and can be prepared, for example, by reacting an organically bonded halogen atom with sodium methylate or with methanolic potassium hydroxide.
- the process according to the invention has the advantage of being simple to carry out and of leading to the desired phenols in one step.
- the quaternary onium salts of the formula (IV) are known as phase transition catalysts in systems with two immiscible liquid phases (DT-OS 2 634 419).
- the method according to the invention is carried out with quaternary onium compounds in a system with only one liquid phase.
- the trifluoromethylphenols are intermediate products for the production of crop protection agents, in particular herbicides (DT-OS 2311 638, DT-OS 1 944 335).
- a trifluoromethylphenol of the formula VI can be reacted with p-nitrochlorobenzene in the presence of potassium m-methylate to give trifluoromethyl-nitrodiphenyl ether.
- Herbicides from new trifluoromethylphenols of the formula VII show improved activity compared to the known herbicides.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2733682 | 1977-07-26 | ||
| DE19772733682 DE2733682A1 (de) | 1977-07-26 | 1977-07-26 | Verfahren zur herstellung von trifluormethylphenolen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000542A1 EP0000542A1 (de) | 1979-02-07 |
| EP0000542B1 true EP0000542B1 (de) | 1981-07-15 |
Family
ID=6014871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100436A Expired EP0000542B1 (de) | 1977-07-26 | 1978-07-19 | Verfahren zur Herstellung von Trifluormethylphenolen |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4225731A (enrdf_load_stackoverflow) |
| EP (1) | EP0000542B1 (enrdf_load_stackoverflow) |
| JP (1) | JPS5424839A (enrdf_load_stackoverflow) |
| DE (2) | DE2733682A1 (enrdf_load_stackoverflow) |
| DK (1) | DK154949C (enrdf_load_stackoverflow) |
| IL (1) | IL55209A (enrdf_load_stackoverflow) |
| IT (1) | IT1105942B (enrdf_load_stackoverflow) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400552A (en) * | 1980-04-21 | 1983-08-23 | The Franklin Institute | Method for decomposition of halogenated organic compounds |
| US4460797A (en) * | 1981-03-05 | 1984-07-17 | The Franklin Institute | Method for decomposition of halogenated organic compounds |
| DE3120912A1 (de) * | 1981-05-26 | 1982-12-16 | Hoechst Ag, 6000 Frankfurt | Verfahren zur herstellung von p-nitrophenetol |
| FR2529197A1 (fr) * | 1982-06-29 | 1983-12-30 | Rhone Poulenc Agrochimie | Procede de preparation de phenates substitues par des groupes halogenes ou des phenols correspondants |
| US4602994A (en) * | 1982-09-30 | 1986-07-29 | The Franklin Institute | Removal of PCBs and other halogenated organic compounds from organic fluids |
| US4417977A (en) * | 1982-09-30 | 1983-11-29 | The Franklin Institute | Removal of PCBS and other halogenated organic compounds from organic fluids |
| HU190439B (en) * | 1983-02-03 | 1986-09-29 | Budapesti Vegyimuevek,Hu | Herbicidal, akaricidal and plant growth regulating compsitions comprising 2-/trifluoromethyl/-4,6-dinitrophenol or its salts as active substance and process for preparing the active substances |
| GB8708517D0 (en) * | 1987-04-09 | 1987-05-13 | Shell Int Research | Preparation of fluorophenols |
| DE3712817A1 (de) * | 1987-04-15 | 1988-10-27 | Bayer Ag | Verwendung von fluormethylphenolen als loesungsmittel fuer lc-polymere, und neue fluormethylphenole |
| EP0537592B1 (de) * | 1991-10-09 | 1996-01-17 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung von 2-Nitro-5-fluor- bzw. -5-chlor-phenol |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB718779A (en) * | 1952-01-05 | 1954-11-17 | Pechney Cie De Prod Chim Et El | Process for manufacturing pentachlorophenol and alkali pentachlorophenates |
| US2872461A (en) * | 1954-10-21 | 1959-02-03 | Schering Ag | Process of producing chloranil |
| US2950325A (en) * | 1958-06-06 | 1960-08-23 | Dow Chemical Co | Process for making fluorophenols |
| BE635553A (enrdf_load_stackoverflow) * | 1962-07-30 | |||
| FR1469596A (fr) * | 1966-01-06 | 1967-02-17 | Saint Gobain | Procédé de préparation du para-trifluorméthylphénol |
| US3813446A (en) * | 1968-06-24 | 1974-05-28 | Sherwin Williams Co | Production of trifluoromethylnitrophenols and related compounds |
| US3943180A (en) * | 1972-02-29 | 1976-03-09 | Bayer Aktiengesellschaft | 2,4-Bis-(trifluoromethyl)-6-nitrophenol compounds and herbicidal compositions |
-
1977
- 1977-07-26 DE DE19772733682 patent/DE2733682A1/de not_active Withdrawn
-
1978
- 1978-07-13 US US05/924,474 patent/US4225731A/en not_active Expired - Lifetime
- 1978-07-19 DE DE7878100436T patent/DE2860838D1/de not_active Expired
- 1978-07-19 EP EP78100436A patent/EP0000542B1/de not_active Expired
- 1978-07-24 IL IL55209A patent/IL55209A/xx unknown
- 1978-07-24 IT IT50434/78A patent/IT1105942B/it active
- 1978-07-25 DK DK330178A patent/DK154949C/da not_active IP Right Cessation
- 1978-07-25 JP JP9004378A patent/JPS5424839A/ja active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| IL55209A0 (en) | 1978-09-29 |
| JPS6256850B2 (enrdf_load_stackoverflow) | 1987-11-27 |
| DE2733682A1 (de) | 1979-02-08 |
| IT1105942B (it) | 1985-11-11 |
| IT7850434A0 (it) | 1978-07-24 |
| DE2860838D1 (en) | 1981-10-22 |
| DK330178A (da) | 1979-01-27 |
| US4225731A (en) | 1980-09-30 |
| IL55209A (en) | 1983-02-23 |
| JPS5424839A (en) | 1979-02-24 |
| DK154949C (da) | 1989-05-29 |
| EP0000542A1 (de) | 1979-02-07 |
| DK154949B (da) | 1989-01-09 |
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