SI7911704A8 - Postopek za pripravo 2-klor-6-nitroanilnov - Google Patents
Postopek za pripravo 2-klor-6-nitroanilnov Download PDFInfo
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- SI7911704A8 SI7911704A8 SI7911704A SI7911704A SI7911704A8 SI 7911704 A8 SI7911704 A8 SI 7911704A8 SI 7911704 A SI7911704 A SI 7911704A SI 7911704 A SI7911704 A SI 7911704A SI 7911704 A8 SI7911704 A8 SI 7911704A8
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- oil
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- nitroaniline
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- VOTXWUCYIOPNNR-UHFFFAOYSA-N 2-chloro-6-nitroaniline Chemical class NC1=C(Cl)C=CC=C1[N+]([O-])=O VOTXWUCYIOPNNR-UHFFFAOYSA-N 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims 3
- 239000012442 inert solvent Substances 0.000 claims 2
- 150000001447 alkali salts Chemical class 0.000 claims 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims 1
- DAWGFZGQZDLEHZ-UHFFFAOYSA-N n-chloro-n-(2-chlorophenyl)nitramide Chemical compound [O-][N+](=O)N(Cl)C1=CC=CC=C1Cl DAWGFZGQZDLEHZ-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- RDCOVUDTFKIURA-UHFFFAOYSA-N 2,3-dichloro-6-nitroaniline Chemical compound NC1=C(Cl)C(Cl)=CC=C1[N+]([O-])=O RDCOVUDTFKIURA-UHFFFAOYSA-N 0.000 description 5
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 4
- NBROUKOXRAMATE-UHFFFAOYSA-N 3,6-dichloro-2-nitroaniline Chemical compound NC1=C(Cl)C=CC(Cl)=C1[N+]([O-])=O NBROUKOXRAMATE-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BGKIECJVXXHLDP-UHFFFAOYSA-N 1,2,3-trichloro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1Cl BGKIECJVXXHLDP-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- OAEVOTPCDGIENV-UHFFFAOYSA-N 2-chloro-3-(3-chlorophenoxy)-6-nitroaniline Chemical compound C1=C([N+]([O-])=O)C(N)=C(Cl)C(OC=2C=C(Cl)C=CC=2)=C1 OAEVOTPCDGIENV-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- IGRZLJGCUVIYRX-UHFFFAOYSA-N C1=CC=C(C=C1)OC2=C(C(=C(C=C2)Cl)N)[N+](=O)[O-] Chemical compound C1=CC=C(C=C1)OC2=C(C(=C(C=C2)Cl)N)[N+](=O)[O-] IGRZLJGCUVIYRX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- RZWQDAUIUBVCDD-UHFFFAOYSA-M sodium;benzenethiolate Chemical compound [Na+].[S-]C1=CC=CC=C1 RZWQDAUIUBVCDD-UHFFFAOYSA-M 0.000 description 2
- HKCQMXITCQCIJT-UHFFFAOYSA-N 2,3-dichloro-n-(2-methylpropyl)-6-nitroaniline Chemical compound CC(C)CNC1=C(Cl)C(Cl)=CC=C1[N+]([O-])=O HKCQMXITCQCIJT-UHFFFAOYSA-N 0.000 description 1
- XPGRZLWURWFSLL-UHFFFAOYSA-N 2,3-dichloro-n-methyl-6-nitroaniline Chemical compound CNC1=C(Cl)C(Cl)=CC=C1[N+]([O-])=O XPGRZLWURWFSLL-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- IVVJVBLAFGJMHP-UHFFFAOYSA-N 2-[2-chloro-3-(4-chlorophenoxy)-6-nitroanilino]ethanol Chemical compound C1=C([N+]([O-])=O)C(NCCO)=C(Cl)C(OC=2C=CC(Cl)=CC=2)=C1 IVVJVBLAFGJMHP-UHFFFAOYSA-N 0.000 description 1
- WKPHVQXTBVFWPE-UHFFFAOYSA-N 2-chloro-6-nitro-3-phenylsulfanylaniline Chemical compound C1=C([N+]([O-])=O)C(N)=C(Cl)C(SC=2C=CC=CC=2)=C1 WKPHVQXTBVFWPE-UHFFFAOYSA-N 0.000 description 1
- YRCBHEHMTAIZNT-UHFFFAOYSA-N 2-chloro-n-(2-chloroethyl)-3-(4-chlorophenoxy)-6-nitroaniline Chemical compound ClC1=C(NCCCl)C([N+](=O)[O-])=CC=C1OC1=CC=C(Cl)C=C1 YRCBHEHMTAIZNT-UHFFFAOYSA-N 0.000 description 1
- ZOCMFEACITYISE-UHFFFAOYSA-N 2-chloro-n-ethyl-3-(4-fluorophenoxy)-6-nitroaniline Chemical compound C1=C([N+]([O-])=O)C(NCC)=C(Cl)C(OC=2C=CC(F)=CC=2)=C1 ZOCMFEACITYISE-UHFFFAOYSA-N 0.000 description 1
- QGXAZUSYFDHXCN-UHFFFAOYSA-N 2-chloro-n-methyl-6-nitro-3-phenylsulfanylaniline Chemical compound C1=C([N+]([O-])=O)C(NC)=C(Cl)C(SC=2C=CC=CC=2)=C1 QGXAZUSYFDHXCN-UHFFFAOYSA-N 0.000 description 1
- -1 3-chlorophenoxy Chemical group 0.000 description 1
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 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 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- DDBMQDADIHOWIC-UHFFFAOYSA-N aclonifen Chemical compound C1=C([N+]([O-])=O)C(N)=C(Cl)C(OC=2C=CC=CC=2)=C1 DDBMQDADIHOWIC-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004476 plant protection product Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- JWYMWHGENDPLFG-UHFFFAOYSA-M sodium;3-chlorophenolate Chemical compound [Na+].[O-]C1=CC=CC(Cl)=C1 JWYMWHGENDPLFG-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 244000045561 useful plants Species 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Izum se nanaša na pripravo novih 2-klor-6-nitroanilinov, ki vplivajo na rast rastlin.
Tehnični problem
Obstajala je potreba po tehnološko naprednem postopku za pripravo novih 2-klor-6-nitroanilinov, ki vplivajo na rast rastlin, v dobrih dobitkih in v zadovoljivi čistoči.
Stanje tehnike
Spojine, definirane s formulo (I) v nadaljevanju, so nove, zato postopek za njihovo pripravo še ni bil opisan.
Opis rešitve tehničnega problema z izvedbenimi primeri
V smislu izuma predlagamo postopek za pripravo novih
2-klor-6-nitroanilinov s splošno formulo
v kateri stojita
R za vodik, fluor, klor, brom, trifluormetil, metil ali metoksil in
X za kisik ali žveplo.
Ostanek R se lahko nahaja v legi 2, 3 ali 4.
Znano je, da imajo nekateri z nitro skupino substituirani difeniletri herbicidne lastnosti (prim. K.H. Buchel, Pflanzenschutz und Schadlingsbekampfung, Georg Thieme Verlag, Stuttgart 1977» str. 166).
Kot smo sedaj ugotovili, se z amino skupino substi tuirane spojine s formulo I odlikujejo po izvrstnem herbicidnem učinku proti številnim travnatim in drugim plevelom.
Poleg tega se da nove spojine uporabiti tudi selektivno v številnih kulturah koristnih rastlin.
Nove spojine pripravimo:
s presnovo fenolov ali tiofenolov s formulo
kjer imata R in X zgoraj navedeni pomen, v prisotnosti sredstva za vezanje kisline, ali - prednostno - v obliki ustreznega fenolata oz. triofenolata, zlasti natrijeve ali kalijeve soli, z 2,3-diklor-6-nitroanilinom s formulo
pri temperaturi med sobno temperaturo in okoli 120°C, prednostno med 50° in 100°C.
Kot reakcijski medij rabi topilo, inertno ob reakcijskih pogojih, zlasti acetonitril ali dimetilformamid, nadalje npr. metiletilketon, dimetilsulfoksid, N-metilpirolidon.
Izhodne snovi s formulama II in III pridobimo na običajen način. Za pripravo anilinov III, ki so deloma novi, lahko 2,3, 4-triklornitrobenzol presnovimo z 2 moloma NH^ v primernem topilu. Na splošno se da anilin II brez čiščenja uporabiti za nadaljnjo presnovo. Včasih pa je prikladno, da spojino III očistimo z destilacijo, prekristalizacijo ali kolonsko kromatografijo. Uporaba očiščenega anilina s formulo III vodi na splošno tudi od boljšega celokupnega dobitka in daje neposredno dovolj Čist končni proizvod.
Izhodne snovi se da dobiti po načinu 1).
Nove spojine s formulo I predstavljajo tudi dragocene intermediate za sredstva za zaščito rastlin in zdravila, ker se jih da na osnovi aminskih in nitro skupin na razne načine pretvarjati.
Za uporabo kot herbicide lahko spojine s formulo I na sam po sebi znan način predelamo z običajnimi pomožnimi in/ali nosilnimi snovmi v običajne pripravke, npr. v emulzijske koncentrate ali suspenzijske praške, pri katerih znaša vsebnost učinkovite snovi med okoli 10 in 95 mas. % ter jih naravnamo na koncentracijo učinkovite snovi, primerno za nanašanje z vodo. Vendar pa lahko pripravimo tudi pripravke, katere se uporablja nerazredčene, npr. praške ali granulate. Pri teh znaša vsebnost učinkovite snovi med 0,2 in 20 mas.. % prednostno med 0,5 in 5 mas. %.
Priprava izhodnih snovi s formulo III.
PRIMER
2,3-diklor-6-nitro-N-izobutilanilin
75,5 g 2,3,4-triklornitrobenzola in 48 g izobutilamina raztopimo v 200 ml toluola in 3 dni vzdržujemo pri sobni temperaturi. Nato dodamo nastavku dodatnih 5 g izobutilamina in 4 ure segrevamo na 60°C. Toluolno raztopino iztresemo z vodo, sušimo in uparimo. Dobimo 86 g (98 % teoret.) naslovne spojine kot rjavkasto olje.
B
-6 H
CH, <^5 CA
CHj
C^H? i-C^ n_^4^9 “”^3^7 (CH3)2CHCH. HcCo CHCHhoch2ch2
H
H
H c2h5 ch3
H
H
H n-C^
H
H
H (ch2)5 (ch2)4
-(ch2)2-n-(ch2)2CH3
-(ch2)2-o-(ch2)2H n“C6H13 n-C^H^
0CH2=CH-CH2-
| Tal.ali 20 | Topilo | Reakcijska tom | |
| D | peratuia | Cas | |
| 166°C | DMSO | 50° | 24 ur |
| 60°C | DMSO | 10° | 3 ure |
| 51°C | DMSO | ST | 4 ure |
| 1,564 | DMSO | s | 5 ur |
| 1,590 | DMF | ST | 5 ur |
| 1,627 | DMSO | ST | 3 ure |
| 1,615 | DMSO | ST | 26 ur |
| 1,613 | DMSO | ST | 2 dneva |
| 1,557 | brez | 00 o o | 9 ur |
| 1,605 | toluol | ST | 3 dni |
| 1,603 | toluol | 80° | 8 ur |
| 94-5°C | DMSO | ST | 16 ur |
| 73-4°C | dioksan | ST | 3 dni |
| 1,600 | toluol | ST | 2 dneva |
| 93-4°C | dioksan | 100° | 10 ur |
| 107-8°C | dioksan | 100° | 10 ur |
| 1,591 | i toluol | ST | 2 dneva |
| 1,593 | i toluoli 1 | ST | 2 dneva |
| 1,615 | toluol | ST | 3 dni |
| 1,636 | toluol | ST | 3 dni |
DMSO: dimetilsulfoksid ST: sobna temperatura
DMF: dimetilformamid
PRIMER 1
a) 2,5-diklor-6-nitroanilin
4-55 E 2,5»4- triki orni trobenz ola (2 mola) raztopimo v 2 1 dimetilsulfoksida in napolnimo v avtoklav z volumnom 5 1. Dodamo 200 ml tekočega amoniaka (8 molov). Potem, ko zapremo avtoklav, segrejemo nastavek ob mešanju ali stresanju na 50°C in 24 ur vzdržujemo pri tej temperaturi.
Po ohlajenju in zračenju avtoklava izlijemo dobljeno raztopino z izločenim NH^Cl na 8 1 vode. Izločeni proizvod odsesamo, izperemo z vodo in sušimo čez noč pri 50°C. Dobimo 400 g (96,5 % teoret.) rumenega, kristalnega proizvoda, ki se tali pri 161 do 164°C. Proizvod je dovolj čist za nadaljnje presnove. Vendar pa ga lahko očistimo tudi s prekristalizacijo, npr. iz metilizobutilketona; dobitek znaša 77 % teoret., tal. 166 do 167°C.
b) 2-klor-5-fenoksi-6-nitroanilin h 1) iz surovega 2,5-diklor-6-nitroanilina
Raztopino 105,5 g 2,5-diklor-6-nitroanilina (0,5 molov) in 65»8 g natrijevega fenolata (0,55 molov) v 1000 ml acetonitrila segrevamo 5 ur ob refluksu in zatem uparimo. Preostanek raztopimo v 750 ml kloroforma in raztopino dvakrat iztresemo s po 200 ml vode. Po sušenju kloroformne raztopine le-to uparimo. Preostanek, 150 g rjavega olja, vroče raztopimo
- 8 v_okoli 700 ml izopropanola in raztopino ohladimo ob mešanju. Naslovna spojina se obori in jo odsesamo. Dobimo 98 g rumenih kristalov (74 % teoret.) s tal. 85°C.
NMR-spekter potrjuje strukturo.
b 2) Iz očiščenega 2,5-diklor-6-nitroanilina; 15,5 g očiščenega 2,3-diklor-6-nitroanilina raztopimo v 75 ml dimetilsulfoksida, dodamo 7,8 g fenola in 11,5 g zmletega kalijevega karbonata in 8 ur mešamo pri 50°C. Zatem nakisamo nastavek z ledoctom, proizvod oborimo z ledeno vodo, odsesamo in sušimo. Dobimo 19,5 g končnega proizvoda (98 %-en dobitek z ozirom na uporabljeni 2,3-diklor-6-nitroanilin). Rumeni kristali, tal. 80 do 82°C.
PRIMER 2
2-klor-5-fenoksi-6-nitroanilin
Raztopino 911 g (4 molov) 2,3,4-triklornitrobenzola raztopimo v 4 1 dimetilsulfoksida ter v 10 1-skem avtoklavu dodamo 400 ml tekočega amoniaka. Avtoklav zapremo in 24 ur vzdržujemo na 50°C, pri čemer se vzpostavi pritisk 5,3 bar.
Po ohlajenju nastavka in zračenju tlačne posode odvzamemo nasta vek in v 15 1-ski posodi pomešamo s 400 g 40 %-ne (utež. %) natrijevega luga. Pri tem uhaja amoniak, katerega odtegnemo. Nato dodamo raztopini 416 g fenola (4,4 mole), segrejemo na
50°C in. dokapavamo 440 g 40 %-nega (utež. %) natrijevega luga in mešamo nastavek 7 ur pri 50 do 60°C. Za dopolnitev reakcije ponovno dodamo 41 g fenola in 44 g 4-0 %-nega (utež. %) natrijevega luga in vzdržujemo nadaljnje 3 ure pri 60°C. Nato pustimo nastavek ohladiti, ga nakisamo s 100 ml ledoeta, nakar oborimo proizvod z ledeno vodo ob zdrgnjenju. Rumenorjavi, trdni surovi proizvod odsesamo, izperemo z vodo in sušimo. Surovi proizvod (980 g, tal. 70 do 78°C) prekristaliziramo iz 2,5 1 izopropanola. Dobitek: 800 g (75,5 % teoret.) rumenorjava trdna snov. Tal. 81,5 do 83,5°C·
PRIMER 3
2-klor-3-feniltio-6-nitro-N-metilanilin
Raztopini 4-,4 g (0,02 molov) 2,3-diklor-6-nitroN-metilanilina, raztopljeni v 50 ml acetonitrila, dodamo
2,9 g natrijevega tiofenolata. Nastavek pol ure segrevamo ob refluksu, zatem uparimo in ostanek prevzamemo s kloroformom in vodo. Kloroformni sloj odločimo, sušimo in uparimo. Dobimo 6 g rjavega olja, ki kristalizira z izopropanolom.
| 4 g rumenih kristalov, tal. 79°C(67,5 % teoret.) | |||||
| Analiza: | C | H | N | Cl | S |
| Izrač.: | 52,7 % | 5,72 % | 9Λ7 % | 12,05 % | 10,9 % |
| Ugot.: | 52,75 % | 5,75 % | 9,55 % | 12,00 % | 10,82 % |
PRIMER 4
2-klor-3-(3-klorfenoksi)-6-nitro-trifluoracetanilid g 2-klor-3-(3-klorfenoksi)-6-nitroanilina delno raztopimo v 500 ml toluola. Ob mešanju dokapavamo 70 6 trifluor acetanhidrida v teku 15 minut. Nastavek mešamo preko noči.
Nato topilo oddestiliramo, preostanek raztopimo v 3θ0 ml etra in proizvod oborimo z dodatkom bencina ob drgnjenju, odsesamo in sušimo. Dobimo 101 g svetlo belo-rumenkasto obarvane, kristalne trdne snovi, tal. 99 do 101°C (85 % teoret.).
PRIMER 5
1,1-dimeti1-3-(2-kl·oΓ-5-fenoksi-6-nitΓofenil)-formamidin
7,9 g 2-klor-3-fenoksi-6-nitroanilina segrevamo z 10 ml dimetilformamida in 10 ml dimetilformamiddimetilacetala 8 ur na 100 do 110°C. Zatem nastavek uparimo v vakuumu pri 90°C. Dobimo rdečerjavo, žilavo maso, ki se strdi pri okoli 0°C. Analiza potrjuje navedeno formulo.
| Analiza: | 0 | H | N | Cl |
| Izrač.: | 56,54 % | 4,41 % | 13,14 % | 11,09 |
| Ugot.: | 56,54 % | 4,39 % | 13,17 % | 11,09 |
PRIMER 6
2-klor-3-(4-klorfenoksi)-6-nitro-N-2-kloretilanilin
4,5 g 2 klor-3-(4-klorfenoksi)-6-nitro-N-2-hidroksi etilanilina raztopimo v 40 ml toluola in dodamo 2,9 g PCl^, pri čemer pride do spontanega segretja in razvijanja plina.
Po 30 minutah iztresemo nastavek z vodo in raztopino Nabikarbonata ter uparimo. Dobimo 3»6 g rumenorjavega olja (76 % teoret.).
PRIMER 7
2-klor-3-feniltio-6-nitroanilin dO3,5 g 2,3-diklor-6-nitroanilina (0,5 molov) in 72,5 g natrijevega tiofenolata (0,55 molov) raztopimo v 800 ml acetonitrila in 5 ur segrevamo ob refluksu. Nastavek predelamo ustrezno primeru 1 bd). Dobimo d08 g okrasto obarvanega, kristalnega proizvoda (77 % teoret.), tal. 144 do d46°C.
PRIMER 8
2-klor-3-(3-klorfenoksi)-6-nitroanilin dO3,5 g 2,3-diklor-6-nitroanilina(0,5 molov) in
82,8 g natrijevega 3-klorfenolata segrevamo v 500 ml dimetilformamida d uro na dOO°C. Po uparenju raztopine prevzamemo ostanek v kloroformu, izperemo z vodo in uparimo sušeno kloroformno raztopino.
Oljnati preostanek v toplem raztopimo v okoli 700 ml izopropanola. Pri ohlajenju kristalizira naslovna spojina. Dobimo 90 g okrasto obarvane, kristalne snovi s tal. 101 do 102°C.
PRIMER 9
2-klor-3-(4-fluorfenoksi)-6-nitro-N-etilanilin
23,5 6 (0,1 ®ol) N-etil-2,3-diklor-6~nitroanilina raztopimo v 150 ml dimetilsulfoksida v 250 ml trogrli buči.
Po dodatku 12,3 6 (0,11 molov) 4-fluorfenola in 15,2 g (0,11 molov) kalijevega karbonata mešamo nastavek 5 ur pri 80°C. Proizvod s počasnim dodajanjem ledene vode oborimo iz ohlajene raztopine in po odsesanju prekristaliziramo iz izopropanola Dobimo 17 g okrasto obarvanega, kristalnega proizvoda, tal.
do 70°C (54,7 % teoret.).
| Analiza: | C | H | H | Gl | F | |
| Izrač.: | 50,99 % | 2,85 % | 9,92 % | 12,55 | % | 6,72 % |
| Ugot.: | 51,17 % | 3,01 % | 9,92 % | 12,35 | % | 6,54 %. |
| Ustrezno | zgornjim | primerom | dobimo | tudi | . naslednje |
spojine
| R | X | A | B l f | i— ' • |
| 4-C1 | 0 | H | I H | 108 |
| 4-CHj | 0 | H | I H | 97-98 |
| 4-0CH3 | '0 | H | H i | 113-115 |
| 3-CH3 | 0 | H | iH I | 112-114 |
| 4-C1 | S | H | jH | 136-138 |
| 4-F | 0 | H | i H | 111-113 |
| 2-C1 | 0 | H | 'H | 85-86 |
| 4-Br | 0 | H | H | 118 |
| 3-CF3 | 0 r | H | h < | 92-93 |
| 3-F | 0 | H | H l | 58-60 |
| 2-F | 0 | H | H | 104-105 |
| 4-C1 | 0 | cocf3 | H ! | 135-137 |
| 4-CHj | 0 | cocf3 | H i | 155 |
| H | 0 | CH3 | H ! i | 76 |
| 4-C1 | 0 | cb3 , | I H i I | 75-77 |
| 3-Cl | 0 | CH3 | H i | olje |
| 4—CHjO | 0 | ch3 | h : | 100-101 |
| 4-F | 0 | ch3 | H : | 103 |
| H | 0 | C2H5 | H | olje |
HF-vrečLnosti (a) (b)
| R | X | A | ------------------ RF-vrednosti | |||
| B | [°cj | |||||
| (a) | (b) | |||||
| 4-F | 0 | CA | H | 71-72 | ||
| 4-C1 | 0 | CA | H | 72-74 | • | |
| 4-CHj | 0 | CA | H | 51-52 | ||
| H | s | C2H5 | H | olje | 0,6 | 0 45 |
| 3-CH3 | 0 | CA | H | olje | 0,61 | . 0,445 |
| 3-C1 | 0 | CA | H | olje | 0,60 | 0,48 |
| 4-CH^C | 0 | C2H5 | H | 47-48 | 1 | |
| 4-Br | 0 | C2H5 | H | 57-59 | ||
| 2-C1 | 0 | CA | H | olje | 0,58 | 1 0,045 |
| 3-CF5 | 0 | CA | H | olje | 0,60 | 0,49 |
| H | 0 | n-C^Hy | H | olje | 0,615 | 0,47 |
| H | 0 | -ch(ch3)2 | H | olje | 0,61 | 0,45 |
| H | 0 | ch3 | ch3 | 69-72 | t | |
| 4-F | 0 | CH3 | ch3 | 43-44 | ||
| H | 0 | CA | CA | olje | ||
| 4-C1 | 0 | n-C^H? | H | olje | 0,63 | 0,525 |
| 4-C1 | 0 | -ch(ch3)2 | » | olje | 0,63 | 0,50 |
| H | 0 | n-C^Hg | H | olje | 0,625 | 0,50 |
| 4-F | 0 | n-C^H? | H | olje | 0,61 | 0,48 |
| 4-F | 0 | ch(ch3)2 | H | olje | 0,62 | 0,46 |
| 4-CH^ | 0 | n-C^H? | H | olje | 0,64 | 0,47 |
| H | 0 | n-C^H? | nC^ H | olje | ||
| 4-F | 0 | n-C4Hg | olje | 0,63 | 0,505 | |
| 4-C1 | 0 | n-C4Hg | H | olje | 0,64 | 0,55 |
| 4-CHj | 0 | n-C4Hg | H | olje | 0,64 | 0,495 |
| St. | R | X | A | B | Tal. [°c] | RF-vrednost | |
| (a) | (b) | ||||||
| 54 | 4-CH^O | 0 | η-Ο^Ηγ | H | olje | 0,59 | 0,29 |
| 55 | 4-ch3o | 0 | -CH(CHj)2 | H | olje | 0,57 | 0,28 |
| 56 | 4-ch3o | 0 | n-C4Hg | H | olje | 0,555 | 0,32 |
| 57 | 4-Br | 0 | η-Ο^Ηγ | H | olje | 0,59 | 0,52 |
| 58 | 4-Br | 0 | n-C^Hg | H | olje | 0,61 | 0,555 |
| 59 | 3-CF3 | 0 | n-C 3H7 | H | olje | 0,59 | 0,53 |
| 60 | H | 0 | ch2ch(ch5)2 | H | olje | 0,60 | 0,51 |
| 61 | H | 0 | -CHC^ | H | olje | 0,61 | 0,50 |
| ch3 | |||||||
| 62 | 4-F | 0 | ch2ch(ch3)2 | H | olje | 0,60 | 0,525 |
| 63 | 4-F | 0 | H | olje | 0,62 | 0,515 | |
| 64 | 4-CI | 0 | CH2CH(CHj)2 | H | olje | 0,63 | 0,56 |
| 65 | H | 0 | C^OH | H | olje | 0,445 | 0,01 |
| 66 | H | S | n“C3^7 | H | olje | 0,62 | 0,49 |
| 67 | H | S | -CH(CHj)2 | H | 56-57 | ||
| 68 | H | s | n—C^Hg | H | olje | 0,63 | 0,52 |
| 69 | H | s | ch2ch(ch3)2 | H | olje | 0,78 | 0,52 |
| 70 | H | 0 | -C2H4OH | H | olje | 0,44 | 0,01 |
| 71 | 4-CH^O | 0 | ch2ch(ch5)2 | H | olje | 0,58 | 0,35 |
| 72 | H | 0 | -(ch2)4- | 106-107 | |||
| 73 | H | 0 | -(CH-)e- | 98-99 | |||
| 74 | H | 0 | -(ch2)2-n-(ch2)2- CH, | 99-101 | |||
| 75 | H | 0 | 109-110 | ||||
| 76 | H | s | ch3 | H | 128-130 | ||
| 77 | 4-F | 0 | nC6H13 | H | olje | 0,63 | 0,57 |
| Št. | R | X | A | B | Tal. [°cl | RF-vrednost | |
| (a) | (h) .. | ||||||
| 78 | H | 0 | nC5Hll | H | olje | 0,62 | 0,54 |
| 79 | 4-C1 | 0 | -(CH2)5- | 105 | |||
| 80 | 4-F | 0 | nC5Hll | H | olje | 0,62 | 0,56 |
| 81 | » | 0 | /—\ -< H > \_/ | H | . olje | 0,61 | 0,52 |
| 82 | H | s | -CH2-CH=CH2 | H | olje | 0,72 | 0,48 |
Claims (2)
1. Postopek za pripravo 2-klor-6-nitroanilinov s formulo v kateri stojita
R za vodik, fluor, klor, brom, jod, trifluormetil, metil, metoksil in nitro,
X za kisik ali žveplo, označen s tem, da fenol ali tiofenol s formulo v danem primeru v obliki soli, zlasti alkalijske soli, ali v prisotnosti sredstva za vezanje kisline, presnovimo z diklornitroanilinom s formulo no2 (III)
18 pri temperaturi med sobno temperaturo in 120°C, v inertnem topilu.
2. Postopek po zahtevku 1, označen s tem, da kot inertno topilo uporabimo acetonitril ali dimetilformamid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782831262 DE2831262A1 (de) | 1978-07-15 | 1978-07-15 | 2-chlor-6-nitroaniline |
| YU1704/79A YU42191B (en) | 1978-07-15 | 1979-07-12 | Process for preparing 2-chloro-6-nitroanilines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SI7911704A8 true SI7911704A8 (sl) | 1994-12-31 |
Family
ID=25775036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SI7911704A SI7911704A8 (sl) | 1978-07-15 | 1979-07-12 | Postopek za pripravo 2-klor-6-nitroanilnov |
Country Status (2)
| Country | Link |
|---|---|
| HR (1) | HRP921323B1 (sl) |
| SI (1) | SI7911704A8 (sl) |
-
1979
- 1979-07-12 SI SI7911704A patent/SI7911704A8/sl unknown
-
1992
- 1992-11-23 HR HR921323A patent/HRP921323B1/xx not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| HRP921323B1 (en) | 1996-02-29 |
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