NO174960B - Fremgangsmåte ved fremstilling av 2-hydroksy-3-halogen-5-nitropyridiner - Google Patents
Fremgangsmåte ved fremstilling av 2-hydroksy-3-halogen-5-nitropyridiner Download PDFInfo
- Publication number
- NO174960B NO174960B NO912792A NO912792A NO174960B NO 174960 B NO174960 B NO 174960B NO 912792 A NO912792 A NO 912792A NO 912792 A NO912792 A NO 912792A NO 174960 B NO174960 B NO 174960B
- Authority
- NO
- Norway
- Prior art keywords
- hydroxy
- nitropyridines
- acid
- preparation
- halo
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 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
- 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
- 239000000460 chlorine Substances 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 238000006396 nitration reaction Methods 0.000 claims 1
- 238000005121 nitriding Methods 0.000 claims 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- QVPFLVIBWRFJDL-UHFFFAOYSA-N 3-chloro-5-nitropyridin-2-amine Chemical compound NC1=NC=C([N+]([O-])=O)C=C1Cl QVPFLVIBWRFJDL-UHFFFAOYSA-N 0.000 description 2
- OLTRUTPHSBQWAZ-UHFFFAOYSA-N 5-chloro-6-oxo-1h-pyridine-3-carboxylic acid Chemical compound OC(=O)C1=CNC(=O)C(Cl)=C1 OLTRUTPHSBQWAZ-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLPDVAVQKGDHNO-UHFFFAOYSA-N 2,3-dichloro-5-nitropyridine Chemical compound [O-][N+](=O)C1=CN=C(Cl)C(Cl)=C1 XLPDVAVQKGDHNO-UHFFFAOYSA-N 0.000 description 1
- GTOXJMNILNYXLE-UHFFFAOYSA-N 3-chloro-5-nitro-1h-pyridin-2-one Chemical compound OC1=NC=C([N+]([O-])=O)C=C1Cl GTOXJMNILNYXLE-UHFFFAOYSA-N 0.000 description 1
- UGSBCCAHDVCHGI-UHFFFAOYSA-N 5-nitropyridin-2-amine Chemical compound NC1=CC=C([N+]([O-])=O)C=N1 UGSBCCAHDVCHGI-UHFFFAOYSA-N 0.000 description 1
- BLHCMGRVFXRYRN-UHFFFAOYSA-N 6-hydroxynicotinic acid Chemical compound OC(=O)C1=CC=C(O)N=C1 BLHCMGRVFXRYRN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Description
Oppfinnelsen vedrører en ny fremgangsmåte ved fremstilling av 2-hydroksy-3-halogen-5-nitropyridiner.
Disse forbindelser er takket være de reaksjonsvillige funksjonelle grupper generelt anvendbare for virkestoffsynteser for farmasøytika eller herbicider. Eksempelvis kan det ifølge CA 70: 106327X (T. Batkowski, Rocz. Chem. 42 (2) 1968, S.2079-2088) ved klorering fremstilte 2,3-diklor-5-nitropyridin ifølge DE-OS 35 45 570 anvendes til syntese av herbicider.
Ifølge CA 70: 106327X (T. Batkowski, Rocz. Chem. 42 (12) 1968, S.2079-2088, var det kjent å fremstille 2-hydroksy-3-klor-5-nitropyridin med utgangspunkt i 2-amino-5-nitropyridin ved klorering til 2-amino-3-klor-5-nitropyridin (utbytte 28%) , og ved påfølgende diazotering/forsåpning av aminogruppen (utbytte 72%) .
De utilfredsstillende utbytter samt det vanskelig tilgjengelige mellomprodukt 2-amino-3-klor-5-nitropyridin ga foranledning til å utvikle en ny fremgangsmåte for fremstilling av 2-hydroksy-3-halogen-5-nitropyridinene.
Denne oppgave kunne løses med en fremgangsmåte ifølge krav 1.
Ifølge oppfinnelsen blir derved en 5-halogen-6-hydroksynikotinsyre med den generelle formel
hvori Hal betyr klor, brom eller jod, i nærvær av salpetersyre og svovelsyre, nitrert til 2-hydroksy-3-halogen-5-nitropyridinene med den generelle formel
hvori Hal har den nevnte betydning.
5-Halogen-6-hydroksynikotinsyre, fortrinnsvis 5-klor-6-hydroksynikotinsyre, kan på enkel måte fremstilles av den i stor skala tilgjengelige 6-hydroksynikotinsyre ved omsetning med et syrehalogenid og påfølgende hydrolyse av det oppståtte 5-halogen-6-hydroksynikotinsyrehalogenid ifølge CH-PS 664 754.
Omsetningen ifølge oppfinnelsen foregår hensiktsmessig ved temperaturer mellom 0 og 100<*>C, fortrinnsvis mellom 40 og 55°C.
Hensiktsmessig kommer blandinger av konsentrert salpetersyre og konsentrert svovelsye i forholdet 4 til 1, fortrinnsvis i forholdet 1 til 1, til anvendelse. Blandinger med mindre svovelsyre kan imidlertid likeså anvendes.
Etter en reaksjonstid på ca. 1 til 3 timer kan reaksjonsblandingen på vanlig måte, fortrinnsvis ved opptak i isvann, opparbeides ved filtrering av den oppståtte oppslemming og tørking av filterkaken.
De resulterende 2-hydroksy-3-halogen-5-nitropyridiner kan på denne måte oppnås i høy renhet og med godt utbytte.
Eksempel
200 ml salpetersyre (70%) ble utmålt og avkjølt til 5°C. 2 00 ml konsentrert svovelsyre ble langsomt tilsatt under omrøring ved 5-10°C. Deretter ble langsomt tilført 100 g (0,576 mol) 5-klor-6-hydroksynikotinsyre ved 5°C. Blandingen ble oppvarmet til 50'C.
Etter at den eksoterme reaksjonen hadde dødd ut, lot man reaksjonsblandingen stå i 2 timer ved 50°C og avkjølte deretter til romtemperatur. Bindingen ble helt over i 1,5 liter isvann, og den oppnådde oppslemming ble avkjølt til -10°C. Man suget av, vasket filterresten pH-nøytral med vann og tørket i vakuum over natten. Det ble oppnådd 74,4 g av et blekgult pulver. Utbytte 74%.
%-NMR: (DMSO d6, 3 00 MHZ) S i ppm 8,45 (d, 3 Hz, Ar-H)
8,72 (d, 3 Hz, Ar-H) 13,25 (bred, -OH) Elementæranalyse for C5H3N2O3CI (174,54)
Beregnet C 34,4% H 1,7% N 16,1%
Funnet C 34,7% H 1,6% N 16,5%
Claims (3)
1. Fremgangsmåte ved fremstilling av 2-hydroksy-3-halogen-5-nitropyridiner med den generelle formel
hvori Hal betyr klor, brom eller jod, karakterisert ved at en 5-halogen-6-hydroksynikotinsyre med den generelle formel
blir nitrert i nærvær av salpetersyre og svovelsyre.
2. Fremgangsmåte ifølge krav 1,
karakterisert ved at nitreringen gjennomføres ved temperaturer mellom 0 og 100°C.
3. Fremgangsmåte ifølge krav 1 eller 2, karakterisert ved at nitreringen gjennomføres med en blanding av konsentrert salpetersyre og konsenrert svovelsyre i et forhold på 4:1 til 1:1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH237390 | 1990-07-17 |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| NO912792D0 NO912792D0 (no) | 1991-07-16 |
| NO912792L NO912792L (no) | 1992-01-20 |
| NO174960B true NO174960B (no) | 1994-05-02 |
| NO174960C NO174960C (no) | 1994-08-10 |
Family
ID=4232257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO912792A NO174960C (no) | 1990-07-17 | 1991-07-16 | Fremgangsmåte ved fremstilling av 2-hydroksy-3-halogen-5-nitropyridiner |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5144038A (no) |
| EP (1) | EP0467308A3 (no) |
| JP (1) | JPH04234364A (no) |
| CA (1) | CA2046676A1 (no) |
| FI (1) | FI913414A (no) |
| NO (1) | NO174960C (no) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4343922A1 (de) * | 1993-12-22 | 1995-06-29 | Basf Ag | Pyridin-2,3-dicarbonsäureimide, Verfahren zu ihrer Herstellung und ihre Verwendung zur Bekämpfung unerwünschten Pflanzenwuchses |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3495969A (en) * | 1967-09-25 | 1970-02-17 | Mobil Oil Corp | Substituted nitropyridines as herbicides |
| US4004012A (en) * | 1975-10-14 | 1977-01-18 | Sterling Drug Inc. | 3-Cyano-5-(pyridinyl)-2(1H)-pyridinones |
| CH664754A5 (en) * | 1985-06-25 | 1988-03-31 | Lonza Ag | 5,6-di:chloro-nicotinic acid prodn. - by reacting 6-hydroxy-nicotinic acid with acid chloride, reacting prod. with chlorine, then with acid chloride and hydrolysing prod |
| CH663957A5 (de) * | 1985-06-25 | 1988-01-29 | Lonza Ag | Verfahren zur herstellung von 3,5-dichlor-2-pyridon. |
| DE3545570A1 (de) * | 1985-12-21 | 1987-06-25 | Hoechst Ag | Neue pyridin-derivate und deren n-oxide, verfahren zu ihrer herstellung und ihre verwendung als zwischenprodukte |
-
1991
- 1991-07-10 CA CA002046676A patent/CA2046676A1/en not_active Abandoned
- 1991-07-15 FI FI913414A patent/FI913414A/fi not_active Application Discontinuation
- 1991-07-16 JP JP3175324A patent/JPH04234364A/ja not_active Withdrawn
- 1991-07-16 NO NO912792A patent/NO174960C/no unknown
- 1991-07-16 EP EP19910111871 patent/EP0467308A3/de not_active Withdrawn
- 1991-07-17 US US07/731,334 patent/US5144038A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| FI913414A0 (fi) | 1991-07-15 |
| FI913414A (fi) | 1992-01-18 |
| NO912792D0 (no) | 1991-07-16 |
| NO174960C (no) | 1994-08-10 |
| US5144038A (en) | 1992-09-01 |
| JPH04234364A (ja) | 1992-08-24 |
| NO912792L (no) | 1992-01-20 |
| EP0467308A3 (en) | 1992-05-20 |
| EP0467308A2 (de) | 1992-01-22 |
| CA2046676A1 (en) | 1992-01-18 |
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