NO152785B - Mellomprodukter til bruk ved fremstilling av substituerte 2-(2-benzimidazoylyl)-pyridiner - Google Patents
Mellomprodukter til bruk ved fremstilling av substituerte 2-(2-benzimidazoylyl)-pyridiner Download PDFInfo
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- NO152785B NO152785B NO840112A NO840112A NO152785B NO 152785 B NO152785 B NO 152785B NO 840112 A NO840112 A NO 840112A NO 840112 A NO840112 A NO 840112A NO 152785 B NO152785 B NO 152785B
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- formic acid
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- 239000000543 intermediate Substances 0.000 title description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 37
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 18
- 235000019253 formic acid Nutrition 0.000 claims description 18
- -1 cyclic secondary alcohol Chemical class 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 150000002978 peroxides Chemical class 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 10
- 230000008707 rearrangement Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 8
- 150000002576 ketones Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 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
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 2
- NDVWOBYBJYUSMF-UHFFFAOYSA-N 2-methylcyclohexan-1-ol Chemical compound CC1CCCCC1O NDVWOBYBJYUSMF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- OXELMKYUIJQOJR-UHFFFAOYSA-N 2-benzylcyclohexan-1-ol Chemical compound OC1CCCCC1CC1=CC=CC=C1 OXELMKYUIJQOJR-UHFFFAOYSA-N 0.000 description 1
- UNGWJJDVLCVVGB-UHFFFAOYSA-N 2-propan-2-ylcyclopentan-1-ol Chemical compound CC(C)C1CCCC1O UNGWJJDVLCVVGB-UHFFFAOYSA-N 0.000 description 1
- GRSUKJPGLIHJRZ-UHFFFAOYSA-N 2-pyridin-2-ylcyclopentan-1-ol Chemical compound OC1CCCC1C1=CC=CC=N1 GRSUKJPGLIHJRZ-UHFFFAOYSA-N 0.000 description 1
- UBIZMIFHVVCVEJ-UHFFFAOYSA-N 6-hydroxyheptanoic acid Chemical compound CC(O)CCCCC(O)=O UBIZMIFHVVCVEJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- SFVWPXMPRCIVOK-UHFFFAOYSA-N cyclododecanol Chemical compound OC1CCCCCCCCCCC1 SFVWPXMPRCIVOK-UHFFFAOYSA-N 0.000 description 1
- QCRFMSUKWRQZEM-UHFFFAOYSA-N cycloheptanol Chemical compound OC1CCCCCC1 QCRFMSUKWRQZEM-UHFFFAOYSA-N 0.000 description 1
- FHADSMKORVFYOS-UHFFFAOYSA-N cyclooctanol Chemical compound OC1CCCCCCC1 FHADSMKORVFYOS-UHFFFAOYSA-N 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- BZKQJSLASWRDNE-UHFFFAOYSA-N ethyl 4-hydroxycyclohexane-1-carboxylate Chemical compound CCOC(=O)C1CCC(O)CC1 BZKQJSLASWRDNE-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002081 peroxide group Chemical group 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P1/00—Drugs for disorders of the alimentary tract or the digestive system
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P1/00—Drugs for disorders of the alimentary tract or the digestive system
- A61P1/04—Drugs for disorders of the alimentary tract or the digestive system for ulcers, gastritis or reflux esophagitis, e.g. antacids, inhibitors of acid secretion, mucosal protectants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P1/00—Drugs for disorders of the alimentary tract or the digestive system
- A61P1/14—Prodigestives, e.g. acids, enzymes, appetite stimulants, antidyspeptics, tonics, antiflatulents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Pharmacology & Pharmacy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Veterinary Medicine (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Nutrition Science (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
Fremgangsmåte for fremstilling av hydroksykarboksylsyrer og estere av disse.
-Nærværende oppfinnelse angår en fremgangsmåte for fremstilling
av hydroksykarboksylsyrer og estere av disse ved syrekatalysert omleiring av et oksydat av en cyklisk sekundær alkohol med formelen
-hvor n betyr et' helt tall fra 4 til 11 og R betegner hydrogen, en alkylgruppe, en arylgruppe, en aralkylgruppe, en heteroaromatisk gruppe, en
karboksylgiuppe, en fluorgruppe eller en klor-gruppe,
hvilket oksydat er opplost i den cykliske sekundære alkohol.
Hydroksykarboksylsyrer og deres estere er av stdrste betydning som kjemiske mellomprodukter. F. ek?,-, er estere av hydroksykapronsyre verdifulle prekursorer for fremsti 11 ingen - av kaprolaktam som er et verdifullt utgangsmateriale for "nylon-6" og kaprolakton. Ved ytterligere oksydasjon kan også adipinsyre fremstilles fra disse estere.
Tidligere metoder for fremstillingen av hydroksykarboksylsyrer og- deres estere, særlig uj-hydroksykapronsyre og uu-hydroksyval e-riansyre, anvendte mineralsyrer som omleiringssyrer .• Anvendel-sen av disse materialer har imidlertid ulemper som har forsinket utviklingen av en fordelaktig kommersiell fremgangsmåte. F. eks',
må mineralsyrene, slik som flussyre, for å være effektive inn-fores ved omleiringen i en i det vesentlige vannfri form. Da flussyren må fores tilbake ved en kommersiell prosess og da ytterligere vann dannes under omleiringen., er det nodvendig å
skille dette vann fra hydrogenfluoridet. Dette er særlig vanskelig på grunn av at flussyren danner en azeotrop med vann som er ytterst vanskelig å skille fra..
I overensstemmelse med nærværende oppfinnelse er det blitt funnet at. "cykloalkanoloksydater" kan omleires til hydroksykarboksylsyrer og estere av disse ved å anvende maur.syre som om-leiringsmiddel. Det for fremgangsmåten ifolge oppfinnelsen karakteristiske består således i at opplosningen av oksydatet ved en temperatur mellom 0 og 200°C, bringes i kontakt med minst 0,2 mol maursyre pr. mol totalt tilstedeværende peroksyd-og hydroksyl grupper i oksydatet.
Cykloalkanolene, hvis oksydater behandles her, kan defineres med den foran angitte generelle formel. Når R i foranstående formel betegner en alky]gruppe har denne fra 1 til 16 karbonatomer, fortrinnsvis fra 1 til 6, som arylgruppe fra 6 til 14 karbonatorner, og som aralkylgruppe" fra 7 til 16 karbonatomer.
Eksempler på forbindelser som omfattes av formelen er cyklo-
pentanol, cykloheksanol, cykloheptanol, cyklooktanol, cyklo-
decanol og cyklododécanol. Substituerte alkylforbindelser om-
fatter 2-metylcykloheksanol, 2,3-dimetylcyklooktanol, 2,2-dimetyl-4-etylcyklododecanol og 2-isopropylcyklopentanol. Andre forbindelser omfatter 2-benzylcykloheksanol, 2-(3-metyl-bénzyl)-cykloheksanol, 2-(2-pyridyl)-cyklopentanol, 3-karbometoksycyklo-heptanol, 4-karbetoksycykloheksanol og 2,3,4,5-tetrafluorcyklo-heksanol.
Hydroksykarboksylsyrene og deres estere er vanligvis av cu-typen, dvs. de har hydroksylradikalet på karbonatomene ved enden av kjeden motsatt karboksylgruppen. Imidlertid i det tilfelle hvor et karbonatom hos et karbonholdig radikal er bundet til orto-stillingen i forhold til peroksydgruppen, dannes syrer i tillegg til cu-typen. Mere spesielt kan det angis at (n+1)-hydroksykar-boksylsyreesterene dannes, hvor (n+l) angir antallet av karbon-
atomer i ringen av cykloalkanolprekursoren, og n er som tidligere definert. Som et eksempel på produkter som dannes, kan angis oksydasjonen og omleiringen av 2-metylcykloheksanol. Hovedpro-
duktet som oppnås fra omleiringen av oksydatet vil være 6-hyd-roksyneptansyre.
"Cykloalkanoloksydatet" oppnås ved reaksjon av molekulart oksy-
gen med cykloalkanolen. Det er foretrukket å oksydere fra 10
til 30 % av cykloalkanolen. Oksydasjonen kan initieres med et peroksyd og fullfores ved å lede molekulart oksygen, rent eller fortynnet, med en inert gass, slik som nitrogen, gjennom cyklo-heksanolen med god omroring ved temperaturer på mellom 60 -
140°C. Trykkene kan være fra atmosfæretrykk til 70 kg/cm^
absolutt eller hdyere. "Oksydatet" består av en opplosning i cykloalkanolen av peroksyd sammen med mindre mengder s.yre, es-
tere og ketoner. Vanligvis inneholder oksydatet fra 0,04 til 0,30 mol peroksydisk oksygen pr. 100 g oksydat.
Ytterligere konsentrasjon av "oksydatet" ved destillasjon, fortrinnsvis under vakuum, kan oppnås for å få peroksydkonsentra-
sjoner på opp til ca. 0,5 mol peroksyd pr. 100 .g. Slike.konsen-
trater er også egnet.
Cykloalkanoloksydatet som er dannet på denne måte" behandles i overensstemmelse med oppfinnelsen ved reaksjonstemperaturer mellom 0 - 200°C, fortrinnsvis fra 25 til 120°C og mest onsket mellom 40 - 95°C. Trykket skal, skjont det ikke er av særlig betydning, fortrinnsvis være tilnærmet atmosfærisk. Når hoyere temperaturer anvendes, slik som over 80°C, er superatmosfæriske trykk hensiktsmessig for å redusere fordampningen av maursyre og andre tilstedeværende komponenter.
Mengden av maursyre skal være minst 0,2 mol pr. mol peroksydisk og hydroksylgruppe. Vanligvis vil 2 mol pr. mol være den prak-tiske ovre grense, men storre mengder kan imidlertid tilsettes uten å virke skadelig på omleiringen. Fortrinnsvis anvendes 0,5 til 1,5 mol pr. totalt mol, og mest onskelig 0,'9 til 1,2 mol pr. totalt mol.
Ved en særlig foretrukket utforelsesform for nærværende oppfinnelse tilsettes et tilsvarende keton for å oke utbytte. F.eks. når et cykloheksanoloksydat omleires, tilsettes cykloheksanon. De tilsvarende ketoner kan karakteriseres ved formelen:
hvor R og n er som tidligere definert.
Generelt brukes mellom 1:1 og 5:1 mol keton pr. mol peroksydisk oksygen, fortrinnsvis mellom 3:1 og 1:1 mol pr. mol. Mengder av ketonet utover 5 mol pr. mol kan brukes, men vanligvis er det ingen fordel, og det er okbnomisk uonsket.
Skjont vannfri maursyre kan brukes, kan-utmerkede resultater også oppnås med vandige oppløsninger. På grunn av vannet som dannes i reaksjonen er det fordelaktig å fore tilbake azeotropen (78 vektsprosent ved atmosfæretrykk koketrykk for maursyre). Denne azeotrop gir resultater i det vesentlige" like så gode som vannfritt materiale. Storre eller mindre konsentrasjoner av maursyre i vann kan også brukes.
Omleiringen av oksydatet i nærvær av en cykloalkanol og maursyre
forer til hydroksykarboksylsyrer og estere av disse. F.eks., hvis reaksjonen utfores uten vann, vil hovedproduktet være formiatesteren av hydroksylsyren"samt noe fri karboksylsyre. Under slike forhold er det klart at man kunne bruke mere maursyre for både å danne esteren og for og delta i omleiringsreak-sjonen. På lignende måte, hvis vann er tilstede i reaksjonsblandingen, oppnås ikke bare maursyreesterene, men også noen hydroksyprodukter, hvilket skyldes nærværet av vann og dét oppnås derfor også vesentlige mengder hydroksykarboksylsyrer. Nærværet av en cykloalkanol.i reaksjonsblandingen forer også til noen forestring av karboksylgrupperi.
Hydroksykarboksylsyrene og deres estere kan lett omdannes til laktamer og laktoner. F.eks. ved oppvarmning av ésterene av hydroksykapronsyre til ca. 300°C i ca. 20 timer i en autoklav ved et trykk på ° 140 - 176 kg/cm 2 absolutt i nærvær av ammoniakk og vann fremstilles kaprolaktam.
De folgende eksempler forklarer oppfinnelsen nærmere:
EKSEMPEL 1
Cykloheksanoloksydat fremstilles ved å blande 700 g cykloheksanol, 7 g kommersielt cykloheksanonperoksyd <p>g 7 g pulverisert magnesiumkarbonat i en flaske. Oksygen bobles gjennom blan-dingen i en mengde av 0,7 liter pr. minutt (N.T.T.), mens temperaturen okes til 120°C. Etter at 8'liter oksygen er absorbert, avkjbles flasken til 110°C og oksygenet fores gjennom den inntil et total av 17 liter oksygen er absorbert. Titrering av oksydatet angir nærværet av tilnærmet 0,1 mol peroksydisk oksygen pr. 100 g oksydat. Etter å ha befridd'oksydatet for faste stof-fer ved filtrering forenes 100 vektsdeler av oksydatet med.25 deler cykloheksanon og 60 deler 98 % maursyre. Tabell A viser resultatene som oppnås med serier av eksempler ved forskjellige temperaturer. Oppholdstid angir tiden som er nodvendig for å spalte minst 95 % av peroksydet. Utbyttet gjengis basert på mol peroksydisk oksygen som anvendes.
Det vil bemerkes at nærværet av maursyre resulterer i markert forbedring i det prosentuelle utbytte som oppnås som motsetning til termisk spaltning av peroksydet hvor mindre enn 5 % omdannes til det onskede sluttprodukt ved 60°C. Det er særlig å merke seg at forsokene innen det foretrukne området for oppfinnelsen,, nemlig 40 til 95°C gir særlig utmerkede resultater vanligvis over 80 %.
EKSEMPEL 2
Ved å anvende 100 deler cykloheksanoloksydat fremstilt i overensstemmelse med eksempel 1, 25 deler cykloheksanon, 60 deler 98 % maursyre og. 15 deler vann ble tilsatt.. Mengden vann som tilsettes simulerer sammensetningen av maursyre-vannazeotrop som oppnås ved atmosfæretemperatur (ca. 78 vektsprosent'maursyre) . Prover utfores ved temperaturer innen det foretrukne området og de folgende resultater oppnås.
Det 3. og 4. forsok angitt ovenfor gir fremragende resultater. Disse eksperimenter viser klart at ekstra gode utbytter ;kan oppnås selv i nærvær av en betydelig mengde vann. Dette viser klart fordelen ved nærværende oppfinnelse overfor den tidligere kjente hvor mineralsyrer anvendes.
EKSEMPEL 3
Ved igjen å bruke 100 deler oksydatopplosning, slik som i eksempel 1, ble forsok utfort for å vise virkningen av tilsetningen av cykloheksanon på utbyttet. Alle forsok ble utfort ved 60°C. Resultatene er gjengitt i tabell C.
Det skal bemerkes at tilsetningen av cykloheksanon selv i et
mol pr. mol peroksydiske oksygenrnengder oker utbyttet til tu-hydroksykapronsyre og estere ca. 50 %. Disse data kan ytterligere sammenlignes med dem angitt i tabell A, særlig forsok 3-6 utfort ved 60°C, hvor 3 mol pr. mol cykloheksanon ble tilsatt.
Betraktelig hbyere utbytter oppnås med denne ytterligere mengde.
Det skal bemerkes at der ikke er noe netto forbruk av cyklohek-
sanonet og det kan kontinuerlig fores tilbake til omleiringen etter utvinning.
EKSEMPEL 4
Et cykloheksanoloksydat fremstilles på en måte lignende den som
er angitt i eksempel 1. Imidlertid er 0,15 mol peroksydisk ok-
sygen tilstede i hvert 100 g oksydat. De folgende forsok viser virkningen av varierende mengder' av maursyre tilsatt til oksy-
datet. Alle forsok ble utfort ved 80°C. f/.aursyren og mengden vann tilstrekkelig til å simulere 78 % azeotropen ble tilsatt.
Etter å ha holdt temperaturen i en tid tilstrekkelig til å for-
bruke minst 95 % av peroksydet, oppnås folgende utbytter.
Det skal bemerkes at systemet er særlig folsomt overfor mengden
tilstedeværende maursyre, og de beste resultater oppnås med
minst 0,6 vektsdeler maursyre pr..del oksydat.
Claims (5)
1. Fremgangsmåte for fremstilling av hydroksykarboksylsyrer og estere av disse ved syrekatalysert omleiring av et oksydat av en cyklisk sekundær.alkohol som har formelen
hvor n betyr et helt tall fra 4 til" 11 og R betegner hydrogen, en alkylgruppe, en arylgruppe,
en aralkylgruppe, en heteroaromatisk gruppe, en karboksylgruppe, en fluorgruppe eller en klor-gruppe,
hvilket oksydat er opplost i den cykliske sekundære alkohol, karakterisert ved at omleiringen utfores ved at oppløsningen av oksydatet ved en temperatur mellom 0 og 200°C bringes i kontakt med minst 0,2 mol maursyre pr. mol totalt tilstedeværende peroksyd- og hydroksylgrupper i oksydatet.
2. Fremgangsmåte etter krav 1 for fremstilling av oj-hydroksykapronsyre ved omleiring av et oksydat av cykloheksanol, karakterisert ved at omleiringen utfores ved en temperatur fra 40 til 95°C.
3. Fremgangsmåte etter krav 1, karakterisert ved at omleiringen utfores i nærvær av et keton som tilsvarer den cykliske sekundære alkohol.
4. Fremgangsmåte etter krav 1, karakterisert ved at den anvendte maursyre inneholder vann.
5. Fremgangsmåte etter krav 4, karakterisert ved at den anvendte maursyre-vannblandingen er en azeotrop som oppnås ved destillasjon ved atmosfærisk trykk.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE7804231A SE7804231L (sv) | 1978-04-14 | 1978-04-14 | Magsyrasekretionsmedel |
Publications (3)
Publication Number | Publication Date |
---|---|
NO840112L NO840112L (no) | 1979-10-16 |
NO152785B true NO152785B (no) | 1985-08-12 |
NO152785C NO152785C (no) | 1985-11-20 |
Family
ID=20334608
Family Applications (5)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO791227A NO152216C (no) | 1978-04-14 | 1979-04-10 | Analogifremgangsmaate til fremstilling av terapeutisk anvendbare substituerte 2-(2-benzimidazolyl)-pyridiner |
NO840112A NO152785C (no) | 1978-04-14 | 1984-01-12 | Mellomprodukter til bruk ved fremstilling av substituerte 2-(2-benzimidazoylyl)-pyridiner. |
NO1994027C NO1994027I1 (no) | 1978-04-14 | 1994-12-21 | Omeprazol |
NO1995006C NO1995006I1 (no) | 1978-04-14 | 1995-06-14 | Omeprazole/ 5-metoksy-2-[[(4-metoksy-3,5-dimetyl-2-pyridinyl)metyl]sulfinyl]-1H-benzimidazol |
NO1995005C NO1995005I1 (no) | 1978-04-14 | 1995-06-14 | Omeprazole/ 5-metoksy-2-[[(4-metoksy-3,5-dimetyl-2-pyridinyl)metyl]sulfinyl]-1H-benzimidazol |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO791227A NO152216C (no) | 1978-04-14 | 1979-04-10 | Analogifremgangsmaate til fremstilling av terapeutisk anvendbare substituerte 2-(2-benzimidazolyl)-pyridiner |
Family Applications After (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO1994027C NO1994027I1 (no) | 1978-04-14 | 1994-12-21 | Omeprazol |
NO1995006C NO1995006I1 (no) | 1978-04-14 | 1995-06-14 | Omeprazole/ 5-metoksy-2-[[(4-metoksy-3,5-dimetyl-2-pyridinyl)metyl]sulfinyl]-1H-benzimidazol |
NO1995005C NO1995005I1 (no) | 1978-04-14 | 1995-06-14 | Omeprazole/ 5-metoksy-2-[[(4-metoksy-3,5-dimetyl-2-pyridinyl)metyl]sulfinyl]-1H-benzimidazol |
Country Status (25)
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US (3) | US4255431A (no) |
EP (1) | EP0005129B1 (no) |
JP (2) | JPS6034956B2 (no) |
AT (2) | AT374471B (no) |
BG (1) | BG61492B2 (no) |
CA (1) | CA1127158A (no) |
CS (1) | CS261851B2 (no) |
CY (1) | CY1232A (no) |
DD (1) | DD142882A5 (no) |
DE (1) | DE2960293D1 (no) |
DK (1) | DK150510C (no) |
FI (1) | FI65067C (no) |
HK (1) | HK15284A (no) |
HU (1) | HU179022B (no) |
IE (1) | IE48370B1 (no) |
LT (1) | LT2274B (no) |
LU (2) | LU88305I2 (no) |
MY (1) | MY8500074A (no) |
NL (2) | NL930074I2 (no) |
NO (5) | NO152216C (no) |
NZ (1) | NZ190203A (no) |
SE (1) | SE7804231L (no) |
SG (1) | SG63383G (no) |
SU (4) | SU895292A3 (no) |
ZA (1) | ZA791586B (no) |
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GB1234058A (no) * | 1968-10-21 | 1971-06-03 | ||
SE418966B (sv) * | 1974-02-18 | 1981-07-06 | Haessle Ab | Analogiforfarande for framstellning av foreningar med magsyrasekretionsinhiberande verkan |
US4045564A (en) * | 1974-02-18 | 1977-08-30 | Ab Hassle | Benzimidazole derivatives useful as gastric acid secretion inhibitors |
SE416649B (sv) * | 1974-05-16 | 1981-01-26 | Haessle Ab | Forfarande for framstellning av foreningar som paverkar magsyrasekretionen |
IN148930B (no) * | 1977-09-19 | 1981-07-25 | Hoffmann La Roche |
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1978
- 1978-04-14 SE SE7804231A patent/SE7804231L/xx unknown
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1979
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- 1979-04-09 CA CA325,188A patent/CA1127158A/en not_active Expired
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- 1979-04-13 SU SU792751500A patent/SU895292A3/ru active
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