NO162385B - Heksanhydropyrrolo-(1, 2-a)kinolin-og heksanhydro-1h-pyrido-(1,2-a)kinolin-forbindelser. - Google Patents
Heksanhydropyrrolo-(1, 2-a)kinolin-og heksanhydro-1h-pyrido-(1,2-a)kinolin-forbindelser. Download PDFInfo
- Publication number
- NO162385B NO162385B NO830900A NO830900A NO162385B NO 162385 B NO162385 B NO 162385B NO 830900 A NO830900 A NO 830900A NO 830900 A NO830900 A NO 830900A NO 162385 B NO162385 B NO 162385B
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- Prior art keywords
- catalyst
- palladium
- air
- nitrogen
- quinoline
- Prior art date
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- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 title 2
- 239000003054 catalyst Substances 0.000 claims description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 150000002940 palladium Chemical class 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- -1 NaBHO Chemical compound 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000021962 pH elevation Effects 0.000 description 1
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/08—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon radicals, substituted by hetero atoms, attached to ring carbon atoms
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
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- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
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- C07C205/33—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups or etherified hydroxy groups bound to carbon atoms of rings other than six-membered aromatic rings of the carbon skeleton
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- C07C33/18—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part
- C07C33/20—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part monocyclic
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- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
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- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
- C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D211/34—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
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- C07D455/03—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing quinolizine ring systems directly condensed with at least one six-membered carbocyclic ring, e.g. protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine
- C07D455/04—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing quinolizine ring systems directly condensed with at least one six-membered carbocyclic ring, e.g. protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing a quinolizine ring system condensed with only one six-membered carbocyclic ring, e.g. julolidine
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- Hydrogenated Pyridines (AREA)
Description
Fremgangsmåte til fremstilling av vinylacetat.
Oppfinnelsen vedrører en fremgangsmåte til fremstilling av vinylacetat fra etylen, eddiksyre og molekylært oksygen, resp. luft i gassfase på en palladiumbærekataly-sator med 0,1 til 10 vekt-% palladium og som fås ved reduksjon av et palladiumsalt til metallisk palladium i nærvær av et taæ-remateriale. Denne omsetning på en palla-diumbærekatalysator som ikke inneholder ytterligere følgemetaller er tidligere bare kjent med små utbytter, resp. rom-tidsutbytter.
Det er nu funnet at det ved fremstilling av vinylacetat fra etylen, eddiksyre og oksygen, resp. luft i gassfase lar seg oppnå spesielt høye rom-tidsutbytter med en Pd-katalysator som fremstilles på den nedenfor omtalte i og for seg kjente måte og etterbehandles ifølge oppfinnelsen.
Som katalysatorbærer benyttes kiselsyre med en aktiv overflate ifølge BET på f.eks. 180 m2/g (BET-metode, Journal of Amer. chem. Soc. 60, 309 [1938]) og en volumtetthet på f.eks. 0,39 kg/l og gjennom-fuktet med en PdCl2-, Pd(NOa)2- eller Pd(CH3COO)2-oppløsning i vann, som er blandet med natronlut og ønskelig konsen-trasj on til begynnende uklarhet.
Palladiumsaltets mengde i den vandige oppløsning, resp. mengden av palladium-saltoppløsning av kjent konsentrasjon be-regnes således at den ferdige, av Pd-metall og Si02 bestående katalysator inneholder 0,1 til 10, fortrinnsvis 4 til 7 vekt-% Pd. Derpå innfører man den under omrøring tørkede masse i en med maursyre til pH = 6 innstillet natriumformiatoppløsning av
60° C, idet det på bæreren adsorberte PdCk øyeblikkelig reduseres til sort Pd og blander blandingen med natronlut av ønskelig konsentrasjon til pH == 8 til 9, heller væsken av og vasker katalysatoren omhyggelig ut med vann. Etter tørkning i vakuumtørke-skap ifylles den på denne måte fremstilte katalysator for etterbehandling i et reak-sjonsrør av f.eks. 25 mm indre diameter, som ved hjelp av væskeoppvarmning holdes på omtrent 170° C, og gjennom røret sendes det 1 til 2 timer en luftstrøm på
3 ata.
Deretter overføres gjennom samme rør over katalysatoren den egentlige reak-sjonsblanding i en sammensetning som lig-ger utenfor eksplosjonsgrensen, feks. 25 vol.-% eddiksyredamp, 46 vol.-% etylen, 23 vol.-% nitrogen og 6 vol.-% oksygen, idet man oppnår et rom-tidsutbytte på 13 g vinylacetat/1 katalysator (4 % Pd) pr. time.
Arbeider man med den etterbehandlede katalysator og overfører en reaksjons-blanding uten nitrogen, altså omtrent i sammensetningen 18 vol.-% eddiksyredamp, 74 vol.-% etylen og 8 vol.-% oksygen, så kommer omsetningen etter noen tid til stillstand.
Hvor viktig etterbehandlingen av katalysatoren ifølge oppfinnelsen med luft er tydeliggjøres når man ifølge eksempel 2 anvender en ikke etterbehandlet katalysator: det danner seg intet vinylacetat. Rik-tignok inneholder reaksjonsblandingen her intet nitrogen, reaksjonsbetingelsene var altså spesielt ugunstige, men selv i nærvær av nitrogen kommer omsetningen ved an-vendelsen av en ikke etterbehandlet katalysator bare langsomt igang, og vinylacetat-dannelsen begrenser seg til påvisbare spor.
Overraskende lar rom-tidsutbytte seg øke langt over 13 g vinylacetat/1 katalysator pr. time, når man til katalysatorens etterbehandling med luft knytter en spyling av katalysatoren med nitrogengass i løpet av noen, f.eks. 4 til 60 timer ved ca. 170° C og deretter fører nitrogenholdig reaksjons-gassblanding over katalysatoren.
I dette tilfelle lar det seg oppnå rom-tidsutbytter på 32 g/l pr. time (4 % Pd; 3 ata), resp. 54 g/l pr. time (4% Pd; 6 ata), resp 70 g/l pr. time (6,5 % Pd; 6 ata) vinylacetat. Det skal spesielt bemerkes at rom-tidsutbyttene minst praktisk talt forblir uforandret over en måned, og etter avstil-lingsperioder med en gang vender tilbake når katalysatoren under avstillingsperioden holdes under nitrogen.
Som katalysatorbærer kan det også benyttes aluminiumoksyd, aluminiumsili-kat, aluminiumfosfat, karbon, enkeltvis eller i blanding som bæremateriale. Bærerens aktive overflate kan ligge mellom 50 og 400 m2/g. Foruten formiatreduksjonen av Pd<11 >til Pd<0>, er det også anvendbart andre kjente reduksjonsmetoder, f.eks. reduksjon med natriumborhydrid (natriumboranat, NaBHO, hydrogen eller hydrazinhydrat. Imidlertid er kombinasjonen av en reduksjon av palladiumklorid med alkaliformiat/ maursyre i nærvær av kiselsyre ved etterbehandling av tørket katalysator med luft og/eller nitrogen spesielt fordelaktig ifølge oppfinnelsen. Katalysatorens behandling med luft eller nitrogen kan fortrinnsvis foregå ved temperaturer mellom 120° og 350° C, fortrinnsvis 150° og 200° C, og ved trykk mellom 1 og 10 ata, mens den egentlige omsetning av etylen, eddiksyre og luft og katalysatoren til vinylacetat foretas ved temperaturer mellom 120° og 250° C, fortrinnsvis 150° og 200° C, og ved trykk mellom 1 og 10 ata.
Fremstillingen ifølge oppfinnelsen av vinylacetat under anvendelse av en med nitrogen eller luft etterbehandlet palla-diumbærekatalysator gir overraskende ikke bare spesielt høye rom-tidsutbytter, men den etterbehandlede katalysators tempera-turfølsomhet som, som kjent, ville gi seg tilkjenne ved en øket biproduktdannelse og forbrenning til C02, er meget mindre enn ved ikke med nitrogen behandlet katalysator.
Oppfinnelsen vedrører altså en frem-
gangsmåte til fremstilling av vinylacetat fra etylen, eddiksyre og molekylært oksygen, resp. luft på en ved reduksjon av et palladiumsalt til metallisk palladium i nærvær av et bæremetall dannet palladium-bærekatalysator med 0,1 til 10 vekt-% palladium ved omsetning av utgangsstoffene i gassfase, idet fremgangsmåten er karakterisert ved at palladiumbærekatalysatoren før bruk i løpet av noen timer behandles med luft og/eller nitrogen. Bærematerialet er fortrinnsvis kiselsyre. Videre er det spesielt hensiktsmessig når reduksjonen av palladiumsaltet ble foretatt med en blanding av alkaliformiatoppløsning og maursyre.
Palladiumbærekatalysatoren kan bli fremstillet ved impregnering av kiselsyre med en vandig, inntil begynnende uklarhet med alkalilut blandet palladiumsaltoppløs-ning, tørkning, innføring av den tørre masse i med maursyre på pH = 6 innstillet, ca. 60° til 90° C varm alkaliformiatoppløsning, alkalisering av blandingen med alkalilut til pH 8 til 9, avdekantering av væsken, ut-vasking med vann, tørkning og behandling av den palladiumholdige kiselsyre i løpet av noen timer med nitrogen og eventuelt luft ved temperaturer mellom 150° og 200° C og trykk mellom 1 og 10 ata.
Såvel katalysatorens fremstilling som også dens etterbehandling og anvendelse skal forklares ved hjelp av følgende ek-sempler.
Eksempel 1.
1 1 kiselsyrestrenger av 4 mm diameter med en aktiv overflate på 180 m<2>/g og en volumtetthet på 0,39 kg/l ble sammenblan-det med 400 cm<3> av en vandig oppløsning av 25,7 g PdCla som ble blandet med 2-normal natronlut til begynnende palla-diumhydroksydutfelling og tørket under tørkning Den tørre masse innføres deretter i 600 cm<3> av en oppløsning som inneholder 80 g maursyre og 65 g NaOH i vann. Oppløsningen skal ikke underskride en temperatur på 60° C. Det inntrer med en gang reduksjon av palladiumklorid ved samtidig utvikling av COa. Etter noen mi-nutter gjør man blandingen alkalisk med natronlut til pH 8 til 9, heller av vannet og ettervasker med meget destillert vann. Katalysatoren tørkes deretter i vakuum ved ca. 60° C. Den inneholder ca. 4 % Pd.
Eksempel 2.
200 cm<3> av den i eksempel 1 beskrevne katalysatormasse ifylles i et rør av 18/8
kromnikkelstål av 25 mm indre diameter hvori det befinner seg et kjernerør a-v samme materiale av 14 mm ytre diameter til opptak av termomotstander for tempera-turmålingen og holdes ved temperering av røret i et væskebad på 170° C. Gjennom det loddrettstående rør fører man ved et trykk på 3 ata pr. time 150 NI av en gass-blanding bestående av 18 vol.-% eddiksyre, 74 vol.-% etylen og 8 vol.-% oksygen. Fra den fra reaksjonsrøret uttredende gass-blanding utskilles ved avkjøling til — 70° C de kondenserbare deler som eventuelt inneholder reaksjonsproduktet og analyseres ved destillering. Det danner seg i løpet av 2 dager intet vinylacetat, senere påvisbare spor.
Eksempel 3 til 7.
En tilsvarende eksempel 1 fremstilt katalysator behandles før driften i den i eksempel 2 beskrevne apparatur med luft, resp. nitrogen<*> Innvirkningsbetingelsene er angitt i følgende tabell. Som oksydasjons-middel i reaksjonsgassblandingen tjener ikke rent oksygen, men luft, således at ut-gangsblandingen består av 25 vol.-% eddiksyre, 46 vol.-% etylen, 6 vol.-% oksygen og 23 vol.-% nitrogen. De herved oppnådde rom-tidsutbytter fremgår av tabellen. Ved siden av vinylacetat danner det seg under de angitte betingelser også acetaldehyd og CO2 i mindre mengder.
Ca. 92 til 94 % av det i disse reaksjons-produkter inneholdte karbon fordeles på vinylacetat, 3 til 5 % på C02 og resten på acetaldehyd.
Eksempel 8.
1 1 kiselsyrestrenger av den i eksempel 1 omtalte type blandes med 400 cm3 av en vandig oppløsning som inneholder 5,6 g PdCl2 og tørkes under omrøring. Den tør-kede masse innføres i en metanolisk opp-løsning av natriumboranat (NaBH4). Re-duksjonsoppløsningen ble fremstilt idet 10 g natriumboranat ble oppløst i 50 cm<3 >vann og deretter innført i 1 1 metanol. Det inntrer øyeblikkelig reduksjon av palla-diumkloridet ved samtidig utvikling av hydrogen. Etter avsluttet reduksjon heller man fra metanol, vasker katalysatoren grundig med vann og tørker ved 60° C i vakuum. Katalysatoren som inneholder ca. 1 % Pd ble behandlet i 2 timer med luft og 5 timer med nitrogen ved 170° C og 6 ata og muliggjorde katalysatoryteiser på 15 g vinylacetat pr. 1 kontakt pr- time.
Claims (1)
- Fremgangsmåte til fremstilling av vinylacetat fra etylen, eddiksyre og molekylært oksygen, resp. luft på en palladium-bærekatalysator med 0,1 til 10 vektspro-sent palladium og som er fremstilt ved reduksjon av et palladiumsalt til metallisk palladium i nærvær av et bærematerialeved omsetning av utgangsstoffene i gassfase, karakterisert ved at palladiumbærekatalysatoren før bruk behandles noen timer med luft og/eller nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO880538A NO163188C (no) | 1982-03-16 | 1988-02-08 | Analogifremgangsm te for fremstilling av terapeutisk aktive heksahydropyrollo-(1,2-a)kinolin-, heksahydro-1h-pyrido-(1,2-a)kinolin-eller oktahydrofenantrenforbindelser. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/358,569 US4476131A (en) | 1982-03-16 | 1982-03-16 | Substituted hexahydropyrrolo[1,2-a]-quinolines, hexahydro-1H-pyrido[1,2-a]-q |
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| Publication Number | Publication Date |
|---|---|
| NO830900L NO830900L (no) | 1983-09-19 |
| NO162385B true NO162385B (no) | 1989-09-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| NO830900A NO162385B (no) | 1982-03-16 | 1983-03-15 | Heksanhydropyrrolo-(1, 2-a)kinolin-og heksanhydro-1h-pyrido-(1,2-a)kinolin-forbindelser. |
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| Country | Link |
|---|---|
| US (1) | US4476131A (no) |
| EP (1) | EP0090516B1 (no) |
| JP (2) | JPS58170724A (no) |
| KR (2) | KR870001126B1 (no) |
| AR (1) | AR240936A1 (no) |
| AT (1) | ATE35544T1 (no) |
| AU (1) | AU543215B2 (no) |
| CA (1) | CA1254567A (no) |
| CS (1) | CS249126B2 (no) |
| DD (2) | DD210270A5 (no) |
| DE (1) | DE3377280D1 (no) |
| DK (1) | DK85183A (no) |
| ES (2) | ES520630A0 (no) |
| FI (1) | FI76334C (no) |
| GR (1) | GR77127B (no) |
| HU (1) | HU189906B (no) |
| IE (1) | IE54897B1 (no) |
| IL (1) | IL68131A (no) |
| NO (1) | NO162385B (no) |
| NZ (1) | NZ203577A (no) |
| PH (1) | PH19998A (no) |
| PL (2) | PL141501B1 (no) |
| PT (1) | PT76390B (no) |
| RO (2) | RO88221B (no) |
| SU (1) | SU1355130A3 (no) |
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| US4576964A (en) * | 1982-03-16 | 1986-03-18 | Pfizer Inc. | Substituted hexahydrobenzo[e]indene and octahydrophenanthrene CNS agents and pharmaceutical compositions thereof |
| US4670562A (en) * | 1985-03-13 | 1987-06-02 | Hoechst-Roussel Pharmaceuticals Inc. | Dihydropyrrolo[1,2-b]isoquinolinedione oximes |
| US5629345A (en) * | 1993-07-23 | 1997-05-13 | Vide Pharmaceuticals | Methods and compositions for ATP-sensitive K+ channel inhibition for lowering intraocular pressure |
| US5965620A (en) * | 1993-07-23 | 1999-10-12 | Vide Pharmaceuticals | Methods and compositions for ATP-sensitive K+ channel inhibition for lowering intraocular pressure |
| CA2187257A1 (en) * | 1995-10-12 | 1997-04-13 | Enrique Luis Michelotti | Aryl-substituted cycloalkanes and cycloalkenes and herbicidal use thereof |
| CN1075498C (zh) * | 1997-05-08 | 2001-11-28 | 车庆明 | 一种查尔酮c甙和它的用途 |
| US6316734B1 (en) | 2000-03-07 | 2001-11-13 | 3M Innovative Properties Company | Flexible circuits with static discharge protection and process for manufacture |
| ITGE20080051A1 (it) | 2008-06-04 | 2009-12-05 | Matteucci Francesco | Metodo per la realizzazione di cavi diamantati rinforzati per il taglio di strutture e materiali in acciaio,calcestruzzo,acciaio e calcestruzzo,materiali litoidi o simili e cavo diamantato rinforzato ottenuto mediante tale metodo. |
| CN112778241A (zh) * | 2021-03-09 | 2021-05-11 | 中国科学院兰州化学物理研究所 | 一种四氢呋喃乙酸及其酯类化合物的制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3045020A (en) * | 1962-07-17 | x xcooa | ||
| FR1490023A (fr) * | 1965-08-17 | 1967-07-28 | Sandoz Sa | Dérivés de l'isoquinoléine et leur préparation |
| US4260764A (en) * | 1976-12-22 | 1981-04-07 | Pfizer Inc. | 9-Hydroxyoctahydrobenzo [C] quinolines and intermediates therefor |
| US4188495A (en) * | 1977-11-14 | 1980-02-12 | Pfizer Inc. | 1,9-Dihydroxyoctahydrophenanthrenes and intermediates therefor |
-
1982
- 1982-03-16 US US06/358,569 patent/US4476131A/en not_active Expired - Fee Related
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1983
- 1983-02-24 DK DK85183A patent/DK85183A/da not_active Application Discontinuation
- 1983-03-08 EP EP83301224A patent/EP0090516B1/en not_active Expired
- 1983-03-08 AT AT83301224T patent/ATE35544T1/de not_active IP Right Cessation
- 1983-03-08 DE DE8383301224T patent/DE3377280D1/de not_active Expired
- 1983-03-11 PL PL1983240989A patent/PL141501B1/pl unknown
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- 1983-03-14 CA CA000423530A patent/CA1254567A/en not_active Expired
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- 1983-03-15 FI FI830857A patent/FI76334C/fi not_active IP Right Cessation
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- 1983-03-15 NO NO830900A patent/NO162385B/no unknown
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- 1983-03-15 AU AU12448/83A patent/AU543215B2/en not_active Ceased
- 1983-03-15 ES ES520630A patent/ES520630A0/es active Granted
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- 1983-03-16 JP JP58042538A patent/JPS58170724A/ja active Pending
- 1983-03-16 CS CS831822A patent/CS249126B2/cs unknown
- 1983-11-07 ES ES527075A patent/ES8504097A1/es not_active Expired
- 1983-11-28 SU SU833665902A patent/SU1355130A3/ru active
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1986
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