NO832350L - PROCEDURE FOR THE PREPARATION OF PHENETYLAMINES. - Google Patents
PROCEDURE FOR THE PREPARATION OF PHENETYLAMINES.Info
- Publication number
- NO832350L NO832350L NO832350A NO832350A NO832350L NO 832350 L NO832350 L NO 832350L NO 832350 A NO832350 A NO 832350A NO 832350 A NO832350 A NO 832350A NO 832350 L NO832350 L NO 832350L
- Authority
- NO
- Norway
- Prior art keywords
- formula
- hydrogen
- group
- alkyl
- cathode
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 15
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- PIAOLBVUVDXHHL-UHFFFAOYSA-N 2-nitroethenylbenzene Chemical compound [O-][N+](=O)C=CC1=CC=CC=C1 PIAOLBVUVDXHHL-UHFFFAOYSA-N 0.000 claims description 8
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229940117803 phenethylamine Drugs 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000011133 lead Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- WTDHULULXKLSOZ-UHFFFAOYSA-N hydroxylamine hydrochloride Substances Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 1
- XBUFCZMOAHHGMX-UHFFFAOYSA-N hydroxylamine;phosphoric acid Chemical compound ON.ON.ON.OP(O)(O)=O XBUFCZMOAHHGMX-UHFFFAOYSA-N 0.000 description 1
- NXPHCVPFHOVZBC-UHFFFAOYSA-N hydroxylamine;sulfuric acid Chemical compound ON.OS(O)(=O)=O NXPHCVPFHOVZBC-UHFFFAOYSA-N 0.000 description 1
- WCYJQVALWQMJGE-UHFFFAOYSA-M hydroxylammonium chloride Chemical compound [Cl-].O[NH3+] WCYJQVALWQMJGE-UHFFFAOYSA-M 0.000 description 1
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- -1 platinum metals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012799 strong cation exchange Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
- C07D209/16—Tryptamines
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Description
Foreliggende oppfinnelse angår en forbedret fremgangsmåte for elektrokjemisk reduksjon av nitrostyrener til fenetylaminer. The present invention relates to an improved method for the electrochemical reduction of nitrostyrenes to phenethylamines.
Skjønt elektrokjemisk reduksjon av nitrostyrener har vært beskrevet i den kjemiske litteratur (se f.eks. japansk patent nr. 49-13777), så har denne teknikk i industriell skala' sjelden blitt brukt på grunn av for lavt kjemisk utbytte. Although electrochemical reduction of nitrostyrenes has been described in the chemical literature (see, for example, Japanese Patent No. 49-13777), this technique has rarely been used on an industrial scale due to too low a chemical yield.
Man har nå oppdaget en ny fremgangsmåte som kan brukes for fremstilling av fenetylaminer i vannoppløsninger med.høyt utbytte og med utmerket renhet. A new process has now been discovered which can be used for the production of phenethylamines in aqueous solutions with high yield and excellent purity.
Denne nye fremgangsmåte erkarakterisert veden elektrokjemisk reduksjon av et nitrostyren med formelen This new method is characterized by the electrochemical reduction of a nitrostyrene with the formula
hvor Ar er en aromatisk gruppe, X er en eller flere substituenter på den aromatiske gruppen og valgt fra gruppen bestående av hydrogen, alkyl, alkoksy, hydroksy, 3 4 (hvor R og R er de samme eller forskjellige og gruppe med fra 1-4 karbonatomer, i nærvær av hydroksylamin eller et salt av denne forbindelsen, og et sterkt negativt katodepotensial under hele prosessen, hvorved man får fremstilt et fenetylamin med formelen where Ar is an aromatic group, X is one or more substituents on the aromatic group and selected from the group consisting of hydrogen, alkyl, alkoxy, hydroxy, 3 4 (where R and R are the same or different and group with from 1-4 carbon atoms, in the presence of hydroxylamine or a salt of this compound, and a strongly negative cathode potential throughout the process, whereby a phenethylamine of the formula is produced
eller et farmasøytisk akseptabelt salt av dette, hvor Ar, R 1 og R 2 har samme betydning som angitt ovenfor, og Y har samme betydning som X med unntak at symbolet ikke representerer -NO2 . or a pharmaceutically acceptable salt thereof, where Ar, R 1 and R 2 have the same meaning as stated above, and Y has the same meaning as X except that the symbol does not represent -NO 2 .
Fenetylaminene har følgende generelle formelThe phenethylamines have the following general formula
hvor Ar er en aromatisk gruppe, Y er en eller flere substituenter på den aromatiske gruppen og valgt fra gruppen bestående av hydrogen, alkyl, alkoksy, hydroksy, where Ar is an aromatic group, Y is one or more substituents on the aromatic group and selected from the group consisting of hydrogen, alkyl, alkoxy, hydroxy,
gruppe med fra 1-4 karbonatomer. group with from 1-4 carbon atoms.
Med en aromatisk gruppe i foreliggende beskrivelse forstås f.eks. fenyl, naftyl eller indolyl. An aromatic group in the present description means e.g. phenyl, naphthyl or indolyl.
Med begrepet alkyl forstås en rett eller grenet alkylgruppe med fra 1-5 karbonatomer, f.eks. metyl, etyl, n-propyl og isopropyl.. The term alkyl means a straight or branched alkyl group with from 1-5 carbon atoms, e.g. methyl, ethyl, n-propyl and isopropyl..
Med alkoksy forstås i denne beskrivelse en alkyl-O-gruppe hvor alkylgruppen er som definert ovenfor. Alkoxy is understood in this description to mean an alkyl-O group where the alkyl group is as defined above.
Med halogen forstås klor, brom og fluor.. Halogen means chlorine, bromine and fluorine.
Også farmasøytisk akseptable salter av forbidnelser med formel I kan fremstilles ved hjelp av foreliggende fremgangsmåte. Slike salter er f.eks. et hydrobromid, hydro-klorid, fosfat, sulfat, citrat og tartrat. Pharmaceutically acceptable salts of compounds of formula I can also be prepared by means of the present method. Such salts are e.g. a hydrobromide, hydrochloride, phosphate, sulphate, citrate and tartrate.
Forbindelser med formel I kan brukes som farmasøytiske forbindelser. Compounds of formula I can be used as pharmaceutical compounds.
De nitrostyrener som brukes som utgangsmateriale i foreliggende fremgangsmåte, har følgende formel The nitrostyrenes used as starting material in the present method have the following formula
12 12
hvor Ar, R og R har samme betydning som angitt ovenfor, og X har samme betydning som Y bortsett fra at den også kan representere -NC^ • where Ar, R and R have the same meaning as above, and X has the same meaning as Y except that it can also represent -NC^ •
Katalytten kan bestå av en fortynnet vandig oppløsning av en sterk syre alene eller en blanding av en sterk styre, vann og et organisk oppløsningsmiddel. Som nevnte sterke syre kan man f.eks. bruke svovelsyre, saltsyre, hydrobrom-syre, fosforsyre eller en sulfonsyre. Konsentrasjonen av syren og det organiske oppløsningsmiddel hvis sistnevnte har syre-base-egenskaper, bør være slik at hydrogenione-konsentrasjonen ligger mellom 10 ^ M og 20 M, fortrinnsvis The catalyst can consist of a dilute aqueous solution of a strong acid alone or a mixture of a strong styrene, water and an organic solvent. As the aforementioned strong acid, you can e.g. use sulfuric acid, hydrochloric acid, hydrobromic acid, phosphoric acid or a sulphonic acid. The concentration of the acid and the organic solvent if the latter has acid-base properties should be such that the hydrogen ion concentration is between 10 ^ M and 20 M, preferably
-3 -3
mer enn 10 M. De relative mengder av vann og organisk oppløsningsmiddel kan variere innenfor vide grenser. Det organiske oppløsningsmidlet kan være en alkohol, en kar- more than 10 M. The relative amounts of water and organic solvent can vary within wide limits. The organic solvent can be an alcohol, a car-
boksylisk syre, en eter, et amid eller et nitritt. For-holdet mellom katolyttvolum og katodeareal bør være så lite som mulig. carboxylic acid, an ether, an amide or a nitrite. The ratio between catholyte volume and cathode area should be as small as possible.
Anolytten bør bestå av" en fortynnet vandig mineralsyre, fortrinnsvis svovelsyre eller saltsyre. Konsentrasjonen ligger fra 2 til 10 volum-%. The anolyte should consist of a dilute aqueous mineral acid, preferably sulfuric or hydrochloric acid. The concentration is from 2 to 10% by volume.
Anoden er normalt en DSA-anode (metallanode pålagt edel-metalloksyder), men kan også bestå av bly, blydioksyd, grafitt eller platinametaller. The anode is normally a DSA anode (metal anode applied to noble metal oxides), but can also consist of lead, lead dioxide, graphite or platinum metals.
Katodematerialet må velges med omhu. Det må ha en elektro-deoverflate med høyt hydrogenoverpotensial. Dette oppnås ved å fremstille katoden av et materiale med høyt hydrogenoverpotensial, eller ved en elektroavsetning av et metall med høyt hydrogenoverpotensial på katoden før eller under prosessen. Selv katodematerialet kan være sink, bly, kadmium, kvikksølv, tinn eller ledende materialer (f.eks. grafitt, bly, nikkel, kopper, aluminium, titan), hvorpå man kan avsette f.eks. sink, bly, kadmium, tinn eller kvikksølv. The cathode material must be chosen carefully. It must have an electrode surface with a high hydrogen overpotential. This is achieved by making the cathode of a material with a high hydrogen overpotential, or by electrodeposition of a metal with a high hydrogen overpotential on the cathode before or during the process. Even the cathode material can be zinc, lead, cadmium, mercury, tin or conductive materials (e.g. graphite, lead, nickel, copper, aluminium, titanium), on which one can deposit e.g. zinc, lead, cadmium, tin or mercury.
Elektrolyttcellen bør være en avdelt celle med gode masse-transportegenskaper. Diafragmaet kan være av ioneutbyt-ningstypen eller av et plastvev. The electrolyte cell should be a compartmentalized cell with good mass transport properties. The diaphragm can be of the ion exchange type or of a plastic fabric.
Temperaturen bør være så lav som mulig. Fremgangsmåten ut-føres vanligvis ved temperaturer under 20°C. The temperature should be as low as possible. The process is usually carried out at temperatures below 20°C.
Katodepotensial, strømtetthet, konsentrasjon av nitrostyren og massetransportegenskapene for katodeoverflaten er en funksjon av hverandre. Ifølge foreliggende oppfinnelse har man funnet at det er viktig med et stort negativt potensial for å utføre reduksjonen med godt resultat. Derfor bør reduksjonen utføres enten som en regulert potensialelektro-lyse med et stort negativt potensial, eller som en konstant strømelektrolyse hvor verdiene for strømtetthet, konsentra sjon av nitrostyren og massetransportegenskapene for katodeoverflaten er slik at potensialet har en stor negativ verdi. Potensialet bør være lavere enn -1,0 V i forhold til en SCE (mettet kalomelelektrode) referanseelektrode. Referanseelektroden plasseres~i kontakt med katoden med Cathode potential, current density, concentration of nitrostyrene and the mass transport properties of the cathode surface are a function of each other. According to the present invention, it has been found that it is important to have a large negative potential in order to carry out the reduction with good results. Therefore, the reduction should be carried out either as a regulated potential electrolysis with a large negative potential, or as a constant current electrolysis where the values for current density, concentration of nitrostyrene and the mass transport properties of the cathode surface are such that the potential has a large negative value. The potential should be lower than -1.0 V relative to an SCE (saturated calomel electrode) reference electrode. The reference electrode is placed~in contact with the cathode with
en vinkel på ca. 45° i forhold til katodeoverflaten.an angle of approx. 45° in relation to the cathode surface.
Ifølge foreliggende oppfinnelse har man videre funnet at for å oppnå en vellykket reduksjon må man tilsette et hydroksylamin eller et salt av dette i katolytten, fortrinnsvis hydroksylamin. Konsentrasjonen kan variere fra spor til en mettet oppløsning. According to the present invention, it has further been found that in order to achieve a successful reduction, a hydroxylamine or a salt thereof must be added to the catholyte, preferably hydroxylamine. The concentration can vary from traces to a saturated solution.
Det kjemisk utbyttet øker med økende konsentrasjon av hydrok-sylaminet. Den øvre grense for hydroksylaminkonsentrasjonen er bestemt av oppløseligheten i katolytten. Man foretrek-ker å bruke en konsentrasjon som ligger over 0,1 M. The chemical yield increases with increasing concentration of the hydroxylamine. The upper limit of the hydroxylamine concentration is determined by the solubility in the catholyte. It is preferred to use a concentration above 0.1 M.
Egnede salter av hydroksylamin som kan brukes er. hydroksyl-ammoniumhydrogensulfat, hydroksylammoniumsulfat, hydroksyl-ammoniumklorid og hydroksylammoniumfosfat. Suitable salts of hydroxylamine that can be used are. hydroxyl ammonium hydrogen sulfate, hydroxyl ammonium sulfate, hydroxyl ammonium chloride and hydroxyl ammonium phosphate.
Isolasjon av produktet oppnås ved hjelp av kjente fremgangs-måter. pH i katolytten justeres passende (pH 4 i de fleste tilfeller) og ekstraheres så f.eks. med toluen eller diklormetan. Etter at pH i vannfasen er øket til ca. pH 9-10, Isolation of the product is achieved using known methods. The pH in the catholyte is adjusted appropriately (pH 4 in most cases) and then extracted, e.g. with toluene or dichloromethane. After the pH in the water phase has been increased to approx. pH 9-10,
når fenetylaminet inneholder en fenolisk gruppe, og til ca. pH 12 i andre tilfeller, så ekstraheres vannfasen flere ganger med f.eks. toluen eller diklormetan. Oppløsnings-midlet kan så fordampes, og man oppnår det frie aminet med høy renhet. when the phenethylamine contains a phenolic group, and to approx. pH 12 in other cases, then the water phase is extracted several times with e.g. toluene or dichloromethane. The solvent can then be evaporated, and the free amine is obtained with high purity.
Ifølge en foretrukken utførelse av oppfinnelsen blir en forbindelse med formelen redusert til According to a preferred embodiment of the invention, a compound of the formula is reduced to
Reduksjonen utføres ved hjelp av en tilsetning av hydroksylamin til katolytten og med et sterkt negativt potensial under hele prosessen (< -1,2 V). The reduction is carried out by means of an addition of hydroxylamine to the catholyte and with a strong negative potential throughout the process (< -1.2 V).
De følgende eksempler illustrerer oppfinnelsen uten at denne er begrenset til disse. The following examples illustrate the invention without it being limited to them.
Eksempel 1Example 1
Det anvendte elektrolytiske utstyret var av filterpresse-typen med DSA anoder og blykatoder. Det eksponerte området på både anoden og katoden var 20 cm2 . Utstyret hadde en referanseelektrode som var plassert i kontakt med katoden i en vinkel på 45° i forhold til katodeoverflaten. Anode- The electrolytic equipment used was of the filter press type with DSA anodes and lead cathodes. The exposed area on both the anode and the cathode was 20 cm2. The equipment had a reference electrode which was placed in contact with the cathode at an angle of 45° in relation to the cathode surface. Anode-
og katodekammerne var skilt av et sterkt kationutbyttende diafragma ("Nation 390"). Både anolytten og katolytten ble pumpet igjennom cellen ved hjelp av sentrifugalpumper. Substratet ble plassert i en beholder fremstilt av et plast-nett. Beholderen ble så dyppet ned i katolyttoppløsningen. and the cathode chambers were separated by a strong cation exchange diaphragm ("Nation 390"). Both the anolyte and the catholyte were pumped through the cell using centrifugal pumps. The substrate was placed in a container made of a plastic mesh. The container was then dipped into the catholyte solution.
Analysene ble utført ved hjelp av høytrykksvæskekromatografi. De anvendte betingelser og de oppnådde resultater er vist The analyzes were carried out using high-pressure liquid chromatography. The conditions used and the results obtained are shown
i tabell 1. Omdannelsen av substratet var i alle eksemplene 100%. in table 1. The conversion of the substrate was in all the examples 100%.
Katolytt pH ble holdt konstant under elektrolysen ved hjelpCatholyte pH was kept constant during the electrolysis using
av syretilsetning.of acid addition.
Anolytten besto av 1 M r^S<O>^. The anolyte consisted of 1 M r^S<O>^.
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE8204015A SE455604B (en) | 1982-06-29 | 1982-06-29 | SET TO MAKE PHENETYLAMINES BY ELECTROCHEMICAL REDUCTION |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO832350L true NO832350L (en) | 1983-12-30 |
Family
ID=20347225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO832350A NO832350L (en) | 1982-06-29 | 1983-06-28 | PROCEDURE FOR THE PREPARATION OF PHENETYLAMINES. |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5953689A (en) |
| AT (1) | ATA236283A (en) |
| DE (1) | DE3323047A1 (en) |
| DK (1) | DK296383A (en) |
| FI (1) | FI832362L (en) |
| GB (1) | GB2122617A (en) |
| NO (1) | NO832350L (en) |
| SE (1) | SE455604B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030232890A1 (en) | 2000-11-01 | 2003-12-18 | Sention, Inc. | Methods for treating an impairment in memory consolidation |
| US7619005B2 (en) | 2000-11-01 | 2009-11-17 | Cognition Pharmaceuticals Llc | Methods for treating cognitive impairment in humans with Multiple Sclerosis |
| CA2427388C (en) | 2000-11-01 | 2011-12-20 | Sention, Inc. | Pharmaceutical compositions and uses for improving memory and learning impairments |
| GB0127559D0 (en) * | 2001-11-16 | 2002-01-09 | Syngenta Participations Ag | Organic compounds |
| JP2008244554A (en) * | 2007-03-26 | 2008-10-09 | Toa Corp | Overcurrent protection circuit of audio system |
| ES2951829T3 (en) | 2018-06-21 | 2023-10-25 | Hoffmann La Roche | Solid forms of 3-((1R,3R)-1-(2,6-difluoro-4-((1-(3-fluoropropyl)acetidin-3-yl)amino)phenyl)-3- tartrate salt methyl-1,3,4,9-tetrahydro-2H-pyrido[3,4-b]indol-2-yl)-2,2-difluoropropan-1-ol, process for its preparation and procedures for its use in the cancer treatment |
-
1982
- 1982-06-29 SE SE8204015A patent/SE455604B/en not_active IP Right Cessation
-
1983
- 1983-06-27 GB GB08317345A patent/GB2122617A/en not_active Withdrawn
- 1983-06-27 DE DE19833323047 patent/DE3323047A1/en not_active Withdrawn
- 1983-06-28 NO NO832350A patent/NO832350L/en unknown
- 1983-06-28 DK DK296383A patent/DK296383A/en not_active Application Discontinuation
- 1983-06-28 FI FI832362A patent/FI832362L/en not_active Application Discontinuation
- 1983-06-28 JP JP58115278A patent/JPS5953689A/en active Pending
- 1983-06-28 AT AT0236283A patent/ATA236283A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DK296383D0 (en) | 1983-06-28 |
| SE8204015D0 (en) | 1982-06-29 |
| DE3323047A1 (en) | 1984-02-23 |
| JPS5953689A (en) | 1984-03-28 |
| FI832362A0 (en) | 1983-06-28 |
| GB8317345D0 (en) | 1983-07-27 |
| SE455604B (en) | 1988-07-25 |
| DK296383A (en) | 1983-12-30 |
| FI832362L (en) | 1983-12-30 |
| GB2122617A (en) | 1984-01-18 |
| ATA236283A (en) | 1984-07-15 |
| SE8204015L (en) | 1983-12-30 |
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