NO147241B - PROCEDURE FOR THE PREPARATION OF GLYCOLE ALDEHYDE - Google Patents
PROCEDURE FOR THE PREPARATION OF GLYCOLE ALDEHYDE Download PDFInfo
- Publication number
- NO147241B NO147241B NO760050A NO760050A NO147241B NO 147241 B NO147241 B NO 147241B NO 760050 A NO760050 A NO 760050A NO 760050 A NO760050 A NO 760050A NO 147241 B NO147241 B NO 147241B
- Authority
- NO
- Norway
- Prior art keywords
- osmium tetroxide
- glycolaldehyde
- reaction
- preparation
- glycole
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title description 4
- 150000001299 aldehydes Chemical class 0.000 title 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 28
- 239000012285 osmium tetroxide Substances 0.000 claims description 23
- 229910000489 osmium tetroxide Inorganic materials 0.000 claims description 23
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 claims description 16
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- -1 alkaline earth metal chlorate Chemical class 0.000 claims description 5
- 239000012736 aqueous medium Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000007059 Strecker synthesis reaction Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007248 oxidative elimination reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Foreliggende oppfinnelse vedrører en fremgangsmåte for fremstilling av glykolaldehyd, og det særegne ved fremgangsmåten i henhold til oppfinnelsen er at etylvinyleter eller vinylacetat ved en temperatur mellom 0 og 100°C oksyderes med en blanding av osmiumtetroksyd og et alkali- eller jordalkali-metallklorat i vandig medium. The present invention relates to a method for the production of glycolaldehyde, and the distinctive feature of the method according to the invention is that ethyl vinyl ether or vinyl acetate is oxidized at a temperature between 0 and 100°C with a mixture of osmium tetroxide and an alkali or alkaline earth metal chlorate in an aqueous medium .
Disse trekk ved oppfinnelsen fremgår av patentkravet. These features of the invention appear in the patent claim.
Ved en slik reaksjon kan osmiumtetroksyd anvendes i katalyt-iske mengder (foretrukket minst 20 mg/g substrat) i og med at det regenereres kontinuerlig av kloratet ved oksyderende spalting av et osmium-tetroksyd-umettet forbindelse-addukt. Kloratet må således være tilstede i minst den støkiometriske mengde. Osmium-tetroksyd kan i tillegg gjenvinnes ved full-ført reaksjon eller også ved stripping med en nitrogenstrøm for å oppfange osmium-tetroksydstrømmen som er flyktig, i en felle som inneholder utgangsproduktet slik at det dermed dannes det ikke-flyktige addukt (som kan anvendes for en ny fremstilling) eller ved selektiv ekstraksjon av osmium-tetroksyd med et passende løsningsmiddel (som f.eks. CCl^, benzen, Et^ O) In such a reaction, osmium tetroxide can be used in catalytic amounts (preferably at least 20 mg/g substrate) in that it is continuously regenerated by the chlorate by oxidative cleavage of an osmium tetroxide-unsaturated compound adduct. The chlorate must thus be present in at least the stoichiometric amount. Osmium tetroxide can additionally be recovered upon completion of the reaction or also by stripping with a stream of nitrogen to capture the volatile osmium tetroxide stream in a trap containing the starting product so that the non-volatile adduct is thus formed (which can be used for a new preparation) or by selective extraction of osmium tetroxide with a suitable solvent (such as CCl^, benzene, Et^O)
og avdampning av løsningsmidlet etter tilsetning av utgangsproduktet til ekstrakten for å danne adduktet, eller med andre fremgangsmåter som måtte være kjent for fagmannen. and evaporating the solvent after adding the starting product to the extract to form the adduct, or by other methods known to those skilled in the art.
Mer detaljert gjennomføres oksydasjonsreaksjonen i et vandig medium ved en temperatur på mellom 0°C og 100°C (vanligvis fra +25°C til +50°C) og under et slikt trykk at væskefasen i systemet opprettholdes. For faste substrater som er vann-uoppløselige foretrekkes det at et konvensjonelt med vann blandbart inert løsningsmiddel tilsettes, som er i stand til å opp-løse substratet i det minste delvis, som f.eks. tetrahydrofuran eller alkoholer, eller et med vann ikke blandbart løsningsmiddel som i det minste delvis er i stand til å oppløse både substratet og osmium-tetroksydet, som f.eks. CCl^, Et20/benzen. In more detail, the oxidation reaction is carried out in an aqueous medium at a temperature of between 0°C and 100°C (usually from +25°C to +50°C) and under such a pressure that the liquid phase in the system is maintained. For solid substrates which are water-insoluble, it is preferred that a conventional water-miscible inert solvent is added, which is able to dissolve the substrate at least partially, such as e.g. tetrahydrofuran or alcohols, or a water-immiscible solvent which is at least partially able to dissolve both the substrate and the osmium tetroxide, such as e.g. CCl 2 , Et 2 O/benzene.
I sammenligning med de konvensjonelle metoder for fremstilling av de forbindelser hvis fremstilling er formålet for den forelig gende oppfinnelse, frembyr fremgangsmåten i henhold til oppfinnelsen den fordel at den ikke bare er billigere, men også enklere fra et økonomisk synspunkt. In comparison with the conventional methods for producing the compounds whose production is the object of the present invention, the method according to the invention offers the advantage that it is not only cheaper, but also simpler from an economic point of view.
Ved den foreliggende oppfinnelse kan man på en enkel With the present invention, one can in a simple
måte fremstille glykolaldehyd ved reaksjon av etylvinyleter eller vinylacetat, ved reaksjon av disse med en oksyderende blanding sammensatt av osmium-tetroksyd og et klorat av et alkalimetall eller jordalkalimetall, idet reaksjonen gjennom-føres i et vandig medium og ved en temperatur mellom 0 og 100°C. method of preparing glycolaldehyde by reacting ethyl vinyl ether or vinyl acetate, by reacting these with an oxidizing mixture composed of osmium tetroxide and a chlorate of an alkali metal or alkaline earth metal, the reaction being carried out in an aqueous medium and at a temperature between 0 and 100° C.
US-patentskrift 2.402.566 lærer fremstilling av polyhydroksyl-derivater av umettede organiske forbindelser, inneholdende olefingrupper eller grupper CO, ved behandling av disse organiske forbindelser med en vannfri oppløsning av hydrogenperoksyd i et inert organisk løsningsmiddel og i nærvær av en kat-alysator (et oksyd). Denne fremgangsmåte gjennomføres ved en temperatur mellom romtemperatur og noen grader under 0°C. US patent 2,402,566 teaches the preparation of polyhydroxyl derivatives of unsaturated organic compounds, containing olefin groups or CO groups, by treating these organic compounds with an anhydrous solution of hydrogen peroxide in an inert organic solvent and in the presence of a catalyst (a oxide). This procedure is carried out at a temperature between room temperature and a few degrees below 0°C.
US-patentskrift 3.488.394 lærer en fremgangsmåte for oksyde-ring av olefinforbindelser hvori angjeldende forbindelser rea-gerer i et vandig medium med pH minst 7 i nærvær av osmium-tetroksyd ved en temperatur fra -10 - +60°C til å danne et addukt med to OH-grupper på olefinforbindelsen. Utgangsole-finet velges blant de umettede hydrokarboner som også er sub-stituert med OH-grupper. Katalysatoren (osmium-tetroksyd) er til stede i så sma mengder som 10 -5 - 10 -3molar. US patent 3,488,394 teaches a method for oxidizing olefin compounds in which the compounds in question react in an aqueous medium with a pH of at least 7 in the presence of osmium tetroxide at a temperature of -10 - +60°C to form a adduct with two OH groups on the olefin compound. The starting olefin is selected from among the unsaturated hydrocarbons which are also substituted with OH groups. The catalyst (osmium tetroxide) is present in amounts as small as 10 -5 - 10 -3 molar.
De to OH-grupper er bundet til to nabo-C-atomer, slik at det dreier seg om annen teknikk enn ved den foreliggende oppfinnelse. The two OH groups are bound to two neighboring C atoms, so that it is a different technique than in the present invention.
J.Am.Chem.Soc., 61, (1939), 1844-1847 beskriver en fremgangsmåte for å addere OH-grupper til forbindelser inneholdende dobbeltbindinger ved siden av CO-grupper under anvendelse av hydrogenperoksyd i tertbutanol med osmium-tetroksyd. Reaksjonen beskrevet i J.Am.Chem.Soc. krever fem døgn ved 0°C for full-føring og også reaksjonen beskrevet i US-patentskrift 2.402.566 J.Am.Chem.Soc., 61, (1939), 1844-1847 describes a method for adding OH groups to compounds containing double bonds adjacent to CO groups using hydrogen peroxide in tert-butanol with osmium tetroxide. The reaction described in J.Am.Chem.Soc. requires five days at 0°C for completion and also the reaction described in US patent 2,402,566
krever fem døgn ved 0°C for tilfredsstillende fullføring. requires five days at 0°C for satisfactory completion.
Den erkjennelse som ligger til grunn for oppfinnelsen er at det er mulig å fremstille glykolaldehyd ved anvendelse av kaliumklorat og osmium-tetroksyd ved en reaksjon som riktignok har et lavere utbytte (50%) men som er fullstendig gjennom-ført i løpet av 15 minutter. The recognition that forms the basis of the invention is that it is possible to produce glycolaldehyde using potassium chlorate and osmium tetroxide in a reaction which admittedly has a lower yield (50%) but which is completely completed within 15 minutes.
Glykolaldehyd er nyttig som synteseutgangsprodukt, f.eks. Glycolaldehyde is useful as a synthesis starting product, e.g.
for fremstilling av alfa-amino-beta-hydroksysyrer ved den velkjente Strecker-reaksjon og modifikasjoner av denne. for the production of alpha-amino-beta-hydroxy acids by the well-known Strecker reaction and modifications thereof.
Videre, for fremstilling av disse aminosyrer, er den foreliggende fremgangsmåte spesielt fordelaktig på den måte at det er mulig å gjennomføre Strecker-reaksjonen direkte med den vandige blanding som oppnås ved fullføring av reaksjonen hvis osmium-tetroksydet fjernes på forhånd, idet det ikke er nødvendig å isolere glykolaldehydet. Furthermore, for the preparation of these amino acids, the present process is particularly advantageous in that it is possible to carry out the Strecker reaction directly with the aqueous mixture obtained at the completion of the reaction if the osmium tetroxide is removed beforehand, since it is not necessary to isolate the glycolaldehyde.
EKSEMPEL 1 EXAMPLE 1
Fremstilling av glykolaldehyd fra etylvinvleter Production of glycolaldehyde from ethyl vinvlether
En blanding av 1,44 g (20 millimol) etylvinyleter, 30 ml vann, 2,80 g (22,8 millimol) kaliumklorat og 0,10 g (0,39 millimol) osmium-tetroksyd omrøres ved romtemperatur i en tohalskolbe forbundet med pH-meter og en automatisk burette fylt med 1-normal NaOH oppløsning. pH i reaksjonsblandingen holdes ved 6,8 - 7,0 under hele reaksjonsforløpet for å hemme den sure hydrolyse-som katalyseres av etylvinyleteren. Etter 4 timer er reaksjonen fullstendig og det oppnås en fargeløs løsning etter at etylvinyleterfasen er fjernet. Ved dette tidspunkt gjenvinnes osmium-tetroksyd fra den vandige løsning med gjen-tatte ekstraksjoner med benzen (hvori glykolaldehyd er uoppløs-elig) .Benzenfasen tilsettes så et overskudd av etylvinyleter (omtrent 0,5 g) i forhold til osmium-tetroksydet for sammen med osmium-tetroksydet å danne det ikke flyktige addukt. Løs- ningsmidlet strippes nå ved romtemperatur under vakuum frem-bragt ved hjelp av en filterpumpe. Resten er osmium-tetroksyd-etylvinyleter-adduktet som kan anvendes for en ny fremstilling av glykolaldehyd. Fra den vandige fase som er tilbake ved fullføringen av ekstraksjonen med benzen strippes vann under vakuum fra en filterpumpe, idet badtemperaturen holde på omtrent 30°C. Ved titrering med hydroksydamin-hydrokloridmetoden (se E. Heuser i "Methoden der Org. Chemie", Houben-Weyl, Georg Thieme Verlag, Stuttgart, 1953, s. 458) som gjennomført på en prøve av den oppnådde rest, bestemmes en glykolaldehydomdann-else på 72%. A mixture of 1.44 g (20 mmol) ethyl vinyl ether, 30 ml water, 2.80 g (22.8 mmol) potassium chlorate and 0.10 g (0.39 mmol) osmium tetroxide is stirred at room temperature in a two-necked flask connected to pH meter and an automatic burette filled with 1-normal NaOH solution. The pH of the reaction mixture is kept at 6.8 - 7.0 during the entire course of the reaction to inhibit the acidic hydrolysis catalyzed by the ethyl vinyl ether. After 4 hours the reaction is complete and a colorless solution is obtained after the ethyl vinyl ether phase has been removed. At this point, osmium tetroxide is recovered from the aqueous solution by repeated extractions with benzene (in which glycolaldehyde is insoluble). The benzene phase is then added with an excess of ethyl vinyl ether (approximately 0.5 g) in relation to the osmium tetroxide for together with the osmium tetroxide to form the non-volatile adduct. The solvent is now stripped at room temperature under vacuum produced by means of a filter pump. The remainder is the osmium tetroxide ethyl vinyl ether adduct which can be used for a new production of glycolaldehyde. From the aqueous phase that remains at the completion of the extraction with benzene, water is stripped under vacuum from a filter pump, keeping the bath temperature at approximately 30°C. By titration with the hydroxy amine hydrochloride method (see E. Heuser in "Methoden der Org. Chemie", Houben-Weyl, Georg Thieme Verlag, Stuttgart, 1953, p. 458) carried out on a sample of the obtained residue, a glycolaldehyde conversion is determined else at 72%.
Resten oppnådd fra avdampingen av den vandige fase tilsettes dioksan, saltene fjernes ved filtrering og filtratet destill-eres. Glykolaldehyd destillerer over ved omtrent 40 til 80°C under et trykk på 1 mmHg abs. Med tiden krystalliserer destil-latet og gir den dimere form av glykolaldehyd. The residue obtained from the evaporation of the aqueous phase is added to dioxane, the salts are removed by filtration and the filtrate is distilled. Glycolaldehyde distills over at about 40 to 80°C under a pressure of 1 mmHg abs. Over time, the distillate crystallizes and gives the dimeric form of glycolaldehyde.
EKSEMPEL 2 EXAMPLE 2
Fremstilling av serin fra vinylacetat via glykolaldehyd Production of serine from vinyl acetate via glycolaldehyde
En blanding av 1,72 g (20 millimol) vinylacetat, 18 ml vann, 2,80 g (22,8 g millimol) kaliumklorat, 0,10 g (0,39 millimol) osmium-tetroksyd og 2,46 g (30 millimol) vannfritt natrium-acetat (for å pufre ved pH 3,0 til 4,5 den eddiksyre som dannes under reaksjonen) omrøres i en lukket beholder ved romtemperatur i 15 minutter. Ved dette trinn gjenvinnes osmium-tetroksyd ved å ekstrahere det med benzen, tilsettes vinylacetat (0,5 g) til ekstrakten og avdampe løsningsmidlet tilsvarende det som er angitt i eksempel 1. Som et alternativ kan gjenviningen av osmium-tetroksydet gjennomføres ved å boble nitrogen gjen-nom beholderen hvori reaksjonen er fullført, idet beholderen i sitt utløp er forsynt med en felle utstyrt med et porøst dia-fragma som dypper ned i avkjølt vinylacetat (omtrent 0°C). A mixture of 1.72 g (20 mmol) vinyl acetate, 18 ml water, 2.80 g (22.8 g mmol) potassium chlorate, 0.10 g (0.39 mmol) osmium tetroxide and 2.46 g (30 millimoles) of anhydrous sodium acetate (to buffer at pH 3.0 to 4.5 the acetic acid formed during the reaction) is stirred in a closed container at room temperature for 15 minutes. In this step, the osmium tetroxide is recovered by extracting it with benzene, adding vinyl acetate (0.5 g) to the extract and evaporating the solvent corresponding to that indicated in Example 1. Alternatively, the recovery of the osmium tetroxide can be carried out by bubbling nitrogen through the container in which the reaction is completed, the container at its outlet being provided with a trap equipped with a porous diaphragm which dips into cooled vinyl acetate (approximately 0°C).
Ved å gjøre dette strippes osmium-tetroksydet av nitrogen som på grunn av at det med vinylacetat danner det ikke flyktige addukt og dette kan så anvendes for en hy fremstilling av glykolaldehyd. Den vandige løsning hvorfra osmium-tetroksyd er strippet avkjøles til 0°C, innstilles ved pH 3 med fortynnet svovelsyre og behandles i 5 minutter med 0,84 g natriumsul-fitt for å fjerne overskudd av kaliumklorat. By doing this, the osmium tetroxide is stripped of nitrogen, which due to the fact that it does not form a volatile adduct with vinyl acetate and this can then be used for a high production of glycolaldehyde. The aqueous solution from which the osmium tetroxide has been stripped is cooled to 0°C, adjusted to pH 3 with dilute sulfuric acid and treated for 5 minutes with 0.84 g of sodium sulphite to remove excess potassium chlorate.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT19167/75A IT1030968B (en) | 1975-01-10 | 1975-01-10 | PROCESS FOR THE PREPARATION OF ALPHA HYDROXYCARBONYL COMPOUNDS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO760050L NO760050L (en) | 1976-07-13 |
| NO147241B true NO147241B (en) | 1982-11-22 |
| NO147241C NO147241C (en) | 1983-03-09 |
Family
ID=11155449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO760050A NO147241C (en) | 1975-01-10 | 1976-01-08 | PROCEDURE FOR THE PREPARATION OF GLYCOLE ALDEHYDE |
Country Status (18)
| Country | Link |
|---|---|
| JP (1) | JPS60328B2 (en) |
| BE (1) | BE837431A (en) |
| CA (1) | CA1058218A (en) |
| CS (1) | CS192526B2 (en) |
| DD (1) | DD121925A5 (en) |
| DE (1) | DE2600657C3 (en) |
| DK (1) | DK7876A (en) |
| FR (1) | FR2297199A1 (en) |
| GB (1) | GB1510051A (en) |
| HU (1) | HU174633B (en) |
| IL (1) | IL48771A (en) |
| IT (1) | IT1030968B (en) |
| LU (1) | LU74143A1 (en) |
| NL (1) | NL162889C (en) |
| NO (1) | NO147241C (en) |
| SE (1) | SE427270B (en) |
| YU (1) | YU4276A (en) |
| ZA (1) | ZA7646B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02142426U (en) * | 1989-05-06 | 1990-12-03 | ||
| DE69116499T2 (en) * | 1990-10-20 | 1996-08-22 | Takasago Perfumery Co Ltd | Process for the preparation of alpha-hydroxyketones |
| JP2017043835A (en) | 2015-08-25 | 2017-03-02 | 株式会社神戸製鋼所 | Steel for machine structural use for cold-working, and production method therefor |
-
1975
- 1975-01-10 IT IT19167/75A patent/IT1030968B/en active
- 1975-12-31 IL IL48771A patent/IL48771A/en unknown
-
1976
- 1976-01-05 ZA ZA00760046A patent/ZA7646B/en unknown
- 1976-01-06 GB GB385/76A patent/GB1510051A/en not_active Expired
- 1976-01-07 CS CS76101A patent/CS192526B2/en unknown
- 1976-01-08 DD DD190736A patent/DD121925A5/xx unknown
- 1976-01-08 NO NO760050A patent/NO147241C/en unknown
- 1976-01-08 FR FR7600337A patent/FR2297199A1/en active Granted
- 1976-01-08 LU LU74143A patent/LU74143A1/xx unknown
- 1976-01-09 DE DE2600657A patent/DE2600657C3/en not_active Expired
- 1976-01-09 JP JP51001662A patent/JPS60328B2/en not_active Expired
- 1976-01-09 NL NL7600225.A patent/NL162889C/en not_active IP Right Cessation
- 1976-01-09 YU YU00042/76A patent/YU4276A/en unknown
- 1976-01-09 BE BE163402A patent/BE837431A/en not_active IP Right Cessation
- 1976-01-09 CA CA243,382A patent/CA1058218A/en not_active Expired
- 1976-01-09 SE SE7600179A patent/SE427270B/en unknown
- 1976-01-09 DK DK7876*#A patent/DK7876A/en not_active Application Discontinuation
- 1976-01-09 HU HU76SA2876A patent/HU174633B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| YU4276A (en) | 1982-02-28 |
| CS192526B2 (en) | 1979-08-31 |
| DE2600657C3 (en) | 1980-07-24 |
| HU174633B (en) | 1980-02-28 |
| SE427270B (en) | 1983-03-21 |
| LU74143A1 (en) | 1976-07-20 |
| FR2297199B1 (en) | 1980-05-30 |
| GB1510051A (en) | 1978-05-10 |
| FR2297199A1 (en) | 1976-08-06 |
| JPS5195009A (en) | 1976-08-20 |
| DE2600657A1 (en) | 1976-07-15 |
| NL162889C (en) | 1980-07-15 |
| AU1000676A (en) | 1977-07-14 |
| IL48771A0 (en) | 1976-02-29 |
| IL48771A (en) | 1979-01-31 |
| BE837431A (en) | 1976-07-09 |
| IT1030968B (en) | 1979-04-10 |
| DK7876A (en) | 1976-07-11 |
| DE2600657B2 (en) | 1979-11-22 |
| NO147241C (en) | 1983-03-09 |
| NO760050L (en) | 1976-07-13 |
| JPS60328B2 (en) | 1985-01-07 |
| NL162889B (en) | 1980-02-15 |
| CA1058218A (en) | 1979-07-10 |
| DD121925A5 (en) | 1976-09-05 |
| ZA7646B (en) | 1976-12-29 |
| NL7600225A (en) | 1976-07-13 |
| SE7600179L (en) | 1976-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6232478B1 (en) | Process for the preparation of chiral 3,4-epoxybutyric acid and the salt thereof | |
| JPS58157739A (en) | Production of 1,9-nonanedial | |
| EP0079206A1 (en) | Process for producing 5-halomethylfurfural | |
| NO147241B (en) | PROCEDURE FOR THE PREPARATION OF GLYCOLE ALDEHYDE | |
| US2456316A (en) | Method for producing alpha-ethylpiperonyl ethers | |
| JPS6024781B2 (en) | Method for producing cis-2-hydroxy-2-phenyl-r-1-cyclohexanecarboxylic acid | |
| EP0169614B1 (en) | Process for the preparation of l-carnitine | |
| KR910007807A (en) | Rhodium recovery from distillation residue after oxo synthesis | |
| SU657749A3 (en) | Method of obtaining 1,1-di-substituted octahydroindole-quinolysidines or their salts, or optically active isomers | |
| US5171867A (en) | Method of preparing 2,5-dimethyl-4-hydroxy-2h-furan-3-one | |
| JPH0140818B2 (en) | ||
| JP3103447B2 (en) | N- (2-chloropyridin-5-yl-methyl) -ethylenediamine | |
| JP3709534B2 (en) | Isolation method of oxycarboxylic acid or oxocarboxylic acid | |
| JPH0796520B2 (en) | New method for producing 1- (4-trifluoromethylphenyl) -1-propanone | |
| US3972922A (en) | Process for preparing ether tricarboxylates | |
| US4232169A (en) | Process for preparing alpha-oxo-esters | |
| JP3382681B2 (en) | Fluorine-containing compound and method for producing the same | |
| JPS61126048A (en) | Production of optically active 4-hydroxy-2-cyclopentenone | |
| US3429897A (en) | 3,6-dihydro-1,2-dioxin and its method of production | |
| JPS62108842A (en) | Production of malonic acid diester | |
| JPS6254416B2 (en) | ||
| CN117222614A (en) | Preparation method of cedrene glycol | |
| US3904649A (en) | Process for producing substituted iodolactone | |
| US3872168A (en) | Synthesis of acids and amides | |
| SU507555A1 (en) | The method of obtaining 1-chloro-3-butene-2-ol |