DK142574B - Process for the preparation of o-phenylphenol. - Google Patents
Process for the preparation of o-phenylphenol. Download PDFInfo
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- DK142574B DK142574B DK141169A DK141169A DK142574B DK 142574 B DK142574 B DK 142574B DK 141169 A DK141169 A DK 141169A DK 141169 A DK141169 A DK 141169A DK 142574 B DK142574 B DK 142574B
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- cyclohexanone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
- C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
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- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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Description
14257Λ14257Λ
Den foreliggende opfindelse angår en fremgangsmåde til fremstilling af o-phenylphenol ud fra cyklohexanon.The present invention relates to a process for preparing o-phenylphenol from cyclohexanone.
Det er kendt at omdanne cyklohexanon til cyklohexenyl-cyklo= hexanon. I DE patentskrift 857.960 beskrives en sådan fremgangsmåde, hvor en kationbytterharpiks anvendes som katalysator. I US patentskrift 3.256.334 beskrives en dampfase-proces til omdannelse af cyklohexanon under anvendelse af et alkalimetalphosphat som katalysator. I patentskriftet angives også, at det er velkendt at anvende mineralsyrer og alkali som katalysatorer ved fremgangsmåden.It is known to convert cyclohexanone to cyclohexenyl-cyclo = hexanone. DE patent specification 857,960 discloses such a process in which a cation exchange resin is used as a catalyst. U.S. Patent 3,256,334 discloses a vapor phase process for converting cyclohexanone using an alkali metal phosphate as a catalyst. The patent also states that it is well known to use mineral acids and alkali as catalysts in the process.
I DS patentskrift 2.719.863 beskrives en selvkondensation af cyklohexanon i nærværelse af forholdsvis store mængder titanalkoxid som katalysator. Hovedproduktet er cyklohexyliden-cykiohexanon og desuden dannes betydelige mængder dicyklohexyliden-cyklo= hexanon.DS patent 2,719,863 describes a self-condensation of cyclohexanone in the presence of relatively large amounts of titanium alkoxide as a catalyst. The main product is cyclohexylidene-cyciohexanone and, in addition, significant amounts of dicyclohexylidene-cyclo = hexanone are formed.
Det er kendt at fremstille o-phenylphenol ved dehydrogenering af 2-(1-cyklohexenyl)-cyklohexanon. Til dette formål var det nødvendigt at fremstille udgangsforbindelsen 2-(1-cyklohexenyl)-cyklohexanon ved en relativt krævende fremgangsmåde. En direkte videreforarbejdning til o-phenylphenol var ikke mulig, da den kendte fremgangsmåde på grund af et for højt energibehov, for dårlige udbytter, for lang reaktionstid og/eller for kompliceret gennemførelse af fremgangsmåden alt i alt var for uøkonomisk.It is known to produce o-phenylphenol by dehydrogenation of 2- (1-cyclohexenyl) -cyclohexanone. For this purpose, it was necessary to prepare the starting compound 2- (1-cyclohexenyl) -cyclohexanone by a relatively demanding process. Direct processing for o-phenylphenol was not possible as the known process due to an excessive energy demand, poor yields, too long reaction time and / or too complicated execution of the process was all too uneconomical.
Basis for den foreliggende opfindelse har været ønsket om at tilvejebringe en fremgangsmåde til fremstilling af o-phenyl= phenol ud fra det let tilgængelige udgangsmateriale cyklohexa= non på økonomisk måde.The basis of the present invention has been the desire to provide a process for preparing o-phenyl = phenol from the readily available starting material cyclohexa = non economically.
Løsningen på denne opgave består i henhold til opfindelsen i, at cyklohexanon selvkondenseres ved en temperatur på 50-250°C Og ved et tryk, som holder reaktionsmediet i den flydende fase, i 142574 2 i nærværelse af en katalytisk virksom mængde af et titan-, vanadium-, mangan-, kobolt-, zink-, zirkonium-, kadmium-, tin-, molybdæn- eller wolframsalt af en alifatisk carboxylsyre med indtil 20 carbonatomer eller af en naphtensyre eller 5 en pbiysyre henholdsvis heteropolysyre af disse metaller, såsom phosphormolybdæn- eller siliciumwolframsyre,og det dannede 2-(l-cyklohexenyl}-cyklohexanon derefter dehydrogeneres på i og for sig kendt måde i nærværelse af en ædelmetalkatalysator, såsom platin anbragt på trækul, siliciumdioxid eller alumi-10 niumoxid eller nikkel og tin anbragt på siliciumdioxid.According to the invention, the solution to this task is to self-condense cyclohexanone at a temperature of 50-250 ° C and at a pressure which keeps the reaction medium in the liquid phase, in the presence of a catalytically effective amount of a titanium. , vanadium, manganese, cobalt, zinc, zirconium, cadmium, tin, molybdenum or tungsten salt of an aliphatic carboxylic acid of up to 20 carbon atoms or of a naphthenic acid or a pybic acid or heteropoly acid respectively of these metals, such as phosphorus molybdenum - or silicon tungsten acid, and the resulting 2- (1-cyclohexenyl} -cyclohexanone is then dehydrogenated in a manner known per se in the presence of a precious metal catalyst such as platinum applied to charcoal, silica or alumina or nickel and tin applied to silica .
Omsætningen af cyklohexanonen gennemføres fortrinsvis i nærværelse af vanadiumstearat, titanpalmitat, vanadiumoleat eller vanadiumnaphtenat som katalysator.The reaction of the cyclohexanone is preferably carried out in the presence of vanadium stearate, titanium palmitate, vanadium oleate or vanadium naphtenate as catalyst.
Mængden af katalytisk virkende metalforbindelse er hcnsigts-15 mæssigt indtil 0,5 mol metal pr. mol tilstedeværende cyklohexanon, fortrinsvis indtil 0,05 mol metal pr. mol tilstede- -5 -2 værende cyklohexanon, specielt i intervallet 10 - 10 mol metal pr. mol tilstedeværende cyklohexanon.The amount of catalytically active metal compound is in the range of up to 0.5 moles of metal per liter. cyclohexanone present, preferably up to 0.05 moles of metal per mole. cyclohexanone present, especially in the range of 10 to 10 moles of metal per mole. mole of cyclohexanone present.
Ved fremgangsmåden ifølge opfindelsen anvendes som udgangs-2Q materiale fortrinsvis cyklohexanon, der foreligger i blanding med cyklohexanol. Idgangsmaterialet er fortrinsvis fremstillet ved oxidation af cyklohexan i nærværelse af en borforbindelse.In the process of the invention, as starting material, preferably cyclohexanone which is in admixture with cyclohexanol is used. The starting material is preferably made by oxidation of cyclohexane in the presence of a boron compound.
Først ved fremstilling af o-phenylphenyl ved dehydrogenering 25 af 2-(i-cyklohexenyl)-cyklohexanon fremstillet ifølge opfindelsen blev det muligt at fremstille o-phenylphenol syntetisk i stor teknisk målestok. Grundlaget for den foreliggende fremgangsmåde er, at der er tilvejebragt en hidtil ukendt fremgangsmåde til at fremstille et kemisk mellemprodukt, nemlig 30 2-(1-cyklohexenyl)-cyklohexanon på en let tilgængelig måde med godt udbytte. Det var ikke tidligere muligt at fremstille den teknisk værdifulde forbindelse o-phenylphenol under anvendelse af cyklohexanon som eneste udgangsmateriale på en 3 142574 sådan måde, at man først omsætter denne forbindelse til mellemproduktet og derefter dehydrogenerer dette til o-phenyl^ phenol. Der er derfor et generelt underskud af o-phenylphenol, specielt efter at phenolfremstillingen ud fra chlorbenzen 5 mere og mere har vist sig at være uøkonomisk,og følgelig blev den eneste kilde til fremstilling af o-phenylphenol reduceret.Only by preparing o-phenylphenyl by dehydrogenation of 2- (i-cyclohexenyl) -cyclohexanone prepared according to the invention did it become possible to synthesize o-phenylphenol synthetically on a large technical scale. The basis of the present process is that there is provided a novel method for preparing a chemical intermediate, namely 2- (1-cyclohexenyl) -cyclohexanone in an easily accessible manner with good yield. It was not previously possible to prepare the technically valuable compound o-phenylphenol using cyclohexanone as the sole starting material in such a way as to first react this compound to the intermediate and then dehydrogenate it to o-phenylphenol. Therefore, there is a general deficit of o-phenylphenol, especially after the phenol production from chlorobenzene 5 has proven increasingly uneconomical, and consequently the only source of o-phenylphenol production was reduced.
Mere end en metalforbindelse kan anvandes ved fremgangsmåden, f.eks. kan blandinger af vanadium- og titanforbindelser benyttes og også blandinger af forbindelser af det samme metal.More than one metal compound can be used in the process, e.g. For example, mixtures of vanadium and titanium compounds can be used and also mixtures of compounds of the same metal.
10 Særligt egnede metalforbindelser er f.eks. vanadiumstearat, titanpalmitat, vanadiumoleat og vanadiumnaphtenat. Når der anvendes et metalcarboxylat,er det hensigtsmæssigt at indføre den tilsvarende carboxylsyre i reaktionsblandingen, f.eks. kan stearinsyre tilsættes, når vanadiumstearat er katalysatoren, 15 Koncentrationen af carboxylsyren er fortrinvis indtil 5 % vægt/ vægt.Particularly suitable metal compounds are e.g. vanadium stearate, titanium palmitate, vanadium oleate and vanadium naphtenate. When a metal carboxylate is used, it is convenient to introduce the corresponding carboxylic acid into the reaction mixture, e.g. For example, stearic acid may be added when vanadium stearate is the catalyst. The concentration of the carboxylic acid is preferably up to 5% w / w.
Som salte af polysyrer oq heteropolysyrer kan f.eks. anvendes phosphormolybdænsyre, siliciumwolframsyre og phosphorvanadium= syre.As salts of polyacids and heteropoly acids, e.g. phosphorus molybdic acid, silicon tungsten acid and phosphorus vanadium = acid are used.
20 Fremgangsmåden udføres i flydende fase under anvendelse af opløselige metalforbindelser, og hvis det er nødvendigt, kan der anvendes et forøget tryk, som i det mindste er tilstrækkeligt til at holde reaktionsblandingen i væskefase ved ar-bejdstemperaturen. Anvendelsen af heterogen væskefase er også 25 mulig.The process is carried out in liquid phase using soluble metal compounds and, if necessary, an increased pressure can be used which is at least sufficient to keep the reaction mixture in liquid phase at the working temperature. The use of heterogeneous liquid phase is also possible.
Fremgangsmåden kan hensigtsmæssigt udføres ved en temperatur i intervallet 120-180°C. Cyklohexanons kogepunkt er en egnet temperatur.The process may conveniently be carried out at a temperature in the range of 120-180 ° C. The boiling point of cyclohexanone is a suitable temperature.
Omsætningen udføres fortrinsvis under anvendelse af cyklo= hexanon som opløsningsmiddel, men hvis der anvendes et inaktivt opløsningsmiddel, er det ønskeligt at holde en høj 4 U2574 koncentration af keton i reaktionszonen. Det er også ønskeligt, at det under processen dannede vand i størst mulig udstrækning fjernes straks, når det dannes, da en ophobning af vand i reaktionsblandingen reducerer reaktionshastigheden, 5 Fjernelse af det dannede vand onnås hensigtsmæssigt, når det·*· te er, muligt ved destillation af en azeotrop af ketonen og vand fra reaktionen. Cyklohexanon danner azeotroper med vand, men hvis det er nødvendigt, kan der til reaktionsblandingen sættes et inaktivt azeotropdannende middel, f.eks. toluen.The reaction is preferably carried out using cyclohexanone as the solvent, but if an inert solvent is used, it is desirable to maintain a high concentration of ketone in the reaction zone. It is also desirable that the water formed during the process be removed as soon as possible when it is formed, as an accumulation of water in the reaction mixture reduces the reaction rate. Appropriate removal of the formed water when it is possible is possible. by distillation of an azeotrope of the ketone and water from the reaction. Cyclohexanone forms azeotropes with water, but if necessary, an inert azeotroping agent may be added to the reaction mixture, e.g. toluene.
10 Spuling med inaktiv gas kan også anvendes for at fremme fjernelsen af vand.Inert gas flushing can also be used to promote water removal.
Det foretrækkes, at oxygen udelukkes fra reaktionen, og at omsætningen udføres i en inaktiv atmosfære, såsom nitrogen eller argon, for at forhindre oxidation af ketonen.It is preferred that oxygen be excluded from the reaction and that the reaction be carried out in an inert atmosphere, such as nitrogen or argon, to prevent oxidation of the ketone.
15 Den dannede 2-(1-cyklohexenyl)-cyklohexanon dehydrogeneres let til orthophenylphenol. Dette produkt er nyttigt som fungicid og konserveringsmiddel.The resulting 2- (1-cyclohexenyl) -cyclohexanone is readily dehydrogenated to orthophenylphenol. This product is useful as a fungicide and preservative.
Cyklohexanon fås kommercielt ved oxidation af cyklohexan med molekylært oxygen ofte i nærværelse af katalysatorer, såsom 20 overgangsmetal- eller borforbindelser. Produktet ved denne oxidation er en blanding af cyklohexanol og cyklohexanon, men da cyklohexanol er i alt væsentlig inaktiv ved de betingelser, som anvendes ved fremgangsmåden ifølge opfindelsen, er det ikke nødvendigt, at den skilles fra cyklohexanonen,og cyklo= 25 hexanol/cyklohexanon-blandingen kan anvendes som udgangsmateriale for fremgangsmåden. De følgende eksempler tjener til yderligere belysning af fremgangsmåden ifølge opfindelsen.Cyclohexanone is commercially obtained by oxidation of cyclohexane with molecular oxygen often in the presence of catalysts such as 20 transition metal or boron compounds. The product of this oxidation is a mixture of cyclohexanol and cyclohexanone, but since cyclohexanol is substantially inactive under the conditions used in the process of the invention, it is not necessary to separate it from the cyclohexanone and cyclo = 25 hexanol / cyclohexanone. the mixture can be used as starting material for the process. The following examples serve to further elucidate the process of the invention.
I, Kondensation af cyklohexanon til 2-(1-cyklohexenyl)-cyklo= hexanqn.I, Condensation of cyclohexanone to 2- (1-cyclohexenyl) -cyclo = hexane.
3Q Eksempel 1-8 I hvert tilfælde blev 5Q g cyklohexanon opvarmet til 155°C og 14257Λ 5 atmosfærisk tryk i 190 min uden nærværelse af luft med 1,4 x — •3 10 mol metal tilsat som metalstearat. Det ved reaktionen dannede vand blev fjernet kontinuerligt ved azeotropisk destillation med cyklohexanon. Det således fjernede cyklohexanon 5 blev ført tilbage til reaktionsblandingen, og blandingen blev analyseret ved gas-væskekromatografi. Produktet,2-(l-cyklo= hexenyl)-cyklohexanon, blev renset ved fraktioneret destillation. Resultatet er vist i tabellen, hvor ketonomdannelsen og udbyttet af 2-(1-cyklohexenyl)-cyklohexanon er udtrykt som 10 mol% af omsat cyklohexanon.Examples 1-8 In each case, 5Q g of cyclohexanone were heated to 155 ° C and atmospheric pressure for 190 minutes without the presence of air with 1.4 x - 3 mol of metal added as metal stearate. The reaction water was removed continuously by azeotropic distillation with cyclohexanone. The cyclohexanone 5 thus removed was returned to the reaction mixture and the mixture was analyzed by gas-liquid chromatography. The product, 2- (1-cyclo = hexenyl) -cyclohexanone, was purified by fractional distillation. The result is shown in the table where the ketone formation and the yield of 2- (1-cyclohexenyl) -cyclohexanone are expressed as 10 mole% of cyclohexanone reacted.
TABEL ITABLE I
Eksempel Anvendt metal Keton- Udbytte af 2-(l-cyklo= (som stearat) omdannelse hexenyl)-cyklohexanon % % 15 1 Vanadium 11 94 2 Mangan 11 94 3 Kobolt 11 90 4 Zirkonium 8 82 5 Zink 9 75 20 6 Kadmium 11 70 7 Tin 9 81 8 Titan 34 92Example Used Metal Ketone - Yield of 2- (1-cyclo = (as stearate) conversion hexenyl) -cyclohexanone%% 15 1 Vanadium 11 94 2 Manganese 11 94 3 Cobalt 11 90 4 Zirconium 8 82 5 Zinc 9 75 20 6 Cadmium 11 70 7 Tin 9 81 8 Titan 34 92
Eksempel 9 50 g cyklohexanon indeholdende 1,4 x 10 mol vanadium i form 20 af vanadiumstearat blev opvarmet under tilbagesvaling uden nærværelse af luft og ved atmosfærisk tryk. Vand blev fjernet kontinuerligt fra reaktionsblandingen ved azeotropisk destillation med cyklohexanon. Reaktionstemperaturen steg,efterhånden som koncentrationen af 2-(1-cyklohexenyl)-cyklohexanon i 25 reaktionsblandingen voksede. Efter 190 min var temperaturen 168°C, cyklohexanon omdannelsen var 40%,og udbyttet af 2-(l- 142574 6 cyklohexenyl) -cyklohexanon var 94%. Efter yderligere 120 min.'s forløb var temperaturen steget til 193°C, og ketonomdannelsen og produktudbyttet var nu henholdsvis 71 og 89 %.Example 9 50 g of cyclohexanone containing 1.4 x 10 mol of vanadium in the form of vanadium stearate 20 was heated at reflux without the presence of air and at atmospheric pressure. Water was continuously removed from the reaction mixture by azeotropic distillation with cyclohexanone. The reaction temperature increased as the concentration of 2- (1-cyclohexenyl) -cyclohexanone in the reaction mixture increased. After 190 minutes, the temperature was 168 ° C, the cyclohexanone conversion was 40%, and the yield of 2- (1- (cyclohexenyl) -cyclohexanone) was 94%. After a further 120 minutes, the temperature had risen to 193 ° C and the ketone formation and product yield were now 71 and 89% respectively.
Eksemplerne 10-12 5 i hvert af de følgende eksempler blev 50 g cyklohexanon opvarmet til 155°C i 190 min ved atmosfærisk tryk i nærværelse af katalysatoren. Det under reaktionen dannede vand blev fjernet kontinuerligt ved azeotropisk destillation med cyklohexanon. Den således fjernede cyklohexanon blev ledt tilbage til reak-10 tionsblandingen. Reaktionsproduktet blev analyseret ved gas-væske-kromatografi. Produktet 2-(1-cyklohexenyl)-cyklohexanon blev renset ved fraktioneret destillation. Resultaterne er anført i den efterfølgende tabel, hvor det molære udbytte af 2-(1-cyklohexenylj-cyklohexanon er baseret på omsat cyklo= 15 hexanon.Examples 10-12 In each of the following examples, 50 g of cyclohexanone was heated to 155 ° C for 190 minutes at atmospheric pressure in the presence of the catalyst. The water formed during the reaction was removed continuously by azeotropic distillation with cyclohexanone. The cyclohexanone thus removed was returned to the reaction mixture. The reaction product was analyzed by gas-liquid chromatography. The product 2- (1-cyclohexenyl) -cyclohexanone was purified by fractional distillation. The results are set out in the following table, where the molar yield of 2- (1-cyclohexenyl) -cyclohexanone is based on cyclo = 15 hexanone reacted.
TABEL 2TABLE 2
Eksempel Kataly- 'lol kata- Ketonomdan- Molært udbytte nr. sator lysator pr. nelse af 2-(l-cyklo= 5Q g cyklo= hexenyl)-cyklo= 20. hexanon % hexanon (som metal) % 10 MoNAP 14,5 x 10~4 11 58 11 P.M.A, 15,5 x 1Q“4 28 77 12 S.W.A. 16,1 x 10 4 70 51 ^5 hvor MoNAP er molybdænnaphtenat P.M.A. er phosphormolybdænsyre S.W.A. er siliciumwolframsyre.Example Catalyst-lol Catalyst-Ketonomdan-Molar yield No. sator lysator pr. 2- (1-cyclo = 5Qg cyclo = hexenyl) -cyclo = 20. hexanone% hexanone (as metal)% 10 MoNAP 14.5 x 10 ~ 4 11 58 11 PMA, 15.5 x 1Q 77 12 SWA 16.1 x 10 4 70 51 ^ 5 where MoNAP is molybdenum naphtenate P.M.A. is phosphorus molybdic acid S.W.A. is silicon tungsten acid.
Eksempel 13-16Examples 13-16
De følgende eksempler belyser krotoniseringen af cyklohexanon 30 under anvendelse af katalytisk aktive mængder af forskellige 7 142574 metalcarboxylater.The following examples illustrate the crotonization of cyclohexanone 30 using catalytically active amounts of various metal carboxylates.
Resultaterne cr angivet i tabel 3.The results are given in Table 3.
I hvert tilfælde blev 50 g (0,51 mol) cyklohexanon opvarmet til 155°C og under atmosfærisk tryk i 3 timer uden nærværelse 5 af luft under tilsætning af 1,4 x 10 mol metal (som metalcarboxylater) . Det under reaktionen dannede vand blev fjernet kontinuerligt ved azeotropisk destillation med cyklohexanon.In each case, 50 g (0.51 mole) of cyclohexanone was heated to 155 ° C and under atmospheric pressure for 3 hours without the presence of 5 with the addition of 1.4 x 10 moles of metal (as metal carboxylates). The water formed during the reaction was removed continuously by azeotropic distillation with cyclohexanone.
Den således fjernede cyklohexanon blev ført tilbage til reaktionsblandingen. Blandingen blev analyseret ved infrarød 10 analyse og ved måling af kernemagnetisk resonans. Resultaterne er angivet i tabel 3 som mol% mængde af 2-{l-cyklo= hexenyl)-cyklohexanon, der er til stede i reaktionsblandingen, Da ingen af analysemetoderne kan give absolut nøjagtige resulater,foreligger der en vis uoverensstemmelse mellem de 15 opnåede resultater, men når analyseresultaterne betragtes sammen, viser de alligevel det væsentlige.The cyclohexanone thus removed was returned to the reaction mixture. The mixture was analyzed by infrared analysis and by nuclear magnetic resonance measurement. The results are given in Table 3 as mole% amount of 2- (1-cyclo = hexenyl) -cyclohexanone present in the reaction mixture. As none of the assay methods can give absolutely accurate results, there is some discrepancy between the 15 results obtained. , but when the analysis results are considered together, they still show the essentials.
TABEL 3TABLE 3
Eksempel Anvendt metal- Mol % bestemt ved nr. forbindelse Infrarød Måling af kerne- 20 analyse' magnetisk resonans 13 Kolboltvalerat 35 21 14 Koboltkapronat 50 26 15 Koboltheptanoat 11 12 25 16 Koboltnonanoat 29 24 II. Dehydrogenering af 2-(1-cyklohexenyl)-cyklohexanon.Example Used Metal Mole% Determined by No. Compound Infrared Measurement of Nuclear Analysis Magnetic Resonance 13 Coal Bolt Valerate 35 21 14 Cobalt Capronate 50 26 15 Cobalt Heptanoate 11 12 25 16 Cobalt Nonanoate 29 24 II. Dehydrogenation of 2- (1-cyclohexenyl) -cyclohexanone.
Eksempel 17Example 17
Det i henhold til de foregående eksempler fremstillede 2-(l-cyklohexenyl)-cyklohexanon blev dehydrogeneret ved 270°C iThe 2- (1-cyclohexenyl) -cyclohexanone prepared according to the preceding examples was dehydrogenated at 270 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK98477A DK98477A (en) | 1968-03-15 | 1977-03-07 | PROCEDURE FOR MAKING 2- (1-CYCLOHEXENYL) -CYCLOHEXANONE |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1264668 | 1968-03-15 | ||
| GB1264668 | 1968-03-15 | ||
| GB5108668A GB1249473A (en) | 1968-03-15 | 1968-03-15 | Process for the production of unsaturated ketones and phenols |
| GB5108668 | 1968-10-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DK142574B true DK142574B (en) | 1980-11-24 |
| DK142574C DK142574C (en) | 1981-07-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK141169A DK142574B (en) | 1968-03-15 | 1969-03-14 | Process for the preparation of o-phenylphenol. |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS506475B1 (en) |
| CH (1) | CH524557A (en) |
| DK (1) | DK142574B (en) |
| FI (1) | FI53570C (en) |
| FR (1) | FR2004026A1 (en) |
| NL (1) | NL153849B (en) |
| NO (1) | NO137594C (en) |
| SE (2) | SE406318B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5033053B1 (en) * | 1971-03-11 | 1975-10-27 | ||
| JPS5124503B2 (en) * | 1972-08-05 | 1976-07-24 |
-
1969
- 1969-03-12 NO NO102369A patent/NO137594C/en unknown
- 1969-03-14 SE SE357969A patent/SE406318B/en unknown
- 1969-03-14 FR FR6907396A patent/FR2004026A1/en not_active Withdrawn
- 1969-03-14 FI FI75669A patent/FI53570C/en active
- 1969-03-14 DK DK141169A patent/DK142574B/en unknown
- 1969-03-14 NL NL6903975A patent/NL153849B/en not_active IP Right Cessation
- 1969-03-15 JP JP1948769A patent/JPS506475B1/ja active Pending
- 1969-03-17 CH CH396669A patent/CH524557A/en not_active IP Right Cessation
-
1974
- 1974-01-16 SE SE7400549A patent/SE419638B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2004026A1 (en) | 1969-11-14 |
| FI53570C (en) | 1978-06-12 |
| SE419638B (en) | 1981-08-17 |
| DK142574C (en) | 1981-07-20 |
| NO137594C (en) | 1978-03-21 |
| NL6903975A (en) | 1969-09-17 |
| DE1966776B2 (en) | 1976-05-06 |
| NL153849B (en) | 1977-07-15 |
| NO137594B (en) | 1977-12-12 |
| DE1966776A1 (en) | 1974-07-25 |
| DE1913182A1 (en) | 1969-10-02 |
| SE406318B (en) | 1979-02-05 |
| DE1913182B2 (en) | 1975-06-26 |
| FI53570B (en) | 1978-02-28 |
| CH524557A (en) | 1972-06-30 |
| JPS506475B1 (en) | 1975-03-14 |
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