NO137594B - PROCEDURES FOR THE PREPARATION OF O-PHENYLPHENOL - Google Patents
PROCEDURES FOR THE PREPARATION OF O-PHENYLPHENOL Download PDFInfo
- Publication number
- NO137594B NO137594B NO102369A NO102369A NO137594B NO 137594 B NO137594 B NO 137594B NO 102369 A NO102369 A NO 102369A NO 102369 A NO102369 A NO 102369A NO 137594 B NO137594 B NO 137594B
- Authority
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- Prior art keywords
- cyclohexanone
- mol
- vanadium
- metal
- acid
- Prior art date
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- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 22
- 235000010292 orthophenyl phenol Nutrition 0.000 title claims description 14
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 82
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- AFSRWGCXJIBKFK-UHFFFAOYSA-I [V+5].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O Chemical compound [V+5].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AFSRWGCXJIBKFK-UHFFFAOYSA-I 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001639 boron compounds Chemical class 0.000 claims description 3
- KECPGEPTEDAJOE-UHFFFAOYSA-J hexadecanoate titanium(4+) Chemical compound C(CCCCCCCCCCCCCCC)(=O)[O-].[Ti+4].C(CCCCCCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCCCCCC)(=O)[O-] KECPGEPTEDAJOE-UHFFFAOYSA-J 0.000 claims description 3
- 229940049964 oleate Drugs 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- HSNVNALJRSJDHT-UHFFFAOYSA-N P(=O)(=O)[Mo] Chemical compound P(=O)(=O)[Mo] HSNVNALJRSJDHT-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 2
- 150000003657 tungsten Chemical class 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 5
- 238000010533 azeotropic distillation Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 238000001030 gas--liquid chromatography Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- UKBYYGGBPKKWEB-UHFFFAOYSA-N 2,3-di(cyclohexylidene)cyclohexan-1-one Chemical compound C1CCCCC1=C1C(=O)CCCC1=C1CCCCC1 UKBYYGGBPKKWEB-UHFFFAOYSA-N 0.000 description 1
- TYDSIOSLHQWFOU-UHFFFAOYSA-N 2-cyclohexylidenecyclohexan-1-one Chemical group O=C1CCCCC1=C1CCCCC1 TYDSIOSLHQWFOU-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000004306 orthophenyl phenol Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 titanium alkoxide Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Denne oppfinnelse angår en fremgangsmåte for fremstilling av.o-fenylfenol fra cykloheksanon. This invention relates to a process for the production of o-phenylphenol from cyclohexanone.
Det er kjent å omdanne cykloheksanon til cykloheksenyl-cykloheksanon. Tysk patent 857.960 beskriver en slik fremgangsmåte hvor en kationebytterharpiks anvendes som katalysator. US-patent 3.256.334 beskriver en dampfaseprosess for omdannelse av cykloheksanon under anvendelse av et alkalimetallfosfat som katalysator. I patentet angis også at det er velkjent å anvende mineralsyrer og alkali som katalysatorer ved fremgangsmåten. It is known to convert cyclohexanone into cyclohexenyl-cyclohexanone. German patent 857,960 describes such a method where a cation exchange resin is used as catalyst. US Patent 3,256,334 describes a vapor phase process for the conversion of 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 method.
US-patent 2.719.863 beskriver en selvkondensasjon av cykloheksanon i nærvær av relativt store mengder titanalkoksyd som katalysator. Hovedproduktet er cykloheksyliden-cykloheksanon, og dessuten dannes betydelige mengder dicykloheksyliden-cykloheksanon. US patent 2,719,863 describes a self-condensation of cyclohexanone in the presence of relatively large amounts of titanium alkoxide as catalyst. The main product is cyclohexylidene-cyclohexanone, and significant amounts of dicyclohexylidene-cyclohexanone are also formed.
Det er kjent å fremstille o-fenylfenol ved dehydrogenering av 2-(1-cykloheksenyl)-cykloheksanon. For dette formål var det nødvendig å fremstille utgangsforbindelsen 2-(1-cykloheksenyl)-cykloheksanon ved en relativt.krevende fremgangsmåte. En direkte viderebearbeidelse til o-fenylfenol var ikke mulig, da den kjente fremgangsmåte på grunn av for høyt energibehov, for dårlige ut-bytter, for lang reaksjonstid og/eller for komplisert gjennomføring av fremgangsmåten, ialt var for uøkonomisk. It is known to prepare 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 method. A direct further processing to o-phenylphenol was not possible, as the known method was altogether too uneconomic due to too high energy requirements, too poor yields, too long a reaction time and/or too complicated execution of the method.
Til grunn for foreliggende oppfinnelse ligger den oppgave The present invention is based on that task
å fremstille o-fenylfenol fra cykloheksanon på økonomisk måte. to produce o-phenylphenol from cyclohexanone economically.
Løsningen på denne oppgave består i henhold til oppfinnelsen i at cykloheksanon omsettes ved en temperatur fra 50-250°C og ved et trykk som holder reaksjonsmediet i flytende fase, i nærvær av en katalytisk mengde av et titan-, vanadium-, mangan-, kobolt-, sink-, zirkonium-, kadmium-, tinn-, molybden- eller wolframsalt av en alifatisk karboksylsyre med opptil 20 karbonatomer eller en naftensyre eller en polysyre resp. heteropolysyre av disse metaller, så som fosformolybden- eller silisiumwolframsyre, According to the invention, the solution to this task consists in cyclohexanone being reacted at a temperature of 50-250°C and at a pressure that keeps the reaction medium in liquid phase, in the presence of a catalytic amount of a titanium, vanadium, manganese, cobalt, zinc, zirconium, cadmium, tin, molybdenum or tungsten salt of an aliphatic carboxylic acid with up to 20 carbon atoms or a naphthenic acid or a polyacid resp. heteropolyacid of these metals, such as phosphomolybdenum or silicotungstic acid,
og det dannede 2- (1-cykloheksenyl)- and the formed 2-(1-cyclohexenyl)-
cykloheksanon dehydrogeneres på i og for seg kjent måte i nærvær av en edelmetallkatalysator så som platina, på trekull, kiselsyre eller aluminiumoksyd, eller nikkel og tinn, på kiselsyre. cyclohexanone is dehydrogenated in a manner known per se in the presence of a noble metal catalyst such as platinum, on charcoal, silicic acid or aluminum oxide, or nickel and tin, on silicic acid.
Fortrinnsvis finner omsetningen sted i nærvær av vanadiumstearat, titanpalmitat, vanadiumoleat eller vanadiumnaftenat som katalysator. Preferably, the reaction takes place in the presence of vanadium stearate, titanium palmitate, vanadium oleate or vanadium naphthenate as catalyst.
Hensiktsmessig er mengden av katalytisk virkende metallforbindelse opptil 0,5 mol metall pr. mol tilstedeværende cykloheksanon, fortrinnsvis opptil 0,05 mol metall pr. mol tilstede--5 -2 Suitably, the amount of catalytically active metal compound is up to 0.5 mol of metal per moles of cyclohexanone present, preferably up to 0.05 moles of metal per moles present--5 -2
værende cykloheksanon, særlig i omradet 10 - 10 mol metall pr. mol tilstedeværende cykloheksanon. being cyclohexanone, particularly in the range of 10 - 10 mol metal per moles of cyclohexanone present.
Ved fremgangsmåten ifølge oppfinnelsen anvendes som utgangsmateriale fortrinnsvis et cykloheksanon som er fremstilt ved oksydasjon av cykloheksan i nærvær av en borforbindelse og foreligger i blanding med cykloheksanon. In the method according to the invention, a cyclohexanone is preferably used as starting material, which is produced by oxidation of cyclohexane in the presence of a boron compound and is present in a mixture with cyclohexanone.
Først ved fremstilling av o-fenylfenol ved dehydrogenering av 2-(1-cykloheksenyl)-cykloheksanon fremstilt ifølge oppfinnelsen, ble det mulig å fremstille o-fenylfenol syntetisk i stor teknisk målestokk. Grunnlaget for foreliggende fremgangsmåte er at det er funnet en ny metode til å fremstille det kjemiske mellomprodukt, nemlig 2-(1-cykloheksenyl)-cykloheksanon på en lettvint måte med godt utbytte. Det var tidligere ikke mulig å fremstille den teknisk verdifulle forbindelse o-fenylfenol under anvendelse av cykloheksanon som eneste utgangsmateriale på en slik måte at man først omsetter denne forbindelse til mellomproduktet og derefter dehydro-generer dette . til o-fenylfenol. Det består derfor en generell knapphet på o-fenylfenol, særlig eftersom fenolfremstilling fra klorbenzen har mer og mer vist seg å være ulønnsom, og følgelig ble den eneste kilde til fremstilling av o-fenylfenol redusert. It was only when o-phenylphenol was produced by dehydrogenation of 2-(1-cyclohexenyl)-cyclohexanone produced according to the invention that it became possible to produce o-phenylphenol synthetically on a large technical scale. The basis for the present method is that a new method has been found to produce the chemical intermediate, namely 2-(1-cyclohexenyl)-cyclohexanone in an easy way with a good yield. It was previously not possible to produce the technically valuable compound o-phenylphenol using cyclohexanone as the only starting material in such a way that one first converts this compound into the intermediate product and then dehydrogenates it. to o-phenylphenol. There is therefore a general scarcity of o-phenylphenol, especially since the production of phenol from chlorobenzene has more and more proved to be unprofitable, and consequently the only source for the production of o-phenylphenol was reduced.
Mer enn én metallforbindelse kan anvendes ved fremgangsmåten, f.eks. kan blandinger av vanadium- og titanforbindelser benyttes, og også blandinger av forbindelser av det samme metall. More than one metal compound can be used in the method, e.g. mixtures of vanadium and titanium compounds can be used, and also mixtures of compounds of the same metal.
Særlig egnede metallforbindelser er f.eks. vanadiumstearat, titanpalmitat, vanadiumoleat og vanadiumnaftenat. Når et metall-karboksylat anvendes, er det hensiktsmessig å innføre den tilsvar-ende karboksylsyre i reaksjonsblandingen, f.eks. kan stearinsyre tilsettes når vanadiumstearat er katalysatoren. Fortrinnsvis er konsentrasjonen av karboksylsyren opptil 5% vekt/vekt. Particularly suitable metal compounds are e.g. vanadium stearate, titanium palmitate, vanadium oleate and vanadium naphthenate. When a metal carboxylate is used, it is appropriate to introduce the corresponding carboxylic acid into the reaction mixture, e.g. can stearic acid be added when vanadium stearate is the catalyst. Preferably, the concentration of the carboxylic acid is up to 5% w/w.
.Som salter av polysyrer og heteropolysyrer, kan f.eks. an- .As salts of polyacids and heteropolyacids, e.g. an-
vendes fosformolybdensyre, silisiumwolframsyre og fosforvanadium-syre. phosphormolybdic acid, silicon tungstic acid and phosphorvanadium acid are reversed.
Fremgangsmåten utføres i flytende fase under anvendelse av oppløselige metallforbindelser, og hvis det er nødvendig kan det anvendes et øket trykk, som i det minste er tilstrekkelig til å holde reaksjonsblandingen i væskefase ved arbeidstemperaturen. Anvendelse av heterogen væskefase er også 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. Application of a heterogeneous liquid phase is also possible.
- Fremgangsmåten kan hensiktsmessig utføres ved en temperatur - The method can conveniently be carried out at a temperature
i området 120 - 180°C. Kokepunktet for cykloheksanon er en egnet temperatur. in the range 120 - 180°C. The boiling point of cyclohexanone is a suitable temperature.
Omsetningen utføres fortrinnsvis under anvendelse av cykloheksanon som oppløsningsmiddel, men hvis et inert oppløsningsmiddel anvendes, er det ønskelig å holde en høy konsentrasjon av keton i reaksjonssonen. Det er også ønskelig at vann som dannes under pro-sessen, i størst mulig utstrekning fjernes straks det dannes, ettersom opphopning av vann i reaksjonsblandingen reduserer reaksjons-hastigheten. Fjernelse av det dannede vann oppnås hensiktsmessig, når dette er mulig, ved destillering av et azeotrop av ketonet og vann fra reaksjonssonen. Cykloheksanon danner azeotroper med vann, men hvis det er nødvendig, kan et inert azeotropdannende middel, f.eks. toluen, settes til reaksjonsblandingen. Spyling med inert gass kan også .anvendes for å fremme fjernelsen av vann. The reaction is preferably carried out using cyclohexanone as 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 water formed during the process is removed to the greatest extent possible as soon as it is formed, as the accumulation of water in the reaction mixture reduces the reaction rate. Removal of the water formed is conveniently achieved, when possible, by distilling an azeotrope of the ketone and water from the reaction zone. Cyclohexanone forms azeotropes with water, but if necessary, an inert azeotrope-forming agent, e.g. toluene, is added to the reaction mixture. Flushing with inert gas can also be used to promote the removal of water.
Fortrinnsvis utelukkes oksygen fra reaksjonssonen, og omsetningen utføres i en inert atmosfære såsom nitrogen eller argon for å forhindre oksydasjon av ketonet. Preferably, oxygen is excluded from the reaction zone, and the reaction is carried out in an inert atmosphere such as nitrogen or argon to prevent oxidation of the ketone.
Det dannede 2-(1-cykloheksenyl)cykloheksanon dehydrogeneres lett til ortofenylfenol. Dette produkt er nyttig som fungicid og konserveringsmiddel. The 2-(1-cyclohexenyl)cyclohexanone formed is easily dehydrogenated to orthophenylphenol. This product is useful as a fungicide and preservative.
Cykloheksanon erholdes kommersielt ved oksydasjon av cykloheksan med molekylært oksygen, ofte i nærvær av katalysatorer såsom overgangsmetall- eller borforbindelser. Produktet ved denne oksydasjon er en blanding av cykloheksanol og cykloheksanon, men ettersom cykloheksanol er tilnærmet inert ved de betingelser som anvendes ved fremgangsmåten i henhold til oppfinnelsen9 er det ikke nødvendig at den skilles fra cykloheksanonet, og cykloheksanol/ cykloheksanon-blandingen kan anvendes som utgangsmateriale for fremgangsmåten. Cyclohexanone is obtained commercially by oxidation of cyclohexane with molecular oxygen, often in the presence of catalysts such as transition metal or boron compounds. The product of this oxidation is a mixture of cyclohexanol and cyclohexanone, but as cyclohexanol is almost inert under the conditions used in the method according to the invention9, it is not necessary for it to be separated from the cyclohexanone, and the cyclohexanol/cyclohexanone mixture can be used as starting material for the procedure.
De følgende eksempler skal tjene til å illustrere fremgangsmåten ytterligere. I. Kondensasjon av cykloheksanon til 2-(1-cykloheksenyl)-cykloheksanon . The following examples shall serve to further illustrate the method. I. Condensation of cyclohexanone to 2-(1-cyclohexenyl)-cyclohexanone.
Eksempel 1- 8 Example 1-8
I hvert tilfelle ble 50 g cykloheksanon oppvarmet ved 155°C og atmosfærisk trykk i 190 minutter i fravær av luft, med In each case, 50 g of cyclohexanone were heated at 155°C and atmospheric pressure for 190 minutes in the absence of air, with
-3 -3
1,4 x 10 mol metall tilsatt som metallstearat. Vann som ble dannet ved reaksjonen, ble fjernet kontinuerlig ved azeotropisk destillasjon med cykloheksanon. Det således fjernede cykloheksanon ble ført tilbake til reaksjonsblandingen, og blandingen ble 1.4 x 10 mol metal added as metal stearate. Water formed in the reaction was removed continuously by azeotropic distillation with cyclohexanone. The cyclohexanone thus removed was returned to the reaction mixture, and the mixture became
analysert ved gass-væske-kromatografi. Produktet 2-(1-cykloheks-enyl ) cykloheksanon ble renset ved fraksjonert destillasjon. Resultatene er vist i tabellen hvor keton-omdannelsen og utbyttet av 2-(1-cykloheksenyl)cykloheksanon er uttrykt som molprosent av omsatt cykloheksanon. analyzed by gas-liquid chromatography. The product 2-(1-cyclohex-enyl)cyclohexanone was purified by fractional distillation. The results are shown in the table where the ketone conversion and the yield of 2-(1-cyclohexenyl)cyclohexanone are expressed as mole percent of converted cyclohexanone.
Eksempel 9 Example 9
-3 -3
50 g cykloheksanon inneholdende 1,4 x 10 mol vanadium i form av vanadiumstearat ble oppvarmet under tilbakeløpskjøling i fravær av luft og ved atmosfærisk trykk. Vann ble fjernet kontinuerlig fra reaksjonsblandingen ved azeotropisk destillasjon med cykloheksanon.. Reaksjonstemperaturen fikk stige ettersom konsentrasjonen av 2-(1-cykloheksenyl)cykloheksanon i reaksjonsblandingen økte. Etter 190 minutter var temperaturen 168°C, cykloheksanon-omdannelsen var 40%, og utbyttet av 2-(1-cykloheksenyl)cykloheksanon var 94%. Etter ytterligere 120 minutter hadde temperaturen steget til 193°C, og keton-omdannelsen og utbyttet av produkt var nå henholdsvis 71 og 89%. 50 g of cyclohexanone containing 1.4 x 10 mol of vanadium in the form of vanadium stearate was heated under reflux in the absence of air and at atmospheric pressure. Water was removed continuously from the reaction mixture by azeotropic distillation with cyclohexanone. The reaction temperature was allowed to rise 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 conversion and yield of product were now 71 and 89% respectively.
Eksempel lo - 12 Example lo - 12
I hvert av de følgende eksempler ble 50 g cykloheksanon. oppvarmet ved 155°C i 190 minutter ved atmosfærisk trykk i nær- In each of the following examples, 50 g of cyclohexanone. heated at 155°C for 190 minutes at atmospheric pressure in the near-
vær av katalysatoren. Vann som ble dannet under reaksjonen, ble fjernet kontinuerlig ved azeotropisk destillasjon med cykloheksanon. Det således fjernede cykloheksanon ble ført tilbake til reaksjonsblandingen. Reaksjonsproduktet ble analysert ved gass-væske-kromatografi. Produktet 2-(1-cykloheksenyl)cykloheksanon ble renset ved fraksjonert destillasjon. Resultatene er vist i den følgende tabell, hvor det molare utbyttet av 2(1-cykloheksenyl)cykloheksanon er basert på omsatt cykloheksanon. be off the catalytic converter. 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 shown in the following table, where the molar yield of 2(1-cyclohexenyl)cyclohexanone is based on converted cyclohexanone.
Eksempel 13 - 17 Examples 13 - 17
De følgende eksempler illustrerer krotoniseringen av cykloheksanon under anvendelse av katalytisk aktive mengder av forskjel-lige metall-karboksylater. The following examples illustrate the crotonization of cyclohexanone using catalytically active amounts of various metal carboxylates.
Resultatene er angitt i tabell 3. The results are shown in table 3.
I hvert tilfelle ble 50 g (0,51 mol) cykloheksanon oppvarmet ved 155°C og atmosfærisk trykk i tre timer i fravær av luft under In each case, 50 g (0.51 mol) of cyclohexanone was heated at 155°C and atmospheric pressure for three hours in the absence of air under
-3 -3
tilsetning av 1,4 x 10 mol metall (som metall-karboksylater). Vannet dannet underreaksjonen ble fjernet kontinuerlig ved azeotropisk destillasjon med cykloheksanon. Det således fjernede cykloheksanon ble ført tilbake til reaksjonsblandingen. Blandingen ble analysert I.R.-analyse og ved måling av kjernemagnetisk resonans. Resultatene er angitt i tabell 3 som molprosent-mengde av 2-(l-cykloheksenyl)-cykloheksanon tilstede i reaksjonsblandingen. Da ingen av analysemetodene kan gi absolutt nøyaktige resultater, foreligger en viss uoverenstemmelse mellom de oppnådde resultater, men når analyseresultatene betraktes sammen, viser de allikevel det vesentlige. addition of 1.4 x 10 mol metal (as metal carboxylates). The water formed in the subreaction was removed continuously by azeotropic distillation with cyclohexanone. The cyclohexanone thus removed was returned to the reaction mixture. The mixture was analyzed by I.R. analysis and by nuclear magnetic resonance measurement. The results are given in Table 3 as the mole percent amount of 2-(1-cyclohexenyl)-cyclohexanone present in the reaction mixture. As none of the analysis methods can give absolutely accurate results, there is a certain discrepancy between the results obtained, but when the analysis results are considered together, they still show the essentials.
II. Dehydrogenering av 2-(1-cykloheksenyl)cykloheksanon. II. Dehydrogenation of 2-(1-cyclohexenyl)cyclohexanone.
Eksempel 18 Example 18
Det i henhold til de foregående eksempler fremstilte 2-(l-cykloheksenyl)-cykloheksanon ble dehydrogenert ved 270°C i hydrogen-atmosfære og under anvendelse av 5 vekt% av en katalysator bestående av trekull med 5 vekt% påført platina. Herved reagerte alt 2-(l-cykloheksenyl)-cykloheksanon og ga et utbytte av o-fenylfenol i størrelsesorden 85%. The 2-(1-cyclohexenyl)-cyclohexanone prepared according to the previous examples was dehydrogenated at 270°C in a hydrogen atmosphere and using 5% by weight of a catalyst consisting of charcoal with 5% by weight applied to platinum. Hereby, all 2-(1-cyclohexenyl)-cyclohexanone reacted and gave a yield of o-phenylphenol in the order of 85%.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO760604A NO137595C (en) | 1968-03-15 | 1976-02-23 | PROCEDURE FOR PREPARATION OF 2 - (- 1-CYCLOHEXENYL) -CYCLOHEXANONE |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1264668 | 1968-03-15 | ||
| GB5108668A GB1249473A (en) | 1968-03-15 | 1968-03-15 | Process for the production of unsaturated ketones and phenols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NO137594B true NO137594B (en) | 1977-12-12 |
| NO137594C NO137594C (en) | 1978-03-21 |
Family
ID=26249166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO102369A NO137594C (en) | 1968-03-15 | 1969-03-12 | PROCEDURE 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 |
| DK142574B (en) | 1980-11-24 |
| 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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