AT363455B - METHOD FOR PRODUCING NEW 3- (2-HYDROXY-4-ALKOXY OR -PHENALKOXYPHENYL) -CYCLOHEXANONES - Google Patents
METHOD FOR PRODUCING NEW 3- (2-HYDROXY-4-ALKOXY OR -PHENALKOXYPHENYL) -CYCLOHEXANONESInfo
- Publication number
- AT363455B AT363455B AT196080A AT196080A AT363455B AT 363455 B AT363455 B AT 363455B AT 196080 A AT196080 A AT 196080A AT 196080 A AT196080 A AT 196080A AT 363455 B AT363455 B AT 363455B
- Authority
- AT
- Austria
- Prior art keywords
- sep
- cyclohexanone
- hydroxy
- ketal
- carbon atoms
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title 1
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 5
- HJIQNULRLPDBIJ-UHFFFAOYSA-N 3-(2,4-dihydroxyphenyl)cyclohexan-1-one Chemical compound OC1=CC(O)=CC=C1C1CC(=O)CCC1 HJIQNULRLPDBIJ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002168 alkylating agent Substances 0.000 claims description 3
- 229940100198 alkylating agent Drugs 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000005905 mesyloxy group Chemical group 0.000 claims description 2
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 2
- 125000005424 tosyloxy group Chemical group S(=O)(=O)(C1=CC=C(C)C=C1)O* 0.000 claims description 2
- 230000002152 alkylating effect Effects 0.000 claims 1
- 238000005907 ketalization reaction Methods 0.000 claims 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- -1 tranquillizers Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- VUEQAXHGKCKXFV-UHFFFAOYSA-N 4-phenylbutyl methanesulfonate Chemical compound CS(=O)(=O)OCCCCC1=CC=CC=C1 VUEQAXHGKCKXFV-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 241000124008 Mammalia Species 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 210000003169 central nervous system Anatomy 0.000 description 2
- 239000012259 ether extract Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KPRQAVMDNFOHNY-UHFFFAOYSA-N 2-methyloctane-1-sulfonic acid Chemical compound CCCCCCC(C)CS(O)(=O)=O KPRQAVMDNFOHNY-UHFFFAOYSA-N 0.000 description 1
- SUOZHKRSCOMOSI-UHFFFAOYSA-N 3-[2-hydroxy-4-(4-phenylbutoxy)phenyl]cyclohexan-1-one Chemical compound C=1C=C(C2CC(=O)CCC2)C(O)=CC=1OCCCCC1=CC=CC=C1 SUOZHKRSCOMOSI-UHFFFAOYSA-N 0.000 description 1
- 241000605281 Anaplasma phagocytophilum Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical class CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229940035676 analgesics Drugs 0.000 description 1
- 239000000730 antalgic agent Substances 0.000 description 1
- 229940125681 anticonvulsant agent Drugs 0.000 description 1
- 239000001961 anticonvulsive agent Substances 0.000 description 1
- 229940125714 antidiarrheal agent Drugs 0.000 description 1
- 239000003793 antidiarrheal agent Substances 0.000 description 1
- 239000002249 anxiolytic agent Substances 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000002243 cyclohexanonyl group Chemical class *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 1
- 239000002934 diuretic Substances 0.000 description 1
- 229940030606 diuretics Drugs 0.000 description 1
- DLLJVQNYBYOKGS-UHFFFAOYSA-N ethoxyethane;pentane Chemical compound CCCCC.CCOCC DLLJVQNYBYOKGS-UHFFFAOYSA-N 0.000 description 1
- ZFLRDIUZHADLSV-UHFFFAOYSA-N heptan-2-yl methanesulfonate Chemical compound CCCCCC(C)OS(C)(=O)=O ZFLRDIUZHADLSV-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- QKPWQFFVHCWCHM-UHFFFAOYSA-N nonan-2-yl methanesulfonate Chemical compound CCCCCCCC(C)OS(C)(=O)=O QKPWQFFVHCWCHM-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229940125723 sedative agent Drugs 0.000 description 1
- 239000000932 sedative agent Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
<Desc/Clms Page number 1>
Die Erfindung betrifft ein Verfahren zur Herstellung von neuen 3- (2-Hydroxy-4-alkoxy oder -phenalkoxyphenyl)-cyclohexanonen. Die erfindungsgemäss herstellbaren Verbindungen sind als ZNS-Mittel brauchbar, d. h. auf das Zentralnervensystem wirkende Mittel, insbesondere als Analgetika, Tranquillizer, Sedativa und Mittel gegen Angstzustände bei Säugetieren und bei Menschen und/oder als anticonvulsiv wirkende Mittel, als Diuretica und als Antidiarrhoemittel bei Säugetieren und bei Menschen.
EMI1.1
EMI1.2
worin R eine Phenylalkylgruppe mit 4 bis 9 C-Atomen im Alkylteil oder eine Alkylgruppe mit 7 bis 9 C-Atomen bedeutet, welches dadurch gekennzeichnet ist, dass man 3- (2, 4-Dihydroxyphenyl)cyclohexanon mit einem Alkohol mit 1 bis 4 Kohlenstoffatomen ketalisiert und dieses Ketal mit einem Alkylierungsmittel der allgemeinen Formel Y-R, (II) worin R obige Bedeutung hat und Y für Chlor, Brom, Mesyloxy oder Tosyloxy steht, in Gegenwart eines Säureakzeptors selektiv alkyliert und anschliessend das Ketal in das Cyclohexanon (I) umwandelt.
Das erfindungsgemässe Verfahren ist eine vorteilhafte Arbeitsweise, welche eine selektive Al-
EMI1.3
einem Alkohol von 1 bis 4 Kohlenstoffatomen, in Anwesenheit einer Säure wie Schwefelsäure, p-Toluolsulfonsäure, Chlorwasserstoff, u. zw. unter Bedingungen, welche das Nebenprodukt Wasser entfernen. Eine vorteilhafte Arbeitsweise umfasst die Reaktion des 3- (2, 4-Dihydroxyphenyl)-cyclo- hexanons mit einem Orthoameisensäureester in Lösung in einem Alkohol, welcher der Alkoholeinheit des Orthoameisensäureesters entspricht. Trimethylorthoformiat und Methanol sind begünstigte Reaktionsteilnehmer zusammen mit konzentrierter Schwefelsäure, wasserfreiem Chlorwasserstoff oder Ammoniumchlorid als Katalysator.
Das auf diese Weise hergestellte Ketal wird dann durch Reaktion mit einem geeigneten Alkylierungsmittel wie Y-R, worin R die zuvor angegebenen Bedeutungen besitzt und Y ein Chlor-, Bromatom, Mesyloxyrest (eH. -SO. -0) oder Tosyloxyrest (p-CH-CeH-SO-O-) ist, in Anwesenheit eines Säureakzeptors, z. B. von Natrium- oder Kaliumcarbonat, alkyliert. Das alkylierte Ketal wird dann nach an sich bekannten Arbeitsweisen durch Behandlung mit wässeriger Säure deketalisiert.
Beispiel 1 : 3- (2, 4-Dihydroxyphenyl) -cyclohexanon-methylketal :
Zu einer auf 0 C gehaltenen Lösung von 7, 0 g = 33, 0 mMol 3- (2, 4-Dihydroxyphenyl)-cyclo- hexanon in 100 ml Methanol und 15 ml Trimethylorthoformiat wurden 10 Tropfen konzentrierte Schwefelsäure gegeben. Das Reaktionsgemisch wurde dann 3 h ohne Kühlung gerührt, dann wurde die Temperatur auf Zimmertemperatur ansteigen gelassen, die Reaktion wurde dann durch Zugabe von überschüssigem, festem Natriumbicarbonat abgestoppt. Das Reaktionsgemisch wurde dann unter vermindertem Druck eingedampft, und der Rückstand wurde in 200 ml Wasser-250 ml Äther aufgelöst.
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Der Ätherextrakt wurde einmal mit 150 ml gesättigter Natriumbicarbonatlösung gewaschen, über Magnesiumsulfat getrocknet und eingedampft.
Der ölartige Rückstand wurde aus Äther-Pentan kri- stallisiert, wobei 5, 74 g (77%) der Titelverbindung mit Fp. 129 bis 130 C erhalten wurden.
IR-Spektrum : (KBr) 3289,1629, 1613 und 1597 cm-' MS : 220 (M ), 205, 203,188, 177,161 und 136
Analyse auf C, H O, :
EMI2.1
<tb>
<tb> berechnet <SEP> : <SEP> C <SEP> = <SEP> 70, <SEP> 89 <SEP> H <SEP> = <SEP> 7, <SEP> 32% <SEP>
<tb> gefunden <SEP> : <SEP> C <SEP> = <SEP> 70,79 <SEP> H <SEP> = <SEP> 7, <SEP> 34%.
<tb>
Beispiel 2 : 3-[2-Hydroxy-4-(4-phenylbutyloxy)-phenyl]-cyclohexanon-methylketal:
Ein Gemisch von 5, 03 g = 22, 8 mMol 3- (2, 4-Dihydroxyphenyl)-cyclohexanon-methylketal, 10, 1 g = 73,2 mMol wasserfreiem Kaliumcarbonat und 6, 12 g = 26,8 mMol 4-Phenylbutylmethansulfonat in 25 ml N, N-Dimethylformamid wurde auf 85 bis 100 C für 4 h erhitzt. Das Reaktionsgemisch wurde abgekühlt und zu 200 ml Wasser-200 ml Äther zugesetzt. Der Ätherextrakt wurde zweimal mit 200 ml Wasser gewaschen, über Magnesiumsulfat getrocknet und zu einem Öl eingedampft.
Das Öl wurde mittels Säulenchromatographie über 400 g Kieselerdegel unter Elution mit 2 : 1 Pentan : Äther gereinigt, wobei 7, 4 g (92%) der Titelverbindung als Öl erhalten wurden.
IR-Spektrum : (CHCl3) 1623 und 1590 cm-'
MS : m/e 352 (M+) und 91
Analyse auf C23H28O3:
EMI2.2
<tb>
<tb> berechnet <SEP> : <SEP> C <SEP> = <SEP> 78, <SEP> 37 <SEP> H <SEP> = <SEP> 8, <SEP> 01% <SEP>
<tb> gefunden <SEP> : <SEP> C <SEP> = <SEP> 78,34 <SEP> H <SEP> = <SEP> 8, <SEP> 07%.
<tb>
Die folgenden Verbindungen wurden in ähnlicher Weise, jedoch unter Verwendung des geeigneten Mesylatderivats statt des 4-Phenylbutylmethansulfonats hergestellt : 3- [2-Hydroxy-4- (2-heptyloxy)-phenyl]-cyclohexanon-methylketal.
6, 13 g (75%) als Öl aus 5, 7 g = 25, 9 mMol 3- (2, 4-Dihydroxyphenyl)-cyclohexanon-methylketal und 6, 2 g = 32, 3 mMol (2-Heptyl)-methansulfonat.
IR-Spektrum : (CHC1,) 1637 und 1600 cm-'
EMI2.3
:5, 03 g (58%) als Öl aus 5, 7 g = 25, 9 mMol 3- (2, 4-Dihydroxyphenyl)-cyclohexanon-methylketal und 7, 3 g = 35, 1 mMol (2-Octyl)-methansulfonat.
IR-spektrum: (CHCl3) 1639 und 1600 cm-'
MS : m/e 332 (M+), 300,289, 272 und 220
3- [2-Hydroxy-4-(2-nonyloxy)-phenyl]-cylohexanon-methylketal.
5, 23 g (59%) als Öl aus 5, 7 g = 25, 9 mMol 3- (2, 4-Dihydroxyphenyl)-cyclohexanon-methylketal und 7, 9 g = 35,5 mMol (2-Nonyl)methanesulfonat,
EMI2.4
: (CHC1,)5, 1 g (56%) als Öl aus 5, 7 g = 25, 9 mMol 3- (2, 4-Dihydroxyphenyl)-cyclohexanon-methylketal und 8, 0 g = 35, 0 mMol 2- (4-Phenylbutyl)-methansulfonat.
IR-Spektrum : (CHC1,) 1639 und 1603 cm-'
MS : m/e 352 (M+), 320,220 und 188.
3- {2-Hydroxy-4-[2-(6-phenyl)-hexylocy]-phenyl}-cyclohexanon-methylketal.
5, 3 g (4%) als Öl aus 5, 7 g = 25, 9 mMol 3- (2, 4-Dihydroxyphenyl)-cyclohexanon-methylketal und 9, 0 g = 35, 5 mMol 2- (6-Phenylhexyl)-methansulfonat.
IR-Spektrum: (CHCl3) 1634 und 1597 cm-'
MS : m/e 380, 2342 (M+), (C H, : 0,), 220, 1088, 188,0986 und 177, 0550.
Beispiel 3 : 3-[2-Hydroxy-4-(4-phenylbutyloxy)-phenyl]-cyclohexanon:
Ein Gemisch von 6, 8 g = 19,3 mMol 3-[2-Hydroxy-4-(4-phenylbutyloxy)-phenyl]-cyclohexanon- - methylketal, 100 ml 2 N Salzsäure und 60 ml Dioxan wurde 1 h unter Rückfluss erhitzt. Das Reak- tionsgemisch wurde abgekühlt und zu 300 ml Äther-500 ml gesättigter Natriumchloridlösung zuge-
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EMI3.1
**WARNUNG** Ende DESC Feld kannt Anfang CLMS uberlappen**.
<Desc / Clms Page number 1>
The invention relates to a process for the preparation of new 3- (2-hydroxy-4-alkoxy or -phenalkoxyphenyl) cyclohexanones. The compounds which can be prepared according to the invention can be used as CNS agents, i.e. H. agents acting on the central nervous system, in particular as analgesics, tranquillizers, sedatives and anti-anxiety agents in mammals and in humans and / or as anticonvulsant agents, as diuretics and as anti-diarrheal agents in mammals and in humans.
EMI1.1
EMI1.2
wherein R is a phenylalkyl group having 4 to 9 carbon atoms in the alkyl part or an alkyl group having 7 to 9 carbon atoms, which is characterized in that 3- (2, 4-dihydroxyphenyl) cyclohexanone with an alcohol having 1 to 4 carbon atoms ketalized and selectively alkylated this ketal with an alkylating agent of the general formula YR, (II) in which R has the above meaning and Y represents chlorine, bromine, mesyloxy or tosyloxy, in the presence of an acid acceptor and then converted the ketal to the cyclohexanone (I).
The method according to the invention is an advantageous method of working which involves selective
EMI1.3
an alcohol of 1 to 4 carbon atoms in the presence of an acid such as sulfuric acid, p-toluenesulfonic acid, hydrogen chloride, and the like. under conditions that remove the by-product water. An advantageous procedure comprises the reaction of 3- (2,4-dihydroxyphenyl) cyclohexanone with an orthoformic acid ester in solution in an alcohol which corresponds to the alcohol unit of the orthoformic acid ester. Trimethyl orthoformate and methanol are favored reactants together with concentrated sulfuric acid, anhydrous hydrogen chloride or ammonium chloride as a catalyst.
The ketal thus produced is then reacted with a suitable alkylating agent such as YR, in which R has the meanings given above and Y is a chlorine, bromine atom, mesyloxy radical (eH. -SO. -0) or tosyloxy radical (p-CH-CeH -SO-O-) is, in the presence of an acid acceptor, e.g. B. of sodium or potassium carbonate, alkylated. The alkylated ketal is then decetalated according to procedures known per se by treatment with aqueous acid.
Example 1: 3- (2,4-Dihydroxyphenyl) cyclohexanone methyl ketal:
10 drops of concentrated sulfuric acid were added to a solution of 7.0 g = 33.0 mmol of 3- (2,4-dihydroxyphenyl) cyclohexanone kept at 0 ° C. in 100 ml of methanol and 15 ml of trimethyl orthoformate. The reaction mixture was then stirred for 3 hours without cooling, then the temperature was allowed to rise to room temperature, the reaction was then stopped by adding excess solid sodium bicarbonate. The reaction mixture was then evaporated under reduced pressure and the residue was dissolved in 200 ml water-250 ml ether.
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The ether extract was washed once with 150 ml of saturated sodium bicarbonate solution, dried over magnesium sulfate and evaporated.
The oily residue was crystallized from ether-pentane, 5.74 g (77%) of the title compound having mp. 129 to 130 C being obtained.
IR spectrum: (KBr) 3289, 1629, 1613 and 1597 cm- 'MS: 220 (M), 205, 203, 188, 177, 161 and 136
Analysis on C, H O,:
EMI2.1
<tb>
<tb> calculates <SEP>: <SEP> C <SEP> = <SEP> 70, <SEP> 89 <SEP> H <SEP> = <SEP> 7, <SEP> 32% <SEP>
<tb> found <SEP>: <SEP> C <SEP> = <SEP> 70.79 <SEP> H <SEP> = <SEP> 7, <SEP> 34%.
<tb>
Example 2: 3- [2-Hydroxy-4- (4-phenylbutyloxy) phenyl] cyclohexanone methyl ketal:
A mixture of 5.03 g = 22.8 mmoles of 3- (2,4-dihydroxyphenyl) cyclohexanone methyl ketal, 10.1 g = 73.2 mmoles of anhydrous potassium carbonate and 6.12 g = 26.8 mmoles of 4-phenylbutyl methanesulfonate in 25 ml of N, N-dimethylformamide was heated to 85 to 100 C for 4 h. The reaction mixture was cooled and added to 200 ml of water-200 ml of ether. The ether extract was washed twice with 200 ml of water, dried over magnesium sulfate and evaporated to an oil.
The oil was purified by column chromatography over 400 g of silica gel eluting with 2: 1 pentane: ether to give 7.4 g (92%) of the title compound as an oil.
IR spectrum: (CHCl3) 1623 and 1590 cm- '
MS: m / e 352 (M +) and 91
Analysis on C23H28O3:
EMI2.2
<tb>
<tb> calculates <SEP>: <SEP> C <SEP> = <SEP> 78, <SEP> 37 <SEP> H <SEP> = <SEP> 8, <SEP> 01% <SEP>
<tb> found <SEP>: <SEP> C <SEP> = <SEP> 78.34 <SEP> H <SEP> = <SEP> 8, <SEP> 07%.
<tb>
The following compounds were prepared in a similar manner, but using the appropriate mesylate derivative instead of the 4-phenylbutyl methanesulfonate: 3- [2-hydroxy-4- (2-heptyloxy) phenyl] cyclohexanone methyl ketal.
6.13 g (75%) as an oil from 5.7 g = 25.9 mmol of 3- (2,4-dihydroxyphenyl) cyclohexanone methyl ketal and 6.2 g = 32.3 mmol (2-heptyl) methanesulfonate .
IR spectrum: (CHC1,) 1637 and 1600 cm- '
EMI2.3
: 5.03 g (58%) as an oil from 5.7 g = 25.9 mmoles of 3- (2,4-dihydroxyphenyl) cyclohexanone methyl ketal and 7.3 g = 35.1 mmoles (2-octyl) - methanesulfonate.
IR spectrum: (CHCl3) 1639 and 1600 cm- '
MS: m / e 332 (M +), 300.289, 272 and 220
3- [2-Hydroxy-4- (2-nonyloxy) phenyl] cyclohexanone methyl ketal.
5.23 g (59%) as an oil from 5.7 g = 25.9 mmol of 3- (2,4-dihydroxyphenyl) cyclohexanone methyl ketal and 7.7 g = 35.5 mmol (2-nonyl) methanesulfonate,
EMI2.4
: (CHC1,) 5.1 g (56%) as an oil from 5.7 g = 25.9 mmol 3- (2,4-dihydroxyphenyl) cyclohexanone methyl ketal and 8.0 g = 35.0 mmol 2- (4-phenylbutyl) methanesulfonate.
IR spectrum: (CHC1,) 1639 and 1603 cm- '
MS: m / e 352 (M +), 320,220 and 188.
3- {2-Hydroxy-4- [2- (6-phenyl) hexylocy] phenyl} cyclohexanone methyl ketal.
5.3 g (4%) as an oil from 5.7 g = 25.9 mmol of 3- (2,4-dihydroxyphenyl) cyclohexanone methyl ketal and 9.0 g = 35.5 mmol of 2- (6-phenylhexyl) methanesulfonate.
IR spectrum: (CHCl3) 1634 and 1597 cm- '
MS: m / e 380, 2342 (M +), (C H,: 0,), 220, 1088, 188.0986 and 177, 0550.
Example 3: 3- [2-Hydroxy-4- (4-phenylbutyloxy) phenyl] cyclohexanone:
A mixture of 6.8 g = 19.3 mmol of 3- [2-hydroxy-4- (4-phenylbutyloxy) phenyl] cyclohexanone methyl ketal, 100 ml of 2N hydrochloric acid and 60 ml of dioxane was heated under reflux for 1 h . The reaction mixture was cooled and added to 300 ml ether-500 ml saturated sodium chloride solution.
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EMI3.1
** WARNING ** End of DESC field may overlap beginning of CLMS **.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT196080A AT363455B (en) | 1977-09-13 | 1980-04-10 | METHOD FOR PRODUCING NEW 3- (2-HYDROXY-4-ALKOXY OR -PHENALKOXYPHENYL) -CYCLOHEXANONES |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US83310277A | 1977-09-13 | 1977-09-13 | |
| US92668778A | 1978-07-25 | 1978-07-25 | |
| AT658778A AT361455B (en) | 1977-09-13 | 1978-09-12 | METHOD FOR PRODUCING NEW SUBSTITUTED 3-PHENYL-CYCLOALKANE OR -CYCLOALKEN-1-OLEN |
| AT196080A AT363455B (en) | 1977-09-13 | 1980-04-10 | METHOD FOR PRODUCING NEW 3- (2-HYDROXY-4-ALKOXY OR -PHENALKOXYPHENYL) -CYCLOHEXANONES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| ATA196080A ATA196080A (en) | 1981-01-15 |
| AT363455B true AT363455B (en) | 1981-08-10 |
Family
ID=27421660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AT196080A AT363455B (en) | 1977-09-13 | 1980-04-10 | METHOD FOR PRODUCING NEW 3- (2-HYDROXY-4-ALKOXY OR -PHENALKOXYPHENYL) -CYCLOHEXANONES |
Country Status (1)
| Country | Link |
|---|---|
| AT (1) | AT363455B (en) |
-
1980
- 1980-04-10 AT AT196080A patent/AT363455B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ATA196080A (en) | 1981-01-15 |
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| Date | Code | Title | Description |
|---|---|---|---|
| ELJ | Ceased due to non-payment of the annual fee | ||
| RER | Ceased as to paragraph 5 lit. 3 law introducing patent treaties |