Structure of 61597-37-3
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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
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| CAS No. : | 61597-37-3 |
| Formula : | C10H16O2 |
| M.W : | 168.23 |
| SMILES Code : | CC(O)(C1=CCC(OC)=CC1)C |
| MDL No. : | MFCD02066210 |
| GHS Pictogram: |
|
| Signal Word: | Warning |
| Hazard Statements: | H302-H315-H319-H332-H335 |
| Precautionary Statements: | P261-P280-P305+P351+P338 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 87% | With sodium hydroxide;tin(IV) chloride; In dichloromethane; water; | EXAMPLE 12 2,7-Dihydroxy-5-isopropylidene-9-(1,1-dimethylheptyl)-2,6-methano-3,4,5,6-tetrahydro-2H-1-benzoxocin A solution of 11.8 g. of 5-(1,1-dimethylheptyl)-resorcinol, 12.0 g. of 1-methoxy-4-(1-hydroxy-1-methyl-ethyl)-1,4-cyclohexadiene and 0.9 ml. of water in 100 ml. of dichloromethane stabilized with cyclohexane (ie. commercial grade dichloromethane) was stirred and cooled to -20 C. in a dry ice-acetone bath. To the cold stirred solution was added 13 ml. of stannic chloride dropwise at a rapid rate over three minutes, during which time the temperature of the reaction mixture increased to -11 C. Immmediately following complete addition of the stannic chloride to the reaction mixture, the mixture was poured into 200 g. of ice, and 50 ml. of water was added to the ice mixture. The organic layer was separated, washed twice with 200 ml. portions of 1N sodium hydroxide and then with 250 ml. of water. The organic layer next was dried, and the solvent was removed by evaporation under reduced pressure to provide 20.5 g. of the product as a solid. The solid thus formed was recrystallized from n-hexane to afford 16.2 g. (87 percent yield) of 2,7-dihydroxy-5-isopropylidene-9-(1,1-dimethylheptyl)-2,6-methano-3,4,5,6-tetrahydro-2H-1-benzoxocin. M.P. 148-152 C. |
| In dichloromethane; trifluoroborane diethyl ether; | EXAMPLE 1 2,7-dihydroxy-5-isopropylidene-9-(1,1-dimethylheptyl)-2,6-methano-3,4,5,6-tetrahydro-2H-1-benzoxocin. A solution of 1.0 g. of 1-methoxy-4-(1-hydroxy-1-methylethyl)-1,4-cyclohexadiene and 1.18 g. of 5-(1,1-dimethylheptyl)resorcinol in 40 ml. of dichloromethane was cooled to 5 C. in an ice-water bath and stirred while 1.5 ml. of boron trifluoride diethyl etherate was added to the mixture in one portion. The reaction mixture then was stirred at 5 C. for 5 hours. The reaction mixture then was washed with aqueous sodium bicarbonate solution and dried. The solvent was removed by evaporation under reduced pressure to provide the product as an oil. The oil so formed was triturated with n-hexane and then allowed to stand at room temperature for 12 hours, during which time the oil solidified. The solid product was collected by filtration and was recrystallized from 10 ml. of methyl cyclohexane to afford 580 mg. of 2,7-dihydroxy-5-isopropylidene-9-(1,1-dimethylheptyl)-2,6-methano-3,4,5,6-tetrahydro-2H-1-benzoxocin. M.P. 158-159 C. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With sodium hydrogencarbonate; In dichloromethane; trifluoroborane diethyl ether; | EXAMPLE 5 2,7-Dihydroxy-5-isopropylidene-9-(1,1-dimethylheptyl)-2,6-methano-3,4,5,6-tetrahydro-2H-1-benzoxocin A solution of 1.0 g. of 1 -methoxy-4-(1-hydroxy- 1-methylethyl)-1,4-cyclohexadiene in 40 ml. of dichloromethane containing 1.18 g. of 5-(1,1-dimethylheptyl) resorcinol was cooled to 5 C. in an ice-water bath and stirred while 1.5 ml. of boron trifluoride diethyl etherate was added dropwise over a five minute period. The reaction mixture was then stirred at 5 C. for five hours. The reaction mixture was next washed with a five-percent aqueous solution of sodium bicarbonate and dried. Removal of the solvent by evaporation under reduced pressure provided the product as an oil. The oil was triturated with n-hexane and then allowed to stand at room temperature for twelve hours, during which time the oil solidified. The solid product was collected by filtration and recystallized from 10 ml. of methyl cyclohexane, providing 580 mg. of 2,7-dihydroxy- 5-isopropylidene-9-(1,1-dimethylheptyl)-2,6-methano-3,4,5,6-tetrahydro-2H-1-benzoxocin. M.P. 158-159 C. Analysis calc. for C24 H36 03 Theory: C, 77.38; H, 9.74. Found: C, 77,33; H, 9.55. nmr (CDCl3): delta6.2 and 6.4 (two doublets, 2H, aromatic) delta4.3 (m, 1H, C6 --H) |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With hydrogenchloride; In benzene; | EXAMPLE 1 dl-cis-1-Hydroxy-3-(1,1-dimethylheptyl)-6,6-dimethyl-6,6a,7,8,10,10a-hexahydro-9H-dibenzo[b,d]pyran-9-one. A solution of 504 mg. of 1-methoxy-4-(1-hydroxy-1-methylethyl)-1,4-cyclohexadiene and 708 mg. of 5-(1,1-dimethylheptyl)resorcinol in 25 ml. of benzene was stirred at 24 C. while 5 ml. of boron trifluoride diethyl etherate was added in one portion. The reaction mixture was stirred at 24 C. for five hours. The reaction mixture then was added to 20 ml. of 6N hydrochloric acid solution. After allowing the benzene solvent to evaporated from the aqueous acid solution, the solution was extracted several times with diethyl ether. The ethereal extracts were combined, washed with water and with aqueous sodium bicarbonate solution, and dried. Evaporation of the solvent under reduced pressure provided an oil, which was crystallized from hexane to afford dl-cis-1-hydroxy-3-(1,1-dimethylheptyl)-6,6-dimethyl-6,6a,7,8,10,10a-hexahydro-9H-dibenzo[b,d]pyran-9-one. nmr (CDCl3): 80 Hz (s, 3H, C-6 -methyl), 84 Hz (s, 3H, C-6 -methyl). | |
| With hydrogenchloride; sodium hydrogencarbonate; In benzene; | EXAMPLE 5 dl-cis-1-Hydroxy-3-(1,1-dimethylheptyl)-6,6-dimethyl-6,6a,7,8,10,10a-hexahydro-9H-dibenzo[b,d]pyran-9-one. Five milliliters of a commercial solution of boron trifluoride diethyl etherate was added in one portion to a stirred solution of 504 mg. of 1-methoxy-4-(1-hydroxy-1-methylethyl)-1,4-cyclohexadiene and 708 mg. of 5-(1,1-dimethylheptyl)resorcinol dissolved in 25 ml. of benzene. The reaction mixture was stirred at 25 C. for five hours, and then added to 75 ml. of 6N hydrochloric acid solution. The benzene was removed from the mixture by evaporation, and then the acidic solution was extracted several times with diethyl ether. The ethereal extracts were combined, washed with water and with an aqueous solution of sodium bicarbonate, and dried. Removal of the solvent by evaporation under reduced pressure provided the product as a solid, which was then recrystallized from hexane to afford 365 mg. of dl-cis-1-hydroxy-3-(1,1-dimethylheptyl)-6,6-dimethyl-6,6a,7,8,10,10a-hexahydro-9H-dibenzo[b,d]pyran-9-one. M.P. 153-158 C. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With sodium hydrogencarbonate; In benzene; | EXAMPLE 6 2-Methoxy-5-isopropylidene-7-hydroxy-9-(1,1-dimethylheptyl)-2,6-methano-3,4,5,6-tetrahydro-2H-1-benzoxocin A solution of 2.02 g. of 1-methoxy-4-(1-hydroxy- 1-methylethyl)-1,4-cyclohexadiene in 100 ml. of benzene containing 2.36 g. of 5-(1,1-dimethylheptyl)resorcinol was stirred at 25 C. while 1 ml. of boron trifluoride diethyl etherate was added in one portion. The reaction mixture was stirred for five hours at 25 C., and was then washed with water and with a five-percent aqueous solution of sodium bicarbonate. After drying the organic solution, the solvent was removed by evaporation under reduced pressure to provide 4.4 g. of an oil. After standing for several hours at 25 C., the oil solidified. The solid product so formed was washed with n-hexane and then recrystallized from cyclohexane, providing 1.55 g. of 2-methoxy-5-isopropylidene-7-hydroxy-9-(1,1-dimethylheptyl)-2,6-methano-3,4,5,6-tetrahydro-2H-1-benzoxocin. M.P. 131-133 C. Mass spectal analysis: molecular ion at m/e 386. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| tin(IV) chloride; In dichloromethane; water; | EXAMPLE 8 dl-cis-1-Hydroxy-3-(1,1-dimethylheptyl)-6,6-dimethyl-6,6a,7,8,10,10a-hexahydro-9H-dibenzo[b,d]pyran-9-one. A solution of 11.8 g. of 5-(1,1-dimethylheptyl)-resorcinol and 10.0 g. of 1-methoxy-4-(1-hydroxy-1-methylethyl)-1,4-cyclohexadiene in 200 ml. of commercial grade dichloromethane was cooled to 5 C. and stirred while 13 ml. of stannic chloride was added dropwise over forty minutes. Following complete addition of the stannic chloride, the reaction mixture was warmed to room temperature and was then stirred for an additional seven hours. The reaction mixture next was diluted with 200 ml. of water. The organic layer was separated, washed with 2N hydrochloric acid, with water, with 1N sodium hydroxide, and again with water. The organic solution was dried and the solvent was removed therefrom by evaporation under reduced pressure to provide a solid residue. The solid so formed was recrystallized from hexane to afford 11.0 g. of dl-cis-1-hydroxy-3-(1,1-dimethylheptyl)-6,6-dimethyl-6,6a,7,8,10,10a-hexahydro-9H-dibenzo[b,d]pyran-9-one, which was found by thin layer chromatography to be identical to the product of Example 5. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 87% | 5-(1 ,1-dimethylheptyl) resorcinol (220 g, 931 mmol) was placed in a 4 neck 3L round-bottomed flask equipped with an overhead stirrer, thermometer, reflux condenser, and dropping funnel. DCM (1320 ml) was added with stirring. Water (50 ml, 2793 mmol) was added to the stirred suspension, followed by the drop-wise addition of triflic anhydride (263 g, 931 mmol) while maintaining a slow reflux of the solvent until the resorcinol was dissolved. The mixture was cooled to -200C and a solution of 1-methoxy-4- (1-hydroxy-1-methyl)-ethyl-1 ,4-cyclohexadiene (261 g, 1396 mmol) in DCM (250 ml) was added drop-wise, keeping the temperature at -20+/-3C. After all the diene was added, the mixture was allowed to warm up to 00C and stirred for 2 hours at this temperature. Additional DCM (1000 ml) was added to the reaction mixture and the solution was washed consecutively with water (2X1 L), brine (0.5L) and dried over sodium sulfate (300 g). The solvent was removed under vacuum. The solidified residue was co-evaporated with hexane (250 ml) to dryness and triturated with a fresh portion of hexane (500 ml) at 65C (bath temperature) for 30 min. The suspension was cooled to at 00C and kept for 1 h. The precipitate was filtered off, washed with 100 ml of cold hexane and dried under vacuum to a constant weight. Yield 289 g (83.3%) of cis-nabilone.Using a similar procedure cis-nabilone was also synthesized under the following conditions: |
Tags: 61597-37-3 synthesis path| 61597-37-3 SDS| 61597-37-3 COA| 61597-37-3 purity| 61597-37-3 application| 61597-37-3 NMR| 61597-37-3 COA| 61597-37-3 structure
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