Psychedelic Chemistry - Hampapartiet

file:///L:/e-books/psychedelicchemistry/chapter2.htmlMethod 2HCA 48,1665(1965) Convert (+) Delta-3 carene to (+) trans-4- acetoxycarane (I) via (+) trans-4-OH-carane. Reflux 50 g (I) for 45minutes (180øC oil bath under N2 or Argon). Cool and can distill (57/10) to get about 25 g mixture of Delta-3 and Delta-4 carene(residue is unchanged starting material) containing about 60% Delta-4 isomer. Alternatively, to 150 ml ethylene diamine addportionwise with stirring at 110øC under Argon or N2, 5.3 g Li metal; after one hour add dropwise 110g (+) Delta-3 carene. Afterone hour cool to 4øC and add water. Extract with ether, wash the ether five times with water and dry, evaporate in vacuum to get100 g of a mix containing about 40% (+) Delta-4 carene (can separate by fractional distillation). Delta-4 carene can also be obtainedfrom Delta-3 carene as follows: (JCS(C)46(1966)): Dissolve 1 g Delta-3 carene in 50 ml propionic acid and heat at a suitabletemperature (e.g., one- half hour at room temperature may do) in presence of 1/2g Palladium-Carbon catalyst (5%) in ethanol andfilter, evaporate in vacuum (can distill 63.5/19.5). See J.Soc. Cosmet. Chem. 22,249(1971) for a review of (+) Delta-3 carenechemistry.Delta-2 Carene oxide (2-epoxycarene) LAC 687,22(1965), (cf. TL2335(1966), and CA 68:22063(1968))To 136 g 04 carene in 330 ml methylene chloride and 120 g anhydrous sodium acetate, add dropwise with vigorous stirring in an icebath, 167 g of 50% peracetic acid and continue stirring for ten hours. Heat to boiling for two hours, cool, wash with water, sodiumcarbonate, water, and dry, evaporate in vacuum the methylene chloride to get about 100 g p-menthadieneol. Apparently (CA68,22063(1968)) substituting sodium carbonate for sodium acetate results in the production of Delta-2 carene oxide (2-epoxycarene)in about 50% yield (can distill 63/7).4-Carbethoxy-1-methyl-cyclohexanone LAC 630,78(1960)Cool 20 g of sodium metal in 325 ml ethanol to -15øC in an ice-salt bath and add in small amounts over one hour a solution of 100 g3-methyl- cyclohexanone and 150 g diethyloxalate (keep temperature below -10øC). Keep three hours in cold and then twelve hoursat room temperature. Add solution of 1.3 L of water, 60 ml 2N sulfuric acid. Separate the yellow- brown oil and extract the waterwith ether or CHCl3 until the yellow is removed. Combine the oil and the extract and distill the solvent and the unchanged startingmaterial (100øC bath, 13 mm). Slowly heat the residue in a one-half liter flask with air cooling. CO2 evolution starts at 160øC.Continue heating to 220øC and keep at this temperature for 1 1/2 hours or until a test with 1% ethanol-FeCl3 solution shows the endof the reaction by a violet color (unconverted material gives a brown color). Can distill two times in Vigreux column to give about83 g of oily colorless product.(-)Verbenol JCS 2232(1961)Racemic alpha-pinene will yield racemic verbenol which will give one- half the yield of (-)verbenol.27 g (-)alpha-pinene in 500 ml dry benzene; heat and keep temperature at 60-65øC throughout. Add with stirring over 20 minutes 84g dry (dry over P2O5) lead tetra-acetate. Stir one-half hour; cool and filter and add filtrate to water. Filter and evaporate in vacuumthe benzene layer (can distill 96-7/9) to get 21.2 g cis-2-acetoxy-pin-3-ene(I). 5 g (I) in 25 ml glacial acetic acid; keep at 20øC forone-half hour and add water and extract with ether. Wash the extract with aqueous Na2CO3 and evaporate in vacuum the ether (candistill 97-8/9) to get 4.3 g trans verbenyl acetate (II). Hydrolyze (II) with NaOH to give the (-) cis and trans verbenol. For othermethods of producing verbenol see CA 37,361(1943), CA 57,16772(1962) and BSC 2184(1964), JCS (B) 1259(1967). The lastpaper also gives a method for converting (-) beta-pinene to (-) alpha-pinene. See also CA 65,2312(66). 5-Alkyl Resorcinols fromAcyl Resorcinols CA 72,66922(1970)Compounds I-III may be able to give active THC analogs if used in place of olivetol for synthesis.45 g 1-(3,5-dimethoxyphenyl)-1-hexanone(I) or analog (for preparation see the following methods) in 400 ml ether and 0.3 Mmethyl-MgI in 150 ml ether react to give 49 g 2-(3,5-dimethoxyphenyl)-2-heptanol(II). Heat 49 g (II) with 1 ml 20% sulfuric acid to105-125øC/30mm for 1 1/2 hours to get 34 g of the 2-heptene compound (III). 33 g (III) in 100 ml ethanol, 6 g Raney- Ni,1500 PSIhydrogen,150øC to get 26 g of the 2- heptane (IV). 26 g (IV), 118 ml 57% hydrogen iodide; add 156 ml acetic anhydride and heat at155o C for two hours to get 22 g of the resorcinol.file:///L:/e-books/psychedelicchemistry/chapter2.html (7 of 14) [02.09.2007 14:38:02]