Hydrochloric Acid → HCID 14692981, compound

HRID 1608068Notes

Reaction equation

HRID 1608068 reaction equation
[Cl-].C[Al+]C.[CH3:5][C:6]1[CH2:11][C:10]([CH3:13])([CH3:12])[CH:9]([C:14]([CH3:16])=[CH2:15])[C:8]([CH3:18])([CH3:17])[CH:7]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[OH-:27].[Na+].Cl.[Al].CCCC[CH2:35][CH3:36]>ClCCl.O>[CH3:36][CH:35]([OH:27])[CH2:15][C:14](=[CH2:16])[CH:9]1[C:10]([CH3:12])([CH3:13])[CH2:11][C:6]([CH3:5])=[CH:7][C:8]1([CH3:18])[CH3:17]

Participants

10

Reactant 7

HCID 313Hydrochloric AcidHCID 8058HexaneHCID 14798Sodium HydroxideHCID 62657Potassium Phosphate, TribasicHCID 1731563,3,5,5-TetramethyllimoneneHCID 5359268AluminumHCID 16686359Dimethylalumanylium chloride

Product 1

HCID 14692981HCID 14692981, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
25 °C

Procedure

Dimethylaluminum chloride (300 mL of a 1M hexane solution) was added to a cooled (10° C.) solution of 1,3,3,5,5-pentamethyl-4-(1-methylethenyl)-1-cyclohexene (46.18 g, 0.24 mol) in dichloromethane (500 mL). The mixture was stirred at 25° C. for 2 hr. Afterwhich the mixture was hydrolyzed by the addition of phosphte buffer solution (200 mL, prepared from 100 mL of 0.1M potassium phosphate, monobasic and 44.8 mL of 0.1M sodium hydroxide diluted to 200 mL with water) followed by the addition of sufficient 1N hydrochloric acid solution to dissolve the aluminum salts. The layers were separated and the aqueous layer extracted with dichloromethane (200 mL). The combined organic layers were washed with water (100 mL) and saturated sodium bicarbonate solution (2×100 mL). The solvents were evaporated and the residue chromatographed. Combination of fractions and distillation provided 27.8 g of α,2,2,4,6,6,-hexamethyl-γ-methylene-3-cyclohexene-1-propanol, bp 100°-105° C., 0.5 mm (GLC purity, two isomers, 41.4% and 56.6%). 1H-NMR (60 MHz, CDCl3) δ0.92 and 0.98 (12H, 2 s), 1.20 (3H, d, J=6 Hz), 1.58 (3H, s), 1.2-2.6 (5H, m) 3.8-4.2 (1H, m), 4.9-5.2 (3H, m); IR (film ) vmax 3340, 2950, 1635, 1440, 1370, 1350 cm-1 ; MS m/e 236, 221, 18, 203, 140, 125, 107, 96.

Workup

  1. customThe layers were separated
  2. extractionthe aqueous layer extracted with dichloromethane (200 mL)
  3. washThe combined organic layers were washed with water (100 mL) and saturated sodium bicarbonate solution (2×100 mL)
  4. customThe solvents were evaporated
  5. customthe residue chromatographed
  6. distillationCombination of fractions and distillation

Sources & evidence

ORD record
ord-8bd657b5061b47a789dfe0f14833ca9a
Source dataset
uspto-grants-1989_09
Patent number
US04868339

Reaction notes

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