Methoxymethyl-triphenylphosphonium chloride → HCID 178494963, compound

HRID 344625Notes

Reaction equation

HRID 344625 reaction equation
[Cl-].[CH3:2][O:3][CH2:4][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CC(C)([O-])C.[K+].[C:30]([C:32]1[CH:37]=[CH:36][C:35]([C@H:38]2[CH2:43][CH2:42][C@H:41]([CH2:44][CH2:45][CH:46]=O)[CH2:40][CH2:39]2)=[CH:34][CH:33]=1)#[N:31].C(C1C=CC([C@H]2CC[C@H](CCCC=O)CC2)=CC=1)#N>O1CCCC1.O.C1(C)C=CC=CC=1>[CH3:2][O:3][CH:4]=[CH:46][CH2:45][CH2:44][C@H:41]1[CH2:40][CH2:39][C@H:38]([C:35]2[CH:34]=[CH:33][C:32]([C:30]#[N:31])=[CH:37][CH:36]=2)[CH2:43][CH2:42]1

Participants

8

Reactant 4

HCID 2723798Methoxymethyl-triphenylphosphonium chlorideHCID 23665647Potassium tert-butoxideHCID 178509796HCID 178509796, compoundHCID 178509797HCID 178509797, compound

Product 1

HCID 178494963HCID 178494963, compoundYield 82%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-10 °C

Procedure

Commercially available methoxymethyltriphenylphosphonium chloride (257 g, 0.75 mol) was added to tetrahydrofuran (500 ml), followed by adding potassium t-butoxide (84.2 g, 0.75 mol) in argon atmosphere with stirring at -10° C. over 40 minutes, agitating the reaction solution at 0° C. for one hour, dropwise adding a solution of 3-[trans-4-(4-cyanophenyl)cyclohexyl]-1-propanal (121 g, 0.50 mol) obtained according to the method of Example 3 (i), in tetrahydrofuran (400 ml) at -10° C. over one hour, agitating the reaction mixture at 0° C. for one hour, further agitating at 20° C. for 2 hours, adding toluene (1 l) and water (1 l) to the reaction mixture at 0° C., four times washing the resulting toluene solution with water (1 l), drying over anhydrous magnesium sulfate, separating the drying agent, distilling off toluene, purifying the resulting residue according to silica gel column chromatography using heptane as an eluent to obtain trans-1-(4-methoxy-3-butenyl)-4-(4-cyanophenyl)cyclohexane (110.8 g, 0.41 mol), adding to the total quantity of this compound, tetrahydrofuran (1.5 l) and 2N-hydrochloric acid (0.4 l), heating the mixture under reflux, with stirring for one hour, cooling the resulting reaction mixture, adding diethyl ether (0.5 l) and water (1 l), three times washing the resulting diethyl ether solution with water (0.5 l), drying over anhydrous magnesium sulfate, separating the drying agent, concentrating under reduced pressure to obtain a residue (120 g), and recrystallizing from a mixed solvent of heptane and ethyl acetate (3:1) to obtain 4-[trans-4-(4-cyanophenyl)cyclohexyl]-1-butanal (93.0 g, 0.36 mol).

Workup

  1. stirringagitating the reaction solution at 0° C. for one hour
  2. customobtained
  3. stirringagitating the reaction mixture at 0° C. for one hour
  4. stirringfurther agitating at 20° C. for 2 hours
  5. washfour times washing the resulting toluene solution with water (1 l)
  6. dry with materialdrying over anhydrous magnesium sulfate
  7. customseparating the drying agent
  8. distillationdistilling off toluene
  9. custompurifying the resulting residue

Sources & evidence

ORD record
ord-58a57e4b41434b3aaa03d02738fa1272
Source dataset
uspto-grants-1991_10
Patent number
US05053162

Reaction notes

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