Benzyl Alcohol → HCID 131735655, compound

HRID 531208Notes

Reaction equation

HRID 531208 reaction equation
[CH:1]1([CH2:4][CH:5]([C:15]#[N:16])[CH:6]([SiH:12]([CH3:14])[CH3:13])[C:7]([O:9][CH2:10][CH3:11])=[O:8])[CH2:3][CH2:2]1.[OH-].[Li+].C(O)[C:20]1[CH:25]=[CH:24]C=[CH:22][CH:21]=1.C1(N=C=NC2CCCCC2)CCCCC1.Cl>ClCCl.CN(C)C1C=CN=CC=1>[CH:1]1([CH2:4][CH:5]([C:15]#[N:16])[CH:6]([SiH:12]([CH3:13])[CH3:14])[C:7]([O:9][CH2:10][C:11]2[CH:24]=[CH:25][CH:20]=[CH:21][CH:22]=2)=[O:8])[CH2:3][CH2:2]1

Participants

8

Reactant 5

HCID 244Benzyl AlcoholHCID 313Hydrochloric AcidHCID 3939Lithium HydroxideHCID 10868DicyclohexylcarbodiimideHCID 131735656HCID 131735656, compound

Product 1

HCID 131735655HCID 131735655, compoundYield 93.2%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

Ethyl 4-cyclopropyl(dimethyl)silyl-3-cyanobutanoate (6.39 g, 26.7 mmol) obtained in Example 3 mentioned above was hydrolyzed by using lithium hydroxide in the same manner as that of the aforementioned examples. The obtained reaction mixture (6.21 g) was dissolved in dichloromethane (85 ml), and the solution was added successively with benzyl alcohol (4.95 ml, 48.1 mmol), dicyclohexylcarbodiimide (8.81 g, 42.8 mmol) and 4-dimethylaminopyridine (163 mg, 1.34 mmol). The mixture was stirred for 30 minutes under ice cooling and for further 17 hours at room temperature. After the reaction vessel was cooled on ice, the reaction mixture was added with aqueous hydrochloric acid (1 N), and the mixture was stirred for 5 minutes, and further stirred for 30 minutes at room temperature. The deposited urea was removed by filtration under reduced pressure, and the filtrate was extracted with chloroform. The organic layer was washed with saturated aqueous sodium hydrogencarbonate, and treated in a conventional manner, and then the residue was purified by silica gel column chromatography [hexane/ethyl acetate (24:1 to 19:1)] to obtain benzyl 4-cyclopropyl(dimethyl)silyl-3-cyanobutanoate (7.50 g, 93%) mentioned in the title as colorless oil.

Workup

  1. temperatureAfter the reaction vessel was cooled on ice
  2. stirringthe mixture was stirred for 5 minutes
  3. stirringfurther stirred for 30 minutes at room temperature
  4. customThe deposited urea was removed by filtration under reduced pressure
  5. extractionthe filtrate was extracted with chloroform
  6. washThe organic layer was washed with saturated aqueous sodium hydrogencarbonate
  7. additiontreated in a conventional manner
  8. customthe residue was purified by silica gel column chromatography [hexane/ethyl acetate (24:1 to 19:1)]

Sources & evidence

ORD record
ord-b5b32e9f76984f779b325b6448270e4d
Source dataset
uspto-grants-2016_05
Patent number
US09353134B2

Reaction notes

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