Sulfuric Acid → 4'-[(2S,4R,5S)-5-octyl-4-methyl-1,3-dioxan-2-yl]-4-cyanobi-phenyl

HRID 440206Notes

Reaction equation

HRID 440206 reaction equation
[CH2:1]([C@H:9]([C@H:12]([OH:14])[CH3:13])[CH2:10][OH:11])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].[C:15]([C:17]1[CH:22]=[CH:21][C:20]([C:23]2[CH:28]=[CH:27][C:26]([CH:29]=O)=[CH:25][CH:24]=2)=[CH:19][CH:18]=1)#[N:16].S(=O)(=O)(O)O.C(=O)([O-])O.[Na+]>C(OCC)(=O)C.CCCCCC.C(Cl)Cl.O.C1(C)C=CC=CC=1>[CH2:1]([C@H:9]1[CH2:10][O:11][C@H:29]([C:26]2[CH:25]=[CH:24][C:23]([C:20]3[CH:21]=[CH:22][C:17]([C:15]#[N:16])=[CH:18][CH:19]=3)=[CH:28][CH:27]=2)[O:14][C@@H:12]1[CH3:13])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8]

Participants

10

Reactant 4

HCID 1118Sulfuric AcidHCID 516892Sodium BicarbonateHCID 27592144'-Formyl-biphenyl-4-carbonitrileHCID 57227381(2S,3R)-2-octyl-1,3-butanediol

Product 1

HCID 677427084'-[(2S,4R,5S)-5-octyl-4-methyl-1,3-dioxan-2-yl]-4-cyanobi-phenylYield 85.7%

Reagents, catalysts & solvents 5

HCID 962WaterSolventHCID 1140TolueneSolventHCID 6344DichloromethaneSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 3.0 g of (2S,3R)-2-octyl-1,3-butanediol, 3.07 g of 4'-cyano-4-biphenylcarboxaldehyde, 0.1 ml of 1N sulfuric acid and 30 ml of toluene was placed under nitrogen in a round flask having a magnetic stirrer, water separator and condenser. The mixture was heated to reflux for 3 hours while separating water. The cooled reaction mixture was poured into aqueous sodium hydrogen carbonate solution and treated with methylene chloride. The aqueous phase was separated and extracted twice with methylene chloride. The combined organic phases were washed twice with water, dried over magnesium sulfate, filtered and evaporated. Recrystallization of the crude product obtained (5.84 g) from a mixture of 200 ml of hexane and 25 ml of ethyl acetate gave 4.97 g of 4'-[(2S,4R,5S)-5-octyl-4-methyl-1,3-dioxan-2-yl]-4-cyanobi-phenyl with m.p. (C-SA) 114.5° C., cl.p. (SA -I) 128.4° C.

Workup

  1. customwas placed under nitrogen in a round flask
  2. temperatureThe mixture was heated
  3. temperatureto reflux for 3 hours
  4. customwhile separating water
  5. customThe cooled reaction mixture
  6. customThe aqueous phase was separated
  7. extractionextracted twice with methylene chloride
  8. washThe combined organic phases were washed twice with water
  9. dry with materialdried over magnesium sulfate
  10. filtrationfiltered
  11. customevaporated
  12. customRecrystallization of the crude product
  13. customobtained (5.84 g)

Sources & evidence

ORD record
ord-843bcc92eced452aaf5e0be8b58223a6
Source dataset
uspto-grants-1996_05
Patent number
US05518653

Reaction notes

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