1,10-Phenanthroline → 4-[4-Chloro-1-[(4-methylphenyl)thio]butyl]-1,2-dimethoxybenzene

HRID 863883

Reaction equation

HRID 863883 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([CH2:9][S:10][C:11]2[CH:16]=[CH:15][C:14]([CH3:17])=[CH:13][CH:12]=2)=[CH:5][C:4]=1[O:18][CH3:19].N1C2C(=CC=C3C=2N=CC=C3)C=CC=1.C([Li])CCC.CCCCCC.Br[CH2:46][CH2:47][CH2:48][Cl:49]>O1CCCC1.C(OCC)(=O)C>[Cl:49][CH2:48][CH2:47][CH2:46][CH:9]([C:6]1[CH:7]=[CH:8][C:3]([O:2][CH3:1])=[C:4]([O:18][CH3:19])[CH:5]=1)[S:10][C:11]1[CH:12]=[CH:13][C:14]([CH3:17])=[CH:15][CH:16]=1

Participants

7

Reactant 4

HCID 13181,10-PhenanthrolineHCID 80061-Bromo-3-chloropropaneHCID 105164711,2-Dimethoxy-4-[[(4-methylphenyl)thio]methyl]benzeneHCID 178418244HCID 178418244, compound

Product 1

HCID 108317364-[4-Chloro-1-[(4-methylphenyl)thio]butyl]-1,2-dimethoxybenzene

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 13.72 g of 1,2-dimethoxy-4-[[(4-methylphenyl)thio]methyl]benzene and a crystal of phenanthroline in 250 mL of tetrahydrofuran (dried over 3A sieves), under nitrogen at -78° C. is added 21.0 mL of 2.5M n-butyl lithium/hexane via a syringe. After 10 minutes, the brown solution is warmed to 0° C. for 1 hour, then it is recooled to -78° C. and 8.02 mL of 1-bromo-3-chloropropane is added via syringe. The reaction is permitted to warm to room temperature overnight. To the now light yellow reaction mixture is added 10 mL of ethyl acetate and the resulting solution concentrated in yacuo. The residue is partitioned between ethyl acetate and water, the organic phase dried (sodium sulfate) and concentrated in vacuo to a yellow oil. Purification by chromatography on silica gel with gradient elution progressing from hexane to chloroform to methyl alcohol, repeated three times, affords 16.47 g of the desired product as a yellow oil. MS(CI): m/z 227 and 229(MH+ (-TolSH)). Calcd for C19H23ClO2S 1/8H2O: C=63.80, H=6.59, Cl=11.15, S=8.95 Found C=63.68, H=6.44, Cl=10.89, S=8.98

Workup

  1. customis recooled to -78° C.
  2. temperatureto warm to room temperature overnight
  3. concentrationthe resulting solution concentrated in yacuo
  4. customThe residue is partitioned between ethyl acetate and water
  5. dry with materialthe organic phase dried (sodium sulfate)
  6. concentrationconcentrated in vacuo to a yellow oil
  7. customPurification by chromatography on silica gel with gradient elution progressing from hexane to chloroform to methyl alcohol

Sources & evidence

ORD record
ord-8d28c9c0f6464ee1aeb57ebfa28db2c8
Source dataset
uspto-grants-1996_10
Patent number
US05561141

Linked notes

Loading…