p-Toluenesulfonic acid → 1-(Dimethoxymethyl)-4-(methylsulfanyl)benzene

HRID 2303464ノート

反応式

HRID 2303464 の反応式
[CH3:1][S:2][C:3]1[CH:10]=[CH:9][C:6](C=O)=[CH:5][CH:4]=1.[CH:11](OC)([O:14][CH3:15])[O:12][CH3:13].CC1C=CC(S(O)(=O)=O)=CC=1.C[O-].[Na+]>CO>[CH3:13][O:12][CH:11]([C:6]1[CH:9]=[CH:10][C:3]([S:2][CH3:1])=[CH:4][CH:5]=1)[O:14][CH3:15]

参加物

6

反応物 4

HCID 6101p-Toluenesulfonic acid2 回HCID 9005Trimethyl orthoformateHCID 769854-(Methylthio)benzaldehydeHCID 10942334Sodium Methoxide

生成物 1

HCID 135965971-(Dimethoxymethyl)-4-(methylsulfanyl)benzene

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

実験手順

A solution of 4-methylsulfanylbenzaldehyde 1 (10 g, 66 mmol), (MeO)3CH (8.6 mL, 79 mmol) and p-TsOH (0.25 g, 1.3 mmol) in MeOH (130 mL) was stirred for 18 h. The remaining pTsOH was decomposed by addition of NaOMe. After 5 min, the mixture was evaporated in vacuo, and passed through a pad of SiO2 (95:5 hexane/Et2O) to afford 1-(1,1-dimethoxy-methyl)-4-methylsulfanyl-benzene 2. The residue after evaporation was dissolved into CH2Cl2 (360 mL) and treated with MCPBA (41 g, 240 mmol). After 18 h, the mixture was filtered and the filtrate evaporated. The residue was partitioned between EtOAc and 1 M NaOH. The organic layer was washed with 1 M NaOH (2×), washed with brine, dried (MgSO4), filtered and evaporated to afford 1-(1,1-dimethoxy-methyl)-4-methanesulfonylbenzene 3. The residue was dissolved into THF (130 mL) and treated with 2% H2SO4 (3.4 mL). After 2 h, the solvent was evaporated, and the residue was partitioned between EtOAc and NaHCO3. The organic layer was dried (MgSO4), filtered and evaporated to afford 12 g (98% for three steps) of 4-methylsulfonylbenzaldehyde 4 as a white solid; 1H NMR δ 3.11 (s, 3H), 8.09 (d, 2H, J=8.6), 8.14 (d, 2H, J=8.6), 10.15 (s, 1H).

後処理

  1. customthe mixture was evaporated in vacuo

出典と根拠

ORDレコード
ord-b6c82b4eb927480e86adc9c61ff2461b
出典データセット
uspto-grants-2002_08
特許番号
US06433005B1

反応ノート

読み込み中…