Benzyl Bromide → HCID 178489634, compound

HRID 442988Notes

Reaction equation

HRID 442988 reaction equation
[CH2:1](Br)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:9][O:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[S:17]([O:20][C:21]1[CH:22]=[C:23]([CH:33]=[C:34]([CH3:36])[CH:35]=1)[O:24][CH2:25][CH2:26][CH:27]=[N:28][NH:29][C:30]([NH2:32])=[S:31])(=[O:19])=[O:18].C(=O)(O)[O-].[Na+]>O1CCCC1.CO>[CH2:1]([N:29]([C:30](=[NH:32])[SH:31])[N:28]=[CH:27][CH2:26][CH2:25][O:24][C:23]1[CH:33]=[C:34]([CH3:36])[CH:35]=[C:21]([O:20][S:17]([C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][C:11]=2[O:10][CH3:9])(=[O:19])=[O:18])[CH:22]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 7498Benzyl Bromide2×HCID 516892Sodium BicarbonateHCID 541667873-[3-(2-Methoxyphenylsulfonyloxy)-5-methylphenoxy]propionaldehyde thiosemicarbazone

Product 1

HCID 178489634HCID 178489634, compoundYield 62%

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 8028TetrahydrofuranSolvent3×

Procedure

A solution of benzyl bromide (15.5 μL, 0.13 mmol) in tetrahydrofuran (1.5 mL) and methanol (0.5 mL) was added dropwise over 20 minutes to a mixture of 3-[3-(2-methoxyphenylsulfonyloxy)-5-methylphenoxy]-propionaldehyde thiosemicarbazone (55.3 mg, 0.13 mmol, as prepared in the preceding step) and sodium bicarbonate (28.8 mg, 0.34 mmol) in tetrahydrofuran (1.5 mL) and methanol (0.5 mL). The reaction was stirred for 5 hours at ambient temperature, then additional benzyl bromide (15.5 μL, 0.13 mmol) in tetrahydrofuran (1 mL) was added dropwise over 5 minutes. The reaction was stirred overnight at ambient temperature then concentrated to remove solvents. The residue was triturated with dichloromethane and filtered through Celite. After concentration, crude product was purified by flash column chromatography through silica gel (1:1 diethyl ether/hexane) to give the title compound as an oil (42 mg, 1:4 mixture of isomers, 62%). 1H-NMR (300 MHz, CDCl3) δ 7.80-7.85 (m, 2H), 7.57-7.63 (m, 1H), 7.23-7.40 (m, 5H), 6.98-7.12 (m, 2H), 6.59 (br s, 1H), 6.52 (br s, 1H), 6.46 (t, 1H, J=2 Hz), 4.29 and 4.28 (s, 1H), 4.10 (t, 2H, J=6.5 Hz), 4.01 (s, 3H), 2.94 and 2.73 (q, 2H, J=6 Hz), 1.55 (s, 3H). Mass spectrum (MALDI-TOF, α-cyano-4-hydroxycinnamic acid matrix) calcd. for C25H27N3O5S2 : 514.1 (M+H). Found: 513.6.

Workup

  1. stirringThe reaction was stirred overnight at ambient temperature
  2. concentrationthen concentrated
  3. customto remove solvents
  4. customThe residue was triturated with dichloromethane
  5. filtrationfiltered through Celite
  6. concentrationAfter concentration, crude product
  7. customwas purified by flash column chromatography through silica gel (1:1 diethyl ether/hexane)

Sources & evidence

ORD record
ord-c9a7761cf31441fca154af15b456a2ef
Source dataset
uspto-grants-1999_04
Patent number
US05891909

Reaction notes

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