Triphenylphosphine → 5-Acetylthiomethyl-1,3-bis(hydroxymethyl)-benzene

HRID 1695314Notes

Reaction equation

C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.O[CH2:33][C:34]1[CH:39]=[C:38]([CH2:40][OH:41])[CH:37]=[C:36]([CH2:42][OH:43])[CH:35]=1.[C:44]([OH:47])(=[S:46])[CH3:45]>C1COCC1>[C:44]([S:46][CH2:33][C:34]1[CH:39]=[C:38]([CH2:40][OH:41])[CH:37]=[C:36]([CH2:42][OH:43])[CH:35]=1)(=[O:47])[CH3:45]

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of triphenylphosphine (577 mg, 2.2 mmol) in anhydrous THF (5 mL) was added diethyl azodicarboxylate (2.2 M in toluene, 791 μL, 1.7 mmol) dropwise at 0° C. After stirred at 0° C. for 50 minutes, a solution of 1,3,5-tri(hydroxymethyl)benzene (269 mg, 1.6 mmol, prepared by reduction of trimethyl 1,3,5-benzenetricarboxylate with lithium aluminum hydride in THF, co-evaporated with dry benzene and dried on high vacuum for couple hours before use) and thioacetic acid (108 μL, 1.45 mmol) in dry THF (4 mL) was added dropwise. After 1 hour, the ice/water bath was removed and the reaction was stirred at room temperature for 15 hours. The solvents were removed by rotary evaporation in vacuo. The residue was purified by flash chromatography to give 5-acetylthiomethyl-1,3-bis(hydroxymethyl)-benzene as colorless solid (110 mg). 1H NMR (400 Hz, CDCl3): δ 7.13-6.99 (m, 3H), 4.45 (apt, J=20.4 Hz, 4H), 3.98 (apt, J=20.4 Hz, 4H), 3.73 (bs, 2H), 2.24 (apt, J=20.4 Hz, 3H); MS (ESI): m/z 249.0 (M+Na)+.

Workup

waitAfter 1 hour
customthe ice/water bath was removed
stirringthe reaction was stirred at room temperature for 15 hours
customThe solvents were removed by rotary evaporation in vacuo
customThe residue was purified by flash chromatography

Sources & evidence

ORD record: ord-913a82acfd344b8bb8faca39bc66a083
Source dataset: uspto-grants-2012_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08163736B2

Reaction notes

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