Triphenylphosphine → 2-Ethylidene-6-methyl-5-hepten-1-thiol acetate

HRID 1493813Notes

Reaction equation

N(C([O:11][CH:12]([CH3:14])C)=O)=NC(OC(C)C)=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C([OH:37])(=[S:36])C.[CH:38](=[C:40]([CH2:43][CH2:44][CH:45]=[C:46]([CH3:48])[CH3:47])[CH2:41]O)[CH3:39]>O1CCCC1>[C:12]([OH:37])(=[O:11])[CH3:14].[CH:38](=[C:40]([CH2:43][CH2:44][CH:45]=[C:46]([CH3:48])[CH3:47])[CH2:41][SH:36])[CH3:39]

Participants

Conditions

Temperature: 0 °C

Procedure

Diisopropyl azodicarboxylate (2.63g, 0.013 mol) was added dropwise over a 5 min period to a cold (0° C.) mixture of triphenylphosphine (3.40g, 0.013 mol) in tetrahydrofuran (20 mL). The mixture was stirred at 0° C. for 0.5h. A solution of thioacetic acid (0.99g, 0.013 mol) and 2-ethylidene-6-methyl5-hepten-1-ol (1.00g, 0.0065 mol) in tetrahydrofuran (20 mL) was then added dropwise over a 0.5h period to the cold (0° C.) reaction mixture. The mixture was stirred for 1h at 0° C. and then 1h at 25° C. The solvent was removed under reduced pressure. Hexane (40 mL) was added and the mixture was filtered to remove solids. Work-up, chromatography, and kugelrohr distillation (bath temp. 100° C., 0.5 mm) provided 1.15g of 2-ethylidene-6-methyl-5-hepten-1-thiol acetate (GLC purity 94.7%; isomers not separated). NMR (60 MHz, CDCl3) δ 1.62 and 1.68 (6H, 2s), 1.63 (3H, d, J=6 Hz) 2.1 (4H, broad s), 3.57 (2H, broad s), 5.0-5.3 (1H, m), 5.49 (1H, q, J=6Hz); IR (film) vmax 2920, 1685, 1430, 1125 940 cm-1 ; MS m/e 212, 197, 169, 136, 69, 43.

Workup

customat 25° C
customThe solvent was removed under reduced pressure
additionHexane (40 mL) was added
filtrationthe mixture was filtered
customto remove solids
distillationWork-up, chromatography, and kugelrohr distillation (bath temp. 100° C., 0.5 mm)

Sources & evidence

ORD record: ord-9a0303d38380499dbe0b7098608781e1
Source dataset: uspto-grants-1991_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05024847

Reaction notes

Loading…