isocyanato(methanesulfonyl)methane synthesis

Yield:1161826-12-5 51%

Reaction Conditions:

Stage #1: Methyl α-(methylsulfonyl)acetatewith hydrazine in ethanol; for 1.5 h;Heating / reflux;
Stage #2: with hydrogenchloride;sodium nitrite in chloroform;water at 0; for 0.0833333 h;

Steps:

52

Synthesis 52S-Methanesulfonylmethyl^-oxo-S^-dihydro-imidazoIδ.i-dlti ^.S.Sltetrazine-δ-carboxylic acid amide (UU-002); To a solution of methanesulfonyl-acetic acid methyl ester (0.5 μl_, 3.71 mmol) in EtOH (4 ml_) was added hydrazine hydrate (216 μL, 4.45 mmol). The mixture was refluxed for 90 minutes before being cooled to room temperature, evaporated to dryness in vacuo. The resulting residue was diluted in 1 N HCI and CHCI₃ to give a biphasic solution to which aqueous NaNO₂ was added dropwise while at 0⁰C. The mixture was stirred like this for 5 minutes before being extracted with CHCI₃ (3 x 1 reaction volumes). The combined organic extracts were then dried (MgSO₄), filtered and concentrated to give a solid residue (256 mg, 51%) which was used without further purification. ¹H NMR (400 MHz, CDCI₃) δ ppm: 4.27 (2H, s), 2.93 (3H, s). IR (λ_max, cm ¹): 3325.4 (w), 3009.1 (w), 2237.5 (m, N=C=O), 1791.9 (w), 1697.4 (w), 1570.1 (w), 1525.7 (w), 1450.5 (w), 1411.9 (W), 1305.8-1282.7-1126.5 (s, SO₂), 922.0 (m), 906.6 (m), 769.6 (m), 634.6 (m).

References:

WO2009/77741,2009,A2 Location in patent:Page/Page column 102-103