Sodium Bicarbonate → Di-tert-butyl (chloromethyl) phosphate

HRID 1367680

Reaction equation

[P:1]([O-:13])([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[K+].C(=O)(O)[O-].[Na+].[Cl:20][CH2:21]OS(Cl)(=O)=O>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.O.ClCCl>[Cl:20][CH2:21][O:2][P:1](=[O:13])([O:3][C:4]([CH3:6])([CH3:7])[CH3:5])[O:8][C:9]([CH3:12])([CH3:11])[CH3:10]

Participants

Conditions

Temperature: 0 °C

Procedure

According to a literature procedure (Tetrahedron Letters; 2002, 43, 3793), compound I was prepared as follows: Potassium di-tert-butyl phosphate (6.35 g), tetra-n-butylammonium hydrogen sulphate (917 mg) and sodium bicarbonate (8.96 g) were dissolved in water (230 mL). Dichloromethane was added (130 mL) and the resulting mixture was cooled down to 0° C. A solution of chloromethylchlorosulphate (917 mg) in dichloromethane (100 mL) was slowly added under vigorous stirring. The reaction mixture was allowed to reach room temperature and further stirred overnight at this temperature. The organic layer was then separated, washed with brine (50 mL), dried over Na2SO4 and concentrated under vacuum. The desired product 1 was obtained as a colourless oil (2.4 g). Phosphoric acid di-tert-butyl ester chloromethyl ester 1. Colourless oil, 1H-NMR (CDCl3) δ 5.65 (d, J=15.0 Hz, 2H), 1.52 (s, 18H); 13C-NMR (CDCl3) δ 84.2 (d, J=7.6 Hz), 73.3 (d, J=6.9 Hz), 29.8 (d, J=4.3 Hz); 31P-NMR (CDCl3) δ −11.8.

Workup

customwas prepared
customThe organic layer was then separated
washwashed with brine (50 mL)
dry with materialdried over Na2SO4
concentrationconcentrated under vacuum

Sources & evidence

ORD record: ord-36e62a7cf9894c37bd01ef5ae2e856ac
Source dataset: uspto-grants-2011_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07893271B2

Linked notes

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