Triphenylphosphine → Methyl 6-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-methyl-1,2,6-thiadiazinan-2-carboxylate 1,1-dioxide

HRID 1522079Notes

Reaction equation

[Cl:1][C:2]1[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:5]=[C:4]([Cl:12])[C:3]=1[NH:13][S:14]([NH:17][C:18](=[O:21])[O:19][CH3:20])(=[O:16])=[O:15].[CH3:22][CH:23]([CH2:26]O)[CH2:24]O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1>[Cl:1][C:2]1[CH:7]=[C:6]([C:8]([F:11])([F:9])[F:10])[CH:5]=[C:4]([Cl:12])[C:3]=1[N:13]1[S:14](=[O:15])(=[O:16])[N:17]([C:18]([O:19][CH3:20])=[O:21])[CH2:24][CH:23]([CH3:26])[CH2:22]1

Participants

Conditions

Temperature: -20 °C

Procedure

Methyl N-(2,6-dichloro-4-(trifluoromethyl)phenyl)sulfamoylcarbamate (6.00 g, 16.34 mmol), 2-methylpropane-1,3-diol (2.21 g, 24.51 mmol) and triphenylphosphine (10.71 g, 40.85 mmol) were dissolved in anhydrous THF (100 mL) in a reactor, and then cooled down −20° C. after removal of air in the reactor by purging nitrogen gas. DIAD (8.2 g, 40.8 mmol) was dropwisely added to the reaction mixture and agitated for 5 hr at room temperature. The resultant was concentrated under reduced pressure and purified by column chromatography (dichloromethane:hexane:ethyl acetate=5:4:1), finally yielding the title compound (3.9 g, 70%, white solid). 1H NMR (300 MHz, CDCl3): δ 7.66 (s, 2H), 4.45-4.39 (m, 1H), 3.88 (s, 3H), 3.84-3.75 (m, 2H), 3.54-3.37 (m, 1H), 2.72-2.69 (m, 1H), 1.02 (d, 3H, J=6.7 Hz).

Workup

customafter removal of air in the reactor
customby purging nitrogen gas
concentrationThe resultant was concentrated under reduced pressure
custompurified by column chromatography (dichloromethane:hexane:ethyl acetate=5:4:1)

Sources & evidence

ORD record: ord-aadb75805a37400f94d6e153190c3167
Source dataset: uspto-grants-2015_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09073906B2

Reaction notes

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