Water → 2-Methanesulfonyloxyimino-4-p-tolyl-but-3-enenitrile

HRID 48129Notes

Reaction equation

[OH:1][N:2]=[C:3]([CH:6]=[CH:7][C:8]1[CH:13]=[CH:12][C:11]([CH3:14])=[CH:10][CH:9]=1)[C:4]#[N:5].[CH3:15][S:16](Cl)(=[O:18])=[O:17].C(N(CC)CC)C.O>O1CCCC1>[CH3:15][S:16]([O:1][N:2]=[C:3]([CH:6]=[CH:7][C:8]1[CH:9]=[CH:10][C:11]([CH3:14])=[CH:12][CH:13]=1)[C:4]#[N:5])(=[O:18])=[O:17]

Participants

Conditions

Temperature: 0 °C

Procedure

2-Hydroxyimino-4-p-tolyl-but-3-enenitrile (1.9 g; 0.01 mol) is dissolved in 15 ml of anhydrous tetrahydrofuran, and cooled to 0° C. Methanesulfonyl chloride (0.93 ml, 0.012 mol) is added at once, followed by triethylamine (2.1 ml, 0.015 mol) dropwise over 20 min, keeping the temperature of the mixture below 5° C. The mixture is then stirred at 5-10° C. for 3.5 hours, and poured into 200 ml of iced water. The suspension is extracted with ethyl acetate, the organic extract is washed neutral with water, then with brine, and dried over magnesium sulfate. Rotary evaporation of the solvent and recrystallization from 50 ml of ethanol yields 2-methanesulfonyloxyimino-4-p-tolyl-but-3-enenitrile (1.7 g; 64%) as off-white crystals, mp 134-135° C. with one part melting at 145° C. 1H-NMR reveals the presence of two isomers (probably E/Z around the imino double bond).

Workup

customthe temperature of the mixture below 5° C
extractionThe suspension is extracted with ethyl acetate
extractionthe organic extract
washis washed neutral with water
dry with materialwith brine, and dried over magnesium sulfate
customRotary evaporation of the solvent and recrystallization from 50 ml of ethanol

Sources & evidence

ORD record: ord-58d073c768784635b9455ee81640d83b
Source dataset: uspto-grants-2004_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06703182B1

Reaction notes

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