Tert-Butoxybis(dimethylamino)methane explained

tert-Butoxybis(dimethylamino)methane is an organic compound with the formula (CH3)3COCH(N(CH3)2)2. The compound is classified as an aminal ester, i.e. the tert-butyl alcohol derivative of the aminal bis(dimethylamino)methane. It is a colorless liquid with a amine odor.

Use as reagent

Also known as Bredereck's reagent, it is used for formylation (introduction of the CHO group).[1] Protonation releases tert-butyl alcohol, giving tetramethylformamidinium, which displaces active C-H bonds:

(CH3)3COCH(N(CH3)2)2 + H+ → (CH3)3COH + [CH(N(CH<sub>3</sub>)<sub>2</sub>)<sub>2</sub>]+

[CH(N(CH<sub>3</sub>)<sub>2</sub>)<sub>2</sub>]+ + CH2Z2 → Z2CHCH(N(CH3)2)2 + H+ The resulting bis(dimethylamino)methyl derivative in turn releases dimethylamine to give an enamine, which hydrolyzes.

Z2CHCH(N(CH3)2)2 → Z2C=CHN(CH3)2 + HN(CH3)2

Z2C=CHN(CH3)2 + H2O → Z2CHCHO + HN(CH3)2

Preparation

Tert-Butoxybis(dimethylamino)methane is obtained from tetramethylformamidinium chloride by reaction with tert-butoxide. Tetramethylformamidinium salts are obtained by the reaction of dimethylformamide (DMF) with dimethylcarbamoyl chloride[2]

References

  1. Book: 10.1002/9780470842898.rb350.pub2. T-Butoxybis(dimethylamino)methane. Encyclopedia of Reagents for Organic Synthesis. 2007. Kantlehner. Willi. Bowers. Albert. 978-0471936237.
  2. Z. . Arnold . Collection of Czechoslovak Chemical Communications . The preparation of tetramethylformamidinium salts and their vinylogues . 24 . 3 . 760–765 . 1959 . 10.1135/cccc19590760.