Preparation, crystal structure and reactions of a new spin-labelling reagent, cis-3,5-dibromo-4-oxo-2,2,6,6- tetramethylpiperidin-1-yloxy

Author:

Alcock Nathaniel W.,Golding Bernard T.,Ioannou Panayiotis V.,Sawyer Jeffrey F.

Publisher

Elsevier BV

Subject

Organic Chemistry,Drug Discovery,Biochemistry

Reference42 articles.

1. Einwirkung von Aminen auf Dibromtriacetonamin

2. Bromination of 4 - oxo - 2,2,6,6 - tetramethylpiperidin - 1 -yloxy with phenyltrimethyl-ammonium perbromide in tetrahydrofuran (Organic Syntheses 53, 111 (1973)) gave a solid product presumed to be 3 - bromo - 4 - oxo - 2,2,6,6 - tetramethylpiperidin - 1 - yloxy. However, the yield of ~90% pure (tlc) material was low. After incubating this substance for 17hr/r.t. with benzylamine (2 mol equiv) in CH2Cl2, work up did not afford 3 - (N - benzyl)aminocarbonyl - 2,2,5,5 - tetramethylpyrrolidin - 1 - yloxy. However, treatment of the monobromonitroxide with NaOH aq in dioxan gave 3 - carboxy - 2,2,6,6 - tetramethylpyrrolidin - 1 - yloxy [m.p. 193–4° dec, 15% overall yield (3 steps) from 4 - oxo - 2,2,6,6 - tetramethylpiperidine; cf. 47% overall yield (5 steps) claimed in Ref. ,2].

3. A Short-cut to Spin-labelled Amides

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