Amino Acid-Based Dithiazines:  Synthesis and Photofragmentation of Their Benzaldehyde Adducts

Abstract

Alpha-amino acids and GABA are functionalized with dithiazine rings via reaction with sodium hydrosulfide in aqueous formaldehyde. The resulting dithiazines are lithiated at -78 degrees C and reacted with benzaldehyde furnishing amino acid-based 2,5-bis-substituted dithiazines. These adducts undergo externally sensitized photofragmentation with quantum efficiency comparable to that of the parent dithiane adducts, thus offering a novel approach to amino acid-based photolabile tethers. [reaction: see text]

Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

“…448 In addition, the dithiane moiety was successfully coupled with amino acids to form novel dithiazane photocleavable linkers. 449 9 H -Thioxanthen-9-one has also been introduced as a sensitizer in the dithiane-, trithiane-, and dithiazane-based photolabile scaffolds. 450 …”

Cyclothiomethylation of primary amines with formaldehyde and hydrogen sulfide to nitrogen- and sulfur-containing heterocycles (review)

“…For the realization of the most effective reagents in industry 1,3,5-dithiazinan-5-ylacetic acid (71a), the capacity of which amounts to 0.9g/g, was used as sorbent for the recovery of silver from the waste products of the photo and cine industry [73]. It was also established [76] that N-substituted dithiazine 71a are promising as biocides -special reagents for suppressing the activity of sulfate-reducing bacteria in various industrial materials. The starting material 71a is nontoxic, inhibits corrosion, and has low solubility in petroleum, surpassing in many respects the well known reagent "Don" widely used in oil production [77].…”

“…The synthesis of 2-substituted 1,3,5-dithiazinan-5-ylcarboxylic acids 78a-d and 82 by the reaction of NaHS with formaldehyde and amino acids 77a-d and 81 at 0°C was described in [76]. By successive treatment of the obtained acids 77a-d and 81 with n-BuLi and benzaldehyde in THF at -78°C it is possible to insert a (hydroxy)benzyl group into the dithiazinane molecule.…”

Efficient method for a synthesis of N-substituted dithiazinanes via transamination of N-methyl-1,3,5-dithiazinane with arylamines and hydrazines

“…[7][8][9][10][11][12][13] Cyclothiomethylation of primary amines with CH 2 O and H 2 S is one of the first and well-known procedures to synthesize N-substituted 1,3,5-dithiazinanes. 14 In recent years, this reaction have been extensively studied on the example of aliphatic 15,16 and aromatic amines, 17,18 aminophenols, 19 amino acids, 20,21 hydrazine and its derivatives. [22][23][24][25] Nevertheless, this method has definite limitation associated with the use of gaseous Н 2 S and aqueous solution of СН 2 О.…”