814876-19-2

Upstream product

• 633303-45-4 3,3-dichloro-2,2,4,4-tetramethylcyclobutan-1-one 
• 933-52-8 2,2,4,4-tetramethyl-1,3-cyclobutanedione 
• 872880-34-7 2,2,8,8-tetrachloro-1,1,3,3,7,7,9,9-octamethyl-5,10,11-trithiadispiro[3.1.3.2]undecane 

Relevant academic research and scientific papers

Stereoselective 1,3-dipolar cycloadditions of thioketones to carbohydrate-derived nitrones

A series of cycloaliphatic thioketones was reacted with selected enantiopure nitrones bearing carbohydrate-derived moieties leading to 1,4,2-oxathiazolidine derivatives in a highly stereoselective manner. Analysis of spectroscopic data supplemented by X-r

Generation and rearrangement of some spirocycloaliphatic thiosulfines and dithiiranes

The flash-vacuum pyrolysis of selected dispirodicycloaliphatic 1,2,4-trithiolanes was studied by using matrix isolation techniques. The formation of thiosulfines and dithiiranes along with the corresponding thioketones was detected spectroscopically and confirmed by comparison with computed spectra. In the case of tetramethylcyclobutanone 1,2,4-trithiolane, the thermal formation of the dithiolactone was observed. Pyrolysis of the (dichloro)tetramethylcyclobutane derivative resulted only in the formation of a mixture of the thiosulfine and dithiirane. In this case, conversion into the corresponding dithiolactone could be achieved photochemically. The dispirodiadamantane derivative gave a mixture of the respective thiosulfine and dithiirane but no dithiolactone could be detected in the mixture. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Addition reactions of sulfenyl and sulfinyl chlorides with 3-phenyl-1-azabicyclo[1.1.0]butane

The reactions of 3-phenyl-1-azabicyclo[1.1.0]butane with α-chlorosulfenyl chlorides and sulfinyl chlorides lead to the corresponding sulfenamides and sulfinamides, respectively, which possess an azetidine ring. It is proposed that a two-step mechanism occurs involving an intermediate carbenium ion, which is formed by the addition of the electrophile at the N-atom and cleavage of the N(1)-C(3) bond. The structures of 9b and 10b are established by X-ray crystallography.

Synthesis and reactions of a new cyclobutanethione derivative

The 3,3-dichloro-2,2,4,4-tetramethylcyclobutanethione (4b) was prepared from the parent diketone by successive reaction with PCl5 and Lawesson reagent in pyridine. This new thioketone 4b was transformed into 1-chlorocyclobutanesulfanyl chloride 5 and chloro 1-chlorocyclobutyl disulfide 9 by treatment with PCl5 and SCl2, respectively, in chlorinated solvents (Schemes 1 and 2). These products reacted with S- and P-nucleophiles by substitution of Cl- at the S-atom; e.g., the reaction with 4b yielded the di- and trisulfides 6b and 11, respectively. Surprisingly, only pentasulfide 12 was formed in the reaction of 9 with thiobenzophenone (Scheme 3). In contrast to 5 and 9, the corresponding chloro 1-chlorocyclobutyl trisulfide 13 could not be detected, but reacted immediately with the starting thioketone 4b to give the tetrasulfide 14 (Scheme 4). Oxidation of 4b with 3-chloroperbenzoic acid (mCPBA) yielded the corresponding thione oxides (=sulfine) 15, which underwent 1,3-dipolar cycloadditions with thioketones 3a and 4b (Scheme 5). Furthermore, 4b was shown to be a good dipolarophile in reactions with thiocarbonylium methanides (Scheme 6.) and iminium ylides (=azomethine ylides; Scheme 7). In the case of phenyl azide, the reaction with 4b gave the symmetrical trithiolane 25 (Scheme 8).