Reaction of 4-fluoro-N-sulfinylaniline with norbornene and norbornadiene has afforded the Diels–Alder adducts of benzothiazine structure that have been oxidized into the corresponding benzothiazine sulfonamides. Structure of the obtained compounds and stereochemistry of the diene addition and epoxidation of norbornene olefin bonds have established by means of X-ray diffraction method.

Synthesis of benzothiazine sulfonamides via heteroatomic Diels–Alder reaction of para-fluoro-N-sulfinylaniline with bicyclo[2.2.1]heptenes

N-Sulfinyl-3-(trifluoromethyl)aniline reacted with bicyclo[2.2.1]hept-2-ene and bicyclo[2.2.1]-hepta-2,5-diene to give the corresponding Diels‒Alder adducts which were oxidized to 8-trifluoromethyl-2,3,4,4a,6,10b-hexahydro-5λ6-1,4-methanodibenzo[c,e][1,2]thiazine-5,5(1H)-diones. The cycloaddition occurred predominantly with participation of the S=N–C1=C6 fragment of N-sulfinyl-3-(trifluoromethyl)aniline and exclusively at the endo side of bicyclo[2.2.1]heptenes.

Synthesis of cyclic sulfonamides by reaction of N-Sulfinyl-3-(trifluoromethyl)aniline with Norbornenes

From classical to supramolecular dynamic stereochemistry: Double crystallization-induced diastereomerization of thiazine sulfonamide.

Assessment of the molecular structure and spectroscopic properties of CF3-substituted sulfinylaniline derivatives

From substituted N-sulfinylanilines acting as dienes in the Diels-Alder reaction with norbornadiene S-oxides of benzo-ortho-thiazines were obtained, which were oxidized into the corresponding S,S-dioxides belonging to the class of hybrid thiazinesulfonamide compounds.

Synthesis of Benzo-ortho-thiazines S-Oxides by Diels—Alder Reaction of N-Sulfinylanilines with Norbornadiene.

Synthesis of benzo- ortho -thiazines S -oxides by Diels-Alder reaction of N -sulfinylanilines with norbornadiene

Natural meroterpenoids often exhibit high and diverse biological activity [1] which is obviously related to their amphiphilicity. Well known examples are tocopherols, tocotrienols [2, 3], cannabinoids [4], prenylflavonoids, etc. [5, 6]. Synthesis of such compounds extends their structural diversity and hence the spectrum of their biological activity. As a rule, synthetic meroterpenoids are more accessible than natural ones whose concentration in natural sources is generally very low. We have studied the Diels–Alder reaction of myrcene as lipophilic diene with 1,4-benzoquinone as hydrophilic dienophile under the conditions allowing both electrophilic double bonds of the dienophile to be involved. Apart from the synthesis of a new meroterpenoid, 2 : 1 adduct of myrcene with benzoquinone, we have determined the regioselectivity of the addition of the second myrcene molecule to initially formed 1 : 1 adduct I which was reported in [7]. By heating benzoquinone with excess myrcene in boiling toluene for 8 h we obtained a crystalline product in ~75% yield. According to the GC/MS data, the crude product was a mixture of four isomers at a ratio of 10 : 15 : 70 : 5 (M 380) with very close retention times ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 12, pp. 1842–1844. © Pleiades Publishing, Ltd., 2014. Original Russian Text © A.V. Chuiko, O.A. Lodochnikova, S.A. Appolonova, V.V. Plemenkov, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 12, pp. 1859–1860.

A. V. Chuiko

Papers

Synthesis of benzo- ortho -thiazines S -oxides by Diels-Alder reaction of N -sulfinylanilines with norbornadiene

Synthesis of Benzo-ortho-thiazines S-Oxides by Diels—Alder Reaction of N-Sulfinylanilines with Norbornadiene.

Synthesis and Structure of 2 : 1 Adduct of Myrcene and 1,4-Benzoquinone