Interaction of 1,3,2,4‐Benzodithiadiazines with Aromatic Phosphines and Phosphites

Grayfer, Tatyana D.; Makarov, Alexander Yu.; Bagryanskaya, I. Yu.; Irtegova, Irina G.; Gatilov, Yuri V.; Zibarev, Andrey V.

doi:10.1002/hc.21209

Cited by 9 publications

(2 citation statements)

References 49 publications

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“…Such a rapid migration from S to N has been demonstrated previously for the reaction of phosphines with sulfur diimides . The reaction of Ph 3 P with 1,3,2,4‐benzodithiadiazines also results in the extrusion of a ring nitrogen atom to form an iminophosphorane substituent at sulfur in a smaller ring . Complete severance of the N1−S3 bond leads to the chain intermediates 3 (all atom numbers refer to usage in Figure ).…”

Section: Resultssupporting

confidence: 47%

Synthesis, Electronic Structures, and Electrochemistry of 3‐Triarylphosphoraniminato‐1,3,5‐trithia‐2,4,6,8‐tetrazocines: Detection of Trithiatetrazocinyl Radical Anions

Roemmele

Boeré

2017

ChemElectroChem

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Reaction of the bicyclic sulfur‐nitrogen heterocycles RC6H4CN5S3 (R=4‐CH3O, 4‐CH3, 4‐H, 4‐Cl, 4‐CF3, 3‐CF3) with PR’3 (R′=C6H5 or 4‐CH3OC6H4) produces 3‐phosphoraniminato‐7‐aryl‐1,3,5‐trithia‐2,4,6,8‐tetrazocines RC6H4CN4S3NPR’3. In all cases, only the endo‐isomers were isolated and characterized by 1H, 31P, and 19F NMR as well as UV spectroscopy and X‐ray crystallography. RB3LYP/6‐311+G(d,p)// RB3LYP/6‐31G(d,p) computations were undertaken to help explain the atom‐exact syntheses via intermediates previously detected spectroscopically. Three reasonable intermediates have been computed as stationary points with energies consistent with the observed reaction path. Cyclic and square‐wave voltammetry studies of RC6H4CN4S3NPR’3, using a glassy carbon working electrode in CH2Cl2 with 0.4 M [nBu4N][PF6], reveal two IRR reduction processes at RT in all cases at approximately −1.9 and −2.2 V, respectively, and one IRR oxidation process at approximately +1.0 V (versus Fc+/0). [RC6H4CN4S3NPR’3]−. radical anions (R’=4‐CH3OC6H4, R=4‐CH3O, 4‐H, 4‐CF3) were detected at −50 °C in CH2Cl2 by using in situ electrolysis and simultaneous electron paramagnetic resonance spectroscopy: [4‐RC6H4CN4S3NP(4‐CH3OC6H4)3]−., estimated a(31P)=0.078 mT, a(14N1)=0.031 mT, a(14N2,3)=0.256 mT, a(14N4,5)=0.341 mT. The signals decay rapidly, but after the electrolysis is ended, a persistent EPR signal is always obtained with EPR parameters that match known 4‐aryl‐1,2,3,5‐dithiadiazolyls, that is, a(N)=0.51 mT and g=2.0105, which are consistent with the production of [4‐CF3‐C6H4CN2S2]..

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Section: Resultssupporting

confidence: 47%

Synthesis, Electronic Structures, and Electrochemistry of 3‐Triarylphosphoraniminato‐1,3,5‐trithia‐2,4,6,8‐tetrazocines: Detection of Trithiatetrazocinyl Radical Anions

Roemmele

Boeré

2017

ChemElectroChem

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“…The type B RAs for 1 – 14 were also optimized. They featured tremendously elongated (by 0.546–0.762 Å) S1−X2 bond lengths (Table ), which assumes weakened or, more likely, bond breaking. The type B RAs have a σ*(S1−X2, X=S or Se) SOMO (see Figure for the RA of 9 ).…”

Section: Resultsmentioning

confidence: 99%

Fused 1,2,3‐Thiaselenazoles Synthesized from 1,2,3‐Dithiazoles through Selective Chalcogen Exchange

Konstantinova

Baranovsky

Pritchina

et al. 2017

Chemistry A European J

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A new approach to the synthesis of fused 1,2,3-thiaselenazoles-rare five-membered heterocycles that contain two different chalcogens-from the corresponding 1,2,3-dithiazoles and SeO was accomplished by selective exchange of S and Se atoms. The fused carbo- and heterocyclic units were indene, naphthalenone, cyclohexadienone, cyclopentadiene, benzoannulene, and benzoxazine. The molecular structures of two of the thiaselenadiazole products and one of the dithiazole precursors were confirmed by single-crystal X-ray diffraction. The reaction is highly solvent selective; it only takes place in solvents that contain a C=O group (e.g., DMF or tetramethylurea). According to DFT calculations, the reaction is thermodynamically favorable. Based on the DFT calculations and Se NMR spectroscopy, two tentative mechanisms that feature isomeric transition states and intermediates are suggested for the reaction via ring-opening addition of SeO to the S-X dithiazole bond (X=N or S). The DFT-calculated first adiabatic electron affinities of the compounds were chalcogen independent and positive in all cases, which assumes formation of thermodynamically stable radical anions (RAs). These calculated RAs featured either normal or abnormal elongation of the S1-X2 (X=S or Se) bond relative to their neutral precursors and possessed π* or σ* SOMOs, respectively.

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Pentafluorophenylboronic Acid

Korenaga

Sakai

Pang

et al. 2019

Encyclopedia of Reagents for Organic Synthesis

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Interaction of 1,3,2,4‐Benzodithiadiazines with Aromatic Phosphines and Phosphites

Cited by 9 publications

References 49 publications

Synthesis, Electronic Structures, and Electrochemistry of 3‐Triarylphosphoraniminato‐1,3,5‐trithia‐2,4,6,8‐tetrazocines: Detection of Trithiatetrazocinyl Radical Anions

Synthesis, Electronic Structures, and Electrochemistry of 3‐Triarylphosphoraniminato‐1,3,5‐trithia‐2,4,6,8‐tetrazocines: Detection of Trithiatetrazocinyl Radical Anions

Fused 1,2,3‐Thiaselenazoles Synthesized from 1,2,3‐Dithiazoles through Selective Chalcogen Exchange

Pentafluorophenylboronic Acid

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