3839-84-7

Upstream product

• 21532-65-0 p-dimethylaminothionylaniline 
• 13066-26-7 N,N-dimethyl-N'-sulfinyl-p-phenylenediamine 
• 4039-32-1 lithium hexamethyldisilazane 

Relevant academic research and scientific papers

Substituted 1,3,2,4-benzodithiadiazines: Novel derivatives, by-products, and intermediates

The synthesis of the title compounds 1 by 1:1 condensation of Ar-N=S=N=SiMe32 with SCl2 followed by intramolecular ortho-cyclization of each [Ar-N=S=N-S-Cl] intermediate is complicated by further reaction of 1 with SCl2 to give Herz salts 3. With the 2:SCl2 ratio of 2:1, the formation of by-products 3 is reduced and novel compounds 1 are accessible. With ortho-I containing starting material 2j, the parent compound 1s is obtained as the result of an unexpected I, not H, substitution. The rate of the 1 + SCl2 reaction depends upon a substituent's position, and the minor 8-R isomers 1l,p (R=Br, I) are isolated for the first time from mixtures with the major 6-R isomers due to reduced reactivity toward SCl2. The synthesized compounds 1-3 are characterized by multinuclear (including nitrogen) NMR and X-ray crystallography. According to the X-ray diffraction data, 1j (6-Br) and 1k (7-Br) derivatives are planar, whereas 1i (5-Br) and 11 (8-Br) are bent along the S1···N4 line by ～5° and ～4°, respectively, and the 1r (7-OCH3) derivative is planar in contrast to the known 5-OCH3 isomer, which possesses a significantly folded heterocycle. The distortion of the planar geometry of some compounds 1 is interpreted in terms of a pseudo-Jahn-Teller effect as the result of π-highest occupied molecular orbital (HOMO) - σ*-(LUMO) lowest unoccupied molecular orbital + 1 mixing in a planar conformation. The 2p compound is the first structurally defined Ar-N=S=N-SiMe3 azathiene. The compound Ar-N=S=N-S-NH-Ar 6 modeling the aforementioned intermediate has been isolated and structurally characterized. We describe the attempts to synthesize compounds 1 from 2-aminobenzenethiols and (SN)4 and from salts 3 and Me3SiN3, and we discuss the reaction pathways.

ELECTRICAL CONDUCTIVITY IN TCNQ SALTS OF BIS(4-DIMETHYLAMINOPHENYLIMINO) SULFUR AND ITS STRUCTURAL ANALOGUES.

Four compounds, N,N,N prime ,N prime -tetramethyl-p-phenylene diamine, N,N,N prime ,N prime -tetramethyl-benzidine, 4,4 prime -bis(dimethylamino)azobenzene and bis(4-dimethylaminophenylimino)sulfur (BAPIS) were examined electrochemically and spectroscopically. Each was shown to be a fairly good donor forming in its first oxidation state a radical-cation. The latter two materials surprisingly exhibited only single one-electron oxidations. Conformational flexibility about the -NSN- unit was studied by NMR spectroscopy and ab initio molecular orbital theory. The experimental DELTA G* for a cis-trans to trans-cis interconversion in BAPIS was found to be 11. 9 kcal/mole. The four donors all form 1:1 adducts with TCNQ. The compaction resistances of the complexes have been measured as a function of temperature. Of the four, (BAPIS)(TCNQ) appears to be a one-dimensional material. The other three complexes behave as typical mixed stack organic semiconductors.