Tetrakis -substituted ethylene

Me Capra in particular proposed n> that the chemiluminescence reactions of a large number of organic compounds had this concerted dioxetane decomposition step as key reaction in the production of electronically excited products, namely acridinium salts 25,26,27) indolylperoxides 28>, activated oxalic esters 29>, diphenyl carbene 30>, tetrakis-dimethylamino-ethylene 31 32>, lucigenin 33>, and substituted imidazoles 23>. 

The anodic behavior of A -substituted alkenes can be described as the oxidation of an electron-rich double bond. Tetraamino-substituted alkenes are extremely easily oxidized. Tetrakis(dimethylamino)ethylene exhibits two reversible one-electron processes at —0.75 and —0.61 V vs. SCE at a dropping mercury electrode in acetonitrile [140]. The anodic behavior of A, A -dimethylaminoalkenes has been studied intensively by cyclic voltammetry and electron spin resonance (ESR) spectroscopy [141]. The anodically E° = 0.48 V vs. SCE) generated cation radical of l,l-bis(iV,iV-dimethylamino)ethylene is shown to undergo C-C coupling, forming l,l,4,4-tetrakis(A, iV-dimethylamino)butadiene, which subsequently is further oxidized to its dication at —0.8 V [141,142]. With vicinal diamino ethylenes, usually two reversible one-electron oxidations are observed [143], while gem-inal diamino ethylenes exhibit an irreversible behavior [141]. Aryl-substituted vicinal diamino ethylenes (endiamines) can undergo a double cyclization to give an indolo-oxazoline when oxidized at 0.4 V vs. SCE in acetonitrile in the presence of 2,6-lutidine [144] ... 

Summary A 9 1 molar ratio mixture of 1,1,2,2-tetrachloromethyldisilane 2 plus pentamethyldisilane 4 reacted with tetrakis(dimethylamino)ethylene (TDAE) to yield, in dimethoxyethane (DME), a crystal mixture of [SiaMesClel ETDAE] (5a) plus [Si3Me2Cl7]"-[TDAE] (5b). The molecular structure of 5b was determined. Conversely, from donor-substituted disilanes such as l,l,2-tris(diethylamino)-2-chloro-dimethyldisilane 6 or the lV,Af -diphenylethylenediamino-substituted dimethyidisilane 7, electron transfer occurs toward tetracyanoethylene (TCNE). 

Scheme 11 Tetrakis(dimethylamino)ethylene dication trifluoromethyl thiolate as a stable reagent for substitution of aromatic halides...

Allyltrimethylsilane undergoes bimolecular rearrangement to vinyltrimethyl-silane and Me4Si through initial Si—C homolysis. The degree of vinylation of vinyltrichlorosilane is determined by the solvent, monosubstitution dominating in hydrocarbon solvents. Tetrakis(trimethylsilyl)ethylene has been prepared from the disilacyclobutene (8). The steric hindrance in such substituted ethylenes. 

The inherent chemistry above is not altered by substituting the phenyl rings of the ketone or pinacol with methyl groups. The ketone 4,4 -dimethylbenzophenone, as well as the pinacol 1,2,2-tetrakis-(4-methylphenyl)ethane-l,2-diol (TBP) react with U giving tetrakis-(4-methylphenyl)ethylene and l,l, ,2-tetrakis(4-methylphenyl)ethane. A lsl mixture of benzophenone and 4,4-dimethylbenzophenone gives the six expected coupling products. 

The kinetics and mechanism for oxygen transfer between 4-cyano-V,V,-dimethylaniline V-oxide and a C2-capped mexo-tetraphenylporphyrinatoiron(III) and mc5 o-tetrakis(pentafiuorophenyl)-porphyrinatoiron(III) have been established. Addition of a copper(II) porphyrin cap to an iron(II)-porphyrin complex has the expected effect of reducing both the affinities and rate constants for addition of dioxygen or carbon monoxide. These systems were studied for tetradecyl-substituted derivatives solubilized by surfactants such as poly(ethylene oxide) octaphenyl ether. ... 

Scheme 16 General stmctural formula of a 4A-t5 pe tetrakis(phenyl)-mero-substituted porphyrin. The binding moiety of an anchoring group is -COOH, -SO3H, -PO3H, etc. M = H2, Zn, or other metal. An aryl, ethylene, etc., spacer may be introduced between the anchoring group and the MP macrocycle...

The tetrakis-sulphoxides (67) have been reported as a new type of PT catalyst in a solid-liquid mode, for example in 5n reactions of 1-bromo-octane. Nucleophilic substitutions of 1-bromo-octane and benzyl bromide are again the test reactions in a report on the use of the sucrose-ethylene oxide adducts (68a) as PT catalysts in both solid-liquid and liquid-liquid modes. The methacrylate ester derivative (68b) has been polymerized to a cross-linked gel that acts in a TC capacity for the same reactions. In a related approach some modified dextran anion exchangers carrying lipophilic substituents, such as the modified hydroxypropylated dextran gel shown in (69), have been synthesized and shown to catalyse displacement reactions including the alkyl bromide to iodide transformation under TC conditions. ... 

Synonyms Edetol EDTP Ethylenedinitrilotetra-2-propanol 1,1, 1",1 "-(Ethylene-dinitriolo)tetra-2-propanol N,N,N, N -Tetra-(2-hydroxypropyl)-1,2-diaminoethane N,N,N, N -Tetrakis (2-hydroxypropyl) ethylenediamine Classification Substituted amine Ionic Nature Cationic Empirical C,4H32N204 Formula (HOC3He)2NCH2CH2N(C3HeOH)... 

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