Diethylamino radical

The behavior of diethylamino radicals is akin to that of alkyl radicals, in that both dimerization and disproportionation occur and at approximately equal rates. However we have no accurate numerical data for the corresponding sec-pentyl radical which may be used to provide the required contrast. The occurrence of DEMA, methane, and ethane in the reaction products suggests that the methyl radical is an essential precursor and the decomposition of diethylamino radicals... 

Both dimethylamino and diethylamino radicals react with nitric oxide to form the corresponding nitrosamine, by Reactions 31 and 39. 

Addition of phenylphosphine to dialkynyl(diethylamino)-boranes proceeds as a radical process, giving rise to l,4-boraphosphacyclohexa-2,5-dienes (171) [Eq. (130)] (75ZN641 83JOM33). 

In the presence of various metal ions, 2-(fluoroenone)benzothiazoline has been found to rearrange to A-2-mercaptophenylenimine, while a free radical mechanism involving the homolysis of C-S and C-N bonds has been invoked to explain the formation of 3-phenyl-1,2,4-triazole derivatives from the thermal fragmentation and rearrangement of 2-(arylidenehydrazino)-4-(5//)-thiazolone derivatives. The cycloadducts (36) formed from the reaction of 3-diethylamino-4-(4-methoxyphenyl)-5-vinyl-isothiazole 1,1-dioxide (34) with nitric oxides or miinchnones (35) have been found to undergo pyrolytic transformation into a, jS-unsaturated nitriles (38) by way of pyrrole-isothiazoline 1,1-dioxide intermediates (37). 

Nucleophilic substitution of chlorine in 2,4-dinitrochlorobenzene by diethylamino group from triethylamine (Scheme 4.18) is a rare example when both the formed opposite-charged ion radicals exist together in the bulk solution for a long time. 

Ketyl radicals have also been implicated in the photoreduction of azo dyes,121 pyrazolone azomethene dye (24),122 4-(diethylamino)-4 -nitro-azobenzene (25),123 and quinizarin (26).124 The reduction of azobenzene by... 

So we were induced to try this approach, too, and we started synthesis work in the field of s-triazines. The result of our primary working hypothesis was disappointing derivatives bearing anilino radicals showed no herbicidal effects. Surprisingly, however, the herbicidal activity reappeared in the structure 2-chloro-4,6-bis-diethylamino-s-triazine, compound G-25804 shown previously. The awareness that we were confronted with a completely new herbicidal matrix with apparently superior usefulness led us to intensive work around the s-triazine ring system. 

An a-hydroxy tertiary amine is oxidized with difficulty. At 60°, however, 2-(7V, Ar-diethylamino)ethanol took up lead tetraacetate, but scission occurred between the carbon-nitrogen bond (instead of between the carbon-carbon bond), possibly by a free-radical mechanism.196... 

Sequential SET desilylation has been used to generate a-amino radicals. The mechanistic and synthetic aspects of the reaction have been briefly surveyed.283 Thus irradiation of A, N- d i e t h y 11 r i m e t h y I si I yl meth y I a m i n e with acenaphthenequinone in acetonitrile or methanol produces 2-hydroxy-2-[(diethylamino)methyl]acenaphthylen-1-one.284... 

Biimidazole-sensitized photooxidation of lenco triphenylmethane dyes. MacLachlan, Alexander Riem, R. H. (Exp. Stan., E. I. DuPont de Nemours and Co., Wilmington, Del.). J. Org. Chem. 1971, 36(1G), 22/5-80 (Eng). Oxidn. of tris(2-methyl4-diethylamino-phenyl)methane by photogenerated 2-(o-chlorophe-nyl)4,5-diphenylimidazolyl radical (Lr) was studied by flash photolysis. An electron-exchange reaction involving L occurs at an unprotonated amino N of the... 

Protonation is another common reaction in this category and reduction of the acceptor via protonation of the radical anion (e.g. by moisture present in the solvent) is often observed as a side process. It may become the main path either under acidic conditions or if the radical cation of the donor is a good proton donor (Scheme 3). As an example, the 1,2-dihydro derivative is the main product from 1,4-dicyanonaphthalene (DON) when irradiated in the presence of a donor and trifluoroacetic acid [33]. Such a reaction is more important when the radical cation is the proton source. Typically, the irradiation of naphthalene with tertiary amines leads to a mixture of 1,4-dihydro- and 1,2,3,4-tetrahydro-naphthalene, as well as tetrahydrobinaphthyl and l(l-diethylamino)ethyl-l,4-... 

The reaction mechanism that was proposed is outlined in Scheme 22. Photoirradiation generates solvent-separated anion radical AR14 and cation radical CR13. Then (diethylamino)methyl radical is produced by desilylation of the cation radical CR13, which couples with the anion radical AR14 to give adduct 15 in 60% yield (Scheme 22 R = 4,4-Mej). 

Diethylamino. The known sources of this radical are analogous to the dimethylamino sources—namely, photolyses of triethylamine (20) and diethylnitros-amine (J) and pyrolyses of triethylamine (29), tetraethyltetrazene (36), and tetraethylhydrazine (34). 

Morpholino- and Amino-Ketones These classes of photoinitiators present a good activity [Is], The cleavage mechanisms ((10.16) and (10.17)) and the reactivity of the excited states have been fully reported [2i,30], Excellent representatives of morpholino ketones are 2-methyl- l-(4-methylthiobenzoyl)-2-morpholino-propan-1-one TMPK (10.16) and 2-methyl-l-(benzoyl)-2-morpholino-propan-l-one MPK. In amino ketones, the introduction of a morpholino moiety on a benzoyl group such as in 2-benzyl-2(diethylamino)-4,-morpholinobutyrophenone MPPK (10.17) red shifts the absorption. In both cases, efficient initiating radicals are generated. 

As mentioned before (Section 2.5.5.2), only primary and secondary amines are able to give a nucleophilic addition to fuUerenes. Tertiary amines, on the other hand, exclusively enter into radical additions. Usually these are initiated photo-chemically, and they are very hard to control. However, the isolation of a triethyl-amine-adduct with Cgo (see below) succeeded when oxygen was scmpulously excluded, while in its presence a completely different product featuring a pyrrolidine ring was generated. Moreover, the aerobic thermal reaction of C > with NEts has successfully been performed just recently. It yields the 3-N,N-diethylamino-5-... 

The aqueous photochemistry of the sodium salt of l-(A, A -diethylamino)dia-zen-l-ium-l,2-diolate (70) (Scheme 12) has been examined experimentally and theoretically. Photolysis of (70) results in formation of the radical anion (71) and NO, via intersystem crossing and a triplet excited state. The product pair either undergoes electron transfer, before escape of NO from the cage, to form triplet NO and nitrosamine (minor pathway), or the radical anion (71) dissociates to give a second NO molecule and (ultimately) diethylamine (major pathway). 

Dimerization of o-fuchsones, generated from o-hydroxybenzyl halides by treatment with either triethylamine or a diethylamino-derivatized polymer, affords dibenzo[i>/][l,5]dioxocin (115) and dinaphtho analogues (116 Ar = Ph, 4-FQH4, 4-MeOC6H4) in unspecified yield (Scheme 34). These reactions are reported to follow a stepwise, ionic pathway rather than radical or concerted [ttSs + r8a] thermal cycloaddition paths <82CCC838>. Curiously, no [4 + 2] dimers are formed in these reactions, although such products are favored for simpler o-quinone methides. 

Formula RC0NH(CH2)2N(CH2CH20H)2, RCO" rep. the stearic acid radical Uses Antistat in cosmetics Stearamidoethyl diethylamine CAS 16889-14-8 EINECS/ELINCS 240-924-3 Synonyms N-[2-Diethylamino) ethyl] octadecanamide Diethylaminoethyl stearamide... 

The one- and two-photon excited fluorescence property and crystal structure of a substituted stilbene-type compound frans-4-diethylamino-4 -bromostilbene (DEARS) has been reported [17]. Results indicate that this compound has a strong two-photon-exdted blue fluorescence at 440 nm when the 700 nm laser is used as the pump source. The one- and two-photon absorption and fluorescence properties of a free radical photopolymerization initiator, ( , )-4- 2-[p -(]yf,N-di-w-butylamino)stil-ben-p-yl]vinyl pyridine (Figure 3.8), in various solvents have been investigated [18]. The dye has a moderate two-photon absorption cross section of = 0.91 x 10 cm s/photon at 532 nm. This compound showed a strong two-photon-induced blue fluorescence of432 nm when pumped with 800 nm laser irradiation. Quantum chemical calculation indicated that the new initiator possesses a large delocalized... 

Still another example is an initiating system composed of 7-diethylamino-3 -(2 -N-methyl-benzimidazolyl)-coumarin and diphenyliodonium hexafluorophosphate. This composition initiates the polymerization of methyl methacrylate in visible light. After the dye absorbs flic light energy, quick electron transfer takes place from the dye to the iodonium salt to produce free radicals. " The light induced reaction is claimed to occur mainly through the excited singlet state of the coumarin and results in low sensitive to O2. The fluorescence of the coumarin compound was reported to be quenched efficiently by the iodonium salt. " The reaction was observed to be in accord with the Stem-Volmer equation. The influence of the concentration of coumarin on the polymerization rate of methyl methacrylate led to the conclusion that the free radicals from coumarin act mainly as chain terminators. ... 

Fouaissier and Chesneau reported that an cosine dye and ketocoumarin in the presence of an amine, acetone and iodonium salts initiate photocuring with light greater in wave length that 400 nm., The ketocoumarin (7-diethylamino-3,3 -oxydo-2H-chromen-2-one) was found by them to be a very useful additive to photo curable formulations, either in free-radical or in ionic curing processes illustrated as follows... 

True radical grafting onto reactions have not been described for PMM A since radical recombination does not occur separately. On the other hand, grafting onto functional groups with reasonable transfer constants are described for poly(vinyl chloride) or chlorinated rubber [150] or for a poly(diethylamino methacrylate) backbone [151],... 

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