5202-81-3

Upstream product

• 55-21-0 benzamide 
• 78-84-2 isobutyraldehyde 
• 33561-48-7 5,5-dimethyl-2-phenyl-4,5-dihydrooxazole 
• 21384-58-7 2,2-dimethylaziridin-1-yl-phenylmethanone 
• 28897-81-6 2-phenyl-4-iso-propyl-4H-oxazolin-5-one 
• 519-73-3 triphenylmethane 
• 709-25-1 N-(2-methylallyl)benzamide 
• 120-12-7 anthracene 

Downstream Products

• 88413-34-7 N-(2-methylpropenyl)thiobenzamide 
• 112081-41-1 N-(2-Methyl-propenyl)-benzimidoyl chloride 
• 14599-03-2 methyl 2-benzamido-3-methylbutanoate 
• 37950-61-1 5,5-Dimethyl-2-phenyl-thiazoline 
• 89002-69-7 1-(2-methylprop-1-enyl)-5-phenyltetrazole 
• 90859-31-7 1,5-dihydro-5-hydroxy-4,4-dimethyl-2-phenyl-4H-imidazole 
• 89002-68-6 4,4,5-trimethyl-2-phenyl-4H-imidazole 
• 112081-44-4 1,5-dihydro-4,4,5-trimethyl-2-phenyl-4H-imidazole 
• 89002-63-1 4,4-dimethyl-2-phenyl-4H-imidazole 
• 13682-20-7 4,5-dimethyl-2-phenyl-1H-imidazole 

Relevant academic research and scientific papers

A convenient synthesis of N-vinyl enamides via the lithiation and ring-opening reaction of 2-phenyl-2-oxazolines

A simple and efficient synthesis of N-vinyl enamides via the lithiation and ring-opening reaction of 2-phenyl-2-oxazolines with lithium diisopropylamide at room temperature has been developed. This method is especially suitable for the synthesis of multif

Bi(OTf)3-Catalyzed Multicomponent α-Amidoalkylation Reactions

A bismuth(III) triflate catalyzed three-component synthesis of α-substituted amides starting from amides, aldehydes, and (hetero)arenes is reported. The reaction has a broad substrate scope, encompassing formaldehyde as well as aryl and alkyl aldehydes. Low catalyst loadings are required, and water is formed as the only side product. The scope and limitation of this method will be discussed.

Aziridines. 76: Neglected aspects of anthracenide (anthracenidyl) chemistry - Reactions with two N-benzoylaziridines

Reaction of anthracenide A.- with N-benzoylaziridines 1a,b forms charged radicals 3a,b by single electron transfer and homolytic ring opening. Reactions follow that are known or expected as e.g. coupling with position 9 of A.- forming dihydroanthracene anions 9a,b that yield amidoethylated dihydroanthracenes 10a,b, or react with 1a,b giving finally 9,10-bis-amidoethylated dihydroanthracenes 11a,b. Results depend on experimental conditions and on the counter ions Na+ or Li+. Coupling is not regiospecific: contributions by positions 2 and 1 reach 29% or 4%, respectively, of total coupling with the primary radical 3a; much higher contributions are possible with Li. Product 21s (probably 3,3′-disubstituted tetrahydrobianthryl) may arise by hydrogen detachment from the first intermediate (29) of coupling with position 2 and dimerization of the formed 2-substituted A.- (30). Coupling products may be fully aromatized or may be hydroxylated in one of the benzylic positions. With counter ion Li+ a non-SET reaction of 1a with the dimer of A.- is indicated by the isolation of 9-benzoyl-dihydroanthracene 15 and by 19% yield of 16a (aromatized 10a). Reaction of 3b with anthracene is indicated by 10,10′-disubstituted tetrahydrobianthryl 37. Wiley-VCH Verlag GmbH, 2000.

Reactions of N-acylaziridines with sodium metal and sodium naphthalenide. Elimination of olefines

Reactions of N-acylaziridines 1a-g (N-benzoyl except 1d) with sodium or naphthalenide N.- in THF provide a variety of products that usually arise via the aziridino ketyls 2. Homolytic ring opening of 2 generates the amidatoalkyl radicals 3. Only with a very short reaction time were small amounts of benzil or benzoylnaphthalenes obtained indicating a reversible trapping of 2 by dimerization or coupling with N.-. Homolysis of 2 produced always the more stable 3 apart from reactions of monomethylaziridines 1c,d where the primary radical i-3c,d is kinetically favoured. The amides R1CONHCHR4CHR2R3 (9, isopropylamides i-9c,d from 1c,d) were usually the main products. 9 arise from 3 either by H atom abstraction from THF (probably in sodium metal runs) or by reduction of 3 to carbanions 5 that abstract a proton from THF (N.- runs). Addition of 5a (R2-4 = H) to 1a gives finally the ketone 8a. Self reaction of primary radical 3a is dimerization. Self reaction of tertiary or secondary radicals is disproportionation when an allylamide arises. This isomerizes to an enamide unless it is conjugated. R2R3C=CHR4 and R1CONH2 arise (probably) always. The mechanism, possibly a cyclic process of anion 6, is not clear. Johann Ambrosius Barth 1996.

Three positional isomers of substituted triphenylmethanes from reactions of trityl anion with 1-acyl-2,2-dimethylaziridines

Ring opening of aziridines 4a-d in reactions with trityl anion Tr(-) proceeds exclusively by cleavage of the NCMe2 bond.Substitution of the benzylic carbon of Tr(-) leads to 'central' products 10a-d in yields of 0-5percent.This is ascribed to an SN2 reaction with borderline character, as is well known from reactions of aziridines 4a-d with other nucleophiles.All remaining ring-opening reactions result from single-electron transfer (SET).This is direct SET from Tr(-) to aziridines 4a-c.For compound 4d (acyl = cinnamoyl), the SET reaction is of the innersphere type and proceeds via Michael addition, at least in part.Homolytic ring opening of the generated aziridino ketyls 5 forms the tertiary amidatoalkyl radicals 6.Main reaction of radicals 6a-c is transfer of a hydrogen atom from one of its two methyl groups to the generated trityl radical Tr..Methallylamides 7 and enamides 8 are the final products. ortho-Substituted triphenylmethanes 12 and/or its olefinic precursors 13 arise in ca. 20percent yield.A mechanism for the formation of these unique products is proposed that first converts the radicals 6 into the corresponding carbanions 16 which undergo an SN2' reaction with one allylic system TrCHCH=CH* of the dimer 14 of Tr..The leaving group Tr(-) is eliminated from this partial structure when carbanions 16 attack the marked carbon converting it finally into the substituted ortho carbon of compounds 12.Addition of radicals 6 to Tr(-) is probably the way to the para-substituted triphenylmethanes 11, which arise in yields of only 0-1percent from aziridines 4a,b (acyl = benzoyl, pivaloyl).Higher yields of para-substituted compounds 11 are obtained from aziridines 4c (acyl = 4-phenylbenzoyl) and 4d.This is ascribed, at least for substrate 4c, to a chain reaction because ketyl 5c must be formed more rapidly than ketyls 5a,b.A substantial part of radical 6d cyclizes, ending up as the triphenylmethane compound 26 that carries a pyrrolidone ring in the para position.

REDUCTIVE RING OPENING OF N-ACYLAZIRIDINES: DIFFERENT OUTCOMES OF CHEMICAL AND ELECTROCHEMICAL REACTIONS

Main products from electrochemical reduction of two N-acylaziridines are the corresponding oxazolines which are not formed in chemical reduction, probably due to a coordination of the oxygen with a metal counter-ion.

Evolutions differentes de radicaux anions formes par voie chimique ou electrochimique

Chemical and electrochemical reductions of N-aroylaziridines 1 are described and compared.The first step is a single electron transfer (1 +e -> 1-. -> 1'-.).But compounds obtained from 1'-. are depending on the method used way followed: chemical reduction of N-cinnamoylaziridine 1e provides pyrrolidone 10e; but oxazoline 11e is available by electrochemical reduction of the same starting material 1e.Counter ion seems responsible of these different results.In agreement with this hypothesis, it is shown that pyrrolidone 10e is obtained from 1j only in presence of a counter ion.

Synthesis and Properties of 4H-Imidazoles

The photolysis of 1-vinyltetrazoles to give 1H-imidazoles is extended to the synthesis of isolable nonaromatic 4H-imidazoles when the vinyl group is terminally disubstituted.Thus photolysis of the 2-phenyltetrazole (7a), prepared from isobutyraldehyde, at

Electron Attachment to N-Benzoylaziridines followed by C-N Homolysis of the Aziridine Ring

Reactions of N-benzoylaziridines with strong electron sources provide direct evidence for the formation of ketyls (2) and radicals (3), both of which are postulated intermediates in the single electron transfer mechanism of nucleophilic ring opening of activated aziridines.