Nucleophilic Addition of Triethylamine to Dimethyl Acetylenedicarboxylate

Alaimo, Robert J.; Farnum, Donald G.

doi:10.1139/v65-088

Cited by 14 publications

(6 citation statements)

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“…Cam6 and co-workers (3) used that chemistry in ring-opening reactions of diaziridines (Scheme 2). Other authors have suggested a similar deprotonation step to account for their observed products (4)(5)(6)(7)(8).…”

Section: Introductionmentioning

confidence: 71%

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The reactions of simple dimethylallylamines with dimethyl acetylenedicarboxylate. Formation of 1-dimethylamino-2-allylmaleates via formal allyl transfer

Schwan¹,

Warkentin²

1988

Can. J. Chem.

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. Can. J. Chem. 66, 1686 (1988). Tertiary amines bearing two methyl groups and an allylic substituent (X) react with dimethyl acetylenedicarboxylate (DMAD) to afford the corresponding 1-dimethylamino-2-X' maleates, in which X' is the allylic isomer of X. The mechanism postulated involves reversible formation of a zwitterion by attack of the amine at an sp-carbon of DMAD. The zwitterion then undergoes intramolecular allyl transfer, through a 6-membered transition state. Evidence for a zwitterionic intermediate (quaternary ammonium allenolate) includes capture of the allenolate centre by intramolecular addition to a carbonyl group and by proton transfer from chloroform. ADRIAN L. SCHWAN et JOHN WARKENTIN. Can. J. Chem. 66, 1686 (1988). Les amines tertiaires qui portent deux groupements mCthyles et un substituant allylique (X) rtagissent avec I'acCtyltnedicarboxylate de dimCthyle (ADDM) pour fournir les maleates correspondants, dimtthylamino-l XI-2 malCates, dans lesquels le groupement X' est I'isomkre allylique de X. Le mecanisme postulC implique la formation reversible d'un zwitterion par I'attaque de I'amine sur le carbone-sp de I'ADDM. Le zwitterion subit alors un transfert allylique intramoleculaire par le biais d'un Ctat de transition a six chainons. Les donntes supportant I'hypothkse de I'existence d'un zwitterion comme intermediaire (allknolate d'ammonium quaternaire) comportent la capture du centre allbnolate par une addition intramoleculaire sur un groupement carbonyle ainsi qu'un transfert de proton B partir du chloroforme.[Traduit par la revue]

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Section: Introductionmentioning

confidence: 71%

“…Treatment of a-(dimethylaminomethyl)-isobutyrophenone (6) with DMAD in CHCI, gave heterocyclic alcohol 7 in 42% yield (reaction [4] Qinyl position was 85-90% deuterated (estimated from 'H nmr of the crude product).…”

Section: Resultsmentioning

confidence: 99%

The reactions of simple dimethylallylamines with dimethyl acetylenedicarboxylate. Formation of 1-dimethylamino-2-allylmaleates via formal allyl transfer

Schwan¹,

Warkentin²

1988

Can. J. Chem.

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“…The corresponding process in N-allylenamines occurs only above 200 "C.' [2,3] And other rearrangements of allylic ammonium ylides have also been described. "…”

Section: Resultsmentioning

confidence: 99%

Reactions of tertiary allylamines with dimethyl acetylenedicarboxylate

Kandeel¹,

Vernon²

1987

J. Chem. Soc., Perkin Trans. 1

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The reaction of some tertiary allylamines with dimethyl acetylenedicarboxylate in acetonitrile results in the formation of 1 : 1 adducts via [3,3] rearrangement of the ally1 group from nitrogen to carbon.Tertiary amines catalyse the nucleophilic addition of species HX to activated acetylenes.' In some other cases, adducts incorporating the amine moiety are obtained as the result of C-N bond cleavage. Winterfeldt has described a variety of such reactions involving the tertiary amino-ester (la) and -ketones (lb) and (2) with methyl propiolate to give p-aminocrotonates (3a) and (3b).' The formation of N-ethylpyrrole derivatives from tertiary amines (lb) and (lc) and acetylene esters involves loss of the second N-ethyl group in each case. Similarly triethylamine is reported to add to dimethyl acetylenedicarboxylate (DMAD) in the presence of a proton source to give compound (4a), for which the maleate configuration, not assigned at the time, is correct by comparison of spectral data with those of analogous corn pound^.^^^ N-Benzylaziridine catalyses the trimerisation of DMAD in aprotic solvents, but in t-butyl alcohol a 1: 1: 1 adduct (4c) is obtained through opening of the aziridine ring.' Meo2c&ozMe Et ,NCH2 R ( 1 ) a; R = CH,CO,Et H NR' R' 1 2 b; R = COPh ( 4 ) a; R = R = E t c; R = C02Me b; R ' , R 2 = (CH,), 1 C; R = CHZPh, R2= C H 2 C H 2 0 8~' d; R'= R2= Me 1 2 e; R , R =(CH212 1 2 1 2 ( C N C ti 2 c H 2)0 f ; R , R = CHzCH=CHCH2 9; R , R = (CH,),R1R2NCH=CHC02Me 1 2 1 ( 3 ) a; R = R = Et b; R , R 2 = (CH215 the same derivative (9b). Authentic samples of the by-products (4a) and (4b) were prepared from DMAD with diethylamine and piperidine, respectively, and similarly converted into the 2,4-dinitrophenylhydrazone derivative (9a). Catalytic hydrogenation of the adduct (7a) gave the corresponding propyl compound (8), which was characterised both as the 2,4-dinitrophenylhydrazone (9d), and by degradation to 2-oxohexanoic acid (Scheme 2). Me02C , C0,Me \ %+ , R1 R'R2NCH2CH=CHR3 -R37(&J,R2 ( 6 ) ( 5 ) a ; R 1 2 = R = E t , R 3 = H c ; R 1 = R 2 = Et, R 3 = Me I b; R', R2 = (CH2I5, R 3 = H Pd I H2 ( 7 a I -CH 1 3 ( 7 ) a ; R = R2= Et, R = H b; R', R 2 = (CH215, R 3 = H 1 c; R = RZ= Et, R3= Me Scheme 1. M e o z c~c o 2 N e -H~O + BuCOC02H Pr NEt, ( 8 1 Scheme 2.Me0,C COzMe Me02C \ /CO2Me Results and DiscussionWe have examined the addition of tertiary allylic amines to DMAD. Although no reaction occurs between allyldiethylamine (5a) and DMAD in dry ether, these compounds react readily in acetonitrile at room temperature to give the 1: 1 adduct (7a) together with smaller amounts of the aminomaleate ( 9 a; = (4a). The proportion of (4a) increased if water was added to the product (7a) even when thoroughly dry acetonitrile was used. the 1: 1 adduct (7b) and a smaller amount of (4b). The constitution of the adducts (7a) and (7b) was proved from their 'H n.m.r. and mass spectra and by hydrolysis in the presence of a x ; : //C -CH Me 2 , 4 -( 0 ,~ ),C~H,NHN ' R (10) system, but it still amounted to a small percentage of the m...

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“…Bislang war lediglich bekannt [6], dass tertiäre aliphatische Amine ohne Protonendonator nicht mit Ace- …”

Section: Entalkylierung N-tertiärer Piperazine Mit Aktivierten Alkinenunclassified

Reaktionen Von Acetylencarbonsäureestern Mit Piperazinderivaten

Möhrle

Azodi

2006

Zeitschrift Für Naturforschung B

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Hg(II)-EDTA-dehydrogenation of benzylpiperazine (5) in 50% ethanol with addition of diethyl acetylenedicarboxylate (2) to a minor extent gives rise to (piperazine-1,4-diyl)-bis(maleate) (9), which is inert to Hg(II)-EDTA and results in quantitative yield when Hg(II)-EDTA is omitted. 4-Benzylpiperazin-1-yl)-monomaleate (8) reacts with 2 in various solvents by addition of water with dealkylation and formation of 9. CH-acidic compounds may also be used as proton donors. Analogous reactions, although with minor yields, occur with the propiolates 11 and 12. 1-Substituted piperazines with benzyl, methine or allylic groups (5 -5c, 27d -g, and 27h) react readily with acetylenedicarboxylic acid esters to give compounds of type 9, whereas benzhydryl, aromatic and most of the unbranched aliphatic substituents are not replaced. The reactivity of 1,4-disubstituted piperazines corresponds largely to the behaviour of the substituents in the monosubstituted derivatives.

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Nucleophilic Addition of Triethylamine to Dimethyl Acetylenedicarboxylate

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Cited by 14 publications

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The reactions of simple dimethylallylamines with dimethyl acetylenedicarboxylate. Formation of 1-dimethylamino-2-allylmaleates via formal allyl transfer

The reactions of simple dimethylallylamines with dimethyl acetylenedicarboxylate. Formation of 1-dimethylamino-2-allylmaleates via formal allyl transfer

Reactions of tertiary allylamines with dimethyl acetylenedicarboxylate

Reaktionen Von Acetylencarbonsäureestern Mit Piperazinderivaten

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