91147-59-0Relevant academic research and scientific papers
Synthesis of Mitomycin C Analogues. 1. Introduction of the Urethane Function at C-10 of the Pyrroloindole Skeleton
Dijksman, Willem C.,Verboom, Willem,Egberink, Richard J. M.,Reinhoudt, David N.
, p. 3791 - 3797 (2007/10/02)
α-(Alkoxymethylene)-2-(1-pyrrolidinyl)benzeneacetonitriles 5b-e, prepared by condensation of 2-(1-pyrrolidinyl)benzeneacetonitrile with ethyl formate and subsequent alkylation of the sodium salt formed, cyclize thermally to the trans- and cis-9-(alkoxymethyl)pyrroloindoles 6b-e and 7b-e, respectively.Treatment of the sodium salt of 5a with acetyl chloride or acetic anhydride affords the 1-alkylindoles 8a and 8b, respectively.The mechanisms of both types of reaction, which are examples of the "tertiary amino effect", are discussed.The CH2OR group of the pyrrolo indoles 6b, d, e and 7b, d, e is deprotected, dependent on the nature of R, by boron tribromide (R=CH3), hydrobromic acid in acetic acid, and subsequent hydrolysis of the acetate formed (R=CH2Ph) and by concentrated hydrochloric acid in methanol (R=CH2OCH3) to give the corresponding alcohols 6a and 7a, respectively.Treatment of the pyrroloindole 7b with sodium in liquid ammonia yields a mixture of isomers of the 9-methylpyrroloindole 12b; in addition to the cyano group at C-9 also the methoxy group has been removed.Under these conditions the alcohol 7a affords a mixture of 12b and the decyanated alcohols cis-12c and trans-12c.The alcohols 7a and trans-12c are transformed to the corresponding urethanes 7g and 12d, respectively.
NOVEL APPLICATIONS OF THE "t-AMINO EFFECT" IN HETEROCYCLIC CHEMISTRY; SYNTHESIS OF 1-ALKYLINDOLES
Dijksman, W.C.,Verboom, W.,Reinhoudt, D.N.,Hale, C.G.,Harkema, S.,van Hummel, G.J.
, p. 2025 - 2028 (2007/10/02)
Thermal rearrangement of 2-vinyl-1-(1-pyrrolidinyl)benzenes varies with the leaving group ability of substituents in the vinyl moiety; compounds 3 having an OR group give 9-(alkoxymethyl)pyrroloindoles and compounds 6 (X=OAc, OTs or Cl) yield 1-alk
