Chemistry of pyrrolizines; reactions with cyanogen bromide and trifluoroacetic anhydride

Interaction of the pyrrolizine 3 with cyanogen bromide in a tetrahydrofuran/water mixture affords addition to the enamine double bond with formation of 5 which can be aromatized to 6 by silica gel. Reaction of 6 with cyanogen bromide in the same solvent mixture yields the indoline 8a which structure is proved in a chemical way by conversion of the product into the aldehyde 8d. The different reaction pathway is discussed in terms of steric hindrance by the ester groups. Treatment of 6 with trifluoroacetic anhydride gives the trifluoroacetylated compound 11. Removal of the sterically hindered ester groups in 6, with acetic acid in quinoline at 200°, is accompanied by the simultaneous decarboxylation to yield the pyrrolo[1,2-a]indole 1

Novel applications of the “t-amino effect” in heterocyclic chemistry; synthesis of 5H-pyrrolo- and 1H,6H-pyrido[1,2-a][3,1]benzoxazines

Trifluoroacetylated N,N-dialkylanilines react in refluxing 1-butanol to benzoxazine derivatives via an intramolecular] [1, 5] hydrogen shift and subsequent cyclization of the dipolar intermediate

On the mechanism of the reaction of enamines and dimethyl acetylenedicarboxylate (DMAD) in polar and apolar solvents

[2+2]-Cycloadducts of enamines and DMAD, formed in apolar solvents, isomerize to pyrrolizine derivatives under mild conditions in protic polar solvents like methanol and 1-butanol

Novel applications of the "t-amino effect" in heterocyclic chemistry. Synthesis of a pyrrolo[1,2-a]quinazoline and 5H-pyrrolo[1,2-a][3,1]benzothiazines

1-(1-Pyrrolidinyl)benzenes substituted with an imino- or an in situ generated thiocarbonyl group in the 2-position rearrange upon heating to quinazoline and benzothiazine derivatives, respectively

The madelung synthesis of dihydro-1H-pyrrolo- and tetrahydropyrido[1,2-a]- indoles under mild conditions

Benzeneacetonitriles substituted with lactam moieties in the ortho-position cyclize under the influence of a base, dependent on the ring-size of the lactam function, to dihydropyrrolo-, tetrahydropyrido[1,2-a]indole or dihydro-1-benzazepin derivatives, respectively

Reductive activation of potential antitumor bis(aziridinyl)benzoquinones by xanthine oxidase: Competition between oxygen reduction and quinone reduction

The reduction of a series of 2,5-bis(1-aziridinyl)-1,4-benzoquinone (BABQ) derivatives with various 3,6 substituents by the enzyme xanthine oxidase has been studied. The reduction rate has been assayed by measuring the rate of reduction of cytochrome c, which is very efficiently reduced by reduced BABQ species. Under nitrogen, the reduction rate correlated with the quinone reduction potential and steric parameters. Comparing reduction rates under nitrogen and air demonstrates that at BABQ concentrations > 25 μm the competition for electrons from xanthine oxidase between oxygen and the BABQ derivative is dominated by the latter. This is also confirmed by the effect of superoxide dismutase (SOD): in the presence of a BABQ derivative, cytochrome c reduction can be totally inhibited by SOD, although the required amount of SOD depends on the redox potential of the quinones. This indicates that SOD causes the equilibrium between semiquinone and superoxide to shift, resulting in a decrease of the semiquinone concentration. It is concluded that reduction by xanthine oxidase is a simple and effective method for reducing aziridinylbenzoquinones

Novel applications of the “t-amino effect” in heterocyclic chemistry; synthesis of 1-alkylindoles

Thermal rearrangerment of 2-vinyl-1-(1-pyrrolidinyl)benzenes varies with the leaving group ability of substituents in the vinyl moiety; compound 3 having an OR group 9-(alkoxy-methyl)pyrrolo[1,2-a]indoles and compounds 6 (X = OAc, OTs or Cl) yield 1-alkylindoles

Electro-optic polymers for high speed modulators

Different electro-optic polymer systems are analyzed with respect to their electro-optic activity, glass transition temperature (Tg) and photodefinable properties. The polymers tested are polysulfone (PS) and polycarbonate (PC). The electro-optic chromophore, tricyanovinylidenediphenylaminobenzene (TCVDPA),which was reported to have a highest photochemical stability [1] has been employed in the current work. Modified TCVDPA with bulky side groups has been synthesized, and a doubling of the electro-optic coefficient (r33) compared to the unmodified TCVDPA has been shown. The plasticizing effect of the chromophore, has been reduced by attaching it to the polymer backbone. SU8 (passive) and PC-TCVDPA (active) channel waveguides were fabricated by photodefinition technique and the passive waveguide losses were measured to be 5 dB/cm at 1550 nm

Photodefinable electro-optic polymers for high speed modulators

We present a series of polymeric electro-optic (EO) materials based on the tricyanovinylidenediphenylaminobenzene (TCVDPA) chromophore which exhibits an exceptionally high photostability combined with a high EO activity. The EO properties of these derivatives are given and the best result was obtained with the di-tBut derivative 2, which showed a nearly doubling effect of $r_{33}$ (14 pm/V to 25 pm/V), while increasing the concentration from 25 wt% to 37.5 wt%. A microring resonator design was made based on the PC-TCVDPA system. Waveguides were fabricated by photodefinition of inverted ridges in VSC, a negative epoxy based photoresist with low refractive index

Synthesis of pyrrolizines by intramolecular capture of 1,4-dipolar intermediates in reactions of enamines with dimethyl acetylenedicarboxylate

Solvent polarity and reaction temperature strongly influence the reactions of dimethyl acetylenedicar-boxylate (DMAD) with 1-pyrrolidinyl enamines of acyclic and cyclic ketones. Whereas DMAD and 1-[1-phenyl-2-(phenylthio)ethenyl]pyrrolidine (3) give only a mixture of the isomeric 1,3-butadienes (5) in apolar solvents, in methanol the main product is the pyrrolizine 7, together with 5. Again in methanol, DMAD reacts at 0-5° with 8, 9 and 10 to give exclusively 1:1 adducts, the pyrrolizines 11,12 and 13, respectively, whereas at −50° 8 and 9 give 1:2 (enamine : DMAD) adducts, the pyrrolizines 14 and 15, respectively; a single crystal X-ray analysis of 14 gave the structure of the 1:2 adducts. In the same solvent methyl propiolate and 8 give only the linear Michael adduct 17. The enamine-ketone 18 reacts with DMAD in propylene carbonate at 0–5° to give, via (2 + 2)-cycloaddition and ring expansion, 19, and the linear Michael adduct 20. The mechanism of (2 + 2)-cycloaddition and pyrrolizine formation is discussed in terms of a common tied-ion pair intermediate formed in the first, rate-determining step, followed by a second solvent-dependent step