A Synthesis of Vinylcyclopropane

Volkenburgh, Ross Van.; Greenlee, Kenneth W.; Derfer, John M.; Boord, Cecil E.

doi:10.1021/ja01179a004

Cited by 53 publications

(20 citation statements)

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“…The polymerizability of VCP with dibenzoyl peroxide (DBPO) and with ultraviolet radiation was reported for the first time in 1949 9) . Some years later, the cationic homopolymerization of VCP and its radical copolymerization with butadiene, styrene, or methyl methacrylate was the subject of two US patents 62,63) .…”

Section: Polymerization Of Vinylcyclopropane and Monosubstituted Derimentioning

confidence: 99%

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Synthesis and polymerization of vinylcyclopropanes

Moszner

Zeuner

Völkel

et al. 1999

Macromol. Chem. Phys.

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SUMMARY: Vinylcyclopropanes are important synthetic intermediates in organic chemistry and are mostly synthesized by the simultaneous introduction of the cyclopropane and the vinyl unit, e. g., by the reaction of trans-1,4-dihalobutenes with b -dicarbonyl compounds or the addition of carbenes to dienes. The polymerization of vinylcyclopropane itself results in vinyl polymers with predominantly 1,2-structural units. The radical polymerization of substituted vinylcyclopropanes results in polymers with mainly 1,5-ring-opened units, whereby radical stabilizing substituents or electron-withdrawing groups increase the radical polymerizability and the ring-opening ability. The vinylcyclopropanes undergo a radical copolymerization with other vinyl monomers, such as methacrylates, and, in comparison to the polymerization of these linear vinyl monomers, the vinylcyclopropanes show a significantly lower volume shrinkage during ring-opening polymerization. Hybrid vinylcyclopropanes are polymerized step-by-step under formation of reactive polymers or polymer networks. Multifunctional cross-linking vinylcyclopropanes can be used as new low-shrinking matrix monomers for photopolymerizable materials. In addition, the sol-gel process of trialkoxysilyl-functionalized vinylcyclopropanes affords low shrinking organic-inorganic nanocomposites.

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Section: Polymerization Of Vinylcyclopropane and Monosubstituted Derimentioning

confidence: 99%

“…Although the polymerization of VCP was already described in 1949 9) , the interest in the polymerization of VCPs has grown recently [10][11][12] , for example, as lowshrinking monomers in photopolymerization systems or for dental applications.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and polymerization of vinylcyclopropanes

Moszner

Zeuner

Völkel

et al. 1999

Macromol. Chem. Phys.

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“…10' O s-', respectively [24]. Ethylcyclopropane (37) was synthesized via Wolff-Kishner reduction of l-cyclopropylethanone [25]. It reacted in 21% yield to afford 40; only unreacted 37, but no products derived from 39 were detected in the reaction mixture.…”

Section: Optimization Of Reaction Conditionsmentioning

confidence: 99%

Rhodium(II)‐Catalyzed CH Insertions with {[(4‐Nitrophenyl)sulfonyl]imino}phenyl‐λ³‐iodane

Nägeli

Baud

Bérnardinelli

et al. 1997

Helvetica Chimica Acta

230

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Dedicated to Prof. Dieter Seebach on the occasion of his 60th birthday (1 3.11.97) The [Rh,(OAc),]-catalyzed decomposition of {[(4-nitrophenyl)sulfonyl]imino}phenyl-13-iodane (NsN=IPh) resulted in formal insertions into CH bonds, activated by phenyl or vinyl groups, or by 0-substituents. Scope and limitations of the reaction were investigated. Yields of up to 84% were achieved in the most favorable cases. Yields were enhanced by electron-releasing substituents and decreased by steric hindrance. Aziridination competed with allylic insertion with olefinic substrates. The insertion reaction proceeded with retention of configuration. With chiral Rh" catalysts, a modest asymmetric induction was observed. A mechanism involving direct insertion by a Rh-complexed nitrene into the CH bond is proposed.

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“…Many of these studies, however, have utilized results from ultraviolet spectroscopic studies, for which i t is not possible to decide if the observed changes attributed to cyclopropyl conjugation arise from interactions in the ground state or an excited state (or both). Other techniques which do not suffer from this difficulty have been employed for the same purpose, including infrared (8) and Raman (9) spectra, dipole moment measurements (lo), exaltation of molecular refraction ( l l ) , heats of combustion data (12), boiling point differences (13), and, more recently, proton spectra of cationic species (14) For personal use only.…”

Section: Introductionmentioning

confidence: 99%

¹³C n.m.r. studies. IX. Carbonyl carbon shieldings of some cyclopropyl ketones

Marr¹,

Stothers²

1967

Can. J. Chem.

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The 15.1 Mc/s 13C nuclear magnetic resonance spectra of 15 aliphatic and alicyclic ketones having a three-membered ring alpha to the carbonyl group have been obtained and the shieldings of their carbonyl carbon nuclei are reported. A number of derivatives of bicyclo-[4.l.O]heptan-2-one, bicyclo[3.l.0]hexan-2-one, spiro[2.5]octan-4-one, and spiro[2.4]heptan-4-one have been included. The primary objective was to investigate the question of conjugation of the cyclopropyl ring with a carbonyl grouping, since we had shown previously that 13C shieldings of carbonyl carbons are significantly affected by conjugative interactions. The 1SC data for several related compounds were obtained to aid in our assessment of the cyclopropyl results. Some evidence of cyclopropyl conjugation is presented.

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A Synthesis of Vinylcyclopropane

Cited by 53 publications

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Synthesis and polymerization of vinylcyclopropanes

Synthesis and polymerization of vinylcyclopropanes

Rhodium(II)‐Catalyzed CH Insertions with {[(4‐Nitrophenyl)sulfonyl]imino}phenyl‐λ³‐iodane

¹³C n.m.r. studies. IX. Carbonyl carbon shieldings of some cyclopropyl ketones

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A Synthesis of Vinylcyclopropane

Cited by 53 publications

References 0 publications

Synthesis and polymerization of vinylcyclopropanes

Synthesis and polymerization of vinylcyclopropanes

Rhodium(II)‐Catalyzed CH Insertions with {[(4‐Nitrophenyl)sulfonyl]imino}phenyl‐λ3‐iodane

13C n.m.r. studies. IX. Carbonyl carbon shieldings of some cyclopropyl ketones

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Rhodium(II)‐Catalyzed CH Insertions with {[(4‐Nitrophenyl)sulfonyl]imino}phenyl‐λ³‐iodane

¹³C n.m.r. studies. IX. Carbonyl carbon shieldings of some cyclopropyl ketones