Synthesis and Reactivity Studies of 2,4-(Dimethylmethano)-2,4-didehydroadamantane: A Comparison with an Unsubstituted Analog

Mlinarić‐Majerski, Kata; Cvitas, Dunja Safar; Veljković, Jelena

doi:10.1021/jo00088a018

Cited by 10 publications

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“…Examining the reaction of propellane 2 with oxygen (Figure ), the changes in band intensities can be observed. The intensity of the characteristic vibration of the carbonyl group at 1720 cm -1 gradually increases due to the reaction products 12b. The CH 2 scissoring vibrations are almost independent of the molecular framework.…”

Section: Resultsmentioning

confidence: 98%

“…[3.1.1]Propellanes 1 and 2 as well as their dihydro congeners 3 and 4 were synthesized following the literature procedures. , The samples of 1 and 2 were prepared in a drybox under nitrogen. For Raman spectroscopy capillary tubes were filled with the neat sample and spectra were recorded immediately after.…”

Section: Methodsmentioning

confidence: 99%

“…Contrary to the usual carbon−carbon single bond, the central bond in small-ring propellanes, such as in 2,4-methano-2,4-didehydroadamantane ( 1 ) and 2,4-(dimethylmethano)-2,4-didehydroadamantane ( 2 ) (Figure ), is highly reactive toward electrophiles and free radicals. − The bond in 1 and 2 can easily be reduced by electron-transfer hydrogenation to give 2,4-methanoadamantane ( 3 ) and 2,4-(dimethylmethano)adamantane ( 4 ), respectively. , Also, [3.1.1]propellanes 1 and 2 readily add disulfides and carbon tetrachloride across the central bond to give the corresponding 2,4-disubstituted 2,4-methanoadamantanes . The unusual chemical reactivities of 1 and 2 have been attributed to the electron-density distribution in the central propellane bond. , Whereas chemical evidence indicates that the electron density on the central bond of small propellanes is considerably higher at the back side of the inverted carbon atoms than between them, more substantial support of this hypothesis was needed. Therefore, we have undertaken a detailed vibrational study of the two [3.1.1]propellane derivatives, 1 and 2 , and their dihydro congeners, 3 and 4 , and determined the changes in energies, geometrical parameters, and normal modes due to the formation of the propellane bond.…”

Section: Introductionmentioning

confidence: 99%

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Nature of Bonding in [3.1.1]Propellane. Vibrational Spectra and Normal Coordinate Analysis of 2,4-Methano-2,4-didehydroadamantane, 2,4-(Dimethylmethano)-2,4-didehydroadamantane, and Their Dihydro Congeners

et al. 1997

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The properties of the propellane bond in 2,4-methano-2,4-didehydroadamantane (1) and 2,4-(dimethylmethano)-2,4-didehydroadamantane (2) have been determined on the basis of the spectroscopic and chemical evidence. A monitoring of reaction of propellane 2 with dimethyl disulfide by Raman spectroscopy has indicated the cleavage of the central bond between inverted carbon atoms. Raman and infrared spectra of 1 and 2 as well as of their dihydro congeners 2,4-methanoadamantane (3) and 2,4-(dimethylmethano)adamantane (4) have been recorded. To describe the vibrational and molecular orbital properties of these compounds (harmonic frequencies, heats of formations, bond orders, and charge distributions), AM1 semiempirical calculations were performed. The calculated properties are found to be in fair agreement with the observed ones. By combining the results of spectroscopic investigations and molecular orbital calculations, the central bond between inverted carbon atoms is associated with the highest occupied molecular orbitals in propellanes 1 and 2. Assuming the transferability of the adamantane scaling factors for force constants within the studied group of molecules, an "a priori" assignment of the observed bands has been obtained.

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Section: Resultsmentioning

confidence: 98%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Nature of Bonding in [3.1.1]Propellane. Vibrational Spectra and Normal Coordinate Analysis of 2,4-Methano-2,4-didehydroadamantane, 2,4-(Dimethylmethano)-2,4-didehydroadamantane, and Their Dihydro Congeners

et al. 1997

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“…The non-standard stereochemistry of carbon atoms in such molecules had intrigued Zdenko Majerski and Kata Mlinarić-Majerski to synthesize and study reactivity of propellanes, [21,22] however later on, they continued with chemistry of adamantane. [23][24][25] The results were presented in a book chapter by K. Mlinarić-Majerski. [26] Definitely, adamantane molecule has been a focal point of her research interest.…”

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confidence: 99%

A Strong Link Between Organic Chemistry and Chemical Crystallography Started a Century Ago

Kojić‐Prodić

Molčanov

2019

Croat. chem. acta (Online)

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The article sheds light on some historical crossings of organic chemistry and chemical crystallography. It connects past and present bringing into the focus Prof. Kata Mlinarić-Majerski’s research. An impact of structural chemistry on organic synthesis and reactivity is shown. X-ray structure analysis was established as a unique method to determine the composition and architecture of synthetic and natural organic molecules, already in the second decade of the last century; some of historical and scientific milestones are shown. Numerous controversies were solved, when intriguing molecular structures had been determined and the nature of chemical bond was clarified. An absolute structure (chirality) determination using an anomalous dispersion of X-rays was an important step forward, particularly in pharmaceutical industry. Structural data provided by X-ray crystallography, stored by Cambridge Structural Data Centre have been of great impact on many areas of science. They are closely related to intra- and intermolecular forces and structure/function correlations directing us to synthesis of compounds with designed properties. The developments of supramolecular chemistry, crystal engineering, materials science, and most of all of molecular machines have been assisted by chemical crystallography. The essay does not aim to review the complete scientific opus of Prof. K. Mlinarić-Majerski but it is focused on some of the highlights of her research. The interdisciplinary approach in her research is related to the use of X-ray structural analysis to define molecular architecture, conformational chirality, conformational isomerism, and get insight into reaction paths, interactions governing molecular assembling, and to recognise chemical properties of new compounds. In these researches the X-ray crystallographers were involved.

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“…MAd can be prepared in two steps from ethanoadamantan-3-one involving diazotization and photolysis . The other pathway to MAd involves formation of a [3.1.1]propellane and its subsequent reduction with Li or by free radical reaction …”

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confidence: 99%

Novel 2,4-Methanoadamantane-Benzazepine by Domino Photochemistry of N-(1-adamantyl)phthalimide

et al. 2008

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The photochemical reaction of N-(1-adamantyl)phthalimide (1) gives cleanly one product, the novel hexacyclic benzazepine derivative of 2,4-methanoadamantane 2. Its structure was characterized by spectroscopic methods and X-ray analysis and represent the first example of the 2-azahexacyclo[8.7.1.1 (1,4).0 (4,9).0 (11,16).0 (12,18)]nonadeca-4,6,8-triene skeleton. The product is formed by a domino process of two consecutive excited-state intramolecular gamma-hydrogen-transfer reactions. Base hydrolysis of the benzazepine 2 gives in high yield the keto derivative of the 1,2-substituted adamantane epsilon-amino acid 3.

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Synthesis and Reactivity Studies of 2,4-(Dimethylmethano)-2,4-didehydroadamantane: A Comparison with an Unsubstituted Analog

Cited by 10 publications

References 1 publication

Nature of Bonding in [3.1.1]Propellane. Vibrational Spectra and Normal Coordinate Analysis of 2,4-Methano-2,4-didehydroadamantane, 2,4-(Dimethylmethano)-2,4-didehydroadamantane, and Their Dihydro Congeners

Nature of Bonding in [3.1.1]Propellane. Vibrational Spectra and Normal Coordinate Analysis of 2,4-Methano-2,4-didehydroadamantane, 2,4-(Dimethylmethano)-2,4-didehydroadamantane, and Their Dihydro Congeners

A Strong Link Between Organic Chemistry and Chemical Crystallography Started a Century Ago

Novel 2,4-Methanoadamantane-Benzazepine by Domino Photochemistry of N-(1-adamantyl)phthalimide

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