Zur Kenntnis des Kohlenstoffringes XV. Über die Herstellung und einige physikalische Daten verschiedener Kohlenstoffringe bis zum 32‐Ring

Růžička, L.; Stoll, M.; Huyser, H. W.; Boekenoogen, H. A.

doi:10.1002/hlca.19300130540

Cited by 61 publications

(4 citation statements)

References 9 publications

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“…The effect of homology within a ring itself is not so simple. The difference in the structure of small and of large rings has been pointed out previously by Ruzicka and coworkers (6,7,8). They have shown that the larger rings consist of two parallel chains of carbon atoms similar to the aliphatic chains, while in the smaller rings the arrangement is more nearly that of regular polygons; in the intermediate rings (of about eight or ten to seventeen carbon atoms) the compression of hydrogen atoms within the center of the ring gives a maximum in the density at = 14.…”

Section: Homologous Seriessupporting

confidence: 52%

Studies of the Physical Properties of Alicyclic Hydrocarbons. I. Molal Volumes of Monoalicyclic Hydrocarbons at 20°C.

Egloff¹,

Kuder²

1942

J. Phys. Chem.

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Section: Homologous Seriessupporting

confidence: 52%

Studies of the Physical Properties of Alicyclic Hydrocarbons. I. Molal Volumes of Monoalicyclic Hydrocarbons at 20°C.

Egloff¹,

Kuder²

1942

J. Phys. Chem.

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“…First prepared in the 1920s and 1930s by Ruzicka et al . in connection with their work on perfumery constituents, most members of the series are beautifully crystalline, moderately high melting solids that are readily prepared (although often in low yield) by well-documented procedures.…”

Section: Introductionmentioning

confidence: 99%

Geometric Requirements for Hydrogen Abstractability and 1,4-Biradical Reactivity in the Norrish/Yang Type II Reaction: Studies Based on the Solid State Photochemistry and X-ray Crystallography of Medium-Sized Ring and Macrocyclic Diketones

et al. 1996

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The Norrish/Yang type II photochemistry of ten even-numbered cyclic diketones ranging in ring size from 10-membered to 26-membered has been studied in the crystalline state as well as in solution. In the solid state, the diketones undergo stereoselective cyclobutanol formation in which the cis or trans ring fusion stereochemistry of the photoproducts is governed by the conformation of the diketone present in the crystal as determined by X-ray crystallography. The reactive γ-hydrogen atoms are identified and the distance and angular parameters associated with their abstraction are derived from the crystallographic data. For the most part, the abstractions occur through boatlike rather than chairlike six-atom geometries, and the average value of d, the CdO‚‚‚H abstraction distance, for 16 reactive γ-hydrogens was found to be 2.74 ( 0.04 Å; the average values of the angular parameters ω (the γ-hydrogen out-of-plane angle), ∆ (the CdO‚‚‚H γ angle), and θ (the C-H γ ‚‚‚O angle) are 53 ( 5°, 83 ( 4°, and 115 ( 2°, respectively. In a similar manner, the geometric parameters associated with the ring closure reactions of the intermediate 1,4-hydroxy biradicals were estimated from the crystallographic data. This indicates that both the pre-cis and pre-trans biradicals are poorly aligned for cleavage but are well oriented for closure, with radical separations of 3.1-3.2 Å. For four of the diketones, the solid state photoproduct ratios were found to be temperature dependent as a result of enantiotropic phase transitions. For two of the diketones, the high-temperature, metastable phases were characterized by solid state 13 C and 2 H NMR spectroscopy. Crystals of 1,14-cyclohexacosanedione were found to be dimorphic, and the conformation adopted by the macrocycle is very different in the two dimorphs. As a result, irradiation of one of the dimorphs leads to cis-cyclobutanol and photolysis of the other gives trans, a particularly clear demonstration of the effect of conformational polymorphism on solid state chemical reactivity. Overall, the solid state results indicate that the product distribution is determined by the relative rates of forward rather than reverse hydrogen atom transfer and that the biradicals react in a least-motion, conformation-specific manner. In solution, on the other hand, the photoreaction is ring size-dependent, resembling the solid state results for the 12-and 14-membered-ring diketones, and consisting mainly of type II elimination accompanied by reduced amounts of nonstereoselective cyclobutanol formation for the 16-26-membered-ring compounds. It is suggested that this ring size dependence stems from the relative conformational freedom of the intermediate 1,4-biradicals in the fluid mediumsmotions that are slow compared to closure for the 12-and 14-membered rings, but that permit alignment for biradical cleavage and alternative modes of closure in the "floppier" 16-membered and larger rings. The one exception to the above generalizations is 1,6-cyclodecanedione, which was found to be photochemically i...

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“…In order to quantify the amounts of 3 , 6 , 7 , and 8 by UV it was first necessary to determine the chromatographic retention characteristics and relative UV response factors (ε ratios) for 6−8 vs 3 . Diketone 3 was prepared by published procedures …”

Section: Resultsmentioning

confidence: 99%

“…All glassware was oven-dried. Diketone 3 was prepared as previously described, except THF was used as solvent, rather than benzene …”

Section: Methodsmentioning

confidence: 99%

Reactions of Molecules with Two Equivalent Functional Groups. 5. Anomalous Reactivity of 1,10-Cyclooctadecanedione. Crystal and Molecular Structures of cis,cis-1,10-Diphenyl-1,10-cyclooctadiene and the Stereoisomers of 1,10-Diphenyl-1,10-cyclooctadecanediol¹

et al. 1996

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The reaction of the title diketone (3) with phenyl Grignard produces (with rate constant k(1)) the conjugate base (6-M) of 10-hydroxy-10-phenylcyclooctadecanone (6), which is subsequently converted (with rate constant k(2)) to the conjugate base of the title diol, as a mixture of the cis (7, 55%) and trans (8, 45%) isomers. The ratio k(2)/k(1), 2.2 +/- 0.4, indicates that the carbonyl group in 6-M is 4.4 times as reactive as each carbonyl in 3. Competition experiments further demonstrate that the relative rates (per carbonyl) for addition of phenylmagnesium bromide to 3, 10-methylenecyclooctadecanone (11), and cyclopentadecanone (12) are 1.0:0.60:1.92. Possible reasons for this order of reactivity are discussed. Diols 7 and 8 undergo facile double dehydration to form the title diene 13, which is predicted by molecular mechanics calculations to be the most stable of the four possible symmetrical diene isomers. The structures of 7, 8, and 13 were secured by single-crystal X-ray studies.

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Zur Kenntnis des Kohlenstoffringes XV. Über die Herstellung und einige physikalische Daten verschiedener Kohlenstoffringe bis zum 32‐Ring

Cited by 61 publications

References 9 publications

Studies of the Physical Properties of Alicyclic Hydrocarbons. I. Molal Volumes of Monoalicyclic Hydrocarbons at 20°C.

Studies of the Physical Properties of Alicyclic Hydrocarbons. I. Molal Volumes of Monoalicyclic Hydrocarbons at 20°C.

Geometric Requirements for Hydrogen Abstractability and 1,4-Biradical Reactivity in the Norrish/Yang Type II Reaction: Studies Based on the Solid State Photochemistry and X-ray Crystallography of Medium-Sized Ring and Macrocyclic Diketones

Reactions of Molecules with Two Equivalent Functional Groups. 5. Anomalous Reactivity of 1,10-Cyclooctadecanedione. Crystal and Molecular Structures of cis,cis-1,10-Diphenyl-1,10-cyclooctadiene and the Stereoisomers of 1,10-Diphenyl-1,10-cyclooctadecanediol¹

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Zur Kenntnis des Kohlenstoffringes XV. Über die Herstellung und einige physikalische Daten verschiedener Kohlenstoffringe bis zum 32‐Ring

Cited by 61 publications

References 9 publications

Studies of the Physical Properties of Alicyclic Hydrocarbons. I. Molal Volumes of Monoalicyclic Hydrocarbons at 20°C.

Studies of the Physical Properties of Alicyclic Hydrocarbons. I. Molal Volumes of Monoalicyclic Hydrocarbons at 20°C.

Geometric Requirements for Hydrogen Abstractability and 1,4-Biradical Reactivity in the Norrish/Yang Type II Reaction: Studies Based on the Solid State Photochemistry and X-ray Crystallography of Medium-Sized Ring and Macrocyclic Diketones

Reactions of Molecules with Two Equivalent Functional Groups. 5. Anomalous Reactivity of 1,10-Cyclooctadecanedione. Crystal and Molecular Structures of cis,cis-1,10-Diphenyl-1,10-cyclooctadiene and the Stereoisomers of 1,10-Diphenyl-1,10-cyclooctadecanediol1

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Reactions of Molecules with Two Equivalent Functional Groups. 5. Anomalous Reactivity of 1,10-Cyclooctadecanedione. Crystal and Molecular Structures of cis,cis-1,10-Diphenyl-1,10-cyclooctadiene and the Stereoisomers of 1,10-Diphenyl-1,10-cyclooctadecanediol¹