The chemical consequences of conformational polymorphism: the phase-transition-dependent photochemistry of crystalline 1,14-cyclohexacosanedione

Lewis, Thillairaj J.; Rettig, Steven J.; Scheffer, John R.; Trotter, James

doi:10.1021/ja00021a061

Cited by 10 publications

(5 citation statements)

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“…FT-IR spectra obtained with crystals of 1c revealed only one broad ester band at 1736 cm -1 and one ketone signal at 1716 cm -1 (Table ). This result is consistent with a single-crystal phase because it is not uncommon for polymorphs and crystals of stereoisomers to have resolvable signals . A differential scanning calorimetric (DSC) analysis is also consistent with a single crystalline phase.…”

Section: Resultssupporting

confidence: 72%

Engineering Reactions in Crystalline Solids: Photochemical Generation of Secondary and Tertiary Enol Radical Pairs from Crystalline Ketodiesters

Yang

2001

J. Org. Chem.

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The photochemical decarbonylation of several crystalline 1,3-acetonedicarboxylates has been analyzed in solution and in the solid state. It is shown that the efficiency of the solid-state reaction depends on the stability of the intermediate acyl-alkyl and alkyl-alkyl radical pairs. Reactions proceeding through tertiary enol radicals are more efficient than reactions proceeding through secondary enol radical centers. Solid-state reactions that require the intermediacy of primary enol radicals do not occur. It is also shown that the selectivity of product formation in crystals depends on the structure of the reactant solid phase.

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Section: Resultssupporting

confidence: 72%

Engineering Reactions in Crystalline Solids: Photochemical Generation of Secondary and Tertiary Enol Radical Pairs from Crystalline Ketodiesters

Yang

2001

J. Org. Chem.

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“…The title compound, (I), was obtained as part of a study of the photochemistry of macrocyclic diketones (Lewis, Rettig, Scheffer, Trotter & Wireko, 1990;Lewis, Rettig, Scheffer & Trotter, 1991), in an (unsuccessful) effort to protect one of the two ketone groups by forming a mono-acetal. …”

Section: Commentmentioning

confidence: 99%

Tricyclo[22.2.2.211,14]triaconta-11,13,24,26,27,29-hexaene-6,19-dione

Rettig¹,

Scheffer²,

Trotter³

et al. 1995

Acta Crystallogr C

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“…For example, Lewis et al. demonstrated that crystalline 1,14‐cyclohexacosanedione exists in two different dimorphs, needles and plates, and that each dimorph displays distinctive photoreactivity (Scheme ) . With the aid of X‐ray crystallography it was confirmed that 1,14‐cyclohexacosanedione is frozen into different conformers in each dimorph and the photoreactivity is conformation‐dependent.…”

Section: Introductionmentioning

confidence: 99%

“…demonstrated that crystalline1 ,14-cyclohexacosanedionee xists in two different dimorphs, needles and plates, and that each dimorph displays distinctive photoreactivity (Scheme 2). [6] With the aid of X-ray crystallography it was confirmed that 1,14-cyclohexacosanedione is frozen into differ-Solid-state photolysis of 3-azido-1,3-diphenyl-isobutyrophenone 1 results in selective formationo fi sobutyrophenone 2 and benzonitrile 3.X -ray structure analysiso fa zide 1 demonstrates that the conformer (1Cr)a dopted for packingi nt he crystal lattice has the carbonyl moiety perpendicular to the a-phenyl group (Ph-C=Ot orsional angle of 858). Laser flash photolysis of azide 1 nanocrystals allows direct detection of the lowest excited triplet ketone (T K )o f1Cr (l max % 475 nm).…”

Section: Introductionmentioning

confidence: 99%

Capturing Conformation‐Dependent Photoreactivity of Crystalline 3‐Azido‐1,3‐diphenylisobutyrophenone

et al. 2017

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Solid‐state photolysis of 3‐azido‐1,3‐diphenyl‐isobutyrophenone 1 results in selective formation of isobutyrophenone 2 and benzonitrile 3. X‐ray structure analysis of azide 1 demonstrates that the conformer (1Cr) adopted for packing in the crystal lattice has the carbonyl moiety perpendicular to the α‐phenyl group (Ph‐C=O torsional angle of 85°). Laser flash photolysis of azide 1 nanocrystals allows direct detection of the lowest excited triplet ketone (TK) of 1Cr (λmax≈475 nm). Thus, in crystals, 1 is proposed to react via the TK state to cleave the Cβ−Cγ bond. Time‐dependent density functional theory (TD‐DFT) calculations verify that the energy of the TK of 1Cr is 79 kcal mol−1 above the ground state (S0), and thus TK has sufficient energy for cleavage of the Cβ−Cγ bond to form products 2 and 3, further supporting this solid‐state reaction mechanism.

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The chemical consequences of conformational polymorphism: the phase-transition-dependent photochemistry of crystalline 1,14-cyclohexacosanedione

Cited by 10 publications

References 1 publication

Engineering Reactions in Crystalline Solids: Photochemical Generation of Secondary and Tertiary Enol Radical Pairs from Crystalline Ketodiesters

Engineering Reactions in Crystalline Solids: Photochemical Generation of Secondary and Tertiary Enol Radical Pairs from Crystalline Ketodiesters

Tricyclo[22.2.2.211,14]triaconta-11,13,24,26,27,29-hexaene-6,19-dione

Capturing Conformation‐Dependent Photoreactivity of Crystalline 3‐Azido‐1,3‐diphenylisobutyrophenone

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