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Crystal structure of 2α-(1,1-di-phenyl-eth-yl)-4-methyl-4α,5α-diphenyl-1,3-dioxolane: the result of a non-acid pinacol rearrangement.

Kirchner RM, Corfield PW, Annabi M, Regan J, Speina K, DiProperzio A, Ciaccio JA, Capitani JF - Acta Crystallogr E Crystallogr Commun (2015)

Bottom Line: The title compound, C30H28O2, was obtained during recrystallization of (±)-1,2-diphenyl-1,2-propane-diol in 1-butanol, from an unexpected non-acid-catalyzed pinacol rearrangement followed by acetal formation of the newly formed aldehyde with the diol.The tri-substituted dioxolane ring has a twist conformation on the C-O bond opposite the methyl-substituted C atom.The chains are linked by a second C-H⋯π inter-action, forming sheets parallel to the bc plane.

View Article: PubMed Central - HTML - PubMed

Affiliation: Department of Chemistry and Biochemistry, Manhattan College, 4513 Manhattan College Pkwy, Bronx NY 10471, USA.

ABSTRACT
The title compound, C30H28O2, was obtained during recrystallization of (±)-1,2-diphenyl-1,2-propane-diol in 1-butanol, from an unexpected non-acid-catalyzed pinacol rearrangement followed by acetal formation of the newly formed aldehyde with the diol. The tri-substituted dioxolane ring has a twist conformation on the C-O bond opposite the methyl-substituted C atom. There is an intra-molecular C-H⋯π inter-action present involving one of the di-phenyl-ethyl rings and an H atom of the phenyl ring in position 4 of the dioxolane ring. In the crystal, mol-ecules are linked by weak C-H⋯O hydrogen bonds, forming chains along [001]. The chains are linked by a second C-H⋯π inter-action, forming sheets parallel to the bc plane.

No MeSH data available.


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Atom numbering in the 1,3-dioxolane ring.
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fig4: Atom numbering in the 1,3-dioxolane ring.

Mentions: To illustrate the conformational properties of the five-membered 1,3-dioxolane ring of the title compound, some B3LYP/6-311+G(d,p) density functional calculation results (Spartan, 2006 ▸) are given in Table 2 ▸. The atom numbering is shown in Fig. 4 ▸. Column two of the table (Ring with H atoms) shows a pattern of dihedral angles similar to the near-perfect twist found in the present crystal structure, shown in column five, where O1—C2 is the twisted bond. Fig. 5 ▸ above offers two views of the density functional theory (DFT) optimized structure. The pattern shown in column three (Ring with CH3 groups), has a much larger (O3—C4—C5—O1) torsional angle. The calculated conformation is still that of a twist, but the twist bond in this CH3 model is C4—C5, not O1—C2. The best plane through O1—C2—O3 has C4 + 0.28 Å above the plane and C5 − 0.28 Å below the plane, giving the CH3 model an ideal twist conformation. The DFT-optimized CH3-substituted structure is depicted in Fig. 6 ▸. Column four of Table 2 ▸ shows the DFT results for the title compound. The predicted conformation is similar to the conformation found in the crystal structure. The differences between columns four and five are presumably due to packing (inter­molecular) forces present in the X-ray structure. The Spartan DFT calculations do not include inter­molecular forces, but are calculations in the gas phase. Comparing distance and angle values in column two (dioxolane ring with only H atom substituents) to columns four and five (dioxolane rings with phenyl and di­phenyl­ethyl substituents) suggests these larger substituents have little effect upon the ring conformation. Fig. 7 ▸ views the title compound as a distorted envelope.


Crystal structure of 2α-(1,1-di-phenyl-eth-yl)-4-methyl-4α,5α-diphenyl-1,3-dioxolane: the result of a non-acid pinacol rearrangement.

Kirchner RM, Corfield PW, Annabi M, Regan J, Speina K, DiProperzio A, Ciaccio JA, Capitani JF - Acta Crystallogr E Crystallogr Commun (2015)

Atom numbering in the 1,3-dioxolane ring.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
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getmorefigures.php?uid=PMC4645051&req=5

fig4: Atom numbering in the 1,3-dioxolane ring.
Mentions: To illustrate the conformational properties of the five-membered 1,3-dioxolane ring of the title compound, some B3LYP/6-311+G(d,p) density functional calculation results (Spartan, 2006 ▸) are given in Table 2 ▸. The atom numbering is shown in Fig. 4 ▸. Column two of the table (Ring with H atoms) shows a pattern of dihedral angles similar to the near-perfect twist found in the present crystal structure, shown in column five, where O1—C2 is the twisted bond. Fig. 5 ▸ above offers two views of the density functional theory (DFT) optimized structure. The pattern shown in column three (Ring with CH3 groups), has a much larger (O3—C4—C5—O1) torsional angle. The calculated conformation is still that of a twist, but the twist bond in this CH3 model is C4—C5, not O1—C2. The best plane through O1—C2—O3 has C4 + 0.28 Å above the plane and C5 − 0.28 Å below the plane, giving the CH3 model an ideal twist conformation. The DFT-optimized CH3-substituted structure is depicted in Fig. 6 ▸. Column four of Table 2 ▸ shows the DFT results for the title compound. The predicted conformation is similar to the conformation found in the crystal structure. The differences between columns four and five are presumably due to packing (inter­molecular) forces present in the X-ray structure. The Spartan DFT calculations do not include inter­molecular forces, but are calculations in the gas phase. Comparing distance and angle values in column two (dioxolane ring with only H atom substituents) to columns four and five (dioxolane rings with phenyl and di­phenyl­ethyl substituents) suggests these larger substituents have little effect upon the ring conformation. Fig. 7 ▸ views the title compound as a distorted envelope.

Bottom Line: The title compound, C30H28O2, was obtained during recrystallization of (±)-1,2-diphenyl-1,2-propane-diol in 1-butanol, from an unexpected non-acid-catalyzed pinacol rearrangement followed by acetal formation of the newly formed aldehyde with the diol.The tri-substituted dioxolane ring has a twist conformation on the C-O bond opposite the methyl-substituted C atom.The chains are linked by a second C-H⋯π inter-action, forming sheets parallel to the bc plane.

View Article: PubMed Central - HTML - PubMed

Affiliation: Department of Chemistry and Biochemistry, Manhattan College, 4513 Manhattan College Pkwy, Bronx NY 10471, USA.

ABSTRACT
The title compound, C30H28O2, was obtained during recrystallization of (±)-1,2-diphenyl-1,2-propane-diol in 1-butanol, from an unexpected non-acid-catalyzed pinacol rearrangement followed by acetal formation of the newly formed aldehyde with the diol. The tri-substituted dioxolane ring has a twist conformation on the C-O bond opposite the methyl-substituted C atom. There is an intra-molecular C-H⋯π inter-action present involving one of the di-phenyl-ethyl rings and an H atom of the phenyl ring in position 4 of the dioxolane ring. In the crystal, mol-ecules are linked by weak C-H⋯O hydrogen bonds, forming chains along [001]. The chains are linked by a second C-H⋯π inter-action, forming sheets parallel to the bc plane.

No MeSH data available.


Related in: MedlinePlus