55 research outputs found
Synthesis, Structures, and Solid State Self-Assemblies of Formyl and Acetyl Substituted Triptycenes and Their Derivatives
Starting from triptycene, 2-, (2,6- or 2,7-)Âdi-, and
(2,6,14- or 2,7,14-)Âtriformyl or acetyl substituted triptycenes were
selectively synthesized. The derivatization of the formyl or acetyl
substituted triptycenes was then investigated. Consequently, it was
found that the formyl-substituted triptycenes could be transformed
into cyano substituted triptycene derivatives by the aldoxime formation
and dehydration. Acetoxyl- and acetamino-substituted triptycenes were
synthesized by Baeyer–Villiger oxidation of acetyl-substituted
triptycenes and Beckmann rearrangement of acetyl-oxime triptycenes,
respectively. Deacetylation of triacetaminotriptycene provided an
alternative way to the synthesis of triaminotriptycene. In addition,
2-ethynyltriptycene could be conveniently synthesized by Corey–Fuchs
reaction of 2-formyltriptycene, and 1,3,5-tritriptycenebenzene was
obtained in high yield by the dehydration cyclotrimerization of 2-acetyltriptycene.
The different functionalized triptycene derivatives and their regioisomers
were well characterized by the FT-IR, <sup>1</sup>H NMR, <sup>13</sup>C NMR, MS spectra, and single crystal X-ray analyses. Moreover, it
was also found that 2,6,14-triacetaminotriptycene with the three amide
groups paralleled to their connected aromatic rings could self-assemble
into a 2D layer with porous structure, and further 3D microporous
architecture by the hydrogen-bond network in the solid state
Synthesis, Structures, and Solid State Self-Assemblies of Formyl and Acetyl Substituted Triptycenes and Their Derivatives
Starting from triptycene, 2-, (2,6- or 2,7-)Âdi-, and
(2,6,14- or 2,7,14-)Âtriformyl or acetyl substituted triptycenes were
selectively synthesized. The derivatization of the formyl or acetyl
substituted triptycenes was then investigated. Consequently, it was
found that the formyl-substituted triptycenes could be transformed
into cyano substituted triptycene derivatives by the aldoxime formation
and dehydration. Acetoxyl- and acetamino-substituted triptycenes were
synthesized by Baeyer–Villiger oxidation of acetyl-substituted
triptycenes and Beckmann rearrangement of acetyl-oxime triptycenes,
respectively. Deacetylation of triacetaminotriptycene provided an
alternative way to the synthesis of triaminotriptycene. In addition,
2-ethynyltriptycene could be conveniently synthesized by Corey–Fuchs
reaction of 2-formyltriptycene, and 1,3,5-tritriptycenebenzene was
obtained in high yield by the dehydration cyclotrimerization of 2-acetyltriptycene.
The different functionalized triptycene derivatives and their regioisomers
were well characterized by the FT-IR, <sup>1</sup>H NMR, <sup>13</sup>C NMR, MS spectra, and single crystal X-ray analyses. Moreover, it
was also found that 2,6,14-triacetaminotriptycene with the three amide
groups paralleled to their connected aromatic rings could self-assemble
into a 2D layer with porous structure, and further 3D microporous
architecture by the hydrogen-bond network in the solid state
Synthesis, Structures, and Solid State Self-Assemblies of Formyl and Acetyl Substituted Triptycenes and Their Derivatives
Starting from triptycene, 2-, (2,6- or 2,7-)Âdi-, and
(2,6,14- or 2,7,14-)Âtriformyl or acetyl substituted triptycenes were
selectively synthesized. The derivatization of the formyl or acetyl
substituted triptycenes was then investigated. Consequently, it was
found that the formyl-substituted triptycenes could be transformed
into cyano substituted triptycene derivatives by the aldoxime formation
and dehydration. Acetoxyl- and acetamino-substituted triptycenes were
synthesized by Baeyer–Villiger oxidation of acetyl-substituted
triptycenes and Beckmann rearrangement of acetyl-oxime triptycenes,
respectively. Deacetylation of triacetaminotriptycene provided an
alternative way to the synthesis of triaminotriptycene. In addition,
2-ethynyltriptycene could be conveniently synthesized by Corey–Fuchs
reaction of 2-formyltriptycene, and 1,3,5-tritriptycenebenzene was
obtained in high yield by the dehydration cyclotrimerization of 2-acetyltriptycene.
The different functionalized triptycene derivatives and their regioisomers
were well characterized by the FT-IR, <sup>1</sup>H NMR, <sup>13</sup>C NMR, MS spectra, and single crystal X-ray analyses. Moreover, it
was also found that 2,6,14-triacetaminotriptycene with the three amide
groups paralleled to their connected aromatic rings could self-assemble
into a 2D layer with porous structure, and further 3D microporous
architecture by the hydrogen-bond network in the solid state
Synthesis, Structures, and Solid State Self-Assemblies of Formyl and Acetyl Substituted Triptycenes and Their Derivatives
Starting from triptycene, 2-, (2,6- or 2,7-)Âdi-, and
(2,6,14- or 2,7,14-)Âtriformyl or acetyl substituted triptycenes were
selectively synthesized. The derivatization of the formyl or acetyl
substituted triptycenes was then investigated. Consequently, it was
found that the formyl-substituted triptycenes could be transformed
into cyano substituted triptycene derivatives by the aldoxime formation
and dehydration. Acetoxyl- and acetamino-substituted triptycenes were
synthesized by Baeyer–Villiger oxidation of acetyl-substituted
triptycenes and Beckmann rearrangement of acetyl-oxime triptycenes,
respectively. Deacetylation of triacetaminotriptycene provided an
alternative way to the synthesis of triaminotriptycene. In addition,
2-ethynyltriptycene could be conveniently synthesized by Corey–Fuchs
reaction of 2-formyltriptycene, and 1,3,5-tritriptycenebenzene was
obtained in high yield by the dehydration cyclotrimerization of 2-acetyltriptycene.
The different functionalized triptycene derivatives and their regioisomers
were well characterized by the FT-IR, <sup>1</sup>H NMR, <sup>13</sup>C NMR, MS spectra, and single crystal X-ray analyses. Moreover, it
was also found that 2,6,14-triacetaminotriptycene with the three amide
groups paralleled to their connected aromatic rings could self-assemble
into a 2D layer with porous structure, and further 3D microporous
architecture by the hydrogen-bond network in the solid state
Synthesis, Structures, and Solid State Self-Assemblies of Formyl and Acetyl Substituted Triptycenes and Their Derivatives
Starting from triptycene, 2-, (2,6- or 2,7-)Âdi-, and
(2,6,14- or 2,7,14-)Âtriformyl or acetyl substituted triptycenes were
selectively synthesized. The derivatization of the formyl or acetyl
substituted triptycenes was then investigated. Consequently, it was
found that the formyl-substituted triptycenes could be transformed
into cyano substituted triptycene derivatives by the aldoxime formation
and dehydration. Acetoxyl- and acetamino-substituted triptycenes were
synthesized by Baeyer–Villiger oxidation of acetyl-substituted
triptycenes and Beckmann rearrangement of acetyl-oxime triptycenes,
respectively. Deacetylation of triacetaminotriptycene provided an
alternative way to the synthesis of triaminotriptycene. In addition,
2-ethynyltriptycene could be conveniently synthesized by Corey–Fuchs
reaction of 2-formyltriptycene, and 1,3,5-tritriptycenebenzene was
obtained in high yield by the dehydration cyclotrimerization of 2-acetyltriptycene.
The different functionalized triptycene derivatives and their regioisomers
were well characterized by the FT-IR, <sup>1</sup>H NMR, <sup>13</sup>C NMR, MS spectra, and single crystal X-ray analyses. Moreover, it
was also found that 2,6,14-triacetaminotriptycene with the three amide
groups paralleled to their connected aromatic rings could self-assemble
into a 2D layer with porous structure, and further 3D microporous
architecture by the hydrogen-bond network in the solid state
Synthesis, Structures, and Solid State Self-Assemblies of Formyl and Acetyl Substituted Triptycenes and Their Derivatives
Starting from triptycene, 2-, (2,6- or 2,7-)Âdi-, and
(2,6,14- or 2,7,14-)Âtriformyl or acetyl substituted triptycenes were
selectively synthesized. The derivatization of the formyl or acetyl
substituted triptycenes was then investigated. Consequently, it was
found that the formyl-substituted triptycenes could be transformed
into cyano substituted triptycene derivatives by the aldoxime formation
and dehydration. Acetoxyl- and acetamino-substituted triptycenes were
synthesized by Baeyer–Villiger oxidation of acetyl-substituted
triptycenes and Beckmann rearrangement of acetyl-oxime triptycenes,
respectively. Deacetylation of triacetaminotriptycene provided an
alternative way to the synthesis of triaminotriptycene. In addition,
2-ethynyltriptycene could be conveniently synthesized by Corey–Fuchs
reaction of 2-formyltriptycene, and 1,3,5-tritriptycenebenzene was
obtained in high yield by the dehydration cyclotrimerization of 2-acetyltriptycene.
The different functionalized triptycene derivatives and their regioisomers
were well characterized by the FT-IR, <sup>1</sup>H NMR, <sup>13</sup>C NMR, MS spectra, and single crystal X-ray analyses. Moreover, it
was also found that 2,6,14-triacetaminotriptycene with the three amide
groups paralleled to their connected aromatic rings could self-assemble
into a 2D layer with porous structure, and further 3D microporous
architecture by the hydrogen-bond network in the solid state
Diastereoselective Synthesis of Cephalotaxus Esters via Asymmetric Mukaiyama Aldol Reaction
We report a protocol
for efficient stereoselective installation
of the chiral oxygen-containing tetrasubstituted tertiary carbon stereocenter
of the side chain of cephalotaxus esters by means of highly diastereoselective
Mukaiyama aldol reactions between α-keto esters (<b>2</b>) and a (<i>Z</i>)-α-chloro ketene silyl acetal.
This protocol permitted synthesis of cephalotaxus esters including
six natural products in good to excellent yields (up to 94%) with
high diastereoselectivities (dr up to 97:3) and could be performed
on a multigram scale
Competitive Halogen Bond in the Molecular Ferroelectric with Large Piezoelectric Response
Molecular piezoelectrics
are attracting tremendous interest because
of their easy processing, light weight, low acoustical impedance,
and mechanical flexibility. However, reports of molecular piezoelectrics
with a piezoelectric coefficient <i>d</i><sub>33</sub> comparable
to piezoceramics such as barium titanate (BTO, 90–190 pC/N)
have been scarce. Here, we present a uniaxial molecular ferroelectric,
trimethylchloromethylammonium tribromocadmiumÂ(II) (TMCM-CdBr<sub>3</sub>), in which the halogen bonding might be a possible critical point
for the stabilization of one-dimensional (1D) {CdBr<sub>3</sub>}<sup>−</sup> chain and further reservation of its ferroelectricity
in such organic–inorganic hybrid crystalline systems. It has
a large <i>d</i><sub>33</sub> of 139 pC/N, 1 order of magnitude
higher than those of most classically uniaxial ferroelectrics such
as LiNbO<sub>3</sub> (6–16 pC/N) and Rochelle salt (∼7
pC/N), and comparable with those of multiaxial ferroelectrics such
as BTO and trimethylbromomethylammonium tribromomanganeseÂ(II) (112
pC/N). Moreover, the simple single-crystal growth and easy-to-find
polar axis enable it to hold a great potential for applying in the
single-crystal form. In light of the strong, specific, and directional
halogen-bonding interactions, this work provides possibilities to
explore new classes of molecular piezoelectrics and contribute to
further developments
Competitive Halogen Bond in the Molecular Ferroelectric with Large Piezoelectric Response
Molecular piezoelectrics
are attracting tremendous interest because
of their easy processing, light weight, low acoustical impedance,
and mechanical flexibility. However, reports of molecular piezoelectrics
with a piezoelectric coefficient <i>d</i><sub>33</sub> comparable
to piezoceramics such as barium titanate (BTO, 90–190 pC/N)
have been scarce. Here, we present a uniaxial molecular ferroelectric,
trimethylchloromethylammonium tribromocadmiumÂ(II) (TMCM-CdBr<sub>3</sub>), in which the halogen bonding might be a possible critical point
for the stabilization of one-dimensional (1D) {CdBr<sub>3</sub>}<sup>−</sup> chain and further reservation of its ferroelectricity
in such organic–inorganic hybrid crystalline systems. It has
a large <i>d</i><sub>33</sub> of 139 pC/N, 1 order of magnitude
higher than those of most classically uniaxial ferroelectrics such
as LiNbO<sub>3</sub> (6–16 pC/N) and Rochelle salt (∼7
pC/N), and comparable with those of multiaxial ferroelectrics such
as BTO and trimethylbromomethylammonium tribromomanganeseÂ(II) (112
pC/N). Moreover, the simple single-crystal growth and easy-to-find
polar axis enable it to hold a great potential for applying in the
single-crystal form. In light of the strong, specific, and directional
halogen-bonding interactions, this work provides possibilities to
explore new classes of molecular piezoelectrics and contribute to
further developments
Competitive Halogen Bond in the Molecular Ferroelectric with Large Piezoelectric Response
Molecular piezoelectrics
are attracting tremendous interest because
of their easy processing, light weight, low acoustical impedance,
and mechanical flexibility. However, reports of molecular piezoelectrics
with a piezoelectric coefficient <i>d</i><sub>33</sub> comparable
to piezoceramics such as barium titanate (BTO, 90–190 pC/N)
have been scarce. Here, we present a uniaxial molecular ferroelectric,
trimethylchloromethylammonium tribromocadmiumÂ(II) (TMCM-CdBr<sub>3</sub>), in which the halogen bonding might be a possible critical point
for the stabilization of one-dimensional (1D) {CdBr<sub>3</sub>}<sup>−</sup> chain and further reservation of its ferroelectricity
in such organic–inorganic hybrid crystalline systems. It has
a large <i>d</i><sub>33</sub> of 139 pC/N, 1 order of magnitude
higher than those of most classically uniaxial ferroelectrics such
as LiNbO<sub>3</sub> (6–16 pC/N) and Rochelle salt (∼7
pC/N), and comparable with those of multiaxial ferroelectrics such
as BTO and trimethylbromomethylammonium tribromomanganeseÂ(II) (112
pC/N). Moreover, the simple single-crystal growth and easy-to-find
polar axis enable it to hold a great potential for applying in the
single-crystal form. In light of the strong, specific, and directional
halogen-bonding interactions, this work provides possibilities to
explore new classes of molecular piezoelectrics and contribute to
further developments
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