3 research outputs found
Nitration Under Continuous Flow Conditions: Convenient Synthesis of 2‑Isopropoxy-5-nitrobenzaldehyde, an Important Building Block in the Preparation of Nitro-Substituted Hoveyda–Grubbs Metathesis Catalyst
Herein, we describe the use of continuous flow chemistry
for selective,
efficient and reproducible nitration of 2-isopropoxybenzaldehyde to
produce the desired 2-isopropoxy-5-nitrobenzaldehyde, an important
building block in the preparation of a ligand of nitro-substituted
Hoveyda–Grubbs metathesis catalyst. Nitration was done with
red fuming HNO<sub>3</sub>, and this challenging and hazardous process
was performed using a flow-through silicon-glass microreactor equipped
with a set of temperature sensors, and with a productivity of 13 g/h,
providing us with a reproducible chemical process amenable for production
of sufficient quantities of 2-isopropoxy-5-nitrobenzaldehyde for ongoing
large-scale synthesis of nitro-substituted Hoveyda–Grubbs metathesis
catalyst
Rational and Then Serendipitous Formation of Aza Analogues of Hoveyda-Type Catalysts Containing a Chelating Ester Group Leading to a Polymerization Catalyst Family
Analogues
of the well-known Hoveyda–Grubbs catalyst bearing
both a chelating ester function and a chelating nitrogen atom were
obtained. These complexes behave differently depending on the character
of the chelating amine. Complexes containing a secondary amine underwent
unexpected spontaneous oxidation of the amine group, leading to the
Schiff base analogues. In contrast, complexes containing a tertiary
amine were prone to intramolecular cyclization in the presence of
a base (Et<sub>3</sub>N). Probing the activity of such (pre)catalysts
in ring-closing metathesis reactions (RCMs) revealed their dormant
character and excellent thermo-switchability. In particular, complexes
bearing an iminium nitrogen fragment were found to be very useful
in a delayed ring-opening metathesis polymerization (ROMP) and were
therefore commercialized
Raman, Surface-Enhanced Raman, and Density Functional Theory Characterization of (Diphenylphosphoryl)(pyridin-2‑, -3‑, and -4-yl)methanol
This work presents near-infrared
Raman spectroscopy (FT-RS) and
surface-enhanced Raman scattering (SERS) studies of three pyridine-α-hydroxymethyl
biphenyl phosphine oxide isomers: (diphenylphosphoryl)(pyridin-2-yl)methanol
(α-Py), (diphenylphosphoryl)(pyridin-3-yl)methanol (β-Py),
and (diphenylphosphoryl)(pyridin-4-yl)methanol (γ-Py) adsorbed
onto colloidal and roughened in oxidation–reduction cycles
silver surfaces. The molecular geometries in the equilibrium state
and vibrational frequencies were calculated by density functional
theory (DFT) at the B3LYP 6-311G(df,p) level of theory. The results
imply that the most stable structure of the investigated molecules
is a dimer created by two intermolecular hydrogen bonds between the
H atom of the α-hydroxyl group (in up (HO<sub>U</sub>) or down
(HO<sub>D</sub>) stereo bonds position) and the O atom of tertiary
phosphine oxide (O) of the two monomers. Comparison the FT-RS
spectra with the respective SERS spectra allowed us to predict the
orientation of the hydroxyphosphonate derivatives of pyridine that
depends upon both the position of the substituent relative to the
ring N atom (in α-, β-, and γ-position, respectively)
and the type of silver substrate