19214-96-1

Usage

Uses

Isopropanol-d7 is a deuterated alcohol used in the study of lignite liquefaction.

Upstream product

• 666-52-4 [⁽²⁾H₆]acetone 
• 22739-76-0 d8-isopropanol 
• 3976-29-2 <1,1,1,3,3,3-D(6)>-Propan-2-ol 

Downstream Products

• 55956-02-0 isopropyl-d₇ chloride 
• 666-52-4 [⁽²⁾H₆]acetone 
• 100-52-7 benzaldehyde 
• 67-64-1 acetone 

Relevant academic research and scientific papers

Imbalanced tunneling ready states in alcohol dehydrogenase model reactions: Rehybridization lags behind H-tunneling

The secondary kinetic isotope effects for the hydride transfer reactions from aliphatic alcohols to two carbocations (NAD+ models) in acetonitrile were determined. The results suggest that the hydride transfer takes place by tunneling and that the rehybridizations of both donor and acceptor carbons lag behind the H-tunneling. This is quite contrary to the observations in alcohol dehydrogenases where the importance of enzyme motions in catalysis is manifested.

Kinetic isotope effect evidence for a concerted hydrogen transfer mechanism in transfer hydrogenations catalyzed by [p-(Me2CH)C6H4Me] Ru-(NHCHPhCHPhNSO2C6H4-p-CH3)

The isotope effects in the reaction of [p-(Me2CH)-C6H4Me]Ru (NHCHPhCHPhNSO2C6H4-p-CH3) (1) with isopropyl alcohol were 1.79 for transfer of hydrogen from OH to N and 2.86 for transfer from CH to Ru. The isotope effect for transfer of deuterium from doubly labeled material (kCHoH/kCDOD = 4.88) was within experimental error of the product of the two individual isotope effects. These isotope effects provide convincing evidence for a mechanism involving concurrent transfer of hydrogen from oxygen to nitrogen and from carbon to ruthenium.

A new mechanism of metal-ligand cooperative catalysis in transfer hydrogenation of ketones

We report iridium catalysts IrCl(η5-Cp?)(κ2-(2-pyridyl)CH2NSO2C6H4X) (1-Me, X = CH3 and 1-F, X = F) for transfer hydrogenation of ketones with 2-propanol that operate by a previously unseen metal-ligand cooperative mechanism. Under the reaction conditions, complexes 1 (1-Me and 1-F) derivatize to a series of catalytic intermediates: Ir(η5-Cp?)(κ2-(C5H4N)CHNSO2Ar) (2), IrH(η5-Cp?)(κ2-(2-pyridyl)CH2NSO2Ar) (3), and Ir(η5-Cp?)(κ3-(2-pyridyl)CH2NSO2Ar) (4). The structures of 1-Me and 4-Me were established by single-crystal X-ray diffraction. A rate-determining, concerted hydrogen transfer step (2 + R2CHOH ? 3 + R2CO) is suggested by kinetic isotope effects, Eyring parameters (ΔH≠ = 29.1(8) kcal mol?1 and ΔS≠ = ?17(19) eu), proton-hydride fidelity, and DFT calculations. According to DFT, a nine-membered cyclic transition state is stabilized by an alcohol molecule that serves as a proton shuttle.

Steric Effects on the Primary Isotope Dependence of Secondary Kinetic Isotope Effects in Hydride Transfer Reactions in Solution: Caused by the Isotopically Different Tunneling Ready State Conformations?

The observed 1° isotope effect on 2° KIEs in H-transfer reactions has recently been explained on the basis of a H-tunneling mechanism that uses the concept that the tunneling of a heavier isotope requires a shorter donor-acceptor distance (DAD) than that of a lighter isotope. The shorter DAD in D-tunneling, as compared to H-tunneling, could bring about significant spatial crowding effect that stiffens the 2° H/D vibrations, thus decreasing the 2° KIE. This leads to a new physical organic research direction that examines how structure affects the 1° isotope dependence of 2° KIEs and how this dependence provides information about the structure of the tunneling ready states (TRSs). The hypothesis is that H- and D-tunneling have TRS structures which have different DADs, and pronounced 1° isotope effect on 2° KIEs should be observed in tunneling systems that are sterically hindered. This paper investigates the hypothesis by determining the 1° isotope effect on α- and β-2° KIEs for hydride transfer reactions from various hydride donors to different carbocationic hydride acceptors in solution. The systems were designed to include the interactions of the steric groups and the targeted 2° H/D's in the TRSs. The results substantiate our hypothesis, and they are not consistent with the traditional model of H-tunneling and 1° /2° H coupled motions that has been widely used to explain the 1° isotope dependence of 2° KIEs in the enzyme-catalyzed H-transfer reactions. The behaviors of the 1° isotope dependence of 2° KIEs in solution are compared to those with alcohol dehydrogenases, and sources of the observed "puzzling" 2° KIE behaviors in these enzymes are discussed using the concept of the isotopically different TRS conformations. (Figure Presented).

Inherent asymmetry of constitutionally equivalent methyl groups in the H/D equilibration of n- and i-C3H7Fe(OH)+ complexes

Transiently formed, constitutionally identical methyl groups remain inequivalent in the course of an n-propyl?isopropyl isomerization (see scheme) operative in Fe÷-mediated dehydration of propanols. The reversibility of the β-hydrogen transfer steps is addressed by examination of the H/D equilibration in metastable complexes of Fe+ with a set of selectivity deuterated propanols by using tandem mass spectrometry.

Thermally Induced Redox Reaction of Carbonyl Compounds and Alcohols in a Radical Chain Reaction

Carbonyl compounds are reduced by alcohols in a thermally initiated radical chain reaction.The reaction of 4-isopropylbenzaldehyde (1i) and 2-propanol (2) has been studied kinetically and is first order with respect to 1i as well as to 2 (kexp. = 7.56 +/- 0.05 - 125 +/- 1/Θ; Θ = 2.303 * R * T in kJ/mol).The results can be satisfactorily explained in terms of a symproportionation of 1i and 2 to give two hydroxylalkyl radicals to initiate the radical chain reaction.This initiation reaction is very slow.The kinetic chain length is very large, ca. 107 at 200 deg C.Kinetic isotopic effects kH/kD of two different metathesis reactions of the radical chain have been measured.The Hammett correlation gives ρ = -0.62 (160 deg C).