84615-40-7

Upstream product

• 2364-59-2 γ-phenoxybutyric acid ethyl ester 
• 84615-38-3 4-Phenoxy-<1,1-D2>-1-butanol 
• 6303-58-8 4-phenyloxybutanoic acid 
• 84615-39-4 p-Toluolsulfonsaeure-(4-phenoxy-<1,1-D2>butylester) 

Downstream Products

• 344308-32-3 1-Phenoxy-<4,4-D2>pentan 
• 136665-54-8 C₂₀H₂₂⁽²⁾H₄O₂ 

Relevant academic research and scientific papers

Regioselectivity, Stereoselectivity, and Isotopically Sensitive Branching in the Fe(I)-Mediated Dehydrogenation of Octane-1,8-diol in the Gas Phase

Regio- and stereospecific labeling experiments are conducted to unravel the mechanistic features of the Fe+-induced dehydrogenation of octane-1,8-diol in the gas phase.With regard to the regioselectivity, ca. 20percent of molecular hydrogen originates from C(3)/C(4) or the equivalent C(5)/C(6) postions.The remaining 80percent are provided by the C(4)/C(5) methylene units.The steps, preceding the reductive elimination of hydrogen, are irreversible, and the overall reaction follows a 1,2-elimination mode.The loss of HD from C(3)/C(4) is associated with a kinetic isotope effect kH2/kHD = 1.68.Formation of D2 from the positions C(4)/C(5) has an isotope effect of kH2/kD2 = 4.7; this figure is slightly dependent on the configuration at C(4)/C(5).Most interesting is the finding that the configuration at C(4)/C5) in octane-1,8-diol, i.e. 5c vs. 5d, plays a pivotal role in the dehydrogenation of the central C(4)/C(5) part.This unexpected and unprecedented result is explained in terms of conformational analysis.A staggered-like conformation serves as a precursor to generate a trans-fused bicyclic intermediate 6.It is this very intermediate from which most of the molecular hydrogen is eliminated.Of minor importance is the cis-fused chelate 7, which is formed from an eclipsed-like conformation of the octane-1,8-diol/Fe+ complex.The contribution of 6 and 7 to the product formation is controlled by the relative configuration at the labeled positions C(4)/C(5).For the D,L-form 5c, we estimate a ratio of ca. 9:1 for the contribution of 6 vs. 7; due to an isotope effect, this ratio drops to 1.85:1 for the meso-form 5d.This finding constitutes the first example for the existence of isotopically sensitive branching ('metabolic switching') in gas-phase organometallic chemistry.

Pseudo One-Step Cleavage of C-C Bonds in the Decomposition of Ionized Carboxyclic Acids. Radical Like Reactions in Mass Spectrometry

Metastable molecular ions of hexanoic acid (1) decompose unimolecularly to C2H5. and protonated methacrylic acid (5-H+)(92percent rel. abund.).Investigation of the mechanism reveals that 1) the branched cation radical 11 must be regarded as the essential intermediate in the course of the rearrangement/dissociation reaction and 2) the process commences with intramolecular hydrogen transfer from either C-3 or C-5 to the ionized carbonyl oxygen ("hidden" hydrogen migration).Hydrogen transfer from C-4, which would correspond to the well-known McLafferty rearrangement, is of no importance in the C2H5.-elimination from 1.The same conclusion applies for various alternative mechanisms, as for example a SRi type reaction, 1 -> 2-H+.The gas phase chemistry of the cation radical of 1, and in particular the hydrogen exchange processes between the methylene groups C-2/C-3 and C-5/C-6, is in surprisingly close correspondence to the chemistry of free alkyl radicals. - The syntheses of various 13C and 2H-labelled model compounds are described.