Unusual reactivity in a highly substituted olefin. 2,2,8,8,10-Pentamethyl-1(9)-octalin system

Hochstetler, Alan R.

doi:10.1021/jo00899a003

Cited by 22 publications

(4 citation statements)

References 19 publications

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“…Epoxidation of carbon–carbon bonds during ozonolysis is another pathway that competes with ozonolysis of alkenes and olefins. , Pathway (D) presents epoxidation of the carbon–carbon bond via a loss of 1 O 2 . Other literature works have also observed loss of triplet oxygen ( 3 O 2 ). , This epoxidation can lead to the formation of two +2O products: an (epoxide) 2 -BPA when the epoxidation occurs a second time or an epoxide–OH-BPA when epoxidation is followed by pathway (A). It is possible that epoxides may undergo hydrolysis under wet and acidic conditions, resulting in diols; however, we did not see any diol products in our ESI analyses.…”

Section: Resultsmentioning

confidence: 99%

“…65 Other literature works have also observed loss of triplet oxygen ( 3 O 2 ). 63,66 This epoxidation can lead to the formation of two +2O products: an (epoxide) 2 -BPA when the epoxidation occurs a second time or an epoxide−OH-BPA when epoxidation is followed by pathway (A). It is possible that epoxides may undergo hydrolysis under wet and acidic conditions, resulting in diols; however, we did not see any diol products in our ESI analyses.…”

Section: Environmentalmentioning

confidence: 99%

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Multiphase Ozonolysis of Bisphenol A: Chemical Transformations on Surfaces in the Environment

Yu,

Gong,

Nair

et al. 2024

Environ. Sci. Technol.

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High global plastic production volumes have led to the widespread presence of bisphenol compounds in human living and working environments. The most common bisphenol, bisphenol A (BPA), despite being endocrine disruptive and estrogenic, is still not fully banned worldwide, leading to continued human exposure via particles in air, dust, and surfaces in both outdoor and indoor environments. While its abundance is well documented, few studies have addressed the chemical transformations of BPA, the properties of its reactive products, and their toxicity. Here, the first gas-surface multiphase ozonolysis experiment of BPA thin films, at a constant ozone mixing ratio of 100 ppb, was performed in a flow tube for periods up to 24 h. Three transformation products involving the addition of 1, 2, and 3 oxygen atoms to the molecule were identified by LC-ESI-HRMS analyses. Exposure of indoor air to thin BPA surface films and BPAcontaining thermal paper over periods of days validated the flow tube experiments, demonstrating the rapid nature of this multiphase ozonolysis reaction at atmospherically relevant ozone levels. Multiple transformation pathways are proposed that are likely applicable to not only BPA but also emerging commercial bisphenol products.

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Section: Resultsmentioning

confidence: 99%

Section: Environmentalmentioning

confidence: 99%

Multiphase Ozonolysis of Bisphenol A: Chemical Transformations on Surfaces in the Environment

Yu,

Gong,

Nair

et al. 2024

Environ. Sci. Technol.

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“…For example, the hindered alkene 62 derived from thujopsene gave the β-epoxide 63 (Scheme 16). 82 Interestingly, this epoxide has the opposite stereochemistry to that which was obtained by epoxidation with per-acid. A similar epoxidation of cholesterol to form the 5β,6β-epoxide has also been observed.…”

Section: Formation Of Epoxidesmentioning

confidence: 99%

The Ozonolysis of Terpenoids, a Pandora's Box of by-Products

Hanson

2017

Journal of Chemical Research

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“…This transformation is proposed to occur via a Mukaiyama hydration followed by loss of bromide. Surprisingly, during attempts to oxidatively cleave the vinyl bromide under ozonolysis conditions in CH 2 Cl 2 with pyridine, cyclic α-hydroxy ketone 7 was obtained instead as a single diastereomer in 85% yield, potentially via the intermediacy of an epoxide . This compound is particularly interesting as this substituent pattern mirrors that which is believed to be the active human metabolite of esketamine (hydroxynorketamine) that is essential for the parent molecule’s antidepressant activity .…”

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confidence: 99%

Stereospecific Overman Rearrangement of Substituted Cyclic Vinyl Bromides: Access to Fully Substituted α-Amino Ketones

et al. 2019

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Materials and Methods Unless otherwise stated, reactions were performed in flame-dried glassware under an argon or nitrogen atmosphere using dry, deoxygenated solvents. Solvents were dried by passage through an activated alumina column under argon. Reaction progress was monitored by thin-layer chromatography (TLC) or Agilent 1290 UHPLC-MS. TLC was performed using E. Merck silica gel 60 F254 precoated glass plates (0.25 mm) and visualized by UV fluorescence quenching, panisaldehyde, or KMnO 4 staining. Silicycle SiliaFlash® P60 Academic Silica gel (particle size 40-63 nm) was used for flash chromatography. The (Z)-enol carbonates were purified by preparative LC on a Teledyne Isco ACCQPrep HP125; column: C-18, 100 Å, 5 µm, ID 20 mm. 1 H NMR spectra were recorded on Varian Inova 500 MHz and Bruker 400 MHz spectrometers and are reported relative to residual CHCl 3 (δ 7.26 ppm). 13 C NMR spectra were recorded on a Varian Inova 500 MHz spectrometer (125 MHz) and Bruker 400 MHz spectrometers (100 MHz) and are reported relative to CHCl 3 (δ 77.16 ppm). Data for 1 H NMR are reported as follows: chemical shift (δ ppm) (multiplicity, coupling constant (Hz), integration). Multiplicities are reported as follows: s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sept = septuplet, m = multiplet, br s = broad singlet, br d = broad doublet. Data for 13 C NMR are reported in terms of chemical shifts (δ ppm). IR spectra were obtained by use of a Perkin Elmer Spectrum BXII spectrometer or Nicolet 6700 FTIR spectrometer using thin films deposited on NaCl plates and reported in frequency of absorption (cm-1). Optical rotations were measured with a Jasco P-2000 polarimeter operating on the sodium D-line (589 nm), using a 100 mm path-length cell. High resolution mass spectra (HRMS) were obtained from Agilent 6200 Series TOF with an Agilent G1978A Multimode source in electrospray ionization (ESI+), atmospheric pressure chemical ionization (APCI+), or mixed ionization mode (MM: ESI-APCI+). Reagents were purchased from commercial sources and used as received unless otherwise stated.

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Unusual reactivity in a highly substituted olefin. 2,2,8,8,10-Pentamethyl-1(9)-octalin system

Cited by 22 publications

References 19 publications

Multiphase Ozonolysis of Bisphenol A: Chemical Transformations on Surfaces in the Environment

Multiphase Ozonolysis of Bisphenol A: Chemical Transformations on Surfaces in the Environment

The Ozonolysis of Terpenoids, a Pandora's Box of by-Products

Stereospecific Overman Rearrangement of Substituted Cyclic Vinyl Bromides: Access to Fully Substituted α-Amino Ketones

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