Thallium in organic synthesis. 51. Oxidation of enolizable ketones to .alpha.-nitrato ketones by thallium(III) nitrate in acetonitrile

McKillop, Alexander; Young, Derek W.; Edwards, M. G.; HUG, R. P.; Taylor, Edward C.

doi:10.1021/jo00413a031

Cited by 27 publications

(6 citation statements)

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“…Gratifyingly the iodoacetone reacted readily with silver nitrate at 60 °C affording 43 ( Scheme 6 ) as a yellow oil in an unoptimized 69% yield. Unfortunately the unstable and reactive properties of 43 meant purification was not straightforward [ 36 ]. However installation of the nitrate group was confirmed via comparison of our data with that in the literature [ 28 ].…”

Section: Resultsmentioning

confidence: 99%

Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(−)-myrtenol nitrate

Bew¹,

Hiatt-Gipson²,

Mills³

2016

Beilstein J. Org. Chem.

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SummaryHere we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a ’halide for nitrate’ substitution. Employing readily available starting materials, reagents and Horner–Wadsworth–Emmons chemistry the synthesis of easily separable, synthetically versatile ‘key building blocks’ (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-methyl-4-bromobut-2-enyloxy)methyl)-4-methoxybenzene has been achieved using cheap, ’off the shelf’ materials. Exploiting their reactivity we have studied their ability to undergo an ‘allylic halide for allylic nitrate’ substitution reaction which we demonstrate generates (E)- and (Z)-3-methyl-4-hydroxybut-2-enyl nitrate, and (E)- and (Z)-2-methyl-4-hydroxybut-2-enyl nitrates (‘isoprene nitrates’) in 66–80% overall yields. Using NOESY experiments the elucidation of the carbon–carbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our ‘halide for nitrate’ substitution chemistry we outline the straightforward transformation of (1R,2S)-(−)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(−)-myrtenol nitrate.

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Section: Resultsmentioning

confidence: 99%

Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(−)-myrtenol nitrate

Bew¹,

Hiatt-Gipson²,

Mills³

2016

Beilstein J. Org. Chem.

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“…2CH3CH(00)CH20N02 -2CH3CH(0)CH20N02 + 02 (6) CH3CH(0)CH20N02 + 02 -CH3C(0)CH20N02 + H02 (7) A sample of «-(nitrooxy)acetone was therefore synthesized according to the procedure of McKillop et al (16) and added to the DNPH reagent. This sample yielded the same earlier HPLC peak, with subsequent heating also producing the methylglyoxal peak, thereby confirming the identification.…”

Section: Resultsmentioning

confidence: 99%

“…Eadie and co-workers (8,9) have studied the dynamics of nepheloid layer formation and destruction in Lake Michigan and its role in suspended sediment and trace organic fluxes. Sandilands and Mudroch (15) and Halfman (16) indicate that the BNL is a common feature whose extent varies with depth in the Great Lakes. Evidence now suggests that seasonal variations in chemical species' concentrations (e.g., PCBs, 137Cs, and suspended solids) may result from mixing of the nepheloid layer throughout the water column under nonstratified conditions.…”

Section: Introductionmentioning

confidence: 99%

Production of organic nitrates from hydroxide and nitrate reaction with propylene

Shepson¹,

Edney²,

Kleindienst³

et al. 1985

Environ. Sci. Technol.

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“…Nitrates can also be prepared directly from acetophenone derivatives. 36 The products are potential synthetic intermediates. Synthetic applications of such trichloromethylcarbinols for the preparation of chloromethyl-α-diketones, highly substituted trichloromethylated dihydrofurans and 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 enol acetates of α-functionalized acid chlorides were demonstrated.…”

Section: Scheme 5 Surzur-tanner Rearrangement Ofmentioning

confidence: 99%

Synthesis of α-Functionalized Trichloromethylcarbinols

Ram

Soni

2015

J. Org. Chem.

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A new series of α-functionalized trichloromethylcarbinols have been synthesized from corresponding α-halomethyl ketones, esters, and amides in 48-78% overall yields. Reactivity of nitrates obtained in the first step was dependent on the electron-withdrawing nature of the functional groups, and increases with increasing electron deficiency. Synthetic applications of such trichloromethylcarbinols for the preparation of chloromethyl-α-diketones, trichloromethylated dihydrofurans, and enol acetates of α-functionalized acid chlorides have been demonstrated. The reaction of these compounds in the Jocic-Reeve reaction was also demonstrated.

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Thallium in organic synthesis. 51. Oxidation of enolizable ketones to .alpha.-nitrato ketones by thallium(III) nitrate in acetonitrile

Cited by 27 publications

References 1 publication

Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(−)-myrtenol nitrate

Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(−)-myrtenol nitrate

Production of organic nitrates from hydroxide and nitrate reaction with propylene

Synthesis of α-Functionalized Trichloromethylcarbinols

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