Reactions of Acrolein and Related Compounds. II. Addition of Unsaturated Esters and of Methacrylonitrile

Smith, Curtis W.; Norton, Douglas G.; Ballard, Seaver A.

doi:10.1021/ja01155a077

Cited by 17 publications

(7 citation statements)

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“…Physical properties, analyses, and spectral data are given in Table I for lated to dissociate in solution to give the free phenylborane 7 and triethylamine. One of the allyl groups of the IV,lV-diallylaniline (1) is hydroborated to give the uncoordinated intermediate 9 which would be expected to exist in equilibrium with its coordinated form 10. The initial hydroboration likely occurs after coordination of the free phenylborane (7) with N,N-diallylaniline 0).…”

Section: Resultsmentioning

confidence: 99%

“…The NMR spectrum exhibited resonances at 6 1.2 (t, 9) . Lithium aluminum deuteride (3.36 g, 0.08 mol) was added to 200 ml of anhydrous diethyl ether (distilled from lithium aluminum hydride) in a three-necked, 500-ml, round-bottomed flask equipped with mechanical stirrer, addition funnel, condenser with drying tube, lowtemperature thermometer, and nitrogen inlet tube.…”

Section: Mophenyl)-5-phenyl-l-aza-5-borabicyclo[330]octanementioning

confidence: 99%

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Synthesis and competitive mechanism of formation of phenyl-substituted 1,2-azaborolidines and 1-aza-5-borabicyclo[3.3.0]octanes

McCormick¹,

Butler²

1976

J. Org. Chem.

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1,2-Azaboroliclines and l-Aza-5-borabicyclo[3,3.0]octanes molar ratio27 Eu(hfc)a/(2R)-la 0.22, c (la) 0.58 M, 1.2-ml solution in a 12-mm 0.d. IVMR tube with a vortex plug; (2S)-la (120 mg), molar ratio E~( h f c )~/ ( B S ) -l a 0.29, c (2S)-la 2.2 M, 320 pl total solution in a 5-mm 0.d. NMR tube; (2R)-la (78 mg), molar ratio Eu(hfc)B/ (2R)-la 0.26, c (2R)-la 2.5 M, 185 p1 total solution in a 5-mm 0.d. tube.The I3C NMR spectra were obtained by pulsed Fourier transform NMR as follows: broad-band (noise modulated) l H decoupling, pulse width 78 ps, acquisition time 0.8 s, no pulse delay; transients, (racemic la) 62K; (2R)-la 232K; (2S)-la 71K. The changes in chemical shifts for the C-1 signalszs in the presence of Eu(hfc)a were racemic la, A616.9, AA6 1.9 ppm; (2S)-laA6 14.9, AA6 1.6 ppm.1,5-Diphenyl-l-aza-5-borabicyclo[3.3.0]octane, 1,2-diphenyl-1,2-azaborolidine, and propene were isolated as the major products of the reaction of triethylamine phenylborane with N.N-diallylaniline. These compounds were characterized by nuclear magnetic resonance, infrared, mass spectroscopy, and elemental analyses. Two mechanisms were proposed for the formation of propene and 1,2-diphenyl-1,2-azaborolidine. Triethylamine dideuteriophenylborane reacted with N,N-diallylaniline to give 3,7-dideuterio-1,5-diphenyl-l-aza-5-borabicyclo[3.3.0]0~tane, 3-deuterio-1,2-diphenyl-l,2-azaborolidine, and 3-deuteriopropene. These products are consistent with one of the proposed mechanisms, a concerted, facile elimination of propene. This elimination mechanism was supported by model studies of the transition states. Triethylamine phenylborane reacted with N,N-di-3-butenylaniline to give 1,2-diphenyl-l-(3-butenyl)-2-hydroazaboracyclohexane and 1,6-diphenyl-l-aza-6-borabicyclo[4.4.0]decane. No butene gas was eliminated, giving further support for the proposed mechanism. Several substituted derivatives of 1,5-diphenyl-l-aza-5-borabicyclo[3.3.0]octane and 1,2-diphenyl-1,2-azaborolidine were also prepared and characterized.

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Section: Resultsmentioning

confidence: 99%

Section: Mophenyl)-5-phenyl-l-aza-5-borabicyclo[330]octanementioning

confidence: 99%

Synthesis and competitive mechanism of formation of phenyl-substituted 1,2-azaborolidines and 1-aza-5-borabicyclo[3.3.0]octanes

McCormick¹,

Butler²

1976

J. Org. Chem.

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“…The third synthetic strategy (S-iii) has also been widely used in the synthesis of 6,8-DOBCO and related natural products, and only some of them will be included in Schemes 6−8. In 1951, Smith 39 reported the isolation of an unexpected bicyclic acetal 46 from the thermal reaction of acrolein (43) and methallyl alcohol (44) (Scheme 6a). In 1969, Kinzer 40 employed this type of oxa-Diels−Alder reaction/cycloketalization for the first synthesis of frontalin (18) (no yield or experimental details) (Scheme 6b).…”

Section: General Strategies Toward 68-dobcosmentioning

confidence: 99%

Synthetic Approaches To Construct the 6,8-DOBCO Framework in Natural Products

Zhang

Tong

2016

J. Org. Chem.

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6,8-Dioxabicyclo[3.2.1]octane skeleton (6,8-DOBCO) is a very common structural motif in many biologically active natural products. This synopsis surveys various approaches used to access the 6,8-DOBCO framework present in natural products and summarizes total syntheses of 6,8-DOBCO-containing psoracorylifol B, ent-psoracorylifol C, didemniserinolipid B, and attenol B from our laboratory and others.

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“…Factors initiating polymerisation include the presence of acids (including sulphur dioxide), oxidising agents, or exposure to light and heat. Acrolein and its dimer are highly toxic and have a very reactive free aldehyde group (Smith et al, 1951). Being highly polar, acrolein is furthermore soluble in water and ethanol, with which it reacts slowly and exothermically to give 3-HPA and 3-ethoxypropionaldehyde (3-EPA) respectively.…”

Section: Stability Of the Acrolein Dimer In Winementioning

confidence: 99%

Acrolein Dimer as a Marker for Direct Detection of Acrolein in Wine

Bauer

Hiten

Crouch

et al. 2016

SAJEV

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Acrolein is highly toxic and its presence in wine has been correlated with the development of bitterness. Analytical detection and quantification in aqueous solutions are challenging due to high reactivity and problems with chemical derivative analysis. Here we demonstrate the potential of a natural derivative, formed under conditions prevailing in wine, as a marker for acrolein detection. Solid-phase microextraction (SPME) coupled with gas chromatograph mass spectrometry (GC-MS) was validated as a technique for direct detection of the acrolein dimer. Conventional GC-MS analysis using a quadrupole mass spectrometer did not provide sufficient chromatographic resolution for the separation of the target analyte from interfering compounds. Accurate mass measurements with time-of-flight (TOF)-MS, on the other hand, allowed qualitative and quantitative measurements of the acrolein dimer. This work lays the analytical foundation for studies on the evolution of acrolein and its dimer in solution.

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Reactions of Acrolein and Related Compounds. II. Addition of Unsaturated Esters and of Methacrylonitrile

Cited by 17 publications

References 0 publications

Synthesis and competitive mechanism of formation of phenyl-substituted 1,2-azaborolidines and 1-aza-5-borabicyclo[3.3.0]octanes

Synthesis and competitive mechanism of formation of phenyl-substituted 1,2-azaborolidines and 1-aza-5-borabicyclo[3.3.0]octanes

Synthetic Approaches To Construct the 6,8-DOBCO Framework in Natural Products

Acrolein Dimer as a Marker for Direct Detection of Acrolein in Wine

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