Reaction of O-methylbenzohydroximoyl chlorides with sodium methoxide.  Inversions of configuration at trigonal carbon during nucleophilic substitution

Johnson, James E.; Nalley, E. Ann; Weidig, Charles

doi:10.1021/ja00787a077

Cited by 14 publications

(5 citation statements)

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“…There are several studies (7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17) on nucleophilic substitutions at the C-N double bond. A nucleophilic additionelimination mechanism or a pathway involving a nitrilium ion intermediate has been suggested.…”

Section: Methodsmentioning

confidence: 99%

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2-Azabuta-1,3-diene-4-carbonitriles: stereoselective synthesis and nucleophilic substitution at the carbon–nitrogen double bond

Lorente¹,

Casillas²,

Gomez-Sal³

et al. 1996

Can. J. Chem.

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Abstract:The synthesis of (E)-l-methoxy-2-azabuta-1,3-diene-4-carbonitriles was performed by methylation of Nalkenylamides 9 and 11. The Z isomers were obtained by treatment of (E)-I-methylthio-2-azabuta-I ,3-diene-4,4-dicarbonitriles with sodium methoxide in methanol. We also describe the reactions of (E)-1-methylthio-2-azabuta-1,3-diene-4,4-dicarbonitriles with pyrrolidine, which afforded 1-(1-pyrrolidinyl) derivatives 20,21, and 23. X-ray crystallographic analyses of 21 and 23 established the E stereochemistry of the C-N double bond. K~) Jwordr: 2-azabuta-l,3-diene-4-carbonitriles: stereoselective synthesis, nucleophilic substitution and X-ray diffraction; Nalkenylamides: methylation.Resume : On a effectui la synthkse des (E)-l-mithoxy-2-azabuta-1,3-di~ne-4-carbonitriles en effectuant la mithylation des Nalkinylamides 9 et 11. On a obtenu les isomkres Zen traitant les (0-1-mithylthio-2-azabuta-1,3-dikne-4,4-dicarbonitriles avec du mithylate de sodium dans le mithanol. On dicrit aussi les riactions des (E)-l-mithylthio-2-azabuta-I,3-dikne-4,4-dicarbonitriles avec la pyrrolidine qui conduisent aux dirivis 1-(I-pyrrolidinyle) 20,21 et 23. On a ditermini la stiriochimie E de la double liaison C-N par une analyse cristallographique par diffusion des rayons X.

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Section: Methodsmentioning

confidence: 99%

“…Ketene dithioacetals (2) were prepared according to the procedure described by R. Gompper and W. Tijpfl (31). The synthesis of methyl (Z)-3-benzamido-2-cyano-3-phenylpropenoate (10) was described in a previous paper (18) and methyl (27-3-benzamido-2-cyano-3-methylthiopropenoate (11) was prepared according to the reported procedure (32).…”

Section: Generalmentioning

confidence: 99%

2-Azabuta-1,3-diene-4-carbonitriles: stereoselective synthesis and nucleophilic substitution at the carbon–nitrogen double bond

Lorente¹,

Casillas²,

Gomez-Sal³

et al. 1996

Can. J. Chem.

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“…This compound was obtained from 2 in the same manner as 3 in 70% yield as an oil, which solidifies at 5 °C: NMR 4.46 (CHF, 1 H, d quint, JHf = 48 Hz, s/hh = 6 Hz), 3.30 (CH2I, 2 H, dd, JjjF = 20 Hz, $/HH = 6 Hz), 0.81- 1.83 3,7-Dimethyl-7-fluoro-6-iodo- 1-octanal (6). A cold (-75 °C) CHC13 solution of 15 mmol of citronellal (5) was added to the IF suspension and allowed to react for 1-2 min. After the usual workup and after chromatography using 10% EtOAc in petroleum ether as eluent, 6 was obtained in 50% yield as an oil: IR (neat) 1720 cm'1; NMR 9.5 (CHO, 1 H, t), 4.30 (CHI, 1 H, m), 1.45 (CH3CF, 3 H, d, s/Hf = 22 Hz), 1.40 (CH3CF, 3 H, d, JHF = 22 Hz), 0.87 (CH3, 3 H, d, JHH = 6 Hz); 19F NMR -134 ppm (m).…”

Section: Methodsmentioning

confidence: 99%

“…Despite its high reactivity, an aldehyde CH3(CH2)"CH=CH2 CH3(CH2)nCHFCH2I function may be present, since unlike IF3 and IF5, IF itself is not a strong oxidizer. Thus citronellal (5) forms only one regiospecific adduct, 3,7-dimethyl-7-fluoro-6-iodo-loctanal (6) in good yield.…”

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confidence: 97%

A new method for introducing iodo and bromo fluorides into organic molecules using elemental fluorine

Rozen¹,

Brand²

1985

J. Org. Chem.

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A new method for introducing IF and BrF into organic compounds is developed. These reagents have been prepared by the direct action of elemental fluorine on the two respective halogens at low temperatures. The reactions of these interhalogen compounds with isolated double bonds are fast even at -75 °C. They were found to be stereospecific (anti mode addition) and in most cases regiospecific too. With conjugated enones the reactions were considerably slower. In this case an easy HF elimination takes place, producing eventually -halo enones. Since the benzylic C-I bond is very weak, the reaction of IF with stilbenes leads to the 1,2-difluoro adducts through a secondary attack of the nucleophilic fluorine on the iodine, either through SN2 or through the rare SNi mechanism. Bromine fluoride on the other hand gave the expected BrF adducts. The BrF reactions are much more forceful than the parallel IF ones, and a proton donor has to be present in order to tame this reagent. The halogen fluoride

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“…Kinetic Behavior iii. Further increase in the electron-withdrawal ability of the substituents will result in an increased importance of route a over routes b and c, and in the extreme case when the second term of eq 5 will be much larger than the first term, the bimolecular reaction will take over ¿obsd = MR2NH] (10) (eq 10). The reaction of compound 11 (where X = Y = p-N02) with piperidine is of pure second order (kinetic behavior iii), and it is very likely that route a is the exclusive substitution pathway.…”

Section: Table VI and Figurementioning

confidence: 99%

Nucleophilic attacks on carbon-nitrogen double bonds. 3. Diversity of mechanisms for the substitution of diarylimidoyl chlorides by amines in acetonitrile

Ta‐Shma¹,

Rappoport²

1976

J. Am. Chem. Soc.

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Reaction of O-methylbenzohydroximoyl chlorides with sodium methoxide. Inversions of configuration at trigonal carbon during nucleophilic substitution

Cited by 14 publications

References 0 publications

2-Azabuta-1,3-diene-4-carbonitriles: stereoselective synthesis and nucleophilic substitution at the carbon–nitrogen double bond

2-Azabuta-1,3-diene-4-carbonitriles: stereoselective synthesis and nucleophilic substitution at the carbon–nitrogen double bond

A new method for introducing iodo and bromo fluorides into organic molecules using elemental fluorine

Nucleophilic attacks on carbon-nitrogen double bonds. 3. Diversity of mechanisms for the substitution of diarylimidoyl chlorides by amines in acetonitrile

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