1‐Morpholino‐1‐Cyclohexene

Hünig, Siegfried; Lücke, Eberhard; Brenninger, W.

doi:10.1002/0471264180.os041.17

Cited by 2 publications

(3 citation statements)

References 8 publications

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“…33 Enamines 2g and 2h were synthesized by condensation of the cycloalkanones with morpholine according to a literature procedure. 34 N-deuteratedmorpholine was synthesized by deuterium exchange of morpholine with D 4 -methanol followed by evaporation of the remaining methanol (3×) before it was dried with sodium. All other chemicals were purchased from commercial sources and used without further purification.…”

Section: ■ Discussionmentioning

confidence: 99%

Quantification of the Ambident Electrophilicities of Halogen-Substituted Quinones

Guo

Mayr

2014

J. Am. Chem. Soc.

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Kinetics and mechanisms of the reactions of p-quinone, 2,5-dichloro-p-quinone, 2,3,4,5-tetrachloro-p-quinone (chloranil), 2,3,4,5-tetrafluoro-p-quinone (fluoranil), and 3,4,5,6-tetrachloro-o-quinone with π-nucleophiles (siloxyalkenes, enamines) and amines have been investigated. Products arising from nucleophilic attack at all conceivable sites, that is, at C and O of the carbonyl groups (pathways a, b) as well as at halogenated and nonhalogenated conjugate positions (pathways c, d), were observed. The partial rate constants for the C-attack pathways (a, c, d), which are derived from the photometrically determined second-order rate constants and the product ratios followed the linear free energy relationship log k (20 °C) = sN(E + N) ( Mayr , H.; J. Am. Chem. Soc. 2001 , 123 , 9500 - 9512 ). It was, therefore, possible to calculate the electrophilicity parameters E of the different positions of the quinones from log k (20 °C) and the N and sN parameters of the nucleophilic reaction partners, which have previously been derived from their reactions with benzhydrylium ions. Almost all rate constants for the C-attack pathways (a, c, d) were considerably larger than those calculated for the corresponding SET processes, indicating the operation of polar mechanisms. SET mechanisms may only account for the formation of the products formed via O-attack. With the E parameters determined in this work, it is now possible to predict rate constants for the reactions of these quinones with a large variety of nucleophiles and, thus, envisage unprecedented reactions of quinones.

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Section: ■ Discussionmentioning

confidence: 99%

Quantification of the Ambident Electrophilicities of Halogen-Substituted Quinones

Guo

Mayr

2014

J. Am. Chem. Soc.

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“…Next, compound 2 , as shown in Scheme , was generated by reacting 1-morpholinecyclohexene (prepared by dehydration of cyclohexanone with morpholine) with 2-nitrobenzoyl chloride under basic conditions followed by refluxing in an aqueous acid for 5 h …”

Section: Chemistrymentioning

confidence: 99%

“…Next, compound 2, as shown in Scheme 3, was generated by reacting 1-morpholinecyclohexene (prepared by dehydration of cyclohexanone with morpholine) 10 with 2-nitrobenzoyl chloride under basic conditions followed by refluxing in an aqueous acid for 5 h. 11 The ratio of enol/keto isomers, determined by 1 H NMR spectra, was found to be 97/3. Unfortunately but not surprisingly, reacting 2-nitrobenzyl bromide with cyclohexane-1,3-dione in triethylamine in CH 2 Cl 2 gave the major undesired vinyl ether 12 and minor desired compound 8 in the ratio of 2/1.…”

Section: Chemistrymentioning

confidence: 99%

Mode of Action of 4-Hydroxyphenylpyruvate Dioxygenase Inhibition by Triketone-type Inhibitors

Huang

Sun

et al. 2002

J. Med. Chem.

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A series of 2-(2-nitrobenzoyl)cyclohexane-1,3-dione analogues (1-9) were designed, synthesized, and evaluated for inhibition of 4-hydroxyphenylpyruvate dioxygenase (4-HPPD), a key enzyme involved in the catabolism of tyrosine which catalyzes the conversion of 4-hydroxyphenylpyruvate to homogentisate. The correlations between the results of enzyme inhibition, ferric chloride tests, and the conformational analysis suggested that the tight binding between triketone-type inhibitors and 4-HPPD is likely due to chelation of the enzyme-bound ferric iron with the enol tautomer of 1,3-diketone moiety of the triketones. The presence of a 2-carbonyl group in the triketone is an essential structural feature for potent 4-HPPD inhibition. Modification of the 3-carbonyl group of triketone moiety to other functionality will reduce the overall planarity and thus prevent keto-enol tautomerization, resulting in a decrease or lack of inhibition activity.

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1‐Morpholino‐1‐Cyclohexene

Abstract: 1‐Morpholino‐1‐cyclohexene product: 1‐Morpholino‐1‐cyclohexene

Cited by 2 publications

References 8 publications

Quantification of the Ambident Electrophilicities of Halogen-Substituted Quinones

Quantification of the Ambident Electrophilicities of Halogen-Substituted Quinones

Mode of Action of 4-Hydroxyphenylpyruvate Dioxygenase Inhibition by Triketone-type Inhibitors

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