Mechanisms of Nucleophilic Attack at Carbon-Nitrogen Double Bonds. The Solvolysis of Substituted Benzohydrazonoyl Halides in Aqueous Binary Mixtures

1991 ◽  
Vol 44 (3) ◽  
pp. 463 ◽  
Author(s):  
JE Rowe
Keyword(s):  
Binary Mixtures ◽  
Aqueous Ethanol ◽  
Nucleophilic Attack ◽  
Rate Data ◽  
Double Bonds ◽  
Aqueous Binary Mixtures ◽  
Mechanism Of The Reaction

Rate data for the solvolysis of a series of substituted benzohydrazonoyl halides in aqueous dioxan at 329 K and in aqueous ethanol and methanol at 303 K are presented. The products in the aqueous alcohols were measured by h.p.l.c ., and the selectivities determined. The data are used to support proposals about the mechanism of the reaction.

Mechanisms of Nucleophilic Attack at Carbon Nitrogen Double-Bonds: The Reaction of Benzohydrazonoyl Halides With Amines

1987 ◽  
Vol 40 (10) ◽  
pp. 1777 ◽  
Author(s):  
AF Hegarty ◽  
P Rigopoulos ◽  
JE Rowe
Keyword(s):  
Double Bond ◽  
Nucleophilic Attack ◽  
Rate Data ◽  
Double Bonds ◽  
Nitrogen Double Bond

Rate data for the reaction of a series of benzohydrazonoyl halides with pyrrolidine and butan- 1-amine at 303 K are presented. Linear Hammett plots were obtained with each amine. The mechanism of the reactions and the stereochemical outcome of these displacements at the carbon-nitrogen double bond are discussed.

Mechanisms of Nucleophilic Attack at Carbon - Nitrogen Double Bonds: Reactions of Benzohydrazonoyl Halides with Secondary Amines in Benzene

1997 ◽  
Vol 50 (8) ◽  
pp. 849 ◽  
Author(s):  
Jeffrey E. Rowe ◽  
Kam Lee
Keyword(s):  
Second Order ◽  
Secondary Amines ◽  
Nucleophilic Attack ◽  
Rate Equations ◽  
Rate Data ◽  
Double Bonds ◽  
Effect Data ◽  
First Order ◽  
Amine Molecule

The reactions of a series of substituted benzohydrazonoyl halides with cyclic secondary amines in benzene as solvent are investigated. The rate equations for these reactions were complex and the derived rate data are reported. The element effect data showed that the fluoro compounds only reacted when a second amine molecule was available to assist the reaction, whereas the chloro and bromo compounds reacted by reactions which were both first order and second order in amine (k′′Br : k′′Cl = 9·5 : 1 and k′′′Br :k′′′Cl : k′′′F = 4·7 : 1 : 0·65). The mechanism of these reactions is discussed.

Mechanisms of Nucleophilic Attack at Carbon-Nitrogen Double Bonds. The Reaction of Benzohydrazonoyl Compounds With Methoxide Ion

1995 ◽  
Vol 48 (12) ◽  
pp. 2041 ◽  
Author(s):  
JE Rowe ◽  
DA Papanelopoulos
Keyword(s):  
Nucleophilic Attack ◽  
Rate Data ◽  
Double Bonds ◽  
Elimination Mechanism ◽  
Methoxide Ion

Rate data for the reaction of a number of benzohydrazonoyl compounds with methoxide ion are reported. The stereochemistry of the products was determined by h.p.l.c. The mechanism of the reactions and the stereochemistry of the products resulting from an addition-elimination mechanism are discussed.

Mechanisms of nucleophilic attack at carbon-nitrogen double bonds. The reaction of aryl N-arylbenzimidates with methoxide ion

1983 ◽  
Vol 36 (6) ◽  
pp. 1259 ◽  
Author(s):  
JE Rowe
Keyword(s):  
Isotope Effects ◽  
Nucleophilic Attack ◽  
Rate Data ◽  
Double Bonds ◽  
Tetrahedral Intermediate ◽  
Methoxide Ion ◽  
Solvent Isotope ◽  
Solvent Isotope Effects

Rate data for the reaction of three series of aryl N-arylbenzimidates with methoxide ion at 303 K are presented. Linear Hammett plots were obtained for each series. Solvent isotope effects have also been measured. The results are interpreted in terms of rate-determining formation of a tetrahedral intermediate, irrespective of the nature of the substituent.

scholarly journals Perception of Aqueous Ethanol Binary Mixtures Containing Alcohol-Relevant Taste and Chemesthetic Stimuli

Beverages ◽  
2021 ◽  
Vol 7 (2) ◽  
pp. 23
Author(s):  
Margaret Thibodeau ◽  
Gary Pickering
Keyword(s):  
Binary Mixture ◽  
Binary Mixtures ◽  
Aqueous Ethanol ◽  
Ethanol Concentration ◽  
Alcoholic Beverages ◽  
Complex Stimulus ◽  
Aluminium Sulphate ◽  
Binary Solutions ◽  
Wide Range ◽  
Thermal Taste

Ethanol is a complex stimulus that elicits multiple gustatory and chemesthetic sensations. Alcoholic beverages also contain other tastants that impact flavour. Here, we sought to characterize the binary interactions between ethanol and four stimuli representing the dominant orosensations elicited in alcoholic beverages: fructose (sweet), quinine (bitter), tartaric acid (sour) and aluminium sulphate (astringent). Female participants were screened for thermal taste status to determine whether the heightened orosensory responsiveness of thermal tasters (n = 21–22) compared to thermal non-tasters (n = 13–15) extends to these binary mixtures. Participants rated the intensity of five orosensations in binary solutions of ethanol (5%, 13%, 23%) and a tastant (low, medium, high). For each tastant, 3-way ANOVAs determined which factors impacted orosensory ratings. Burning/tingling increased as ethanol concentration increased in all four binary mixture types and was not impacted by the concentration of other stimuli. In contrast, bitterness increased with ethanol concentration, and decreased with increasing fructose concentration. Sourness tended to be reduced as ethanol concentration increased, although astringency intensity decreased with increasing concentration of fructose. Overall, thermal tasters tended to be more responsive than thermal non-tasters. These results provide insights into how the taste and chemesthetic profiles of alcoholic beverages across a wide range of ethanol concentrations can be manipulated by changing their composition.

Ketoconazole solubility in aqueous binary mixtures of 1‑propanol at various temperatures

2019 ◽  
Vol 292 ◽  
pp. 111382 ◽  
Author(s):  
Ayda Hatefi ◽  
Elaheh Rahimpour ◽  
Fleming Martinez ◽  
Mohammad Barzegar-Jalali ◽  
Abolghasem Jouyban
Keyword(s):  
Binary Mixtures ◽  
Aqueous Binary Mixtures

Reactions of bridging C3 ligands in diiron complexes: Unconventional routes to new functionalized organic frames

2010 ◽  
Vol 82 (7) ◽  
pp. 1555-1568 ◽  
Author(s):  
Valerio Zanotti
Keyword(s):  
Functional Groups ◽  
Nucleophilic Addition ◽  
Metal Center ◽  
Unusual Reaction ◽  
Nucleophilic Attack ◽  
Double Bonds ◽  
Bridging Ligands ◽  
Reaction Patterns

Diiron complexes containing C3 ligands, such as vinyliminium and vinylalkylidene bridging units, display unusual reaction patterns, not observed when the same organic fragments are bound to a single metal center, or not coordinated. Bridging vinyliminium complexes [Fe2{μ-η1:η3-C(NMe2)CH=CR}(μ-CO)(CO)(Cp)2][SO3CF3] undergo nucleophilic addition at the iminium C or at α-C position, which is uncommon since non-coordinated vinyliminium species generally undergo conjugated (Michael type) nucleophilic attack. Likewise, bridging vinyliminium ligands undergo new and unusual transformations consisting of the deprotonation and replacement of the α-CH by a variety of functional groups. These reactions, resulting in the formation of C–C and C–heteroatom single and double bonds, produce new bridging ligands of the type [μ-C(NMe2)C(X)CR) (X = S, O, Se, SPh, CNMe, NNCHCO2Me]. Removal of the vinylalkylidene ligands from the bridging coordination is achieved by a [3 + 2] cycloaddition with alkynes. The reaction leads to the formation of ferrocenes containing one polysubstituted Cp ring, which results from the cycloaddition of the bridging C3 ligand with alkynes. This result suggests a new possible route for the synthesis of polyfunctionalized ferrocenes.

Sign in / Sign up

Export Citation Format

Share Document