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

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

Australian Journal of Chemistry ◽

10.1071/ch9831259 ◽

1983 ◽

Vol 36 (6) ◽

pp. 1259 ◽

Cited By ~ 3

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.

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

Australian Journal of Chemistry ◽

10.1071/ch9871777 ◽

1987 ◽

Vol 40 (10) ◽

pp. 1777 ◽

Cited By ~ 4

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.

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

Australian Journal of Chemistry ◽

10.1071/c97050 ◽

1997 ◽

Vol 50 (8) ◽

pp. 849 ◽

Cited By ~ 3

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.

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

Australian Journal of Chemistry ◽

10.1071/ch9910463 ◽

1991 ◽

Vol 44 (3) ◽

pp. 463 ◽

Cited By ~ 3

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.

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

Pure and Applied Chemistry ◽

10.1351/pac-con-09-07-05 ◽

2010 ◽

Vol 82 (7) ◽

pp. 1555-1568 ◽

Cited By ~ 14

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.

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