p-(tricyanovinylidene)phenylhydrazones. Nucleophilic attack on carbon-carbon double bonds

1988 ◽  
Vol 119 (12) ◽  
pp. 1375-1384 ◽  
Author(s):  
Paolo Bruni ◽  
Barbara Cardillo ◽  
Giorgio Tosi ◽  
Gabriele Bocelli
Keyword(s):  
Nucleophilic Attack ◽  
Double Bonds

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.

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.

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.

Ozonation of Carbon-Nitrogen Double Bonds. I. Nucleophilic Attack of Ozone1

1960 ◽  
Vol 82 (7) ◽  
pp. 1801-1807 ◽  
Author(s):  
Alexander H. Riebel ◽  
Ronald E. Erickson ◽  
Claude J. Abshire ◽  
Philip S. Bailey
Keyword(s):  
Nucleophilic Attack ◽  
Double Bonds

scholarly journals Palladium(0)-Catalyzed Difunctionalization of 1,3-Dienes: From Racemic to Enantioselective

Synthesis ◽  
2018 ◽  
Vol 51 (01) ◽  
pp. 122-134 ◽  
Author(s):  
Xiang Wu ◽  
Liu-Zhu Gong
Keyword(s):  
Oxidative Addition ◽  
Catalytic Reactions ◽  
Nucleophilic Attack ◽  
Insertion Reaction ◽  
Wide Scope ◽  
Double Bonds ◽  
Asymmetric Catalytic ◽  
The Creation

1,3-Dienes are easily accessible chemicals that participate in a series of reactions acting on the carbon–carbon double bonds. Catalytic difunctionalization of 1,3-dienes provides a wide scope of functionalized chemicals. Pd(0) catalysts provide a diverse set of principles for the creation of asymmetric catalytic reactions, which are initiated with the oxidative addition and then undergo insertion reaction with one of double bonds of the 1,3-diene to become a π-allyl palladium species that is reactive toward nucleophilic attack. This review summarizes typical advances on the Pd(0)-catalyzed difunctionalization of 1,3-dienes in recent decades, particularly emphasizing the concepts that enable the switch from a racemic reaction to an enantioselective version.1 Introduction2 Amination3 Boration4 Carbonation5 Hydrogenation6 Oxygenation7 Silylation8 Conclusion and Outlook

The pattern of additions to fullerenes

1993 ◽  
Vol 343 (1667) ◽  
pp. 87-101 ◽  
Keyword(s):  
Mass Spectrometry ◽  
Reaction Mechanism ◽  
Nucleophilic Attack ◽  
Reaction Products ◽  
Double Bonds ◽  
Bond Localization ◽  
Selection Of

Conjugation in C 60 is not as extensive as was originally anticipated because, for various reasons, the pentagon rings avoid containing double bonds. As a consequence, there is extensive bond localization and the molecule, which is quite reactive, and displays superalkene rather than superaromatic properties. C 70 behaves in a similar fashion; other fullerenes may follow suit. Additions predominate and C 60 is particularly susceptible to nucleophilic attack. Added groups may also be readily replaced by nucleophiles, although the reaction mechanism is uncertain at present: The functionalized molecule tends to revert to the parent fullerene at moderate temperatures, and characterization of reaction products by mass spectrometry is thus particularly difficult. This fact, coupled with the complexity of the addition products, makes work with fullerenes exacting. A selection of reactions studied to date and the progress made towards identifying various patterns of addition are described.

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.

Sign in / Sign up

Export Citation Format

Share Document