Studies in ferrocene derivatives. VII. The synthesis of ferrocenyl ethylenes via an abnormal Grignard reaction

1969 ◽  
Vol 47 (17) ◽  
pp. 3085-3088 ◽  
Author(s):  
W. H. Horspool ◽  
R. G. Sutherland ◽  
J. R. Sutton
Keyword(s):  
Grignard Reagent ◽  
Acid Strength ◽  
Nucleophilic Attack ◽  
Grignard Reaction ◽  
Ferrocene Derivatives ◽  
Carbonium Ions ◽  
General Synthesis

RMgBr reacts normally with acylferrocenes to give the corresponding alcohols. RMgI gives good yields of the most highly substituted ferrocenyl ethylene. In solutions of moderate acid strength, α-ferrocenyl carbonium ions lose a proton to form the substituted alkene rather than undergo nucleophilic attack by water to give the corresponding alcohol. Since the alcohols are more basic than the alkenes, it is possible to devise a general synthesis of ferrocenyl ethylenes by the reaction of any Grignard reagent with an acylferrocene.

On the Determination and Use of Reduction Potentials of Short-Lived Radicals. A Review

2000 ◽  
Vol 65 (6) ◽  
pp. 829-843 ◽  
Author(s):  
Henning Lund ◽  
Karen Skov ◽  
Steen Uttrup Pedersen ◽  
Torben Lund ◽  
Kim Daasbjerg
Keyword(s):  
Aqueous Solution ◽  
Electron Transfer ◽  
Reaction Mechanisms ◽  
Nucleophilic Attack ◽  
Grignard Reaction ◽  
Hydroxide Ion ◽  
Reduction Sequence ◽  
Reduction Potentials ◽  
Srn1 Reaction

A method, the "competition method", for the determination of reduction potentials and estimation of standard potentials for short-lived radicals is reviewed. Applications of the reduction potentials of radicals as arguments for reaction mechanisms are presented for the Grignard reaction, the photoreduction of ketones with alcohols, and the SRN1 reaction. Reductions induced by hydroxide ions are discussed in more detail, and the classic reaction between nitrosobenzene and hydroxide ion in aqueous solution is used as an example of such a reaction. A nucleophilic attack by hydroxide ion rather than an electron transfer initiates the reduction sequence. A review with 26 references.

scholarly journals Unveiling the Reaction Mechanism of the Das/Chechik/Marek Synthesis of Stereodefined Quaternary Carbon Centers

2021 ◽  
Vol 11 (11) ◽  
pp. 5002
Author(s):  
Pedro J. Silva ◽  
Carlos E. P. Bernardo
Keyword(s):  
Reaction Mechanism ◽  
Grignard Reagent ◽  
Density Functional ◽  
Initial Step ◽  
Nucleophilic Attack ◽  
Carbon Centers ◽  
Rate Limiting Step ◽  
Cu Catalyst ◽  
Rate Limiting ◽  
Zinc Carbenoid

The reaction mechanism of the Cu+-catalyzed introduction of two all-carbon-substituted stereocenters in an ynamide system using a Grignard reagent, a zinc carbenoid, and an aldehyde, was investigated using density-functional theory. In contrast to the formation of an organocopper(I) compound and subsequent carbocupration reaction, previously postulated as the initial step, the reaction proved to instead proceed through an initial complexation of the substrate alkyne bond by the Cu+-catalyst, which primes this bond for reaction with the Grignard reagent. Subsequent addition of the zinc carbenoid then enables the nucleophilic attack on the incoming aldehyde, which is revealed as the rate-limiting step. Our computations have also identified the factors governing the regio- and setereoselectivity of this interesting reaction, and suggest possible paths for its further development

scholarly journals SINTESIS FEROMON 6-METIL-2-HEPTEN-4-OL DARI KROTONALDEHID MELALUI PEMBENTUKAN REAGEN GRIGNARD ISOBUTILMAGNESIUM BROMIDA

2010 ◽  
Vol 5 (2) ◽  
Author(s):  
Putu Indrayani ◽  
Aliefman Hakim
Keyword(s):  
Grignard Reagent ◽  
Refraction Index ◽  
Magnesium Bromide ◽  
Grignard Reaction ◽  
Stretching Vibration ◽  
Nh4cl Solution

Abstrak : Sintesis 6-metil-2-hepten-4-ol diawali dengan pembentukan reagen Grignard isobutilmagnesium bromida pada 400C selama 1 jam, dilanjutkan dengan pembentukan garam alkoksi magnesium bromida pada 00C.Hidrolisis terhadap garam alkoksi magnesium bromida dengan larutan NH4Cl jenuh menghasilkan 6-metil-2-hepten-4-ol. Hasil sintesis kemudian diuji sifat fisiko-kimianya meliputi berat jenis, indeks bias serta identifikasi denganSpektrofotometer Inframerah (IR), Kromatografi Gas (GC) dan Kromatografi Gas-Spektrometer Massa (GC-MS). Hasil sintesis menghasilkan cairan beraroma manis segar, berwarna kekuningan, berat jenis 0,81529 g/mL, indeks bias 1,40830, kemurnian 66,07 % dan hasil 46,31 %. Karakter IR senyawa hasil sintesis menunjukkan vibrasi ulur O-H alkohol pada 3361 cm-1, vibrasi ulur C-OH pada 1049,2 cm-1, vibrasi ulur C=C pada 1676 cm-1 dan serapan 2956,7 dan 2920 cm-1 untuk vibrasi ulur C-H dalam CH 3 dan spektra massa dengan m/e 128 yang dicapai pada waktu retensi 6,284 menit. Data-data tersebut mendukung bahwa senyawa hasil sintesis adalah 6-metil-2-hepten-4-ol.Kata kunci : Sintesis, reaksi Grignard dan 6-metil-2-hepten-4-olAbstract : Synthesis of 6-methyl-2-hepten-4-ol was generated with formation of Grignard reagent Isobutylmagnesium bromide carried out at 400C for one hour, then formation of alcoxide salt magnesium bromide carried out at 00C. Alcoxide salt magnesium bromide were hydrolyzed by saturated NH4Cl solution producing 6-methyl-2-hepten-4-ol. Results were examined physically and chemically including density, refraction index, pure percentage and yield percentage were 0,81529 g/mL, 1,40830, 66,07 % and 46,31 % respectively. The IR characters showed stretching vibration of O-H group at 3361 cm-1, stretching vibration C-OH group at 1049,2 cm-1, stretching vibration C=C group at 1676 cm-1 and absorption of C-H in CH3 2956,7 and 2920 cm-1. Identification using GC-MS resulted spectra m/e 128 at time retention 6,284 minutes. The proven data indicated that the resulted compound was 6-methyl-2-hepten-4-ol.Keywords : synthesis, Grignard reaction and 6-methyl-2-hepten-4-ol

Hyperbranched Conductive Polymers Constituted of Triphenylamine

1999 ◽  
Vol 600 ◽  
Author(s):  
S. Tanaka ◽  
K. Takeuchi ◽  
M. Asai ◽  
T. Iso ◽  
M. Ueda
Keyword(s):  
Molecular Weight ◽  
Conjugated Polymer ◽  
Grignard Reagent ◽  
Average Molecular Weight ◽  
Catalytic Amount ◽  
Oxidation Potential ◽  
Grignard Reaction ◽  
Step Process ◽  
One Step ◽  
Dark Blue

AbstractA hyperbranched conjugated polymer containing triphenylamine was prepared by the Grignard reaction of tris(4-bromophenyl)amine 1, via the coupling of N, N-bis(4-bromophenyl)-N-(4-bromomagnesiophenyl)amine 2 with the catalytic amount of Ni(acac)2. Grignard reagent 2 reacted as an AB2-type monomer to give hyperbranched conjugated polymer 3 in a one-step process. Polymer 3 was also obtained via the Pd-catalyzed coupling of N, N-bis(4-bromophenyl)-4-animobenzeneboronic acid 4. Polymer 3 had an average molecular weight of 4.0–6.3×103 and was found to be soluble in organic solvents such as THF and CHC13. A cast film had an anodic peak at 0.95–1.20 V vs. Ag wire. It was dark blue above the oxidation potential and brown-yellow in the neutral state. When polymer 3 was doped with iodine, its conductivity rose to 0.8–3.0 S/cm

Study on Synthesis of 2-Hydroxy-6-Naphthoic Acid from 2-Naphthol and Improve the Synthetic Process

2013 ◽  
Vol 634-638 ◽  
pp. 2044-2048
Author(s):  
Yang Wang ◽  
Qiang Li ◽  
Xian Feng Gong ◽  
Xue Ling Zhao ◽  
Yu Zhang
Keyword(s):  
Carbon Dioxide ◽  
Grignard Reagent ◽  
Reducing Agent ◽  
Raw Material ◽  
Grignard Reaction ◽  
Solid Carbon ◽  
Solid Carbon Dioxide ◽  
Synthetic Process ◽  
Naphthoic Acid

2-Hydroxy-6-naphthoic acid is an main raw material for the synthesis of polyaromatic ester, it was synthesized from 2-Naphthol by methoxylation, bromization, grignard reaction and demethylation before recrystallization (C2H5OH:H2O=2.8:1 m/m) with an overall yield of 78.5% and content of 99.1%. Furthermore, the results showed that the 6-bromo-2-methoxynaphthalene was prepared using Sn as reducing agent with 96.2% of the yield which is higher than 6-bromo-2-methoxynaphthalene was prepared using solid carbon dioxide and grignard reagent with 23.8% of the yield.

Studies in ferrocene derivatives. IX. The dimerization of α-ferrocenyl carbonium ions

1970 ◽  
Vol 48 (22) ◽  
pp. 3542-3544 ◽  
Author(s):  
W. M. Horspool ◽  
R. G. Sutherland ◽  
J. R. Sutton
Keyword(s):  
Ferrocene Derivatives ◽  
Carbonium Ions ◽  
Ionic Addition

Ferrocenylethylenes dissolve in 90% HCOOH to give solutions of the α-ferrocenyl carbonium ions in equilibrium with the unprotonated species. These subsequently react by an ionic-addition mechanism to give dimeric carbonium ions which can cyclize by both homo-and heteroannular pathways.

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