The Synthetic Methods Structures, and Properties of the Ca-C σ Bond Organocalcium Containing Compounds - Nejib Ben Hussein Mekni - E-Book

The Synthetic Methods Structures, and Properties of the Ca-C σ Bond Organocalcium Containing Compounds E-Book

Nejib Ben Hussein Mekni

0,0
33,33 €

-100%
Sammeln Sie Punkte in unserem Gutscheinprogramm und kaufen Sie E-Books und Hörbücher mit bis zu 100% Rabatt.
Mehr erfahren.
Beschreibung

This reference describes the chemistry of organocalcium compounds that contain a Ca-C σ-bond. It collects the information about this niche group of organometallic compounds into 4 easy-to-read chapters. It is intended for scholars in the field of organic chemistry, and researchers in industrial chemistry and chemical engineering departments.

Key features:
- Presents a comparison to homologous compounds of other alkaline earth metals.
- Explains the main problems encountered in the synthesis of organocalcium compounds with reference to the reactivity of calcium, the low solubility in common solvents and the high reactivity of the formed intermediates and products
- Highlights many concepts about the Ca-C bond such as the steric hindrance, degrading agent properties, organocalcium spectroscopy, and more

Sie lesen das E-Book in den Legimi-Apps auf:

Android
iOS
von Legimi
zertifizierten E-Readern

Seitenzahl: 134

Veröffentlichungsjahr: 2002

Bewertungen
0,0
0
0
0
0
0
Mehr Informationen
Mehr Informationen
Legimi prüft nicht, ob Rezensionen von Nutzern stammen, die den betreffenden Titel tatsächlich gekauft oder gelesen/gehört haben. Wir entfernen aber gefälschte Rezensionen.



Table of Contents
BENTHAM SCIENCE PUBLISHERS LTD.
End User License Agreement (for non-institutional, personal use)
Usage Rules:
Disclaimer:
Limitation of Liability:
General:
PREFACE
CONSENT FOR PUBLICATION
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
ACKNOWLEDGEMENTS
General Introduction
Abstract
General Introduction
Conclusion
Calcium Element
Abstract
1. Calcium element
1.1. Introduction
1.2. Calcium Physical Properties
1.3. Calcium Chemical Properties
1.4. Calcium-Carbon Bonding in Organic Compounds
2. Short Historical View on Ca-Cσ-bond Organocalcium Containing Compounds
3. Challenges for the Synthesis of Organocalcium Ca-C Containing Compounds
Conclusion
References
Organocalcium (Ca-C) σ-bond Containing Compounds
Abstract
1. Ca-Cσ-bond Alkylcalcium Compounds
1.1. Introduction
1.2. Silyl Substituted Methylcalcium Derivatives
1.3. Calcium Transmetalation of Dialkylzinc
1.4. Cycloalkylcalcium Derivatives
2. Benzylcalcium Compounds
2.1. Introduction
2.2. Benzyl Ca-C Bond Formation
3. Alkenyl Calcium Compounds
4. Alkynyl Calcium Compounds
5. Reaction of Diene and Diynecompounds with Calcium
5.1. Reaction of Diene Compounds with Calcium
5.2. Reaction of Diynecompounds with Calcium
6. Ca-C Aryl Compounds
6.1. PhenylCalcium Compounds
6.2. Biphenyl Naphthalene Anthracene Halo-Derivatives
6.3. Anthracene Reduction
7. Heteroaromatic Calcium Compounds
7.1. Halo-Thiophene Derivatives
7.2. Picoline Derivatives
7.2.1. Reaction of bis(allyl)calcium with 2-Picoline
7.2.2. Reaction of bis(allyl)calcium with 4-picoline
7.2.3. Reaction of bis(allyl)calcium with 4-t-Bu-pyridine
7.2.4. Reaction of bis(allyl)calcium with 2,6-Lutidine
Conclusion
References
Coordination, Degrading Agent, Catalyst Property and Spectroscopy of Organocalcium Compounds
Abstract
1. Carbon-Carbon π-Bond Calcium Coordination
2. Organocalcium Compounds and Solvent Degradation
2.1. Ether Degradation
2.2. Durability in Ethereal Solutions
3. Organocalcium Ca-C σ-Bond Containing Catalysts
4. NMR Spectroscopy of Organocalcium Compounds
4.1. 43Ca NMR Spectroscopy
4.2. 13C NMR Spectroscopy
4.3. 1H NMR Spectroscopy
Conclusion
References
Conclusion
The Synthetic Methods, Structures, and Properties of the Ca-C σ Bond Organocalcium Containing Compounds
Authored by
Nejib Ben Hussein Mekni
High Institute of Medical Technologies of Tunis
Tunisia.9, Avenue Docteur Zouhaier Essafi
1006, Tunis
Tunisia
&
Noureddine Raouafi
Faculty of Science of Tunis, University of Tunis El Manar
Tunisia.20, Rue de Tolède
2092 Tunis,
Tunisia

BENTHAM SCIENCE PUBLISHERS LTD.

End User License Agreement (for non-institutional, personal use)

This is an agreement between you and Bentham Science Publishers Ltd. Please read this License Agreement carefully before using the ebook/echapter/ejournal (“Work”). Your use of the Work constitutes your agreement to the terms and conditions set forth in this License Agreement. If you do not agree to these terms and conditions then you should not use the Work.

Bentham Science Publishers agrees to grant you a non-exclusive, non-transferable limited license to use the Work subject to and in accordance with the following terms and conditions. This License Agreement is for non-library, personal use only. For a library / institutional / multi user license in respect of the Work, please contact: [email protected].

Usage Rules:

All rights reserved: The Work is the subject of copyright and Bentham Science Publishers either owns the Work (and the copyright in it) or is licensed to distribute the Work. You shall not copy, reproduce, modify, remove, delete, augment, add to, publish, transmit, sell, resell, create derivative works from, or in any way exploit the Work or make the Work available for others to do any of the same, in any form or by any means, in whole or in part, in each case without the prior written permission of Bentham Science Publishers, unless stated otherwise in this License Agreement.You may download a copy of the Work on one occasion to one personal computer (including tablet, laptop, desktop, or other such devices). You may make one back-up copy of the Work to avoid losing it.The unauthorised use or distribution of copyrighted or other proprietary content is illegal and could subject you to liability for substantial money damages. You will be liable for any damage resulting from your misuse of the Work or any violation of this License Agreement, including any infringement by you of copyrights or proprietary rights.

Disclaimer:

Bentham Science Publishers does not guarantee that the information in the Work is error-free, or warrant that it will meet your requirements or that access to the Work will be uninterrupted or error-free. The Work is provided "as is" without warranty of any kind, either express or implied or statutory, including, without limitation, implied warranties of merchantability and fitness for a particular purpose. The entire risk as to the results and performance of the Work is assumed by you. No responsibility is assumed by Bentham Science Publishers, its staff, editors and/or authors for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products instruction, advertisements or ideas contained in the Work.

Limitation of Liability:

In no event will Bentham Science Publishers, its staff, editors and/or authors, be liable for any damages, including, without limitation, special, incidental and/or consequential damages and/or damages for lost data and/or profits arising out of (whether directly or indirectly) the use or inability to use the Work. The entire liability of Bentham Science Publishers shall be limited to the amount actually paid by you for the Work.

General:

Any dispute or claim arising out of or in connection with this License Agreement or the Work (including non-contractual disputes or claims) will be governed by and construed in accordance with the laws of Singapore. Each party agrees that the courts of the state of Singapore shall have exclusive jurisdiction to settle any dispute or claim arising out of or in connection with this License Agreement or the Work (including non-contractual disputes or claims).Your rights under this License Agreement will automatically terminate without notice and without the need for a court order if at any point you breach any terms of this License Agreement. In no event will any delay or failure by Bentham Science Publishers in enforcing your compliance with this License Agreement constitute a waiver of any of its rights.You acknowledge that you have read this License Agreement, and agree to be bound by its terms and conditions. To the extent that any other terms and conditions presented on any website of Bentham Science Publishers conflict with, or are inconsistent with, the terms and conditions set out in this License Agreement, you acknowledge that the terms and conditions set out in this License Agreement shall prevail.

Bentham Science Publishers Pte. Ltd. 80 Robinson Road #02-00 Singapore 068898 Singapore Email: [email protected]

PREFACE

The organocalcium compounds may include organic compounds that contain calcium atom(s) in their molecular formula, in which calcium is not bonded to carbon atoms, but generally bonded to a heteroatom (e. g. O, N, S, etc.) as an ionic bond or coordinated to heteroatoms as complexes.

As a contribution to the organometallic field and especially the organocalcium chemistry, the organocalcium compounds that contain Ca-C σ-bond are described here. The main problems encountered in the synthesis of such compounds compared to their homologous organomagnesium derivatives are expected to be due to the low reactivity of calcium element, the low solubility in common solvents and the high reactivity of the formed intermediates and products and their instability, are detailed and discussed.

We scanned the different Ca-C σ-bond containing organocalcium compounds and compared some of their properties to those of the alkaline and alkaline earth organometallic homologous compounds.

In this work, several important notes such as the restriction of the Ca-C double bond from real experimental examples are highlighted. Calcium may form two σ-bonds with two different carbon atoms in very difficult geometrical situations in the presence of high hindrances under the effect of bulky groups, but it cannot form a double bond. Besides, many interesting ideas such as degrading agent property, organocalcium spectroscopy and others are discussed.

In addition to research groups in the academic field of organometallic compounds, many other readers may benefit from this book reference as well as the catalyst, polymer, petroleum, pharmacology and pipeline fields, especially in the scarcity of reference books on the subject.

CONSENT FOR PUBLICATION

Not applicable.

CONFLICT OF INTEREST

The author declares no conflict of interest, financial or otherwise.

ACKNOWLEDGEMENTS

Declared none.

Nejib Ben Hussein Mekni High Institute of Medical Technologies of Tunis Tunisia.9, Avenue Docteur Zouhaier Essafi 1006, Tunis Tunisia &Noureddine Raouafi Faculty of Science of Tunis, University of Tunis El Manar Tunisia.20, Rue de Tolède

ACKNOWLEDGEMENTS

The authors would like to thank their colleague Dr. Amr Eddeck, a member of Taibah University teaching and research staff (Saudi Arabia), Miss Nour El Houda Mekni and the professor Sliman Ben Ghorbal for their helpful technical efforts and Pr. Dr. Mohamed Abderrahmane Sanhoury, Ph.D., MRSC (Member of the Chemical Royal Society) for technical and language assistance.

We thank all our professors from the Faculty of Sciences of Tunis (Tunisia), all our colleagues, and all our teachers.

We dedicate this work to the Soul of our fathers, our mothers, our wives and all our family members.

General Introduction

Nejib Ben Hussein Mekni,Nourdine Raouafi

Abstract

This first chapter is a general introduction to the book in which we give a background on the Ca-Cσ-bond containing organocalcium compounds, which are less studied as compared to other organometallic compounds.

We describe the interest in synthesizing the synthesized organometallic intermediates and products as well as their application fields such as chemistry, biology, medicine, pharmacology, and industry.

It is indicated that such compounds are not well-known because of the low reactivity of calcium elements, the low solubility of oraganocalcium intermediates and products in common organic solvents, their instability resulting from their high reactivity, cause their degradation and the degradation of their preferred ethereal solvents.

Despite the significant difference in electronegativity value between the two elements, the Ca-Cσ-bonds have a covalent polar character. In many cases, the coordination considerably decreases the calcium electropositive character, facilitating the formation of the Ca-Cσ-covalent bond.

The difficulties in synthesizing such compounds, their degradation property and catalytic behaviour as well as the spectroscopy technics used to identify their structures are also described.

Keywords: Alkylcalcium, Alkaline earth metals, Ca-Cσ bond, Calcium, Calcium coordination, Catalytic properties, Calcium reactivity, Covalent bond, d- orbitals, Degradation, Ethereal solvents, Electronegativity, Intermediates, Ionic bond, Organometallic, Organocalcium, Phenylcalcium, Solvent degradation, Spectroscopic technics.

General Introduction

Organometallic compounds are increasingly attracting great interest as witnessed by the number of their newly synthesized intermediates and products, involving different applications, in chemistry, biology, medicine, pharmacology, and industry fields.

Compared to the other alkali, alkaline earth and transition element organometallic derivatives, the Ca-Cσ-bond containing organocalcium compounds are less known for many reasons, which are related to the low reactivity of calcium element, the low solubility of the oraganocalcium intermediates and products in common organic solvents, their instability coming from their high reactivity, that causes their degradation and the degradation of their preferred ethereal solvents.

The high difference in electronegativity value between calcium and carbon elements could be expected to result in the formation of a Ca-C ionic bond. However, the observed Ca-Cσ-bond confirms its polar covalent character. The formation of such bonds may be due to the high coordination number of calcium atom from its d-vacuum orbitals to both n lone electron pairs of heteroatoms of the main product as well as the ethereal solvents and to the π-bonding pairs. Such coordination would considerably decrease the calcium electropositive character, yielding the formation of a Ca-Cσ-covalent bond.

From the above-described behavior, we were inspired in this work by the idea of grouping all information and the behavior of such compounds. So, our main goal is focused on the organocalcium compounds that contain Ca-Cσ-bond.

Herein, we enumerate the synthetic methods and encountered difficulties, the structures, degradation and catalytic behaviour of such compounds and the spectroscopic techniques used to identify their structures.

We have grouped almost all kinds of previously synthesized Ca-Cσ-bond containing organocalcium intermediates and products including alkylcalcium, allylcalcium, alkynylcalcium, diene calcium, diyne calcium phenylcalcium, benzylcalcium, arene calcium and heteronuclear aromatic calcium derivatives.

Conclusion

The polar covalent Ca-Cσ-bond-containing compounds are less known than the other organometallic compounds; because of the different encountered problems, before, and during the synthetic process.

The n and π electron pairs of organic compounds coordinate to the d-vacuum orbitals of calcium atom, to decrease its electrophilicity and facilitate the formation of the Ca-C bond.

This work grouped all kinds of synthesized Ca-Cσ-bond containing compounds, the encountered synthetic problems, and their solutions.

Calcium Element

Nejib Ben Hussein Mekni,Nourdine Raouafi

Abstract

In this second chapter, we have grouped the physical and chemical properties of elemental calcium and calcium cation species as well as their importance in the human body, especially in the skeleton and cell, as well as their applications in the chemical, electrical, and biological life fields.

In a nutshell, we describe the history of the organocalcium Ca-Cσ-bond containing compounds.

Then, we expose the encountered challenges and difficulties in the synthesis of organocalcium Ca-C containing compounds: before, during and after the organocalcium preparation and the solutions to overcome these difficulties.

We have grouped the calcium activation methods, the nature of the solvent, the substrate structure, temperature and the optimal experimental reaction conditions.

Keywords: Alkali earth metal, Calcium element, Calcium-Carbon covalent bond, Calcium electron configuration, Calcium activation, Calcium electronegativity, Calcium isotopes, Calcium ion, Calcium d-orbitals, Calcium physical properties, Calcium chemical properties, Calcium-Carbon σ-bonding, Calcium reactivity, Covalent bonds, Organocalcium halides, s-bloc elements, Organocalcium Ca-C compounds, Organocalcium challenges, Organocalcium problems, Organometallics.

1. Calcium element

1.1. Introduction

Calcium is the fifth most abundant element by mass in both Earth's crust and seawater (3.4%) [1-3] and the most abundant mineral in the human body. Likewise, calcium cation (Ca2+) is the fifth-most-inexhaustible dissolved seawater metallic ion by both mass and molarity [4, 5]. Calcium element was isolated for the first time by Humphry Davy in 1808 [6, 7]. It is the second alkaline earth metal in the periodic table, with two allotropes [8].

External to earth, two ionized calcium lines were detected (H- and K- lines at 3968.5 Å and 3933.7 Å, respectively) in the visible spectra of many stars, including the sun [9].

Calcium weighs more than 1 Kg in the adult human body. It is essential for living organisms, especially as a cellular ionic messenger, with many other functions, such as the stabilization of the endoskeleton. Particularly, the passage of the calcium through the cytoplasm represents the signal for many cellular processes, including cellular mobility, neuronal transmission as in excitatory synapse [10], fertilization [11], cell growth [12] or proliferation [12, 13], muscle contraction [14], learning [14, 15], memory [16, 17], and saliva secretion [18, 19]. The study of calcium flagging can be monitored by loading the cell’s cytoplasm with a calcium-sensitive fluorescent dye for example Fura-2 [20, 21].

In its solid state (elemental metallic form), calcium is hazardous, causing violent reactions with water and acid contact (producing hydrogen [22]). Because of its high reactivity with oxygen and sulfur-containing impurities, calcium is also used in metallurgy as decarbonizer, deoxidizer, and desulfurizer to produce some alloys [23]. When lit, calcium burns in the air producing a high-intensity orange-red brilliant light.

Calcium ion and most calcium compounds, found in many foods and useful materials have low toxicity. But, a high calcium intake or absorption contributes to the development of kidney stones [24-26] and causes few serious health problems. When swallowed, calcium metal can be fatal [27]. In addition, some studies have suggested that excessive intake of calcium as supplements could cause an increased cardiovascular mortality [28-31]; however, other investigations found that there is no risk [32].

1.2. Calcium Physical Properties

Calcium is a silvery metallic element, extracted through electrolysis from calcium-containing compounds such as calcium chloride. It is harder than lead, with a lower electrical conductibility than aluminium and copper. It has potential uses as wiring in off-world applications [33] but its use in other application fields is limited by its high reactivity with air.

Among the known 26 isotopes of calcium (35Ca to 60Ca), there are five stable isotopes (40Ca, 42Ca, 43Ca, 44Ca, 46Ca), one that has a long half-life (47Ca) and a cosmogenic isotope (48Ca), and one radioactive 41