Preparative polar organometallic chemistry

著者

• Brandsma, L. (Lambert)
• Verkruijsse, H. D. (Hermann D.)

書誌事項

Preparative polar organometallic chemistry

L. Brandsma, H.D. Verkruijsse ; foreword by Paul von Ragué Schleyer

Springer-Verlag, c1987-c1990

• v. 1 : U.S.
• v. 1 : Berlin
• v. 2 : U.S.
• v. 2 : Berlin

注記

Vol. 2. by L. Brandsma ; experimental collaboration, H. Andringa ... [et al.]

Includes references

内容説明・目次

巻冊次

v. 1 : Berlin ISBN 9783540169161

内容説明

Polar organometallic compounds are indispensable for the synthetic chemist. As this book shows, these almost ideal reagents are easy to prepare with high specificity under mild conditions and yet react quite readily with a great variety of substrates. Many compounds can be metallated directly at positions which would otherwise be difficult to substitute. Functional groups and heteroatoms already present in a molecule direct metallation to sites in their vicinity. The rules which govern polar organometallic chemistry often are not dominated by the usual n-delocalization and inductive effects; dipolar interactions, chelation, polarization, etc. often can be much more important. This affords novel synthetic opportunities. A good example is the development of a basically new type of aromatic substitution chemistry not based on positively charged intermediates. Seebach's injunction, "Thinking of polar organometallic compounds as carbanions is an impoverishment rather than a simplification" (International Symposium, Chemistry of Carbanions, Durham 1984), stresses the need to consider the metal not only as an integral, but perhaps also as the key component of these reagents. Rather than wandering off as solvated cations and acting as uninvolved spectators, the metals, rather than the anion moieties, can initiate and govern the subsequent reactions. To the founders of this field, e. g. Grignard, Ziegler, Gilman, Wittig, and their followers, the metal was critical. The title of Schlosser's book, "Polare Organometalle", certainly was apt.

目次

• to Volume 1 and Instructions for the Use of this Book and its Indexes.- I. Organometallic Reagents, Solvents and Laboratory Equipment.- 1. Strongly Basic Reagents used in Organic Synthesis.- 2. Solvents and Some Reagents: Their Analysis, Purification and Storage.- 3. Laboratory Equipment and Some General Remarks Concerning Performance of the Procedures.- 4. Safety, Handling and Methods of Disposal.- 4.1 Introduction.- 4.2 Organoalkali Reagents.- 4.3 Alkali Metals.- 4.4 Alkali Metal Amides.- 5. Experimental Procedures.- 5.1 n-Butyllithium in Diethyl Ether.- 5.2 n-Butyllithium TMEDA (in Hexane).- 5.3 n-Butyllithium, Complexed with Potassium t-Butoxide in THF.- 5.4 n-Butyllithium, Complexed with Sodium- or Potassium t-Butoxide and TMEDA in Hexane or Pentane.- 5.5 Lithium Diisopropylamide.- 5.6 Lithium Amide in Liquid Ammonia.- 5.7 Sodamide in Liquid Ammonia.- 5.8 Potassium Amide in Liquid Ammonia.- II Reactivity of Polar Organometallic Intermediates.- 1. Introduction.- 2. General Remarks About Reactivity.- 3. Alkylation Reactions.- 3.1 Reactivity of the Various Types of Alkylation Reagents.- 3.2 Possible Influence of the Thermodynamic Basicity and Polarisability.- 3.3 Reactivity of Some ortho-Lithiated Benzene Derivatives.- 4. Acylation Reactions.- 5. Carboxylation.- 6. Additions to Carbonyl Compounds.- 7. Additions to Heterocumulenes.- 8. Reactions with Sulfenylating Reagents.- 9. Reactions with Elemental Sulfur, Selenium and Tellurium.- 10. Reactions with Sulfur Dichloride.- 11. Trimethylsilylation.- 12. Introduction of Chlorine, Bromine and Iodine.- 13. Protonation and Deuteration.- 14. Exchange Between Counter Ions.- III. Metallated Olefinic and Allenic Hydrocarbons.- 1. Deprotonation with Strongly Basic Reagents.- 2. Halogen-Lithium and Tin-Lithium Exchange.- 3. Direct Preparation from Halogen Compounds and Metal.- 4. Experimental Procedures.- 4.1 Vinylmagnesium Bromide.- 4.2 Trimethylsilylethene.- 4.3 Tetravinyltin.- 4.4 Reaction of Alkenylmagnesium Bromide with Benzaldehyde.- 4.5 1-Cyclohexenyl- and 1-Cycloheptenyllithium.- 4.6 1-Cyclohexenecarboxaldehyde and 1-Cycloheptenecarboxaldehyde.- 4.7 Metallation of Norbornene and Norbornadiene.- 4.8 Norbornadienecarboxaldehyde.- 4.9 Reaction of Norbornenyllithium with Methyl Choroformate.- 4.10 Metallation of Cyclopentene and Subsequent Methylthiolation.- 4.11 2-Hexyl-1-Methylcyclopropene.- 4.12 Lithiation of 1-Methylcyclopropene and Subsequent Reaction with Benzaldehyde.- 4.13 1,3-Dimetallation of Vinylacetylene and Subsequent Reaction with two Equivalents of Me3SiCl and one Equivalent of w-C7H15Br.- 4.14 Metallation of Allene with Butyllithium.- 4.15 1,2-Decadiene from Allenyllithium.- 4.16 2,3-Butadienoic Acid from Allenyllithium.- 4.17 Allenylmagnesium Bromide.- 4.18 Lithiation of 1.1-Dimethylallene.- 4.19 Metallation of 2-Alkynes with Butyllithium.- 4.20 1-Chlorocyclohexene and 1-Chlorocycloheptene.- 4.21 l-Bromo-2-Merliylpropene.- 4.22 Vinylacetylene.- 4.23 1-Methylcyclopropene.- 4.24 Metallation of Ethene.- 4.25 Metallation of Norbornene and Norbornadiene with BuLi * t-BuOK * TMEDA.- 4.26 Z-2-Lithio-l-Ethoxyethene.- 4.27 1-Lithio-l-Phenylethene.- IV. Metallation of Hetero-Substituted Unsaturated Systems.- 1. Introduction.- 2. ?-Metallation of 1-Alkenyl Ethers, -Thioethers and Related Systems.- 3. ?-Metallation of 1.3-Dienyl Ethers and -Thioethers.- 4. ?-Metallated Haloalkenes.- 5. ?-Metallated Allenic Ethers, -Thioethers and -Amines.- 6. Metallated 1,2,3-Butatrienyl Ethers, -Sulfides and -Amines.- 7. Addendum: Metallation of N,N-Dialkylformamides and-Thioformamides.- 8. Experimental Procedures.- 8.1 Metallation of Ethyl Vinyl Ether.- 8.2 Coupling of Metallated Ethyl Vinyl Ether with Nonyl Bromide and Acetone.- 8.3 Metallation of 2,3-Dihydrofuran and 2,3-Dihydropyran and Subsequent Alkylthiolation.- 8.4 Metallation of 5-Chloro-2,3-Dihydropyran and Subsequent Methylthiolation.- 8.5 ?-Metallation of Methyl Vinyl Sulfide.- 8.6 Reaction of Metallated Methyl Vinyl Sulfide with Oxirane, Acetone and Methyl Isothiocyanate.- 8.7 Lithiation of Z-1,2-bis (Methylthio)Ethene and Subsequent Methylation.- 8.8 Lithiation of 1,4-Dithiin and Subsequent Functionalization.- 8.9 Metallation of E- and Z-1-Methoxy-1,3-Butadiene and 1-Methylthio-1,3-Butadiene.- 8.10 Metallation of 2H-Thiopyran.- 8.11 Metallation of Zs-Dichloroethene and Subsequent Alkylation with Bromohexane.- 8.12 Conversion of 2-Chloro-1,1-bis(Dimethylamino)Ethene into bis(Dimethylamino)Ethyne.- 8.13 Metallation of Methoxyallene.- 8.14 Metallation of 1-Alkynyl Sulfides in Organic Solvents.- 8.15 Metallation of Allenic Amines and Acetylenic Amines.- 8.16 Trimethylsilylation of Metallated Diethylaminoallene.- 8.17 Conversion of a 2-Alkynyl Ether into an 1-Alkylated Allenyl Ether.- 8.18 Conversion of a Tertiary Acetylenic Amine into the Allenic Isomer via the Metallic Intermediates.- 8.19 Preparation of Dimethylaminobutatriene via the Metallic Intermediate.- 8.20 Preparation of a Metallated Cumulenic Amine via 1,4-Elimination, and Subsequent Reaction with Trimethylchlorosilane.- 8.21 Lithiation of l-Ethylthio-3-Buten-l-Yne and Subsequent Hydrolysis to Ethylthiobutatriene.- 8.22 5-Chloro-2,3-Dihydropyran.- 8.23 Vinyl Alkyl and Vinyl Aryl Sulfides.- 8.24 Z-bis(Methylthio)Ethene.- 8.25 2H-Thiopyran.- 8.26 1,2-Chloro-1,1-Bis(Dimethylamino/Ethene.- 8.27 3-Methoxy 3-Methyl-l-Butyne and l-(Dimethylamino)-4-Methoxy-4-Methyl-2-Pentyne.- 8.28 Lithiation of N,N-Dimethylformamide and N,N-Dimethyl-thioformamide.- 8.29 N,N-Dimethylthioformamide.- V. Metallated Hetero-Aromatic Compounds.- 1. Introduction.- 2. Metallated Furans, Pyrroles, Thiophenes, Selenophenes and Tellurophenes.- 2.1 Direct Metallation by Strong Bases.- 2.2 Halogen-Lithium Exchange.- 2.3 Grignard Derivatives.- 3. Metallated Pyridines.- 3.1 Direct Metallation.- 3.2 Halogen-Lithium Exchange.- 4. Metallated Hetero-Aromatics with more than one Hetero Atom.- 5. Experimental Procedures.- 5.1 2-Methylthiophene.- 5.2 3-Allylthiophene.- 5.3 2-Butylthiophene.- 5.4 2-(2-Thienyl)Ethanol.- 5.5 2-Furancarboxaldehyde Diethylacetal and 2-Thiophenecarboxaldehyde Diethylacetal.- 5.6 2-Octylfuran.- 5.7 2-Benzylfuran and 2-Benzylthiophene.- 5.8 2-Butyl-l-Methylpyrrole.- 5.9 3-Bromo-2-Ethylthiophene and 3-Bromo-2-(l-Hydroxyethyl)-Thiophene.- 5.10 5-Ethyl-2-(Methylthio)Thiazole.- 5.11 2-Methyl-2H-Thieno[2,3-b]Thiopyran.- 5.12 2-Bromofuran.- 5.13 2-Iodofuran.- 5.14 l-Methylpyrrole-2-Carboxylic Acid.- 5.15 l-Methyl-2-(Methylthio)Imidazole.- 5.16 2-Trimethylsilyl-1.3-Thiazole.- 5.17 2-(Trimethylsilyl)Benzothiazole.- 5.18 Reaction of Benzothiazole with Sodamide in Liquid Ammonia and Subsequent Ethylation and Methylthiolation. Formation of 2-(Ethylthio)Phenyl Isocyanide and 2-(Methylthio)benzothiazole.- 5.19 4-Methyl-2-Thiazolecarboxaldehyde.- 5.20 2-Tellurophenecarboxaldehyde.- 5.21 2-Selenophenecarboxaldehyde.- 5.22 Methyl 2-Thiophenecarboxylate.- 5.23 N,N-Dimethyl-2-Furancarboxamide and N,N-Dimethyl-2-Thiophenecarboxamide.- 5.24 Methyl-2-Thiophenecarbodithioate.- 5.25 Methyl-2-Furancarbodithioate.- 5.26 3-Thiophenethiol.- 5.27 2-(Methylseleno)Thiophene and 2-(Methyltelluro)Thiophene.- 5.28 Reaction of Metallated Hetero-Aromates with Methyl Isothiocyanate Phenyl Isothiocyanate, Phenyl Isocyanate and Phenyl Sulfinylamine.- 5.29 Regiospecific Vicinal Metallation of 3-Bromothiophene and Preparation of Derivatives.- 5.30 Lithiation of 2-Bromofuran and 2-Bromothiophene in the 5-Position
• Preparation of 2-Bromo-5-(Methylthio)Furan and-Thiophene.- 5.31 3-Iodothiophene.- 5.32 3-t-Butoxythiophene.- 5.33 3-Substituted Thiophenes from 3-Bromothiophene.- 5.34 2-Formyl-3-(Methoxymethyl)Thiophene.- 5.35 Di(2-Furyl)Sulfide,di(2-Thienyl)Sulfide and di(3-Thienyl)Sulfide.- 5.36 2,2?-Bifury1, 2,2?-Bithienyl and 3,3?-Bithienyl.- 5.37 2,5-Dimetallation of Thiophene. Preparation of 2,5-bis(Trimethylsilyl)Thiophene.- 5.38 2,5-Dimetallation of Furan. Preparation of 2,5-bis(Methylthio)Furan.- 5.39 1-Methyl-2-(Methylthio)Pyrrole.- 5.40 2-Iodo-1-Methylpyrrole.- 5.41 2-Chlorobenzo(b)Thiophene.- 5.42 2-Fluoro-3-Methylthio-Pyridine.- 5.43 3-Chloro-4-Trimethylsilyl-Pyridine.- 5.44 3-Deuterio- and 3-Methylthio-Pyridine.- 5.45 3-Trimethylsilyl-Quinoline.- 5.46 4-Iodopyridine.- 5.47 3-Bromothiophene.- 5.48 2-Bromothiophene.- 5.49 3-Bromoquinoline.- 5.50 2-Thienyl Propargyl Sulfide 2H-Thieno(2,3-b)Thiopyran and 2-Methylthieno(2,3-b)Thiophene.- 5.51 Methyl Dithiocarbamate.- 5.52 2-Methylthio-Thiazole and 4-Methyl-2-Methylthio-Thiazole.- 5.53 Thiazole and 4-Methylthiazole.- 5.54 Selenophene and Tellurophene.- 5.55 Methyl Thiocyanate.- 5.56 Sulfur Dichloride.- VI. Metallated Aromatic Compounds.- 1. Metallated Aromatic Hydrocarbons.- 1.1 Deprotonation by Strongly Basic Reagents.- 1.2 Bromine-Lithium Exchange.- 1.3 Reaction of Arene Derivatives with Metals.- 2. Metallated Hetero-Substituted Arenes.- 2.1 Deprotonation by Strongly Basic Reagents.- 2.2 Halogen-Lithium Exchange.- 3. Experimental Procedures.- 3.1 General Procedure for Bromine-Lithium Exchange.- 3.2 Derivatization Reactions with Aryllithium, Obtained by Br-Li Exchange.- 3.3 Reaction of Aryllithium with Carbon Disulfide and Subsequent Methylation.- 3.4 Reaction of ?-Fluorophenyllithium with Epoxyethane and Paraformaldehyde.- 3.5 Phenyllithium from Benzene and BuLi * TMEDA in Hexane.- 3.6 Phenylpotassium from Benzene, BuLi * t-BuOK and TMEDA in Hexane.- 3.7 Metallation of Naphthalene with BuLi, t-BuOK * TMEDA and Subsequent Methylthiolation.- 3.8 Preparation of 1,8-Dilithionaphthalene.- 3.9 Reaction of Phenyllithium.TMEDA with Elemental Selenium and Tellurium.- 3.10 ortho-Metallation of Hetero-Substituted Benzene and Naphthalene with BuLi * TMEDA in Hexane.- 3.11 Ring-Metallation of Benzyl Dimethylamine, N,N-Dimethylaniline and Benzylalcohol.- 3.12 Metallation of Phenyl Ethers with BuLi in THF.- 3.13 Metallation of Fluorobenzene with BuLi * t-BuOK and BuLi * TMEDA.- 3.14 Dimetallation of Phenylacetylene with BuLi * t-BuOK in THF-Hexane and with BuLi * t-BuOK * TMEDA in Hexane.- 3.15 Lithiation of N,N-Dimethyl-Benzenesulfonamide and Subsequent Methylation.- 3.16 Metallation of N-Methyl Benzenecarbothioamide and Subsequent Trimethylsilylation.- 3.17 Protection of the Formyl Group in Benzaldehyde and Subsequent ortho-Lithiation and Trimethylsilylation.- 3.18 Reaction and Phenylmagnesium Bromide with 1,2-Dibromodiethyl Ether, Preparation of 1-Ethoxy-l-Phenylethene.- 3.19 Generation of o-Lithiochlorobenzene from 2-Bromochlorobenzene.- 1. Generation of Polar Organometallic Intermediate by Deprotonation with Strongly Basic Reagents.- 2. Metallation-Functionalization Index.- 3. Index of Reaction Types.- References.

巻冊次

v. 2 : Berlin ISBN 9783540527497

内容説明

Preparative Polar Organometallic Chemistry is a collection of laboratory procedures for the synthesis and functionalization of organoalkali and Grignard compounds. The second volume with methods for generation and transformation of compounds bearing the metal at an sp3 carbon complements the first in which the metal was bound to an sp2 carbon atom in the reagent. Synthetically important intermediates such as metallated S,S-acetales, imines, nitriles, isonitriles and ketones are illustrated. All procedures have been worked out in full detail and tested in the author's own laboratory. Both books are intended to be practical bench-top laboratory manuals for working organic chemists, from the student to the advanced scientist.

目次

I. Reactivity of Polar Organometallic Intermediates.- 1 Introduction.- 2 Alkylation.- 2.1 Reactivity-A Qualitative Comparison of the Polar Organometallics.- 2.2 Scope of the Alkylation Reaction.- 2.3 Dialkylation.- 2.4 Remarks on the Reaction Conditions of Alkylations.- 3 Hydroxyalkylation with Epoxides.- 4 Hydroxyalkylation with Carbonyl Compounds.- 5 Formylation with Dimethylformamide.- 6 Carboxylation.- 7 Reaction of Organoalkali Compounds with Carbon Disulfide.- 8 Addition of Organoalkali Compounds to Isocyanates and Isothiocyanates.- 9 Sulfenylation.- 10 Trimethylsilylation.- 11 Reactions of Organometallic Compounds with Chloroformates and Dimethylcarbamoyl Chloride.- 12 Reactions of Organoalkali Compounds with Halogenating Agents.- 13 Conjugate Additions.- II. Metallation of Aromatic and Olefinic Hydrocarbons.- 1 Introduction.- 2 Metallation of Alkylbenzenes and Alkylnaphthalenes.- 3 Dimetallation of Aromatic Compounds.- 4 Metallation of Olefinic Compounds.- 5 Stereochemistry of Allylic Metallations.- 6 Dimetallation of Olefins.- 7 Experiments.- 7.1 Metallation of Toluene with BuLi * t-BuOK in Hexane.- 7.2 Metallation of 1- and 2-Methylnaphthalene with BuLi * t-BuOK.TMEDA in Hexane.- 7.3 ?-Metallation of Ethylbenzene.- 7.4 ?,??-Dimetallation of m-Xylene.- 7.5 Lithiation of Toluene, Xylene, Mesitylene with BuLi * TMEDA..- 7.6 Metallation of Propene and Isobutene.- 7.7 Metallation of Various Olefins with Strongly Basic Reagents.- 7.8 Metallation of Cyclohexene.- 7.9 Dimetallation of Isobutene.- 7.10 Metallation of Isoprene.- 7.11 Metallation of ?-Methylstyrene.- 7.12 Metallation of Indene.- 7.13 Metallation of Cyclopentadiene.- 7.14 Preparation of 1,4-Cyclohexadiene.- 7.15 Allylbenzene.- 8 Selected Procedures from Literature.- III. Metallation of Saturated Sulfur Compounds.- 1 Introduction.- 2 Substrates and Metallation Conditions.- 2.1 S,S-Acetals.- 2.2 Methoxymethyl Phenyl Sulfide.- 2.3 Ethythiomethyl Ethyl Sulfoxide.- 2.4 Orthothioformates.- 2.5 Dialkyl Sulfides and Alkyl Aryl Sulfides.- 2.6 Dialkyl and Alkyl Aryl Sulfoxides and Sulfones.- 3 Experiments.- 3.1 Lithiation of Formaldehyde Dimethylthioacetal with BuLi in THF and Hexane.- 3.2 Lithiation of Formaldehyde Dimethylthioacetal with BuLi * TMEDA in Hexane.- 3.3 Reaction of Lithiated Bis(methylthio)methane with Alkyl Halides.- 3.4 Hydroxyalkylation of Lithiated Bis(methylthio)methane with Epoxides.- 3.5 Reaction of Lithiated 1,3-Dithiane with 1-Bromo-3-chloropropane and Ring Closure of the Coupling Product Under the Influence of Butyllithium.- 3.6 Hydroxymethylation of Bis(methylthio)methane with Paraformaldehyde.- 3.7 Reaction of Lithiated Bis(methylthio)methane with Dimethylformamide and Subsequent Acid Hydrolysis.- 3.8 Reaction of Lithiated Bis(methylthio)methane with Carbon Dioxide.- 3.9 Reaction of Lithiated Bis(methylthio)methane with Dimethyl Disulfide and Trimethylchlorosilane.- 3.10 Lithiation of Methoxymethyl Phenyl Sulfide and Subsequent Reaction with Dimethylformamide.- 3.11 Reaction of Lithiated Bis(methylthio)methane with Methyl Isothiocyanate and N,N-Dimethyl Carbamoyl Chloride.- 3.12 Peterson Olefination Reactions with Lithiated Trimethylsilyl Bis(methylthio)methane. Preparation of Ketene Thioacetals.- 3.13 Conjugate Addition of Lithiated S,S-Acetals and Corresponding S-Oxides to 2-Cyclohexen-1-one and Methyl Acrylate.- 3.14 Lithiation of Dimethyl Sulfide and Methyl Phenyl Sulfide and Subsequent Reaction of the Lithium Compounds with Benzaldehyde and Trimethylchlorosilane.- 3.15 Lithiation of (Trimethylsilylmethyl)Phenyl Sulfide and Subsequent Reaction with Acetone.- 3.16 Dilithiation of Methyl Phenyl Sulfide and Subsequent Trimethylsilylation.- 3.17 Reaction of Bis(methylthio)methane with Potassium Amide in Liquid Ammonia and Subsequent Reaction with Oxirane..- 3.18 Reaction of Dimethylsulfoxide with Sodamide in Liquid Ammonia and Subsequent Alkylation with Bromohexane.- 3.19 Mono-Deuteration of Bis(ethylthio)methane.- 3.20 Lithiation of Methyl Phenyl Sulfoxide with LDA and Subsequent Alkylation with Butyl Bromide.- 3.21 Preparation of Formaldehyde-S,S-Acetals.- 3.22 Preparation of Ethylthiomethyl Ethyl Sulfoxide and Methyl Phenyl Sulfoxide.- 3.23 Preparation of Benzaldehyde Dimethylthioacetal.- 4 Selected Procedures from Literature.- IV. ?-Metallation of Derivatives of Toluene Containing Heterosubstituents.- 1 Scope of this Chapter.- 2 Experiments.- 2.1 Metallation of N,N-Dimethyl-ortho-Toluidine.- 2.2 Synthesis of ortho-Pentylphenol via Potassiation of O-Protected ortho-Cresol.- 2.3 Dimetallation of ortho-Cresol.- 2.4 Metallation of o-and p-Tolunitrile with Alkali Amides in Liquid Ammonia and Alkali Diisopropylamide in THF-Hexane Mixtures.- 2.5 ?-Lithiation of p-Toluene-N,N-Dimethylsulfonamide.- V. Metallation of Heterosubstituted Allylic and Benzylic Compounds.- 1 Introduction.- 2 Substrates and Metallation Conditions.- 2.1 Allylic Amines and Ethers.- 2.2 Allylic and Pentadienylic Sulfur, Silicon and Selenium Compounds.- 2.3 Benzylic Amines, Silanes and Sulfides.- 2.4 Regiochemistry of the Reactions of Allylic Alkali Metal Compounds with Electrophiles.- 3 Experiments.- 3.1 Metallation of N,N-Dialkyl Allylamines with BuLi * TMEDA and BuLi * t-BuOK.- 3.2 Metallation of Allyl t-Butyl Ether with BuLi * t-BuOK.- 3.3 Lithiation of Allyl Trimethylsilane with BuLi * TMEDA.- 3.4 Lithiation of Methyl Allyl Sulfide and Phenyl Allyl Sulfide with BuLi.- 3.5 Metallation of Methyl Isopropenyl Ether with BuLi * t-BuOK.- 3.6 ?-Metallation of Benzyl Dimethylamine with BuLi * t-BuOK.- 3.7 Lithiation of Methyl Benzyl Sulfide and Benzyl Trimethylsilane.- 3.8 Preparation of N,N-Dimethyl Allylamine and N,N-Diethyl Allylamine.- 3.9 Preparation of t-Butyl Allyl Ether.- 3.10 Methyl Allyl Sulfide, Methyl Benzyl Sulfide and Phenyl Allyl Sulfide.- 3.11 Preparation of Allyl Trimethylsilane.- VI. Metallation of Heterocyclic Compounds.- 1 Introduction.- 2 Metallation of Alkyl Derivatives of Pyridine and Quinoline.- 3 Lateral Metallation of 2-Substituted Oxazolines, Thiazolines, Dihydrooxazines and Thiazoles.- 4 Experiments.- 4.1 General Procedure for the Metallation of Mono-, Di- and Trimethyl Pyridines and Quinolines in Liquid Ammonia and the Subsequent Alkylation.- 4.2 Conversion of 2-Methylpyridine, 2,4-Dimethylpyridine, 2,6-Dimethylpyridine and 2,4,6-Trimethylpyridine into the 2-Lithiomethyl Derivatives.- 4.3 Regiospecific Generation of 4-Metallomethylpyridines in Organic Solvents.- 4.4 Metallation of 3-Methylpyridine.- 4.5 Lithiation of 2-Methylthiazoline.- 4.6 Lithiation of 2,4,4,6-Tetramethyl-5,6-dihydro-1,3-oxazine.- 4.7 Dimetallation of 2,6-Dimethylpyridine.- 5 Organic Syntheses Procedures.- VII. Metallation of Aldimines and Ketimines.- 1 Introduction.- 2 Conditions for the Metallation.- 3 Experiments.- 3.1 Lithiation of Aldimines and Ketimines with LDA.- 3.2 Alkylation of Lithiated Imines.- 3.3 Metallation of Aldimines by Sodamide in Liquid Ammonia.- 3.4 Trimethylsilylation and Methylthiolation of Lithiated Imines.- 3.5 Conversion of Imines into Aldehydes and Ketones.- 3.6 Synthesis of ?,?-Unsaturated Aldehydes from Trimethylsilylated Aldimines.- 3.7 Preparation of Aldimines and Ketimines.- 4 Organic Syntheses Procedures.- VIII. Metallation of Nitriles and Isonitriles.- 1 Introduction.- 2 ?-Metallation of Nitriles.- 3 Metallation of Isonitriles.- 4 Experiments.- 4.1 Metallation of Nitriles with Alkali Amide in Liquid Ammonia.- 4.2 Lithiation of Nitriles and Isonitriles in a Mixture of THF and Hexane.- 4.3 Alkylation of Metallated Nitriles in Liquid Ammonia and in Organic Solvents.- 4.4 Reaction of Metallated Nitriles with Aldehydes and Ketones.- 4.5 Reaction of Lithioacetonitrile with Epoxides.- 4.6 Reaction of Lithiomethyl Isocyanide with Hexyl Bromide, Oxirane and Cyclohexanone.- 4.7 Conversion of Acetaldehyde into the Cyanohydrine and Protection of the OH-Group of the Cyanohydrine with Ethyl Vinyl Ether.- IX. Generation of Lithium Halocarbenoids.- 1 Introduction.- 2 Methods of Generation of Lithium Halocarbenoids.- 3 Experimental Conditions and Techniques in Carbenoid Chemistry.- 4 Experiments.- 4.1 Lithiation of Dichloromethane.- 4.2 Lithiation of 1,1-Dichloroalkanes.- 4.3 Lithiation of Dibromomethane.- 4.4 Lithiation of Chloroform.- 4.5 Lithiation of Bromoform.- 4.6 Lithiation of 7,7-Dibromonorcarane.- 4.7 Lithiation of Ethyl Bromoacetate.- X. Metallation of Carbonyl and Thiocarbonyl Compounds.- 1 Introduction.- 2 Mono Metallation of Carbonyl and Thiocarbonyl Compounds.- 3 Other Methods for the Generation of Enolates and Enethiolates.- 4 Dimetallation of Carbonyl and Thiocarbonyl Compounds.- 5 Experiments.- 5.1 Conversions of Ketones into Lithium Enolates and Subsequent Trimethylsilylation (General Procedure).- 5.2 Reaction of 1-Trimethylsilyloxy-l-Heptene with Butyllithium.- 5.3 Metallation of Carboxylic Esters with LDA.- 5.4 Metallation of Carboxylic Esters with Alkali Amides in Liquid Ammonia.- 5.5 Metallation of N-Methylpyrrolidine and ?-Butyrolactone with LDA.- 5.6 Lithiation of Methyl Crotonate.- 5.7 Lithiation of Thiolesters, Thionesters and Dithioesters with LDA (General Procedure).- 5.8 Metallation of Dithioesters with Alkali Amides in Liquid Ammonia.- 5.9 Dimetallation of Carboxylic Acids.- 5.10 Dimetallation of Pentane-2,4-dione with Sodamide in Liquid Ammonia.- 5.11 Dimetallation of Pentane-2,4-dione with LDA.- 5.12 1-Trimethylsilyloxy-l -heptene.- Metallation-Functionalization Index (Vol. 2).- Syntheses of Reagents and Starting Compounds (Vols. 1 and 2)..- Complementary Index (Vols. 1 and 2).- Typical Procedures and Special Techniques (Vols. 1 and 2).- Purification and Storage and Some Reagents and Solvents (Vols. 1 and 2).

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詳細情報

• NII書誌ID(NCID): BA00753873
• ISBN:
  • 0387169164
  • 3540169164
  • 0387527494
  • 3540527494
• LCCN: 86017896
• 出版国コード: gw
• タイトル言語コード: eng
• 本文言語コード: eng
• 出版地: Berlin ; Tokyo
• ページ数/冊数: 2 v.
• 大きさ: 25 cm
• 分類:
  • LCC : QD411
  • DC19 : 547/.05
• 件名:
  • LCSH : Organometallic chemistry