Primary Alkyl Bromides Research Articles

Bromoalkane-Silver Fluoride Complexes in Anhydrous Hydrogen Fluoride

Abstract Ag+ (RBr), complexes, (n=1,2 or 3), have been characterized in anhydrous HF as long-lived transition species for a number of primary and secondary alkyl bromides. Their relative stabilities and dissociation constants have been determined by potentiometry and voltammetry at a silver electrode (e. g. pK1 = 3.5; pK2 = 7.0; pK3 = 10.0 for C2H5Br). A structural approach and a quantitative comparison with Mac Caulay's arene-silver fluoride complexes are also proposed.

ChemInform Abstract: REACTION OF ALKYL HALIDES WITH MERCURY(II) SALTS IN TETRAHYDROFURAN. A FACILE PREPARATION OF 4‐ALKOXYBUTYL ACETATES AND CHLORIDES

AbstractDie Reaktion der prim. und sek. Alkyljodide und ‐bromide (I) mit Hg(II)‐acetat oder ‐chlorid in THF führt zu den THF‐inkorporierten Verbindungen (II) und in einigen Fällen zu den 1:2‐Verbindungen (III).

Reaction of Alkyl Halides with Mercury(II) Salts in Tetrahydrofuran. A Facile Preparation of 4-Alkoxybutyl Acetates and Chlorides

Abstract The reaction of primary and secondary alkyl iodides and bromides with Hg(OAc)2 and HgCl2 in tetrahydrofuran (THF) affords the THF-incorporated compounds (1), RO(CH2)4X [X=OAc and Cl, respectively], in good yields. When HgBr2 and aqueous or alcoholic Hg(ClO4)2 were used as mercury(II) salts, the yields of 1(X=Br, OH, and OR′) were low. Similar treatment with HgI2 gave scarcely any 1. A reaction scheme which involves O-alkyltetrahydrofuranium ion as the intermediate is proposed for the formation of 1.

Alkylation of salts of N-nitroarenesulfonamides by alkyl halides

1. Primary and secondary alkyl bromides and iodides react with the silver salts of N-nitroarenesulfonamides to form usually a mixture of N-and O-alkylation products. Tertiary alkyl iodides, according to the structure of the alkyl group, afford either the nitroamides or O-alkylation products. 2. The contribution of O-alkylation increases on passing from primary to secondary alkyl halides and from iodides to bromides, and decreases when electron-acceptor groups are introduced into the aromatic ring of the N-nitroarenesulfonamide. 3. The contribution of O-alkylation increases on passing from protic polar or aprotic dipolar to nonpolar solvents.

Enolates d'esters : V. Preparation des analogues lithiens des reactifs de reformatsky a partir des esters α,α-dichlores et α-monohalogenes. Reactivite

The reaction of lithium on α,α-dichloroesters and α,α-disubstituted α-monohaloesters in THF at 0 to −5°C leads to the formation of the lithioanalogs of the corresponding Reformatsky reagents in good yields (80–90%). Their reactivity has been tested toward various electrophiles. It illustrates the wide scope of synthetic utility of these reagents (alkylation with primary and secondary alkyl bromides, hydroxy alkylation, acylation) and provides new routes to esters and α-chloroesters.

Copper-catalyzed coupling of grignard reagents and akyl halides in tetrahydrofuran solutions

The stoichiometry and the kinetics of tho reaction between various Grignard reagents and alkyl halides with a copper catalyst have been examined in tetrahydrofuran solutions. The catalytically active species is an organocopper(I) complex produced by the rapid motathesis between copper(I) and -(II) halides and Grignard reagents. Primary alkyl bromides react with various Grignard reagents under these conditions to produce cross-coupled dimers exclusively. A mechanism is proposed in which coupling occurs between the alkyl halide and the alkylcopper(I) intermediate by displacement of the halide. On the other hand, only disproportionation products are produced from secondary and tertiary alkyl halides due to the unfavorable displacement process. The rate and the mechanism of the thermal decomposition of alkylcopper(I) species under the reaction conditions as well as sidereactions involved in the coupling reaction are described.

Oxidative addition reactions of group III metals in low oxidation states. Reactions of Ga 2Br 4 with alkyl bromides

The oxidative addition reactions of gallium “dibromide” with several primary, secondary and tertiary alkyl bromides, and bromides of the type (CH 2) n Br 2 have been examined. Whilst all the organic halides readily react with Ga 2Br 4, only in two reactions, namely with methyl and ethyl bromides are isolatable compounds produced and in these cases oxidative addition may be represented as: Ga 2Br 4+RBr→RGa 2Br 5. Spectroscopic and other evidence indicates that these products are pure compounds rather than mixtures of the known compounds Ga 2Br 6 and Ga 2Br 4R 2.

Factors in the formation of isomerically and optically pure alkyl halides. Part VIII. Rearrangements in the reactions of branched-chain alcohols with boron trichloride and boron tribromide

Reactions of branched-chain alcohols with boron trichloride and boron tribromide afford mixtures of alkyl halide isomers in almost all cases. Only the reaction of boron trichloride with t-butyl alcohol gives an isomerically pure product. The dichloroborinates (alkoxydichloroboranes) of primary alcohols are the only intermediates which are isolable at room temperature. Rearrangements are largely in accord with a carbonium ion mechanism, although isomerisation of t-pentyl products can yield 2-halogeno-3-methylbutanes. The unexpected formation of primary alkyl bromides in the isopropyl, t-butyl, and t-pentyl systems, is probably due to free-radical combination of alkene and hydrogen bromide which are by-products of the reaction; no rearrangement accompanies the nitrous acid deamination of the corresponding primary amines.

Dimethyl sulfoxide as a solvent in the Williamson ether synthesis

Using the conventional Williamson ether synthesis, n-butyl ether was prepared from sodium hydroxide, n-butyl alcohol, and n-butyl chloride using excess of the alcohol as solvent in 61% yield after 14 h reaction time. However, when the excess alcohol was replaced by dimethyl sulfoxide, the yield of ether rose to 95% with 9.5 h reaction time. Other primary alkyl chlorides exhibited similar behavior to n-butyl chloride, but secondary alkyl chlorides and primary alkyl bromides gave little etherification, elimination being the major reaction. Unreactive halides, such as vinyl chloride, phenyl bromide, and 2,4-dinitrobromobenzene, were not etherified in dimethyl sulfoxide. The reaction products obtained from aliphatic dichlorides depended upon the relative positions of the chlorine atoms. Secondary alcohols reacted to give ethers, but tertiary alcohols were very unreactive. Polyols generally gave high yields of ethers, the major product being that in which all but one of the hydroxyl groups became etherified. Under forcing conditions, however, completely etherified polyols could be obtained.

Alkylation of carborane grignard reagents

1. Carborane C-magnesium derivatives, similar to carborane C-lithium derivatives, are alkylated by primary alkyl bromides and iodides, dialkyl sulfates, alkyl p-toluenesulfonates, and benzyl chloride-type compounds. 2. The existence of an equilibrium in THF solution of carboranylmagnesium bromide ⇆ bis(bromomagnesium)carborane +carborane, and the equilibrium in ether of carboranyllithium ⇆ dilithiocarborane +carborane were shown.

Reactivities of Several ι-Substituted Primary Alkyl Bromides with Tertiary Amines1,2

Reactivities of Several ι-Substituted Primary Alkyl Bromides with Tertiary Amines^1,2

The Kinetics of the Reaction of Lithium Aluminum Hydride with Some Primary Alkyl Bromides1

The Kinetics of the Reaction of Lithium Aluminum Hydride with Some Primary Alkyl Bromides¹

Electrophilic Attack on Halogen in a Homogeneous Medium: Reaction of Mercuric Nitrate with some Primary and Secondary Alkyl Bromides

Electrophilic Attack on Halogen in a Homogeneous Medium: Reaction of Mercuric Nitrate with some Primary and Secondary Alkyl Bromides

THE IDENTIFICATION OF PRIMARY ALKYL BROMIDES AND IODIDES

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTHE IDENTIFICATION OF PRIMARY ALKYL BROMIDES AND IODIDESC. S. Marvel, C. G. Gauerke, and E. L. HillCite this: J. Am. Chem. Soc. 1925, 47, 12, 3009–3011Publication Date (Print):December 1, 1925Publication History Published online1 May 2002Published inissue 1 December 1925https://doi.org/10.1021/ja01689a026RIGHTS & PERMISSIONSArticle Views62Altmetric-Citations11LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (200 KB) Get e-Alerts Get e-Alerts