935-56-8

Usage

Uses

Used in Antiviral Applications:
1-Chloroadamantane is used as a virucidal agent for its activity against the Newcastle disease virus in chick embryo fibroblasts. This makes it a promising candidate for antiviral applications, particularly in controlling viral infections in avian species.
Used in Chemical Synthesis:
1-Chloroadamantane serves as a precursor for the synthesis of perfluoroadmantane derivatives through aerosol direct fluorination. This highlights its utility in the production of advanced chemical compounds with potential applications in various industries.
Used in Photoinduced Electron-Transfer Reactions:
In the field of photochemistry, 1-chloroadamantane is used in the generation of unusual zwitterionic diradical intermediate complexes during the photoinduced electron-transfer substitution reaction with the tert-butylamine system in a hydrocarbon glass. This demonstrates its potential in the development of novel photochemical processes and materials.

Synthesis Reference(s)

Synthetic Communications, 19, p. 1697, 1989 DOI: 10.1080/00397918908051068

Purification Methods

Crystallise the chloride from aqueous MeOH and sublime it at 100o/12torr. It also crystallises from MeOH at -70o. [Stetter et al. Chem Ber 92 1629 1959, Schleyer & Nicholas J Am Chem Soc 83 2700 1961, Beilstein 5 IV 469.]

InChI:InChI=1/C10H15Cl/c11-10-4-7-1-8(5-10)3-9(2-7)6-10/h7-9H,1-6H2

Upstream product

• 108-05-4 vinyl acetate 
• 281-23-2 adamantane 
• 64-17-5 ethanol 
• 5854-52-4 1-adamantyl chloroformate 
• 75-89-8 2,2,2-trifluoroethanol 
• 372-46-3 fluorocyclohexane 
• 35537-98-5 1-bromo-3-chloroadamantane 
• 2154-65-6 1,3,5-triphenylverdazyl 
• 768-93-4 1-iodoadamantane 
• 22635-62-7 1-acetyloxyadamantane 
• 24375-06-2 1-(Chloroamino)adamantane 
• 60389-53-9 1-Chloro-3-iodoadamantane 
• 16200-57-0 Toluene-4-sulfonic acid adamantan-1-yl ester 
• 19026-84-7 N-(adamantan-1-yl)benzamide 

Downstream Products

• 6221-74-5 1-methoxyadamantane 
• 53799-14-7 4-((3r,5r,7r)-adamantan-1-yl)-2-methylphenol 
• 41031-52-1 2-Methyl-6-(1-adamantyl)-phenol 
• 38614-06-1 2-((3r,5r,7r)-adamantan-1-yl)phenol 
• 3716-62-9 N-(1-Adamantyl)-2-pyrrolidone 
• 83610-13-3 3-(1-adamantyl)-3,4-dihydroquinazolin-4-one 
• 702-79-4 1,3-dimethyladamantane 
• 281-23-2 adamantane 
• 768-91-2 1-methyl-adamantane 
• 1687-36-1 1,3,5,7-tetramethyladamantane 
• 707-35-7 1,3,5-trimethyladamantane 
• 768-90-1 1-Adamantyl bromide 
• 75-36-5 acetyl chloride 
• 507-20-0 tertiary butyl chloride 

Relevant academic research and scientific papers

Alkylphosphinites as Synthons for Stabilized Carbocations

We present a new acid-free method for the generation of carbocations based on a redox condensation reaction that enables SN1 reactions with a variety of nucleophiles. We utilize readily synthesized phosphinites that are activated by diisopropyl azodicarboxylate to form betaine structures that collapse upon adding a pronucleophile, thereby yielding reactive carbocation intermediates. We also employ this approach for the alkylation of some bioactive molecules.

Non-Heme-Iron-Mediated Selective Halogenation of Unactivated Carbon?Hydrogen Bonds

Oxidation of the iron(II) precursor [(L1)FeIICl2], where L1 is a tetradentate bispidine, with soluble iodosylbenzene (sPhIO) leads to the extremely reactive ferryl oxidant [(L1)(Cl)FeIV=O]+ with a cis disposition of the chlorido and oxido coligands, as observed in non-heme halogenase enzymes. Experimental data indicate that, with cyclohexane as substrate, there is selective formation of chlorocyclohexane, the halogenation being initiated by C?H abstraction and the result of a rebound of the ensuing radical to an iron-bound Cl?. The time-resolved formation of the halogenation product indicates that this primarily results from sPhIO oxidation of an initially formed oxido-bridged diiron(III) resting state. The high yield of up to >70 % (stoichiometric reaction) as well as the differing reactivities of free Fe2+ and Fe3+ in comparison with [(L1)FeIICl2] indicate a high complex stability of the bispidine-iron complexes. DFT analysis shows that, due to a large driving force and small triplet-quintet gap, [(L1)(Cl)FeIV=O]+ is the most reactive small-molecule halogenase model, that the FeIII/radical rebound intermediate has a relatively long lifetime (as supported by experimentally observed cage escape), and that this intermediate has, as observed experimentally, a lower energy barrier to the halogenation than the hydroxylation product; this is shown to primarily be due to steric effects.

Copper-Catalyzed Intermolecular Functionalization of Unactivated C(sp3)-H Bonds and Aliphatic Carboxylic Acids

Intermolecular functionalization of C(sp3)-H bonds and aliphatic carboxylic acids enables the efficient synthesis of high value-added organic compounds from readily available starting materials. Although methods involving hydrogen atom transfer have been developed for such functionalization, these methods either work for only activated C(sp3)-H bonds or bring in a narrow set of functional groups. Here we describe a Cu-catalyzed process for the diverse functionalization of both unactivated C(sp3)-H bonds and aliphatic carboxylic acids. The process is enabled by the trapping of alkyl radicals generated through hydrogen atom abstraction by arylsulfonyl-based SOMO-philes, which introduces a large array of C, N, S, Se, and halide-based functional groups. The chemoselectivity can be switched from C-H functionalization to decarboxylative functionalization by matching the bond dissociation energy of the hydrogen atom transfer reagent with that of the target C-H or O-H bond.

Practical and Selective sp3 C?H Bond Chlorination via Aminium Radicals

The introduction of chlorine atoms into organic molecules is fundamental to the manufacture of industrial chemicals, the elaboration of advanced synthetic intermediates and also the fine-tuning of physicochemical and biological properties of drugs, agrochemicals and polymers. We report here a general and practical photochemical strategy enabling the site-selective chlorination of sp3 C?H bonds. This process exploits the ability of protonated N-chloroamines to serve as aminium radical precursors and also radical chlorinating agents. Upon photochemical initiation, an efficient radical-chain propagation is established allowing the functionalization of a broad range of substrates due to the large number of compatible functionalities. The ability to synergistically maximize both polar and steric effects in the H-atom transfer transition state through appropriate selection of the aminium radical has provided the highest known selectivity in radical sp3 C?H chlorination.

Exhaustive One-Step Bridgehead Methylation of Adamantane Derivatives with Tetramethylsilane

A methylation protocol of adamantane derivatives was investigated and optimized using AlCl3 and tetramethylsilane as the methylation agent. Substrates underwent exhaustive methylation of all available bridgehead positions with yields ranging from 62 to 86 %, and up to six methyl groups introduced in one step. Scaling-up of the reaction was demonstrated by performing the >40 gram-scale synthesis of 1,3,5,7-tetramethyladamantane with 62 % yield. For several substrates, rearrangements were observed, as well as cleavage of functional groups or Csp3?Csp2 bonds or even cyclohexyl-adamantyl bonds. Based on mechanistic studies, it is suggested that a reactive methylation complex is formed from tetramethylsilane and AlCl3. X-ray diffraction structures of hexamethylated bis-adamantyls reveal elongation or widening of sp3 carbon bonds between adamantyl moieties to 1.585(3) ? and 125.26(9)° due to repulsive H???H contacts.

Iron-Catalyzed C-C Single-Bond Cleavage of Alcohols

An iron-catalyzed deconstruction/hydrogenation reaction of alcohols through C-C bond cleavage is developed through photocatalysis, to produce ketones or aldehydes as the products. Tertiary, secondary, and primary alcohols bearing a wide range of substituents are suitable substrates. Complex natural alcohols can also perform the transformation selectively. A investigation of the mechanism reveals a procedure that involves chlorine radical improved O-H homolysis, with the assistance of 2,4,6-collidine.

Thiourea-Mediated Halogenation of Alcohols

The halogenation of alcohols under mild conditions expedited by the presence of substoichiometric amounts of thiourea additives is presented. The amount of thiourea added dictates the pathway of the reaction, which may diverge from the desired halogenation reaction toward oxidation of the alcohol, in the absence of thiourea, or toward starting material recovery when excess thiourea is used. Both bromination and chlorination were highly efficient for primary, secondary, tertiary, and benzyl alcohols and tolerate a broad range of functional groups. Detailed electron paramagnetic resonance (EPR) studies, isotopic labeling, and other control experiments suggest a radical-based mechanism. The fact that the reaction is carried out at ambient conditions, uses ubiquitous and inexpensive reagents, boasts a wide scope, and can be made highly atom economic, makes this new methodology a very appealing option for this archetypical organic reaction.

Mechanism of Ni-catalyzed oxidations of unactivated C(sp3)-H Bonds

The Ni-catalyzed oxidation of unactivated alkanes, including the oxidation of polyethylenes, by meta-chloroperbenzoic acid (mCPBA) occur with high turnover numbers under mild conditions, but the mechanism of such transformations has been a subject of debate. Putative, high-valent nickel-oxo or nickel-oxyl intermediates have been proposed to cleave the C-H bond, but several studies on such complexes have not provided strong evidence to support such reactivity toward unactivated C(sp3)-H bonds. We report mechanistic investigations of Ni-catalyzed oxidations of unactivated C-H bonds by mCPBA. The lack of an effect of ligands, the formation of carbon-centered radicals with long lifetimes, and the decomposition of mCPBA in the presence of Ni complexes suggest that the reaction occurs through free alkyl radicals. Selectivity on model substrates and deuterium-labeling experiments imply that the m-chlorobenzoyloxy radical derived from mCPBA cleaves C-H bonds in the alkane to form an alkyl radical, which subsequently reacts with mCPBA to afford the alcohol product and regenerate the aroyloxy radical. This free-radical chain mechanism shows that Ni does not cleave the C(sp3)-H bonds as previously proposed; rather, it catalyzes the decomposition of mCPBA to form the aroyloxy radical.

A quaternary ammonium salt containing adamantane of ionic liquid and its preparation method

The invention relates to a quaternary ammonium salt containing adamantane of ionic liquid and its preparation method, the invention designed and prepared ionic liquid containing adamantane of a quaternary ammonium salt of the formula: Wherein: n=6, 9 or 11. The invention containing adamantane of a quaternary ammonium salt of the ionic liquid is 1 - adamantane formic acid as raw materials, through a three-step reaction: first of all by the 1 - adamantane carboxylic acid with thionyl chloride synthesized by the reaction of acyl 1 - adamantane chloride, 1 - adamantane chloride with the OH (CH2 )n After the esterification reaction with Br N, N - dimethyl benzylamine by quaternary amine to form the quaternary ammonium salts containing adamantane of ionic liquid. The adamantane obtained by the present invention of a quaternary ammonium salt of the ionic liquid to the mild reaction conditions, raw materials are easy, high-purity product, in super-molecular chemical, catalytic, battery, nano materials and other fields has potential application prospect.

N -Hydroxyphthalimide/benzoquinone-catalyzed chlorination of hydrocarbon C-H bond using N -chlorosuccinimide

The direct chlorination of C-H bonds has received considerable attention in recent years. In this work, a metal-free protocol for hydrocarbon C-H bond chlorination with commercially available N-chlorosuccinimide (NCS) catalyzed by N-hydroxyphthalimide (NHPI) with 2,3-dicyano-5,6-dichlorobenzoquinone (DDQ) functioning as an external radical initiator is presented. Aliphatic and benzylic substituents and also heteroaromatic ones were found to be well tolerated. Both the experiments and theoretical analysis indicate that the reaction goes through a process wherein NHPI functions as a catalyst rather than as an initiator. On the other hand, the hydrogen abstraction of the C-H bond conducted by a PINO species rather than the highly reactive N-centered radicals rationalizes the high chemoselectivity of the monochlorination obtained by this protocol as the latter is reactive towards the C(sp3)-H bonds of the monochlorides. The present results could hold promise for further development of a nitroxy-radical system for the highly selective functionalization of the aliphatic and benzylic hydrocarbon C-H.