768-91-2

Basic information

• Product Name: 1-METHYLADAMANTANE
• Synonyms: 1-METHYLADAMANTANE;tricyclo[3.3.1.1~3,7~]decane, 1-methyl-;1-Methyl-tricyclo[3.3.1.13,7]decane
• CAS NO: 768-91-2
• Molecular Formula: C₁₁H₁₈
• Molecular Weight: 150.26
• Product Categories: Adamantane derivatives;Intermediates & Fine Chemicals;Pharmaceuticals
• Mol File: 768-91-2.mol

Chemical Properties

• Boiling Point: 192.8 °C at 760 mmHg
• Flash Point: 55.4 °C
• Appearance: /
• Density: 0.974 g/cm³
• Vapor Pressure: 0.668mmHg at 25°C
• Refractive Index: 1.519
• Storage Temp.: Refrigerator
• CAS DataBase Reference: 1-METHYLADAMANTANE(CAS DataBase Reference)
• NIST Chemistry Reference: 1-METHYLADAMANTANE(768-91-2)
• EPA Substance Registry System: 1-METHYLADAMANTANE(768-91-2)

Safety Data

• HazardClass: IRRITANT
• Hazardous Substances Data: 768-91-2(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Industry:
1-Methyladamantane is used as an intermediate in the preparation of Amidoadamantanes for their potential applications in the development of drugs targeting various diseases, including neurological disorders and certain types of cancer. Its rigid structure and chemical properties contribute to the stability and effectiveness of the resulting compounds.
Used in Chemical Synthesis:
1-Methyladamantane is used as a building block in the synthesis of various organic compounds due to its unique structure and reactivity. Its presence in the molecular framework can influence the properties of the final product, making it a valuable component in the development of new materials and chemicals.
Used in Research and Development:
1-Methyladamantane serves as a valuable reference compound in academic and industrial research, particularly in the fields of organic chemistry, medicinal chemistry, and materials science. Its distinct properties and structural features make it an interesting subject for studying molecular interactions, reaction mechanisms, and the development of novel synthetic methods.

Purification Methods

Purify it by zone melting, chromatography through an Al2O3 column and eluting with pentane, and sublime it repeatedly at 90-95o/12mm. [Stetter et al. Chem Ber 92 1629 1959, Schleyer & Nicholas Tetrahedron Lett 9 305 1961, Beilstein 5 IV 479,]

InChI:InChI=1/C11H18/c1-11-5-8-2-9(6-11)4-10(3-8)7-11/h8-10H,2-7H2,1H3

Upstream product

• 67-56-1 methanol 
• 88459-01-2 (1s,3s)-adamantan-1-yl(phenyl)sulfide 
• 768-90-1 1-Adamantyl bromide 
• 917-64-6 methyl magnesium iodide 
• 75-76-3 tetramethylsilane 
• 768-93-4 1-iodoadamantane 
• 935-56-8 1-chloroadamantane 
• 281-23-2 adamantane 
• 768-95-6 1-adamanthanol 
• 593-90-8 trimethylborane 
• 770-14-9 3,7-dimethylenebicyclo[3.3.1]nonane 
• 3732-31-8 1,1'-Biadamantane 
• 1678-91-7 ethyl-cyclohexane 
• 696-29-7 (1-methylethyl)-cyclohexane 

Downstream Products

• 33649-73-9 1-Methyladamantane-3-carboxylic acid 
• 702-77-2 1-bromo-3-methyladamantane 
• 17837-93-3 5-methyladamantane-1,3-diol 
• 778-09-6 1-acetamido-3-methyltricyclo[3.3.1.1^3,7]decane 
• 281-23-2 adamantane 
• 702-81-8 3-methyl-1-adamantanol 
• 17768-37-5 acetate de methyl-3 adamantyl-1 
• 127526-24-3 3-methyl-1-adamantyl trifluoroactate 
• 1687-34-9 1-ethyl-3-methyladamantane 
• 14202-13-2 (3-methyladamantan-1-yl)acetic acid 
• 78056-28-7 3-methyl-1-aminoadamantane 
• 99998-84-2 N'--N-<3-methyl-adamantyl>-harnstoff 
• 1353745-35-3 5-methyladamantan-2-one azine 

Relevant articles and documents

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.

Direct observation of cyclic carbenium ions and their role in the catalytic cycle of the methanol-to-olefin reaction over chabazite zeolites

Carbenium ions in zeolites: Two important carbenium ions have been observed for the first time under working conditions of the methanol-to-olefins (MTO) reaction over chabazite zeolites using 13C NMR spectroscopy. Their crucial roles in the MTO

Alkylation of adamantane with alkyl halides catalyzed by ruthenium complexes

The feasibility of catalytic alkylation of adamantane and 1-bromoadamantane with alkyl halides in the presence of ruthenium-containing catalysts was revealed. The optimum molar ratios between the catalyst components and the reactants, as well as the reaction conditions for the selective synthesis of mono-and dialkylsubstituted adamantane derivatives with a 70-98% yield, were determined. Nauka/Interperiodica 2006.

The mechanism of conversion of saturated hydrocarbons catalyzed by sulfated metal oxides: Reaction of adamantane on sulfated zirconia

The high activity of sulfated zirconia (SZ) toward hydrocarbon conversions has been confirmed by the study of the isomerization of methylcyclopentane to cyclohexane. This catalytic activity is generally rationalized by the catalyst having superacidic strength. The reaction of methylcyclopentane with superacids is initiated, however, by the cleavage of a carbon-carbon bond with the formation of an acyclic carbocation, followed by hydride transfer giving the methylcyclopentyl cation which undergoes rearrangement. By contrast, no isohexanes (products of ring cleavage) were formed in the reaction on SZ, suggesting a different reaction mechanism. The mechanism of interaction of SZ with saturated hydrocarbons was elucidated by a study of adamantane. Small amounts of 1-adamantanol and adamantanone and traces of 2-adamantanol were observed after reaction at temperatures from 65 to 135°C, indicating that the reaction is an oxidation followed by hydride transfers. Small amounts of diadamantanes were also formed, proving that oxidation to carbocations goes through the free radical stage. At 150°C, additional reaction products were observed, 1-adamantanethiol (larger amount) and 2-adamantanethiol (smaller amount), indicating reduction of sulfate all the way to sulfide, which then traps the adamantyl cation in competition with the oxygen anions or water formed in the redox process. Ring cleavage and disproportionation to form alkyladamantanes and aromatics also occurred. Thus, the increase in activity of SZ over the parent oxide for carbocationic alkane and cycloalkane reactions can be ascribed to initiation through a one-electron oxidation of the hydrocarbon by sulfate to a carbocation precursor.

Tri(1-adamantyl)methane and its Thermolysis

The synthesis of the title compound, a new tri(tert-alkyl)methane, and the kinetics and products of its thermolysis are described.

Photochemistry of phenyl thioethers and phenyl selenoethers. Radical vs ionic behavior

In analogy with alkyl iodides and bromides, the phenyt thio- and selenoethers 2a,b, 13a, 21b,c and 35 displayed competing radical and ionic photobehavior on irradiation in solution, via a mechanism thought to involve initial homolytic cleavage of the alkyl C-S or C-Se bond followed by electron transfer within the resulting radical pair cage (Scheme I). These are the first examples of ionic photobehavior to be recognized for the C-SAr and C-SeAr chromophores. The electronegatively substituted pentafiuorophenyl analogues 2c, 13b, and 21d displayed enhanced ionic photobehavior. By contrast, the 4-methoxyphenyl derivative 21a exhibited almost exclusively radical behavior. The sulfoxide (2R*,R*s)-21f displayed principally radical behavior, accompanied by epimerization at sulfur. The quantum yields for the disappearance of the 2-norbornyl ethers 21b and 21c were 0.53-0.64 in solution and rose to 0.89-0.95 in the presence of suspended fumed silica. Irradiation of the phenyl thioether 21b on silica gel resulted in nucleophilic trapping by surface silanol groups to afford covalently bound material (33), which afforded chloride 34 on treatment with SOCl2. Irradiation of phenyl thioethers 2a and 35, phenyl selenoether 2b, or C6H5SH in allyl alcohol solution afforded acetal 11, apparently via isomerization of some of the solvent to propanal (44) followed by acetalization. Irradiation of alcoholic solutions of aldehydes containing C6H5SH is a useful means of generating acetals under neutral conditions.

Reductive Alkylation and Reduction of Tertiary, Secondary, and Benzylic Alcohols with Trimethyl-, Triethyl-, and Triisopropylboron/Trifluoromethanesulfonic (Triflic) Acid

Tertiary, secondary, and benzylic alcohols were reductively alkylated and reduced with trimethyl-, triethyl-, and triisopropylboron/trifluoromethanesulfonic (triflic) acid.A postulated mechanism for the reactions is discussed.

Novel Rearrangement of 5,6-Disubstituted Bicyclooctan-2-ones with AlCl3. Application to Total Synthesis of (+/-)-5-Oxosilphiperfol-6-ene and (+/-)-Silphiperfol-6-ene

The acid-catalyzed rearrangement of bi- and tricyclic cyclobutyl ketones 8-20 having a bicyclooctan-2-one moiety with AlCl3 was studied to elucidate the scope and limitations of the novel rearrangement by which the tricyclic ketone 1 gave the angul

Cross-Coupling Reaction of tert-Alkyl halides with Grignard Reagents in Dichloromethane as a Non-Lewis Basic Medium

In dichloromethane as a non-Lewis basic solvent, 1-haloadamantane 1 underwent a cross-coupling reaction with Grignard reagents to give bridgehead-substituted products 3-16 in moderate yields.In this case the same kind of halogen in both 1 and a Grignard reagent was favored; if not, functional exchange (i.e., 1a to 1c) occurred first.The reaction using 5-hexenylmagnesium bromide as a radical probe afforded uncyclized/cyclized coupling products in a 6/4 ratio.These fact suggested the significant participation of the single-electron-transfer process in these reactions.The present method could be extended to tert-butylation with some Grignard reagents.Interestingly, 1,3-dichloro-3-methylbutane coupled with butylmagnesium chloride selectively at the tertiary position. for the above displacement reaction of 1, an organozinc was also found to be effective.

Contribution a l'etude des reactions d'alkylation et de polyalkylation de l'adamantane et de ses homologues

A method for preparing alkyl derivatives of cage-structure compounds is proposed.It relies on the use of Grignard reactions with a high boiling point solvent.The reactions take place at atmospheric pressure.Methylation of adamantane, diamantane, and homoadamantane occurs with quantitative yield.With other primary alkyl groups, yields are better than 60percent.Competition between alkylation and secondary reactions is discussed on the basis of a free radical mechanism.