13609-59-1

Basic information

• Product Name: (R)-4α-Methylcycloheptane-1-one
• Synonyms: (4R)-4α-Methylcycloheptanone;(R)-4-Methylcycloheptanone;(R)-4α-Methylcycloheptane-1-one
• CAS NO: 13609-59-1
• Molecular Formula: C₈H₁₄O
• Molecular Weight: 126.2
• Mol File: 13609-59-1.mol

Chemical Properties

• Boiling Point: 184.9±8.0 °C(Predicted)
• Appearance: /
• Density: 0.897±0.06 g/cm3(Predicted)
• CAS DataBase Reference: (R)-4α-Methylcycloheptane-1-one(CAS DataBase Reference)
• NIST Chemistry Reference: (R)-4α-Methylcycloheptane-1-one(13609-59-1)
• EPA Substance Registry System: (R)-4α-Methylcycloheptane-1-one(13609-59-1)

Safety Data

• Hazardous Substances Data: 13609-59-1(Hazardous Substances Data)

Usage

Uses

Used in Organic Synthesis:
(R)-4α-Methylcycloheptane-1-one is utilized as a building block in the synthesis of various organic compounds, contributing to the creation of a wide range of chemical products.
Used in Fragrance and Flavoring Formulations:
Due to its unique properties, (R)-4α-Methylcycloheptane-1-one may also find applications in the fragrance and flavoring industries, where it can be used to develop new scents and tastes for consumer products.
Used in Pharmaceutical Industry:
(R)-4α-Methylcycloheptane-1-one, with its specific stereochemistry, could be employed in the development of pharmaceutical compounds, potentially offering novel therapeutic solutions.
Used in Chemical Research:
(R)-4α-Methylcycloheptane-1-one's unique structure and properties make it a valuable subject for research in the field of chemistry, where it can be studied for its reactivity, stability, and potential interactions with other molecules.

Upstream product

• 67-56-1 methanol 
• 35895-70-6 tetrabutylammonium trifluoromethylsulfonate 
• 186581-53-3 diazomethane 
• 13368-65-5 (3R)-3-methylcyclohexanone 

Relevant articles and documents

Photosolvolysis of optically active 4-methyl-cyclohexylidenemethyl(aryl)iodonium tetrafluoroborate

The title reaction gives largely racemized 4-methylcycloheptanone, but the enantiomeric product in slight excess has a different form depending on the leaving group, ArI, of the iodonium salt. The results indicate that the photosolvolysis does not proceed via a completely achiral state.

Cycloheptyne intermediate in the reaction of chiral cyclohexylidenemethyliodonium salt with sulfonates

Reactions of (R)-4-methylcyclohexylidenemethyl(phenyl)iodonium salt and its 3-trifluoromethylphenyl and 4-methoxyphenyl derivatives (1) with tetrabutylammonium mesylate and triflate were carried out in chloroform at 60 °C. The products include (S)-4-methylcyclohexylidenemethyl sulfonate (2) and (R)-5-methylcyclohept-1-enyl sulfonate (3) as well as iodoarene. Reactions of (S)-1 were confirmed to provide the counterpart results. The rearranged triflate (R)-3Tf formed in the reaction with triflate maintains mostly the ee (enantiomeric excess) of (R)-1, while the ee of the mesylate product 3Ms is largely lost. The 13C-labeling at the exocyclic position of 1 results in the isotopic scrambling of C-1 and C-2 of 3Ms in the mesylate reaction. The degree of the scrambling agrees well with that of the loss of ee of (R)-3Ms obtained from (R)-1, implying that the racemization is not due to the intermediate formation of achiral, primary 4-methylcyclohexylidenemethyl cation. Reaction of 1 with mesylate in the presence of CH3OD provided the 3Ms deuterated at the 2-position. When tetraphenylcyclopentadienone was added to the mesylate reaction system, the adduct of the 4-methylcycloheptyne intermediate was obtained in 24% yield, but the normal products 2Ms and 3Ms were still formed. The 3Ms obtained here in a low yield maintains the high ee of 1. These results indicate that the cycloheptyne is an intermediate responsible for the formation of racemic product 3Ms in the mesylate reaction. It is also concluded that the unrearranged products 2 are formed via the competitive pathways of in-plane and out-of-plane SN2 reactions.

Solvolysis of optically active 4-methylcyclohexylidenemethyl triflate: Evidence against a primary vinyl cation as an intermediate

Solvolysis of (R)-4-methylcyclohexylidenemethyl triflate in aqueous methanol at 140 °C gave stereospecifically (R)-4-methylcycloheptanone to definitively rule out intermediate formation of the achiral primary vinyl cation. The rearrangement must occur via concerted σ-bond participation.

Solvolysis of 4-methylcyclohexylidenemethyliodonium salt: Chirality probe approach to a primary vinyl cation intermediate

Optically active 4-methylcyclohexylidenemethyl(aryl)iodonium tetrafiuoroborate (1·BF4-) was prepared and its solvolysis was carried out at 60 °C in various solvents. The main product is optically active 4-methylcycloheptanone (or its enol derivative) in unbuffered solvents, accompanied by the iodoarene. The rearranged product always maintains the optical purity of the starting 1. Its stereochemistry conforms to a mechanism involving the rearrangement via the σ-bond participation in departure of the nucleofuge, followed by trapping of the resulting chiral 5-methylcyclohept-1-enyl cation with a nucleophilic solvent. That is, the achiral, primary vinyl cation is not involved during the reaction. The unrearranged substitution product is also obtained in a minor fraction in unbuffered methanol, ethanol, and acetic acid, but not in trifluoroethanol or hexafluoro-2-propanol: the methoxy product from methanolysis is largely racemized, but the acetolysis product is obtained mainly via retention of configuration. Reactions of 1 with bromide, acetate, and trifluoroacetate in chloroform give unrearranged substitution products in different degrees of inversion. These unrearranged products are concluded to be formed via the direct nucleophilic substitutions. Added bases such as sodium acetate in methanol lead to the unrearranged methoxy products of complete racemization, which is ascribed to the α elimination (to give an alkylidene-carbene) followed by the solvent insertion.

Solvolysis of chiral cyclohexylidenemethyl triflate. Evidence against a primary vinyl cation intermediate

Solvolysis of (R)-4-methylcyclohexylidenemethyl triflate (6) was examined at 140°C in various aqueous methanol and some other alcoholic solvents. The main product was (R)-4-methylcycloheptanone that maintains the stereochemical purity of 6, with accompanying 4-methylcyclohexanecarbaldehyde. In the presence of bromide ion, the bromide substitution product was also obtained, mostly with inversion of configuration. It is concluded that the solvolysis does not involve the formation of the primary vinyl cation but proceeds via σ-bond participation to form the rearranged cycloheptenyl cation as an intermediate. Copyright