Dimethyl 2-Methylenepentanedioate: Properties & Applications

Dimethyl 2-methylenepentanedioate is a bifunctional activated alkene featuring an exo-methylene group flanked by two ester moieties, making it a versatile electrophilic Michael acceptor and building block in organic synthesis.

IUPAC Name

Dimethyl 2-methylenepentanedioate

Molecular Formula

C7H10O4

Molecular Weight

158.15 g/mol

Functional Groups

Exo-methylene, two methyl ester groups

Key Reactivity

Michael acceptor; participates in conjugate addition reactions

CAS-related SKU

D698124 (Aladdin Scientific)

Chemical Identity and Structure

Dimethyl 2-methylenepentanedioate (CAS registry; SKU D698124) is the dimethyl diester of 2-methylenepentanedioic acid. Its defining structural feature is an exo-methylene group at the C-2 position, conjugated simultaneously with two electron-withdrawing methyl ester groups. This arrangement creates a highly electrophilic alkene carbon that is polarized toward nucleophilic attack.

The compound belongs to the class of activated methylene diesters and is closely related to dimethyl itaconate (dimethyl methylenesuccinate), differing by one additional methylene unit in the carbon chain. This extra carbon modulates steric and electronic properties relative to itaconate derivatives, offering complementary reactivity profiles for synthetic chemists.

Synthesis and Preparation Routes

Dimethyl 2-methylenepentanedioate can be accessed through several established synthetic routes commonly applied to exo-methylene dicarboxylate systems. A principal approach involves the Knoevenagel-type condensation or Mannich-based elimination sequences starting from dimethyl glutarate or related precursors bearing an alpha-methylene handle.

Alternatively, the compound may be prepared via methylene transfer to a dimethyl glutarate backbone using formaldehyde equivalents under basic conditions, analogous to methods employed for the synthesis of dimethyl itaconate from dimethyl succinate. Researchers should consult primary literature for optimized reaction conditions, as specific yields and reagent ratios are substrate-dependent and not detailed in current supplier documentation.

Reactivity and Applications in Organic Synthesis

The principal synthetic utility of dimethyl 2-methylenepentanedioate arises from its role as a doubly activated Michael acceptor. The exo-methylene carbon is activated by two flanking ester groups, substantially lowering the LUMO energy of the alkene and facilitating conjugate addition with a broad range of soft nucleophiles, including thiols, amines, malonates, and carbon nucleophiles generated under organocatalytic or metal-catalyzed conditions.

In polymer and materials chemistry, exo-methylene diesters structurally related to this compound have been investigated as bio-derived monomers for radical polymerization, yielding polyesters with pendant ester side chains. The additional methylene unit relative to itaconate-based monomers may influence glass transition temperature and polymer backbone flexibility, making this compound of interest for structure–property relationship studies.

The compound also serves as a precursor for further functionalization: selective reduction of one ester group, cycloaddition reactions exploiting the activated alkene, or hydrolysis to the free diacid for downstream conjugation chemistry.

Handling, Storage, and Safety Considerations

As with most alpha,beta-unsaturated carbonyl compounds, dimethyl 2-methylenepentanedioate should be handled with standard laboratory precautions appropriate for reactive electrophilic alkenes. The compound may act as a skin and eye irritant due to its Michael acceptor reactivity toward biological nucleophiles such as cysteine residues. Use of appropriate personal protective equipment — including nitrile gloves, safety glasses, and a lab coat — is recommended.

The compound should be stored in a cool, dry location away from strong nucleophiles, bases, and reducing agents. Inert atmosphere storage may be employed to prevent moisture ingress or adventitious polymerization if the compound is used over extended periods. Specific hazard classifications and GHS data should be confirmed from the current Safety Data Sheet (SDS) available from Aladdin Scientific prior to use.

Note: Users should always consult the official SDS for regulatory and disposal information specific to their jurisdiction. The handling guidance provided here is general and does not substitute for site-specific risk assessment.

Sourcing from Aladdin Scientific

Aladdin Scientific supplies Dimethyl 2-methylenepentanedioate under SKU D698124. Researchers and procurement teams can request purity specifications, certificate of analysis (CoA), and SDS documentation directly through the Aladdin Scientific platform. Bulk quantities and custom packaging may be available upon inquiry.

For order placement, pricing, and availability, please visit the Aladdin Scientific website or contact your regional sales representative. Aladdin Scientific is committed to providing research-grade reagents with full documentation support to facilitate reproducible science.

Frequently asked questions

What is Dimethyl 2-methylenepentanedioate used for in organic chemistry?

Dimethyl 2-methylenepentanedioate functions primarily as a doubly activated Michael acceptor, enabling conjugate addition reactions with thiols, amines, and carbon nucleophiles. It also serves as a monomer candidate in radical polymerization studies and as a versatile building block for further functional group interconversion.

How does Dimethyl 2-methylenepentanedioate differ from dimethyl itaconate?

Both compounds share an exo-methylene diester motif, but Dimethyl 2-methylenepentanedioate contains one additional methylene unit in the carbon backbone compared to dimethyl itaconate (dimethyl methylenesuccinate). This structural difference modulates steric bulk and may influence reactivity rates, polymer properties such as glass transition temperature, and overall chain flexibility.

What safety precautions should be taken when handling Dimethyl 2-methylenepentanedioate?

Standard precautions for reactive electrophilic alkenes apply: wear nitrile gloves, safety glasses, and a lab coat to prevent skin and eye contact. Store the compound in a cool, dry place away from nucleophiles and bases. Always consult the current SDS from Aladdin Scientific for up-to-date hazard classification, first-aid measures, and disposal requirements.

Where can I purchase Dimethyl 2-methylenepentanedioate?

Dimethyl 2-methylenepentanedioate is available from Aladdin Scientific under SKU D698124. You can place an order through the Aladdin Scientific website or by contacting your regional sales representative for pricing, availability, and bulk order inquiries.

References

1. General principles of Michael addition to activated alkenes are described in standard organic chemistry textbooks (e.g., March's Advanced Organic Chemistry).
2. Exo-methylene dicarboxylate monomers as bio-based building blocks for radical polymerization — general literature area; specific primary citations should be identified by the reviewer.
3. Aladdin Scientific product listing for Dimethyl 2-methylenepentanedioate, SKU D698124.

Products are supplied for research and development use only. Not for use in humans, animals, diagnosis, or therapy.