METHYL 2-BUTYNOATE

Base Information

• Chemical Name: METHYL 2-BUTYNOATE
• CAS No.: 23326-27-4
• Molecular Formula: C5H6O2
• Molecular Weight: 98.1014
• Hs Code.: 29161900
• Mol file: 23326-27-4.mol

Synonyms:Tetrolicacid, methyl ester (6CI,7CI,8CI);Methyl 2-butynoate;Methyl3-methylpropiolate;Methyl methylacetylenecarboxylate;Methyl tetrolate;NSC244950;

Chemical Property of METHYL 2-BUTYNOATE

Chemical Property:

• Appearance/Colour: clear colorless to yellowish liquid
• Vapor Pressure: 6mmHg at 25°C
• Refractive Index: 1.436-1.438
• Boiling Point: 140.9 °C at 760 mmHg
• Flash Point: 45 °C
• PSA: 26.30000
• Density: 1.002 g/cm³
• LogP: 0.18270
• Storage Temp.: Flammables area

Purity/Quality:

98%, ^*data from raw suppliers

Methyl2-Butynoate ^*data from reagent suppliers

Safty Information:

• Pictogram(s): Xn
• Hazard Codes: Xn
• Statements: 10-36/37/38-20/21/22
• Safety Statements: 16-36/37/39-26

MSDS Files:

SDS file from LookChem

Useful:

• General Description: METHYL 2-BUTYNOATE is an acetylenic ester that serves as a key reactant in a novel "umpolung" C-C bond formation catalyzed by triphenylphosphine, where its γ-carbon unexpectedly behaves as an electrophile rather than a nucleophile. This reactivity enables nucleophilic addition by compounds like dimethyl malonate, forming a 1:1 adduct with high regioselectivity and atom economy. The reaction demonstrates broad applicability with pronucleophiles of pKa < 16, though alkyl substitution on the acidic carbon reduces efficiency. Methyl 2-butynoate's versatility is further highlighted by its compatibility with various electron-withdrawing substituents on acetylenic acceptors, making it a valuable synthon in unconventional bond-forming strategies.

Technology Process of METHYL 2-BUTYNOATE

There total 10 articles about METHYL 2-BUTYNOATE which guide to synthetic route it. The literature collected by LookChem mainly comes from the sharing of users and the free literature resources found by Internet computing technology. We keep the original model of the professional version of literature to make it easier and faster for users to retrieve and use. At the same time, we analyze and calculate the most feasible synthesis route with the highest yield for your reference as below:

synthetic route:

Reference yield: 71.0%

[acetyl(methoxycarbonyl)methylene]triphenylphosphorane (1743-62-0) → Methyl 2-butynoate (23326-27-4)

Guidance literature:

under 15 Torr; Heating;

DOI:10.1002/1099-0690(200207)2002:13<2094::AID-EJOC2094>3.0.CO;2-E

Reference yield: 67.0%

methanol (67-56-1) + 2-Butynoic acid (590-93-2) → Methyl 2-butynoate (23326-27-4)

Guidance literature:

With sulfuric acid; at 20 ℃; for 96h;

DOI:10.1002/ejic.200800356

Reference yield: 60.0%

1,2-dihydro-5-methyl-3H-pyrazol-3-one (4344-87-0) + methanol (67-56-1) → Methyl 2-butynoate (23326-27-4)

Guidance literature:

With [bis(acetoxy)iodo]benzene; at -23 ℃; for 1h;

DOI:10.1039/c39870000711

upstream raw materials:

methanol

2-Butynoic acid

[acetyl(methoxycarbonyl)methylene]triphenylphosphorane

diazomethane

Downstream raw materials:

2,6-dimethyl-cyclohexa-1,4-dienecarboxylic acid

7-Methyl-2,3-dihydro-imidazo<2,1-b>-1,3-thiazin-5-on

4-(methoxycarbonyl)-1(E)-phenyl-1,4,5-hexatrien-3-ol

trans,trans-3,7-Dimethyl-deca-2,6-diensaeuremethylester

Refernces

Novel "Umpolung" in C-C Bond Formation Catalyzed by Triphenylphosphine

10.1021/ja00086a074

The study investigates a novel "umpolung" in C-C bond formation catalyzed by triphenylphosphine. The Michael addition reaction, where a nucleophile adds to an α,β-unsaturated carbonyl compound, is a fundamental synthetic reaction in organic chemistry. Typically, the γ-carbon in such compounds acts as a nucleophile due to conjugation with an electron-withdrawing group. However, this study demonstrates that triphenylphosphine can induce the γ-carbon to act as an electrophile, facilitating nucleophilic addition. The researchers used a mixture of methyl 2-butynoate and dimethyl malonate, with triphenylphosphine as a catalyst, acetic acid, and sodium acetate in toluene. They observed the formation of a 1:1 adduct, with yields varying based on the concentration of triphenylphosphine. The study explores the range of pronucleophiles that can participate in this reaction, finding that compounds with pKa < 16 work well, while introducing alkyl groups on the acidic carbon of the pronucleophile reduces yield. The study also examines the effects of different substituents on the acetylenic acceptor, such as esters, amides, and ketones, and proposes a mechanism where triphenylphosphine acts as a nucleophilic trigger, enabling unprecedented regioselectivity and atom economy in the addition process.