67751-25-1

Basic information

• Product Name: dimethyl (2E)-2-(dimethylamino)but-2-enedioate
• Synonyms: 2-butenedioic acid, 2-(dimethylamino)-, dimethyl ester, (2E)-; Dimethyl (2E)-2-(dimethylamino)but-2-enedioate
• CAS NO: 67751-25-1
• Molecular Formula: C₈H₁₃NO₄
• Molecular Weight: 187.1931
• Mol File: 67751-25-1.mol
• Article Data: 4

Chemical Properties

• Boiling Point: 257.1°C at 760 mmHg
• Flash Point: 109.3°C
• Density: 1.112g/cm³
• Vapor Pressure: 0.0148mmHg at 25°C
• Refractive Index: 1.462
• CAS DataBase Reference: dimethyl (2E)-2-(dimethylamino)but-2-enedioate(CAS DataBase Reference)
• NIST Chemistry Reference: dimethyl (2E)-2-(dimethylamino)but-2-enedioate(67751-25-1)
• EPA Substance Registry System: dimethyl (2E)-2-(dimethylamino)but-2-enedioate(67751-25-1)

Safety Data

• Hazardous Substances Data: 67751-25-1(Hazardous Substances Data)

Upstream product

• 594-27-4 tetramethylstannane 
• 100-39-0 benzyl bromide 
• 762-42-5 dimethyl acetylenedicarboxylate 
• 68-12-2 N,N-dimethyl-formamide 
• 591-50-4 iodobenzene 
• 74-88-4 methyl iodide 
• 88-67-5 2-Iodobenzoic acid 
• 65-85-0 benzoic acid 
• 88-65-3 2-bromobenzoic-acid 
• 321-21-1 4-fluoro-2-methylbenzoic acid 
• 74-11-3 para-chlorobenzoic acid 
• 618-51-9 3-Iodobenzoic acid 
• 118-90-1 ortho-methylbenzoic acid 
• 64-19-7 acetic acid 

Downstream Products

• 42545-22-2 dimethyl 1-methyl-1H-imidazole-4,5-dicarboxylate 

Relevant articles and documents

Fullerene C60promoted photochemical hydroamination reactions of an electron deficient alkyne with trimethylsilyl group containing tertiaryN-alkylbenzylamines

C60-promoted photoaddition reactions of both trimethylsilyl- and a variety of alkyl group containing tertiary benzylamines (i.e.,N-α-trimethylsilyl-N-alkylbenzylamines) with dimethyl acetylenedicarboxylate (DMAD) were carried out to explore the synthetic utility of trimethylsilyl group containing tertiary amines as a substrate in the photochemical hydroamination reactions with dimethyl acetylenedicarboxylate (DMAD). The results showed that photoreactions of all the trimethylsilyl containingN-alkylbenzylamines with DMAD, under an O2-purged environment, produced non-silyl containing enamines efficiently through a pathway involving addition of secondary amines to DMAD, the former of which are produced by hydrolytic cleavage ofin situformed iminium ions. Exceptionally, five-membered N-heterocyclic rings, pyrroles, could be produced competitively in photoreaction of bulky alkyl (i.e.,tert-butyl) group substituted benzylamines through a pathway involving 1,3-dipolar cycloaddition of azomethine ylides to DMAD. Furthermore, C60-sensitized photochemical reactions of non-silyl containing benzylamines with DMAD under oxygenated conditions took place in a less efficient and non-regioselective manner to produce enamine photoadducts. The observations made in this study show that regioselectivity of C60-promoted photochemical reactions ofN-α-trimethylsilyl-N-alkylbenzylamines, leading to formation of secondary amines, can be controlled by the presence of the trimethylsilyl group, and that these trimethylsilyl containing tertiary amines can serve as a precursor of secondary amines for hydroamination reactions with a variety of electron deficient acetylenes.

Dimethylbut-2-ynedioate mediated esterification of acids via sp3 C-N bond cleavage of benzylic tertiary amines

A straightforward synthetic transformation of tertiary amines to the esterification of equimolar amounts of acids was demonstrated in this manuscript. The present protocol can be regarded as a straightforward synthetic transformation of tertiary amines to the esterification of equimolar amounts of acid. Moreover, the reaction is fundamentally new chemistry for the sp 3 C-N bond cleavage coupled with esterification. The esterification reaction conditions are very mild and functional group-tolerated, such as hydrosilanes, alcohols, phenol, and amino acids. A mechanism is proposed in which the tertiary amine reacts with dimethyl but-2-ynedioate to form zwitterionic salt, and then the zwitterionic intermediate subsequently accept hydrogen to assist the nucleophilic attack of oxygen atom of carboxyl group at the benzyl group of tertiary amine, while a separate reaction pathway leads to esterification.