138858-22-7

Upstream product

• 53215-95-5 N-(trimethylsilylmethyl)benzylamine 
• 105-36-2 ethyl bromoacetate 
• 100-46-9 benzylamine 

Downstream Products

• 6436-90-4 ethyl 2-(benzylamino)acetate 
• 138858-29-4 C₂₄H₂₁NO₄ 
• 138858-23-8 2-hydroxy-2-<methyl>acenaphthylen-1-one 
• 138858-24-9 2-hydroxy-2-<amino>carbethoxymethyl>acenaphthylen-1-one 
• 1619229-77-4 C₇₅H₂₃NO₂Si 
• 1619229-71-8 C₇₂H₁₇NO₂ 

Relevant academic research and scientific papers

Photoaddition reactions of azomethine ylides generated from α-aminonitriles to fullerene C60: Formation of fulleropyrrolidines and reaction efficiencies changes depending on reaction conditions

Photoaddition reactions of C60 with both (trimethylsilyl)methyl and either benzyl or phenethyl group containing α-aminonitriles were carried out to explore how product distributions and reaction efficiencies can be influenced by reaction solvent systems. The results show that photoreactions produce both trimethylsilyl- and cyano group containing fulleropyrrolidines as a major (or exclusive) product. Especially, photoreactions performed in either EtOH containing solution or oxygenated environment take place with a much more efficient manner.

Control of Chemoselectivity of SET-Promoted Photoaddition Reactions of Fullerene C60with α-Trimethylsilyl Group-Containing N-Alkylglycinates Yielding Aminomethyl-1,2-dihydrofullerenes or Fulleropyrrolidines

Knowledge about factors that govern chemoselectivity is pivotal to the design of reactions that are utilized to produce complex organic substances. In the current study, single-electron transfer (SET)-promoted photoaddition reactions of fullerene C60 with both trimethylsilyl and various alkyl group-containing glycinates and ethyl N-alkyl-N-((trimethylsilyl)methyl)glycinates were explored to evaluate how the nature of N-alkyl substituents of glycinate substrates and reaction conditions govern the chemoselectivity of reaction pathways followed. The results showed that photoreactions of C60 with glycinates, performed in deoxygenated conditions, produced aminomethyl-1,2-dihydrofullerenes efficiently through a pathway involving the addition of α-amino radical intermediates that are generated by sequential SET-solvent-assisted desilylation of glycinate substrates to C60. Under oxygenated conditions, photoreactions of glycinate substrates, except N-benzyl-substituted analogues, did not take place efficiently owing to quenching of 3C60? by oxygen. Interestingly, N-benzyl-substituted glycinates did react under these conditions to form fulleropyrrolidines through a pathway involving 1,3-dipolar cycloaddition of in situ formed azomethine ylides to C60. The ylide intermediates were formed by regioselective H-atom transfer from glycinates by singlet oxygen. Furthermore, methylene blue (MB)-photosensitized reactions of C60 with glycinates under oxygenated conditions took place efficiently to produce fulleropyrrolidines independent of the nature of N-alkyl substituents of glycinates.

Photoaddition reactions of N-benzylglycinates containing α-trimethylsilyl group with dimethyl acetylenedicarboxylate: competitive formation of pyrroles vs. β-enamino esters

A study was conducted to gain insight into the preparative potential of photosensitized reactions of acyclic N-benzylglycinates containing an α-trimethylsilyl group with dimethyl acetylenedicarboxylate (DMAD). The photosensitizers employed in the reactions include 9,10-dicyanoanthracene (DCA), 1,4-dicyanonaphthalene (DCN), rose bengal (RB) and fullerene C60. The results show that photoirradiation of oxygenated solutions containing the photosensitizers, glycinates and dimethyl acetylenedicarboxylate leads to competitive formation of pyrroles and β-enamino-esters. The distributions of pyrrole and β-enamino-ester products formed in these reactions are highly influenced by the electronic nature of the phenyl ring substituent on the benzylglycinates and the photosensitizer used. These photoaddition reactions take place via mechanistic pathways involving competitive formation of azomethine ylides and secondary amines, generated by a mechanistic routes involving initial SET from the benzylglycinates to photosensitizers.

Catalyst free, visible-light promoted photoaddition reactions between C60 and N-trimethylsilylmethyl-substituted tertiary amines for synthesis of aminomethyl-1,2-dihydrofullerenes

An efficient and benign method for the preparation of aminomethyl-substituted fullerenes has been developed. The process, involving catalyst free, visible-light irradiation of 10% EtOH-toluene solutions containing fullerene C60 and N-trimethyls

Synthesis of functionalized fullerenes by photoaddition of N-α-trimethylsilyl-ncarboxymethyl-N-benzylamines to C60

Photoaddition reactions of fullerene C60 with N-α-trimethylsilyl-N-carboxymethyl-N-benzylamines, which contain various para-substituents, were explored in order to evaluate factors governing efficiencies of this potentially useful method for preparing functionalized fullerene derivatives. Observations made in this study show that two reaction pathways are followed in these photoreactions. The first involves initial formation of α-trimethylsilyl-aminium radicals and the C60 anion radical by SET from the amines to the triplet excited state of C60. This step is followed by desilylation to produce α-amino radicals. Coupling of these radicals with the anion radical of C60 followed by protonation or with the hydrofullerene radical generated by protonation of the anion radical of C60 then produces aminomethyl-1,2-dihydrofullerenes. When limited amounts of 3O2 are present in the reaction medium, fulleropyrrolidines are generated in low yields by a competitive pathway involving formation of singlet oxygen, which undergoes sequential H-atom abstractions from the N-α-trimethylsilyl-N-carboxymethyl-N-benzylamines to produce azomethine ylide intermediates. Dipolar cyloaddition of the ylides to C60 then produces fulleropyrrolidines. Photoreactions of the C60 and the amines in the presence of high 3O2 concentrations exclusively produce fulleropyrrolidine. In addition, the results show that photoreactions of non-silicon substituted, N-methyl-N-carboxymethyl-N-benzylamines with C60 form fulleropyrrolidines independent of the concentration of 3O2 present in the media.

Method for the synthesis of amine-functionalized fullerenes involving set-promoted photoaddition reactions of -silylamines

A novel method for the preparation of structurally diverse fullerene derivatives, which relies on the use of single electron transfer (SET)-promoted photochemical reactions between fullerene C60 and α-trimethylsilylamines, has been developed. Photoirradiation of 10% EtOH-toluene solutions containing C60 and α-silylamines leads to high-yielding, regioselective formation of 1,2-adducts that arise through a pathway in which sequential SET-desilylation occurs to generate α-amino and C60 anion radical pair intermediates, which undergo C-C bond formation. Protonation of generated α-aminofullerene anions gives rise to formation of monoaddition products that possess functionalized α-aminomethyl-substituted 1,2-dihydrofullerene structures. Observations made in this effort show that the use of EtOH in the solvent mixture is critical for efficient photoproduct formation. In contrast to typical thermal and photochemical strategies devised previously for the preparation of fullerene derivatives, the new photochemical approach takes place under mild conditions and does not require the use of excess amounts of substrates. Thus, the method developed in this study could broaden the scope of fullerene chemistry by providing a simple photochemical strategy for large-scale preparation of highly substituted fullerene derivatives. Finally, the α-aminomethyl-substituted 1,2-dihydrofullerene photoadducts are observed to undergo photoinduced fragmentation reactions to produce C60 and the corresponding N-methylamines.

Photoaddition Reactions of Acenaphthylenedione with α-Silyl n-Electron Donors via Triplet Single Electron Transfer-Desilylation and Triplet Hydrogen Atom Abstraction Pathways

Studies have been conducted to explore single electron transfer (SET) induced photoaddition reactions of acenaphthylenedione (ACND) with the n-electron donors Et2NCH2SiMe3, n-PrSCH2SiMe3, EtOCH2SiMe3, EtCO2CH2N(CH2Ph)CH2SiMe3, and EtCO2CH2N(CH2Ph)CH3.Photoaddition of α-silyl amine Et2NCH2SiMe3 to ACND occurs in CH3OH and CH3CN to produce 2-hydroxy-2-acenaphthylen-1-one.In contrast, photoaddition of n-PrSCH2SiMe3 to ACND generates two photoadducts, 2-hydroxy-2-acenaphthylen-1-one and 2-hydroxy-2-acenaphthylen-1-one, along with a ACND photoreduction dimer.Photoaddition of EtOCH2SiMe3 to ACND produces two diastereomers of 2-hydroxy-2-acenaphthylen-1-one along with the reduction dimer.The formation of all photoproducts in these photoreactions is quenched by oxygen, indicating that the triplet of ACND is the reactive excited state.Based on a consideration of the oxidation potentials of the α-silyl n-electron donors, and the nature of photoproducts, mechanisms for these photoadditions involving triplet SET-desilylation and triplet H atom abstraction pathways are proposed.Photoaddition of EtCO2CH2N(CH2Ph)CH2SiMe3 to ACND provides two major products, 2-hydroxy-2-methyl>acenaphthylen-1-one and 2-hydroxy-2-amino>carbethoxymethyl>acenaphthylen-1-one along with several minor products.The formation of the major products via sequential SET-deprotonation pathways shows that the electron-withdrawing carbethoxy substituent serves to control the regioselectivity for deprotonation of the amine radical cation intermediate.Results obtained from the study of the photoaddition of the non-silicon-containing amino ester, EtCO2CH2N(CH2Ph)CH3, also demonstrate the effect of electron-withdrawing carbethoxy substitutent on amine radical cation deprotonation regiochemistry.