2763-67-9

Upstream product

• 109-72-8 n-butyllithium 
• 201230-82-2 carbon monoxide 
• 111-36-4 n-butyl isocyanide 
• 14475-42-4 nonan-5-one oxime 
• 38614-35-6 C₉H₁₃NO₃ 
• 109-73-9 N-butylamine 
• 502-56-7 nonanone-5 
• 107-10-8 propylamine 
• 638-29-9 n-valeryl chloride 
• 38291-82-6 valeric acid hydrazide 

Downstream Products

• 39536-61-3 N-butylpentylamine 

Relevant academic research and scientific papers

PRODUCTION METHOD OF AMIDE COMPOUND

PROBLEM TO BE SOLVED: To provide a production method of an amide compound, which can use a variety of carboxylic acid halides and can produce a desired amide compound at a yield higher than a batch process by suppressing a side reaction. SOLUTION: Provided is a production method of an amide compound using a flow type reactor, in which the flow type reactor includes: a first flow path; a second flow path; a first mixing means provided at a confluent part of the first flow path and the second flow path; and a third flow path that is connected to the first mixing means and arranged on a down stream side of the first mixing means, the production method comprising: a mixing step of obtaining a mixed liquid by circulating a first liquid containing the carboxylic acid halide in the first flow path, circulating a second liquid containing an amine compound having a molecular weight of 1,000 or less, an inorganic alkali and water in the second flow path, and mixing the first liquid and the second liquid by the first mixing means to obtain a mixture; and a reaction step of obtaining an amide compound by circulating the mixed liquid in the third flow path and reacting the carboxylic acid halide and the amine compound in the third flow path. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2020,JPO&INPIT

Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles

The Schmidt reaction has been an efficient and widely used synthetic approach to amides and nitriles since its discovery in 1923. However, its application often entails the use of volatile, potentially explosive, and highly toxic azide reagents. Here, we report a sequence whereby triflic anhydride and formic and acetic acids activate the bulk chemical nitromethane to serve as a nitrogen donor in place of azides in Schmidt-like reactions. This protocol further expands the substrate scope to alkynes and simple alkyl benzenes for the preparation of amides and nitriles.

Selective α-Oxyamination and Hydroxylation of Aliphatic Amides

Compared to the α-functionalization of aldehydes, ketones, even esters, the direct α-modification of amides is still a challenge because of the low acidity of α-CH groups. The α-functionalization of N?H (primary and secondary) amides, containing both an unactived α-C?H bond and a competitively active N?H bond, remains elusive. Shown herein is the general and efficient oxidative α-oxyamination and hydroxylation of aliphatic amides including secondary N?H amides. This transition-metal-free chemistry with high chemoselectivity provides an efficient approach to α-hydroxy amides. This oxidative protocol significantly enables the selective functionalization of inert α-C?H bonds with the complete preservation of active N?H bond.

Remodeling and Enhancing Schmidt Reaction Pathways in Hexafluoroisopropanol

The effect of carrying out two variations of the Schmidt reaction with ketone electrophiles in hexafluoroisopropanol (HFIP) solvent has been studied. When TMSN3 is reacted with ketones in the presence of triflic acid (TfOH) promoter, tetrazoles are obtained as the major products. This observation is in contrast to established methods, which usually lead to amides or lactams arising from formal NH insertion as the major products. The full product profiles of several examples of this reaction are also reported and found to include mechanistically interesting products (e.g., double ring expansion). Application of TfOH promoter in HFIP was also found to promote the reaction of a hydroxyalkyl azide with a ketone, which affords lactams following nucleophilic opening of initially formed iminium ether more efficiently than previously reported methods. (Chemical Equation Presented).

Synthesis, X-ray crystallography, and reactions of N-acyl and N-carbamoyl succinimides

A collection of N-acyl and N-carbamoyl succinimides were prepared by acylation of succinimide with acyl chlorides or by ethylene dichloride (EDC) coupling of carboxylic acids. The x-ray crystal structures of N-benzoyl and N-p-nitrobenzoyl succinimides were determined. The N-acyl succinimides were effective in acylating primary amines, a secondary amine, and an aromatic amine. Copyright

Solid phase synthesis of amides by the Beckmann rearrangement of ketoxime carbonates

In the presence of trifluoroacetic acid, ketoxime benzyl carbonates undergo a Beckmann rearrangement to the corresponding amides. This reaction was translated to a solid support by immobilizing oximes in the form of mixed carbonates derived from hydroxymethylpolystyrene in order to produce a diversity of amides with high efficiency.

Effect of a hydrophobic environment on the hydrogen exchange kinetics of model amides determined by 1H-NMR spectroscopy

In proteins, backbone amide hydrogen exchange rates can reveal important information about protein structure and dynamics. In order to assess the possible effects of detergent on the hydrogen exchange rates of detergentsolubilized proteins, we have synthesized a series of model aliphatic amides and measured their amide proton exchange rates in water and sodium dodecyl sulfate (SDS) micelles. Hydrogen exchange was measured using steady-state saturation-transfer proton nuclear magnetic resonance (NMR) spectroscopy. The extent of interaction of the model compounds with SDS was determined by measuring the longitudinal relaxation times, chemical shifts, and temperature coefficients of the amide protons. The sensitivity of the amide proton chemical shift to hydrogen bonding was found to be a particularly useful indicator of the extent of interaction of the amides with the hydrophobic core of the micelle. It is argued that the measured hydrogen exchange parameters reflect the dynamics of exchange of the molecules between bulk solvent and the surface and core of the micelle. Two major effects of the micelle on hydrogen exchange were measured: First, an electrostatic effect due to the negatively charged sulphate groups of SDS causes a decrease of the local pH at the micellar surface. This effect increases with the affinity of the amides for the micelle and enhances acid-catalyzed exchange and decreases base-catalyzed exchange. Second, a hydrophobic effect of the core of the micelle causes a depression of the minimum rate of exchange, which, for the most nonpolar molecule, is 25-fold. This effect is similar in magnitude to the slowing of exchange by hydrogen bonding reported by Perrin et al. (J. Am. Chem. Soc. 1990, 112, 3122-3125). The hydrophobic effect is likely to be an important factor in the slowing of exchange in the solvent-excluded interior of water-soluble proteins as well as in the exchange of detergent-solubilized peptides and proteins.

High Yield Acyl Anion Trapping Reactions: Direct Nucleophilic Acylation of Isocyanates and Isothiocyanates.

The reactions of t-BuLi, sec-BuLi and n-BuLi with CO in the presence of isothiocyanates and isocyanates gives, after hydrolytic work-up, α-oxothioamides, RC(O)C(S)NHR', and α-oxoamides, RC(O)C(O)NHR', respectively, in good yield.Competition from the direct reaction of RLi with the substrate is encountered only in the case of reactions of the n-BuLi/CO system with isocyanates.