Day: November 18, 2022

Taguchi, Tanezo published the artcileHeteroalicyclic aminoalkanols. II. Reactions of DL-2-piperidylmethanol involving the formation of DL-1-azabicyclo[4.1.0]heptane, Quality Control of 27483-92-7, the main research area is .

2-Piperidylmethanol (I) (5 g.) in 5 cc. Et2O treated simultaneously with stirring at 0° with 6 g. BzCl in 20 cc. Et2O and 20 cc. aqueous NaOH and stirred 1 h. at room temperature yielded 7.2 g. 1-Bz derivative (II) of I, granules, m. 94-5° (Et2O). II (0.5 g.) in 20 cc. 2% aqueous HCl gave 0.53 g. benzoate (III) of I.HCl, rods, m. 243-4° (MeOH-EtOH). II with 2% HBr gave similarly 91% I.HBr, needles, m. 233-4° (decomposition) (EtOH). III.HCl (0.2 g.) stirred 0.5 h. with 10 cc. 5% aqueous NaOH yielded 0.15 g. II, granules, m. 74° (Et2O). I (1.15 g.) in 10 cc. Et2O treated dropwise with 9 cc. aqueous NaOH and then with 3 g. BzCl and stirred 3 h. yielded 2.8 g. 1-benzoyl-2-piperidylmethanol benzoate (IV), granules, m. 65-7° (Et2O-ligroine). II (0.5 g.) in 5 cc. C6H6 and 5 cc. 10% aqueous NaOH treated dropwise with stirring with 0.4 g. BzCl gave 0.66 g. IV, m. 65°. I ( 1 g.), 0.88 cc. BzH, and 10 cc. C6H6 refluxed 1 h. with 1 cc. AcOH with the azeotropic removal of H2O gave 1.3 g. V, b8 134-6°. V (0.5 g.) in 2 cc. CHCl3 treated dropwise with cooling and stirring with 0.4 g. Br in 2 cc. CHCl3 and then stirred with 2 cc. 10% aqueous NaOH gave 0.67 g. III.HBr, needles, m. 233° (EtOH). 2-ClCH2 analog (VI) (4 g.) of I.HCl and 2 g. CS(NH2)2 in 12 cc. EtOH refluxed 10 h. gave 2.5 g. 2-(2-pyridylmethyl)-2-thiopseudourea-2HCl (VIa.2HCl), needles, m. 182-4° (EtOH), and 0.8 g. VII.HCl, rods, m. 186-8° (BuOH). VIa.2HCl (0.2 g.) in 2 cc. BuOH refluxed 1 h. yielded 0.18 g. VII.HCl, needles, m. 186-8° (BuOH). VIa.2HCl (50 mg.) in 2 cc. EtOH treated successively with 0.57 cc. 2% alc. KOH, 41 mg. 2,4-(O2N)2C6H3Cl in 2 cc. EtOH, and 1.14 cc. 2% alc. KOH yielded 25 mg. 1-(2,4-dinitrophenylamidino)-2-(2,4-dinitrophenylthiomethyl)piper-idine, brownish yellow granules, m. 185-7° (decomposition). 1-Methyl-2-piperidylmethanol (VIII) (3 g.) in 30 cc. dry Et2O and then 1.8 cc. CS2 added dropwise with cooling and stirring to 0.46 g. powd. Na in 25 cc. dry Et2O, treated with 1.24 cc. MeI in 5 cc. dry Et2O, and worked up gave 3.1 g. Me 1-methyl-2-piperidylmethyl xanthate (IX), yellow oil; picrate, yellow needles, m. 124-6° (EtOH); IX.HCl m. 134-5° (EtOH-Et2O). The alk. hydrolysis of IX yielded VIII. VIII (4 g.) heated 0.5 h. at 130° yielded 3.5 g. S-(1-methyl-2-piperidylmethyl) S’-Me dithiolcarbonate (X), light yellow oil, b1 119-20°; picrate m. 164-5° (EtOH). VIII (7 g.) in 20 cc. dry CHCl3 refluxed 3 h. with 6 cc. SOCl2 gave 7.1 g. 2-ClCH2 analog (XI) of VIII.HCl, needles, m. 159-61° (Me2CO). XI.HCl (3 g.) and 1.23 g. CS(NH2)2 in 10 cc. EtOH refluxed 4 h. yielded 2.8 g. 2-(1-methyl-2-piperidylmethyl)-2-thiopseudourea-2HCl (XII.2HCl), needles, m. 192-3° (BuOH). XII.2HCl (0.7 g.) heated 1 h. on the water bath with 5 cc. 2N NaOH and treated with a stream of air gave 0.68 g. bis(1-methyl-2-piperidylmethyl) disulfide (XIII); dipicrate m. 153-5° (MeOH). X (1 g.) and 40 cc. 5% alc. NaOH heated I hr. on the water bath, treated dropwise with 10% alc. HCl (EtSH evolved), and the crude product treated in aqueous K2CO3 with air overnight yielded 0.8 g. XIII picrate, m. 151-4° (MeOH). VIII.MeI (8 g.) and Ag2O from 12 g. AgNO3 and 20 cc. 10N NaOH stirred 5 h., filtered, and evaporated, and the residue heated 3 h. at 100° in vacuo under N gave 1 g. VIII and 1.1 g. Me2N(CH2)5CHO, b3 168-70°; picrate m. 146-8° (H2O). I (6 g.) added with cooling to 5 cc. concentrated H2SO4 and heated gradually to 240° yielded 7.4 g. 2-HO3SOCH2 analog (XIV) of I, rods, m. 262-3° (decomposition) (MeOH). XIV (6 g.) in 40 cc. H2O and 100 cc. 10% aqueous NaOH distilled and the distillate treated with solid KOH gave 0.2 g. XV, b80 65°, which polymerized completely within several hrs., even under N; XV picrate m. 151-2° (Et2O-AcOEt). XV (0.1 g.) in Et2O stirred 1 h. and treated with K2CO3, and the basic product treated with picric acid gave the picrate of I, m. 115° (EtOH-Et2O). XV (0.1 g.) in Et2O treated with dry HCl and kept overnight gave VI.HCl, m. 187-8°. XV (0.1 g.) in Et2O treated overnight with 0.1 g. MeBr in Et2O gave 0.16 g. 2-bromomethyl-1,1-dimethylpiperidinium bromide (XVI), granules, m. 230° (EtOH). XV (0.14 g.), 0.1 g. CS(NH2)2, 1.32 cc. N HCl, and 2 cc. H2O stirred a few min., treated with an addnl. 1.32 cc. N HCl, and stirred 1 h., and the crude product refluxed 1 h. in BuOH gave VII isolated as the picrate, m. 1523° (H2O). I (3 g.) in 30 cc. 48% aqueous HBr refluxed 10 h. yielded 4.1 g. 2-bromomethylpiperidine-HBr (XVII.HBr), needles, m. 188-90° (EtOH). XVII.HBr (0.5 g.) in 10 cc. Et2O treated overnight with 20 cc. 10% MeBr-Et2O gave 0.57 g. XVI, granules, m. 233-4° (decomposition) (EtOH).

Chem. Pharm. Bull. (Tokyo) published new progress about Alcohols. 27483-92-7 belongs to class piperidines, name is 2-(Chloromethyl)-1-methylpiperidine hydrochloride, and the molecular formula is C7H15Cl2N, Quality Control of 27483-92-7.

Referemce:
Piperidine – Wikipedia,
Piperidine | C5H11N – PubChem

Gomez, Elena published the artcile1,4-Dihydropicolinic acid derivatives: novel NADH analogues with an altered connectivity pattern, Synthetic Route of 1690-74-0, the main research area is alkylpyridinium reduction dithionite dihydropyridine NADH analog preparation.

Sodium dithionite reduction of α-substituted N-alkylpyridinium salts derived from picolinic acid derivatives afforded the corresponding 1,4-dihydropyridines with a new substitution pattern, in which the electron-withdrawing group is at the α-position. These compounds promote biomimetic reductions and are hence considered functional NADH analogs.

Tetrahedron Letters published new progress about Reduction. 1690-74-0 belongs to class piperidines, name is Methyl 1-methylpiperidine-2-carboxylate, and the molecular formula is C8H15NO2, Synthetic Route of 1690-74-0.

Referemce:
Piperidine – Wikipedia,
Piperidine | C5H11N – PubChem

Meenal, K. Mrs. published the artcileThallium(III) acetate oxidation of some substituted-4-piperidones: a kinetic and mechanistic study, COA of Formula: C6H11NO, the main research area is oxidation piperidone thallium 3 kinetics.

Kinetics of oxidation of 4-piperidone, 3-methyl-2,6-diphenyl-4-piperidone, 3-alkyl-, and 3,3- and 3,5-dimethylpiperidone with Tl3+ in aqueous acetic acid in the presence of sulfuric acid at constant ionic strength (μ = 2.25 M) at 30-55° have been investigated. The reactions obey second order kinetics. Dependence on acidity is unity added sodium sulfate does not have any effect. Activation parameters have been calculated and the structure-reactivity relationships discussed. A mechanism involving fast enolization step is postulated.

Journal of the Indian Chemical Society published new progress about Oxidation. 5773-58-0 belongs to class piperidines, name is 3-Methylpiperidin-4-one, and the molecular formula is C6H11NO, COA of Formula: C6H11NO.

Referemce:
Piperidine – Wikipedia,
Piperidine | C5H11N – PubChem

Zhang, Chaohong published the artcileTop-down strategy identifying molecular phase stabilizers to overcome microstructure instabilities in organic solar cells, Safety of Bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate, the main research area is organic solar cell microstructure instability mol phase stabilizer.

The operational stability of organic solar cells (OSCs) is the essential barrier to commercialization. Compared to thermally-induced degradation, photo-stability of OSCs is far away from being resolved. Here, we demonstrate that the thermal- and photo-degradation of metastable bulk-heterojunction OSCs are governed by the same mechanism. Understanding the fundamental principles behind this mechanism is of significant importance to fully address the instability issues. Structural incompatibilities between the donor and acceptor mols. are identified as the main origin of the instability. Further, we introduce a top-down approach mainly based on their melting temperature and interaction parameters to rationally screen mol. phase stabilizers from a database with more than 10 000 small mols. Eventually, five chems. were selected to validate our concept and tested in unstable organic solar cells. 1,4-Piperazine, which possesses a high m.p., good miscibility with polymers and the capability of forming inter-mol. hydrogen bonding, can indeed stabilize the mixed amorphous phases, leading to significantly improved stability of otherwise metas table OSCs.

Energy & Environmental Science published new progress about Annealing. 52829-07-9 belongs to class piperidines, name is Bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate, and the molecular formula is C28H52N2O4, Safety of Bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate.

Referemce:
Piperidine – Wikipedia,
Piperidine | C5H11N – PubChem

Zhang, Wenliang published the artcileAmine hydrochloride salts as bifunctional reagents for the radical aminochlorination of maleimides, Quality Control of 73874-95-0, the main research area is pyrrole dione phenyl chloro amino preparation green chem; maleimide amine radical oxidative aminochlorination copper catalyst.

Herein, a new utilization of amine hydrochloride as a bifunctional reagent was disclosed and demonstrated via the copper-catalyzed aminochlorination of maleimides I (R = Me, Ph, cyclohexyl, thiophen-2-ylmethyl, etc.). The prominent features of this transformation were found to include the simple and efficient catalyst system, broad substrate scope, readily scalable reaction, and late-stage modification of small-mol. drugs such as maprotiline hydrochloride, fluoxetine hydrochloride, nortropine hydrochloride, etc.

Organic Chemistry Frontiers published new progress about Amination. 73874-95-0 belongs to class piperidines, name is tert-Butyl piperidin-4-ylcarbamate, and the molecular formula is C10H20N2O2, Quality Control of 73874-95-0.

Referemce:
Piperidine – Wikipedia,
Piperidine | C5H11N – PubChem

Andrews, Jonathan A. published the artcileSulfinates from Amines: A Radical Approach to Alkyl Sulfonyl Derivatives via Donor-Acceptor Activation of Pyridinium Salts, Application of tert-Butyl piperidin-4-ylcarbamate, the main research area is alkyl sulfinate preparation photochem; Katritzky pyridinium salt preparation carbon electrophile alkylation; primary amine triphenylpyrylium tetrafluoroborate amination.

Synthetically versatile alkyl sulfinates RSO2R1 (R = cyclobutyl, Bn, pyridin-2-ylmethyl, etc.; R1 = F, 2-(tert-butoxy)-2-oxoethyl, Ph, Bn, etc.) can be prepared from readily available amines RNH2, using Katritzky pyridinium salt intermediates I. In a catalyst-free procedure, primary, secondary, and benzylic alkyl radicals are generated by photoinduced or thermally induced single-electron transfer (SET) from an electron donor-acceptor (EDA) complex, and trapped by SO2 to generate sulfonyl radicals. Hydrogen atom transfer (HAT) from Hantzsch ester gives alkyl sulfinate products, which are used to prepare a selection of medicinal chem. relevant sulfonyl-containing motifs.

Organic Letters published new progress about Amination. 73874-95-0 belongs to class piperidines, name is tert-Butyl piperidin-4-ylcarbamate, and the molecular formula is C10H20N2O2, Application of tert-Butyl piperidin-4-ylcarbamate.

Referemce:
Piperidine – Wikipedia,
Piperidine | C5H11N – PubChem

Chen, Kai published the artcileCatalytic Amination of Phenols with Amines, Quality Control of 73874-95-0, the main research area is aryl amine preparation; phenol amine amination rhodium catalyst.

Herein, a rhodium-catalyzed amination of phenols, which provided concise access to diverse anilines, with water as the sole byproduct was described. The arenophilic rhodium catalyst facilitated the inherently difficult keto-enol tautomerization of phenols by means of π-coordination, allowing for the subsequent dehydrative condensation with amines. The generality of this redox-neutral catalysis by carrying out reactions of a large array of phenols with various electronic properties and a wide variety of primary and secondary amines was demonstrated. Several examples of late-stage functionalization of structurally complex bioactive mols., including pharmaceuticals, further illustrated the potential broad utility of the method.

Journal of the American Chemical Society published new progress about Amination. 73874-95-0 belongs to class piperidines, name is tert-Butyl piperidin-4-ylcarbamate, and the molecular formula is C10H20N2O2, Quality Control of 73874-95-0.

Referemce:
Piperidine – Wikipedia,
Piperidine | C5H11N – PubChem

Zhou, Xueying published the artcileCu-catalyzed vinylamination of S-alkylisothiouronium salts with maleimides and alkylamines, HPLC of Formula: 73874-95-0, the main research area is aminoalkylthiolated maleimide preparation; alkylisothiouronium salt maleimide alkylamine vinylamination copper catalyst.

A copper-catalyzed vinylamination of S-alkylisothiouronium salts with maleimide and organic amines with the assistance of FeCl3, enabling the preparation of structurally diverse aminoalkylthiolated maleimides and applying them to late-stage modification of pharmaceuticals is reported. Importantly, this strategy makes it possible to introduce the SCD3 functional group into the maleimide skeleton by using the prepared S-trideuteromethyl isothiouronium iodide. Preliminary mechanistic investigation shows that FeCl3 is essential to the current multi-component reaction by triggering S-alkylisothiouronium salts.

Applied Organometallic Chemistry published new progress about Amination. 73874-95-0 belongs to class piperidines, name is tert-Butyl piperidin-4-ylcarbamate, and the molecular formula is C10H20N2O2, HPLC of Formula: 73874-95-0.

Referemce:
Piperidine – Wikipedia,
Piperidine | C5H11N – PubChem

Kathiravan, Subban published the artcileElectrooxidative Amination of sp2 C-H Bonds: Coupling of Amines with Aryl Amides via Copper Catalysis, Application In Synthesis of 73874-95-0, the main research area is electrooxidative amination amine aryl amide; copper catalyzed cross coupling amine aryl amide.

Metal-catalyzed cross-coupling reactions are among the most important transformations in organic synthesis. However, the use of C-H activation for sp2 C-N bond formation remains one of the major challenges in the field of cross-coupling chem. Described herein is the first example of the synergistic combination of copper catalysis and electrocatalysis for aryl C-H amination under mild reaction conditions in an atom-and step-economical manner with the liberation of H2 as the sole and benign byproduct.

Organic Letters published new progress about Amination. 73874-95-0 belongs to class piperidines, name is tert-Butyl piperidin-4-ylcarbamate, and the molecular formula is C10H20N2O2, Application In Synthesis of 73874-95-0.

Referemce:
Piperidine – Wikipedia,
Piperidine | C5H11N – PubChem

Onodera, Toshiharu published the artcilePEGylated AdipoRon derivatives improve glucose and lipid metabolism under insulinopenic and high-fat diet conditions, HPLC of Formula: 73874-95-0, the main research area is adiponectin glucose lipid metabolism insulinopenic high fat diet; INS-1 beta cells; adiponectin; ceramides; diabetes; drug optimization; drug therapy/hypolipidemic drugs; high-fat diet; insulin resistance; lipid metabolism; sphingosine-1-phosphate.

The pleiotropic actions of adiponectin in improving cell survival and metabolism have motivated the development of small-mol. therapeutic agents for treating diabetes and lipotoxicity. AdipoRon is a synthetic agonist of the adiponectin receptors, yet is limited by its poor solubility and bioavailability. In this work, we expand on the protective effects of AdipoRon in pancreatic β-cells and examine how structural modifications could affect the activity, pharmacokinetics, and bioavailability of this small mol. We describe a series of AdipoRon analogs containing amphiphilic ethylene glycol (PEG) chains. Among these, AdipoRonPEG5 induced pleiotropic effects in mice under insulinopenic and high-fat diet (HFD) conditions. While both AdipoRon and AdipoRonPEG5 substantially attenuate palmitate-induced lipotoxicity in INS-1 cells, only AdipoRonPEG5 treatment is accompanied by a significant reduction in cytotoxic ceramides. In vivo, AdipoRonPEG5 can substantially reduce pancreatic, hepatic, and serum ceramide species, with a concomitant increase in the corresponding sphingoid bases and improves insulin sensitivity of mice under HFD feeding conditions. Furthermore, hyperglycemia in streptozotocin (STZ)-induced insulinopenic adiponectin-null mice is also attenuated upon AdipoRonPEG5 treatment. Our results suggest that AdipoRonPEG5 is more effective in reducing ceramides and dihydroceramides in the liver of HFD-fed mice than AdipoRon, consistent with its potent activity in activating ceramidase in vitro in INS-1 cells. Addnl., these results indicate that the beneficial effects of AdipoRonPEG5 can be partially attributed to improved pharmacokinetics as compared with AdipoRon, thus suggesting that further derivatization may improve affinity and tissue-specific targeting.

Journal of Lipid Research published new progress about Adipocyte. 73874-95-0 belongs to class piperidines, name is tert-Butyl piperidin-4-ylcarbamate, and the molecular formula is C10H20N2O2, HPLC of Formula: 73874-95-0.

Referemce:
Piperidine – Wikipedia,
Piperidine | C5H11N – PubChem