Month: November 2022

Vil’yams, V. V. published the artcileThe ring isomerization in some nitrogen-containing heterocyclic compounds. Synthesis of amino and hydroxy derivatives of β-methylpiperidine, Formula: C7H16N2, the publication is Dokl., Rossiisk. Sel’skokhoz. Akad. (1964), 553-7, database is CAplus.

The synthesis of 1-methyl-3-(aminomethyl)piperidine (I) and 3-piperidinylmethanol (II) was described. A mixture of 61 g. nicotinamide, 106.5 g. MeI, 200 ml. MeOH, and a trace of nicotinamide methiodide was refluxed 3 hrs., the solution evaporated in vacuo, the residue dissolved in 150 ml. H₂O and boiled with freshly prepared AgCl (from 120 g. AgNO₃ and 42 g. NaCl) for 5 hrs. The reaction mixture was filtered (charcoal) and hydrogenated over 0.4 g. PtO₂ 36 hrs. at 3.5-1.5 atm. to give 87% nipecotamide methochloride (III), m. 239°. III heated with an equal amount P₂O₅ 5 hrs. at 180°, treated with hot H₂O, neutralized with K₂CO₃, and extracted with AcOEt yielded 76% 1-methyl-3-cyanopiperidine (IV), b₂₃ 106°, b₁₄ 92°, n²⁰_D 1.4630, d²⁰₂₀ 0.9560, surface tension σ₂₀ 34.34 ergs/cm.² To a solution of 6.5 g. LiAlH₄ in 600 ml. absolute Et₂O at 0°, a solution of 25 g. IV in 200 ml. absolute Et₂O was added dropwise during 2 hrs., and the mixture left overnight at room temperature and then refluxed 1.5 hrs. After the usual treatment, 89% I was obtained, b₄ 52°, n²⁰_D 1.4739, d²⁰₂₀ 0.9096, σ₂₀ 32.67 ergs/cm.² [I.PtCl₆ m. 212° (decomposition); I.(AuCl₄)₂ m. 177° (decomposition); picrate m. 234° (decomposition)]. A solution of 30.2 g. Et nicotinate (b₃ 77-80°, n¹⁶_D 1.504, d¹⁶₁₆ 1.1136, σ₂₀ 37.23 ergs/cm.²) in 600 ml. absolute EtOH was added to 62 g. Na, the reaction completed by short refluxing, and the solution decomposed by addition of 150 ml. H₂O, concentrated in vacuo, and extracted with AcOEt. After fractionation, 57% II was obtained, b₃ 103-4°, n²⁰_D 1.4971, d²⁰₂₀ 1.0283, σ₂₀ 44.39 ergs/cm.²

Dokl., Rossiisk. Sel’skokhoz. Akad. published new progress about 14613-37-7. 14613-37-7 belongs to piperidines, auxiliary class Piperidine,Amine, name is (1-Methylpiperidin-3-yl)methanamine, and the molecular formula is C3H6O2, Formula: C7H16N2.

Referemce:
https://en.wikipedia.org/wiki/Piperidine,
Piperidine | C5H11N – PubChem

Grandberg, I. I. published the artcileDemjanov rearrangement in a series of nitrogenous heterocycles, Application In Synthesis of 14613-37-7, the publication is Doklady TSKhA (1970), 226-31, database is CAplus.

Three isomeric compounds, 2-, 3- and 4-aminomethyl-N-methylpiperidine, were diazotized and the degradation products obtained at 0°, pH 5.5, separated and identified. The 2-substituted derivative gave 2-hydroxymethyl-N-methylpiperidine, 6-methylaminohexan-2-one, 1,2-dimethylpiperidin-2-one, and 2,3-dehydro-1-methylhexamethylenimine in the proportion 49:16:-26:9. The 3-substituted derivative gave 3-hydroxymethyl-N-methylpiperidine, 3(4)-hydroxy-1-methylhexamethylenimine, 1,-3-dimethyl-3-hydroxypiperidine, 2 unsaturated piperidine derivatives (estimated together) and an unsaturated hexamethylenimine derivatives in the proportion 62:2:14:16:6. The ratios of corresponding products with the 4-substituted derivative were 38:1:39:16:6. Two mechanisms based on the conformation of the piperidine ring are proposed to explain the unusually low ratio of rearrangement products and the predominance of H over C atom migration in these reactions.

Doklady TSKhA published new progress about 14613-37-7. 14613-37-7 belongs to piperidines, auxiliary class Piperidine,Amine, name is (1-Methylpiperidin-3-yl)methanamine, and the molecular formula is C7H16N2, Application In Synthesis of 14613-37-7.

Referemce:
https://en.wikipedia.org/wiki/Piperidine,
Piperidine | C5H11N – PubChem

Wang, Xiaolei published the artcileEfficient activation of peroxymonosulfate by copper sulfide for diethyl phthalate degradation: Performance, radical generation and mechanism, HPLC of Formula: 826-36-8, the publication is Science of the Total Environment (2020), 142387, database is CAplus and MEDLINE.

Copper-containing minerals have been extensively used in Fenton-like processes for degradation of pollutants and have exhibited great potential for environmental remediation. This work reports the first use of copper sulfide (CuS), a typical Cu-mineral, for the activation of peroxymonosulfate (PMS) for pollutant degradation; the study also elucidates the underlying mechanism of these processes. Copper sulfide effectively activated PMS to degrade di-Et phthalate (DEP). ESR, free radical quenching, XPS, X-ray diffraction analyses and DFT calculations confirmed that Ξ Cu (I)/ ΞCu (II) cycling on the surface of CuS provided the main pathway to activate PMS to produce highly oxidative species. Unlike conventional sulfate radical-based PMS activation processes, hydroxyl radical (·OH) were found to be the dominant radical in the tested CuS/PMS system, which performed more efficiently than an alternative ·OH-based oxidation system (CuS/H₂O₂) for DEP degradation In addition, the presence of anions such Cl- and NO^-3 has limited inhibition effects on DEP degradation Overall, this study provides an efficient pathway for PMS-based environmental remediation as well as a new insight into the mechanism of PMS activation by Cu-containing minerals.

Science of the Total Environment published new progress about 826-36-8. 826-36-8 belongs to piperidines, auxiliary class Natural product, name is 2,2,6,6-Tetramethylpiperidin-4-one, and the molecular formula is C6H10O7, HPLC of Formula: 826-36-8.

Referemce:
https://en.wikipedia.org/wiki/Piperidine,
Piperidine | C5H11N – PubChem

Yang, Xianglong published the artcileSuperoxide anion and singlet oxygen dominated faster photocatalytic elimination of nitric oxide over defective bismuth molybdates heterojunctions, Quality Control of 826-36-8, the publication is Journal of Colloid and Interface Science (2022), 248-258, database is CAplus and MEDLINE.

Establishing an ideal photocatalytic system with efficient reactive oxygen species (ROS) generation has been regarded as the linchpin for realizing efficient nitric oxide (NO) removal and unveiling the ROS-mediated mechanism. In this work, a novel oxygen-deficient 0D/1D Bi_3.64Mo_0.36O_6.55/Bi₂MoO₆ heterojunctions (BMO-12-H) were successfully synthesized under the enlightenment of clarified crystal growth mechanism of bismuth molybdates. Because of the synergies between defect-engineering and heterojunction-construction, BMO-12-H demonstrated improved photoelectrochem. properties and O₂ adsorption capacity, which in turn facilitated the ROS generation and conversion. The enhancement of •O_-2 and ¹O₂ endowed BMO-12-H with strengthened NO removal efficiency (59%) with a rate constant of 12.6*10^-2 min^-1. A conceivable NO removal mechanism dominated by •O_-2 and ¹O₂ was proposed and verified based on the theor. calculations and in-situ IR spectroscopy tests, where hazardous NO was oxidized following two different exothermic pathways: the •O_-2-induced NO → NO_-3 process and the ¹O₂-induced NO → NO₂ → NO_-3 process. This work offers a basic guideline for accelerating ROS generation by integrating defect-engineering and heterojunction-construction, and provides new insights into the mechanism of efficient NO removal dominated by •O_-2 and ¹O₂.

Journal of Colloid and Interface Science published new progress about 826-36-8. 826-36-8 belongs to piperidines, auxiliary class Natural product, name is 2,2,6,6-Tetramethylpiperidin-4-one, and the molecular formula is C10H10CoF6P, Quality Control of 826-36-8.

Referemce:
https://en.wikipedia.org/wiki/Piperidine,
Piperidine | C5H11N – PubChem

Herbrandson, Harry F. published the artcileDerivatives of aromatic sulfinic acids. II. The reaction of thionyl chloride with sulfinic esters, Safety of 1-(Phenylsulfinyl)piperidine, the publication is Journal of the American Chemical Society (1956), 2576-8, database is CAplus.

cf. C.A. 49, 9370i. PhSOCl (22.5 g.) added to 11.1 g. dry pyridine and 5 g. absolute MeOH in 60 cc. dry Et₂O, the mixture kept at -10° until no more precipitate was formed, and diluted with H₂O, the Et₂O layer washed, dried, and evaporated, and the residue distilled yielded 14.0 g. PhSO₂Me (I), b_0.04 67-8°, b_0.03 63°, n_D²⁰ 1.5400. In the same manner was prepared p-MeC₆H₄SO₂Me (II), 91%, b_0.001 68°, n_D²⁰ 1.5380. II (20.1 g.) and 14.0 g. pure SOCl₂ kept a few days in the dark and distilled gave 3.5 g. ClCO₂Me, b. 104-6°, n_D²⁰ 1.4629, and 18.7 g. p-MeC₆H₄SOCl, lemon-yellow oil, b_0.012 79°, n_D²⁰ 1.6007; it gave with NH₃ in dry Et₂O the p-MeC₆H₄SONH₂, m. 120-20.5° (from aqueous EtOH). I gave in the same manner 84% PhSOCl, yellow oil, b_0.012 65° [PhSONH₂, m. 122° (from aqueous EtOH); piperidide, m. 82-3° (from petr. ether)]. l-Menthyl 1-p-toluenesulfinate (III), m. 106-7° (corrected), [α]_D²⁵ -199.19° (c 2, Me₂CO), was prepared by the method of Phillips (C.A. 20, 397). Et₄NBr in H₂O treated with a slight excess Ag₂O, the mixture triturated twice, and the filtrate acidified to Congo red with 20% HCl and evaporated gave Et₄NCl (IV). A series of kinetic runs was carried out with III and SOCl₂ in PhNO₂ at 24.88 ± 0.05° (molar concentrations of IV, SOCl₂, and IV, and k × 10⁴ sec.^-1 given): 0.0554, 0.0616, 0.00093, 0.62; 0.0551, 0.0616, 0.00-213, 1.18; 0.0626, 0.0616, 0.00309, 1.68; 0.0590, 0.123, 0.00309, 1.92; 0.0516, 0.0616, 0.00425, 2.30; 0.0604, 0.0616, 0.00463, 2.06; 0.0779, 0.0616, 0.00463, 2.12; 0.0520, 0.0616, 0.00850, 3.55; 0.0409, 0.0616, 0.0106, 3.80; 0.0635, 0.0616, 0.0160, 4.28; 0.0548, 0.0492, 0.0213, 3.82; 0.0423, 0.0492, 0.0213, 4.24; 0.0774, 0.123, 0, 0; 0.0542, 0, 0.00617, 0; 0.0845, 0, 0.0213,0; 0.0663, 0, – (0.00525 HCl), 0; 0.0594, 0.0616, – (0.00525 HCl), 0; 0.0510, 0.0616, 0.00378 (MeOH), 0; 0.0408, 0.0616, – (0.0035 H₂O), 0; 0.0732, 0.0860, 0.0232, 7.30; 0.0703, 0.0860, 0.0232 + 0.1M SO₂, 7.63. In the absence of added chloride the reaction is slow; it is 1st order in ester and 1st order in added chloride ion. Trace impurities of the SOCl₂, probably mainly HCl, also affect the rate.

Journal of the American Chemical Society published new progress about 4972-31-0. 4972-31-0 belongs to piperidines, auxiliary class Piperidine,Benzene, name is 1-(Phenylsulfinyl)piperidine, and the molecular formula is C11H15NOS, Safety of 1-(Phenylsulfinyl)piperidine.

Referemce:
https://en.wikipedia.org/wiki/Piperidine,
Piperidine | C5H11N – PubChem

Mohd Sarofil, Anith Dzhanxinah published the artcileToad egg-like bismuth nanoparticles encapsulated in an N-doped carbon microrod via supercritical acetone as anodes in lithium-ion batteries, Computed Properties of 826-36-8, the publication is Journal of Industrial and Engineering Chemistry (Amsterdam, Netherlands) (2022), 128-141, database is CAplus.

A toad egg-inspired structure comprising bismuth (Bi) nanoparticles (NPs) contained in a carbon microrod shell (Bi@C) was synthesized via the one-pot supercritical acetone (scAct) route and subsequent carbonization. During the formation of Bi NPs in scAct in the presence of nitric acid, a few decomposed acetone mols. acted as carbon sources, which generated an albumen-like N-doped carbon microrod with an average shell thickness of 38 nm and were embedded with yolk-like Bi NPs having size in the range of 30-200 nm. The densely packed Bi NPs inside the carbon micron shell resulted in a high Bi loading of 78 wt%. When utilized for Li storage, the Bi@C delivered a high reversible capacity of 337 mAh g^-1 after 70 cycles at 0.05 A g^-1, long-term cyclability of 0.04 decay per cycle for 1000 cycles at 1 A g^-1, and high volumetric energy d. of 870 mAh cm^-3. The use of a mixed ether- and ester-based electrolyte in the Bi@C cell reduced the resistivity and increased the capacitive contribution, thereby resulting in a better high-rate performance and long-term stability than those obtained using conventional ester-based electrolytes.

Journal of Industrial and Engineering Chemistry (Amsterdam, Netherlands) published new progress about 826-36-8. 826-36-8 belongs to piperidines, auxiliary class Natural product, name is 2,2,6,6-Tetramethylpiperidin-4-one, and the molecular formula is C9H17NO, Computed Properties of 826-36-8.

Referemce:
https://en.wikipedia.org/wiki/Piperidine,
Piperidine | C5H11N – PubChem

Johannes, Jeffrey W. published the artcileStructure-Based Design of Selective Noncovalent CDK12 Inhibitors, Safety of (R,E)-N-(4-(3-((5-Chloro-4-(1H-indol-3-yl)pyrimidin-2-yl)amino)piperidine-1-carbonyl)phenyl)-4-(dimethylamino)but-2-enamide, the publication is ChemMedChem (2018), 13(3), 231-235, database is CAplus and MEDLINE.

Cyclin-dependent kinase (CDK) 12 knockdown via siRNA decreases the transcription of DNA-damage-response genes and sensitizes BRCA wild-type cells to poly(ADP-ribose) polymerase (PARP) inhibition. To recapitulate this effect with a small mol., we sought a potent, selective CDK12 inhibitor. Crystal structures and modeling informed hybridization between dinaciclib and SR-3029, resulting in lead compound 5 [(S)-2-(1-(6-(((6,7-difluoro-1H-benzo[d]imidazol-2-yl)methyl)amino)-9-ethyl-9H-purin-2-yl)piperidin-2-yl)ethan-1-ol]. Further structure-guided optimization delivered a series of selective CDK12 inhibitors, including compound 7 [(S)-2-(1-(6-(((6,7-difluoro-1H-benzo[d]imidazol-2-yl)methyl)amino)-9-isopropyl-9H-purin-2-yl)piperidin-2-yl)ethan-1-ol]. Profiling of this compound across CDK9, 7, 2, and 1 at high ATP concentration, single-point kinase panel screening against 352 targets at 0.1 μM, and proteomics via kinase affinity matrix technol. demonstrated the selectivity. This series of compounds inhibits phosphorylation of Ser2 on the C-terminal repeat domain of RNA polymerase II, consistent with CDK12 inhibition. These selective compounds were also acutely toxic to OV90 as well as THP1 cells.

ChemMedChem published new progress about 1702809-17-3. 1702809-17-3 belongs to piperidines, auxiliary class Cell Cycle,CDK, name is (R,E)-N-(4-(3-((5-Chloro-4-(1H-indol-3-yl)pyrimidin-2-yl)amino)piperidine-1-carbonyl)phenyl)-4-(dimethylamino)but-2-enamide, and the molecular formula is C30H32ClN7O2, Safety of (R,E)-N-(4-(3-((5-Chloro-4-(1H-indol-3-yl)pyrimidin-2-yl)amino)piperidine-1-carbonyl)phenyl)-4-(dimethylamino)but-2-enamide.

Referemce:
https://en.wikipedia.org/wiki/Piperidine,
Piperidine | C5H11N – PubChem

Sugasawa, Shigehiko published the artcileSynthesis of piperidine derivatives, Safety of (1-Methylpiperidin-3-yl)methanamine, the publication is Yakugaku Zasshi (1956), 968-70, database is CAplus.

4-MeO₂CC₅H₄N (60 g.) and 60 ml. 28% NH₄OH at 0° saturated with NH₃ gas, kept overnight and the product recrystallized from EtOH gave 44.2 g. 4-H₂NOCC₅H₄N (I), m. 152-5°. I or 3-H₂NCOC₅H₄N (10 g.), 17.5 g. MeI, and 30 ml. MeOH refluxed 5 hrs., the MeI and MeOH removed in vacuo, the residue in 30 ml. water converted to its acid chloride by usual method, reduced with PtO₂ and H until absorption of 3 moles H, and the product concentrated and recrystallized from EtOH yielded about 85% 1,x-Me(H₂NOC)C₅H₉N.HCl (II, x = 3, m. 232°; x = 4, hygroscopic). II (7 g.) and 7 g. P₂O₅ heated 3 hrs. at 160-80°, cooled, 50 ml. water added, neutralized with K₂CO₃ and the product extracted with AcOEt yielded about 80% 1,x-Me(NC)C₅H₉N (III, x = 3, b₂₀ 95-6°; x = 4, b₂₁ 97°). LiAlH₄ (1.3 g.) and 150 ml. Et₂O at 0° treated dropwise with 5 g. III in 50 ml. Et₂O, stirred 1.5 hrs., refluxed 30 min., cooled, 15 ml. water added, the precipitate filtered off, treated with 50 ml. 20% Rochelle salt solution, extracted with Et₂O, the Et₂O layer and the Et₂O extract combined and distilled yielded about 90% 1,x-Me(H₂NCH₂)C₅H₉N {IV, x = 3, b₂₀ 81-2° [dipicrate, m. 231° (decomposition)]; x = 4, b₂₀ 80-1° [dipicrate, m. 236° (decomposition)]}. KOH (32 g.) in 400 ml. water treated with 6.4 g. Br, the solution at 0° treated with 5.7 g. II in a small amount of water, heated 1 hr. at 70°, made strongly alk. with KOH, the product steam distilled into dilute HCl, the solution concentrated, made alk. with KOH and extracted with Et₂O yielded about 65% 1,x-Me(H₂N)C₅H₉N {V, x = 3, b₄₃ 74-5° [dipicrate, m. 277° (decomposition)]; x = 4, b₃₅, 70-1° [dipicrate, m. 263° (decomposition)]}. R₂NH (0.6 mole) in 200 ml. PhMe poured dropwise into 50% COCl₂, refluxed 1 hr. and the product distd, yielded 71% R₂NCOCl (VI, R = Me, b_55-60 85-8°; R = Et, b_17-20 80°). IV or V (2 moles) and 1 mole VI in Et₂O mixed at 0°, let stand 1.5 hrs. at room temperature, refluxed 10 min., the solution filtered and the filtrate concd, gave 1,x-Me[R₂NCONH(CH₂)_n]C₅H₉N (x, n, R, and m.p. given): 4, 1, Me, 40-4° [HCl salt, 230° (decomposition)]; 4, 1, Et, 66-8°; 4, 0, Me, 138-9°; 4, 0, Et, 89-90°; 3, 1, Me, 66-9°; 3, 1, Et, -(sirup); 3, 0, Me, 110-2°; 3, 0, Et, -(sirup) (picrolonate, m. 195-7°).

Yakugaku Zasshi published new progress about 14613-37-7. 14613-37-7 belongs to piperidines, auxiliary class Piperidine,Amine, name is (1-Methylpiperidin-3-yl)methanamine, and the molecular formula is C17H16O2, Safety of (1-Methylpiperidin-3-yl)methanamine.

Referemce:
https://en.wikipedia.org/wiki/Piperidine,
Piperidine | C5H11N – PubChem

Crich, David published the artcileSynthesis of the mannosyl erythritol lipid MEL A; confirmation of the configuration of the meso-erythritol moiety, Application In Synthesis of 4972-31-0, the publication is Tetrahedron (2002), 58(1), 35-44, database is CAplus.

The total synthesis of the two possible diastereomers of mannosylerythritol lipid A, a novel biosurfactant from Candida antarctica T-34 with promising anti-proliferative properties in several cell lines, is described. By comparison with an authentic sample, the natural material is confirmed as a single diastereomer with the 4-O-(β-D-mannopyranosyl)-D-erythritol configuration.

Tetrahedron published new progress about 4972-31-0. 4972-31-0 belongs to piperidines, auxiliary class Piperidine,Benzene, name is 1-(Phenylsulfinyl)piperidine, and the molecular formula is C11H15NOS, Application In Synthesis of 4972-31-0.

Referemce:
https://en.wikipedia.org/wiki/Piperidine,
Piperidine | C5H11N – PubChem

Crich, David published the artcileInfluence of the 4,6-O-benzylidene, 4,6-O-phenylboronate, and 4,6-O-polystyrylboronate protecting groups on the stereochemical outcome of thioglycoside-based glycosylations mediated by 1-benzenesulfinyl piperidine/triflic anhydride and N-iodosuccinimide/trimethylsilyl triflate, Category: piperidines, the publication is Journal of Organic Chemistry (2003), 68(21), 8142-8148, database is CAplus and MEDLINE.

The effect of 4,6-O-benzylidene acetals, 4,6-O-phenylboronate esters, and 4,6-O-polystyrylboronate esters on the stereoselectivity of couplings to galacto-, gluco-, and mannopyranosyl thioglycosides, otherwise protected with benzyl ethers, has been investigated by the benzenesulfinyl piperidine/trifluoromethanesulfonic anhydride (BSP), di-Ph sulfoxide/trifluoromethanesulfonic anhydride (Ph₂SO), and N-iodosuccinimide/trimethylsilyl trifluoromethanesulfonate (NIS/TMSOTf) methods. The BSP and Ph₂SO methods give comparable results in all three systems whereas the NIS method affords significantly different stereoselectivities in both the gluco and manno, but not the galacto series. The benzylidene acetal and boronate esters influence the stereochem. in a similar manner in the β-selective manno series and the α-selective galacto series but show significant differences with the glucose donors. The differences between the glucose, galactose, and mannose series reflect the established differences in reactivity and, especially for mannose, those in the anomeric effect and are best interpreted in terms of changes in the relative energetics between the α- and β-covalent triflate intermediates and the various contact ion pairs with which they are necessarily in equilibrium

Journal of Organic Chemistry published new progress about 4972-31-0. 4972-31-0 belongs to piperidines, auxiliary class Piperidine,Benzene, name is 1-(Phenylsulfinyl)piperidine, and the molecular formula is C11H15NOS, Category: piperidines.

Referemce:
https://en.wikipedia.org/wiki/Piperidine,
Piperidine | C5H11N – PubChem