The equimolar mixture of N‐(hydroxyalkyl)pyrazoles and borane formed boric ester complex, in which the remaining borane was stabilized by the adjacent nitrogen of thr pyrazole ring. The borane complex derived from the chiral pyrazoles such as 3‐phenyl‐l‐menthopyrazole reduced p‐methylacetophenone ( 21 ) enantioselectively. When (2′S)‐2‐(2′‐phenyl‐2′‐hydroxyethyl)‐3‐phenyl‐l‐menthopyrazole ((2′S)‐ 10b ) was used, 21 was reduced into (S)‐p‐methylphenyl‐1‐ethanol ( 22 ) in moderate chemical and optical yields. Due to the inconvenience of the preparation and the lower optical yield, the use of N‐(α‐hydroxyalkyl)pyrazoles was unpromising for the enantioselective reduction of ketones by borane. 相似文献
Herein, the reaction between CO2 and piperidine, as well as commercially available functionalised piperidine derivatives, for example, those with methyl‐, hydroxyl‐ and hydroxyalkyl substituents, has been investigated. The chemical reactions between CO2 and the functionalised piperidines were followed in situ by using attenuated total reflectance (ATR) FTIR spectroscopy. The effect of structural variations on CO2 absorption was assessed in relation to the ionic reaction products identifiable by IR spectroscopy, that is, carbamate versus bicarbonate absorbance, CO2 absorption capacity and the mass‐transfer coefficient at zero loading. On absorption of CO2, the formation of the carbamate derivatives of the 3‐ and 4‐hydroxyl‐, 3‐ and 4‐hydroxymethyl‐, and 4‐hydroxyethyl‐substituted piperidines were found to be kinetically less favourable than the carbamate derivatives of piperidine and the 3‐ and 4‐methyl‐substituted piperidines. As the CO2 loading of piperidine and the 3‐ and 4‐methyl‐ and hydroxyalkyl‐substituted piperidines exceeded 0.5 moles of CO2 per mole of amine, the hydrolysis of the carbamate derivative of these amines was observed in the IR spectra collected. From the subset of amines analysed, the 2‐alkyl‐ and 2‐hydroxyalkyl‐substituted piperidines were found to favour bicarbonate formation in the reaction with CO2. Based on IR spectral data, the ability of these amines to form the carbamate derivatives was also established. Computational calculations at the B3LYP/6‐31+G** and MP2/6‐31+G** levels of theory were also performed to investigate the electronic/steric effects of the substituents on the reactivity (CO2 capture performance) of different amines, as well as their carbamate structures. The theoretical results obtained for the 2‐alkyl‐ and 2‐hydroxyalkyl‐substituted piperidines suggest that a combination of both the electronic effect exerted by the substituent and a reduction in the exposed area of the nitrogen atom play a role in destabilising the carbamate derivative and increasing its susceptibility to hydrolysis. A theoretical investigation into the structure of the carbamate derivatives of these amines revealed shorter N? C bond lengths and a less‐delocalised electron distribution in the carboxylate moiety. 相似文献
Summary: Poly(alkylene hydrogen phosphonate)s with a number‐average molecular weight of about 3 000 Da were obtained by a transesterification of dimethyl hydrogen phosphonate with poly(ethylene glycol) (PEG 400) under microwave irradiation with a very short reaction time (55 min) relative to that of classical thermal heating (9 h). The structure of the resulting polymer was confirmed by 1H, 31P, and 13C NMR spectroscopy. The molecular weight was determined by 1H, 31P{H} NMR spectroscopy, MALDI‐TOF, and GPC.
The transesterification of dimethyl hydrogen phosphonate with poly(ethylene glycol). 相似文献
Dedicated to Dr. János Császár on the occasion of his 70th birthday Ring transformation of 2‐cyanoimido‐3‐methyl‐1,3‐oxazolidine ( 10 ) yielded 5‐amino‐3‐[N‐(2‐hydrox‐yethyl)‐N‐methyl]amino‐1H‐1,2,4‐triazole ( 6 ) that was ring closed with different β‐keto esters to 2‐[N‐(2‐hydroxyethyl)‐N‐methyl]amino‐1,2,4‐triazolo[1,5‐a]pyrimidinones ( 4 ). Cyclisation of derivatives 4 led to imidazo[2′,1′:3,4][1,2,4]triazolo[1,5‐a]pyrimidines ( 2 ) and imidazo[1′,2′:2,3][1,2,4]triazolo[1,5‐a]pyrim‐idines ( 3 ) representing 10 novel ring systems. Besides spectroscopical evidence of structure of derivatives 2 and 3 X‐ray diffraction analysis of derivative 2b was also performed. 相似文献
The reaction of 5‐chloro‐3‐methyl‐1‐phenyl‐1H‐pyrazole‐4‐carbaldehyde and N‐benzylmethylamine under microwave irradiation gives 5‐[benzyl(methyl)amino]‐3‐methyl‐1‐phenyl‐1H‐pyrazole‐4‐carbaldehyde, C19H19N3O, (I). Subsequent reactions under basic conditions, between (I) and a range of acetophenones, yield the corresponding chalcones. These undergo cyclocondensation reactions with hydrazine to produce reduced bipyrazoles which can be N‐formylated with formic acid or N‐acetylated with acetic anhydride. The structures of (I) and of representative examples from this reaction sequence are reported, namely the chalcone (E )‐3‐{5‐[benzyl(methyl)amino]‐3‐methyl‐1‐phenyl‐1H‐pyrazol‐4‐yl}‐1‐(4‐bromophenyl)prop‐2‐en‐1‐one, C27H24BrN3O, (II), the N‐formyl derivative (3RS )‐5′‐[benzyl(methyl)amino]‐3′‐methyl‐1′,5‐diphenyl‐3,4‐dihydro‐1′H ,2H‐[3,4′‐bipyrazole]‐2‐carbaldehyde, C28H27N5O, (III), and the N‐acetyl derivative (3RS )‐2‐acetyl‐5′‐[benzyl(methyl)amino]‐5‐(4‐methoxyphenyl)‐3′‐methyl‐1′‐phenyl‐3,4‐dihydro‐1′H ,2H‐[3,4′‐bipyrazole], which crystallizes as the ethanol 0.945‐solvate, C30H31N5O2·0.945C2H6O, (IV). There is significant delocalization of charge from the benzyl(methyl)amino substituent onto the carbonyl group in (I), but not in (II). In each of (III) and (IV), the reduced pyrazole ring is modestly puckered into an envelope conformation. The molecules of (I) are linked by a combination of C—H…N and C—H…π(arene) hydrogen bonds to form a simple chain of rings; those of (III) are linked by a combination of C—H…O and C—H…N hydrogen bonds to form sheets of R 22(8) and R 66(42) rings, and those of (IV) are linked by a combination of O—H…N and C—H…O hydrogen bonds to form a ribbon of edge‐fused R 24(16) and R 44(24) rings. 相似文献
A new synthetic route to 6‐substituted‐imidazo[4,5‐c]pyridin‐2‐ons from 4‐aminopyridine has been investigated. 4‐Aminopyridine protected as alkyl carbamates were nitrated with dinitrogen pentoxide to the corresponding methyl, i‐propyl and t‐butyl 3‐nitropyridin‐4‐yl carbamates ( 5a‐c ) in 51‐63 % yields. Attempts to substitute these in the 6‐position by the ONSH and the VNS techniques succeeded with butyl‐amine and the t‐butyl carbamate 9 . From the methyl or t‐butyl 3‐nitropyridin‐4‐yl carbamates 5a, 5c 1,3‐dihydro‐2H‐imidazo[4,5‐c]pyridin‐2‐one ( 1 ) was formed in 73 and 39 % yields, respectively. t‐Butyl 6‐N‐butylamin‐3‐aminopyridin‐4‐yl carbamate ( 6 ) gave 6‐butylamino‐1,3‐dihydro‐2H‐imidazo[4,5‐c]‐pyridin‐2‐one (7) in 53 % yield. 相似文献
The title compounds, rac‐(1′R,2R)‐tert‐butyl 2‐(1′‐hydroxyethyl)‐3‐(2‐nitrophenyl)‐5‐oxo‐2,5‐dihydro‐1H‐pyrrole‐1‐carboxylate, C17H20N2O6, (I), rac‐(1′S,2R)‐tert‐butyl 2‐[1′‐hydroxy‐3′‐(methoxycarbonyl)propyl]‐3‐(2‐nitrophenyl)‐5‐oxo‐2,5‐dihydro‐1H‐pyrrole‐1‐carboxylate, C20H24N2O8, (II), and rac‐(1′S,2R)‐tert‐butyl 2‐(4′‐bromo‐1′‐hydroxybutyl)‐5‐oxo‐2,5‐dihydro‐1H‐pyrrole‐1‐carboxylate, C13H20BrNO4, (III), are 5‐hydroxyalkyl derivatives of tert‐butyl 2‐oxo‐2,5‐dihydropyrrole‐1‐carboxylate. In all three compounds, the tert‐butoxycarbonyl (Boc) unit is orientated in the same manner with respect to the mean plane through the 2‐oxo‐2,5‐dihydro‐1H‐pyrrole ring. The hydroxyl substituent at one of the newly created chiral centres, which have relative R,R stereochemistry, is trans with respect to the oxo group of the pyrrole ring in (I), synthesized using acetaldehyde. When a larger aldehyde was used, as in compounds (II) and (III), the hydroxyl substituent was found to be cis with respect to the oxo group of the pyrrole ring. Here, the relative stereochemistry of the newly created chiral centres is R,S. In compound (I), O—H...O hydrogen bonding leads to an interesting hexagonal arrangement of symmetry‐related molecules. In (II) and (III), the hydroxyl groups are involved in bifurcated O—H...O hydrogen bonds, and centrosymmetric hydrogen‐bonded dimers are formed. The Mukaiyama crossed‐aldol‐type reaction was successful when using the 2‐nitrophenyl‐substituted hydroxypyrrole, or the unsubstituted hydroxypyrrole, and boron trifluoride diethyl ether as catalyst. The synthetic procedure leads to a syn configuration of the two newly created chiral centres in all three compounds. 相似文献
Bioassay‐directed isolation and purification of the methanol extract of Moringa oleifera fruits yielded bioactive N‐benzyl thiocarbamates, N‐benzyl carbamates, benzyl nitriles, and a benzyl ester. Among these, methyl 2‐[4‐(α‐L ‐rhamnopyranosyl)phenyl]acetate ( 2 ), N‐[4‐(β‐L ‐rhamnopyranosyl)benzyl]‐1‐O‐α‐D ‐glucopyranosylthiocarboxamide ( 3 ), 1‐O‐phenyl‐α‐L ‐rhamnopyranoside ( 5 ), and 4‐[(β‐D ‐glucopyranosyl)‐(1→3)‐(α‐L ‐rhamnopyranosyl)]phenylacetonitrile ( 6 ) are novel, and their structures were determined by spectroscopic methods. The known compounds isolated and characterized from the MeOH extract were niazirin (=4‐(α‐L ‐rhamnopyranosyl)phenylacetonitrile; 1 ), niazicin A (=methyl N‐{4‐[(4′‐O‐acetyl‐α‐L ‐rhamnopyranosyl)benzyl]}thiocarbamate; 4 ), methyl N‐{4‐[(α‐L ‐rhamnopyranosyl)benzyl]}carbamate ( 7 ), and methyl N‐{4‐[(4′‐O‐acetyl‐α‐L ‐rhamnopyranosyl)benzyl]}carbamate ( 8 ). The combined yield of these compounds from dried M. oleifera fruits was 1.63%. In rodent pancreatic β‐cells (INS‐1), compounds 4, 5, 6, 7 , and 8 at 100 ppm significantly stimulated insulin release. Cyclooxygenase‐1 (COX‐1) and cyclooxygenase‐2 (COX‐2) enzyme inhibition assays revealed that 5 and 6 were most active at 83 ppm. Compound 6 , however, demonstrated greater specificity for inhibition of COX‐2 enzyme (46%) than COX‐1 enzyme. Lipid peroxidation assays revealed that 4 and 6 at 50 ppm inhibited peroxidation reactions by 80 and 95%, respectively, while 3 and 8 inhibited lipid peroxidation by 35%. These compounds did not inhibit the cell growth when tested with human breast (MCF‐7), central nervous system (CNS, SF‐268), lung (NCI‐H460), or colon (HCT‐116) cancer cell lines. Moreover, these compounds were not cytotoxic at the concentrations tested. 相似文献
Four new pyrrole alkaloids, methyl 2‐[2‐formyl‐5‐(methoxymethyl)‐1H‐pyrrol‐1‐yl]propanoate ( 1 ), methyl 2‐[2‐formyl‐5‐(methoxymethyl)‐1H‐pyrrol‐1‐yl]‐3‐(4‐hydroxyphenyl)propanoate ( 2 ), dimethyl 2‐[2‐formyl‐5‐(methoxymethyl)‐1H‐pyrrol‐1‐yl]butanedioate ( 3 ), and dimethyl 2‐[2‐formyl‐5‐(methoxymethyl)‐1H‐pyrrol‐1‐yl]pentanedioate ( 4 ), were isolated from the AcOEt extract of the fruits of Lycium chinense Miller (Solanaceae). The stereogenic center C(2) in the bulky N‐alkyl side chain in each of 1 – 4 seems to hold the H‐atoms of nearby CH2 groups, CH2(7′) and CH2(3) (if R≠H), leading to two different chemical shifts in the 1H‐NMR spectrum due to their diastereotopic characteristics. In the 1H‐NMR data of each of 2 – 4 , the enhancement of H? C(2) signal was inhibited by the R group, probably due to steric hindrance, and its chemical shift was influenced by the anisotropy effect. The structures of 1 – 4 were elucidated by analysis of various spectroscopic data, including 1D‐ and 2D‐NMR. 相似文献
The one-pot synthesis of N-substituted (3-oxobutanyl)carbamates via the tandem condensation of primary amines with methyl chloroformate, followed by the conjugate addition of the resulting carbamate with methyl vinyl ketone in the presence of Sn4+ modified zeolite Hβ (Hβ-SnA) at room temperature is described. 相似文献
For substituted phenyl‐N‐butyl carbamates (1) and 4‐nitrophenyl‐N‐substituted carbamates (2), linear relationships between values of NH proton chemical shift (δNH), pKa, and logk[OH] and Hammett substituent constant (σ) or Taft substituent constant (σ*) are observed. Carbamates 1 and 2 are pseudo‐substrate inhibitors of porcine pancreatic cholesterol esterase. Thus, the mechanism of the reaction necessitates that the inhibitor molecule and the enzyme form the enzyme‐inhibitor tetrahedral species at the Ki step of the reaction and then form the carbamyl enzyme at the kc step of the reaction. Linear relationships between the logarithms of Ki and kc for cholesterol esterase by carbamates 1 and σ are observed, and the reaction constants (ρs) are ?3.4 and ?0.13, respectively. Therefore, the above reaction forms the negative‐charge tetrahedral species and follows the formation of the relatively neutral carbamyl enzymes. For the inhibition of cholesterol esterase by carbamates 2 except 4‐nitrophenyl‐N‐phenyl carbamate and 4‐nitrophenyl‐N‐t‐butyl carbamate, linear relationships of ‐logKi and logkc with σ* are observed and the ρ* values are ?0.50 and 1.03, respectively. Since the above reaction also forms the negative‐charge tetrahedral intermediate, it is possible that the Ki step of this reaction is further divided into two steps. The first Ki step is the development of the positive‐charge at the carbamate nitrogen from the protonation of the carbamate nitrogen. The second Ki step is the formation of the tetrahedral intermediate with the negative‐charge at the carbonyl oxygen. From Arrhenius plots of a series of inhibition reactions by carbamates 1 and 2, the isokinetic and isoequilibrium temperatures are different from the reaction temperature (25°C). Therefore, the observed ρ and ρ* values only depend upon the electronic effects of the substituents. Taken together, the cholesterol esterase inhibition mechanism by carbamates 1 and 2 is proposed. 相似文献
The novel spirooxindoline fused [1,3]oxazines were efficiently synthesized from Diels‐Alder reaction of N‐arylmaleimides with 1,2‐dihydro‐2‐oxospiro[3H‐indole‐3,2′‐[2H,9aH‐pyrido[2,1‐b][1,3]oxazines], which were generated in situ from three‐component reactions of substituted pyridines and isatins with methyl propiolate, or dimethyl acetylenedicarboxylate. The stereochemistry of the products was clearly clarified by the analysis of 1H NMR data and single crystal structures of the obtained polycyclic compounds. 相似文献
The automated on‐line synthesis of DNA‐3′‐PNA chimeras 1 – 4 and (2′‐O‐methyl‐RNA)‐3′‐PNA chimeras 5 – 8 is described, in which the 3′‐terminal part of the oligonucleotide is linked to the N‐terminal part of the PNA via N‐(ω‐hydroxyalkyl)‐N‐[(thymin‐1‐yl)acetyl]glycine units (alkyl=Et, Ph, Bu, and pentyl). By means of UV thermal denaturation, the binding affinities of all chimeras were directly compared by determining their Tm values in the duplex with complementary DNA and RNA. All investigated DNA‐3′‐PNA chimeras and (2′‐O‐methyl‐RNA)‐3′‐PNA chimeras form more‐stable duplexes with complementary DNA and RNA than the corresponding unmodified DNA. Interestingly, a N‐(3‐hydroxypropyl)glycine linker resulted in the highest binding affinity for DNA‐3′‐PNA chimeras, whereas the (2′‐O‐methyl‐RNA)‐3′‐PNA chimeras showed optimal binding with the homologous N‐(4‐hydroxybutyl)glycine linker. The duplexes of (2′‐O‐methyl‐RNA)‐3′‐PNA chimeras and RNA were significantly more stable than those containing the corresponding DNA‐3′‐PNA chimeras. Surprisingly, we found that the charged (2′‐O‐methyl‐RNA)‐3′‐PNA chimera with a N‐(4‐hydroxybutyl)glycine‐based unit at the junction to the PNA part shows the same binding affinity to RNA as uncharged PNA. Potential applications of (2′‐O‐methyl‐RNA)‐3′‐PNA chimeras include their use as antisense agents acting by a RNase‐independent mechanism of action, a prerequisite for antisense‐oligonucleotide‐mediated correction of aberrant splicing of pre‐mRNA. 相似文献