A novel method for synthesis of 2-butyl-5 -chloro-3H-imidazole-4-carbaldehyde 2, a key intermediate of Losartan was reported. The compound 2 was synthesized from starting material dimethyl malonate 6 and n-valeronitri...A novel method for synthesis of 2-butyl-5 -chloro-3H-imidazole-4-carbaldehyde 2, a key intermediate of Losartan was reported. The compound 2 was synthesized from starting material dimethyl malonate 6 and n-valeronitrile 8 by six steps with an overall yield of 40%. The key step including the reaction of compound 5 with POCl3/DMF followed by hydrolysis to give compound 2 with the yield of 68%.展开更多
Coupling reaction of 4-chloro-7-H-pyrrolo[2,3-d]pyrimidine with 2,3,5-tri-O-acetyl -β-D-ribofuranosyl chloride under the basic condition was investigated. An abnormal coupling reaction, in which the heterocyclic base...Coupling reaction of 4-chloro-7-H-pyrrolo[2,3-d]pyrimidine with 2,3,5-tri-O-acetyl -β-D-ribofuranosyl chloride under the basic condition was investigated. An abnormal coupling reaction, in which the heterocyclic base attacked at the carbon of 1,2-O-methylidene moiety instead of anomeric carbon of ribose was observed and the structure of products 5a, 5b were identified by NMR and X-Ray diffraction.展开更多
The title compound 2-(2-chloro-4-nitrophenyl)-4-(4-chlorophenyl)-3a,4- diethoxy- 2,3,3a, 4-tetrahydrochromeno[3,4-d][1,2,3]diazaphosphole 2 (C29H30Cl2N3O7P, Mr = 633.44) was synthesized and its structure was cha...The title compound 2-(2-chloro-4-nitrophenyl)-4-(4-chlorophenyl)-3a,4- diethoxy- 2,3,3a, 4-tetrahydrochromeno[3,4-d][1,2,3]diazaphosphole 2 (C29H30Cl2N3O7P, Mr = 633.44) was synthesized and its structure was characterized by IR, MS, ^1H NMR, ^13C NMR, ^31p NMR, elemental analysis and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1^-, a = 9.1549(3), b = 10.7168(4), c = 17.6272(6)A, α = 102.9363(12), β = 90.2713(9), γ = 117.4265(10)°, V= 1484.41(9)A^3, Z= 2,μ(MoKa) = 0.323, F(000) = 658, Z= 2, De= 1.417 g/cm^3, the final R = 0.0687 and wR = 0.2066 for 4943 observed reflections (I 〉 2σ(I)). X-ray analysis reveals that the diazaphospholine ring is almost planar and the two ethoxy groups bonded on the 3a- and 4-positions are in trans configurations. Its antiproliferative activity was also tested in vitro against four human tumor cell lines.展开更多
Synthesis of the title compound was carried out by base-catalyzed cyclization of 1-pivaloyl-3-(2-chloro-4-nitrophenyl) thiourea with α-bromoacetone produced in situ. The structure was confirmed by the spectroscopic a...Synthesis of the title compound was carried out by base-catalyzed cyclization of 1-pivaloyl-3-(2-chloro-4-nitrophenyl) thiourea with α-bromoacetone produced in situ. The structure was confirmed by the spectroscopic and elemental analysis and single crystal X-ray diffraction data. It crystallizes in the triclinic space group P-1 with unit cell dime sions a = 8.7137(10), b = 10.2010(14), c = 10.6593(13), α = 62.671(9), β = 82.701(10), γ = 79.762(10), V = 827.21(8) ?3, Z = 2.展开更多
The title compound (R)-N′-[2-(4-methoxy-6-chloro)-pyrimidyl]-N-[3-methyl-2-(4- chlorophenyl)butyryl]-urea has been synthesized, and its crystal structure and biological behaviors were studied. Crystallographic ...The title compound (R)-N′-[2-(4-methoxy-6-chloro)-pyrimidyl]-N-[3-methyl-2-(4- chlorophenyl)butyryl]-urea has been synthesized, and its crystal structure and biological behaviors were studied. Crystallographic data: C17H18C12N4O3, Mr = 397.25, monoclinic, space group P21/c, a = 12.331(2), b = 14.025(3), c = 23.085(5) A, β = 99.607(4)°, Z = 8, V = 3936.2(13) A3, Dc = 1.341 g/cm^3, F(000) = 1648, R = 0.0718, wR = 0.1585 and/t(MoKα) = 0.353 mm^-1. The preliminary biological tests showed that the title compound has definite insecticidal and fungicidal activities.展开更多
We report here a generic,green synthesis of 17 valuable syn-aryl-(2S,3R)-2–chloro-3–hydroxy esters(syn-(2S,3R)-1)in 73%-99%isolated yields along with 6.1:1–83:1 dr and 31%~>99%ee,through dynamic reductive kineti...We report here a generic,green synthesis of 17 valuable syn-aryl-(2S,3R)-2–chloro-3–hydroxy esters(syn-(2S,3R)-1)in 73%-99%isolated yields along with 6.1:1–83:1 dr and 31%~>99%ee,through dynamic reductive kinetic resolution of racemic arylα–chloroβ-keto esters(2)catalyzed by an engineered ketoreductase which was obtained via ep PCR-based directed evolution.The hectogram scale synthesis of syn-(2S,3R)-1b at a substrate concentration of 120 g/L showcased the application potential of the biocatalytic method developed presently.展开更多
The ionic cross-linking treatment with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride( CHTAC) and 1,2,3,4-butanetetracarboxylic acid( BTCA) was treated on untreated and plasma treated Tencel fabrics,and then TiO...The ionic cross-linking treatment with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride( CHTAC) and 1,2,3,4-butanetetracarboxylic acid( BTCA) was treated on untreated and plasma treated Tencel fabrics,and then TiO_2/SiO_2 sol was applied to the treated samples. Self-cleaning characteristic was investigated using the color measurement spectrophotometer with 7 h UV irradiation. Moreover, the surface morphology, structure change of samples were observed by scanning electron microscopy( SEM) and Fourier transform infrared spectroscopy( FTIR),respectively. The results revealed that with the increase of CHTAC concentration, breaking strength of Tencel fabric increased,whiteness index decreased,and wrinkle recovery angle first dropped and then rose. It was also found that increasing concentration of BTCA,breaking strength of Tencel fabric decreased,whiteness index and wrinkle recovery angle increased. FTIR studies revealed that CHTAC and BTCA had grafted on Tencel fabric. Nevertheless,the molar ratio of 50∶1 of TiO_2/SiO_2 sol endowed Tencel fabric with better self-cleaning properties,compared with sample treated with pure TiO_2. Furthermore,compared with sample treated with TiO_2/SiO_2 sol alone, the combination of plasma and cross-linking treatment( plasma + CHTAC + BTCA + TiO_2/SiO_2) decreased the value of K/S,and increased the value of ΔE,ensured more efficient photodegradation of methylene blue, and thus got a better performance of self-cleaning.展开更多
Asymmetric reduction of 2-chloro-3-oxo esters was achieved by catalytic transfer hydrogenation using [RuCl2(p-cymene)](S,S)-TsDPEN as the chiral catalyst and HCOOH-Et3N as the hydrogen source. Moderate to good yie...Asymmetric reduction of 2-chloro-3-oxo esters was achieved by catalytic transfer hydrogenation using [RuCl2(p-cymene)](S,S)-TsDPEN as the chiral catalyst and HCOOH-Et3N as the hydrogen source. Moderate to good yields (up to 85%) and good enantioselectivities (up to 98% ee) were obtained.展开更多
A series of(Z)-2-chloro-1,3-diarylpropen-1-ones were unexpectedly synthesized in moderate yields by treatment of easily available 2,3-epoxy-1,3-diarylpropan-1-ones with Vilsmeier reagent,which was derived from bis(...A series of(Z)-2-chloro-1,3-diarylpropen-1-ones were unexpectedly synthesized in moderate yields by treatment of easily available 2,3-epoxy-1,3-diarylpropan-1-ones with Vilsmeier reagent,which was derived from bis(trichloromethyl) carbonate(BTC, triphosgene) and DMF.A possible mechanism was also proposed,where sequential ring-opening,halogenation and elimination reactions were involved.展开更多
The synthetic method of the novel chiral synthon, 5-/-menthyloxy-3-chloro-2-(5H)-furanone 5a and its application in asymmetric reactions were investigated. 5a is easily obtained in highly optical purity, and acts as a...The synthetic method of the novel chiral synthon, 5-/-menthyloxy-3-chloro-2-(5H)-furanone 5a and its application in asymmetric reactions were investigated. 5a is easily obtained in highly optical purity, and acts as a stable acceptor of Michael addition with oxygen nucleophiles in tandem double Michael addition / internal nucieophilic substitution to offer the spiro-cyclopropane derivative containing four stereogenic centers 8, which it is difficult to obtain by routine methods. The synthetic methods for 5a and 8 are reported in detail and the new compounds are identified on the basis of their analytical data and spectroscopic data, such as UV, IR, H NMR,13 C NMR, MS and elementary analysis. The absolute configuration of the interesting spiro-cyclopropanes, spiro [1-chloro-4-(/-menthyloxy)-5-oxo-6-oxa-biscyclo[3.1.0]hexane-2,3i(4’-/-menthyloxy-5’-/-menthyloxy- butyrolactone)] 8 was established by X-ray crystallography. This result can provide important synthetic strategy in synthesis of some complex展开更多
In this paper, stereocontrolled tandem Michael addition-elimination reaction of the novel chiral source, S-(ι-menthyloxy)-3,4-dichloro-2(5H)-furanone, with various thiols and amines has been investigated. A series of...In this paper, stereocontrolled tandem Michael addition-elimination reaction of the novel chiral source, S-(ι-menthyloxy)-3,4-dichloro-2(5H)-furanone, with various thiols and amines has been investigated. A series of new enantiomerically pure compounds, 5-(ι-menthyloxy)-4-substituted-3-cnloro-2(5H)-furanones, were obtained in good yields with d. e.(?)98% under mild conditions.展开更多
A new hemiterpenoid, (+)-(2R,3S)-2-chloro-3-hydroxy-3-methyl-T-buty-rolactone was isolatexi from the leaves of Prinsepia utilis Royle. Its structure was clucidatexi by spectroscopic methods and X-ray crystallogra...A new hemiterpenoid, (+)-(2R,3S)-2-chloro-3-hydroxy-3-methyl-T-buty-rolactone was isolatexi from the leaves of Prinsepia utilis Royle. Its structure was clucidatexi by spectroscopic methods and X-ray crystallographic analysis.展开更多
Some 1-(6-chloroquinoxalin-2-yl)-2-[4-(trifluoromethyl)-2,6-dinitrophenyl] hydrazine derivatives have been synthesized via both conventional and microwave assisted organic synthesis(MAOS) methods. The MAOS metho...Some 1-(6-chloroquinoxalin-2-yl)-2-[4-(trifluoromethyl)-2,6-dinitrophenyl] hydrazine derivatives have been synthesized via both conventional and microwave assisted organic synthesis(MAOS) methods. The MAOS method is more effective on synthesizing these compounds than the conventional method in regard to the higher chemical yields of products(76%-98%) and the shorter reaction time(1-15 min).展开更多
We have investigated the fast ethylamine gas sensing of 2-chloro-3,5-dinitrobenzotrifluoride(CDBF) loaded poly(acrylonitrile) nanofiber based on an intermolecular charge-transfer complexation.Reversible response a...We have investigated the fast ethylamine gas sensing of 2-chloro-3,5-dinitrobenzotrifluoride(CDBF) loaded poly(acrylonitrile) nanofiber based on an intermolecular charge-transfer complexation.Reversible response and recovery were achieved using alternating gas exposure.This system shows a fast ethylamine gas sensing within 0.4 s.展开更多
基金supported by Outstanding Youth Foundation of Heilongjiang Province(No.JC200706)
文摘A novel method for synthesis of 2-butyl-5 -chloro-3H-imidazole-4-carbaldehyde 2, a key intermediate of Losartan was reported. The compound 2 was synthesized from starting material dimethyl malonate 6 and n-valeronitrile 8 by six steps with an overall yield of 40%. The key step including the reaction of compound 5 with POCl3/DMF followed by hydrolysis to give compound 2 with the yield of 68%.
基金This work was supported by the National Natural Science Foundation of China.
文摘Coupling reaction of 4-chloro-7-H-pyrrolo[2,3-d]pyrimidine with 2,3,5-tri-O-acetyl -β-D-ribofuranosyl chloride under the basic condition was investigated. An abnormal coupling reaction, in which the heterocyclic base attacked at the carbon of 1,2-O-methylidene moiety instead of anomeric carbon of ribose was observed and the structure of products 5a, 5b were identified by NMR and X-Ray diffraction.
文摘The title compound 2-(2-chloro-4-nitrophenyl)-4-(4-chlorophenyl)-3a,4- diethoxy- 2,3,3a, 4-tetrahydrochromeno[3,4-d][1,2,3]diazaphosphole 2 (C29H30Cl2N3O7P, Mr = 633.44) was synthesized and its structure was characterized by IR, MS, ^1H NMR, ^13C NMR, ^31p NMR, elemental analysis and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1^-, a = 9.1549(3), b = 10.7168(4), c = 17.6272(6)A, α = 102.9363(12), β = 90.2713(9), γ = 117.4265(10)°, V= 1484.41(9)A^3, Z= 2,μ(MoKa) = 0.323, F(000) = 658, Z= 2, De= 1.417 g/cm^3, the final R = 0.0687 and wR = 0.2066 for 4943 observed reflections (I 〉 2σ(I)). X-ray analysis reveals that the diazaphospholine ring is almost planar and the two ethoxy groups bonded on the 3a- and 4-positions are in trans configurations. Its antiproliferative activity was also tested in vitro against four human tumor cell lines.
文摘Synthesis of the title compound was carried out by base-catalyzed cyclization of 1-pivaloyl-3-(2-chloro-4-nitrophenyl) thiourea with α-bromoacetone produced in situ. The structure was confirmed by the spectroscopic and elemental analysis and single crystal X-ray diffraction data. It crystallizes in the triclinic space group P-1 with unit cell dime sions a = 8.7137(10), b = 10.2010(14), c = 10.6593(13), α = 62.671(9), β = 82.701(10), γ = 79.762(10), V = 827.21(8) ?3, Z = 2.
基金This work was sponsored by the National Key Technologies R & D Programs (No. 2004BA308A22-8)
文摘The title compound (R)-N′-[2-(4-methoxy-6-chloro)-pyrimidyl]-N-[3-methyl-2-(4- chlorophenyl)butyryl]-urea has been synthesized, and its crystal structure and biological behaviors were studied. Crystallographic data: C17H18C12N4O3, Mr = 397.25, monoclinic, space group P21/c, a = 12.331(2), b = 14.025(3), c = 23.085(5) A, β = 99.607(4)°, Z = 8, V = 3936.2(13) A3, Dc = 1.341 g/cm^3, F(000) = 1648, R = 0.0718, wR = 0.1585 and/t(MoKα) = 0.353 mm^-1. The preliminary biological tests showed that the title compound has definite insecticidal and fungicidal activities.
基金The National Key Research and Development Program of China(Nos.2021YFA0911400 and 2021YFF0600704)the National Natural Science Foundation of China(Nos.22071033 and 21801047)are acknowledged for the financial supports。
文摘We report here a generic,green synthesis of 17 valuable syn-aryl-(2S,3R)-2–chloro-3–hydroxy esters(syn-(2S,3R)-1)in 73%-99%isolated yields along with 6.1:1–83:1 dr and 31%~>99%ee,through dynamic reductive kinetic resolution of racemic arylα–chloroβ-keto esters(2)catalyzed by an engineered ketoreductase which was obtained via ep PCR-based directed evolution.The hectogram scale synthesis of syn-(2S,3R)-1b at a substrate concentration of 120 g/L showcased the application potential of the biocatalytic method developed presently.
文摘The ionic cross-linking treatment with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride( CHTAC) and 1,2,3,4-butanetetracarboxylic acid( BTCA) was treated on untreated and plasma treated Tencel fabrics,and then TiO_2/SiO_2 sol was applied to the treated samples. Self-cleaning characteristic was investigated using the color measurement spectrophotometer with 7 h UV irradiation. Moreover, the surface morphology, structure change of samples were observed by scanning electron microscopy( SEM) and Fourier transform infrared spectroscopy( FTIR),respectively. The results revealed that with the increase of CHTAC concentration, breaking strength of Tencel fabric increased,whiteness index decreased,and wrinkle recovery angle first dropped and then rose. It was also found that increasing concentration of BTCA,breaking strength of Tencel fabric decreased,whiteness index and wrinkle recovery angle increased. FTIR studies revealed that CHTAC and BTCA had grafted on Tencel fabric. Nevertheless,the molar ratio of 50∶1 of TiO_2/SiO_2 sol endowed Tencel fabric with better self-cleaning properties,compared with sample treated with pure TiO_2. Furthermore,compared with sample treated with TiO_2/SiO_2 sol alone, the combination of plasma and cross-linking treatment( plasma + CHTAC + BTCA + TiO_2/SiO_2) decreased the value of K/S,and increased the value of ΔE,ensured more efficient photodegradation of methylene blue, and thus got a better performance of self-cleaning.
文摘Asymmetric reduction of 2-chloro-3-oxo esters was achieved by catalytic transfer hydrogenation using [RuCl2(p-cymene)](S,S)-TsDPEN as the chiral catalyst and HCOOH-Et3N as the hydrogen source. Moderate to good yields (up to 85%) and good enantioselectivities (up to 98% ee) were obtained.
基金the National Natural Science Foundation of China(Nos.20806073 and 20876147)the National Key Technology Research and Development Program(No.2007BAI34B06) for financial support
文摘A series of(Z)-2-chloro-1,3-diarylpropen-1-ones were unexpectedly synthesized in moderate yields by treatment of easily available 2,3-epoxy-1,3-diarylpropan-1-ones with Vilsmeier reagent,which was derived from bis(trichloromethyl) carbonate(BTC, triphosgene) and DMF.A possible mechanism was also proposed,where sequential ring-opening,halogenation and elimination reactions were involved.
文摘The synthetic method of the novel chiral synthon, 5-/-menthyloxy-3-chloro-2-(5H)-furanone 5a and its application in asymmetric reactions were investigated. 5a is easily obtained in highly optical purity, and acts as a stable acceptor of Michael addition with oxygen nucleophiles in tandem double Michael addition / internal nucieophilic substitution to offer the spiro-cyclopropane derivative containing four stereogenic centers 8, which it is difficult to obtain by routine methods. The synthetic methods for 5a and 8 are reported in detail and the new compounds are identified on the basis of their analytical data and spectroscopic data, such as UV, IR, H NMR,13 C NMR, MS and elementary analysis. The absolute configuration of the interesting spiro-cyclopropanes, spiro [1-chloro-4-(/-menthyloxy)-5-oxo-6-oxa-biscyclo[3.1.0]hexane-2,3i(4’-/-menthyloxy-5’-/-menthyloxy- butyrolactone)] 8 was established by X-ray crystallography. This result can provide important synthetic strategy in synthesis of some complex
基金Project (No. 29132036) supported by the National Natural Science Foundation of China
文摘In this paper, stereocontrolled tandem Michael addition-elimination reaction of the novel chiral source, S-(ι-menthyloxy)-3,4-dichloro-2(5H)-furanone, with various thiols and amines has been investigated. A series of new enantiomerically pure compounds, 5-(ι-menthyloxy)-4-substituted-3-cnloro-2(5H)-furanones, were obtained in good yields with d. e.(?)98% under mild conditions.
文摘A new hemiterpenoid, (+)-(2R,3S)-2-chloro-3-hydroxy-3-methyl-T-buty-rolactone was isolatexi from the leaves of Prinsepia utilis Royle. Its structure was clucidatexi by spectroscopic methods and X-ray crystallographic analysis.
文摘Some 1-(6-chloroquinoxalin-2-yl)-2-[4-(trifluoromethyl)-2,6-dinitrophenyl] hydrazine derivatives have been synthesized via both conventional and microwave assisted organic synthesis(MAOS) methods. The MAOS method is more effective on synthesizing these compounds than the conventional method in regard to the higher chemical yields of products(76%-98%) and the shorter reaction time(1-15 min).
基金supported by Basic Science Research Program through the National Research Foundation(NRF) grant funded by the Korea Government(MEST)(No.2011-0001084)supported by a grant from the Fundamental R&D Program for Core Technology of Materials funded by the Ministry of Knowledge Economy, Republic of Korea
文摘We have investigated the fast ethylamine gas sensing of 2-chloro-3,5-dinitrobenzotrifluoride(CDBF) loaded poly(acrylonitrile) nanofiber based on an intermolecular charge-transfer complexation.Reversible response and recovery were achieved using alternating gas exposure.This system shows a fast ethylamine gas sensing within 0.4 s.