An extension of our methodology on solid-phase synthesis of 3,4,5-trisubstituted-1,2,4-triazoles under mild conditions has been developed. Firstly, the resin-bound acylhydrazine is reacted with orthoesters to provide ...An extension of our methodology on solid-phase synthesis of 3,4,5-trisubstituted-1,2,4-triazoles under mild conditions has been developed. Firstly, the resin-bound acylhydrazine is reacted with orthoesters to provide resin-bound 1,3,4-oxadiazoles. Secondly, condensation of 1,3,4-oxadiazoles resin with the corresponding arylamines hydrochloride to form the the resin-bound triazoles. 3,4,5-Trisubstituted-1,2,4-triazoles derivatives were obtained from resin-bound acylhydrazines in several steps providing 78% - 87% overall yields and excellent purity. The advantages of this method include straightforward operation and high yield and purity of the products.展开更多
The synthesis of 1,3,5-substituted-1,2,4-triazoles from α-imino-3-pyridine formic acid,acetamidine and anisole hydrazine as a model reaction in this paper and the synthesis mechanism of 1,3,5-substituted-1,2,4-triazo...The synthesis of 1,3,5-substituted-1,2,4-triazoles from α-imino-3-pyridine formic acid,acetamidine and anisole hydrazine as a model reaction in this paper and the synthesis mechanism of 1,3,5-substituted-1,2,4-triazole compounds from carboxylic acids,amidines and hydrazines have been first investigated with the B3 LYP/6-311＋＋G＊＊ method.According to the potential energy profile,it can be predicted that the course of the reaction consists of five reactions containing six elementary reactions.The α-imino-3-pyridine formic acid and acetamidine form first an intermediate product through a dehydration reaction; the intermediate product further combines with hydrogen ion to form a positive ion; the positive ion reacts with anisole hydrazine by a dehydration reaction to form another positive ion; then,followed by two isomerization reactions,the final reaction with the acetate ion（Ac-） produces the final product.The research results reveal the laws of synthesis reaction of 1,3,5-substituted-1,2,4-triazoles by the carboxylic acids,amidines,hydrazines and their derivatives on theoretical level.It provides the systemic theoretical basis for the synthesis,development and application of 1,3,5-substituted-1,2,4-triazole compounds.展开更多
The title compound2-p-methyloxyphenyl-3a-（2-phenyl-1,2,3-triazole-4-yl）-3,4- dihydro-1,2,4-oxa-diazolo[4,5-d][1,5] benzothiazepine （C31H25N5O2S, Mr = 531.63） has been synthesized and its structure was determined b...The title compound2-p-methyloxyphenyl-3a-（2-phenyl-1,2,3-triazole-4-yl）-3,4- dihydro-1,2,4-oxa-diazolo[4,5-d][1,5] benzothiazepine （C31H25N5O2S, Mr = 531.63） has been synthesized and its structure was determined by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P1^- with a = 10.888（2）, b = 15.115（3）, c = 16.702（3）A, α = 99.90（3）, β = 95.21（3）, γ = 100.41（3）°, V = 2642.1（9） nm^3, Dc = 1.336 g/cm^3, Z = 4, F（000） = 1112, μ = 0.162 mm^-1 ,λ（MoKα） = 0.071073 nm, R = 0.0357 and wR = 0.1126 for 10620 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the molecular backbone consists of a tricyclic system with the central seven- membered ring in a twisted boat-like conformation.展开更多
The crystal structure of the title compound 3-phenyl-6-（4-methylphenyl）-1,2,4- triazolo[4,3-b]-1,2,4-triazine （C17H13N5, Mr = 287.32） was synthesized and determined by singlecrystal X-ray diffraction. It belongs t...The crystal structure of the title compound 3-phenyl-6-（4-methylphenyl）-1,2,4- triazolo[4,3-b]-1,2,4-triazine （C17H13N5, Mr = 287.32） was synthesized and determined by singlecrystal X-ray diffraction. It belongs to monoclinic, space group P21/c, with α = 11.4038（18）, b = 11.7675（18）, c = 11.0904（18） A, β = 108.439（7）°, V = 1411.9（4） A^3, Z = 2, Dc = 1.352 g/cm^3, p = 0.085 mm^-1, F（000） = 600, R = 0.0445 and wR = 0.1041 for 2888 unique reflections with 1501 observed ones （I 〉20（I））. In the crystal structure, the triazine moiety is almost coplanar with the triazole ring, and the largest deviation for atom C（4） is -0.026 A. The intermolecular hydrogen bond in the crystal lattice plays an important role in stabilizing the structure.展开更多
文摘An extension of our methodology on solid-phase synthesis of 3,4,5-trisubstituted-1,2,4-triazoles under mild conditions has been developed. Firstly, the resin-bound acylhydrazine is reacted with orthoesters to provide resin-bound 1,3,4-oxadiazoles. Secondly, condensation of 1,3,4-oxadiazoles resin with the corresponding arylamines hydrochloride to form the the resin-bound triazoles. 3,4,5-Trisubstituted-1,2,4-triazoles derivatives were obtained from resin-bound acylhydrazines in several steps providing 78% - 87% overall yields and excellent purity. The advantages of this method include straightforward operation and high yield and purity of the products.
基金supported by the National Natural Science Foundation of China(No.51102114)
文摘The synthesis of 1,3,5-substituted-1,2,4-triazoles from α-imino-3-pyridine formic acid,acetamidine and anisole hydrazine as a model reaction in this paper and the synthesis mechanism of 1,3,5-substituted-1,2,4-triazole compounds from carboxylic acids,amidines and hydrazines have been first investigated with the B3 LYP/6-311＋＋G＊＊ method.According to the potential energy profile,it can be predicted that the course of the reaction consists of five reactions containing six elementary reactions.The α-imino-3-pyridine formic acid and acetamidine form first an intermediate product through a dehydration reaction; the intermediate product further combines with hydrogen ion to form a positive ion; the positive ion reacts with anisole hydrazine by a dehydration reaction to form another positive ion; then,followed by two isomerization reactions,the final reaction with the acetate ion（Ac-） produces the final product.The research results reveal the laws of synthesis reaction of 1,3,5-substituted-1,2,4-triazoles by the carboxylic acids,amidines,hydrazines and their derivatives on theoretical level.It provides the systemic theoretical basis for the synthesis,development and application of 1,3,5-substituted-1,2,4-triazole compounds.
基金This work was supported by the National Natural Science Foundation of China (No. 29702007 and 20162004)
文摘The title compound2-p-methyloxyphenyl-3a-（2-phenyl-1,2,3-triazole-4-yl）-3,4- dihydro-1,2,4-oxa-diazolo[4,5-d][1,5] benzothiazepine （C31H25N5O2S, Mr = 531.63） has been synthesized and its structure was determined by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P1^- with a = 10.888（2）, b = 15.115（3）, c = 16.702（3）A, α = 99.90（3）, β = 95.21（3）, γ = 100.41（3）°, V = 2642.1（9） nm^3, Dc = 1.336 g/cm^3, Z = 4, F（000） = 1112, μ = 0.162 mm^-1 ,λ（MoKα） = 0.071073 nm, R = 0.0357 and wR = 0.1126 for 10620 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the molecular backbone consists of a tricyclic system with the central seven- membered ring in a twisted boat-like conformation.
基金The project was supported by the NNSFC (20572057) and NSF of Shandong Province (Y2006B011)
文摘The crystal structure of the title compound 3-phenyl-6-（4-methylphenyl）-1,2,4- triazolo[4,3-b]-1,2,4-triazine （C17H13N5, Mr = 287.32） was synthesized and determined by singlecrystal X-ray diffraction. It belongs to monoclinic, space group P21/c, with α = 11.4038（18）, b = 11.7675（18）, c = 11.0904（18） A, β = 108.439（7）°, V = 1411.9（4） A^3, Z = 2, Dc = 1.352 g/cm^3, p = 0.085 mm^-1, F（000） = 600, R = 0.0445 and wR = 0.1041 for 2888 unique reflections with 1501 observed ones （I 〉20（I））. In the crystal structure, the triazine moiety is almost coplanar with the triazole ring, and the largest deviation for atom C（4） is -0.026 A. The intermolecular hydrogen bond in the crystal lattice plays an important role in stabilizing the structure.
