剑桥结构数据库在立体化学教学中的应用实践

应用英国剑桥结构数据库并结合相关三维可视化软件于立体化学中关于构型、构象、手性等概念的教学,增加立体化学教学的直观性和可视性,便于学生对相关知识的理解和掌握。     

Synthesis and Crystal Structure of (9S)-2′-O-Benzoyl-9,11-[carbonylbis(oxy)]-9-deoxo-5-O-(β-D-desosaminyl)-12,21-anhydro-9-hydroxy-erythronolide A

The title compound (9S)-2′-O-benzoyl-9,11-[carbonylbis(oxy)]-9-deoxo-5-O-(-D-desosaminyl)-12,21-anhydro-9-hydroxyerythronolide A 1 was synthesized. The crystal structure of the acetone solvate of 1, C37H55NO11·C3H6O, was determined by single-crystal X-ray diffraction analysis. It belongs to monoclinic system, space group P21 with a = 14.4691(10), b = 8.2626(6), c = 17.5990(11) , β = 94.167(1)°, V = 2098.4(2)3, Mr = 748, Z = 2, Dc = 1.184 g/cm3, μ = 0.087 mm-1, F(000) = 808, S = 1.026, R = 0.0542 and wR = 0.1322 for 3331 observed reflections (I > 2σ(I)). In the solid state, molecules of 1 are linked into spirals along the b axis by O(25)- H(25)···O(29) intermolecular hydrogen bond.     

不含手性碳的手性化合物及其绝对构型——剑桥结构数据库实例分析

利用英国剑桥结构数据库中的实例并结合相关三维可视化软件,介绍了含有氮/磷等手性杂原子、轴手性、平面手性、螺旋手性、超分子手性等手性因素的手性化合物及其绝对构型,以加深对手性概念的认识和理解。     

平面手性化合物的绝对构型及其判定的教学方法

平面手性是手性的一种特殊情形。结合实例详细阐述了手柄化合物、环蕃化合物、反式环烯烃、轮烯类化合物、金属茂化合物等平面手性化合物的绝对构型及判定方法。     

4-(7-Methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl)-N-(pyridin-2-yl)thiazol-2-amine:Chiral Crystal from Achiral Molecule

The title compound 4-(7-methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl)-N- (pyridin-2-yl) thiazol-2-amine was synthesized by reacting 2-bromo-1-(7-methoxy-2,2-dime-thyl-2,3-dihydrobenzofuran-5-yl)ethanone with 1-(pyridine-2-yl)thiourea, and its crystal was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, chiral space group C2 with a = 18.1328(14), b = 5.5969(5), c = 19.2195(15),μ= 115.5420(10)°, V = 1759.9(2)3, Z = 4, F(000) = 744, C19H19N3O2S, Mr = 353.43, Dc = 1.334 g/cm3, S = 1.15, μ = 0.201 mm-1, the final R = 0.035 and wR = 0.111 for 2307 observed reflections (I > 2δ(I)). The Flack parameter is -0.03(10). The preliminary bioassay result indicated that the title compound exhibits strong insecticidal activity (93.75% mortality) against Mythimna separate at the concentration of 1.000 g/L.     

2,2-二甲基-5-取代苯基-3-(1,2,4-三唑-1/4-甲基)-3-戊醇类化合物的合成、表征及生物活性

取代苯甲醛经缩合、催化氢化、环氧化和开环反应合成了9种2,2-二甲基-5-取代苯基-3-(1,2,4-三唑-1-基甲基)-3-戊醇类化合物和2种2,2-二甲基-5-取代苯基-3-(1,2,4-三唑-4-基甲基)-3-戊醇类新化合物. 并对1,2,4-三唑-1-基衍生物和1,2,4-三唑-4-基衍生物的选择性合成进行了研究; 新化合物结构经质谱, ¹H NMR, 元素分析等确证, 并用单晶X射线衍射测定了化合物1a的晶体结构. 生物活性测试结果表明, 部分化合物具有强杀菌活性.     

Synthesis, Crystal Structure and Antidepressant Activity of 5-[4-(Benzyloxy)phenyl]-9-(n-propyl)-4,6-dioxa-1-azabicyclo[3.3.1]nonane Hydrochloride 0.5Hydrate

The title compound 2(C22H28N+O3)·H2O·2Cl-was synthesized by the reaction of 2-bromo-1-[4-(benzyloxy)phenyl]-1-pentone with 2,2'-azanediyldiethanol. The crystal determined by X-ray diffraction analysis belongs to the monoclinic system, space group Pc with a = 18.312(3), b = 14.838(3), c = 7.6227(14) , β = 97.981(4)°, Z = 2, Mr = 797.82, V = 2051.1(6) 3, Dc = 1.292 g/cm3, S = 0.956, μ = 0.21 mm-1, F(000) = 852, the final R = 0.0625 and wR = 0.1428 for 5683 observed reflections (Ⅰ > 2σ(Ⅰ)). Flack parameter is 0.10(9). The title compound is composed by four non-coplanar ring systems, two benzenes and two morpholines. One morpholine ring (C(3)-C(4)-N(1)-C(1)-C(2)-O(1)) forms a chair conformation, while the other (C(4)-C(3)-O(2)-C(6)-C(5)-N(1)) assumes a boat conformation. X-ray crystal structure displays extensive N-H…Cl and O-H…Cl intermolecular hydrogen bonds. The preliminary antidepressant activity test indicates that the inhibition ratio of SERT (5-HT Transporter) was 35.9% at the dosage of 10.0 mg/L.     

2-芳基-2-吗啉醇的合成

醇胺分别与2-溴-4′-甲氧基苯乙酮、2-溴-3′-氯苯丙酮、2-溴-4′-苄氧基苯基丙酮、2-溴-4′-苄氧基苯戊酮、6-甲氧基-2-溴乙酰基萘和6-甲氧基-2-(2-溴丙酰基)萘反应,合成相应的2-芳基-2-吗啉醇(产率80.7%～97.5%)及其盐酸盐.其结构经1H NMR,IR,MS确证.     

萘普生2-芳基吗啉乙酯的合成及其对环氧合酶-2的抑制活性

基于萘普生的构效关系对其羧基进行结构修饰, 设计合成了萘普生2-芳基吗啉乙酯类化合物. 芳基乙酮经过溴代、胺化、还原得到的2-芳基-4-羟乙基吗啉在三乙胺作缚酸剂存在下与萘普生酰氯反应得到萘普生2-芳基吗啉乙酯类化合物, 收率24.2%～76.5%. 新化合物结构经1H NMR确认. 生物活性实验结果表明: 在10 μmol/L质量浓度时, 化合物1d对COX-2的抑制率达96.32%.     

Synthesis and Crystal Structure of 4-tert-Butyl-6-（4-chlorophenyl）-3,6- dihydro-2H-1,3-thiazin-2-iminium Chloride

The title compound, 4-tert-butyl-6-（4-chlorophenyl）-3,6-dihydro-2H-1,3-thiazin- 2-iminium chloride （C14H18C12N2S）, has been synthesized by the reaction of 1-（4-chlorophenyl）- 4,4-dimethylpent-1-en-3-one with thiourea, and its crystal structure was determined by single- crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P211c with a = 16.3064（11）, b = 9.4471（6）, c = 11.2626 （8）A, β = 108.400（1）°, Z = 4, V = 1646.28（19） A^3, Mr = 317.26, Dc = 1.280 g/cm^3, S = 1.078,μ = 0.510 mm^-1, F（000） = 664, the final R = 0.0514 and wR = 0.1412 for 3210 observed reflections （I 〉 2σ（I））. The thiazine ring system displays a twisted boat conformation, and three N-H,..Cl hydrogen bonds exist in the crystal. The combination of two N-H...Cl hydrogen bonds generate an R2^1 （6） ring.