多取代1,4-戊二烯-3-醇的合成及其在螺环四氢喹啉衍生物合成中的应用

以取代邻氨基苯甲酸为起始原料,经6步反应合成了7个多取代1,4-戊二烯-3-醇（7a~7g）;以7a~7g为原料,5 mol%FeCl₃为催化剂,CH₂Cl₂为溶剂,于室温反应合成了7个螺环四氢喹啉衍生物（8a~8g）,其结构经¹H NMR, ¹³C NMR, IR和HR-MS(ESI)表征。采用X-射线单晶衍射研究了8d的晶体结构。结果表明：8d的晶胞参数a=14.001(3) , b=12.335(2) , c=11.587(3) , α=90°, β=95.497(2)°, γ=90°, V=1 991.9(7) ³, Z=4, μ=0.182 mm^-1, F(000)=816.0, R[F²>2σ(F²)］=0.053 7, wR(F²)=0.132 5。     

合成3,3-二芳基氧化吲哚的新方法

报道了一种合成3,3-二芳基氧化吲哚的新方法。以取代靛红为起始原料,THF为溶剂,在室温下用新制芳基格氏试剂与靛红的3-位羰基发生双芳基化反应,合成了12个未见文献报道的3,3-二芳基氧化吲哚(3a~3l),产率56%~78%,其结构经¹H NMR, ¹³C NMR和HR-MS（ESI-TOF）表征。并分析了3a(CCDC: 1960434)和3b(CCDC: 1960436)的单晶结构。结果表明：3a属triclinic晶系,P-1空间群,晶胞参数a=8.736(2) , b=8.887(2) , c=13.862(3) , α=77.505(18)°, β=72.01(2)°, γ=64.68(2)°; 3b属monoclinic晶系,P2₁/c空间群,晶胞参数a=8.8877(10) , b=24.734(2) , c=8.5441(8) , α=90°, β=113.994(12)°, γ=90°。     

新型苯并咪唑-5,6-二羧酸锌配合物的合成及其性能研究

以ZnSO₄·7H₂O和苯并咪唑-5,6-二羧酸为原料，采用水热法合成了一种新型的锌配合物{\[Zn(H₂-bidc)₂(H₂O)₄]·(H₂O)₄}_n[1 (CCDC: 1007038), H₃-bidc=苯并咪唑-5,6-羧酸]，产率48%，其结构经IR,元素分析和X-射线单晶衍射表征。结果表明：1属正交晶系，Pnnm空间群，晶胞参数a=9.6451(19) ， b=19.459(4) ， c=6.6895(13) ，α=β=γ=90°， V=1255.5(4) ³， Dc=1.634 g·cm^-3， Z=8。采用FL和TGA研究了1的性能。结果表明：1具有一定的热稳定性，最大发射峰位于420 nm和416 nm， 1的荧光发射属于发射配体荧光。     

新型氮杂异香豆素化合物的合成

以4-氯烟酸和芳基乙腈为原料,经取代和环合反应合成了3个新型的氮杂异香豆素化合物（3a~3c）,收率32.1%~89.0%,其结构经¹H NMR, IR, ESI-MS和元素分析表征。用X-单晶衍射研究了3a的亚甲基衍生物（4a）的晶体结构。4a(CCDC: 935 919)属三斜晶系,空间群P ī, 晶胞参数a=6.881(2) , b=9.768(2) , c=11.809(2) , β=104.125(10)°, V=732.1³, Dc=1.331 mg·cm^-3 , Z=2, F(000)=308, μ=0.090 mm^-1。并对环合反应机理进行了研究。     

4-甲胺基-6-三氟甲基-2-甲砜基嘧啶的合成及其晶体结构

以三氟乙酰乙酸乙酯和硫脲为原料,经环化、氯化和亲核取代反应制得中间体4-甲胺基-6-三氟甲基-2-甲硫基嘧啶(3); 以间氯过氧苯甲酸为氧化剂,3经氧化反应合成了新化合物--4-甲胺基-6-三氟甲基-2-甲砜基嘧啶(4),其结构经¹H NMR,MS,元素分析和X-射线单晶衍射表征。 4（CCDC：973037）属单斜晶系,空间群:P₂(1)/c,晶胞参数a=5.068 7(4) , b=15.296 8(11) , c=13.833 9(10) , β=13.833 9(10)°, V=1 065.81(14) ³, Z=4, Dc＝1.591 g·cm-³, μ=0.336 mm^-1, F(000)=520, R₁=0.051 1, wR₂=0.135 3。     

2,6-二甲基-3,5-二（吡唑-3-基）吡啶构筑的新型八钼酸盐的合成及其电化学性质

利用六水合硫酸锌（ZnSO₄· 6H₂O）、七钼酸铵［(NH₄)₆Mo₇O₂₄· 4H₂O］和2,6-二甲基-3,5-二（吡唑-3-基）吡啶（H₂L）为原料，通过水热反应，合成了一个新型的八钼酸盐［Zn(H₃L)₂(H₄Mo₈O28), 1）］，其结构和性能经IR、元素分析,X 射线单晶衍射和TGA表征。结果表明:〖STHZ〗1〖STBZ〗(CCDC: 1860339)属三斜晶系，P₁空间群，晶胞参数a=9.421(5) , b=10.737(5) , c=11.826(5) , α=100.340(5)°, β=97.939(5)°, γ=100.053(5)°, V=1140.9(4) ³, Z=1, R₁=0.029 2, wR₂=0.0769。1的结构中，锌离子被质子化的有机配体H₃L⁺连接形成一维链结构，同多钼酸簇{Mo₈O₂₈}将相邻的一维链连接起来形成二维层结构。电化学分析结果表明：1对亚硝酸根离子还原具有较好的催化作用，当亚硝酸根离子浓度为5 mmol·L^-1时，催化效率为61%。     

五价钒的二苯羟乙酸和吡啶混合配体配合物的研究(Ⅱ)——配合物单晶的制备和结构的测定

本文报道了PyH[(VO)(Bz)₂Py]Py配合物的单晶制备及其晶体结构和分子结构。该配合物晶体属三斜晶系,P1空间群,晶胞参数为:a=12.400(5)Å,b=14.042(5)Å,c=10.441(4)Å,α=91.92(3)°,β=93.57(3)°,γ=74.41(3)°,V=1847.7(1.2)ų,Z=2。最后一致性因子为R=0.045,讨论了结构与性质。     

2-(2-苯并咪唑基)-4,4,5,5-四甲基-3-氧化咪唑啉-1-氧基自由基的合成、晶体结构与量化计算

报道了2-(2-苯并咪唑基)-4, 4, 5, 5-四甲基-3-氧化咪唑啉-1-氧基自由基(NITBzImH)的合成和晶体结构.晶体属正交晶系Pbca空间群.a=0.87446(4), b=1.55600(8), c=2.01139(1) nm,α=β=γ=90°,Z=8,V=2.7368(2) nm³, R=0.0478,ωR=0.1101;并用密度泛函(DFT)计算了该自由基的自旋密度分布.     

3,5-二(4-甲基苯基)吡啶的Suzuki偶联合成及其光学性能

以3,5-二溴吡啶和对甲基苯硼酸为原料,醋酸钯为催化剂,经Suzuki偶联反应合成了3,5-二(4-甲基苯基)吡啶(1),收率73%,其结构和性能经¹H NMR, ¹³C NMR, IR, 元素分析, UV-Vis, FL和X-射线单晶衍射表征。结果表明：1（CCDC: 1509844）属正交晶系,空间群P2₁2₁2₁,晶胞参数a=6.447 8(12) , b=7.240 2(14) , c=29.890 0(6) ,β=90°。1为非平面刚性共轭分子,荧光量子产率13.9%。     

阿西美辛的合成新方法

报道了一条合成阿西美辛的新路线。以吲哚美辛为起始原料，先与溴乙酸苄酯反应制得阿西美辛苄酯，然后在AlCl₃催化下选择性脱除苄基得阿西美辛粗品，最后用丙酮和水重结晶制得阿西美辛一水合物(Acn·H₂O, CCDC: 1856291); Acn·H₂O于80 ℃真空干燥24 h得阿西美辛,其结构经¹H NMR和¹³C NMR确证。采用XRD表征了Acn·H₂O的晶体结构。结果表明：Acn·H₂O属三斜晶系，P-1空间群，晶胞参数a=7.773(3) , b=10.222(4) , c=13.517(5) , α=97.306(6)°, β=96.162(6)°, γ=106.944(6)°。     

新型哌嗪化合物的合成及其晶体结构

以2-［1,2-二(2-羟基苯甲氨基)-2-(吡啶基)乙基］苯酚和2-［1,2-二(2-羟基苯甲氨基)-4-(吡啶基)乙基］苯酚为原料,分别与乙二醛经缩合反应,合成了两个新型的哌嗪化合物--2-【{12-(2-吡啶基)-3,20-二氧-11,21-二氮杂五环［11.7.1.O^2,11.O^4,9.O^14,19］二十一-4,6,8,14,16,18-六环-21-基}甲基】苯酚(2a)和2-【{12-(4-吡啶基)-3,20-二氧-11,21-二氮杂五环［11.7.1.O^2,11.O^4,9.O^14,19］二十一-4,6,8,14,16,18-六环-21-基}甲基】苯酚(2b),其结构经¹H NMR, ¹³C NMR, FT-IR, ESI-MS和X-射线单晶衍射表征。2a(CCDC: 1 439 422)属单斜晶系,空间群P2₁/n,晶胞参数a=12.250 2(16) , b=10.299 6(13) , c=18.296(2) , β=95.798(2)°, V=2 296.6(5) ³, Dc=1.341 mg·cm^-3,Z=4, F(000)=976, μ=0.088 mm^-1。     

C(3)-酯基取代的1,5-苯并硫氮杂卓的合成、晶体结构及抑菌和构效关系的研究

设计、合成了三类C(3)酯基取代的1,5-苯并硫氮杂卓衍生物: 2,3/2,5-二氢和2,3,4,5-四氢-1,5-苯并硫氮杂卓-3-甲酸乙酯, 采用元素分析、IR、MS、1H NMR及X射线衍射法确定了标题化合物的分子结构．结构分析表明, 2,5-二氢-1,5-苯并硫氮杂卓-3-甲酸乙酯属单斜晶系, C2/c空间群, 晶胞参数为: a＝2.0319(4) nm, b＝1.4985(3) nm, c＝1.3659(3) nm, α＝90°, β＝120.49(3)°, γ＝90°, V＝3.5840(12) nm3, Z＝8, Dc＝1.397 g/cm3, μ＝0.351 mm－1, F(000)＝1560, R＝0.0478, Rw＝0.1304; 研究了2,3/2,5-二氢-1,5-苯并硫氮杂卓的合成反应条件, 发现该两种互变异构体分别是速度控制产物和平衡控制产物; 抑菌活性及抑真菌构效关系研究表明, 亚胺型的2,3-二氢-1,5-苯并硫氮杂卓具有明显的抑菌活性, 亚胺官能团是其抑真菌的药效团．     

Synthesis and Crystal Structure of Trans-4-[(5-(2,4-Dichlorophenoxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one

The title compound trans-4-[(5-(2,4-dichlorophenoxy)-3-methyl-1-phenyl-1H-pyra-zol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 (C28H23Cl2N5O2, Mr = 532.41) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1 with a = 8.9438(4), b = 11.6065(5), c = 14.2215(6) , α = 112.566(1), β = 92.324(2), γ = 102.91(1)o, V = 1315.65(10) 3, Z = 2, Dc = 1.344 g/cm3, μ(MoKα) = 0.282 mm-1, λ = 0.71073 , F(000) = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections (I > 2σ(I)). X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra-and intermolecular C(12)-H(12)···O(1) and C(28)-H(28)···O(1)#1 hydrogen bonds were observed in the title compound.     

Synthesis,Crystal Structure and Thermal Properties of N,N＇-Bis（5,5-dimethyl- 2-phospha-2-thio-1,3-dioxan-2-yl） Ethylene Diamine

The title compound N,N＇-bis（5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl） ethylene diamine （DPTDEDA, C12H26N2O4P2S2） was synthesized by the reaction of neopentyl glycol, phosphorus thio-chloride and 1,2-ethylenediamine, and characterized by elemental analysis, IR and ^1H NMR spectra. Its crystal structure was determined by single-crystal X-ray diffraction analysis and the thermal property was analyzed by TG analysis. The crystal structure belongs to monoclinic, space group P21/c, with a = 14.557（16）, b = 11.299（12）, c = 12.163（13）A,β = 98.707（19）^o, Dc = 1.305 g/cm^3, Z = 4, γ = 0.71073A,μ（MoKa） = 0.447 mm^-1, Mr = 388.41, V = 1977（4）A3, F（000） = 824, S = 1.107, the final R = 0.0478 and wR = 0.0810 for 1738 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the crystal structure is centrosymmetrically distributed through 1,2-ethylenediamine to join two distorted six-membered rings. The weak N-H…S interactions are observed and link the molecules into sheets. TG analysis shows that the title compound has good thermal stability and char-forming capability, which are required for an excellent intumescent fire retardant.     

5,6-二甲氧基-N-[(R)-4-甲氧基-2-(丙烯-2-基)-2,3-二氢苯并呋喃-5-基]-1,1a,2,7b-四氢环丙并[c]苯并吡喃-7b-基甲酰胺的合成与表征

鱼藤酮与氧硫叶立德反应得到关键中间体(5,6-二甲氧基-1,1a,2,7b-四氢环丙并[c]苯并吡喃-7b-基)[(R)-4-羟基-2-(丙烯-2-基)-2,3-二氢苯并呋喃-5-基]甲酮(2),2再通过醚化、肟化、贝克曼重排得到5,6-二甲氧基-N-[(R)-4-甲氧基-2-(丙烯-2-基)-2,3-二氢苯并呋喃-5-基]-1,1a,2,7b-四氢环丙并[c]苯并吡喃-7b-基甲酰胺(5),化合物的结构经1H NMR,MS和元素分析确认,采用单晶X射线衍射法确定化合物5的晶体结构.化合物5属于三斜晶系,P1空间群,晶胞参数:a=0.95772(5)nm,b=1.06591(6)nm,c=1.30112(7)nm,α=111.8460(10)°,β=109.8870(10)°,γ=93.0870°,V=1.13429(11)nm3,Z=2,Dc=1.281 g/cm3,μ(Mo Kα)=0.092 mm-1,F(000)=464.     

3-氯-4-二苄胺基-5-甲氧基-2(5H)-呋喃酮的合成与晶体结构

在THF溶液中合成了标题化合物3-氯-4-二苄胺基-5-甲氧基-2(5H)-呋喃酮,并用FT-IR、UV-Vis、1HNMR、13C NMR、MS、元素分析和X-射线衍射等进行了表征。结果表明此化合物属正交晶系,空间群为Pbca,晶胞参数为:a=15.891(16),b=11.126(11),c=19.778(19),α=β=γ=90°,V=3497(6)3,Z=8,Dc=1.306Mg/m3,μ=0.234 mm-1,F(000)=1440。在化合物的分子结构中,两个苯环几乎垂直于呋喃酮平面,且它们与呋喃酮平面的两面角分别为89.38°和88.19°。     

1-苯基-3-甲基-4-甲酰基-5-吡唑啉酮Cu(Ⅱ)配合物的合成及晶体结构

A novel Cu(Ⅱ) complex of 1-phenyl-3-methyl-4-acyl-5-pyrazolone was synthesized and crystallogra-phically characterized. The single-crystal structure of the complex reveals that the crystal belongs triclinic, space group P1 with cell parameters a=0.938 7(4) nm, b=1.124 4(5) nm, c=1.222 3(5) nm, α=99.538(7)°, β=104.049(8)°, γ=113.806(6)°, and Z=2, V=1.093 3(8) nm³. Cu(Ⅱ) ion is coordinated by two 1-phenyl-3-methyl-4-acyl-5-pyrazolone ligands, and one methanol molecule giving a coordination number of five, the coordination polyhedron around Cu(Ⅱ) ion can be described as a square pyramid. Two complex units link to each other through the hydrogen-bonding interactions to form a dimer. Meanwhile, a staircase-like layer structure was built up by offset face-to-face π…π stacking interactions and weak interactions between the dimers. CCDC: 625422.     

Synthesis,Crystal Structure and Anticancer Property of （Z）-N-（4-Bromo-5-ethoxy-3,5-dimethyl-furan-2（5H）-ylidene）-4-methylbenzenesulfonamide

The novel title compound(Z)-N-(4-bromo-5-ethoxy-3,5-dimethylfuran-2(5H)-yli-dene)-4-methylbenzenesulfonamide 1(C15H18BrNO4S) has been unexpectedly synthesized by the aminohalogenation reaction of ethyl 2-methylpenta-2,3-dienoate with TsNBr2,and characterized by mp,IR,1H NMR,EIMS,ESIHRMS and single-crystal X-ray diffraction.It crystallizes in mono-clinic,space group P21/c with a = 11.714(5),b = 14.106(5),c = 10.402(4) ,β = 97.298(8)°,V = 1704.9(12) 3,Mr = 388.27,Z = 4,Dc = 1.513 g/cm3,μ(MoKα) = 2.549 mm-1,F(000) = 792,the final R = 0.033 and wR = 0.062 for 3098 observed reflections(Ⅰ 2σ(Ⅰ)).     

Synthesis and Crystal Structure of 4,4′-(4-(1-Naphthyl)-4-phenyl- 1,3-butadienylidene)-bis[N,N-diethylbenzenamine]

The title compound (C40H42N2) has been synthesized by the reaction of 1-(1-naphthyl)-1-phenyl-3-chloropropylene and bis(4-(diethylamino) phenyl)methanone, and characterized by IR, 1H NMR, MS and X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 17.047(3), b = 10.807(2), c = 1&494(4) (A), β = 105.727(4)°, V=3279.4(11) A3, Mr = 550.76, Z = 4, Dc = 1.115 g/cm3, μ(MoKα) = 0.085 mm-1, F(000) = 1184, the final R = 0.0625 and wR = 0.1384 for 2276 observed reflections (I ＞ 2σ(Ⅰ)). X-ray analysis reveals that the butadiene fragment adopts a planar cisiod conformation and makes a dihedral angel of 69.4(2)° with the naphthalene ring.     

Synthesis and Crystal Structure of 4-Phenyl-5-(1′- t-butyl-5′-methyl-4′-pyrazolyl)-1,2,4-triazol-3-thione

The crystal structure of 4-phenyl-5-(1′-t-butyl-5′-methyl-4′-pyrazolyl)-1,2,4-triazol- 3-thione 5 (C16H19N5S, Mr = 313.42) has been determined by single-crystal X-ray diffraction analysis. The crystal belongs to monoclinic, space group P21/c with a = 6.680(2), b = 27.44(1), c = 9.388(4)(A。), β = 106.738(6)°, V = 1648(1)(A。)3, Z = 4, Dc = 1.263 g/cm3, μ= 0.200 mm-1, F(000) = 664, R = 0.0608 and wR = 0.1176. The results confirmed that 5 can be assigned to the thione tautomeric form.