2-氨基-3-氰基-4-(4-氟苯基)-4H-苯并[h]苯并吡喃的合成和晶体结构

标题化合物与N,N-二甲基甲酰胺(DMF)形成的1:1混合结晶物C20H23FN2OC3H7NO由对氟苯甲醛、丙二腈、-萘酚在六氢吡啶存在下合成并经DMF与水的混合溶剂重结晶而得, 其结构通过元素分析、IR 和1H NMR对化合物进行了表征,用X-射线单晶衍射法测定了该化合物的晶体结构。结果表明,晶体属于单斜晶系,P21/n空间群,a = 6.365(1), b = 10.620(2), c = 29.122(6) ? b = 92.00(1), V = 1967.3(6) ?, Mr = 389.42, Z = 4, Dc = 1.315 g/cm3, m (MoKa) = 0.092 mm-1, F(000) = 816。晶体结构用直接法解出,经全矩阵最小二乘法修正,最终偏离因子R = 0.047, wR = 0.1053。化合物分子中,原子C(1), C(2), C(3), C(4), C(5) 和O(1)形成1个六员环,该六员环中C(1)C(2)键长为1.346(3) 牛砻魑肆被肺焦瓜蟆?     

3-甲基-1a-(4-甲氧基苯基)-1,1-二氯-1,1a,2,3-四氢-吖丙啶并[2,1-d][1,5]苯并硫氮杂的合成和晶体结构

通过2-甲基-4-(4-甲氧基苯基)-2,3-二氢-1,5-苯并硫氮杂与二氯卡宾的[2 1]环加成反应制备了标题化合物,用X射线单晶衍射测定了其晶体结构.分子式C_(18)H_(17)Cl_2NOS,分子量366.30,晶体属正交晶系,空间群P_(bca),晶胞参数:a=1.2246(3)nm,b=1.5219(4)nm,c=1.9272(9)nm,V=3.592(2)nm~3,Z=8,D_c=1.355g·cm~(-3).位于中心的1,5-硫氮杂环为扭曲的类船式构象,船头与苯环并合,船底与吖丙啶环并合.     

改进的2-巯基-5-甲氧基咪唑并[4,5-b]吡啶合成法

以2,6-二氯吡啶为起始原料,经甲氧基化、硝化、氨基化、还原及成环5步反应得到2-巯基-5-甲氧基咪唑并[4,5-b]吡啶,总收率45.7%。重点比较了2-氯-6-甲氧基吡啶和2,6-二氯吡啶硝化反应条件及收率的差异,讨论了水合肼、NaOH的用量对目标产物收率的影响。用1HNMR、MS和IR测试技术对目标产物结构进行了表征。     

7-乙氧基-4'-甲氧基异黄酮磺酸铜的合成及其晶体结构

以芒柄花素为先导化合物,合成了水溶性异黄酮化合物7-乙氧基-4'-甲氧基异黄酮磺酸铜(1),其结构经1H NMR,IR,元素分析和X-射线单晶衍射表征.结果表明,1的组成为Cu(H2O)6(C18H15O4SO3)2*4H2O,属三斜晶系,P-1空间群,晶胞参数: a=0.723 1(6) nm,b=0.854 5(8) nm,c=1.723 9(15) nm,α=81.220(14)°,β=82.974(15)°,γ=81.416(15)°,Dc=1.668 mg*m-3,V＝1.032 9 nm3,Z=2. 在1的晶体结构中,Cu(Ⅱ)位于对称中心并被6分子水所配位,[Cu(H2O)6]2+,C18H15O4SO-3 和H2O之间存在多种氢键作用;还存在π┈π及C-H┈π芳香堆积作用.氢键、芳香堆积作用以及阴阳离子之间的静电引力共同将1组装成具有三维网络结构的超分子.     

7-乙氧基-4′-甲氧基异黄酮磺酸铜的合成及其晶体结构

以芒柄花素为先导化合物,合成了水溶性异黄酮化合物7-乙氧基4′-甲氧基异黄酮磺酸铜（1）,其结构经^1H NMR,IR,元素分析和X-射线单晶衍射表征。结果表明,1的组成为Cu（H2O）6（C18H15O4SO3）2·4H2O,属三斜晶系,P-1空间群,晶胞参数：n=0．7231（6）nm,b=0．8545（8）nm,c=1．7239（15）nm,α=81．220（14）°,β=82．974（15）°,γ=81．416（15）°,Dc=1．668mg·m^-3,V=1．0329nm^3,Z=2。在1的晶体结构中,Cu（Ⅱ）位于对称中心并被6分子水所配位,[Cu（H2O）6]^2＋,C18H15O4SO3^-和H2O之间存在多种氢键作用;还存在π…π及C—H…π芳香堆积作用。氢键、芳香堆积作用以及阴阳离子之间的静电引力共同将1组装成具有三维网络结构的超分子。     

桥连的双[噻吩并[2,3-d]嘧啶-4(3H)-酮]的合成

2-氨基-4-三氟甲基-5-甲基-噻吩-3-羧酸乙酯(1)与三苯基膦、六氯乙烷及三乙胺反应,以84％的产率得到膦亚胺2.在碳酸钾的催化下,膦业胺2与芳基异氰酸酯和双官能亲核试剂的串联氮杂Wittig反应制得新型桥连的双[噻吩并[2,3-d]嘧啶-4(3H)-酮]3,产率为58％～82％.所有产物结构经IR,1HNMR,MS表征和元素分析确证.     

2-氨基-3-氰基-4-芳基-6-甲氧基-1,4,9,10-四氢萘并[2,1-b]吡喃衍生物的一步合成

以芳醛、丙二腈和7-甲氧基-1,2,3,4-四氢萘-2-酮为原料,在六氢吡啶催化下以乙醇为溶剂,在室温合成了一系列新的2-氨基-3-氰基-4-芳基-6-甲氧基-1,4,9,10-四氢萘并[2,1-b]吡喃衍生物,反应条件温和,产率较高,并通过IR,1H NMR和元素分析表征产物的结构,还通过单晶X射线衍射分析确证产物的构象.     

稠杂环化合物的研究(Ⅻ)——3(1-萘亚甲基)-6-己基均三唑并[3,4-b]-1,3,4-噻二唑的合成及晶体结构研究

由3(1-萘亚甲基)-4-氨基-5-巯基-均三唑和庚酸在POCl_3存在下反应制得3(1-萘亚甲基)-6-己基均三唑并[3,4-b]-1,3,4-噻二唑,由X射线衍射方法确定其晶体及分子结构.该化合物属于C2/C空间群,a=2.8680(6)nm,b=0.8356(2) nm,c=1.6578(3)nm,β=114.92(2)°,Z=8,最终偏离因子R=0.070.对其键长等数据的分析表明:该化合物具有10π电子离域π键的结构.     

2-[3-苯氧甲基-4-苯基-[1,2,4]三唑-5-硫基]乙酰胺的合成、晶体结构表征及生物活性

在微波辐射下, 由苯氧乙酰肼出发, 合成了一系列三唑类衍生物, 利用单晶X射线衍射法测定了化合物5f的单晶结构. 化合物5f通过分子间氢键及范德华力形成了三维网状结构的超分子. 这些化合物对植物根的生长具有比较明显的促进活性.     

10-氯-5-二乙氧基甲基-1,3-二甲基色烯并[4,3-d]吡唑并[3,4-b]吡啶-6(3H)-酮的合成和晶体结构

利用L-脯氨酸催化的5-氯水杨醛(1)与6-甲基-4-羟基吡喃酮(2)的缩合反应及硫酸铜催化下与1,3-二甲基-5-氨基吡唑(3)的串联反应,合成得到了10-氯-1,3-二甲基-5-(2-氧代丙基)色烯并[4,3-d]吡唑并[3,4-b]吡啶-6(3H)-酮(4)和10-氯-5-二乙氧基甲基-1,3-二甲基色烯并[4,3-d]吡唑并[3,4-b]吡啶-6(3H)-酮(5).化合物5的结构通过单晶X射线衍射法确定:晶体属于三斜晶系,空间群P-1;相对分子质量Mr=803.68;晶胞参数a=1.03160(10)nm,b=1.42900(13)nm,c=1.44268(15)nm;V=1.9448(3)nm~3;Z=2;晶胞密度Dc=1.372g/cm~3;吸收系数μ=0.228mm-1;单胞中电子的数目F(000)=840.晶体结构用直接法解出,经全矩阵最小二乘法对原子参数进行修正,最终的偏离因子为R=0.0681,w R=0.2051.在晶体结构中色烯环与吡啶环及吡唑环近似于共平面.     

Synthesis of 5-[2-(Phenoxy)ethyl] Derivatives of 6-Methyluracil, 6-Methyl-2-thioxo-2,3-dihydro-1H-pyrimidin-4-one,and 2-Imino-6-methyl-2,3-dihydro-1H-pyrimidin-4-one

A synthesis of novel derivatives of 6-methyluracil, 6-methyl-2-thioxo-, and 2-imino-6-methyl-2,3-dihydro-1H-pyrimidin-4-one containing a 2-(phenoxy)ethyl substituent at position 5 of the pyrimidine ring has been carried out. It was found that 5-[2-(phenoxy)ethyl] derivatives of 6-methyl-2-thioxo- and 2-imino-6-methyl-2,3-dihydro-1H-pyrimidin-4-one are obtained by the condensation of the corresponding ethyl 3-oxo-2-(2-phenoxyethyl)butanoates with thiourea or guanidine. 6-Methyl-5-[2-(phenoxy)ethyl]uracils can be prepared by treating 6-methyl-5-[2-(phenoxy)ethyl]-2-thioxo-2,3-dihydro-1H-pyrimidin-4-ones with an excess of aqueous monochloroacetic acid solution. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1213–1217, August, 2005.     

Synthesis of some 5H-benzo[a]phenothiazin-5-one derivatives

Several substituted 6-anilino-5H-benzo[a]phenothiazin-5-one derivatives were prepared by condensation of substituted 1,4-naphthoquinones with 2-aminobenzenethiol in pyridine. The reduction and acetylation of the resulting compounds were also investigated.

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Synthese einiger 5H-Benzo[a]phenothiazin-5-on-Derivate

Zusammenfassung Es wurden mittels Kondensation substituierter 1,4-Naphthochinone mit 2-Aminothiophenol in Pyridin einige substituierte 6-Anilino-5H-benzo[a]phenothiazin-5-one dargestellt. Die Reduktion und Acetylierung der resultierenden Verbindungen wurde ebenfalls untersucht.

     

Synthesis and Crystal Structure of 7-Ethoxycarbonyl-2-methyl-6-methylthio-lH-imidazo[1,2-b]pyrazole

The title compound 7-ethoxycarbonyl-2-methyl-6-methylthio-1H-imidazo[1,2-b]-pyrazole (Mr = 239.29) was synthesized and structurally characterized by IR, 1H NMR and single-crystal X-ray diffraction. It belongs to the triclinic system, space group P1, with a = 8.0461(10), b = 8.5534(11), c = 9.5605(12) A, α = 64.804(2), β = 74.231(2), γ = 76.885(2)°, V= 568.27(12) A3, Z = 2, Dc = 1.398 g/cm3,μ= 0.274 mm-1, F(000) = 252, the final R.= 0.0454 and wR = 0.1261. A total of 3360 reflections were collected, of which 2466 were independent (Rint = 0.0138) and 2154 were observed with I > 2σ(Ⅰ).     

Synthesis and Crystal Structure of 7-Ethoxycarbonyl-2-methyl-6-methylthio-1H-imidazo[1,2-b]pyrazole

The title compound 7-ethoxycarbonyl-2-methyl-6-methylthio-lH-imidazo[1,2-b]- pyrazole （Mr = 239.29） was synthesized and structurally characterized by IR, ^1H NMR and single-crystal X-ray diffraction. It belongs to the triclinic system, space group P1, with a =8.0461（10）, b = 8.5534（11）, c = 9.5605（12）А,α= 64.804（2）,β= 74.231（2）, γ= 76.885（2）°, V = 568.27（12）А^3, Z = 2,Dc= 1.398 g/cm^3,μ= 0.274 nunl, F（000） - 252, the final R = 0.0454 and wR = 0.1261. A total of 3360 reflections were collected, of which 2466 were independent （R_int = 0.0138） and 2154 were observed with I〉2σ（I）.     

Synthesis of 3-amino-4-methyl-6-trifluoromethylthieno[2,3-b]pyridine-2-carboxanilide and its crystal and molecular structure

4-Methoxy-1,1,1-trifluoropent-3-en-2-one reacts with cyanothioacetamide to give 3-cyano-4-methyl-6-trifluoromethylpyridine-2(1H)-thione, which was transformed into 3-amino-4-methyl-6-trifluoromethylthieno[2,3-b]pyridine-2-carboxanilide by the reaction with chloroacetanilide. The crystal and molecular structure of the amide obtained was studied by X-ray analysis. Translated fromIzvestiya Akademii Nauk Seriya Khimicheskaya, No. 4, pp. 701–703, April, 1998.     

Convenient Ultrasound-Promoted Regioselective Synthesis of Fused 6-Amino-3-methyl-4-aryl-1H-pyrazolo[3,4-b]pyridine-5-carbonitrile

A multicomponent, catalyst-free reaction for the synthesis of fused 6-amino-3-methyl-4-aryl-1H-pyrazolo [3,4-b] pyridine-5-carbonitrile from 3-amino-5-methylpyrazole, malononitrile, and substituted aldehydes under ultrasound irradiation in short reaction times (8–10 min) with good yields (85–98%) is reported.

Synthesis and Crystal Structure of 3-Benzyl-5-cyclohexylamino-6-phenyl-3,6-dihydro-l,2,3-triazolo[4,5-d]pyrimidin-7-one

The title compound 3-benzyl-5-cyclohexylamino-6-phenyI-3,6-dihydro-1,2,3-triazolo[4,5-d]pyrimidin-7-one (C23H24N6O, Mr = 400.48) has been synthesized by means of tandem aza-Wittig reaction, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a = 6.5550(6), b - 10.3711(10), c = 31.265(3)(A), β = 93.827(2)° ,V = 2120.8(4) (A)3, Z = 4, Dc = 1.254 g/cm3, S = 1.025, μ(MoKa) = 0.081 mm-1, F(000) = 848, R = 0.0576 and wR = 0.1368. X-ray analysis reveals that all ring atoms in the triazolopyrimidinone moiety are almost coplanar and the cyclohexyl ring adopts a chair conformation.     

Synthesis and mesomorphic properties of 7-alkoxybezopyrano[2,3-c]pyrazol-3-one

A new series of fused polyheterocyclic aromatic compounds, 7-alkoxybezopyrano[2,3-c]pyrazol-3-one (C- n BPP), were synthesised and characterised by infrared, ¹H-nuclear magnetic resonance (NMR), ¹³C-NMR and two-dimensional ¹H-¹³C cosy spectra. Their phase transition behaviour was investigated by differential scanning calorimetry and polarising optical microscopy. All of these compounds showed enantiotropic mesophases with temperature domains of 12–60°C and 22–69°C on heating and cooling processes for a carbon number of the alkoxy chain from 2 to 10. The effect of the length of the alkoxy chain on the mesomorphic properties was discussed. Comparison of C- n BPP and several kinds of coumarin derivatives indicated that the intermolecular hydrogen bonding acted as the driving force of the mesophase formation.     

2,6-二甲基-3-苯基-4a-对甲苯基-7-苯甲酰基-4a,5,6,12-四氢-1H,7H-1,3-噁嗪并[3,2-d][1,5]-苯并二氮杂-1-酮的合成及晶体结构

通过2-甲基-4-对甲苯基-1-苯甲酰基-2，3-二氢-1H－1，5-苯并二氮杂与由不对称1-苯基-2-偶氮-1，3-丁二酮热解产生的a-羰基烯酮的[2＋4]环加成反应制备了标题化合物（C34H30N2O3，Mr=514．62），用X射线衍射测定了其单晶结构。晶体属单斜晶系，空间群为P21／n，a=11．560（1），b=19．058（3），c=13．207（2）A，β=106.82（1）°，V=2785.2（7）A3，Z=4，Dc=1．230g．cm-3，MoKa（λ=0.71073A），μ=0．064mm-1，F（000）=1088，2278个可观测衍子射点，R=0．046，Rw=0．049。分子骨架为由苯环、具有类扭船式构象的七元二氮杂环和略微扭曲的唑酮环构成的三环体系。     

Synthesis of Substituted Pyrazino[5,6-b]pyrimidine and Some Indole Derivatives

Refluxing dimethyl acetylenedicarboxylate (DMAD) or 1,2-dibenzoylacetylene with isatin-3-thiosemicarbazone or isatin-3-thiocarbohydrazone in methanol produced 3-substituted oxindoles in good yields. Reaction of equimolecular amounts of 5,6-diamino-urasil-solfate, trans-(1R,2R)-diaminocyclohexane, and 3,4-diamino-1,2,4-triazol-5-methyl hydrochlorid with isatin in ethanol (85%) afforded tetracyclic ring systems and ring-opened products in mild reaction conditions.