一种合成2-硝亚胺基-5-硝基-六氢化-1,3,5-三嗪(NNHT)的新方法

主要研究了合成2-硝亚胺基-5-硝基-六氢化-1,3,5一三嗪(NNHT)的新方法.该方法以硝基胍、乌洛托品、浓盐酸为原料,第一步通过成环反应生成中间产物NIHT·HCI,第二步通过硝化中间产物生成目标产物NNHT;中间产物的收率可达到78.3%,目标产物的总收率可达到64.3%以上.同时对影响反应的各种因素进行了分析讨论,如反应温度、反应时间、硝化条件等.利用傅立叶变换红外光%(FT-IR),氢核磁(1H NMR)、碳核磁(13C NMR)、高效液相色谱(HPLC)、元素分析等方法对目标产物进行了表征,确定为目标产物.     

1,3,5-三乙酰基六氢均三嗪的小分子法合成反应机理研究

1,3,5-三乙酰基六氢均三嗪(1,3,5-triacetyl-1,3,5-triazacyclohexane,TRAT)是高性能单质炸药黑索金的关键硝化前体.本研究以小分子三聚甲醛和乙腈为原料,浓硫酸为催化剂,合成了TRAT,产率为89%.合成并表征了N,N'-亚甲基二乙酰胺和未见报道的三乙酰基二亚甲基三胺.根据已得到的几个中间体,推测了TRAT合成反应的可能机理.     

离子色谱法测定1,3,5-三(3-二甲基氨丙基)六氢三嗪含量

建立了环状有机多胺类化合物1,3,5-三(3-二甲基氨丙基)六氢三嗪(PC41)的离子色谱测定法。研究表明,采用Ionpac CS12A阳离子交换柱,抑制电导模式,以25 mmol/L硫酸溶液为淋洗液,可对1,3,5-三(3-二甲基氨丙基)六氢三嗪进行定量测定。多胺类化合物在抑制电导下为非线性响应,故采用二次抛物线方法定量,线性范围为0~17.84 mg/L,线性方程为y=–0.001 8x2+0.231 3x+0.011 5,相关系数为0.999 8,测量结果的相对标准偏差小于1%(n=5),3水平加标回收率为99.3%~100.2%。该方法操作简单,测定结果准确可靠,可用于测定合成聚亚胺酯原料1,3,5-三(3-二甲基氨丙基)六氢三嗪的含量。     

1-甲基-3,4-二苯基喹啉-2(1H)-酮的合成和结构表征

以N-甲基苯胺和苯丙炔酸为原料,经过缩合、亲电环化、偶联反应合成了1-甲基-3,4-二苯基喹啉-2(1H)-酮;利用核磁共振谱和气相色谱-质谱表征了产物的结构.结果表明,所用合成方法具有产率高、反应条件温和、操作简单等优点,目标产物的总产率达62.7%.     

2,4,6-三(对甲氧基苯乙烯基)-1,3,5-均三嗪光转换剂的合成

合成了新化合物2,4,6-三(对甲氧基苯乙烯基)-1,3,5-均三嗪(TMST);利用红外光谱、元素分析和核磁共振(1 H NMR)分析了化合物的组成和结构,利用紫外和荧光光谱分析了其光谱特征.结果表明,在375nm的紫外光激发下,化合物在410～480nm区域发出较强的蓝光,对应于叶绿素a的主吸收峰;这表明其可望作为一种新的蓝光光转换剂而应用于农用薄膜.     

2,4,6-三(芳基氨基)-1,3,5-三嗪衍生物的合成方法和微波效应研究

用碳酸氢钠作扑酸剂,将芳香胺和氰尿酰氯在1,4-二氧六环中回流状态下反应合成了7个2,4,6-三(芳基氨基)-1,3,5-三嗪衍生物,其中6个是新化合物.与已有文献报道的方法相比,条件温和,易于操作,收率高.所合成化合物的结构通过元素分析,FAB-MS,IR确定.在二氧六环:DMF为10:3(V:V)的混合溶剂中,研究了在微波照射下和常规加热下反应速率的差异.结果表明,微波加热比常规加热下的反应速率至少高10倍以上.     

2-甲基-2-(2-硝基乙烯基)-1-苯并环酮的对映选择合成

在有些具有强烈生理活性的天然产物分子中,存在保持其特殊分子骨架的不对称季碳,是具有特定生理活性的决定性因素．利用ＳＭＰ［Ｓ－（－）－２－ｍｅｔｈｏｘｙｍｅｔｈｙｌ－ｐｙｒｒｏｌｉｄｉｎｅ］作为手性离去基团,通过对映选择加成－消除反应构筑不对称季碳,是...     

2,4,6-三(2′-吡啶基)-1,3,5-三嗪作显色剂分光光度法测定手面皮肤的铁含量

应用铁(Ⅱ)与2,4,6-三(2′-吡啶基)-1,3,5-三嗪(TPTZ)的显色反应,用分光光度法测定了手表面皮肤上沾染铁的含量。测定时,用在去离子水中浸湿的脱脂棉擦拭手皮肤上铁的印迹,将脱脂棉中的液体挤出并接盛于小烧杯中,重复操作一次。将两次擦拭所得液体移入25mL容量瓶中,加入30g·L-1抗坏血酸溶液2mL,1g·L-1 TPTZ溶液2mL及pH 4.2乙酸铵缓冲溶液3mL,加水至刻度,在室温下放置10min。测定波长为596nm,按此条件,铁(Ⅱ)的质量浓度在2.0mg·L-1以内遵守比耳定律。试验结果表明:手与铁器接触时间长,则沾染在手面的铁量多;手面的湿度越高,沾染的铁量也越多,其最大值和最小值之间相差可达12μg。     

1-(三氟甲基)-1,2-苯碘酰-3(1H)-酮在芳杂环上三氟甲基化的应用研究

以1-(三氟甲基)-1,2-苯碘酰-3(1H)-酮为三氟甲基源,并以2-氨基-5-溴吡啶为三氟甲基化底物,采用响应面分析法对合成工艺进行了分析优化,确定了最佳反应条件为:反应时间4 h,催化剂用量0.16 eq,反应温度50℃.经过3次验证实验,其平均收率为87％.最后继续合成了多个三氟甲基杂环芳香胺,且化合物结构经1...     

2,4,6-三萘基-1,3,5-三嗪的合成与光谱行为

本文通过Suzuki偶联反应高效合成了两种三萘基三嗪化合物,即2,4,6-三(1-萘基)-1,3,5-三嗪(T1NT)和2,4,6-三(2-萘基)-1,3,5-三嗪(T2NT). 考察了介质的极性、温度以及THF-H₂O二元溶剂体系中的溶解性等因素对它们吸收和发射光谱行为的影响.研究发现, 由于T1NT比T2NT具有更好的分子平面性,其激发态下分子内电荷转移的程度较大,导致其在溶液中吸收光谱、发射光谱比T2NT呈现显著红移.冻结态下,分子平面性较差的T2NT显示出较短波长的发光.     

Condensed tetrazolo-1,3,5-triazines. 4. Synthesis of salts of 5-aminotetrazolo[1,5-a]-1,3,5-triazin-7-one

2-Amino-4-azido-1,3,5-triazin-6(1H)-ones were synthesized by successive substitution of the trinitromethyl groups in 2-amino-4,6-bis(trinitromethyl)-1,3,5-triazines under the influence of azide and nitrite ions. Interaction of 2-amino-4-azido-1,3,5-triazin-6(1H)-ones with bases led to the azido-tetrazole tautomeric conversion give salts of 5-aminotetrazolo[1,5-a]-1,3,5-triazin-7-one. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1211–1219, August, 2006.     

Synthesis, Crystal Structure and Antibacterial Activity of 1-（（2-Chloroquinolin-3-yl）-methyl）-pyridin-2（1H）-one

On the basis of the interesting structures and biological activities exhibited by several heterocyclic systems possessing the pyridone nucleus such as mappcine and camptothecin, we have planed to design the synthesis, crystal studies and antibacterial activity of the new 1-((2- chloroquinolin-3yl)-methyl)-pyridine-2(1H)-one building block. An X-ray analysis has provided valuable insight into the effect of steric factors on the three-dimensional shape of this compound which serves as a useful advanced intermediate in the synthesis of these biologically active molecules. A multistep synthesis of camptothecin (5) has been designed by retrosynthetic analysis as part of an ongoing program on lead anticancer drug.     

Synthesis,structures, and properties of bis(4,6-disubstituted 1,3,5-triazin-2-yl) ethers

Reactions of (4,6-disubstituted 1,3,5-triazin-2-yl)trimethylammonium chlorides with glycine sodium salt in the presence of Et₃N afforded bis(triazin-2-yl) ethers instead of the expected triazinylaminoacetic acids. The structures of the resulting compounds were established by the independent synthesis, spectroscopic data, and X-ray diffraction analysis.     

Molecular structure of a zwitter-ionic 2-piperidinyl-4-dinitromethyl-1,3,5-triazin×(1H, 5H)-6-one salt

A zwitter-ionic salt 2-piperidinyl-4-dinitromethyl-1,3,5-triazin(1H,5H)-6-one is studied by the single crystal X-ray analysis. The crystals are monoclinic: a = 11.526(1) Å, b = 9.211(1) Å, c = 12.182(1) Å; β = 110.69(1)°, V = 1209.9(2) ų, space group P2₁/n; Z = 4, ρ_calc = 1.560 g/cm³. The transformation of the dinitromethyl fragment conformation, the conjugation of one of nitrogroups with the 1,3,5-triazine ring, and an intramolecular hydrogen bond are revealed. The 1,3,5-triazine cycle is strongly distorted due to lactam-lactim tautomerism.     

Synthesis and Crystal Structure of （Z）-1- （3-Fluorobenzyl）-5-（（3-fluorobenzylimino）（2-hydroxy-4-methoxyphenyl）methyl）pyridin-2（1H）-one

The title compound （Z）-1-（3-fluorobenzyl）-5-（（3-fluorobenzylimino）（2-hydroxy-4- methoxyphenyl）methyl）pyridin-2（1H）-one （C27H22F2N2O3,Mr = 460.47） was synthesized and crystallized. The crystal belongs to the triclinic system,space group P1 with a = 9.951（6）,b = 10.059（6）,c = 12.927（7）A,α = 109.828（7）,β = 102.304（7）,γ = 104.898（7）°,Z = 2,V = 1110.2（11）A^3,Dc =1.377 Mg/m^3,μ（MoKα） = 0.102 mm^-1,F（000） = 480,the final R = 0.0449 and Rw = 0.1250 for 4595 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that both m-fluorobenzyl groups are diorientationally disordered because of the rotation of C–C single bond which was represented as F（1）,F（2） and F（1＇）,F（2＇）. The diorientational disorder was refined and gave the occupancies of 0.665（4） and 0.335（4） for F（1） and F（1＇）,0.631（3） and 0.369（3） for F（2） and F（2＇）. Hydrogen bonds existing in the cell link different components to stabilize the crystal structure. The active data proved that the title compound has good anti-HBV activity.     

3-苯基喹唑啉-4(3H)-酮的合成及晶体结构

标题化合物C14H10ON2是由邻硝基苯甲酰苯胺与原甲酸三乙酯在低价钛试剂作用下反应而得。结构通过单晶X-射线衍射分析确定, 其晶体属于单斜晶系, 空间群P21/c, a = 12.080(2), b = 7.793(1), c = 11.599(1) ? b = 97.56(1), Mr = 222.24, V = 1082.4(2) ?, Dc = 1.364 g/cm3, Z = 4, m(MoKa) = 0.88 mm-1, F(000) = 464, R = 0.0385, wR = 0.0851。X-衍射分析表明: 平面I (C(1)~C(6))与平面II (C(9)~C(14))之间的夹角为124.38; 平面I与平面III (ON(1)?N(2)C(7)C(8)C(9)C(14))之间的两面角为125.47; 平面II与平面III之间的两面角为2.76。     

Formation of hexahydro-1,3,5-triazin-2-one and hexahydro-1,3,5-triazine2-thione derivatives in reactions of glycylglycine with paraformaldehyde andN,N′-disubstituted ureas and thioureas

Hexahydr-1,3,5-triazin-2-one and hexahydro-1,3,5-triazine-2-thione derivatives were shown to be formed selectively in reactions of glycylglycine with paraformaldehyde and N,N'-dialkylureas, NN'-diethylthiourea, and glycoluril.     

无溶剂条件下方便、有效的方法合成3-氰基-2-吡啶酮衍生物

芳醛、丙酮和氰乙酰胺为原料,氢氧化钠为催化剂,在无溶剂条件下加热反应有效地合成2-吡啶酮衍生物,本方法具有反应时间短、条件温和、处理简单和环境友好等优点.     

The Reactions of 6-(tert-Butyl)-3-hydrazino-1,2,4-triazin-5(2H)-one with Carbonyl Compounds

The reaction of 6-(tert-butyl)-3-hydrazino-1,2,4-triazin-5(2H)-one with acetone and benzaldehyde yields the corresponding hydrazones. In the presence of thionyl chloride the benzaldehyde hydrazone is converted to 3-(tert-butyl)-6-phenyl-1,2,4-triazolo[4,3-b]-1,2,4-triazin-2(1H)-one and this can also be formed via the acylation of the starting hydrazinotriazinone using benzoyl chloride.     

Synthesis and Crystal Structure of a New Quinazolinone Compound 2,3-Dihydro-2-（2-hydroxyphenyl）-3-phenyl-quinazolin-4（1H）-one

A new quinazolinone compound 2,3-dihydro-2-(2-hydroxyphenyl)-3-phenylquinazolin-4(IH)-one 3 ([C2oH16O2N2]-C2H5OH, Mr = 362.42) and compound 2-(2-hydroxybenzylidene-amino)-N-phenyl-benzamide 2 (C2oH16O2N2, Mr = 316.34) were prepared from a precursor of 2-amino-N-phenyl-benzamide 1 (C13H12ON2, Mr = 212.25). Compound 3 was characterized by single-crystal X-ray diffraction analysis. The crystal belongs to orthorhombic,space group Pbca with a = 1.2889(11), b = 1.6170(14), c = 1.7729(15) nm, V= 3.695(6) nm^3, Z= 8, F(000) = 1536, Mr = 362.42, Dc = 1.303 g/cm^3, μ(MoKa) = 0.087 mm^-1, R = 0.0447 and wR= 0.0879. The crystal structure analysis indicates that the title compound has a two-dimensional network structure formed by hydrogen bonds and electrostatic interactions.