3-碘-N1-(2-甲基-4-七氟异丙基苯基)-N2-(1,1-二甲基-2-甲砜基乙基)-1,2-苯二甲酰胺的合成

以邻苯二甲酸酐为原料,经酰胺化、氧化、碘化反应制得3-碘-N1-(2-甲基-4-七氟异丙基苯基)-N2-(1,1-二甲基-2-甲硫基乙基)-1,2-苯二甲酰胺。讨论了反应物料摩尔比、催化剂用量、反应温度、反应时间等因素对产品收率的影响。优化后四步反应总收率61.1%,含量96.5%。产物及中间体结构经1HNMR和ESI-MS确证。通过对钯碳的回收套用大大降低了成本。该合成路线具有原料易得,操作简便,收率高等优点,具有较好的工业化应用前景。     

Preparation and characterization of indium based complex perovskites-Pb(In1/2Nb1/2)O3 (PIN), Ba Ba(In1/2Nb1/2)O3 (BIN), and Ba(In1/2Nb1/2)O3 (BIT)

The processing of order-disorder perovskites Ba(In_1/2Nb_1/2)O₃ (BIN), Ba(In_l/2Ta_1/2)O₃ (BIT), and the lead analogue Pb(In_1/2Nb_1/2)O₃ (PIN) was investigated with an emphasis on improving and expanding our knowledge of microwave dielectric materials. Both BIN and BIT were shown to be paraelectric perovskites. The processing and annealing of PIN were related to the perovskite and its transformation to pyrochlore. Dielectric and physical characteristics were examined by X-ray diffraction profiles (XRD), scanning electron microscopy (SEM), and dielectric behavior. Attempts to enhance B-site cation order in PIN by thermal annealing were unsuccessful due to a pyrochlore formation.     

3-碘-N1-(2-甲基-4-七氟异丙基苯基)-N2-(1,1-二甲基-2-甲砜基乙基)-1,2-苯二甲酰胺的合成

以邻苯二甲酸酐为原料,经酰胺化、氧化、碘化反应制得3-碘-N1-(2-甲基-4-七氟异丙基苯基)-N2-(1,1-二甲基-2-甲砜基乙基)-1,2-苯二甲酰胺。讨论了反应物料摩尔比、催化剂用量、反应温度、反应时间等因素对产品收率的影响。优化后4步反应总收率61.1%,产物HPLC纯度96.5%。产物及中间体结构经1HNMR和ESI-MS确证。通过对钯碳的回收套用降低了成本,该合成路线具有原料易得,操作简便,收率高等优点,具有较好的工业化应用前景。     

2-(2-氯苄基)-2-(1-氯环丙基)环氧乙烷的合成

报道了丙硫菌唑中间体2-(2-氯苄基)-2-(1-氯环丙基)环氧乙烷的合成方法。以1-氯-N,N-二甲基环丙基甲酰胺和邻氯氯苄为原料,经格氏反应制备2-氯苄基-(1-氯环丙基)酮;后者再与硫叶立德试剂反应得到相应的环氧化物。     

1-羟乙基-2-苯并咪唑氨基甲酸甲酯和1-乙基(2’一丙烯酸酯-1’-基)-2-苯并咪唑氨基甲酸甲酯的合成及用薄层一紫外分光光度法测定其含量

１－乙基（２’－丙烯酸酯－１’－基）－２－苯并咪唑氨基甲酸甲酯是合成多菌灵高 分子化学型缓释剂的重要单体。本文报道了１－乙基（２’－丙烯酸酯－１’－基）－２－苯并 咪唑氨基甲酸甲酯及其制备过程中的中间体－１－羟乙基－２－苯并咪唑氨基甲酸甲酯的 合成和分析方法。     

反式β-甲基-β-硝基苯乙烯类化合物的制备

提供一种快速高效反式β-甲基-β-硝基苯乙烯类化合物的环境友好合成方法,超声波辅助下利用苯甲醛与硝基乙烷烃反应生成硝基烯烃,得到较高的收率,探索了对合成硝基烯烃影响的各种因素。实验表明,最适反应条件为：原料配比（硝基乙烷：苯甲醛）为1．6：1,反应的催化剂用量用量为7％,反应温度为45℃,反应时间为5h。     

Negative thermal expansion of (Al1/3Fe1/3Cr1/3)2(Mo1/2W1/2)3O12 (AFCMW) and low thermal expansion of AFCMW-(Co1/2Ni1/2)(Mo1/2W1/2)O4 with high entropy

A₂Mo₃O₁₂ (A-Al, Fe, Cr) have large negative thermal expansion (NTE) coefficients and structural stability but high phase-transition temperatures (PTTs). Herein, we prepared (Al_1/3Fe_1/3Cr_1/3)₂(Mo_1/2W_1/2)₃O₁₂ (AFCMW), and found it to have a low NTE coefficient and a low PTT. Furthermore, combination of AFCMW with (Co_1/2Ni_1/2)(Mo_1/2W_1/2)O₄ (CNMW) afforded an AFCMW–CNMW composite with a low thermal expansion (LTE). We determined that the PTT reductions in A₂Mo₃O₁₂ are largely due to the high-entropy effect resulting from the introduction of different ions into its A and M sites. Moreover, we found that the low LTE of the AFCMW–CNMW composite is attributable to the opposite thermal expansion behaviours of AFCMW and CNMW. We suggest that the suppressed thermal expansion during the phase transition process of the AFCMW–CNMW composite could be derived from the high-entropy effect resulting from its increased diversity of polyhedra, the influence of Co²⁺ and Ni²⁺ dopants, and CNMW-induced lattice distortion.     

苯并咪唑炔丙基硫醚的合成

以２－巯基苯并咪唑和炔丙基氯为原料在碱性条件下缩合成苯并咪唑炔丙基硫醚。反应条件温和,产率６０％。     

头孢他啶侧链酸合成工艺研究

研究了头孢他啶侧链酸乙酯在碱性条件下水解得头孢他啶侧链酸。讨论了不同溶剂、碱的用量、不同温度对反应收率的影响,优选出较佳的反应条件：头孢他啶侧链酸乙酯35．6g,氢氧化钠6．4g,反应溶剂V（甲醇）／V（水）=2：1,共500mL,于45-50℃反应8h,收率为86％。     

阿西替尼中间体(E)-6-碘-3-(2-(吡啶-2-基)乙烯基)-1-(四氢-2H-吡喃-2-基)-1H-吲唑的合成研究

(E)-6-碘-3-(2-(吡啶-2-基)乙烯基)-1-(四氢-2 H-吡喃-2-基)-1 H-吲唑是阿西替尼的关键中间体,以6-硝基-1 H-吲唑为起始原料,经过碘代、加成、偶联、还原、碘代得到目标化合物。探讨了用微波辐射加热偶联反应的问题,并对各步反应合成条件进行了优化。改进后工艺总收率达42.32%(6-硝基-1 H-吲唑为原料计),收率比文献报道值提高近5%,目标化合物和各中间体经1 H NMR和MS等确证结构。改进后的工艺降低了成本,简单可行,适合工业化生产。     

Tetrazolverbindungen. 2. (1-Aryl-1H-tetrazol-5-yl)-acetaldehyd-Derivate aus 1-Aryl-5-(2-dimethylamino-vinyl)-1H-tetrazolen

Tetrazole Compounds. 2. 1-Aryl-1H-tetrazole-5-acetaldehyde Derivatives from 1-Aryl-5-(2-dimethylamino-vinyl)-1H-tetrazoles 1-Aryl-5-(2-dialkylamino-vinyl)-1H-tetrazoles 2 , easily accessible by the reaction of 3-chloro-propeniminium salts 1 with excess sodium azide in refluxing alcohols, represent enamines of the hitherto unknown 1-aryl-1H-tetrazole-5-acetaldehydes 3 . Attempts to isolate the latter after acid-catalyzed hydrolysis of 2 were unsuccessful. However, generated in situ, they can be trapped by suitable aldehyde reagents. Thus, starting from 1-aryl-5-(2-dimethylamino-vinyl)-1H-tetrazoles 4 , the 4-nitrophenylhydrazones 5a--hyphen;i , 2,4-dinitrophenylhydrazones 5j--hyphen;r , and thiosemicarbazones 6 of the corresponding 1-aryl-1H-tetrazole-5-acetaldehydes 3 were obtained. Analogously, acid-catalyzed hydrolysis of 4 in the presence of 1,2-dianilinoethane resulted in 1-aryl-5-(1,3-diphenyl-2-imidazolidinylmethyl)-1H-tetrazoles 7 . --hyphen; The structure of the aldehyde derivatives 5 , 6 , and 7 was proved by ¹H n.m.r. spectroscopy.     

Microwave dielectric dispersion in T1(InS2)0.985 (FeSe2)0.015

This paper presents the results of an investigation of microwave dielectric dispersion in the semiconductive ferroelectric T1(InS₂) _0.985 (FeSe₂) _0.015 in the frequency range 1 MHz to 110 GHz. Dielectric dispersion did not give any evidence for the existence of an incommensurate phase in these crystals. It is shown that dielectric dispersion is Debye type in the frequency range 10⁶ to 10¹¹ Hz and is caused by two relaxational soft modes. The magnitude of the activation energy for the higher frequency relaxational mode is found to be U = 0.1 eV.     

Synthesis of biologically active 4-benzyl-1(2H)-phthalazinones and 2-aryl-3(2H)-1-benzal-isoindolinones

4-Benzyl-2-1(2H) phthalazonyl derivatives of type 2, 3, 5a, b were synthesized by Mannich reaction of 4-benzylphthalazinone 1 which by the reaction with diazomethane yielded O-methylated derivative 4 . Various 1-benzal-2-substituted aryl-3(2H) isoindolinones 7a–f, 8a–e were also prepared. Its i.r., ¹H-n.m.r. and mass spectra were discussed. Some of them exhibit pronounced antimicrobial activities. A number of phthalazinones have found application in clinical medicine [1–3] due to the their pronounced antipyretic, analgesic and tuberculostatic activity and the importance of some benzylidenephthalimidines as stabilisers for halogen containing high polymers [4] and the local anesthetic activity superior to that of procaine [5], tempted us to procure some new phthalazinones and isoindolinones with biological interest.     

(E)-2-(1-萘亚胺)苊酮席夫碱的合成及晶体结构

以1,2-苊二酮和甲萘胺为原料合成标题化合物,其结构经1HNMR、MS和单晶X-射线衍射技术表征。实验结果表明,该化合物晶体为单斜晶系,P21/c空间群,化合物分子式为C22H13NO,分子量为307.33,晶胞参数为a=0.825 90(11)nm,b=1.551 4(2)nm,c=1.202 39(16)nm,α=90.00°,β=100.342(4)°,γ=90.00°,V=1.515 6(3)nm3,Z=4,CCDC:1035525。     

1-(Pyridin-2-ylmethyl)-2-(3-(1-(pyridin-2-ylmethyl)benzimidazol-2-yl) propyl) benzimidazole and its copper(II) complex as a new fluorescent sensor for dopamine (4-(2-aminoethyl)benzene-1,2-diol)

A new ligand 1-(pyridin-2-ylmethyl)-2-(3-(1-(pyridin-2-ylmethyl)benzimidazol-2-yl) propyl) benzimidazole (L) and its Cu(II) complex (1) have been synthesized and characterized spectroscopically and structurally. The Cu(II) ion is coordinated by two nitrogen atoms of benzimidazole groups, two oxygen atoms of the nitrate anions and one oxygen atom of a water molecule forming distorted trigonal bipyramidal geometry. The ligand and its complex have been utilized as a fluorescent sensor for 4-(2-aminoethyl)benzene-1,2-diol. A plot of F₀/F − F₀ vs 1/Conc (4-(2-aminoethyl)benzene-1,2-diol) at a selected wavelength of 306 nm with (L) that shows a straight line behavior, supports the validity of the assumption of 1:1 complex formation and the association constant of (L) with 4-(2-aminoethyl)benzene-1,2-diol is calculated to be 9868 M^− 1. Sensor (L) is found to be selective for 4-(2-aminoethyl)benzene-1,2-diol over aromatic amines, phenols, amino catechol (L-3,4-dihydroxyphenylalanine) and 4,6-ditertiarybutyl benzene-1,2-diol.     

Properties and structure of (As2Se3)1 − z (SnSe)z − x(GeSe)x and (As2Se3)1 − z (SnSe2)z − x(GeSe2)x glasses

Two valence states of tin atoms in (As₂Se₃)_{1 ? z} (SnSe)_{z ? x}(GeSe)_x and (As₂Se₃)_{1 ? z} (SnSe₂)_{z ? x}(GeSe₂)_x glasses are identified by Mössbauer and photoelectron spectroscopy. It is demonstrated that the presence of doubly charged tin ions in the structural glass network does not give rise to impurity conduction or impurity optical absorption. The inference is made that these glasses can be treated as semiconductor solid solutions.     

N-(4-羟基苯基)-2-(1H-咪唑-1-基)乙酰胺的合成

对硝基苯酚经铁粉/氯化铵还原得到对氨基苯酚,后者经氯乙酰化和N-烷基化反应合成N-(4-羟基苯基)-2-(1H-咪唑-1-基)乙酰胺。并考察了酰化以及N-烷基化等关键步骤的反应条件,较佳的反应条件为酰化反应以乙酸钠作为缚酸剂,反应温度20℃;N-烷基化以碳酸钾作为缚酸剂,碘化钠为催化剂。总收率31.4%,产物经过1H NMR和MS表征。     

2-氯-1-(1-氯环丙基)乙酮的合成

以α-乙酰基-γ-丁内酯为起始原料,经过氯代、水解、关环和氯代制得目标产物2-氯-1-(1-氯环丙基)乙酮,总收率约为70%。其结构经~1H NMR确证。     

1—（2—溴苯基）—2—丙醇的合成

以邻溴苯甲醛及硝基乙烷为原料,合成了１－（２－溴苯基）－２硝基丙烯,经氧化得邻溴苯基因酮,再用四氢化铝锂还原合成了标题化合物。经外红、质谱、核磁共振分析确定 了化合物的结构。