dppm与CH2Cl2在Pd（OAc）2作用下反应stopped—flow动态学研究

ｄｐｐｍ与ＣＨ２Ｃｌ２在Ｐｄ（ＯＡｃ）２作用下反应ｓｔｏｐｐｅｄ＿ｆｌｏｗ动态学研究韦凤萍黄永仁（华东师范大学分析测试中心上海２０００６１）汪汉卿（中国科学院物理研究所兰州７３００００关键词动态学Ｐｄ（ＯＡｃ）２ｄｐｐｍＣＨ２Ｃｌ２停－流中图分类号Ｏ...     

新显色剂2-(2-咪唑偶氮)-5-二乙氨基苯胺与钯显色反应的研究

研究了新显色剂2-2-(咪唑偶氮)-5-二乙氨基苯胺(IZAEA)与Pd2+显色反应的条件。试验结果表明,在pHL5. 0的HOAc-NaOAc介质中,试剂与Pd2+形成稳定的紫红色络合构,此络合物不被强酸分解,其它金属离子与试剂形成的有色络合构均被强酸分解。络合物的λmax为564nm,试剂的λmax为476nm,对比度△λ为88nm,Pd2+与试剂的络合比为l2,表观摩尔吸光系数为2．81×104L·mol-1·cm-1,Pdz+浓度在0～0．8mg·L-1范围内遵守比耳定律。所拟方法直接测定催化剂和分子筛中微量钯,结果满意。     

REACTION OF PENTAERYTHRITOL WITH DIETHYL PHOSPHOROCHLORIDATE PENTAERYTHRITOL BIS-, TRIS- AND TETRAKIS(DIHYDROGEN PHOSPHATES)

Abstract

Reaction of pentaerythritol 1 with 1, 2 or 3 equivalents of diethyl phosphorochloridate 2 yielded pentaerythritol tris(diethyl phosphate) 5. Treatment of pentaerythritol with 4 or more equivalents of 2 gave pentaerythritol tetrakis(diethyl phosphate) 6. Transesterification of 5 and 6 with trimethylsilyl chloride and sodium iodide in acetonitrile followed by treatment with water gave pentaerythritol tris (dihydrogen phosphate) 7 and pentaerythritol tetrakis(dihydrogen phosphate) 8 respectively. Pentaerythritol bis(dihydrogen phosphate) 9 was prepared by the hydrolysis of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane 3,9-dioxide 10. The compounds 7,8 and 9 were isolated as anilinium salts and characterized by 1H, 13C and 31P NMR spectra.     

(S)-2,2,2-三氟-1-(2-甲基-1H-1-吲哚基)乙胺的不对称合成

以2-甲基吲哚为原料,在碱性条件下与α-三氟甲基醛亚胺经加成反应合成了关键中间体——含三氟甲基的(S)-叔丁基亚磺酰胺(3),收率95%,d/r99/1;3脱除保护基得(S)-2,2,2-三氟-1-(2-甲基-1H-1-吲哚基)乙胺(4),收率97%,其结构经1H NMR,13C NMR,19F NMR,FT-IR,EI-MS和HR-EI-MS确证。     

OCCURRENCE OF LIGAND COUPLING IN THE REACTIONS OF VARIOUS SULFOXIDES WITH GRIGNARD REAGENTS

Abstract

Ligand coupling reactions take place not only between benzyl and 2-pyridyl groups and two 2-pyridyl groups in the treatment of benzyl, alkyl and aryl 2-pyridyl sulfoxides with Grignard reagents, but also between such groups as p-benzenesulfonylphenyl, 4-pyridyl, 2-quinolyl and 2-pyrimidyl, and the benzyl group. There are cases in which ligand exchange precedes ligand coupling, especially with 2-heteroaryl groups. In addition, even some alkyl groups were found to couple with the 2-pyridyl group. The ease of coupling seems to be associated with the electronegativity of the coupling carbon atom of the ligand, when one compares the ¹³C NMR chemical shifts.     

REACTION OF SCHIFF BASE OF THIOHYDRAZIDES WITH P(NR2)3

Abstract

Three pathways were observed in the reactions of Schiff bases of Thiohydrazides with P(NR₂)₃. (a) MeS-R₂N exchange: MeS-C([dbnd]S)-NHN[dbnd]CHPh (1) reacted with P(NR₂)₃ led to new Schiff bases, R₂N-C([dbnd]S)-NHN[dbnd]CH = Ph (2). (b) Cleavage of C[dbnd]S bond and the formation of P[dbnd]S bond: H₂N-C([dbnd]S)-NHN[dbnd]CH = Ph (3) reacted with P(NR₂)₃ gave rise to the thiophosphoric amide. (Et₂N)₂P([dbnd]S)-NH-CH = N-N[dbnd]CH-Ph (4). (c) Formation of thiadiazole and triazole: Schiff bases 2a and H₂N(MeS)C = N-N[dbnd]CH-Ph (6) reacted with P(NR₂)₃ respectively and produced 5-dimethylamino-2-phenyl-2,3-(2H)-1,3,4-thiadiazole (5) and 5-methylthio-2-phenyl-2,3-(2H)-1,3,4-triazole (7).     

REACTIONS OF COPPER (I) THIOLATES WITH HALOAROMATICS

Abstract

Recent studies have shown that replacement of I or Br and not C1 or F in haloaromatic compounds occurred when copper (I) thiolates, CuSR, were used as nucleophiles. Some proto debromination was also observed. Conversely using the free thiolate anion, SR^?, in solution, replacement of F or C1 rather than I or Br in haloaromatic compounds was observed. These general observations have been confirmed in the reactions of the isomeric dibromotetrafluorobenzenes with copper (I) methanethiolate, copper (I) pentafluorothiophenolate, and the methanethiolate anion.     

Proton sponges-based (2-naphthyl)pyridylmethanol

The action of 2-, 3-, and 4-pyridinecarboxaldehydes on 1,8-bis(dimethylamino)-2-lithium-and 1,8-bis(dimethylamino)-2,7-dilithiumnaphthalenes gave secondary mono-and dicarbinols containing pyridylcarbinol groups at C-2 and C-7 of the proton sponge. Spectral and X-ray diffraction structural data were used to study the molecular structure of these products. Dedicated to Academician B. A. Trofimov, an outstanding organic chemist, who has made a major contribution to the chemistry of acetylenes and nitrogen heterocycles on the occasion of his seventieth jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1409–1417, September, 2008.     

Rhenium(V) Complexes of N,N′-Ethylenebis(2-mercaptopropanamide). Synthesis,Characterization, and X-ray Crystal Structures

The preparation of benzoyl-protectcd N,N′-ethylenebis(2-mercaptopropanamide) (H₄emp) and its ligand-exchange reaction with ReO₂(en)₂Cl are described. Three diastereomers, [syn-ReO(meso-emp)]; [anti-ReO(meso-emp)]-, and a pair of cnantiomers, [ReO(rac-emp)]-, were formed due to syn and anti orientation of the two methyl groups of the ligand relative to the ReO core. The diastereomers were separated by reverse phase C₁₈ semipreparative HPLC and isolated as salts of [Ph₄As][ReO-(emp)]. The structures of [Ph₄ As][ReO(meso-emp)] were determined by single-crystal X-ray analyses. [Ph₄As][syn-ReO(mesocmp)]H₂O crystallizes in triclinic space group Pl with a = 10.326(3) Å, b = 13.672(4) A, c = 14.023(5) Å, α = 61.20(2)°, β =74.74(3)°, γ= 75.68(2)° V = 1656.6(8) ų, Z = 2, Dc = 1.676 gmL^?1, F(000) = 824 and R = 0.0329 for 5877 unique reflections. For (he complex [Ph₄As][anti-ReO(meso-emp)], the crystal data are: monoclinic, space group P2₁/n, a = 9.128(2) Å, b = 24.284(7) Å, c = 14.112(4) Å, β = 93.41(2)° V = 3122.5(15) À³, Z = 4, Dc = 1.740 gmL^?1, F(000) = 1608 and R = 0.0361 for 5487 unique reflections. In both structures the rhenium atom is penta-coordinated and in an approximately square pyramidal environment.     

SYNTHESIS OF NOVEL BIDENTATE (Te,N) LIGANDS-2-ARYLTELLUROETHYLAMINES AND THEIR COMPLEXATION WITH MERCURY (II)

Abstract

Sodium aryltellurolate (ArTe^?Na⁺, where Ar = 4-MeOC₆H₄ or 4-EtOC₆H₄) reacts with 2- bromoethylamine resulting in the (Te, N) ligands 2-aryltelluroethylamine (ArTeCH₂CH₂NH₂, 1) which have been characterized by elemental analyses, molecular weight, IR, ¹H and ¹³C NMR spectra. With HgCI₂, they form HgC1₂·1 type of complexes. IR, ¹H and ¹³C NMR spectra of the complexes suggest that 1 ligates as a bidentate ligand with respect to Hg(II). Osmometric molecular weight measurements suggest that on heating the mercury complex HgCl₂·lb (Ar = 4-EtOC₆H₄) in solution, relatively less soluble species result. It seems to have two Hg atoms bridged by two (Te, N) ligands. The HgC₂·la (Ar = 4-MeOC₆H₄) has very low solubility in organic solvents and. therefore, seems to be dimerized or polymerized during the synthesis. Analysis of CH₂ rocking bands in IR spectra suggests that two CH₂ groups of the ligands are most probably in a gauche conformation in the mercury complexes.     

1—（2—羟基—3,5—二硝基苯基）—3—[4—（苯基偶氮）苯基]—三氮烯与镉的显色反应

研究了新合成的1-(2-羟基-3,5-二硝基苯基)-3-[4-(苯基偶氮)苯基]-三氟烯(HDNPAPF)试剂,在乳化剂OP存在下与镉的显色反应。在pH为10.30～10.80的Na_2B_4O_7-NaOH介质中,镉与HDNPAPT形成1:1的红色配合物,表观摩尔吸光系数ε_(530)=1.85×10~5L/(mol·cm),镉浓度在0～0.6mg/L范围内符合比尔定律。该方法可用于电镀废水和环境水样中微量镉的测定。     

新试剂2-(6-甲基-2-苯并噻唑偶氮)-5-二乙氨基酚与铂的显色反应及配合物结构研究

研究新试剂2-(6-甲基-2-苯并噻唑偶氮)-5-二乙氨基酚(MBTAE)与铂的显色反应。在1-羟基-2-萘甲酸(R)存在下,于pH 5．5的乙酸盐缓冲溶液中,形成配位比为PtMBTAER＝111的三元配合物,λmax＝592nm,表观摩尔吸光系数ε＝6．84×104L·mol-1·cm-1。通过配合物的紫外和红外光谱性质,研完了三元配合物的结构,方法应用于催化剂中铂的测定,结果满意。     

(S)-(4-溴-2-甲苯)(3-甲基吗啉)甲酮的合成

以(S)-2-氨基丙醇和氯乙酰氯为起始原料,经酰化和环合反应制得(S)-5-甲基吗啉-3-酮（4）; 4经还原制得(S)-3-甲基吗啉(5); 5与4-溴-2-甲基苯甲酸酰化缩合合成了(S)-(4-溴2-甲基苯基)(3-甲基吗啉)-甲酮,总收率57%,其结构经¹H NMR 和 ¹³C NMR确证。     

自由基C59N及双体(C59N)2的理论研究

用INDO系列方法对自由基C59N及双体(C59N)2进行了理论研究,结果表明: N的掺入使C60笼发生畸变, N向笼外突出, 碳氮6-6键上的C自旋密度较大, 两C59N自由基在这个碳上以C-C单键连接形成双体为C2h, C2v对称性。其中C2v构型更稳定, 且N与附近的三个碳均以单键连接。理论计算的电子光谱与实验吻合较好。(C59N)2易分解为单体C59N。     

Bis(O-nitrophenyl) Carbonate as a New Reagent for the Synthesis of Chiral Oxazolidin-2-ones

Bis(o-nitrophenyl) carbonate reacts under mild conditions with chirals 1,2-amino alcohols and, after addition of DMAP, affords the corresponding oxazolidin-2-ones in very good yields.     

由对苯二甲酰胺二醇合成聚酯酰胺及其扩链反应的研究

以N,N′-二(2-羟乙基)对苯二甲酰胺与己二酸及丁二醇缩聚,合成了同时带有端羧基与端羟基的聚酯酰胺预聚体,研究了不同扩链剂的扩链反应,获得了特性黏度达1.05 dL/g的聚酯酰胺.对预聚体及扩链后聚合物进行了红外与核磁表征,研究了聚合物的结构,并对聚合物进行了DSC与TG分析.     

镍硫配合物(Me3C+)2Ni(SCH2CH2S)2的合成及结构表征

以NiCl2,Bu4NBr,HSCH2CH2SH为原料合成了配合物(Me3C^ )2Ni(SCH2CH2S)2,其结构经元素分析、IR,UV和^1H NMR确证,X-射线四圆衍射仪测其晶胞参数为：a=0.9127(1)nm,b=1．2424(0)nm,c=1．3906(2),v=1．57685(2)nm^3,z=4,晶体属正交晶系。晶体结构经块状矩阵最小二乘法修正后,最终偏离因子R=0．089。