一步法合成N-1,3-二羟基丙烷-2-基烷基乙酰胺

以5-氨基烷基-2,2-二甲基-1,3-二噁烷为起始原料, 乙酸酐为酰化剂, 一步法选择性地合成氨基二醇类氨基乙酰化产物N-1,3-二羟基丙烷-2-基烷基乙酰胺. 该方法操作简便, 收率高. 所合成的4个新化合物的结构均经FTIR, ¹H NMR, ¹³C NMR及HRMS确证. N-3-(1,3-二羟基丙烷-2-基)丙基乙酰胺(1a)作为关键的中间体, 可以用于HIV-1 Tat/ PCAF BRD抑制剂4的合成.     

1,3-二(乙氧基甲基)-5-N,N-二甲氨基-6-甲基尿嘧啶的合成

报道了1,3-二(乙氧基甲基)-5-N,N-二甲氨基-6-甲基尿嘧啶方便、高产率的合成方法. 以6-甲基尿嘧啶(1)为起始物, 经硝化、嘧啶N¹,N ³-烷基化、还原及氨基甲基化, 首次高产率合成了1,3-二(乙氧基甲基)-5- N,N -二甲氨基-6-甲基尿嘧啶(5), 并对其化学结构进行了表征.     

1,3-二(2,6-二甲基苯基)-2-四氢咪唑基-苯亚甲基-二吡啶基-二氯合钌 化合物的合成

设计了由1,3-二(2,6-二甲基苯基)-2-四氢咪唑基-苯亚甲基-三苯基膦-二氯合钌(7)和吡啶反应生成无膦型金属钌卡宾化合物1,3-二(2,6-二甲苯基)-2-四氢咪唑基-苯亚甲基-2-吡啶基-二氯合钌(8), 8作为高效催化剂用于丙烯腈和烯丙基苯的交叉交互置换反应. 新化合物7, 8经核磁共振氢谱、碳谱和高分辨率质谱予以证实.     

1,3-偶极环加成合成双-4,5-二氢-1,2,4-噁二唑啉衍生物

用2-苯基-1,2,3-三唑基-4-甲醛(1)或喹喔啉基-2-甲醛(2)与乙二胺缩合成双席夫碱3或4, 然后与α-氯代肟在三乙胺条件下发生1,3-偶极环加成得到双-4,5-二氢-1,2,4-噁二唑啉衍生物6a～6f或7a～7f. 目标化合物的结构经元素分析, IR, ¹H NMR和MS确认.     

α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5] 十一烷基]}苯基卟啉星形化合物的合成

以对苯二甲醛、丙二腈、季戊四醇和吡咯为原料, 合成了含有螺环结构单元的中间体3-[4-(2,2-二氰基)乙烯基]苯基-9-(4-甲酰基)苯基-2,4,8,10-四氧杂螺[5.5]十一烷(3)和α,β,γ,δ-四-(4-甲酰基苯基)卟啉(4). 4与过量的季戊四醇反应, 得到α,β,γ,δ-四-{4-[2-(5,5-二羟甲基-1,3-二噁烷基)]}苯基卟啉(5), 5与3的反应产物经10% NaOH 处理后, 再与过量的季戊四醇反应, 得到α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二羟甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(6), 6与乙酐、丙酐、苯甲酰氯反应, 得到α,β,γ,δ-四-{4-[3-(9-(4-(3- (9-(4-(2-(5,5-二乙酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(7), α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二丙酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(8)和α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二苯甲酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(9)等三种卟啉星形化合物. 中间体1～6和星形化合物7～9均进行了IR, ¹H NMR, MS和元素分析等结构表征. 对影响反应的诸因素进行了讨论.      

9-(β-D-2'-脱氧核糖基)-6-甲基嘌呤的合成

报道了9-(β-D-2'-脱氧核糖基)-6-甲基嘌呤合成的新方法. 以肌苷1为原料, 经酯化、氯化、氨解得6-氯嘌呤核苷(4), 再经过羟基保护、6-位甲基化反应及脱保护反应得到关键中间体6-甲基嘌呤核苷7, 用1,3-二氯-1,1,3,3-四异丙基二硅氧烷保护7核糖上的3,5-二羟基, 2-羟基与苯氧基硫代甲酰氯反应后得到9, 然后与氢化三正丁基锡[HSn(Bu-n)₃]还原脱氧, 最后脱保护得到目标化合物11. 产物结构经MS, ¹H NMR, 元素分析等鉴定.     

1,1-二取代炔丙醇氯代产物与4-甲基-7-羟基香豆素的异常缩合产物

报道了一类1,1-二取代炔丙醇(1)氯代产物与4-甲基-7-羟基香豆素反应的异常缩合产物. 一些实验数据表明1,1-二取代炔丙醇(1)的氯代反应中有一类未见报道的2,4-二氯-2-烯化合物(5)生成.     

贫电子环丙烷衍生物与2-巯基苯骈噻唑的反应研究

贫电子环丙烷衍生物1以精制四氢呋喃为溶剂, 与2-巯基苯骈噻唑(2)封管加热反应, 得到产物3和4. 产物3经IR, MS, ¹H NMR, ¹³C NMR和元素分析等数据确定其结构为: (R)-β-取代-(R)-γ-(2-巯基)苯骈噻唑基-γ-对位取代苯基丁酸或(S)-β-取代-(S)-γ-(2-巯基)苯骈噻唑基-γ-对位取代苯基丁酸(3); 产物4通过IR, MS, ¹H NMR, ¹³C NMR, 2D-NOESY谱和元素分析等数据确定其结构为: 反式-β-取代-γ-对位取代苯基-3-丁烯酸(4). 对生成产物的机理也进行了推测.     

微波作用下1-苯基-5-[5-(芳胺羰基甲硫基)-4-苯基-1,2,4-三唑-3-甲硫基]四唑的合成及生物活性

采用微波和相转移催化法通过1-苯基-5-(4-苯基-1,2,4-三唑-5-巯基-3-甲硫基)四唑(2)与2-氯乙酰芳胺(3)反应高效、快速地合成了10种尚未见文献报道的1-苯基-5-[5-(芳胺羰基甲硫基)-4-苯基-1,2,4-三唑-3-甲硫基]四唑. 其结构经 IR, ¹H NMR, ¹³C NMR 和元素分析表征. 生物活性实验结果表明, 该类化合物在较低浓度下部分化合物对小麦芽有很好的促进作用.     

无溶剂条件下合成2-[3-氧代-1,3-二(未)取代苯基丙基]-1,2,3,4-四氢萘-1-酮

以3,4-二氢-1-萘酮和查尔酮为原料, 在 K₂CO₃-NaOH 存在下, 无溶剂室温研磨反应, 方便地得到2-[3-氧代-1,3-二(未)取代苯基丙基]-1,2,3,4-四氢萘-1-酮. 该方法具有反应条件温和、操作简单和产率较高等优点, 并通过IR, ¹H NMR, 元素分析确定了产物的结构, 3b晶体结构通过X衍射测定.     

Functional polymers LII Synthesis and polycondensation of 2(2,4-Dihydroxyphenyl)2H-1,3-bis[4-carboxy (or 4-carbomethoxy)2H-benzotriazole]

Carboxy- and carbomethoxy derivatives of resorcinols with two benzotriazole substituents have been synthesized. 2(2,4-Dihydroxyphenyl)2H-1,3-bis-(4-carboxybenzotriazole) [2,4-bis(2H-4-carboxybenzotriazole-2-yl)-1,3-dihydroxybenzene] (DCBDH) was prepared by azo coupling of 4-carboxy-2-nitrobenzene diazonium chloride with resorcinol followed by reductive cyclization. 2(2,4-Dihydroxyphenyl)2H-1,3-bis(4-carbomethoxy-benzotriazole) [2,4-bis-(2H-4-carbomethoxy-benzotriazole-2-yl)-1,3-dihydroxybenzene] (DCMBDH) was obtained by esterification of the free dicarboxylic acid with methanol. The compounds were characterized by their elemental analyses and melting points, and by their IR, UV,¹H NMR, and¹³C NMR spectra.Copolycondensations were carried out to incorporateDCBDH orDCMBDH into polyamides or polyesters. The condensation copolymers were briefly characterized.Functional Polymers LI:M. D. Purgett,W. J. MacKnight, andO. Vogl, Polym. Eng. and Sci.27(19), 1461 (1987)     

Theoretical and experimental study on metal(II) halide complexes of 1,3-bis(4-pyridyl)propane

We report the results of detailed experimental and theoretical studies on the molecular structure and vibrational spectra of metal(II) halide complexes of 1,3-bis(4-pyridyl)propane [M(N₂C₁₃H₁₄)X₂, where M represents Zn or Hg, and X represents Cl, Br, or I]. The FT–infrared spectra (FT-IR) and FT-Raman spectra of the metal complexes of the 1,3-bis(4-pyridyl)propane molecule in the powder form were recorded between the 400–4000 and 5–3500 cm^?1 regions, respectively. The molecular geometry and vibrational frequencies of the metal complexes of 1,3-bis(4-pyridyl)propane in the ground state were calculated using density functional theory (B3LYP functional) with LANL2DZ and SDD as basis sets. The total energy distributions (TED) among the symmetry coordinates of the normal modes were computed for the low-energy structure of the molecules. Complete vibrational assignments based on the calculated TED values are given.     

Preparation of palladium complexes of 1,3-di(2-pyridyl)propane derivatives and their use in norbornene polymerization

A variety of neutral palladium(II) complexes [Pd(L–L)Cl₂] containing 1,3-di(2-pyridyl)propane (1), 1,3-bis(2-pyridyl)-2-pentylpropane (2), 1,3-bis(2-pyridyl)-2-phenylpropane (3a), 1,3-bis(2-pyridyl)-2-tolylpropane (4), and 1,3-bis(2-pyridyl)-2-ferrocenylpropane (5) as chelate ligands (L–L) have been synthesized. The crystal structures of 1,3-diphenyl-2,4-di-pyridin-2-yl-butan-1-ol (3b), 5, [(2)PdCl₂], [(4)PdCl₂], and [(5)PdCl₂] have been determined and show a square planar geometry at palladium(II). The neutral complexes were tested in the polymerization of norbornene and copolymerization of norbornene with norbornene derivatives. The complex bearing the pentyl group exhibited high reactivity to give up to 5.9×10⁵ in molecular weight for the homopolymerization. When [(4)PdCl₂] or [(5)PdCl₂] was used as a catalyst, homopolymers insoluble at 150 °C in trichlorobenzene were obtained. However, copolymerization of norbornene with norbornene derivatives 8a–d catalyzed by [(4)PdCl₂] gave soluble copolymers with molecular weights up to 5.1×10⁵.     

New Approach to Synthesize Symmetrical and Unsymmetrical 6-(N-Alkyl(Aryl)Amino)- and 6-(N,N-Dialkyl(Aryl)Amino)-2,4-Bis(Alkyl(Aryl)Thio)Pyrimidines as anti-Platelet Agents

Abstract

A new and straightforward procedure has been developed for the preparation of symmetrical and unsymmetrical 6-(N-alkyl(aryl)amino)- and 6-(N,N-bisalkyl(aryl)amino)-2,4-bis(alkyl(aryl)thio)pyrimidines. The two identical or different alkylthio groups were successfully introduced into the pyrimidine ring of 4-amino-6-hydroxy-2- mercaptopyrimidine via S-alkylation with alkyl halides, and via a nucleophilic displacement with sodium alkylmercaptides, affording the key intermediate symmetrical and unsymmetrical 2,4-bis(alkyl(aryl)thio)-6-aminopyrimidines. Subsequently, N-alkylation of the 2,4-bis(alkyl(aryl)thio)-6-aminopyrimidines with alkyl halides conveniently gave the desired products. The human anti-platelet activities of all the synthesized new compounds were also evaluated.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

1,3-bis(2,4,6-trinitrophenylaminooxy)propane and its 4-cyano-2,6-dinitrophenyl congener: Synthesis and properties

Starting from N-hydroxyphthalimide (5) and 1,3-dibromopropane (6) we obtained 1,3-bis(phthalimidooxy)propane (7) which led to 1,3-bis(aminooxy)propane dihydrochloride (8). From its reaction with picryl chloride or 4-cyano-2,6-dinitrochlorobenzene, the two title compounds (4b, 4a) were obtained. ¹H-NMR and ¹³C-NMR spectra are presented. For comparison with the analogous N-methoxy-2,6-dinitro-4-R-anilines 1a, 1b (R=CN or R=NO₂), wer report the hydrophobic characteristics (by RPTLC), electronic spectra for the neutral compounds and their anions, pK _a values, and the behavior towards oxidizers (DPPH, PbO₂, Pb(CH₃COO)₄, KMnO₄ and Ag₂O); DPPH converts compounds 1a, 1b and 4a, 4b into betainic structures 2a, 2b respectively.     

Die Synthese von 1,3-Bis(dichlorcarbo)-2,4-bis(dihalogen)cyclo-diborazanen

Zusammenfassung 1,3-Bis(dichlorcarbo)-2,4-bis(dihalogen)cyclodiborazane wurden durch Umsetzung von Rhodantrichlorid mit Trihalogenboranen dargestellt. Die Massenspektren und IR-Spektren bestätigen die Struktur der Verbindung, für welche die Punktgruppe D_2h angenommen wird.

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From the reaction of thiocyanogen trichloride with trihaloboranes 1,3-bis(dichlorcarbo)-2,4-bis(dihalogeno)cyclodiborazanes have been obtained. IR and mass spectra confirm the structure of these compounds, for which a D_2h symmetry is proposed.

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Mit 1 Abbildung     

Spectroscopic, thermal and structural studies of cocrystal of 2,2′-diamino-4,4′-bis(1,3-thiazole) with 4,4′-bipyridine, 1,2-bis(4-pyridyl)ethylene and 1,3-bis(4-pyridyl)propane

Three new cocrystals based upon 2,2′-diamino-4,4′-bis(1,3-thiazole) (DABTZ) with 4,4′-bipyridine (4,4′-bipy), 1,2-bis(4-pyridyl)ethylene (bpe) and 1,3-bis(4-pyridyl)propane (bpp): [(DABTZ) (4,4′-bipy)], [(DABTZ) (bpe)] and [(DABTZ) (bpp)] have been synthesized and characterized by elemental analysis, IR-, ¹H NMR-, ¹³C NMR spectroscopy and studied by thermal and X-ray crystallography. Self-assembly of these compounds in the solid state is likely caused by both hydrogen bonding, and π-π stacking.     

Three Mn(II) complexes with 1,3-bis(4-pyridyl)propane and their supramolecular nets

Three complexes, [Mn(bpp)₄(H₂O)₂](ClO₄)₂?·?1.5H₂O (1), [Mn(bpp)₃Br₂]?·?2H₂O (2), and [Mn(bpp)₂(H₂O)₂](ClO₄)?·?I?·?H₂O?·?bpp (3) (bpp?=?1,3-bis(4-pyridyl)propane), were synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 is mononuclear where M(II) is coordinated to a monodentate TT-bpp, three monodentate TG-bpp, and two water molecules. Complex 2 possesses a single-stranded helical chain formed from MnN₄Br₂ octahedra by a single TT-bpp, with pendant monodentate TG-bpp ligands. Complex 3 consists of a ribbon-type double-stranded chain formed from MnN₄O₂ octahedra by double TG-bpp ligands. 2-D supramolecular architectures of 1–3 are formed by hydrogen bonds. The fluorescence of the three complexes comes from the π*–π transition of the ligand.     

对苯二甲酸·1,3-二(4-吡啶基)丙烷的水热合成和晶体结构(英文)

用1,3-二(4-吡啶基)丙烷、对苯二甲酸和去离子水在413K下通过水热反应法得到了标题化合物(C13H14N2).(C8H6O4).该化合物晶体属于三斜晶系,空间群为P墿,晶胞参数为a=0.95267(19)nm,b=1.1927(2)nm,c=1.6959(3)nm,α=96.40(3)°,β=98.12(3)°,γ=101.52(3)°,Z=2.单晶衍射结果表明标题化合物由对苯二甲酸分子和1,3-二(4-吡啶基)丙烷通过两种类型的分子间π-π堆积作用以及O—H…N氢键作用构成.同时,还对标题化合物进行了元素分析和红外测试.     

2,3-Bis(diphenylphosphino)-1,3-butadien

2,3-Bis(diphenylphosphino)-1,3-butadiene A method for synthesis of the title compound is described, using the readily available 2,3-bis(diphenylphosphinoyl)-1,3-butadiene ( 1 ) as the starting material. For the protection of the diene system, 1 is first converted into the 1,4-dibromo- and 1,4-dichloro derivatives 2a and b , respectively, by addition of Br₂ or Cl₂, respectively. The structure of 2b has been determined by single-crystal X-ray diffraction. The molecule has a centrosymmetrical (E)-configuration. Reduction of the phosphinoyl groups by HSiCl₃(to give the bis(diphenylphosphino)compound 3), followed by removal of the Cl-atoms using Zn powder, affords the bis(diphenylphosphino)butadiene 4 . Compounds 3 and 4 give quaternary phosphonium salts 5 and 6 , respectively, on addition of CH₃OSO₂F or CH₃I. The sulfur analogue of 1 is formed on treatment of 4 with elemental sulfur.