4-羟基-5-乙氧基苯胺的合成

以苯胺为原料,经重氮化、偶合、还原得到4-羟基-5-乙氧基苯胺。合成中,通过保险粉还原偶氮化合物的方法在芳香环上引进氨基,不仅产物收率高(总收率86%,较文献提高了26.3%),而且还原产物容易分离,粗品纯度可达95%。本合成路线中间体均不经提纯,且氨基的引入中避免了贵金属的加氢还原,是一条适合大规模生产4-羟基-5-乙氧基苯胺的新合成工艺路线。     

Asymmetric Syntheses of Osmundalactones and 5-Hydroxy-2-hexen 4-olides from 4-Benzyloxy-5-hydroxy-2（E）-hexenoate

( )-(4S,5R)-Osmundalactone 1 was isolated from the fungus Paxillus atrotomentosus (Paxillaceae) by Buchanan1. (-)-(4R,5S)-Osmundalactone 1 and ( )-(4R,5S)-5-hydroxy- 2-hexen-4-olide 2 were isolated from Osmunda japonica (Osmundaceae) as feeding inhibitors…     

{[Cu4(nip)4(4，4′-bipy)4(DMF)4]·CH3OH}n配合物的合成与晶体结构

A coordination polymer, {[Cu₄(nip)₄(4，4′-bipy)₄(DMF)₄]·CH₃OH}_n, have been synthesized by the layer method using 5-nitroisophthalic acid (H₂nip), Cu(CH₃COOH)₂ and 4,4′-bipyridine(4,4′-bipy) with three solutions in a marrow tube and structurally characterized by X-ray single-crystal structure analysis. The results indicated that the nip ligand has a μ₂ mono-atomic bridging-monodentate coordination mode and the structure is a two-dimensional network. CCDC: 623420.     

4-氧代-3（4H）-喹唑啉-5-羧酸的合成

以2-氨基-6-甲基苯甲酸为起始原料,通过合环反应生成两种4-氧代-3(4H)-喹唑啉-5-羧酸衍生物(1a, 1b), 1a, 1b分别经高锰酸钾氧化合成了4-氧代-3(4H)-喹唑啉-5-羧酸（2a, 2b）,其结构经¹H NMR, ¹³C NMR和MS表征。研究了投料比｛r［n(高锰酸钾) :n(5-甲基-3(4H)-喹唑啉-4-酮)］｝和反应温度等对收率的影响。结果表明：在最佳反应条件（r=7:1,中性高锰酸钾氧化,于90 ℃反应）下合成2总收率可达66%。     

Asymmetric Synthesis of （-）-（4R, 5R）-4-[5-（Benzo[1, 3]dioxol-5-yl）-4- hydroxyl- 1-（pyridin-2-yl）-4, 5-dihydro- 1H-pyrazol-3-yl]benzamide

For discovering novel small molecule inhibitors of transforming growth factor-β1(TGF-β1)type-I receptor(ALK5),we designed1,3,5-triaryl-4-hydroxyl-4,5-dihydro-1H-pyrazole(1)as target compound,mimic the structure of SB-431542which is a2-pyridyl substituted triarylimiazole inhibitor of ALK51.Racemic compound1showed moderate ALK5inhibitory activity in luciferase reporter assays[inhibition(%control):0.1umol/L8.79%;1umol/L19.05%].To investigate the influence of the absolute configuration of…     

SHG Materials Based on the AlPO4-5 Single Crystals

Large AlPO4-5 molecular sieve single crystals with high optical quality were synthesized hydrothermally by using TPA as template. As-synthesized crystals were calcined under O2 atmosphere to remove the organic templates in the channels. Disperse-Red-1 (DR1) and p-nitroaniline (pNA) molecules have been successfully incorporated into the one-dimensional channels of AlPO4-5 single crystals respectively by means of vapor phase diffusion. XRD patterns reveal that the loading of organic molecules has not destroyed the structures of AlPO4-5 crystals. Polarizing microscope and SHG results indicate that the DR1 and pNA molecules are well aligned in a preferred direction along the crystal channels. The different polarization-dependence SH intensity shows that different SHG processes occur in the DR1- and pNA-loaded AlPO4-5 crystals.     

Synthesis and Biological Activities of 4-Arylmethylidene-1-aryl-2-（selenomorpholin-4-yl） -2-imidazolin-5-one

In a search for novel agrochemical with high activity and low toxicity, a series of substituted 4,5-dihydro-imidazol-5-one containing selenomorpholine group were synthesized by a three-step synthetic route starting from 2-azido-3-aryl-acrylic acid ethyl ester. The structures of title compounds were confirmed by ^1H NMR, IR, mass spectroscopy and elemental analysis. The preliminary bioassay against GibbereUa zeae, Fusarium oxysporum, Pellicularia sasakii, Physalospora piricola and Cercospora beticola indicated that most title compounds displayed fungicidal activity at the concentration of 50 ppm and compounds 41,4n, 40 were found to have particularly high activities against Physalospora piricola. A further in vivo test showed that compounds 41, 4n and 4o possessed better fungicidal activity against Physalospora piricola at a concentration of 100 ppm than Carbendazim. To our knowledge, this is first report that 4,5-dihy-dro-imidazol-5-one containing selenomorpholine group display fungicidal activity against Physalospora piricola.     

Reaction of Ketene Dithioacetals with Pyrazolylcarbohydrazide： Synthesis and Biological Activities of Ethyl 5-Amino-1-（5＇-methyl-1 ＇-t-butyl-4＇-pyrazolyl）carbonyl-3-methylthio-1 H-pyrazole-4-carboxylate

The title compound, C16H23N5O3S, ethyl 5-amino-1-(5‘-methyl-1‘-t-butyl-4‘-pyrazolyl)carbonyl-3-methylthio-1H-pyrazole-4-carboxylate (5) has been synthesized by the treatment of ethyl 2-cyano-3,3-dimethylthioacrylate with 1-t-butyl-5-methyl-4-hydrazinocarbonylpyrazole (4) in refluxed ethanol. The possible mechanism of the above reaction was also discussed. The results of biological test show that the title compound has fungicidal and plant growth regulation activities.     

Total Synthesis of Two 4, 5-Dioxo-seco-eudesmane Sesquiterpenes

A facile synthetic route to two seco-eudesmane, 4, 5-dioxo-10-epi-4, 5-seco-γ-eudesmane (1) and 4, 5-dioxo-10-epi-4, 5-seco-γ-eudesmol (2) from ( )-dihydrocarvone has been described. Avoiding expensive reagents, this highly economic method especially suits for the synthesis of 4, 5-seco-eudesman-type and ophianon-type sesquiterpenes with a double bond at position 11 and 12.     

Asymmetric Synthesis of （S）-Dimethyl -4, 4＇-dimethoxy-5, 6, 5＇, 6＇-dimethenedioxybiphenyl-2, 2＇-dicarboxylate

(S)-Dimethyl-4, 4‘-dimethoxy-5, 6, 5‘, 6‘-dimethenedioxy-biphenyl-2, 2‘-dicarbonylate was synthesized in reasonable yield through a series of reactions, including chiral oxazolinemediated asymmetric Ullmann coupling, from methyl 2-bromo-5-methoxy-3, 4-methenedioxybenzoate.     

Syntheses of 4‐(5‐oxo‐1,2,4‐triazol‐3‐yl)‐sydnones and 4‐(4‐arylamino‐5‐oxo‐1,2,4‐triazol‐3‐yl)‐sydnones from Sydnone Derivatives and Their Fragments

4‐(5‐oxo‐1,2,4‐triazol‐3‐yl)‐sydnones 11 and 4‐(4‐arylamino‐5‐oxo‐1,2,4‐triazol‐3‐yl)‐sydnones 13 have been obtained from a‐chloroformylarylhydrazine hydrochloride 2 . Moreover, the intermediates, including 3, 4 , 9 and 10 , in this study are synthetically informative and valuable. It is also noteworthy that three reactants, 1, 2 and sydnonecarbaldehydes, were prepared from sydnone derivatives and their fragments. The oxidative cyclizations of sydnonecarbaldehyde semicarbazones 9 and carbazones 10 with two different oxidizing agents (Cu(ClO₄)₂ and Fe(ClO₄)₃) have been extensively examined. The reaction time and the yields of cyclizations were affected by the substituents of semicarbazones 9 and carbazones 10.     

Synthesis of Macrocyclic Lactones via Ring Transformation of 4‐(ω‐Hydroxyalkyl)‐1,3‐oxazol‐5(4H)‐ones

The synthesis of α‐benzamido‐α‐benzyl lactones 23 of various ring size was achieved either via ‘direct amide cyclization’ by treatment of 2‐benzamido‐2‐benzyl‐ω‐hydroxy‐N,N‐dimethylalkanamides 21 in toluene at 90 – 110° with HCl gas or by ‘ring transformation’ of 4‐benzyl‐4‐(ω‐hydroxyalkyl)‐2‐phenyl‐1,3‐oxazol‐5(4H)‐ones under the same conditions. The precursors were obtained by C‐alkylations of 4‐benzyl‐2‐phenyl‐1,3‐oxazol‐5(4H)‐one ( 15 ) with THP‐ or TBDMS‐protected ω‐hydroxyalkyl iodides. Ring opening of the THP‐protected oxazolones by treatment with Me₂NH followed by deprotection of the OH group gave the diamides 21 , whereas deprotection of the TBDMS series of oxazolones 25 with TBAF followed by treatment with HCl gas led to the corresponding lactones 23 in a one‐pot reaction.     

Pseudopolymorphs of 2,6‐diaminopyrimidin‐4‐one and 2‐amino‐6‐methylpyrimidin‐4‐one: one or two tautomers present in the same crystal

The derivatives of pyrimidin‐4‐one can adopt either a 1H‐ or a 3H‐tautomeric form, which affects the hydrogen‐bonding interactions in cocrystals with compounds containing complementary functional groups. In order to study their tautomeric preferences, we crystallized 2,6‐diaminopyrimidin‐4‐one and 2‐amino‐6‐methylpyrimidin‐4‐one. During various crystallization attempts, four structures of 2,6‐diaminopyrimidin‐4‐one were obtained, namely solvent‐free 2,6‐diaminopyrimidin‐4‐one, C₄H₆N₄O, (I), 2,6‐diaminopyrimidin‐4‐one–dimethylformamide–water (3/4/1), C₄H₆N₄O·1.33C₃H₇NO·0.33H₂O, (Ia), 2,6‐diaminopyrimidin‐4‐one dimethylacetamide monosolvate, C₄H₆N₄O·C₄H₉NO, (Ib), and 2,6‐diaminopyrimidin‐4‐one–N‐methylpyrrolidin‐2‐one (3/2), C₄H₆N₄O·1.5C₅H₉NO, (Ic). The 2,6‐diaminopyrimidin‐4‐one molecules exist only as 3H‐tautomers. They form ribbons characterized by R²₂(8) hydrogen‐bonding interactions, which are further connected to form three‐dimensional networks. An intermolecular N—H...N interaction between amine groups is observed only in (I). This might be the reason for the pyramidalization of the amine group. Crystallization experiments on 2‐amino‐6‐methylpyrimidin‐4‐one yielded two isostructural pseudopolymorphs, namely 2‐amino‐6‐methylpyrimidin‐4(3H)‐one–2‐amino‐6‐methylpyrimidin‐4(1H)‐one–dimethylacetamide (1/1/1), C₅H₇N₃O·C₅H₇N₃O·C₄H₉NO, (IIa), and 2‐amino‐6‐methylpyrimidin‐4(3H)‐one–2‐amino‐6‐methylpyrimidin‐4(1H)‐one–N‐methylpyrrolidin‐2‐one (1/1/1), C₅H₇N₃O·C₅H₇N₃O·C₅H₉NO, (IIb). In both structures, a 1:1 mixture of 1H‐ and 3H‐tautomers is present, which are linked by three hydrogen bonds similar to a Watson–Crick C–G base pair.     

A two‐dimensional cadmium(II) coordination polymer constructed from 4‐carboxy‐1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐5‐carboxylate and 1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐4‐carboxylate ligands

Crystals of poly[[aqua[μ₃‐4‐carboxy‐1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐5‐carboxylato‐κ⁵O¹O^1′:N³,O⁴:O⁵][μ₄‐1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐4‐carboxylato‐κ⁷N³,O⁴:O⁴,O^4′:O¹,O^1′:O¹]cadmium(II)] monohydrate], {[Cd₂(C₁₅H₁₄N₂O₄)(C₁₆H₁₄N₂O₆)(H₂O)]·H₂O}_n or {[Cd₂(Hcpimda)(cpima)(H₂O)]·H₂O}_n, (I), were obtained from 1‐(4‐carboxybenzyl)‐2‐propyl‐1H‐imidazole‐4,5‐dicarboxylic acid (H₃cpimda) and cadmium(II) chloride under hydrothermal conditions. The structure indicates that in‐situ decarboxylation of H₃cpimda occurred during the synthesis process. The asymmetric unit consists of two Cd²⁺ centres, one 4‐carboxy‐1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐5‐carboxylate (Hcpimda²⁻) anion, one 1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐4‐carboxylate (cpima²⁻) anion, one coordinated water molecule and one lattice water molecule. One Cd²⁺ centre, i.e. Cd1, is hexacoordinated and displays a slightly distorted octahedral CdN₂O₄ geometry. The other Cd centre, i.e. Cd2, is coordinated by seven O atoms originating from one Hcpimda²⁻ ligand and three cpima²⁻ ligands. This Cd²⁺ centre can be described as having a distorted capped octahedral coordination geometry. Two carboxylate groups of the benzoate moieties of two cpima²⁻ ligands bridge between Cd2 centres to generate [Cd₂O₂] units, which are further linked by two cpima²⁻ ligands to produce one‐dimensional (1D) infinite chains based around large 26‐membered rings. Meanwhile, adjacent Cd1 centres are linked by Hcpimda²⁻ ligands to generate 1D zigzag chains. The two types of chains are linked through a μ₂‐η² bidentate bridging mode from an O atom of an imidazole carboxylate unit of cpima²⁻ to give a two‐dimensional (2D) coordination polymer. The simplified 2D net structure can be described as a 3,6‐coordinated net which has a (4³)₂(4⁶.6⁶.8³) topology. Furthermore, the FT–IR spectroscopic properties, photoluminescence properties, powder X‐ray diffraction (PXRD) pattern and thermogravimetric behaviour of the polymer have been investigated.     

A series of substituted (2E)‐3‐(2‐fluoro‐4‐phenoxyphenyl)‐1‐phenylprop‐2‐en‐1‐ones

In the molecular structures of a series of substituted chalcones, namely (2E)‐3‐(2‐fluoro‐4‐phenoxyphenyl)‐1‐phenylprop‐2‐en‐1‐one, C₂₁H₁₅FO₂, (I), (2E)‐3‐(2‐fluoro‐4‐phenoxyphenyl)‐1‐(4‐fluorophenyl)prop‐2‐en‐1‐one, C₂₁H₁₄F₂O₂, (II), (2E)‐1‐(4‐chlorophenyl)‐3‐(2‐fluoro‐4‐phenoxyphenyl)prop‐2‐en‐1‐one, C₂₁H₁₄ClFO₂, (III), (2E)‐3‐(2‐fluoro‐4‐phenoxyphenyl)‐1‐(4‐methylphenyl)prop‐2‐en‐1‐one, C₂₂H₁₇FO₂, (IV), and (2E)‐3‐(2‐fluoro‐4‐phenoxyphenyl)‐1‐(4‐methoxyphenyl)prop‐2‐en‐1‐one, C₂₂H₁₇FO₃, (V), the configuration of the keto group with respect to the olefinic double bond is s‐cis. The molecules pack utilizing weak C—H...O and C—H...π intermolecular contacts. Identical packing motifs involving C—H...O interactions, forming both chains and dimers, along with C—H...π dimers and π–π aromatic interactions are observed in the fluoro, chloro and methyl derivatives.     

catena‐Poly­[[(pyridin‐4‐ol‐κN)silver(I)]‐μ‐pyridin‐4‐olato‐κ2N:O]

The title complex, [Ag(C₅H₄NO)(C₅H₅NO)]_n, consists of a polymeric neutral chain involving both a neutral pyridin‐4‐ol ligand and a deprotonated pyridin‐4‐olate monoanion. The Ag^I atom shows a T‐shaped coordination geometry, defined by one N atom of the pyridin‐4‐ol and one O and one N atom of two independent pyridin‐4‐olate bridges; the N—Ag—N moiety is approximately linear. The polymeric chains are connected via strong O—H⋯O hydrogen bonds and offset π–π interactions into a three‐dimensional network.     

Three polymorphs of 4‐4′‐diiodobenzalazine,and 4‐chloro‐4′‐iodobenzalazine

Three polymorphs of 4,4′‐diiodobenzalazine (systematic name: 4‐iodobenzaldehyde azine), C₁₄H₁₀I₂N₂, have crystallographically imposed inversion symmetry. 4‐Chloro‐4′‐iodobenzalazine [systematic name: 1‐(4‐chlorobenzylidene)‐2‐(4‐iodobenzylidene)diazane], C₁₄H₁₀ClIN₂, has a partially disordered pseudocentrosymmetric packing and is not isostructural with any of the polymorphs of 4,4′‐diiodobenzalazine. All structures pack utilizing halogen–halogen interactions; some also have weak π (benzene ring) interactions. A comparison with previously published methylphenylketalazines (which differ by substitution of methyl for H at the azine C atoms) shows a fundamentally different geometry for these two classes, namely planar for the alazines and twisted for the ketalazines. Density functional theory calculations confirm that the difference is fundamental and not an artifact of packing forces.     

3‐Benzyl‐2‐(4‐fluorophenyl)‐1,3‐thiazolidin‐4‐one

The title compound, C₁₆H₁₄FNOS, crystallizes with Z′ = 2 in the space group P2₁/c. In one of the two independent molecules, the heterocyclic ring is effectively planar, but in the other molecule this ring adopts an envelope conformation. The molecules are weakly linked by two C—H...O hydrogen bonds to form C₂²(14) chains. Comparisons are made with some symmetrically substituted 2‐aryl‐3‐benzyl‐1,3‐thiazolidin‐4‐ones.     

4‐Carboxypyridinium perchlorate 18‐crown‐6 dihydrate clathrate and 4‐carboxypyridinium tetrafluoroborate 18‐crown‐6 dihydrate clathrate

Mixtures of 4‐carboxypyridinium perchlorate or 4‐carboxypyridinium tetrafluoroborate and 18‐crown‐6 (1,4,7,10,13,16‐hexaoxacyclooctadecane) in ethanol and water solution yielded the title supramolecular salts, C₆H₆NO₂⁺·ClO₄⁻·C₁₂H₂₄O₆·2H₂O and C₆H₆NO₂⁺·BF₄⁻·C₁₂H₂₄O₆·2H₂O. Based on their similar crystal symmetries, unit cells and supramolecular assemblies, the salts are essentially isostructural. The asymmetric unit in each structure includes one protonated isonicotinic acid cation and one crown ether molecule, which together give a [(C₆H₆NO₂)(18‐crown‐6)]⁺ supramolecular cation. N—H...O hydrogen bonds between the protonated N atoms and a single O atom of each crown ether result in the 4‐carboxypyridinium cations `perching' on the 18‐crown‐6 molecules. Further hydrogen‐bonding interactions involving the supramolecular cation and both water molecules form a one‐dimensional zigzag chain that propagates along the crystallographic c direction. O—H...O or O—H...F hydrogen bonds between one of the water molecules and the anions fix the anion positions as pendant upon this chain, without further increasing the dimensionality of the supramolecular network.     

A three‐dimensional polymeric potassium complex of 5‐sulfonobenzene‐1,2,4‐tricarboxylic acid: poly[μ‐aqua‐aqua‐μ9‐(2,4‐dicarboxy‐5‐sulfonatobenzoato)‐dipotassium(I)]

The asymmetric unit in the structure of the title compound, [K₂(C₉H₄O₉S)(H₂O)₂]_n, consists of two eight‐coordinated K^I cations, one 2,4‐dicarboxy‐5‐sulfonatobenzoate dianion (H₂SBTC²⁻), one bridging water molecule and one terminal coordinated water molecule. One K^I cation is coordinated by three carboxylate O atoms and three sulfonate O atoms from four H₂SBTC²⁻ ligands and by two bridging water molecules. The second K^I cation is coordinated by four sulfonate O atoms and three carboxylate O atoms from five H₂SBTC²⁻ ligands and by one terminal coordinated water molecule. The K^I cations are linked by sulfonate groups to give a one‐dimensional inorganic chain with cage‐like K₄(SO₃)₂ repeat units. These one‐dimensional chains are bridged by one of the carboxylic acid groups of the H₂SBTC²⁻ ligand to form a two‐dimensional layer, and these layers are further linked by the remaining carboxylate groups and the benzene rings of the H₂SBTC²⁻ ligands to generate a three‐dimensional framework. The compound displays a photoluminescent emission at 460 nm upon excitation at 358 nm. In addition, the thermal stability of the title compound has been studied.