4-(羟芳基)二氮烯基邻苯二腈类化合物的合成及表征

以4-氨基邻苯二腈、酚(羟基芳醛或羟基喹啉)为原料,经重氮化及偶合反应,合成了六种4-(羟芳基)二氮烯基邻苯二腈类化合物,产率为63.8%~84.2%。用核磁、红外等测试手段对化合物进行了表征。该方法具有反应条件温和、操作简单等优点,为4-(羟芳基)二氮烯基邻苯二腈类化合物的合成提供了新的方法。     

6-羟基-2-氟-N-取代芳基苄胺类化合物的合成

6-羟基-2-氟-N-取代芳基苄胺类化合物是合成含氟嘧啶氧苄胺类除草剂的关键中间体,本文以2,6-二氟苯醛为起始原料,合成6-羟基-2-氟苯甲醛,再与芳胺缩合成Schiff 碱,最后经硼氢化钠还原,合成了5个化合物,其结构经1HNMR和MS表征.     

(E)-β-溴芳基乙烯及芳基乙炔合成方法的改进

(E)-β-溴芳基乙烯和芳基乙炔是重要的有机合成原料及中间体,由于这些原料难以在市场上买到,通常在实验室自己制备。(E)-β-溴芳基乙烯的制备方法主要有：1.由(Z)-β-溴芳基乙烯进行构型转化[1];2.芳基乙烯溴代后,脱去一分子溴化氢,得两种构型的β-溴芳基乙烯[2];3.肉桂酸溴代后,用碳酸氢钠的丙酮溶液脱臭化氢[3]等。芳基乙炔可用芳基溴代乙烯经碱脱去溴化氢而制得[4],也可用芳基乙酮与五氯化磷反应,经脱去氯化氢后制得[5]。我们对上述方法进行了改进,以取代肉桂酸为原料,经纂代,在碳酸钾水溶液中加热脱溴化氢,高产率、高选择性地合成了(E)-β-溴闭幕词基乙烯,后者经三甘醇碱溶液处理,脱去臭化氢,得芳基乙炔。     

4-(1H-3-吡唑基)苯甲酸甲酯的合成研究

以廉价易得的4-甲酰基苯甲酸甲酯为原料,经过Witting-Horner反应及关环反应得到目标化合物4-(1H-吡唑-3-基)苯甲酸甲酯,其结构经1 HNMR和ESI-MS确证.分别考察了两步反应的主要影响因素,确定Wittig-Horner反应的适宜条件为:N,N-二甲基甲酰胺为反应溶剂;物料比n(4-甲酰基苯甲酸甲酯)∶n((E)-{2-[2-(4-甲苯磺酰基)肼基]乙基}磷酸二乙酯)=1.1∶1.关环反应的适宜条件为:n(对甲苯磺酸钠)∶n(4-[(1E,3E)-3-(2-对甲苯磺酰肼叉)丙-1-烯-1-基]苯甲酸甲酯)=3.0 ∶ 1;反应时间为2h.在该反应条件下,两步反应的收率分别为89.4％和92.2％,以4-甲酰基苯甲酸甲酯计,4-(1H-吡唑-3-基)苯甲酸甲酯的总收率为82.4％.     

N-(4-二苯胺苯甲基)-甘氨酰丝氨酸甲酯的合成

主要以甘氨酸和4-二苯氨基苯甲醛为原料,通过还原氨化反应得到4-二苯胺-苯甲氨基乙酸,用叔丁氧羰基保护二级氨后,与丝氨酸甲酯脱水缩合生成N-(4-二苯胺苯甲基)-N-叔丁氧羰基-甘氨酰丝氨酸甲酯,脱去保护基后得到标题化合物.用1HNMR、13CNMR、IR、MASS、HRMS和HPLC对目标化合物的结构进行了表征.     

4-(4-甲酯基苯基)丁醛的合成

以对溴苯甲酸为原料,经酯化后与3-丁烯-1-醇偶联,再与亚硫酸氢钠反应形成磺酸钠盐,经盐酸酸化后得4-(4-甲酯基苯基)丁醛。总收率可达37.3%。     

新环3-氧代-5H-5-取代芳基异(噁)唑[3,4-e]并-1,2,3,4-四嗪衍生物的合成

合成了6种3-氨基-5-氧代-4-芳基偶氮异唑衍生物和3-氧代-5-取代芳基异唑[3,4-e]并-1,2,3,4-四嗪衍生物,经元素分析I、R和质谱分析确定了其结构。     

2-氨基-4-香豆素基-5-芳基吡咯合成方法研究

介绍了一种不需要使用金属催化剂进行多组分反应合成2-氨基-4-香豆素基-5-芳基吡咯及其衍生物的方法.该方法的优点为操作简单、安全、产率高.对反应溶剂、反应温度和反应时间进行了优化,最终可使产品产率达到90％以上.     

3-甲基-4-丁酰氨基-5-氨基苯甲酸甲酯的合成

3-甲基-4-丁酰氨基-5-氨基苯甲酸甲酯是重要的药物中间体。以3-甲基-4-丁酰氨基苯甲酸甲酯为原料，经硝硫混酸硝化、铁粉还原得到目标化合物3-甲基-4-丁酰氨基-5-氨基苯甲酸甲酯，总收率72％。研究了硝硫混酸配比、硝化反应时间、还原反应温度、还原反应时间等因素对产物收率的影响，该工艺具有生产成本低，产品质量稳定，收率高的优点。     

1-(1,3-二硫戊环/二噻烷)-2-亚甲基-1-芳偶氮基丙酮类化合物的合成研究

研究了二硫缩烯酮类化合物α-碳原子上的反应,以α-羰基/羧基二硫缩烯酮与芳基重氮盐作用,以较高产率获得了系列1-(1,3-二硫戊环/二噻烷)-2-亚甲基-1-芳偶氮基丙酮类化合物。该反应条件温和,操作方法简单,同时对其反应机理进行了初步探讨。     

1-[2-(2,4-二氯苯基)-4-烃氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑类化合物的合成及杀菌活性研究

2,4-二氯苯乙酮经溴化得ω-溴-2,4-二氯苯乙酮,该化合物与丙三醇在对甲基苯磺酸催化下脱水,得2-(2,4-二氯苯基)-2-溴甲基-4-羟甲基-1,3-二氧戊环,该中间体与苯甲酰氯在常温下反应,合成了2-(2,4-二氯苯基)-2-溴甲基-4-苯甲酰氧基甲基-1,3-二氧戊环,然后与三氮唑钠盐在130℃反应36 h,之后在碱性条件下水解,获得1-[2-(2,4-二氯苯基)-4-羟甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑,再以吡啶为缚酸剂继续与甲磺酰氯反应,合成了1-[2-(2,4-二氯苯基)-4-甲磺酰氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑,最后在碱性条件下,与12个不同结构的酚缩合成标题化合物1-[2-(2,4-二氯苯基)-4-烃氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑。标题化合物的结构用GC-MS、FTIR进行了表证。生物活性实验结果表明,12个标题化合物对水稻稻瘟病菌的抑菌率均在88.0%以上,其中,1-[2-(2,4-二氯苯基)-4-间甲基苯氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑达100%。1-[2-(2,4-二氯苯基)-4-苯氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑和1-[2-(2,4-二氯苯基)-4-对硝基苯氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑对油菜菌核病菌的抑菌率分别为100%和97.8%;1-[2-(2,4-二氯苯基)-4-间甲基苯氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑对小麦赤霉病菌的抑制活性为91.2%。     

(3aS,6aR)-1,3-二苄基-四氢-4H-呋喃并[3,4-d]咪唑-2,4(1H)-二酮的立体选择性合成

以顺-1,3-二苄基-5-[(1S,2S)-(+)-苏式-1-羟甲基-2-(对硝基苯基)-2-羟乙基]-四氢-4H-吡咯并[3,4-d]咪唑-2,4,6-三酮为原料,经单乙酰化、NaBH4还原和酸水解得到标题化合物,与直接还原或是先经双乙酰化再还原的工艺相比,单乙酰化后再还原的选择性高达97.25%。并对单乙酰化物和双乙酰化物结构做了X单晶衍射测定,单乙酰化物的原子空间排布更利于选择性还原。     

Alkoxyalkyl-substituted glycerol acetals: New hydrophobic intermediates for surfactant synthesis

In acid-catalyzed, one-step reactions of monofunctional alcohol (I) and glycerol mixture with a simple α,β-unsaturated carbonyl compound (acrolein, crotonaldehyde or methylvinyl ketone), four component glycerol acetals [mixtures ofcis-+trans-2-(2-alkoxyalkyl)-substituted derivatives of 4-hydroxymethyl-1,3-dioxolanes and 5-hydroxy-1,3-dioxanes] or two component glycerol ketals [mixtures ofcis-+trans-2-(2-alkoxyethyl)-2-methyl-4-hydroxymethyl-1,3-dioxolanes] were obtained, respectively. These compounds may be used as a new group of hydrophobic intermediates for synthesis of chemodegradable surfactants, which rapidly hydrolyze to nonsurfactant compounds in acidic aqueous solutions. Methods of synthesis, yields, compositions and chemical structures of components of reaction products, and products of their chemical degradation have been discussed. Part XX in the series: Acetals and Ethers. Part XIX, A. Piasecki,Polish J. Chem. 62:579 (1988).     

Synthesis and surface properties of oxyethylenated 2-alkyl-5-hydroxymethyl-5-ethyl-1,3-dioxanes

In acid-catalyzed reactions of long chain aliphatic aldehydes (I) (R=n−C₇H₁₅; n−C₉H₁₉; n−C₁₁H₂₃) with 1,1,1-tris(hydroxymethyl)propane (II), 2-alkyl-5-hydroxymethyl-5-ethyl-1,3-dioxanes (III) were obtained. The latter were then reacted with ethylene oxide in the presence of sodium methoxide. Three series of oxyethylenated cyclic acetal derivatives (IV) were obtained. They constitute a new group of chemodegradable surfactants which readily hydrolyze and oxidize in natural water reservoirs. Physical data of the new compounds and some surface properties such as cloud points (Cp), critical micelle concentrations (cmc), changes of free energy of micellization, (ΔG°_cmc), surface tensions of aqueous solutions near cmc, γ_min, and wetting and foaming properties, were determined. The surfactants (IV) have aqueous solution properties similar to those of oxyethylenated longchain aliphatic alcohols. It is shown that the micellization of surfactants (IV), expressed in terms of ΔG°_cmc, depends both on the length of the aliphatic chain at the C-2 carbon atom and on the presence of ethyl group at C-5 of 1,3-dioxane ring which enhances the hydrophobic character of derivatives (III). Hence, the surfactants have a higher surface activity than oxyethylenated 2-alkyl-4-hydroxymethyl-1,3-dioxolanes or 2-alkyl-5,5-bis-(hydroxymethyl)-1,3-dioxanes. The use of 2-alkyl-5-hydroxymethyl-5-ethyl-1,3-dioxanes (III) in surfactant synthesis is an example of applying hydrophobic intermediates obtained from aldehydes only. This, and the chemodegradability mentioned make the compounds a very interesting group of new surfactants. Part XVII in the series: Chemical Structure and Surface Activity.     

Regioselective synthesis of new 5H,10H-dipyrimido[2,1-b:4′,5′-d][1,3]thiazine: a combined experimental and computational study

Several derivatives of the novel tricyclic system ‘dipyrimido[2,1-b:4′,5′-d][1,3]thiazine’ were synthesized via inter- and intramolecular heterocyclization of 2,4-dichloro-5-(chloromethyl)-6-methylpyrimidine and 6-amino-4-aryl-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carbonitrile in short reaction times under mild conditions. An x-ray analysis together with computational calculations was performed to gain an in-depth understanding of regioselectivity of the reaction.     

Synthesis and surface properties of chemodegradable anionic surfactants: Sodium salts of sulfated 2-n-alkyl-5-hydroxymethyl-5-methyl-1,3-dioxanes

In acid-catalyzed reactions of long-chain aliphatic aldehydes (Ia-d) (a,R=n-C₅H₁₁; b,R=n-C₇H₁₅; c,R=n-C₉H₁₉; d,R=n-C₁₁H₂₃) with 1,1,1-tris(hydroxymethyl)-ethane (II), 2-n-alkyl-5-hydroxymethyl-5-methyl-1,3-dioxanes (IIIa-d) were obtained. Then they were reacted with SO₃·pyridine complex in dry carbon tetrachloride solution, to obtain trisubstituted derivatives of 1,3-dioxane (IVa-d). They constitute a new group of chemodegradable, acetal-type anionic surfactants, which may readily hydrolyze and oxidize to nonsurfactant compounds. Physical data of the new compounds and some surface properties, such as Krafft point, critical micelle concentration (CMC), surface tension of aqueous solution near CMC (γ_CMC) and wetting and foaming properties, were determined. Sodium salts of sulfated 2-n-alkyl-5-hydroxymethyl-5-methyl-1,3-dioxanes (IVa-d) exhibit aqueous solution properties similar to those of the well-known sodium alkyloligooxyethylene sulfates. Presence of the 5-methyl-1,3-dioxane moiety in molecules of compounds IVa-d introduces hydrophobic character comparable to the effect of three oxyethylene groups (-CH₂CH₂O-) or of two methylene groups (-CH₂-) of the alkyl chain in sodium alkyl ether sulfates [R(OCH₂CH₂)_mOSO₃Na] with equal R value. Part XXV in the series: Chemical Structure and Surface Activity. Part XXIV: A. Sokołowski, B. Burczyk, H.-R. Holzbauer, M. Herbst,Colloids Surfaces 57: 307 (1991).     

2-Fettalkyl-2-oxazoline - ein vielversprechendes oleochemisches Reaktivsystem - Synthese und Folgechemie

2-Fatty-Alkyl-2-Oxazolines - a Most Promising Oleochemical Reactive System - Synthesis and Reaction Products A new process has been developed for synthesizing imidic acid esters such as 2-alkyl-2-oxazolines and 2-alkyl-5,6-dihydro-4H-1,3-oxazines. This process exhibits all the preconditions necessary for manufacturing such heterocyclic compounds with fatty alkyl groups in the 2-position on an industrial scale. These reactive oleochemical compounds can be polymerized, and react with numerous nucleophiles by introducing the alkanoyl-aminoalkyl group. Catalytic hydrogenation and reactions with some nitrogen components are described. The corrosion-resistant and antimicrobial properties of the new reaction products (imidazole, 1,2,4-triazole and tetrazole derivatives) are then treated.     

Thiation of new 5-(2-aryl-2-oxoethyl)-2,4-dioxo-1, 3-thiazolidines

Abstract

The hitherto unknown 5-(2-aryl-2-oxoethyl)-3-substituted-2,4-dioxo-1,3-thiazolidines 2 and 5-(2-aryl-2-oxoethylidene)-3-aryl-2,4-dioxo-1,3-thiazolidines 4 have been prepared from their 2-thioxo- homologues 1 and 3, respectively, via treatment with CrO₃. Compound 4 has also been obtained by treating 1 and/or 2 with bromine at different experimental conditions. Thiation of 2 and/or 4, gave a mixture of 3,5-di-substituted-2,3-dihydro-2-oxothieno[2,3-d]thiazoles 5 and the respective 2-thioxo derivatives 6. Reactions of hydrazine hydrate with 1c, d, were carried out at room temperature as well as under reflux, affording di-(3-oxo-6-aryl-4,5-dihydropyridazin)disulfides 7c, d and di-(3-oxo-6-arylpyridazin)disulfides 8c, d, respectively, together with 4-arylthiosemi carbazides 9c, d, under both conditions. Structures of the above products have been elucidated based on their microanalytical and spectroscopic data. Compound 2e exhibited pronounced antischistosomal activity.     

(2S,4E)-5-氯-2-异丙基-4-戊烯酸乙酯的简易合成

以异戊酸乙酯与(E)-1,3-二氯丙烯为原料,通过烷基化反应得到(±)-(4E)-5-氯-2-异丙基-4-戊烯酸乙酯,经猪肝酯酶催化(进行动力学拆分)得到纯阿利克仑(Aliskiren)中间体(2S,4E)-5-氯-2-异丙基-4-戊烯酸乙酯。通过回收拆分母液以88%的收率得到(2R,4E)-5-氯-2-异丙基-4-戊烯酸。该方法绿色环保,操作简洁易行,具有工业化应用前景。     

1-[2-(2,4-二氯苯基)-4-酰氧基甲基-1,3-二氧戊环-2-基]甲基-1H-1,2,4-三氮唑的合成及生物活性

2, 4 二氯苯乙酮经溴化得ω 溴 2, 4 二氯苯乙酮,该化合物与丙三醇反应并脱水得 2 (2, 4 二氯苯基 ) 2 溴甲基 4 羟甲基 1, 3 二氧戊环,再在常温下与苯甲酰氯反应合成 2 (2, 4 二氯苯基) 2 溴甲基 4 苯甲酰氧基甲基 1, 3 二氧戊环,然后在 130℃与 1H 1, 2, 4 三唑钠反应 36h,所得产物经水解得 1 [2 (2, 4 二氯苯基 ) 4 羟甲基 1, 3 二氧戊环 2 基]甲基 1H 1, 2, 4 三氮唑,再在室温以吡啶作缚酸剂,与甲磺酰氯反应 20h,合成 1 [2 (2, 4 二氯苯基) 4 甲磺酰氧基甲基 1, 3 二氧戊环 2 基]甲基 1H 1, 2, 4 三氮唑,最后与各类羧酸的钾盐反应,合成了 10种 1 [2 (2, 4 二氯苯基 ) 4 酰氧基甲基 1, 3 二氧戊环 2 基 ]甲基 1H 1, 2, 4 三氮唑类化合物。产物的结构经GC MS、IR证实。对目标产物进行了杀菌活性测定,结果表明,各化合物均具有不同程度的生物活性,其中: 1 [2 (2, 4 二氯苯基) 4 (α 甲基苯乙酰氧基)甲基 1, 3 二氧戊环 2 基]甲基 1H 1, 2, 4 三氮唑对水稻稻瘟病菌和油菜菌核病菌的抑制率,分别达到 92 1%与 95 6%,对小麦赤霉病菌和瓜类灰霉病菌的抑制率达到 80%以上;1 [2 (2, 4 二氯苯基) 4 对氟苯甲酰氧基甲基 1, 3 二氧戊环 2 基 ]甲基 1H 1, 2, 4 三氮唑对水稻稻瘟病菌和油菜菌核病菌的抑制率分别为 9