3-聚苯乙烯磺酰基丙醇的制备及其在固相有机合成中的应用

本文采用聚苯乙烯亚磺酸钠树脂1与3-氯丙醇在碘化四正丁胺和碘化钾的存在下反应制备了3-聚苯乙烯磺酰基丙醇树脂2.以该树脂为载体固载了Boc保护的L-丙氨酸,再经封羟基、脱保护、中和,与异氰酸苯酯反应制得聚合物支载的脲6.脲树脂6在酸性或强碱条件下解脱得到取代的海因化合物,在弱碱条件下解脱得到取代的脲化合物.     

温和条件下Sc(OTf)3催化合成聚酯二元醇

以三氟甲烷磺酸钪-Sc(CF3SO3)3(简称Sc(OTf)3)为催化剂,在低于120℃的温和条件下,合成了聚己二酸1,4-丁二醇酯二醇.研究了反应温度、催化剂用量、合成工艺等对酯化反应和缩聚反应的影响,并采用FT-1R、1H NMR、GPC等测试技术对合成的产物进行了结构表征.结果表明,不除水时的最佳反应条件为:温度90℃,催化剂用量占单体摩尔数的0.1%,n(醇):n(酸)=1.1∶1,回流11 h,酯化率为93%;而减压除水时,在相同条件下,反应8 h,酯化率可达到99%.不除水时酯化速率和缩聚速率均较慢,减压除水后速率明显加大,产物分子量增加,分子量分布变窄.FT-IR和1H NMR图谱分析表明,几乎无副产物生成.     

Aqueous-Phase Synthesis and Solid-Phase Fluorescence of 3-(Methoxyphenyl)-2-cyanoacrylamides

Russian Journal of Organic Chemistry - Reactions of methoxybenzaldehydes with cyanoacetamide in water in the presence of cocamidopropylamine oxide afforded 84–94% of...     

Doubly Decarboxylative Synthesis of 4-(Pyridylmethyl)chroman-2-ones and 2-(Pyridylmethyl)chroman-4-ones under Mild Reaction Conditions

The doubly decarboxylative Michael–type addition of pyridylacetic acid to chromone-3-carboxylic acids or coumarin-3-carboxylic acids has been developed. This protocol has been realized under Brønsted base catalysis, providing biologically interesting 4-(pyridylmethyl)chroman-2-ones and 2-(pyridylmethyl)chroman-4-ones in good or very good yields. The decarboxylative reaction pathway has been confirmed by mechanistic studies. Moreover, attempts to develop an enantioselective variant of the cascade are also described.     

Synthesis of β-(1-3)-D-glucan under high pressure

The polycondensation of 1,2-0-exo-cyanethylidene-4,6-di-0-acetyl-3-0-trityl--D-glucopyranose (I) was accomplished in the presence of triphenylmethylium perchlorate in CH₂Cl₂ under the pressure of 14 kbar. The reaction was performed in the frozen solution after the phasic transition of the system, and led to the product of polycondensation which, after the removal of the protecting groups, gave the exactly regio- and stereo-regular -(1–3)-D-glucan.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2129–2132, September, 1990.     

Synthesis of 3-Chloro-3-(trimethylsilyl)prop-2-enoic Acid Amides and Hydrazides from 3-(Trimethylsilyl)propynoic Acid

Russian Journal of Organic Chemistry - A number of previously unknown and difficultly accessible polyfunctional β-chloro-β-(trimethyl­silyl)prop-2-enoic acid amides and hydrazides...     

温和条件下邻甲基苯磺酸铜催化三组分“一锅法”合成喹唑啉-4(3H)-酮衍生物

室温、无溶剂条件下,邻甲基苯磺酸铜可有效催化邻氨基苯甲酸、胺和原甲酸酯三组分"一锅法"合成喹唑啉-4(3H)-酮衍生物.考察了原料配比及催化剂用量对产率的影响.经催化剂循环研究,催化活性无明显变化.产物的结构通过熔点,IR,1HNMR和元素分析进行测定和结构表征.同时给出了可能的反应机理.     

Ytterbium(III) Triflate as an Efficient Catalyst for the Synthesis of Perimidine Derivatives under Mild Conditions

Various biologically important perimidine derivatives have been efficiently synthesized in excellent yields using naphthalene‐1,8‐diamine with various ketones in the presence of a catalytic amount of Yb(OTf)₃. The influence of the loading of Yb(OTf)₃, reaction solvent, the structure of ketones was studied. This method is a very easy, simple and high yielding reaction for the synthesis of perimidine derivatives.     

1-(2,6-二氯-4-三氟甲基苯基)-3-氰基-5-氨基吡唑及其磺酰胺的合成及晶体结构

2,6-二氯-4-三氟甲基苯胺经重氮化后与2,3-二氰基丙酸酯反应合成了1-(2,6-二氯-4-三氟甲基苯基)-3-氰基-5-氨基吡唑(1), 1与苯磺酰氯、对甲基苯磺酰氯、甲基磺酰氯反应, 得到1的苯磺酰胺2a、对甲基苯磺酰胺2b和双甲基磺酰胺2c. 通过元素分析、红外光谱、核磁共振氢谱、核磁共振碳谱、质谱等手段对其结构进行了表征. 用X射线单晶衍射测定了化合物1, 2a和2c的晶体结构. 1属于正交斜方晶系, Pbca空间群, 晶胞参数 a＝1.61739(7) nm, b＝1.62480(7) nm, c＝3.10857(13) nm, ＝＝＝90, V＝8.1691 nm³, Z＝24, R＝0.1089, wR＝0.2545. 2a属于单斜晶系, C2/c空间群, 晶胞参数 a＝3.35144(18) nm, b＝0.97948(5) nm, c＝2.44717(12) nm, β＝102.460(1), V＝7.8440(7) nm³, Z＝8, R＝0.1831, wR＝0.2600. 2c属于三斜晶系, P-1空间群, 晶胞参数 a＝0.84681(7) nm, b＝0.89652(83) nm, c＝1.43497(12) nm, α＝75.198(2), β＝87.918(1), γ＝65.395(1), V＝0.9546 nm³, Z＝2, R＝0.049, wR＝0.135.     

N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)酰胺类新化合物的合成及生物活性

以N-吡啶基吡唑甲酸和2-氨基-3-甲基苯甲酸为起始原料,经由亲核加成、环化和酰化等多步反应合成了一系列结构新颖的N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)酰胺类化合物.测试了所合成化合物的杀虫及抑菌活性,结果表明,新化合物大多化合物在200 mg·L^-1浓度下对东方粘虫(Mythimna separataWalker)具有一定的杀虫活性,尤其是N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)乙酰胺(8a)和N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-3-氯-2,2-二甲基丙酰胺(8e)致死率可达70%;部分化合物在50 mg·L^-1浓度下对油菜菌核病菌的抑菌活性相对较好(54.5%~63.6%),优于triadimefon和chlorantraniliprole;部分化合物如N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-3,3-二甲基丁酰胺80和N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-4-氟苯甲酰胺(8h)对苹果轮纹病菌具有中等抑菌活性.值得注意的是,化合物8e的杀粘虫活性和对油菜菌核病菌的抑菌活性都较为突出,可用作新农药创制研究的新型参考结构.     

Preparation of Highly Fluorinated Poly(ether sulfone)s under Mild Polycondensation Conditions Using Molecular Sieves

Highly fluorinated poly(ether sulfone)s were prepared by a modified polycondensation technique, using a molecular sieve dehydrating apparatus in order to efficiently remove water under mild conditions. Consequently, side reactions were minimized, which resulted in the formation of polymers free of microgels. This reaction was also used to introduce pentafluorostyrene moieties into the polymer to provide crosslinking functionalities.     

Solid-Phase Synthesis of Phenylacetylene Oligomers Utilizing a Novel 3-Propyl-3-(benzyl-supported) Triazene Linkage

Sequence-specific phenylacetylene oligomers consisting of functionalized monomers (hexyl benzoate, hexyl phenyl ether, benzonitrile, and tert-butylphenyl) are synthesized in gram quantities using solid-phase methods. Growing oligomers are attached to a divinylbenzene cross-linked polystyrene support by the 1-aryl-3-propyl-3-(benzyl-supported) triazene moiety. This linkage is obtained by reaction of arenediazonium tetrafluoroborate salts with a n-propylamino-modified Merrifield resin. Condensation strategies are described, producing oligomers with higher yields and simplified procedures compared to solution-phase methods. Terminal acetylene is protected with a trimethylsilyl group. After deprotection of the resin-bound terminal acetylene, an aryl iodide monomer or an aryl iodide-terminated oligomer is coupled to the supported oligomer using a palladium(0) catalyst. The cycle can be repeated to produce sequence-specific oligomers of varying length and functionality. The resulting oligomers are liberated from the polymer support by cleavage of the 1-aryl-3-propyl-3-(benzyl-supported) triazene group by reaction with iodomethane producing an aryl iodide.     

Efficient Building Blocks for Solid-Phase Peptide Synthesis of Spin Labeled Peptides for Electron Paramagnetic Resonance and Dynamic Nuclear Polarization Applications

Specific spin labeling allows the site-selective investigation of biomolecules by EPR and DNP enhanced NMR spectroscopy. A novel spin labeling strategy for commercially available Fmoc-amino acids is developed. In this approach, the PROXYL spin label is covalently attached to the hydroxyl side chain of three amino acids hydroxyproline (Hyp), serine (Ser) and tyrosine (Tyr) by a simple three-step synthesis route. The obtained PROXYL containing building-blocks are N-terminally protected by the Fmoc-protection group, which makes them applicable for the use in solid-phase peptide synthesis (SPPS). This approach allows the insertion of the spin label at any desired position during SPPS, which makes it more versatile than the widely used post synthetic spin labeling strategies. For the final building-blocks, the radical activity is proven by EPR. DNP enhanced solid-state NMR experiments employing these building-blocks in a TCE solution show enhancement factors of up to 26 for ¹H and ¹³C (¹H→¹³C cross-polarization). To proof the viability of the presented building-blocks for insertion of the spin label during SPPS the penta-peptide Acetyl-Gly-Ser(PROXYL)-Gly-Gly-Gly was synthesized employing the spin labeled Ser building-block. This peptide could successfully be isolated and the spin label activity proved by EPR and DNP NMR measurements, showing enhancement factors of 12.1±0.1 for ¹H and 13.9±0.5 for ¹³C (direct polarization).     

1-(2,6-二氯-4-三氟甲基苯基)-3-氰基-5-氨基吡唑及其酰胺、二酰亚胺的合成及晶体结构

2,6-二氯-4-三氟甲基苯胺经重氮化后与2,3-二氰基丙酸酯反应合成了1-(2,6-二氯-4-三氟甲基苯基)-3-氰基-5-氨基吡唑(1), 1与乙酸酐、顺丁烯二酸酐、苯甲酰氯反应得到1的乙酰胺2a、顺丁烯酰亚胺2b和苯甲酰胺2c. 通过元素分析、红外光谱、核磁共振氢谱、核磁共振碳谱、质谱等手段对其结构进行了表征. 用X射线单晶衍射测定了化合物2a, 2b和2c的晶体结构. 2a属于单斜晶系, C2/c空间群, 晶胞参数a＝1.88282(6) nm, b＝0.86541(3) nm, c＝1.90766(6) nm, β＝95.5830(10)°, V＝3.09362 nm³, Z＝8, R＝0.064, wR＝0.170. 2b属于单斜晶系, P2₁/n空间群, 晶胞参数 a＝1.28261(10) nm, b＝0.89942(7) nm, c＝1.46896(12) nm, β＝104.217(1)°, V＝1.6427(2) nm³, Z＝4, R＝0.055, wR＝0.165. 2c属于三斜晶系, P-1空间群, 晶胞参数a＝0.84613(11) nm, b＝0.98923(13) nm, c＝1.14305(15) nm, β＝96.002(2)°, V＝0.9326 nm³, Z＝2, R＝0.0684, wR＝0.1795.     

Iron‐Catalyzed CαH Oxidation of Tertiary,Aliphatic Amines to Amides under Mild Conditions

De novo syntheses of amides often generate stoichiometric amounts of waste. Thus, recent progress in the field has focused on precious metal catalyzed, oxidative protocols to generate such functionalities. However, simple tertiary alkyl amines cannot be used as starting materials in these protocols. The research described herein enables the oxidative synthesis of amides from simple, noncyclic tertiary alkyl amines under synthetically useful, mild conditions through a biologically inspired approach: Fe‐catalyzed C_α? H functionalization. Mechanistic investigations provide insight into reaction intermediates and allow the development of a mild C_α? H cyanation method using the same catalyst system. The protocol was further applied to oxidize the drug Lidocaine, demonstrating the potential utility of the developed chemistry for metabolite synthesis.     

3-(3''''-羟基丁基)异苯并呋喃-1(3H)-酮的合成

由邻苯二甲酸酐为原料 ,经中间体 3 羟基苯酞 (3 ) ,再经溴丙烯及锡存在下 3的烯丙基化、硼氢化氧化、铬酐氧化、二甲基锌甲基化 ,共 6步反应合成了 3 (3’ 羟基丁基 )异苯并呋喃 1(3H) 酮。     

Synthesis of 1-(2-Ethoxyethyl)-4-hydroxy-4-[2-(1-hydroxycyclohexyl)ethynyl]piperidine and Heterocyclization under the Conditions of Hydration

The reaction of 1-(2-ethoxyethyl)piperidin-4-one with ethynylcyclohexanol led to the synthesis of a glycol, the hydration of which gave a mixture of spirocyclic compounds with a carbonyl group at various positions in the furan ring. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1649–1652, November, 2005.     

Synthesis of 1-(3-methylpyrazolyl-1)anthraquinone

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, p. 1695, December, 1990.