A Facile Route to Quinazolin-4(3H)-ones Functionalised at the 2-Position

Treatment of 2-methoxyacetamidobenzonitriles or 2-chloroacetamidobenzonitrile with UHP and K₂CO₃ provides a convenient route to 2-methoxymethyl-or 2-chloromethylquinazolin-4(3H)-ones. In addition, demethylation of 2-methoxymethylquinazolin-4(3H)-ones with 48% HBr gives 2-hydroxymethylquinazolin-4(3H)-ones.     

Reactions of 3, 5-Dimethyl-4-Carbethoxy-2-Cyclohexen-1-One at α-Position

3, 5-Dimethyl-4-carbethoxy-2-cyclohexen-1-one has been synthesized through the Knoevenagel condensation¹, which is then subjected to alkylation and acylation at α-position. The resulting products are hydrolyzed and decarboxylated to α-substituted cyclohexenones. 3, 5-Dimethyl-2-cyclohexen-1-one is converted by N-bromosuccinimide to phenol via enolization².     

Synthesis and Characterization of Partially Substituted at Lower Rim Phosphorus Containing Calix(4)arenes

The synthesis and characterization of several new phosphorus-containing partially lower rim substituted derivatives of 5,11,17,23-tetra(t-butyl) calix(4)arene (I) and 5,11,17,23-tetra(t-octyl)calix(4)arene (II), namely 5,11,17,23-tetra(t-butyl)-25,27-dihydroxy-26,28-bis(diphenylphosphinoyl-oxy) calix(4)arene (IV); 5,11,17,23-tetra(t-butyl)-25-hydroxy-26,27,28-tris(tetramethyldiamido-phosphinoyl-oxy) calix(4)arene (Vb); 5,11,17,23-tetra(t-butyl)-25,27-dihydroxy-26,28-bis(dimethyl-phosphinoyl-methoxy) calix(4)arene (VI); 5,11,17,23-tetra (t-octyl)-25,27-dihydroxy-26,28-bis(dimethyl-phosphinoyl-methoxy) calix(4)arene (VII) are reported. The structure of the synthesized calix(4)arene derivatives are identified and confirmed by elemental analysis, IR, ¹H, ¹³C, ³¹P{¹H} NMR spectroscopy and mass spectrometry as and X-ray crystallographic analysis of 5,11,17,23-tetra(t-butyl)-25,27-dihydroxy-26,28-bis(dimethyl-phosphinoyl-methoxy) calix(4)arene VI. According to the NMR spectra, all calix(4)arenes are in cone conformation.     

The Synthesis of a Novel Phosphorus Containing Antigen

The hydrolysis of peptide is one of the most important chemical processes in life chemistry. It is of great significance to study catalytic antibody, which is capable of catalyzing the hydrolysis on a specific peptide bond. In recent years, we have successfully synthesized some tetrahedral geometry analogues mimicking that of the hippuryl phenylalanine 1 hydrolyzing transition state catalyzed by carboxypeptidase A(CPA)1,2, which is specific for cleavage of the C-terminal amino acid from an o…     

Transformations of 2-Ethyl-2-methyl-2,3-dihydro-1H-indole at the 3-Position

Russian Journal of Organic Chemistry - The oxidation of N-acetyl-2-ethyl-2-methyl-2,3-dihydro-1H-indole with pyridinium chlorochromate, CrO3 · 2 Py, or CrO3 gave...     

3-位苯并含氮杂环取代的焦脱镁叶绿酸-a甲酯的合成

以焦脱镁叶绿酸-a甲酯(MPP-a)(1)为起始原料，在二氯甲烷中与醋酸锌共回流得锌配合物2，在四氯钯锂催化下，通过与苯基氯化汞的偶联反应生成3b-苯基焦脱镁叶绿酸-a甲酯(3)．分别选用四氧化锇、高钌酸四丙基铵(TPAP)和N-甲基吗啉N-氧化物将环外烯键氧化成邻二酮(4)．在酸性条件下，4与邻苯二胺的缩合形成了3-位喹喔啉取代的焦脱镁叶绿酸-a甲酯(5)．用四氧化锇和高碘酸钠将1的3-位碳碳双键氧化，则生成焦脱镁叶绿酸-d甲酯(6)．所得卟吩醛与环己二酮和萘胺进行一锅法反应，得到3-位苯并吖啶取代的焦脱镁叶绿酸-a甲酯(7)．所合成的新卟吩化合物均经UV，IR，^1H NMR及元素分析证明其结构．     

3-位苯并含氮杂环取代的焦脱镁叶绿酸-α甲酯的合成

以焦脱镁叶绿酸-a甲酯(MPP-a)(1)为起始原料,在二氯甲烷中与醋酸锌共回流得锌配合物2,在四氯钯锂催化下,通过与苯基氯化汞的偶联反应生成3b-苯基焦脱镁叶绿酸-a甲酯(3).分别选用四氧化锇、高钌酸四丙基铵(TPAP)和N-甲基吗啉N-氧化物将环外烯键氧化成邻二酮(4).在酸性条件下,4与邻苯二胺的缩合形成了3-位喹喔啉取代的焦脱镁叶绿酸-a甲酯(5).用四氧化锇和高碘酸钠将l的3-位碳碳双键氧化,则生成焦脱镁叶绿酸-d甲酯(6).所得卟吩醛与环己二酮和萘胺进行一锅法反应,得到3-位苯并吖啶取代的焦脱镁叶绿酸-a甲酯(7).所合成的新卟吩化合物均经UV,IR,1H NMB及元素分析证明其结构.     

Synthesis,Reactions and Applications of Phosphorus Containing Carbon Centered Radicals

A general method for synthesis of C_n-C (n=1, 2...) phosphonate bonds involving a reaction of 1-diethoxy-phosphorylalkan-1-, -2-and -3-yl radicals 1,3,6 with alkenes 4, a new example of functional group interconversion in 1-heterosubstituted phosphonates and synthesis of useful phosphoroorganic compounds and methylenomycin B are described.     

5-氨基异噁唑的4-位芳基化

在温和、简单条件下实现了5-氨基异噁唑C4位芳基化的反应，以中等到优秀的产率（最高达99%）合成了一系列4-芳基-5-氨基异噁唑类衍生物，产物结构经核磁与高分辨质谱确证。      

Synthesis of Some Flame-Retardants Containing Phosphorus and Halogen

Polyphosphonates, one of the longest known classes of organophosphonic compounds, are of interest because they can confer low flammability, plasticity, thermal stability, and lubrication properties on polymers.     

A Stereoselective Synthesis of Two 2-Deoxy-3-Phosphasugars Epimeric at Phosphorus

Abstract

A synthetic route to 2-deoxy-3-phosphasugar derivatives utilising a stereoselective addition of a phosphinate to an aldehyde is described.     

Synthesis and Antimicrobial Activity of Some New 1,3-Diphenylpyrazoles Bearing Pyrimidine,Pyrimidinethione, Thiazolopyrimidine,Triazolopyrimidine, Thio-and Alkylthiotriazolop-Yrimidinone Moieties at the 4-Position

1,3-diphenyl-1H-pyrazole-4-carboxaldehyde (1) reacted with ethyl cyanoacetate and thiourea to give the pyrimidinethione derivative 2. The reaction of 2 with some alkylating agents gave the corresponding thioethers 3a–e and 7. Thione 2 was cyclized to 5 and 6 upon a reaction with chloroacetic acid and with benzaldehyde, respectively. Thioether 3c was cyclized to 4 upon boiling with sodium acetate in ethanol, and 7 was cyclized to 8 upon boiling in an acetic anhydride-pyridine mixture. The hydrazino derivative 9 was prepared either by boiling 2 and/or 3a with hydrazine. The reaction of 9 with nitrous acid, acetylacetone, triethyl orthoformate, acetic anhydride, and carbon disulfide gave 10–14. The alkylation of 14 with ethyl iodide, phenacyl bromide, and ethyl chloroacetate afforded the alkythiotriazolo pyrimidinone derivatives 15a–c. The dialkyl derivative 16 was produced upon the treatment of 2 with two equivalents of ethyl iodide. Boiling 16 with hydrazine afforded the hydrazino 17. The reaction of 17 with nitrous acid, carbon disulfide, ethyl cyanoacetate, ethyl acetoacetae, and phenacyl bromide gave 18–22, respectively. Some of the newly obtained compounds were tested for their antibacterial and antifungal activities.     

Novel Synthesis of Macrocylic Systems Containing Phosphorus and Sulfur

Abstract

Macrocyclic systems containing phosphine. phosphoryl or thiophosphoryl functions in the ring demonstrate high ability to complex metal ions Complexed structures of this type show interesting Fatalytic properties and can be used in homogenous and heterogenous catalysis^[1,2] Macrocyclic compounds containg phosphorus are also useful as complexing agents for ammonlum salts. anions. etc [3,4] Generally three types of reactions are used to synthesize phosphorus containing macrocyclic compounds the cyclocondensation, the ring opening reaction and the reaction with metal as a matrix^[5]. We have devoloped a new procedure for the synthesis of the title systems of different sizes and of different P and S contents It is based on a double conjugate addition of dithiolates to divlnyl phosphine oxides and sulfides and makes use of the so-called “cesium effect”.     

3-位环庚烷(酰)基取代的焦脱镁叶绿酸-a甲酯的合成

以焦脱镁叶绿酸-a甲酯(MPP-a)为起始原料, 在对其E-环羰基进行保护的前提下, 经焦脱镁叶绿酸-d甲酯与环庚基溴化镁进行Grignard反应; 所生成新的卟吩仲醇再经脱保护、脱水和氧化等诸多反应, 将3-位仲羟基转化成碳碳双键和羰基, 其碳氧双键再行Grignard反应并脱水成烯, 完成一系列未见报道的3-位环庚基取代的焦脱镁叶绿酸-a甲酯衍生物的合成. 其化学结构均经UV, IR, ¹H NMR及元素分析予以证实.     

一种新型磷系阻燃剂的合成

以甲基丙烯酸羟乙酯(1),三氯氧磷(2)和甲醇为原料,合成了一种新型磷系阻燃剂--甲基丙烯酰氧乙基二甲基磷酸酯(3),其结构经1H NMR和IR表征.合成3的较适宜反应条件为:1 0.5 mol,n(1):n(2)=1.0:1.3,于0℃反应6 h.     

新型侧基含磷共聚酯的合成、表征及性能

以精制对苯二甲酸（TPA）、乙二醇（EG）和含磷反应型阻燃剂9,10-二氢-9-氧杂-10-[2,3-二（2-羟基乙氧基）羰基丙基]-10-磷杂菲-10-氧化物为原料,利用熔融缩聚法合成了含磷量分别为0．35％、0．65％的阻燃聚酯。通过熔融纺丝法将聚酯制成纤维及织物,研究了纤维的染色性能,并通过极限氧指数法和垂直燃烧法研究了织物的阻燃性能。FT-IR和NMR研究结果表明：阻燃共聚酯含磷量为0．35％时,其氧指数（LOI）达31．5％,并无熔滴、烟雾产生,具有优异的阻燃性能和抗熔滴性能。DSC、TG和XPS的研究结果表明：侧基舍磷单元的引入降低了聚酯的Tg和Tm,较低的Tm将有利于材料加工性能的改善;阻燃聚酯侧基上的P-C、P-O键易断裂并挥发至气相中,从而降低了聚酯热稳定性,阻燃聚酯可能以气相阻燃机理为主发挥阻燃作用。此外,含磷共聚酯纤维具有较优异的染色性能。     

Cyanoethylation of Aromatic Aldehyde Imines Containing a Hydroxy Group in the β- or γ-Position. Synthesis of 3-Cyanoethyl-1,3-oxazacycloalkanes

Acrylonitrile reacts with aromatic aldehyde imines containing a hydroxy group in the β- or γ-position to give 70–85% of the corresponding 2-aryl-3-cyanoethyltetrahydro-1,3-oxazines or 2-aryl-3-cyanoethyl-1,3-oxazolidines, respectively. The results of these reactions are rationalized in terms of ring-chain isomerism of the initial imines.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 7, 2005, pp. 1064–1066.Original Russian Text Copyright © 2005 by Kon’kova, Abovyan, Khachatryan, Badasyan, Panosyan, Sargsyan.     

Synthesis of o-Carboranyl Containing Esters of Pentavalent Phosphorus Acids

Abstract

A new method for the synthesis of o-carboranyl containing phosphoric, phosphonic and phosphinic acid esters, where the o-carboranil group is in the ester group, has been developed. The propargyl esters of these acids were prapared in two ways: by the reaction of phosphorus acid salts with propargyl chlorid and by interaction of propargyl alcohol with acid chlorides in the presence of Et₃N. The propargyl esters have been converted into carboranyl containing compounds upon treatment with decaborane and dimethyl aniline     

New Synthesis of Acetaminophen Derivatives Containing a Phosphorus Atom

Two derivatives of acetaminophen have been efficiently prepared from 4-aminophenol via a two-step procedure involving acetylation of OH and NH ₂ groups and then the reaction of the acetylated compounds with diakyl acetylenedicarboxylate in the presence of triphenylphosphine. The products were obtained in good yields.     

Synthesis of N-Substituted 3-Aminothiazolidin-4-ones Containing Hetaryl Fragments

Condensation of the N-(3,5-dichloropyridyl-2)- and N-(benzothiazolyl-2-thioacetyl)hydrazones of carbonyl compounds with thioglycolic acid gave the 3-(3,5-dichloropyridyl-2)amino- and 3-[N-(benzothiazolyl-2-thioacetyl)amino]-2-R¹-2-R²-thiazolidin-4-ones. Reaction of 1-(benzothiazolyl-2-thioacetyl)-4-R-thiosemicarbazides with chloroacetic acid in the presence of sodium acetate gave the 2-[N-(benzothiazolyl-2-thioacetyl)hydrazono]-3-R-thiazolidin-4-ones. It was found that the N-(benzothiazolyl-2-thioacetyl)hydrazones, both in the solid state and in solution, exist in the form of an equilibrium mixture of the EZ'- and EE'-isomers as a result of hindered rotation around the amide N-CO bond.