Mild,Efficient, and Rapid Dehydration of Aldoximes to Nitriles Mediated by Phthalic Anhydride Under Microwave Irradiation

Summary.  Aldoximes can be efficiently and rapidly dehydrated to nitriles by treatment with phthalic anhydride under microwave irradiation. Received April 18, 2001. Accepted (revised) June 7, 2001     

Synthesis of Nitriles from Aldoximes Using Silica Gel as Catalyst Under Microwave Irradiation

Abstract

A rapid and efficient synthesis of nitriles via dehydration from the corresponding aldoximes has been carried out in the presence of Silica gel as catalyst under microwave irradiation in 83–95% yield.     

邻苯二甲酸酐化学修饰对辣根过氧化物酶催化活性的影响

通过采用邻苯二甲酸酐(PA)对辣根过氧化物酶(HRP)的蛋白链进行修饰, 研究了PA化学修饰对HRP的稳定性、催化活性、活性中心结构、酶对底物的亲合性和专一性等催化性质的影响. 结果显示: 酸性条件下(pH=3), 4小时后PA-HRP的催化活性比天然HRP提高了7.5%;碱性条件下(pH=10), 4小时后PA-HRP的催化活性比天然HRP提高了27%. PA-HRP的K_m值为8.16 (mmol/L), 小于天然HRP的K_m值12.99 (mmol/L), 而PA-HRP的k_(cat)/K_m值为7.86(10~4(L/ mmol· min)大于天然HRP的k_(cat)/K_m的6.70(10~4(L/ mmol· min). 这些催化活性和动力学数据表明了PA-HRP与天然HRP相比其稳定性、酶对底物的亲和性和专一性得到了提高. 紫外-可见光谱、拉曼光谱数据显示: 修饰剂PA 改变了天然HRP血红素周围的微环境, 对酶蛋白分子的活性中心结构并没有影响. 差示光谱显示PA修饰剂可以提高酶对底物的亲和力.     

Efficient Dehydration of Aldoximes to Nitriles with TiCl3(OTf)

Aromatic, alicyclic, olefinic as well as heterocyclic aldoximes, were dehydrated to their corresponding nitriles with 0.15 molar equivalents of TiCl₃(OTf) in sealed tube at 80°C in 85-97% yield.     

Simple and Highly Efficient Procedure for Conversion of Aldoximes to Nitriles Using N-(p-Toluenesulfonyl) Imidazole

A facile and efficient method for dehydration of aldoximes into nitriles using N-(p-toluenesulfonyl) imidazole (TsIm) is described. In this method, aldoximes were refluxed with TsIm in the presence of 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU) in dimethylformamide (DMF) to afford the corresponding nitriles in good yields. This methodology is highly efficient for various structurally diverse aldoximes including aromatic, heteroaromatic, and aliphatic oximes. A plausible mechanism for the conversion of aldoxime into nitriles using TsIm/DBU is explained.     

微波催化氧化邻二甲苯制苯酐

微波催化氧化邻二甲苯制苯酐刘晔，刘省明，殷元骐（中国科学院兰州化学物理研究所，兰州７３００００）关键词催化氧化，邻二甲苯，苯酐，微波幅射ＣａｔａｌｙｔｉｃＯｘｉｄａｔｉｏｎｏｆｏ－ＸｙｌｅｎｅｔｏＰｈｔｈａｌｉｃＡｎｈｙｄｒｉｄｅｕｎｄｅｒＭｉｃｒｏ...     

Heterogeneous Catalytic Method for the Conversion of Aldoximes into Nitriles Using Molecular Sieve Modified with Copper(II)

A simple heterogeneous metal-catalyzed method was developed for the transformation of aldoximes into nitriles. Molecular sieve (4 Å) modified with copper(II) proved to be an efficient catalyst for the conversion.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

An Efficient Synthesis of Nitriles from Aldoximes in the Presence of Trifluoromethanesulfonic Anhydride in Mild Conditions

Russian Journal of Organic Chemistry - A new and convenient protocol has been proposed for the transformation of aldoximes to nitriles using trifluoromethanesulfonic anhydride and triethylamine....     

A Convenient Method for the Preparation of Nitriles from Aldehydes and Aldoximes

Nitriles were prepared from their corresponding aldehydes or aldoximes with the Vilsmeier reagent in a one-pot reaction or without another solvent at room temperature in 74-98% yields.     

稀土对钒—钛苯酐催化剂活性的影响

在邻二甲苯气相氧化制苯酐的Ｖ２Ｏ５－ＴｉＯ２催化剂中，添加少量Ｌａ、Ｐｒ、Ｓｍ或Ｎｄ后，催化剂活性有不同程度的提高。本文应用ＦＴ－ＩＲ研究了氧化有后的苯酐催化剂，明显观察到在Ｖ－Ｔｉ苯酐催化剂中添加稀土后，Ｖ－Ｏ键的吸收峰发生红移，最大红移达到２３５ｃｍ＾－１。苯酐催化剂加入稀土后，对分子的活化作用与催化活性剂评价的结果是一致的。     

Na 2 SO 3 /SOCl 2 , an Efficient Reagent for the Dehydration of Aldoximes to Nitriles

Aldoximes undergo rapid dehydration with sodium sulfite, thionyl chloride, under mild reaction condition to afford nitriles in excellent isolated yields. Dehydration reactions were performed in solvent and under solvent free conditions.     

Ac2O/K2CO3/DMSO: an efficient and practical reagent system for the synthesis of nitriles from aldoximes

The transformation of aldoximes to nitriles using acetic anhydride as dehydration agent under mild reaction conditions is reported. The reaction, which proceeds under weak alkaline condition, allows for the conversion of a range of aldoximes including aromatic aldoximes, alphatic aldoximes, and heterocyclic aldoximes in good to excellent yields. This method has also been successfully applied to the synthesis of calcium channel blocker nilvadipine in pilot scale.     

Investigation of Mechanisms About Effects of Promoters P_2O_5,K_2O and A1_2O_3 on Oxidation of o-Xylene to Phthalic Anhydride

We succeeded in designing an effective catalyst, V2O5-P2O5-K2O/Al2O3. SiO2, by which a high yield of PA,105wt% can be gained in middle-sized industrial fluidized bed apparatus without addition of any promoting gas.The mechanisms of effects of P2O5, K2O and Al2O3 on the surface properties of V2O5 were investigated by means of TPD and XRD. And the selectivity of oxidation are explained.Addition of a great deal of P2O5 restrains the activity of donating surface oxygen from V2O5, but increases the number of sites which donate surface oxygen. Addition of K2O promotes donation of surface oxygen from V2O6, and decreases the number of sites of donating oxygen, on the other hand, addition of K|O makes the surface structure of V2O5 catalysts more stable. Coating a small amount of Al2O2 onto support, SiO2, restrains the activity of donating oxygen and increases the number of sites of donating surface oxygen from V2O5.     

Investigation of Mechanisms About Effects of Promoters P2O5,K2O and Al2O3 on Oxidation of o-Xylene to Phthalic Anhydride

We succeeded in designing an effective catalyst, V₂O₅-P₂O₅-K₂O/Al₂O₃. SiO₂, by which a high yield of PA,105wt% can be gained in middle-sized industrial fluidized bed apparatus without addition of any promoting gas.The mechanisms of effects of P₂O₅, K₂Oand Al₂O₃ on the surface properties of V2O₅ were investigated by means of TPDand XRD. And the selectivity of oxidation are explained.Addition of a great deal of P₂O₅ restrains the activity of donating surface oxygen from V2O₅, but increases the number of sites which donate surface oxygen. Addition of K₂Opromotes donation of surface oxygen from V2O₆, and decreases the number of sites of donating oxygen, on the other hand, addition of K|Omakes the surface structure of V₂O₅ catalysts more stable. Coating a small amount of Al₂O₂ onto support, SiO₂, restrains the activity of donating oxygen and increases the number of sites of donating surface oxygen from V₂O₅.     

An Environmentally Benign System; A Simple and Effective Procedure for Dehydration of Oximes into Nitriles in Solvent Free Conditions

In an environmentally benign solvent free system aldoximes are rapidly transformed into nitriles using trimethylsilylchloride under mild conditions.     

SO3H-Functionalized Ionic Liquids: Green, Efficient and Reusable Catalysts for the Facile Dehydration of Aldoximes into Nitriles

Easily synthesized aldoximes have been converted to the corresponding nitriles under very mild conditions by a simple reaction using two halogen‐free SO₃H‐functionalized ionic liquids, 3‐methyl‐1‐(4‐sulfonic acid)butylimi‐ dazolium hydrogen sulfate [MIM(CH₂)₄SO₃H][HSO₄] and 1‐(4‐sulfonic acid)butylpyridinium hydrogen sulfate [PY(CH₂)₄SO₃H][HSO₄], as catalyst and reaction medium without any additional organic solvent. The method was equally effective for aromatic aldoximes bearing electron‐donating and electron‐withdrawing substituents. Taking into account environmental and economical consideration, the protocol presented here has the merits of environmentally friendly, simple operation, easy work‐up and very good yields. The catalysts could be recycled and reused for several times without noticeably decreasing in their catalytic activities.     

Triphenylphosphine-Promoted Synthesis of Spiroketals from Phthalic Anhydride with Dialkyl Acetylenedicarboxylates

Triphenylphosphine, dialkyl acetylenedicarboxylates, and phthalic anhydride react in one pot to afford novel spirocyclic compounds in fairly good yields at room temperature.     

Triflic Anhydride: A Mild Reagent for Highly Efficient Synthesis of 1,2-Benzisoxazoles,Isoxazolo, and Isothiazolo Quinolines Without Additive or Base

The synthetic utility of trifluoromethanesulphonic anhydride (triflic anhydride, TA) without additive or base for the high-yielding synthesis of a wide variety of 1,2-benzisoxazoles from 2-hydroxyaryl aldoximes and ketoximes under mild conditions has been carried out for the first time. As a continuation of our study, syntheses of isoxazolo and isothiazolo quinolones have also been demonstrated using triflic anhydride under similar conditions. This method is simple and has benefits from the easy way to isolate the products in excellent yields.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

A Rapid and Efficient Method for Dehydration of Primary Amides to Nitriles. Preparation of Acrylonitrile Derivatives

Chloromethylene iminium salts (Vilsmeier reagents) have a long history and thoroughly investigated chemistry⁽¹⁾. Chloro-N, N-dimethylforminium chloride 1 is most conveniently generated by the reaction of N, N-dimethylformamide (DMF) with oxalyl chloride⁽²⁾. The reagent has also been obtained usingthicnyl chloride at elevated temperature and a variety of acid chlorides^(1b). The literature describes several examples of the use of thionyl chloride in combination with DMF in which 1 or a related species is thought to function as the reactive intermediate in the transformation of amides to nitriles⁽³⁾.