Iodobenzene Dichloride II - An Efficient Reagent for Deoximation

Reaction of Aromatic and Aralkyl ketoximes with iodobenzene dichloride leads to the formation of corresponding ketones in good yields in a single pot reaction.     

A Convenient Synthesis of Nitrile Oxides from Aldoximes by 1-Chlorobenzotriazole

Nitrite oxides can be conveniently prepared from aldoximes utilizing 1-chlorobenzotriazole in dichloromethane. The reaction and work-up procedures are simple and the isolated yields high.     

无碱条件下由芳香醛肟和磺酰氯制备O-磺酰基芳香醛肟

在氧化银和碘化钾存在下,磺酰氯与肟室温反应合成一系列O-磺酰基肟.芳香醛肟和酮肟作为底物,产率56%～87%.不过,对硝基苯甲醛肟、脂肪醛肟及α,β-不饱和醛肟作为该反应底物时,没有获得目标产物.     

An Efficient Method for the Preparation of Nitriles via the Dehydration of Aldoximes with Phthalic Anhydride

A new and highly efficient method for the conversion of aldoximes to nitriles was established. By fusing with phthalic anhydride, aldoximes were efficiently and smoothly converted into nitriles, in high yields (over 85%) and in a short time (within 5 minutes). The mixture of phthalic anhydride, a cyclic anhydride, and aldoximes in fusing state set up an ideal transition state for a selective [3.3]‐sigmatropic rearrangement of the acylated aldoximes to nitriles.     

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.     

Visible-Light-Induced Cross-Dehydrogenative Coupling of Heteroarenes with Aliphatic Alcohols Mediated by Iodobenzene Dichloride

With the irradiation of visible light, α-heteroarylation of aliphatic alcohol was selectively achieved under gentle conditions in the present of iodobenzene dichloride. The Minisci-type cross-dehydrogenative coupling reaction was performed in the absence of metal and acid. Readily available primary alcohols and electron-withdrawing heteroarenes can be applied smoothly. Mechanism studies indicated that the PhICl radical and chlorine radical formed from iodobenzene dichloride were responsible for the selective hydrogen atom abstraction of alcohols.     

Addition of Nitrile Oxides to N-Allylsaccharin

The addition of nitrile oxides to N-allylsaccharin has been studied and it has been shown that the reaction occurs regiospecifically to form a 5-substituted isomer. The molecular structure of 2-{ 5-[(3-methyl)isoxazolin-2-yl]methyl}-3-oxo-2,3-dihydrobenz[d]isothiazole 1,1-dioxide has been determined by X-ray analysis. A feature of the crystal of this compound is the presence of a supersymmetrical crystalline structure with two independent molecules associated by a center of pseudoinversion.Dedicated to Professor V. I. Minkin on the occasion of his anniversary__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 450–456, March, 2005.     

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.     

Thionyl Chloride-Benzotriazole: An Efficient System For Transformation Of Aldoximes to Nitriles

Dehydration of aromatic as well as aliphatic aldoximes using thionyl chloride-benzotriazole combination in dry DCM proceeds smoothly at room temperature to give the corresponding nitriles in high yields (>90%) in shorter time(~20min).     

The 1,3-Dipolar Cycloadditions of Nitrile Oxides and Nitrile Imines to Alkyl Dicyanoacetates

The readily available alkyl dicyanoacetates 1 reacted with the 1,3-dipolar reagents arenecarbonitrile oxides 2 ′ and arenecarbonitrile imines 5 ′ to afford 1,2,4-oxadiazol and 1,2,4-triazol derivatives. The arenecarbonitrile oxides 2 ′ with electron-donating groups on the arene ring gave products 3a – d resulting from addition on both CN groups of 1 , and those with electron-withdrawing groups provided mono-adducts 4a – e (Scheme 1). Arylnitrile imines 5 ′ reacted with 1 to offer both bis- and mono-addition products (Scheme 2); the bis-adducts 8a , b possess an ester structure, whereas the mono-adducts 6a – d present a ketene-hemiacetal structure.     

一种有效的从五氟氯乙烷合成五氟碘乙烷的方法

本文发展了一种有效的从五氟氯乙烷合成五氟碘乙烷的方法。仔细考察了五氟氯乙烷亚磺化脱氯的条件,由此生成的五氟乙基亚磺酸盐无须纯化,可以直接进行碘化,能以中等收率生成相应的五氟碘乙烷。     

Addition of Nitrile Oxides to Aryl Allyl Ethers

3,5-Disubstituted isoxazolines with an aryloxymethyl group in position 5 have been synthesized. The [2+3] cycloaddition reaction of benzonitrile oxide to a 5-chlorosalicylic acid derivative containing two allyl groups occurs to give a compound with an oxazolinylmethyl fragment both in the ester and the ether parts of the molecule. The addition of nitrile oxides to the aryl allyl ethers occurs regiospecifically to give the 5-substituted isomer.     

An Alternative Method to Prepare Nitrile Oxides from Primary Nitro Compounds by Using Thionyl Chloride and Triethylamine

The dehydration of PhCH₂NO₂ (1a), PhCOCH₂NO₂ (1b), and MeOOCCH₂NO₂ (1c) with SOCl₂ in the presence of Et₃N gave three corresponding nitrile oxides. Each nitrile oxide was trapped by various dipolarophiles to obtain the cycloadducts of 2-isoxazolines.     

Efficient Preparation of Isothiocyanates From Dithiocarbamates Using Bromineless Brominating Reagent

For the first time, the crystal structure of a ditribromide reagent 1,1′-(ethane-1,2-diyl)dipyridinium bistribromide (EDPBT) has been determined. Utilizing this thiophilic bromineless brominating agent EDPBT, highly useful synthetic intermediates (alkyl and aryl isothiocyanates) have been achieved directly from dithiocarbamates. EDPBT can be easily prepared from readily available reagents. It has been used as a thiophilic reagent, and its thiophilicity dominates over its brominating ability for substrates amenable to bromination. This is a sustainable process for the preparation of isothiocyantes because the spent reagent can be recovered, regenerated, and reused.