Reaction of dialkyl carbonates with alcohols: Defining a scale of the best leaving and entering groups*

نویسندگان

  • Pietro Tundo
  • Fabio Aricò
  • Anthony E. Rosamilia
  • Maurizio Rigo
  • Andrea Maranzana
  • Glauco Tonachini
چکیده

A series of dialkyl and methyl alkyl carbonates has been synthesized and their reactivity investigated. The behavior of preferential leaving and entering groups for the newly synthesized carbonates has been accurately investigated. Both experimental and computational studies agreed that the scale of leaving groups follows the trend: PhCH2O –, MeO– ≥ EtO–, CH3(CH2)2O –, CH3(CH2)7O – > (CH3)2CHO – > (CH3)3CO –. Accordingly, the scale of the entering group has the same trend, with t-butoxide being the worst entering group. A preliminary attempt to rationalize the nucleofugality trends, limited to the (CH3)3CO – and CH3O – groups, has indicated that a likely origin of the observed trends lies in the different entropic contributions and solvation effects.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Improving reservoir rock classification in heterogeneous carbonates using boosting and bagging strategies: A case study of early Triassic carbonates of coastal Fars, south Iran

An accurate reservoir characterization is a crucial task for the development of quantitative geological models and reservoir simulation. In the present research work, a novel view is presented on the reservoir characterization using the advantages of thin section image analysis and intelligent classification algorithms. The proposed methodology comprises three main steps. First, four classes of...

متن کامل

LITHIUM PERCHLORATE MEDIATED AMINATION REACTION OF ALDEHYDES: A NOVEL METHOD FOR SYNTHESIS OF N, N-DIALKYL-p-SILYLATED AMINES*

P-Silylated N,N-dialkyl amines (5) were easily synthesized in good to excellent yield from aldehydes (1), trimethylsilyldialkylamines (2), and trimethylsilylmethylmagnesium chloride (4) in the presence of 5 M lithium perchlorate solution in diethyl ether. The reaction Of (2) with aldehyde proceeded smoothly in the LiCI0 , to give the imimum salt (3). Addition of trimethylsilylmethylrnagnes...

متن کامل

Functionalized cyclobutenes via multicomponent thermal [2 + 2] cycloaddition reactions.

[reaction: see text] Enamine [2 + 2] cycloadditions can be achieved in useful yields simply by stirring a mixture of an aldehyde, diethylamine, a dialkyl fumarate, and potassium carbonate in acetonitrile at 25 degrees C, conditions that are compatible with the presence of a potential leaving group on the beta-position of the intermediate enamine. Methylation and elimination of the product cyclo...

متن کامل

An Efficient One-pot Synthesis of Dialkyl fumarates Mediated by inyltriphenylphosphonium Salt in the Intramolecular Wittig Reaction

An efficient three-component reaction of dialkyl acetylendicarboxylates and 2-Pyrrolidin in the presence of triphenylphosphine produces dialkyl 2-(2-Pyrrolidin-N-yl)-3-(triphenylphosphanylidene)succinate. These phosphoranes undergo mild intramolecular Wittig reaction to produce dialkyl (E)-2-(4,5-dihydro-3H-pyrrol-2-yl)fumarate in excellent yields.

متن کامل

Oxidation of benzylic alcohols with molecular oxygen catalyzed by Cu3/2[PMo12O40]/SiO2

The aerobic oxidation of alcohols was efficiently completed in high conversion and selectivity using Cu3/2[PMo12O40]/SiO2 as catalyst under mild reaction condition. This reaction provides a new environmentally friendly rout to the conversion of alcoholic function to carbonyl groups.

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:

دوره   شماره 

صفحات  -

تاریخ انتشار 2009