High-Pressure Kinetic Studies of a Transition State. The Diels-Alder Condensation of Methoxybutadiene-Maleic Anhydride

1971 ◽  
Vol 10 (3) ◽  
pp. 369-372 ◽  
Author(s):  
Richard A. Grieger ◽  
Charles A. Eckert
Keyword(s):  
High Pressure ◽  
Maleic Anhydride ◽  
Transition State ◽  
Kinetic Studies ◽  
Diels Alder

scholarly journals KINETIC STUDIES ON THE HIGH-PRESSURE DIELS–ALDER REACTION OF TROPONE WITH MALEIC ANHYDRIDE

1984 ◽  
Vol 13 (10) ◽  
pp. 1855-1858 ◽  
Author(s):  
Hitoshi Takeshita ◽  
Shigeru Sugiyama ◽  
Toshihide Hatsui
Keyword(s):  
High Pressure ◽  
Maleic Anhydride ◽  
Kinetic Studies ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction

Hydrolysis of aryl hydrogen maleate esters mediated by cyclodextrins — Effect on the intramolecular catalysis

2005 ◽  
Vol 83 (9) ◽  
pp. 1281-1286 ◽  
Author(s):  
Gabriel O Andrés ◽  
O Fernando Silva ◽  
Rita H de Rossi
Keyword(s):  
Maleic Anhydride ◽  
Transition State ◽  
Rate Constant ◽  
Association Constant ◽  
Kinetic Studies ◽  
Association Constants ◽  
Bulk Solution ◽  
Intramolecular Catalysis ◽  
Hydrolysis Of ◽  
Nonlinear Fashion

Kinetic studies of the hydrolysis of Z-aryl hydrogen maleates (Z = H, p-CH3, m-CH3, p-Cl, m-Cl) were carried out in the presence and absence of hydroxypropyl-β-cyclodextrin (HPCD) at variable pH from 1.00 to 3.00. The reaction involves the formation of maleic anhydride as an intermediate and the rate of its formation is strongly dependent on the pH. This is because the neighboring carboxylate group is a better catalyst than the carboxylic group. The rate constant for the formation of maleic anhydride decreases as the HPCD concentration increases in a nonlinear fashion. The results were interpreted in terms of the formation of a 1:1 inclusion complex of the esters with HPCD. The neutral (HA) and anionic (A) species of the substrate have different association constants (K[Formula: see text] and K[Formula: see text]). In all cases studied, K[Formula: see text] is higher than K[Formula: see text] for the same substrate. This difference is responsible for a decrease in the amount of the anionic substrate (reactive species) in the presence of HPCD, which results in a diminution of the observed rate constant. Besides, the rate constant for the reaction of the complexed substrate is smaller than that in the bulk solution indicating that the transition state of the cyclodextrin mediated reaction is less stabilized than the anionic substrate. The values of ΔΔG‡ are almost independent of the substituent on the aryl ring and range within 0.48 and 1.05 kcal mol–1 (1 cal = 4.184 J). There is no correlation between KTS and the association constant of the substrate indicating that the factors stabilizing the transition state are different from those that stabilize the substrate. Key words: cyclodextrins, intramolecular catalysis, hydrolysis, inhibition.

Effect of high pressure on the rate constant of the Diels-Alder reaction between furan and maleic anhydride

1990 ◽  
Vol 39 (3) ◽  
pp. 456-459 ◽  
Author(s):  
V. M. Zhulin ◽  
M. V. Kel'tseva ◽  
V. S. Bogdanov ◽  
Yu. D. Koreshkov ◽  
E. B. Kabotyanskaya
Keyword(s):  
High Pressure ◽  
Maleic Anhydride ◽  
Rate Constant ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction

Synthesis of functionalized hexahydro-, octahydro-, and decahydro-1H-phenalenes via Diels–Alder reactions of 1-methylene-4a-methoxycarbonyl-1,2,3,4,4a,5,6,7-octahydronaphthalene and related dienes

1993 ◽  
Vol 71 (9) ◽  
pp. 1463-1483 ◽  
Author(s):  
Edward Piers ◽  
Richard W. Friesen ◽  
Paul Kao ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Maleic Anhydride ◽  
Transition State ◽  
Methyl Acrylate ◽  
Diels Alder ◽  
Cycloaddition Reactions ◽  
Methoxycarbonyl Group ◽  
The Face ◽  
Group Reaction ◽  
Bicyclic Dienes

The results of a study of Diels–Alder reactions of the bicyclic dienes 6–8 with a variety of dienophiles are reported. Although 6 and 7 undergo cycloaddition reactions smoothly and efficiently, thermal Diels–Alder reactions of 8 are generally sluggish or, under the conditions investigated, do not proceed at all. Additions of tetracyanoethylene (TCNE) to 6–8 are highly face-selective, with preferential attack of the dienophile on the side of the dienes opposite to the angular methoxycarbonyl group. Reaction of 7 with maleic anhydride (MAN) is completely face-selective and proceeds preferentially via an endo transition state. Diels–Alder reactions of 6 and 7 with methyl acrylate (MAC) and nitroethylene (NE) are entirely regioselective, but the face-selectivities, which vary from ~2:1 to ~3:1, are rather low. The use of this chemistry as a method for the synthesis of functionalized, stereochemically defined, perhydro-1H-phenalenes is demonstrated.

High pressure organic chemistry. 2. Diels-Alder reaction of thiophene with maleic anhydride at very high pressure

1978 ◽  
Vol 43 (7) ◽  
pp. 1471-1472 ◽  
Author(s):  
Hiyoshizo Kotsuki ◽  
Sachio Kitagawa ◽  
Hitoshi Nishizawa ◽  
Takashi Tokoroyama
Keyword(s):  
Organic Chemistry ◽  
High Pressure ◽  
Maleic Anhydride ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction ◽  
Very High
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