The products of hydrolysis of cyclic orthoesters as a function of pH and the theory of stereoelectronic control

1985 ◽  
Vol 63 (9) ◽  
pp. 2485-2492 ◽  
Author(s):  
Pierre Deslongchamps ◽  
Jean Lessard ◽  
Yves Nadeau
Keyword(s):  
Acid Hydrolysis ◽  
Hydroxy Ester ◽  
The Other ◽  
Relative Percentage ◽  
Stereoelectronic Control ◽  
Hydrolysis Of ◽  
Tetrahedral Intermediates

The acid hydrolysis of cyclic orthoesters 1, 3–6 (R = Me), and 2 (R = Me and Et) as a function of pH was studied. The bicyclic orthoester 5 yields mainly the hydroxy-ester (less than 5% lactone), and this result is essentially independent of pH. For the other orthoesters, the relative percentage of products differs for each case and varies with pH. At pH ≤ 3, the percentage of lactone is always larger than at pH > 3. These results are explained on the basis of the stereoelectronic theory for the cleavage of tetrahedral intermediates.

The Hydrolysis of Cyclic Orthoesters. Stereoelectronic Control in the Cleavage of Hemiorthoester Tetrahedral Intermediates

1975 ◽  
Vol 53 (11) ◽  
pp. 1601-1615 ◽  
Author(s):  
Pierre Deslongchamps ◽  
Robert Chênevert ◽  
Roland J. Taillefer ◽  
Claude Moreau ◽  
John K. Saunders
Keyword(s):  
Experimental Evidence ◽  
Acid Hydrolysis ◽  
Alkoxy Group ◽  
Gauche Conformer ◽  
Group A ◽  
Stereoelectronic Control ◽  
Hydroxy Esters ◽  
Hydrolysis Of Esters ◽  
Hydrolysis Of ◽  
Tetrahedral Intermediates

The synthesis of several cyclic dialkoxy orthoesters is reported. Acid hydrolysis of these orthoesters under kinetically controlled conditions gives the corresponding hydroxy esters only. Conformationally rigid cyclic mixed orthoesters give a hydroxy ester by exclusive loss of the axial alkoxy group. A cyclic orthoester can have nine different gauche conformations. It is shown that they are hydrolyzed through only one gauche conformer. These results bring further experimental evidence that there is a stereoelectronic control in the cleavage of tetrahedral intermediates in the hydrolysis of esters.

Thermal rearrangement of functionalized 1,2-divinylcyclopropane systems. A convenient synthesis of substituted 4-cyclohepten-1-ones

1986 ◽  
Vol 64 (1) ◽  
pp. 180-187 ◽  
Author(s):  
Edward Piers ◽  
Max S. Burmeister ◽  
Hans-Ulrich Reissig
Keyword(s):  
Acid Hydrolysis ◽  
The Other ◽  
Thermal Rearrangement ◽  
Enol Ethers ◽  
Acyl Chlorides ◽  
Silyl Ethers ◽  
Convenient Synthesis ◽  
Enol Silyl Ethers ◽  
Hydrolysis Of ◽  
Subsequent Acid

Reaction of the acyl chlorides 14–21 with lithium (phenylthio)(cis-2-vinylcyclopropyl)cuprate (2) provided the ketones 22–29. Compounds 22–25, upon treatment with i-Pr2NLi-Me3SiCl, were converted cleanly into the enol silyl ethers 30–33, which gave the 1,4-cycloheptadienes 34–37 upon thermolysis (100–110 °C). Acid hydrolysis of the latter materials produced the corresponding 4-cyclohepten-1-ones 38–41. However, subjection of the cis-2-vinylcyclopropyl ketones 26–29 to i-Pr2NLi-t-BuMe2SiCl afforded, in each case, a mixture of isomeric enol ethers (26 → 42 + 44 (1:1); 27 → 43 + 45 (1:9); 28 → 56 + 58 (1:1); 29 → 57 + 59 (4:1)). Thermolysis (150–175 °C) of these mixtures, followed by acid hydrolysis of the resultant products, gave the 4-cyclohepten-1-ones 54, 55, 64, and 65, admixed with the corresponding 3-methylenecyclopentenes 52, 53, 62, and 63. On the other hand, treatment of the trans-2-vinylcyclopropyl ketones 70–74 with i-Pr2NLi–t-BuMe2SiCl provided exclusively or predominantly the enol ethers 75–79. Thermolysis (230 °C) of the latter materials and subsequent acid hydrolysis of the resultant products 80, 50, 51, 60, and 61 afforded the 4-cyclopenten-1-ones 38, 54, 55, 64, and 65.

Partial hydrolysis of acyl 1,6-anhydro-β-D-glucopyranose

1984 ◽  
Vol 49 (8) ◽  
pp. 1780-1787 ◽  
Author(s):  
Štefan Kučár ◽  
Juraj Zámocký ◽  
Juraj Zemek ◽  
Dušan Anderle ◽  
Mária Matulová
Keyword(s):  
Acid Hydrolysis ◽  
Hydrazine Hydrate ◽  
Hydrogen Chloride ◽  
Ester Group ◽  
The Other ◽  
Hydroxyl Group ◽  
Partial Hydrolysis ◽  
Substantial Influence ◽  
Hydrolysis Of ◽  
Derivatives Of

Partial hydrolysis of per-O-acetyl- and per-O-benzoyl derivatives of 1,6-anhydro-β-D-glucopyranose with methanolic hydrogen chloride and hydrazine hydrate was investigated. The acyl group at C(3) is of substantial influence on the course of hydrolysis. The esterified hydroxyl group at C(3) was found to be most stable on acid hydrolysis with methanolic hydrogen chloride when compared with that at C(2), or C(4); on the other hand, this ester group is the most labile upon hydrolysis with hydrazine hydrate. Selectivity of the respective ester groups towards hydrolysis made it possible to prepare all variations of acetyl and benzoyl derivatives of 1,6-anhydro-β-D-glucopyranose.

Measurement of β-Glucan in Mushrooms and Mycelial Products

2016 ◽  
Vol 99 (2) ◽  
pp. 364-373 ◽  
Author(s):  
Barry V McCleary ◽  
Anna Draga
Keyword(s):  
Enzymatic Hydrolysis ◽  
Glucose Oxidase ◽  
Acid Hydrolysis ◽  
Trifluoroacetic Acid ◽  
Ganoderma Lucidum ◽  
Reliable Method ◽  
The Other ◽  
Free Glucose ◽  
The Difference ◽  
Hydrolysis Of

Abstract A robust and reliable method has been developed for the measurement of β-glucan in mushroom and mycelial products. Total glucan (plus free glucose and glucose from sucrose) was measured using controlled acid hydrolysis with H2SO4 and the glucose released specifically was measured using glucose oxidase/peroxidase reagent. α-Glucan (starch/glycogen) plus free glucose and glucose from sucrose were specifically measured after hydrolysis of starch/glycogen to glucose with glucoamylase and sucrose to glucose plus fructose with invertase and the glucose specifically measured with GOPOD reagent. β-Glucan was determined by the difference. Several acid and enzyme-based methods for the hydrolysis of the β-glucan were compared, and the best option was the method using H2SO4. For most samples, similar β-glucan values were obtained with both the optimized HCl and H2SO4 procedures. However, in the case of certain samples, specifically Ganoderma lucidum and Poria cocus, the H2SO4 procedure resulted in significantly higher values. Hydrolysis with 2 N trifluoroacetic acid at 120°C was found to be much less effective than either of the other two acids evaluated. Assays based totally on enzymatic hydrolysis, in general, yielded much lower values than those obtained with the H2SO4 procedure.

scholarly journals Stopped-Flow Kinetic Study of Reduction of Ferric Maltol Complex by Ascorbate

2016 ◽  
Vol 12 (4) ◽  
pp. 4338-4341
Author(s):  
Shabana Amin ◽  
Shazia Nisar ◽  
S Arif Kazmi
Keyword(s):  
Kinetic Study ◽  
Acid Hydrolysis ◽  
Rate Constant ◽  
Free Ligand ◽  
Low Ph ◽  
Reducing Agent ◽  
The Other ◽  
Stopped Flow ◽  
Kinetic Investigation ◽  
Hydrolysis Of

Stopped-flow kinetic investigation of reduction of Fe(III)-maltol complex is reported. The rates are dependent on pH in a complex way. On one hand at low pH there is a predominance of Fe(III)(maltol)2 which is easier to reduce compared to Fe(III) (maltol)3 which is more resistant to reduction. On the other hand ascorbate is a stronger reducing agent at higher pH. The rates are also found to be inversely dependent on the concentration of free ligand. These observations are explained by the following rate law:Rate = ((k0 +k1[H+])k2 [Asc-]/ (k-1[HMal] + k2[Asc-])) + k3 [Asc-] ) [FeIII(Mal)3] Here k1 is the rate constant for acid hydrolysis of the Fe(maltol)3 complex to Fe(maltol)2 complex and is directly controlled by H+, k0 is the rate constant for hydrolysis of the Fe(maltol)3 complex to Fe(maltol)2 complex and is an intrinsic process, k-1 is the rate constant of reformation of the tris complex by reaction of the bis complex and the free ligand, k2 is the rate constant for reduction of the bis complex by ascorbate and k3 is the rate constant for the reduction of the tris complex by ascorbate.

ChemInform Abstract: THE HYDROLYSIS OF CYCLIC ORTHOESTERS. STEREOELECTRONIC CONTROL IN THE CLEAVAGE OF HEMIORTHOESTER TETRAHEDRAL INTERMEDIATES

1975 ◽  
Vol 6 (38) ◽  
pp. no-no
Author(s):  
PIERRE DESLONGCHAMPS ◽  
ROBERT CHENEVERT ◽  
ROLAND J. TAILLEFER ◽  
CLAUDE MOREAU ◽  
JOHN K. SAUNDERS
Keyword(s):  
Stereoelectronic Control ◽  
Hydrolysis Of ◽  
Tetrahedral Intermediates

FORMATION OF CYCLIC O-2′-HYDROXYETHYLIDENE ACETALS FROM POLYALCOHOLS OF 4-O-LINKED POLYSACCHARIDES

1965 ◽  
Vol 43 (11) ◽  
pp. 2978-2984 ◽  
Author(s):  
P. A. J. Gorin ◽  
J. F. T. Spencer
Keyword(s):  
Acid Hydrolysis ◽  
Sodium Periodate ◽  
Rhodotorula Glutinis ◽  
Membered Ring ◽  
The Other ◽  
Complete Oxidation ◽  
Partial Acid Hydrolysis ◽  
Ring Form ◽  
Hydrolysis Of ◽  
By Products

Partial acid hydrolysis of polyalcohols derived from some 1,4-O-linked polysaccharides gave cyclic O-2′-hydroxyethylidene derivatives as by-products in yields of 6–18%. Polysaccharides containing β-links such as Rhodotorula glutinis mannan and cellulose gave rise to 6-membered ring acetals with lesser amounts of the 5-membered ring form. On the other hand, two α-linked polyalcohols, obtained following partial and complete oxidation of starch with sodium periodate, were converted to 5-membered O-2′-hydroxyethylidene acetals.

Sign in / Sign up

Export Citation Format

Share Document