Some properties of the ecgonines and their esters. VI. The calcium and lead salts of l-ecgonine, the conversion of l-ecgonine into l-benzoylecgonine and its esterification with methyl alcohol and benzoic anhydride or benzoyl chloride

2010 ◽  
Vol 66 (9) ◽  
pp. 544-548 ◽  
Author(s):  
A. W. K. de Jong

To understand deeply the process of acylation of natural polyphenol gossypol, its stepwise benzoylation was performed using benzoyl chloride and benzoic anhydride as acylating agents in the presence of pyridine-N-oxides. The influence of the composition of a reaction mixture on the benzoylation process and reaction products was analyzed by the method of reversed-phase high-performance liquid chromatography. It was established that benzoylation of gossypol leads to the tautomeric transition of the respective fragment from aldehyde to lactol tautomeric form. This transition is most likely due to the breaking of the hydrogen bond C(7)–OHO=C(11) in combination with the displacement of the aldehyde group by the benzoyl fragment from the naphthyl ring plane (in the case of benzoylation of C(7)–OH group); benzoylation of C(6)–OH group is accompanied by the breaking of the hydrogen bond C(6)–OHO–C(7). These changes of configuration significantly facilitate the proton transfer from the C(1)–OH group to oxygen at C(11) followed by the formation of the lactol cycle. The use of benzoyl chloride as an acylating agent in combination with triethylamine and 4-methoxypyridine-N-oxide allows benzoylating gossypol quickly. However, the variety of formed benzoates is quite large because of the similar reactivity of different hydroxyl groups. In the case of benzoic anhydride, the number of isomeric gossypol benzoates remains quite high. Much more esters with higher retention time are accumulated due to a higher degree of benzoylation.


2000 ◽  
Vol 65 (5) ◽  
pp. 644-650 ◽  
Author(s):  
Eva Veverková ◽  
Battsengel Gotov ◽  
Róbert Mitterpach ◽  
Štefan Toma

Benzoylations of several benzene, naphthalene and thiophene derivatives with benzoyl chloride or benzoic anhydride, catalyzed with EPZG® catalyst and in the absence of solvents were studied under microwave irradiation (MWI). Reasonable to good yields of products were achieved in short times.


1958 ◽  
Vol 11 (3) ◽  
pp. 336
Author(s):  
M Karelsky ◽  
KH Pausacker

When benzoyl peroxide was heated with phosphorus trichloride (1 and 2 mol) in benzene, or chlorobenzene solution, carbon dioxide, benzoyl chloride, and phenyl phosphonyl chloride were the major products. Diphenyl phosphonyl chloride was also formed in small yield, p-Chlorobenzoyl peroxide reacted with phosphorus trichloride, in benzene solution, yielding carbon dioxide, p-chlorobenzoyl chloride, p-chlorophenyl phosphonyl chloride, and p-chlorobenzoic anhydride. The reaction of benzoyl peroxide with phosphorus trichloride alone yielded benzoyl chloride only. Phosphorus oxychloride, on the other hand, does not enter into the reaction. Thionyl chloride, in benzene, gave a complex mixture consisting of carbon dioxide, chlorobenzene, benzoyl chloride, phenyl benzoate, benzene sulphonyl chloride, diphenyl, and benzoic anhydride. Sulphuryl chloride in benzene yielded a mixture of carbon dioxide, chlorobenzene, benzoic acid, phenyl benzoate, and diphenyl. The mechanisms of these various reactions are discussed.


Author(s):  
J.R. Walton

In electron microscopy, lead is the metal most widely used for enhancing specimen contrast. Lead citrate requires a pH of 12 to stain thin sections of epoxy-embedded material rapidly and intensively. However, this high alkalinity tends to leach out enzyme reaction products, making lead citrate unsuitable for many cytochemical studies. Substitution of the chelator aspartate for citrate allows staining to be carried out at pH 6 or 7 without apparent effect on cytochemical products. Moreover, due to the low, controlled level of free lead ions, contamination-free staining can be carried out en bloc, prior to dehydration and embedding. En bloc use of lead aspartate permits the grid-staining step to be bypassed, allowing samples to be examined immediately after thin-sectioning.Procedures. To prevent precipitation of lead salts, double- or glass-distilled H20 used in the stain and rinses should be boiled to drive off carbon dioxide and glassware should be carefully rinsed to remove any persisting traces of calcium ion.


Author(s):  
Julio H. Garcia ◽  
Janice P. Van Zandt

Repeated administration of methyl alcohol to Rhesus monkeys (Maccaca mulata) by intragastric tube resulted in ultrastructural abnormalities of hepatocytes, which persisted in one animal twelve weeks after discontinuation of the methyl alcohol regime. With dosages ranging between 3.0 to 6.0 gms. of methanol per kg. of body weight, the serum levels attained within a few hours averaged approximately 475 mg. per cent.


Author(s):  
R. L. Lyles ◽  
S. J. Rothman ◽  
W. Jäger

Standard techniques of electropolishing silver and silver alloys for electron microscopy in most instances have relied on various CN recipes. These methods have been characteristically unsatisfactory due to difficulties in obtaining large electron transparent areas, reproducible results, adequate solution lifetimes, and contamination free sample surfaces. In addition, there are the inherent health hazards associated with the use of CN solutions. Various attempts to develop noncyanic methods of electropolishing specimens for electron microscopy have not been successful in that the specimen quality problems encountered with the CN solutions have also existed in the previously proposed non-cyanic methods.The technique we describe allows us to jet polish high quality silver and silver alloy microscope specimens with consistant reproducibility and without the use of CN salts.The solution is similar to that suggested by Myschoyaev et al. It consists, in order of mixing, 115ml glacial actic acid (CH3CO2H, specific wt 1.04 g/ml), 43ml sulphuric acid (H2SO4, specific wt. g/ml), 350 ml anhydrous methyl alcohol, and 77 g thiourea (NH2CSNH2).


Author(s):  
Jenan Mohammed Ubaid ◽  
Abeer Fauzi Al-Rubaye ◽  
Imad Hadi Hameed

Methanolic extract of bioactive compounds of Trogoderma granarium was assayed. GC-MS analysis of Trogoderma granarium revealed the existence of the Pentanoic acid , 1,1-dimethylpropyl ester , (1H)-Pyrimidinone , 5-chloro-4,6- diphenyl, Cyclobutanemethanol , α-methyl- , Nitro-2-methyl-1,3-propanediol , Hydroxylamine ,O-(2-methylpropyl)- , Uridine , 2',3'-O-(phenylmethylene)- ,Acetic acid ,2-benzoylthio-,2-oxo-2-phenylethyl ester , methylpropyl)- , Uridine , 2',3'-O-(phenylmethylene)- , 5'-(4-methylbenzenesulfo , Indolinol , 1-benzoyl-, Benzeneethanol , β-methyl-,(s)- , Acetic acid ,2-benzoylthio-,2-oxo-2-phenylethyl ester , Phenacyl thiocyanate , Deoxy-L-ribose-2,5-dibenzoate , Methenamine , Alanine , N-methyl-n-propargyloxycarbonyl-, decyl ester , Benzoyl chloride , Thiophene-2-ol , benzoate , Ethanone , -(5- nitrotetrazol-2-yl)-1-phenyl- , 2,5-Dimethylhexane-2,5-dihydroperoxide , Benzamide , N-(3-benzylthio-1,2,4-thiadiazol- 5-yl)- , Methyl p-(2-phenyl-1-benzimidazolyl)benzoate , Methyl-2-phenoxyethylamine , Pentaborane(11) , cis-Methoxy- 5-trans-methyl-1R-cyclohexanol , Nitro-1-phenyl-3-(tetrahydropyran-2-yloxy)propan-1-one , cis-Methoxy-5-transmethyl-1R-cyclohexanol. Trogoderma granarium produce many important secondary metabolites with high biological activities.


1966 ◽  
Vol 31 (9) ◽  
pp. 3702-3709
Author(s):  
Z. Spurný ◽  
F. Spurný
Keyword(s):  

The influence of small amounts of dissolved foreign substances on the growth of crystals from saturated solutions has been the subject of much investigation. Usually the added substances have been electrolytes. Dyestuffs have not been neglected, but with some few exceptions comparatively little attention has been given to the effect of non-ionized water-soluble electrolytes such as gelatine or dextrine. As a rule, the presence of the foreign substances is found to cause the crystals to assume a different habit. Whenever this occurs the absorption must have occurred on certain crystal-faces in preference to others, but, although the added material is active by virtue of its close attachment to such faces, it is rarely found to be incorporated into the solid to any great extent. The growing crystals appear to reject the impurity—thrusting it outwards as the growth advances. The action of water-soluble colloids on the halides and certain other salts of lead is exceptional in several ways. Although when such colloids are present in small concentrations one can generally observe a modification of habit, at higher concentrations there may be little selective adsorption, and the result may be a rounded crystal on which no plane faces at all can be distinguished, as if the forces by which atoms are attracted to the structure had been equalized in every direction.


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