Maltose methylation

The problem of the acid-catalyzed hydrolysis of the carbohydrate orthoesters was brought nearer to the final solution by Pacsu s experiments on the hydrolysis of maltose methyl 1,2-orthoacetate. Since two adjacent hydroxyl groups on the same side of the plane are necessary for the formation of orthoester derivatives, the maltose methyl orthoacetate must have an -configuration. Hydrolytic experiments with very dilute hydrochloric acid confirmed this. Two consecutive reactions took place at a pH of 4. In the first reaction, the original specific rotation, Co ]d - -103.7 in pure water, increased to -1-134.6° within two minutes. The latter figure corresponds to the specific rotation of a-maltose 2-acetate. The second reaction k = 0.0095) corresponded to the downward muta-rotation of a-maltose 2-acetate. When the hydrogen-ion concentration,... 

Hydrogenated lanolin Hydrogenated lecithin Hydrolyzed almond protein Hydrolyzed collagen Hydrolyzed elastin Hydrolyzed oats Hydrolyzed pea protein Hydrolyzed protein Hydrolyzed rice protein Hydroxypropyltrimonium hydrolyzed collagen Isohexyl neopentanoate Isononyl isononanoate Isopentyidiol Isopropyl lanolate Isostearyl isononanoate Lactoyl methylsilanol elastinate Lanolin alcohol Laureth-50 Lauryl methyl gluceth-10 hydroxypropyidimonium chloride Lauryl PCA Linoleamidopropyl PG-dimonium chloride phosphate Macadamia ternifolia seed oil Maleated soybean oil Maltose Methyl gluceth-10... 

Hehre and coworkers showed that beta amylase from sweet potatoes, an inverting, a-specific exo-(l 4)-glucanase, catalyzes the hydrolysis of jS-maltosyl fluoride with complex kinetics which indicated the participation of two substrate molecules in the release of fluoride ion. Furthermore, the reaction was strongly accelerated by the addition of methyl ) -maltoside. Hydrolysis of a-maltosyl fluoride, on the other hand, obeyed Michaelis-Menten kinetics. The main product with both a- and yj-maltosyl fluoride was )S-maltose. The results with )3-maltosyl fluoride were interpreted by the assumption of a glycosylation reaction preceding hydrolysis by which a malto-tetraoside is formed by the replacement of fluoride ion by a second substrate molecule or added methyl -maltoside (see Scheme 5). 

It is puzzling that the chlorine and other halogen substituents are not known to enhance the sweetness of other sugars, such as methyl -d-glycopyranosides, a,a-trehalose, maltose, or lactose. On the contrary, all of the deoxyhalo sugar derivatives tasted were extremely bitter. The high sweetness of the deoxyhalosucroses is clearly inexplicable in terms of either... 

One notices that the data from the oxidation of melezitose by per-iodic acid confirm the pyranose structure of the D-glucose unit in turanose, and therefore also in the case of maltose, in agreement with the original assignments for both of these disaccharides from methylation studies. 

Addition of an aqueous solution of PEG to a saturated aqueous solution of a-CD at room temperature did not lead to complex formation unless the average molecular weight of PEG exceeded 200 [46]. Moreover, carbohydrate polymers such as dextran and pullulan failed to precipitate complexes with PEG, and the same was true for amylose, glucose, methyl glucose, maltose, maltotriose, cyclodextrin derivatives, such as glucosyl-a-CD and maltosyl-a-CD, and water-soluble polymers of a-CD crosslinked by epichlorohydrin. These facts suggested to Harada et al. the direction for further research. 

The rate of oxidation of ethylene glycol was found268-269 to attain a broad maximum between pH 2.5 and 6. In a very complete study of the effect of pH on the periodate oxidation of carbohydrates, Neumiiller and Vasseur260 showed that the oxidation of maltose, melibiose, methyl a-D-... 

A remarkable inertness towards acylation is shown by the secondary hydroxyl group on C-3 in maltose, lactose, and their methyl j8-glycosides. Benzoylation of maltose with 10 molar equivalents of the acid chloride in pyridine gave122 the octabenzoate and the l,2,6,2, 3, 4, 6 -hepta-0-benzoyl derivative in the ratio of 5 6, and treatment of /3-maltose monohydrate with 8.8 molar equivalents of acetyl chloride in pyridine-toluene at 0° gave123 the 1,2,6,2, 3, 4, 6 -heptaacetate and the octaacetate in the ratio of 27 10. Under similar conditions of benzoylation, cellobiose was converted into its oc-... 

The two primary hydroxyl groups in maltose and its derivatives show a large difference in reactivity. On selective tritylation, /3-maltose,238 benzyl /3-maltoside,239 and methyl 3-0-(methylsulfonyl)-/3-maltoside127 all gave mainly 6 -0-trityl compounds. Tritylation of cyclohexaamylose130 and amylose132,240 yielded the expected 6-0-trityl derivatives. 

This particular trimethylglucose is unique in that it was separated in crystalline form from the hydrolyzates of the methyl ethers of several naturally-occurring glucose polymers almost two decades before it was synthesized from glucose. These natural sources, which still furnish the most convenient routes for the preparation of 2,3,6-trimethyl-D-glucose, include maltose,124-128 cellobiose,127,128 lactose,122-181 starch,71,182 glycogen,188,184 cellulose,185-187 and lichenin. 188,189 The literature pub-... 

Tetramethyl-D-glucose is frequently isolated after hydrolysis of the methyl ethers of naturally-occurring glucose polymers (e.g. maltose,... 

Sucrose Maltose Lactose Methyl a-glucoside0 Glucosyl resorcinol ... 

The third group is that of compounds which may potentially be transported by the PTS and inhibit cAMP production. Cellulase synthesis is initiated after these compounds are consumed for cell growth. This group includes D-glucose, D-fructose, maltose, mannitol, glycerol, sorbitol, and -methyl glucoside. The presence of these compounds in Solka Floe fermentations, enhanced enzyme yields (132 to 254%) but the time required to complete cellulase synthesis took longer (106 to 148%) than the control. 

P. L. Durette, L. Hough, and A. C. Richardson, The chemistry of maltose. Part 1. The reaction of methyl a-maltoside with sulphuryl chloride, Carbohydr. Res., 31 (1973) 114—119. 

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