Ring oxygen replacement

Carbon, ring oxygen replacement by, 141-143 2-Carboxy-5-(2-hydroxymethyl)-4-methylthiazole, synthesis and transformations, 284-286 Carrageenans, 366-368,418-419 Cellotetraose hemihydrate, 331 Cellulose, 326, 329-332 alternate unit cells, 329-330 derivatives, 332... 

Nitrogen, ring oxygen replacement by, 140-141 Nomenclature, 44-177, see also... 

Rea.ctlons, Butyrolactone undergoes the reactions typical of y-lactones. Particularly characteristic are ring openings and reactions in which ring oxygen is replaced by another heteroatom. There is also marked reactivity of the hydrogen atoms alpha to the carbonyl group. 

Butyrolactone and hydrogen sulfide heated over an alumina catalyst result in replacement of ring oxygen by sulfur (151). 

Fig. 3. Spectral sensitizing dyes for silver haUdes. (a) Blue sensitizers (400—500 nm) are designated BN (b) green sensitizers (500—600 nm) are designated GN (the ring oxygen may be replaced by N(R)) (c) red sensitizers (600—700 nm) are designated RN (d) MN designates a merocyanine dye and (e),...

A point to be emphasized about glycoside fonnation is that, despite the presence of a number of other hydroxyl groups in the carbohydrate, only the anomeric hydroxyl group is replaced. This is because a carbocation at the anomeric position is stabilized by the ring oxygen and is the only one capable of being fomned under the reaction conditions. 

Carb-34. Replacement of ring oxygen by other elements... 

Replacement of the ring oxygen atom of the cyclic form of an aldose or ketose by sulfur is indicated in the same way, the number of the non-anomeric adjacent carbon atom of the ring being used as locant. 

The (non-detachable) prefix carba- signifies replacement of a heteroatom by carbon in general natural product nomenclature [26], and may be applied to replacement of the hemiacetal ring oxygen in carbohydrates if there is a desire to stress homomorphic relationships. If the original heteroatom is unnumbered, the new carbon atom is assigned the locant of the non-anomeric adjacent skeletal atom, with suffix a . 

As it has been revealed that replacement of the ring-oxygen atom in a pyranoid sugar by a CH2 group is not detrimental to its sweetness, 6a-carba- -D-fructopyranose may have the same intense sweetness as D-fruc-tose. To substantiate this prediction, the following two reaction routes have been successfully developed for 6a-carba-y -DL-fructopyranose, as well as for the enantiomers. 

As with five-membered heterocycles, phosphorus pentasulfide may replace a ring oxygen atom by sulfur, or it may effect replacement in an acyclic precursor and then bring about cyclization. Thus isochroman-l-one (99) is converted into thioisochroman-l-thione (100) under the same conditions a 3-arylisocoumarin( 101) produces a 3-ary 1-1-thioisocoumarin (102) only, with no replacement of the ring oxygen atom.122 A typical example of thiation, followed by cyclization, is the formation of 2-alkyl- or 2-aryl-3,l-benzo-thiazine-4-thiones (103) from /V-acylanthranilic acid esters (104) by treatment with phosphorus pentasulfide in boiling xylene.122... 

Other class of polyhydroxylated derivatives acting as sugar mimics consists of carbasugars i.e. sugars in which the ring-oxygen atom is replaced by the carbon atom. Their synthesis can be initiated either from achiral (or racemic) derivatives (this approach will not be dealt with) or more conveniently from simple sugars (chirons). Syntheses of these important compounds were comprehensively reviewed recently.4... 

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