Deoxy compounds

Numerous derivati es of morphine have been devised for use in medicine including acyl derivatives, of which diacetylmorphine (C], Hj,03N, Ac2, m.p. 173°, [a]J°° — 166° (MeOH) B. HCl. 2H2O, m.p. 231-2°) is the best known, alkyl and other ethers such as the ethyl-and benzyl-morphines, dihydro- and dihydroketo-compounds such as dihydromorphine, dihydrocodeine, dihydromorphinone, dihydrocodeinone and hydroxydihydrocodcinone, and the deoxy-compounds, e.g., dihydro-deoxymorphine and methyldihydrodeoxymorphine. 

The systematic name consists of the prefix deoxy- , preceded by the locant and followed by the stem name with such configurational prefixes as necessary to describe the configuration(s) at the asymmetric centres present in the deoxy compound. Configurational prefixes are cited in order commencing at the end farthest from C-l. Deoxy is regarded as a detachable prefix, i.e. it is placed in alphabetical order with any substituent prefixes. 

As shown in Scheme 16, the A-oxidations of 112 can yield 4-oxides 113 and/or 5-oxides 114 can be formed. In some special cases (e.g., if R3 = Br), formation of exclusively 114 was experienced. The reverse transformation was also carried out reduction of the A-oxides (113, 114) by triethylphosphite or Zn/acetic acid yielded the deoxy compound 112. 

Photolysis of deoxyiodo sugars is an effective method for forming the corresponding deoxy compounds (see Scheme 33) however, both... 

Tables V-LVII detail H and F shift and coupling information, and Tables LVIII to LXXI incorporate the C-n.m.r. data. The data within this compilation are arranged according to the following outline hexoses prior to pentoses, followed by anhydro sugars, sugar acids and lactones, amino sugars (and their synthetic, A -containing precursors), mono-, di-, and tri-deoxy sugars, branched derivatives, ketoses, polyfluorinated monosaccharides, and, finally, difluorinated amino sugars. Within this compilation, and even within each table, pyranoid derivatives are listed prior to their furanoid counterparts, hexoses prior to pentoses, functionalized prior to deoxy compounds the arrangement within each sub-table is made alphabetically.

A third strategy was applied to the synthesis of a neighboring family of amphiphilic carbohydrates. The starting material was 5,6-anhydro-l,2-0-iso-propylidene-a-D-glucofuranose, easily obtained in a few steps from o-glucose. The latter was reacted with M-benzyl-n-hexadecylamine to afford regioselec-tively the 6-alkylamino-6-deoxy compound 35 [ 119]. 

Danilov and coworkers79 treated l,4 3,5-dianhydro-DL-xylitol with a number of primary and secondary amines. The 3,5-anhydro ring was opened, to give the corresponding 5-amino-5-deoxy compounds. 

The classic ionic methods for the removal of an unwanted hydroxyl group are summarized in detail in the book by Larock [6]. One method involves—for primary and unhindered secondary alcohols—the synthesis of the corresponding mesylates or tosylates. These compounds are prepared readily and then transformed into the corresponding deoxy compounds by reduction [7], Alternatively, introduction of a thiolate or halogen by a nucleophilic reaction can also be used. These compounds can then be readily desulfurized or dehalogenated (Scheme 1). Tertiary alcohols present no problem either, because a... 

Radical chain chemistry is often employed for the transformation of an alcohol to the corresponding deoxy derivative. The secondary alcohol 1 is first converted into a suitable thiocarbonyl derivative. The first derivatives investigated were thioxobenzoates 2, xan-thates 3, and thiocarbonylimidazolides 4 (Scheme 2). On reduction with tributyltin hydride, these derivatives afforded a good yield of the appropriate deoxy compounds [8-10]. 

The crude deoxy compound (before chromatography) can be used for deprotection with TBAF and THF. 

The mass spectrum of the 2-deoxy compound (20) is characterized by the absence of the C and D series, by a diminished intensity of the J peak (m/e 75), and by an increasing intensity of the E series. The formation of the fragments of the latter series is sterically favored because of the absence of substituents at C-2. 

Oxygen suppresses the formation of deoxy compounds, and enhances the formation of fragmentation products. As expected from the results obtained with neutral sugars (see Sect. Ill,2b), the most prominent fragment-product here is 2-acetamido-2-deoxy-L-fhreo-tetro-dialdose.37... 

HI hi acetic acid allows the reduction of jS-peracetates of the higher sugar N-acetylneuraminic acid to the corresponding anomeric deoxy compounds.277 At room temperature this method gave exclusively the a-anomer, whereas at —20 °C a 4 1 a [i ratio resulted. This may be explained by thermodynamic and kinetic protonation of ester enolates generated in situ from anomeric iodide in a manner reminiscent of previous reductions of 2-iodo sugar lactones.278... 

Nitrobenzene-p-sulphonyI)neopine has been converted into the 6/3-chloro- and 6j0-bromo-6-deoxy-compounds by heating with lithium chloride and bromide,154 and the 6-O-methanesulphonyl analogue gives the same products together with the A6-8-deoxy-compound, which is the sole product when the ester is heated with sodium iodide.155 2-Nitromorphine and 2-nitrocodeine have been reduced to the 2-amino-compounds in 60% and 81% yield respectively.156... 

Details of the Diels-Alder addition of aromatic nitroso-compounds to thebaine to give adducts (117), the ring-opening of these to 14-hydroxylamino-compounds (118 R = OH), the reduction of these to 14-arylamino-compounds (118 R = H), and cyclization to (119) have been published.162 Dihydro-thebaine-< 4-phenyl ether (120 R = OPh) has been transformed into the benzylisoquinoline (121) by potassamide in liquid ammonia, but the same transformation could not be effected with the free phenol (120 R = H) or with the deoxy-compound (120 R = H).163... 

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