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O- halides

In the following subsections, only cationic and anionic species containing at least one M-H or M-G bond are considered. Consequently, compounds containing exclusively M-X bonds (X = N, O, halide) are not discussed. (Interested readers are referred to Refs 178 and 179.)... [Pg.297]

The above-mentioned synthetic schemes for synthesis of hexaazacyclotetradecines can be successfully realised, if the reactions are controlled by the presence of suitable metal ions acting as templates. Thus, o-halide-o -aminoazo compounds of the L93 type (Eq. 2.56 like LlOl, L103, L105 below) do not self-condense to give macrocycles in the absence of metal salts [132, 133]. [Pg.66]

Table A2.3.2 Halide-water, alkali metal cation-water and water-water potential parameters (SPC/E model). In the SPC/E model for water, the charges on H are at 1.000 A from the Lennard-Jones centre at O. The negative charge is at the O site and the HOH angle is 109.47°. Table A2.3.2 Halide-water, alkali metal cation-water and water-water potential parameters (SPC/E model). In the SPC/E model for water, the charges on H are at 1.000 A from the Lennard-Jones centre at O. The negative charge is at the O site and the HOH angle is 109.47°.
Acyl halides, both aliphatic and aromatic, react with the sodium derivative, but the product depends largely on the solvent used. Thus acetyl chloride reacts with the sodium derivative (E) suspended in ether to give mainly the C-derivative (t) and in pyridine solution to give chiefly the O-derivative (2). These isomeric compounds can be readily distinguished, because the C-derivative (1) can still by enolisation act as a weak acid and is therefore... [Pg.270]

The following give abnormal results when treated with chlorosulphonio acid alone, preferably at 50° for 30-60 minutes —fluobenzene (4 4 -difluorodiplienyl-sulphone, m.p. 98°) j iodobenzene (4 4 -di-iododiphenylsulplione, m.p. 202°) o-diclilorobenzene (3 4 3. -4 -tetrachlorodiphenylsulphone, m.p. 176°) and o-dibromobenzene (3 4 3 4 -tetrabromodiphenylsulphone, m.p. 176-177°). The resulting sulphones may be crystallised from glacial acetic acid, benzene or alcohol, and are satisfactory for identification of the original aryl halide. In some cases sulphones accompany the sulphonyl chloride they are readily separated from the final sulphonamide by their insolubility in cold 6N sodium hydroxide solution the sulphonamides dissolve readily and are reprecipitated by 6iV hydrochloric acid. [Pg.543]

Alkyl halides and sulfonates are the most frequently used alkylating acceptor synthons. The carbonyl group is used as the classical a -synthon. O-Silylated hemithioacetals (T.H. Chan, 1976) and fomic acid orthoesters are examples for less common a -synthons. In most synthetic reactions carbon atoms with a partial positive charge (= positively polarized carbon) are involved. More reactive, "free carbocations as occurring in Friedel-Crafts type alkylations and acylations are of comparably limited synthetic value, because they tend to react non-selectively. [Pg.15]

Several Pd(0) complexes are effective catalysts of a variety of reactions, and these catalytic reactions are particularly useful because they are catalytic without adding other oxidants and proceed with catalytic amounts of expensive Pd compounds. These reactions are treated in this chapter. Among many substrates used for the catalytic reactions, organic halides and allylic esters are two of the most widely used, and they undergo facile oxidative additions to Pd(0) to form complexes which have o-Pd—C bonds. These intermediate complexes undergo several different transformations. Regeneration of Pd(0) species in the final step makes the reaction catalytic. These reactions of organic halides except allylic halides are treated in Section 1 and the reactions of various allylic compounds are surveyed in Section 2. Catalytic reactions of dienes, alkynes. and alkenes are treated in other sections. These reactions offer unique methods for carbon-carbon bond formation, which are impossible by other means. [Pg.125]

In the reaction of Q,/3-unsaturated ketones and esters, sometimes simple Michael-type addition (insertion and hydrogenolysis, or hydroarylation, and hydroalkenylation) of alkenes is observed[53,54]. For example, a simple addition product 56 to methyl vinyl ketone was obtained by the reaction of the heteroaromatic iodide 55[S5]. The corresponding bromide affords the usual insertion-elimination product. Saturated ketones are obtained cleanly by hydroarylation of o,/3l-unsaturated ketones with aryl halides in the presence of sodium formate, which hydrogenolyses the R—Pd—I intermediate to R— Pd—H[56]. Intramolecular hydroarylation is a useful reaction. The diiodide 57 reacts smoothly with sodium formate to give a model compound for the afla-toxin 58. (see Section 1.1.6)[57]. Use of triethylammonium formate and BU4NCI gives better results. [Pg.136]

Reactions of Organic Halides and Pseudo-Halides. COjMe Pd2(dba)], (o-toOaP... [Pg.139]

Aryl or alkenyl halides attack the central carbon of the allene system in the 2,3-butadien-l-ol 120 to form the 7r-allyl intermediate 121, which undergoes elimination reaction to afford the o,/3-unsaturated ketone 122 or aldehyde. The reaction proceeds smoothly in DMSO using dppe as a ligandflOl]. [Pg.145]

In the reaction of aryl and alkenyl halides with 1,3-pentadiene (248), amine and alcohol capture the 7r-allylpalladium intermediate to form 249. In the reactions of o-iodoaniline (250) and o-iodobenzyl alcohol (253) with 1,3-dienes, the amine and benzyl alcohol capture the Tr-allylpalladium intermediates 251 and 254 to give 252 and 255[173-175]. The reaction of o-iodoaniline (250) with 1,4-pen tadiene (256) affords the cyclized product 260 via arylpalladiuni formation, addition to the diene 256 to form 257. palladium migration (elimination of Pd—H and readdition to give 258) to form the Tr-allylpalladium 259, and intramolecular displacement of Tr-allylpalladium with the amine to form 260[176], o-Iodophenol reacts similarly. [Pg.164]

The formation of disubstituted alkynes by coupling of terminal alkynes, followed by intramolecular attack of an alcohol or amine, is used for the preparation of benzofurans and indoles. The benzo[il)]furan 356 can be prepared easily by the reaction of o-iodophenol with a terminal alkyne[262]. The 2-substituted indole 358 is prepared by the coupling of 2-ethynylaniline (357) with aryl and alkenyl halides or triflates, followed by Pd(ll)-catalyzed cycliza-tion[263]. [Pg.178]

Pyrrole derivatives are prepared by the coupling and annulation of o-iodoa-nilines with internal alkynes[291]. The 4-amino-5-iodopyrimidine 428 reacts with the TMS-substituted propargyl alcohol 429 to form the heterocondensed pyrrole 430, and the TMS is removed[292]. Similarly, the tryptophane 434 is obtained by the reaction of o-iodoaniline (431) with the internal alkyne 432 and deprotection of the coupled product 433(293]. As an alternative method, the 2,3-disubstituted indole 436 is obtained directly by the coupling of the o-alky-nyltrifluoroacetanilide 435 with aryl and alkenyl halides or triflates(294]. [Pg.186]

The o-keto ester 513 is formed from a bulky secondary alcohol using tricy-clohexylphosphine or triarylphosphine, but the selectivity is low[367-369]. Alkenyl bromides are less reactive than aryl halides for double carbonyla-tion[367], a-Keto amides are obtained from aryl and alkenyl bromides, but a-keto esters are not obtained by their carbonylation in alcohol[370]. A mechanism for the double carbonylation was proposed[371,372],... [Pg.199]

Carbonylation of halides in the presence of terminal and internal alkynes produces a variety of products. The substituted indenone 564 is formed by the reaction of o-diiodobenzene. alkyne, and CO in the presence of Zn[414]. [Pg.205]


See other pages where O- halides is mentioned: [Pg.123]    [Pg.382]    [Pg.995]    [Pg.66]    [Pg.223]    [Pg.29]    [Pg.123]    [Pg.382]    [Pg.995]    [Pg.66]    [Pg.223]    [Pg.29]    [Pg.82]    [Pg.166]    [Pg.221]    [Pg.235]    [Pg.265]    [Pg.280]    [Pg.359]    [Pg.399]    [Pg.409]    [Pg.413]    [Pg.425]    [Pg.434]    [Pg.2219]    [Pg.24]    [Pg.131]    [Pg.418]    [Pg.20]    [Pg.24]    [Pg.48]    [Pg.160]    [Pg.6]    [Pg.86]    [Pg.130]    [Pg.147]    [Pg.187]    [Pg.215]   


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