Iodides, from alcohols, methyl

Indole, sodium salt, preparation of, 54, 60 Indole, 1-benzyl, 54, 50, 58 Indoles, iV-alkyl-, 54, 58, 60 Iodides, from alcohols, methyl iodide, and triphenyl phosphite, 51, 47 ... 

N-Methyl-N,N -dicyclohexylcarbodiimidium iodide Iodides from alcohols Inversion of configuration... 

Ammodendrine, C jH oONj, HjO (No. 1, table, p. 116). The base has m.p. 73 °, becomes anhydrous at 70-80°, and then melts at 50-60°, Wd i 0°. The salts are amorphous and deliquescent except the hydriodide B. HI, which forms a crystalline precipitate, m.p. 218-20°, from alcohol, and the perchlorate, m.p. 199-200°. An amorphous A-benzoyl derivative was obtained. With methyl iodide ammodendrine behaves as a secondary base, yielding first A-methylammodendrine hydriodide (a crystalline precipitate, m.p. 183-5°, from a mixture of alcohol and acetone), and at the second stage iV-methylammodendrine methiodide, m.p. 163-5°. On hydrogenation ammodendrine furnishes a dihydro-base, which is hydrolysed into acetic acid and 2 3 -dipiperidyl, C oHjoNj, and must be dZ-A-acetyl-3-a-piperidylpiperidine. Ammodendrine should therefore be acetyltetrahydroanabasine and is of biological interest as the first recorded occurrence of this type of alkaloid in the Leguminoss. ... 

Worenine. This alkaloid, also obtained by Kitasato from Coptis japonica was isolated as the tetrahydro-base, C,oHjg04N, which crystallises from alcohol in colourless prisms, m.p. 212-3°, and is oxidised by iodine in alcohol to worenine iodide, yellow crystals from which worenine chloride, thin orange-yellow prisms, m.p. 295° (dec.), can be obtained. Tetrahydro-worenine behaves as a tertiary base, contains methylenedioxy- but no methoxyl groups, and its absorption spectrum closely resembles that of tetrahydrocoptisine from which it differs in empirical composition by. CHj. Worenine is, therefore, represented by (XXX), the alternative position (a) for the methyl group being untenable, since a-methyltetra-hydrocoptisine obtained by Freund s method is not identical with... 

The required xanthates 1 can be prepared from alcohols 5 by reaction with carbon disulfide in the presence of sodium hydroxide and subsequent alkylation of the intermediate sodium xanthate 6. Often methyl iodide is used as the alkylating agent ... 

Alkyl esters are efficiently dealkylated to trimethylsilyl esters with high concentrations of iodotrimethylsilane either in chloroform or sulfolane solutions at 25-80° or without solvent at 100-110°.Hydrolysis of the trimethylsilyl esters serves to release the carboxylic acid. Amines may be recovered from O-methyl, O-ethyl, and O-benzyl carbamates after reaction with iodotrimethylsilane in chloroform or sulfolane at 50—60° and subsequent methanolysis. The conversion of dimethyl, diethyl, and ethylene acetals and ketals to the parent aldehydes and ketones under aprotic conditions has been accomplished with this reagent. The reactions of alcohols (or the corresponding trimethylsilyl ethers) and aldehydes with iodotrimethylsilane give alkyl iodides and a-iodosilyl ethers,respectively. lodomethyl methyl ether is obtained from cleavage of dimethoxymethane with iodotrimethylsilane. 

The use of iodotrimethylsilane for this purpose provides an effective alternative to known methods. Thus the reaction of primary and secondary methyl ethers with iodotrimethylsilane in chloroform or acetonitrile at 25—60° for 2—64 hours affords the corresponding trimethylsilyl ethers in high yield. The alcohols may be liberated from the trimethylsilyl ethers by methanolysis. The mechanism of the ether cleavage is presumed to involve initial formation of a trimethylsilyl oxonium ion which is converted to the silyl ether by nucleophilic attack of iodide at the methyl group. tert-Butyl, trityl, and benzyl ethers of primary and secondary alcohols are rapidly converted to trimethylsilyl ethers by the action of iodotrimethylsilane, probably via heterolysis of silyl oxonium ion intermediates. The cleavage of aryl methyl ethers to aryl trimethylsilyl ethers may also be effected more slowly by reaction with iodotrimethylsilane at 25—50° in chloroform or sulfolane for 12-125 hours, with iodotrimethylsilane at 100—110° in the absence of solvent, " and with iodotrimethylsilane generated in situ from iodine and trimcthylphenylsilane at 100°. ... 

With both building blocks 103 and 109 in hand, the total synthesis of lb was completed as shown in Scheme 17. Coupling of acid 103 and alcohol 109 under Yamaguchi conditions to give ester 110 and subsequent desilylation followed by chemoselective oxidation provided hydroxy acid 111. Lactonization of the 2-thiopyridyl ester derived from 111 in the presence of cupric bromide produced the macrodiolide 112 in 62% yield, which was finally converted to pamamycin-607 (lb) via one-pot azide reduction/double reductive AT-methylation. In summary, 36 steps were necessary to accomplish the synthesis of lb from alcohols 88 and 104, sulfone 91, ketone 93, and iodide rac-97. 

Pseudo-first-order rate constants for carbonylation of [MeIr(CO)2l3]" were obtained from the exponential decay of its high frequency y(CO) band. In PhCl, the reaction rate was found to be independent of CO pressure above a threshold of ca. 3.5 bar. Variable temperature kinetic data (80-122 °C) gave activation parameters AH 152 (+6) kj mol and AS 82 (+17) J mol K The acceleration on addition of methanol is dramatic (e. g. by an estimated factor of 10 at 33 °C for 1% MeOH) and the activation parameters (AH 33 ( 2) kJ mol" and AS -197 (+8) J mol" K at 25% MeOH) are very different. Added iodide salts cause substantial inhibition and the results are interpreted in terms of the mechanism shown in Scheme 3.6 where the alcohol aids dissociation of iodide from [MeIr(CO)2l3] . This enables coordination of CO to give the tricarbonyl, [MeIr(CO)3l2] which undergoes more facile methyl migration (see below). The behavior of the model reaction closely resembles the kinetics of the catalytic carbonylation system. Similar promotion by methanol has also been observed by HP IR for carbonylation of [MeIr(CO)2Cl3] [99]. In the same study it was reported that [MeIr(CO)2Cl3]" reductively eliminates MeCl ca. 30 times slower than elimination of Mel from [MeIr(CO)2l3] (at 93-132 °C in PhCl). 

Methylcyclohexene, from 2-methyl-cyclohexanone tosylhydrazone and methyllithium, 51,69 Methylenecyclopropanes, 50,30 Methyl iodide, with triphenyl phosphite and cyclohexanol, 51,45 with triphenyl phosphite and neopentyl alcohol, 51,44 METHYL ftrans-2-IODO-l-TETRA-LIN)CARBAMATE, 51,112 Methyl (frans-2-iodo-l-tetralin)carba-mate, with potassium hydroxide to give 1,2,3,4-tetrahydronaph-thalene(l,2)imine, 51,53 Methyllithium, with camphor tosylhydrazone to give 2-bomene, 51, 66... 

EXTENSIONS AND COMMENTARY N-Methyltryptamine (monomethyltryptamine, NMT) is an alkaloid that has been found in the bark, shoots and leaves of several species of Virola, Acacia and Mimosa. However, the major snuffs associated with these plant have been shown to also contain 5-MeO-DMT and are discussed there. NMT has been synthesized in a number of ways. One can react 3-(2-bromoethyl)indole with methylamine. NMT can be isolated as the benzoyl derivative from the methylation of tryptamine with methyl iodide followed by reaction with benzoyl chloride, with the hydrolysis of this amide with alcoholic KOH. It can also be synthesized from indole with oxalyl chloride, with the resulting glyoxyl chloride reacting with methylamine in ether to give indol-3-yl N-methylglyoxalylamide (mp 223-224 °C from IPA) which is obtained in a 68% yield, which is reduced to NMT to give the amine hydrochloride (mp 175-177 °C from ) in a 75% yield. The most simple and direct synthesis is the formamide reduction given above. 

Phenyl methyl selenium di-iodide, (C6H5)(CH3)SeI2, occurs when the corresponding dibromide is triturated at 40° C. with a concentrated solution of potassium iodide. It crystallises from alcohol in glistening, purple, short prisms, M.pt. 69° to 71° C. 

Phenyl methyl selenium bromo-iodide, (C6H5)(CH3)SeIBr, is obtained when the dibromide is triturated with a cold solution of potassium iodide of the same concentration. The yield is quantitative, and the product separates from alcohol as red, ill-defined, compact crystals, M.pt. 85° C. with decomposition. Heating at 100° C. causes quantitative decomposition to methyl iodide and bromoselenobenzene, the reaction being represented as follows r... 

Methyl-j8-naphthylselenone, C10H7.SeO2.CH3, occurs when the sodium salt of naphthalene-j8-seleninic acid in methyl alcohol is boiled with methyl iodide for a long period. After treatment with water and extraction with ether, removal of the latter and crystallisation from alcohol gives a 48 per cent, yield as golden-yellow crystals, M.pt. 136° C. The selenone may also be obtained by the oxidation of methyl-j3-naphthyl selenide with permanganate. 

Methyl iodide combines at ordinary temperatures to form a meth-iodide, having the constitution shown below. This crystallises from alcohol as leaflets and from water as needles, M.pt. 197° C. When warmed with caustic alkalis it is decomposed in a similar manner to thioantipyrine ... 

Di-m-tolyl methyl tellurium iodide,3 (C7H7)2(CH3)TeI, is obtained in quantitative yield from its components. It crystallises in four-sided columns, soluble in chloroform, insoluble in ether. It melts at 121° to 122° C.s splitting up again into its components. When boiled with water and silver oxide and the solution treated with picric acid, a picrate is formed this separates from alcohol with five molecules of solvent of crystallisation, and melts at 114° to 115° C. The platinichloride melts with decomposition at 154° to 155° C. 

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