Iodide treatment with

The racemic aminoalcohol 207 has been resolved into both enantiomeric forms with (D)-(-)-mandelic acid. Liberation of the amines, following by quaternization with methyl iodide, treatment with silver oxide, and heating in water gave the optically active oxiranes 208 and 209. 

Mercury di-isoamyl is insoluble in water, slightly in alcohol, but readily soluble in ether. It does not oxidise in air, but when dropj ed into chlorine it forms isoamyl mercuric chloride. In contact with solid iodine it reacts with a hissing sound, and the reaction with bromine is still more violent. An ethereal solution of mercury di-isoamyl treated first with alcoholic and then with solid iodine gives isoamyl mercuric iodide and isoamyl iodide. Treatment with an excess of mercuric chloride in alcohol yields isoamyl mercuric chloride. 

I he methyl iodide is transferred quantitatively (by means of a stream of a carrier gas such as carbon dioxide) to an absorption vessel where it either reacts with alcoholic silver nitrate solution and is finally estimated gravimetrically as Agl, or it is absorbed in an acetic acid solution containing bromine. In the latter case, iodine monobromide is first formed, further oxidation yielding iodic acid, which on subsequent treatment with acid KI solution liberates iodine which is finally estimated with thiosulphate (c/. p. 501). The advantage of this latter method is that six times the original quantity of iodine is finally liberated. 

CAUTION. Ethers that have been stored for long periods, particularly in partly-filled bottles, frequently contain small quantities of highly explosive peroxides. The presence of peroxides may be detected either by the per-chromic acid test of qualitative inorganic analysis (addition of an acidified solution of potassium dichromate) or by the liberation of iodine from acidified potassium iodide solution (compare Section 11,47,7). The peroxides are nonvolatile and may accumulate in the flask during the distillation of the ether the residue is explosive and may detonate, when distilled, with sufficient violence to shatter the apparatus and cause serious personal injury. If peroxides are found, they must first be removed by treatment with acidified ferrous sulphate solution (Section 11,47,7) or with sodium sulphite solution or with stannous chloride solution (Section VI, 12). The common extraction solvents diethyl ether and di-tso-propyl ether are particularly prone to the formation of peroxides. 

C—C double bonds may be protected against electrophiles by epoxidation and subsequent removal of the oxygen atom by treatment with zinc and sodium iodide in acetic acid (J.A. Edwards, 1972 W. Kndll, 1975). Halogenation has often been used for protection, too. The C—C double bond is here also easily regenerated with zinc (see p. 138, D.H.R. Barton, 1976). 

The carbonyiation of o-diiodobenzene with a primary amine affords the phthalimide 501 [355,356]. Carbonyiation of iodobenzene in the presence of (9-diaminobenzene (502) and DBU or 2,6-lutidine affords 2-phenylbenzimida-zole (503)[357, The carbonyiation of aryl iodides in the presence of pentaflnor-oaniline affords 2-arylbenzoxazoles directly, 2-Arylbenzoxazole is prepared indirectly by the carbonyiation of (9-aminophenol[358j. The optically active aryl or alkenyl oxazolinc 505 is prepared by the carbonyiation of the aryl or enol triflates in the presence of the opticaly active amino alcohol 504, followed by treatment with thionyl chloride[359]. 

Curiously enough, bulky substituents on nitrogen increase this reactivity towards methyl iodide (119). This has been related to a steric decompression of the thiocarbonyl group in the transition state. Furthermore, knowledge of the ratio of conformers in the starting 4-alkyl-3-i-Pr-A-4-thiazoline-2-thiones and in the resulting 4-alkyl-3-i-Pr-2-methylthiothi-azolium iodides combined with a Winstein-Holness treatment of the kinetic data indicates that in the transition state, the thiocarbonyl bond is approximately 65% along the reaction coordinate from the initial state... 

Acetamido-4-methylselenazole can react with mercuric acetate to yield 5-mercuriacetate derivatives that can be converted to the chloro derivatives by the action of sodium chloride. Treatment with potassium iodide leads to reduction regenerating the initial compound with loss of mercury (Scheme 16) (4). 

Iodide ion (I ) Alkyl chlorides and bromides are converted to alkyl iodides by treatment with sodium iodide in acetone Nal is soluble in acetone but NaCI and NaBr are insoluble and crystallize from the reaction mixture making the reac tion irreversible... 

The halide anion of quaternary ammonium iodides may be replaced by hydroxide by treatment with an aqueous slurry of silver oxide Silver iodide precipitates and a solu tion of the quaternary ammonium hydroxide is formed... 

Dichlorobutyne [821-10-3] and dibromobutyne [2219-66-1] are readily prepared by treatment with thionyl or phosphoms haUdes. The less-stable diiodobutyne is prepared by treatment of dichloro- or dibromobutyne with an iodide salt (52). 

A high yield chemical pulp, eg, 52—53% bleached yield from softwoods, can be obtained, but strength properties ate inferior to those obtained from the kraft process. If a protector, eg, potassium iodide, is added, an additional 2—3% yield is obtained, as is an improvement in all strength properties. The gas penetration problem can be minimized if ftbetization is accompHshed before treatment with oxygen. Oxygen treatment of virtually all types of semichemical and mechanical pulps has been explored (55). Caustic, sodium bicarbonate, and sodium carbonate have been used as the source of base (56,57). In all cases, the replacement of the kraft by these other processes has not been justified over the alternative of pollution abatement procedures. 

Ha.loisoquinolines, The Sandmeyer reaction is commonly used to prepare chloroisoquinolines from the amino compound. The corresponding hydroxy compounds are also used by treatment with chlorides of phosphoms. The addition of bromine to a slurry of isoquinoline hydrochloride in nitrobenzene gives a 70—80% yield of 4-bromoisoquinoline [1532-97-4J. Heating 1-chloroisoquinoline [19493-44-8] with sodium iodide andhydriodic acid gives 1-iodoisoquinoline [19658-77-6] (179). 

Trimethylsulfoxonium iodide (11) is of interest because treatment with sodium hydride or dimsyl sodium produces dimethyl sulfoxonium methylide [5367-24-8] (12) (eq. 22), which is an excellent reagent for introducing a methylene group into a variety of stmctures (53) ... 

Conversion to a more facile, sulfur-derived, leaving group can be achieved by treatment with sodium thiosulfate or salts of thio and dithio acids (75,87). Under anhydrous conditions, boron tribromide converts the 3 -acetoxy group to a bromide whereas trimethyl silyl iodide gives good yields of the 3 -iodide (87,171,172). These 3 -halides are much more reactive, even when the carboxyl group is esterified, and can be displaced readily by cyano and by oxygen nucleophiles (127). 

The reaction of calcium iodide and strontium iodide and the ion in tetrahydrofuran (THF) followed by treatment with acetonitrile... 

IV-Methylated pyridazinones can be obtained from 3,6-dialkoxypyridazines by treatment with alkyl halides or dialkyl sulfates. Methyl iodide and dimethyl sulfate are most frequently used. According to the proposed mechanism, an intermediate quaternary pyridazinium salt is formed, followed by elimination of a group R from the alkoxy group. At higher temperature, l,2-dimethylpyridazine-3,6(l//,2//)-dione is formed with dimethyl sulfate. 

The 4-thioxoazetidin-2-one (281) (c/. Section 5.09.3.3.5) is reported to undergo exclusive 5-alkyIation on treatment with methyl iodide in the presence of base to yield the 2-methylthio-l-azetin-4-one (282) (80TL4247). 

Isopropyl iodide (2-iodopropane) [75-30-9] M 170.0, b 88.9 , d 1.70, n 1.4987. Treated with bromine, followed by extraction of free halogen with aqueous Na2S203 or NaHS03, washing with water, drying (MgS04 or CaCl2) and distn. (The treatment with bromine is optional.) Other purification methods include... 

Anhalonine and Lophophorine. Spath and Gangl showed that each of these alkaloids contains a methylenedioxy group and that the quarternary iodide prepared from dZ-anhalonine is identical with lophophorine methiodide so that lophophorine must be N-methylanhalonine. Anhalonine was synthesised from 3 4-methylenedioxy-5-methoxybenzaldehyde by condensation with nitromethane, reduction of the product to the corresponding -ethylamine, the acetyl derivative (VII) of which, on treatment with phosphoric anhydride, condensed to 6-methoxy-7 8-methylenedioxy-l-methyl-3 4-dihydrofsoquinoline, m.p. 60-2°. This, on reduction, furnished the corresponding tetrahydrofsoquinoline, which proved to be anhalonine (VIII), and on conversion to the quaternary methiodide the latter was found to be lophophorine (IX) methiodide. The possible alternative, 8-methoxy-6 7-methylenedioxy-l 2-dimethyl-l 2 3 4-tetrahydrofsoquinoline, was prepared by Freund s method and the methiodide shown not to be identical with lophophorine methiodide. 

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