Landauer, S. R. published the artcileThe organic chemistry of phosphorus. I. Some new methods for the preparation of alkyl halides, Recommanded Product: Ethyl 2-Iodopropionate, the publication is Journal of the Chemical Society (1953), 2224-34, database is CAplus.
cf. C.A. 45, 9456e. (MeO)3P (I) (0.1 mol) refluxed 30 min. at 100° with MeI and the product distilled, gave MePO(OMe)2 (II); with molar ratios of I:MeI = 1:1, 2:1, 10:1, and 100:1, the yields of II were 90, 88, 93, and 80%, resp. I (6.2 g.) and 0.06 g. Me2SO4 refluxed 15 min. at 100° gave 8% recovered I and 81% II, b12 66°. (PhO)3P (III) (31 g.) and 21 g. MeI refluxed 36 h. with exclusion of H2O, the mixture treated with anhydrous ether, and the solid washed with anhydrous ether, dried, and weighed in vacuo, gave 42 g. (PhO)3PMeI (IV), which was stored under ether, dried, and weighed in vacuo before use; IV taken up in Me2CO and precipitated with anhydrous ether gave pure IV, m. 146°. IV (7.95 g.) in 30 mL. absolute EtOH and 150 mL. saturated alc. AgNO3 gave after 3, 6, 10, 20, 80, 150, and 1440 min. 67, 73, 76, 79, 86, 92, and 100%, resp., total yield of AgI (204.5 mg. IV gave 09.6% AgI after 3 min.). IV (21 g.) shaken several min. with 35 mL. absolute EtOH and the solution distilled, gave 62% EtI, b. 72° (PhNEtMe2I, m. 136-7°), PhOH, and 91% MePO(OPh)2 (V), m. 35-6°. In a 2nd experiment in which the mixture was distilled at 0.5 mm., 66% EtI was collected in a trap at -80°; the residue, washed with 2N NaOH gave 86% V; the alk. washings gave with acid 96% PhOH. Iodides were similarly prepared from IV and the appropriate alc., cooling being necessary with reactive alcs., warming with less reactive alcs.; the iodide was isolated by distillation of the reaction mixture in vacuo, with the iodide collected at -80° in a trap (when the b.p. was much lower that of PhOH), by distillation with PhOH in vacuo and separation of the PhOH with cold dilute NaOH, or by removal of the PhOH from the reaction mixture with dilute NaOH and distillation The method is satisfactory with primary, secondary, tertiary (76% yield of Me3CI), and unsaturated alcs. (83% yield of MeCH:CHCH2I, b40-5 55-6°), glycols (95% yield of CH2(CH2I)2, b0.5 50-1°, n21D 1.6420), and Et lactate (92% yield of MeCHICO2Et, b8 65-6°, n20.5D 1.5000), giving 60-95% yields. Cholesterol (9.5 g.) mixed with 12 g. IV, 10 mL. MeI added, the mixture refluxed 1 h. at 50-60°, kept overnight, extracted with 100 mL. petr. ether (b. 40-60°), the extract evaporated, the residue treated with 100 mL. H2O, the insoluble part washed with Me2CO, taken up in 200 mL. hot Me2CO, cooled, and the solution decanted from the oil and cooled at 2° gave 30% cholesteryl iodide, m. 105° (from EtOAc), [α]21.2D -12.7° (CHCl3). III (34 g.) and 13 g. PhCH2Cl heated 60 h. at 170-5° and the mixture washed with petr. ether (b. 40-60°), gave 25 g. oily (PhO)3P(CH2ph)Cl (VI). VI (10 g.) kept overnight at room temperature with 2 g. (+)-2-octanol, α21.4D 7.72°, and the mixture distilled gave 79% (-)-2-chloroöctane, b13 60°, n20D 1.4275, [α]22.4D -24.72°. PCl3 (23 g.) added (20 min.) to 54 g. stirred, cooled PhCH2OH, 61 g. PhNMe2, and 100 mL. absolute ether, the mixture filtered, and the filtrate distilled twice gave 8 g. (PhCH2O)2P(O)H, b0.05 145-60°, 10 g. mixture, b0.05 160-80°, and 18 g. (PhCH2O)3P (VII), b0.05 180-95°, m. 52° (from petr. ether). VII and MeI heated 30 h. at 100° gave no addition product; heated 3 h. at 150°, VII and MeI gave PhCH2I. Summaries are given for the preparation of 12 iodides, 4 bromides, and 5 chlorides directly from III, the halide (MeI, PhCH2Br, or PhCH2Cl), and the alc. III (68 g.), 40 g. BuI, and 6.4 g. absolute MeOH heated 24 h. at 165-85°, with the MeI fractionated off continuously, gave 16 g. MeI, b. 42-3°, n20D 1.5290. MeBr passed slowly (through a sintered glass plate) into a mixture of 50 g. III and 11 g. BuOH heated 12 h. (155-35°), the mixture distilled, and the product collected at -80°, gave 63% BuBr, b. 101.5°, n20D 1.4400. (EtO)3P (16.6 g.), 14.2 g. MeI, and 22.2 g. BuOH refluxed 1 h. gave 64% impure EtI and 36% BuI, b. 110-30°, n20D 1.4935. Dry HCl passed (1.5 h.) into equimol. amounts of III and BuOH gave 76% BuCl, b. 77-9°, n17D 1.4025; similarly (-)-2-octanol (kept overnight with III before HCl was added for 1 h.) gave 44% (+)-2-chloroöctane, b8-10 53-6°, [α]22.2D 18.8°; 2 g. cholesterol, 5 g. III, and HCl (30 min. addition), treated with 20 mL. Me2CO, gave 2.2 g. cholesteryl chloride, m. 95° (from EtOAc), [α]20D -33.3° (CHCl3). III (34 g.), 7.4 g. BuOH, and 6 g. NH4Cl refluxed 84 h. at 140° gave 63% BuCl, b. 77-8°, n22D 1.4015. Similarly III and BuOH with 6 g. NaCl (heated 120 h. at 170-80°) gave 16% BuCl; with 9.6 g. LiBr (heated 64 h. at 140°), 40% BuBr; with 16.5 g. NaI (heated 64 h. at 160-70°), 18.5% BuI. IV (7 g.), 1.5 g. absolute EtOH, and 3 g. PhNMe2 warmed 15 min. on a steam bath and diluted with ether gave 3.8 g. PhNMe2EtI, m. 131° (from EtOH). III (68 g.) and 14.8 g. BuOH heated 16 h. at 100° gave 18.5 g., b10 60-80° (mainly PhOH), 7.5 g., b10 80-120°, n25D 1.4580 [mainly (BuO)3P], 7.8 g. mixture, b10 120-40°, n25D -1.4840, of (BuO)3P and (BuO)2P(O)Ph, 9 g., b10 140-70°, n25D 1.5302, [mainly BuOP(OPh)2 (VIII)], 4.1 g., b10 170-80°, n25D 1.5819, (mixture of VIII and III), and 28 g. residue, n25D 1.5815. III (68 g.) and 14.8 g. BuOH kept 30 min. at room temperature and distilled gave 18 g. PhOH and a mixture of phosphites which, refluxed 3 h. with 13 g. MeI, gave 13 g. BuI, n23D 1.4990; the residue heated 24 h. with 28 g. MeI gave 15.1 g. addnl. BuI, b. 125-31°, n22D 1.4980. IV (23 g.) and 3 g. V refluxed 1 h. and distilled gave 5 g. MeI, b. 42-4°, n20D 1.5055. IV (5 g.) and 2.5 g. (BuO)3P mixed to give a solution and distilled gave 1.8 g. BuI, b. 125-32°, n23D 1.4970. Et(O)PCl2 (IX) (147 g., b. 117-18°) and 500 mL. absolute ether cooled in a freezing mixture and treated portion wise with NaOMe (from 46 g. powd. Na and 64 g. MeOH) in 500 mL. ether, the mixture kept 1 h. at room temperature, filtered, the filtrate distilled, and the product fractionated gave 56 g. EtOP(OMe)2 (X), b. 124-7°, equivalent 138.0 (equivalents were determined by hydrolysis of about 150 mg. alkyl phosphite 1 h. at 100° with 5 mL. 70% alc. NaOH, dilution with 0.1N HCl, and titration of the excess alkali with bromophenol blue; the authors found that equivalents gave a better criterion of purity than elemental anal.). X (27.6 g.) refluxed 1 h. with 28.4 g. MeI and fractionated gave 27.5 g. MeI and 27 g. EtO(MeO)P(O)Me, b15 74-5°, equivalent 137.8. X (13.8 g.), 2 g. H2O, and 10 mL. Me2CO kept 1 h. and distilled gave P-containing fractions, 1.3 g., b15-17 65-73°, 9 g. EtO(MeO)(HO)P, b15-17 73-5°, equivalent 124.0, and 1.3 g., b15-17 75-7°. Absolute MeOH (32 g.) and 121 g. PhNMe2 added (1 h.) to 137 g. PCl3 cooled, stirred in 1 l. absolute ether, 92 g. absolute EtOH, and 242 g. PhNMe2 then added (2 h.), the mixture diluted with 500 mL. ether, filtered, the filtrate distilled, and the fraction, b10-15 50-90°, fractionated gave 35 g. (EtO)2POMe (XI), b. 136-9°, equivalent 152.6. XI (10 g.) and 8.5 g. MeI refluxed 30 min. and distilled gave 6.8 g. MeI and 6 g. (EtO)2P(O)Me, b. 190-2°, n23D 1.4110, equivalent 152.0. XI (10 g.), 1.5 g. H2O, and 10 mL. Me2CO gave 5.3 g. (EtO)2POH, b8 65-6°, n21D 1.4070, equivalent 137.2. iso-PrOH (120 g.) and 242 g. PhNMe2 added (80 min.) to cold 130 g. IX in 500 mL. absolute ether, the mixture stirred 30 min. and filtered, and the filtrate fractionated gave 97 g. (iso-PrO)2POEt (XII), b10 69-71°, equivalent 192.1. XII (19.5 g.) and 14.2 g. MeI refluxed 30 min. at 100° and distilled gave 12 g. EtI, b. 71-3°, and 17 g. (iso-PrO)2P(O)Me, b5 7-5-6°, n20D 1.4158. XII (19.5 g.), 2 g. H2O, and 10 mL. Me2CO refluxed 14 h. and distilled gave 12.5 g. (iso-PrO)2P.OH, b10 89-90°, equivalent 159.3. The mechanism for the formation of alkyl halides is discussed. Halides included in tables: EtI, iso-PrI, n-BuI, sec-BuI, tert-BuI, (+)- and (-)-2-iodoöctane, cyclohexyl iodide, CH2:CHCH2I, MeCH:CHCH2Cl, PhCH2I, PhCH2CH2I, PhCHIMe, CH2(CH2I)2, MeCHICO2Et, Me2C(CH2I)2, and Me3CCH2I; BuBr, CH2:CHCH2Br, CH2(CH22Br)2, MeCHBrCO2Et; BuCl, CH2:CHCH2Cl, CH2(CH2Cl)2, MeCHClCO2Et, and n-C6H13Cl.
Journal of the Chemical Society published new progress about 31253-08-4. 31253-08-4 belongs to iodides-buliding-blocks, auxiliary class Iodide,Ester, name is Ethyl 2-Iodopropionate, and the molecular formula is C5H9IO2, Recommanded Product: Ethyl 2-Iodopropionate.
Referemce:
https://en.wikipedia.org/wiki/Iodide,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com