Okay we have Rhodiums Synths
https://www.thevespiary.org/rhodium/Rhodium/chemistry/nitroalkane.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/nitroalkane.html)
https://www.thevespiary.org/rhodium/Rhodium/chemistry/methyliodide.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/methyliodide.html)
Here is a possible variation on the RedP procedure above.
Improved preparation of methyl iodide
Kizlink, Juraj; Rattay, Vladimir.
Chem. Listy (1980), 74(1), 91-2.
Abstract
MeI was prepd. in .apprx.90% yield by the red P-catalyzed reaction of MeOH with I2. The reaction rate was controlled by the rate of addn. of MeOH to a mixt. of I2 and P.
I'll add a few more.
Alkyl iodides.
Patent US3053910 (http://l2.espacenet.com/dips/viewer?PN=US3053910&CY=gb&LG=en&DB=EPD)
Abstract
Alkyl iodides were prepd. by treating a dialkyl sulfate at pH 1-6.5 with an iodide prepd. by the action of a reducing agent, e.g., Al, Fe, Sn, SO4, oxalic acid, or N2H4, on an aq. slurry of elemental iodine. In an example, 241 g. Fe powder was added to 820 g. H2O and 1050 g. com. iodine during 2-3 hrs. at 20-60°, at pH 5.3. Et2SO4 (1540 g.) was added dropwise at 70-80°, while distg. the EtI as formed. The reaction mixt. was heated to 95° to complete the EtI distn., and the product was washed with cold H2O, 5% N2CO3, and dried (CaCl2) to give 99% EtI. Similarly prepd. were 99.1% MeI, 97.2% PrI, and 99.4% AmI.
Preparation of alkyl iodides or aryl iodides.
Patent JP62246527 (http://l2.espacenet.com/dips/viewer?PN=JP62246527&CY=gb&LG=en&DB=EPD)
Abstract
Alkyl iodides or aryl iodides, useful as methylating agents and cocatalysts for carbonylating agents, were prepd. by a reaction of group IA, IIA, IIIA, IB, IIB, or IVB metals and iodine or iodides of metals and alcs., carboxylic acid esters, dialkyl ethers, and/or diaryl ethers at 15-150° and 1-50 atm without formation of H2O and corrosive materials. Thus, a soln. of iodine in AcOMe was added dropwise to a mixt. of Al and AcOH over 60 min and then heated at 65° for 150 min to give 65.4% (based on iodine) MeI.
Methyl iodide.
Zadorozhnaya, I. E.
Khim. Reaktivov Prep. (1967), No. 15 96-7.
Abstract
MeI was prepd. in 91.5% yielded by adding 1.55 kg. PhSO3Me dropwise to a soln. of 1.35 kg. NaI in 1.35 1. H2O, first at room temp. until one third of the ester had been added, and then at 60-70° in a system which provided for distg. the product at this temp. into a receiver contg. ice and H2O.
Antoncho might find this one funny ;)
Preparation of alkyl halides and sulfur from hydrogen sulfide, alcohols, and halides
Patent US3649197 (http://l2.espacenet.com/dips/viewer?PN=US3649197&CY=gb&LG=en&DB=EPD)
Abstract
Alkyl halides were prepd., by reaction of H2S, Br or I, and EtOH or MeOH in the presence of an alkali metal halide and, optionally, a hydrohalic acid, in a 2-stage reaction. Thus, a mixt. of EtOH, Br, LiBr, and 12M HCl was treated with 15 psi H2S, S filtered, and the filtrate heated 2 hr at 130° to give 65% EtBr. Similarly prepd. were 89.0% EtI and 43.0% MeI.
Alkyl iodides
Patent JP50121205 (http://l2.espacenet.com/dips/viewer?PN=JP50121205&CY=gb&LG=en&DB=EPD)
Abstract
Alkyl iodides were prepd. by treating fatty acid alkyl esters with stoichiometric amts. of metal iodides at 100-250°. Thus, a mixt. of 2.02 g Me oleate (I) and 10 g CaI2 was stirred 2 hr at 200° under N to give 6 g MeI (purity 99%). PrI was similarly prepd.; MgI2, MnI2, LiI, AlI3, and SrI2 were also used in place of CaI2. AcOMe was also used in place of I.
Methyl iodide.
Patent CS164707 (http://l2.espacenet.com/dips/viewer?PN=CS164707&CY=gb&LG=en&DB=EPD)
Abstract
Hot aq. KI was continuously treated with a 3:2 mixt. of H2SO4 and MeOH, and MeI was gradually distd. in 90% yield.
Hydrogen iodide, lithium iodide and methyl iodide.
Patent US4302432 (http://l2.espacenet.com/dips/viewer?PN=US4302432&CY=gb&LG=en&DB=EPD)
Abstract
HI is prepd. by reaction under anhyd. conditions of H2 and I2 in a non-alc. solvent using a homogeneous Rh catalyst [e.g., Rh2(CO)4Cl2]. LiI and/or MeI are obtained by including LiOAc and/or MeOAc in the reaction medium.
Anhydrous alkyl iodide.
Patent EP46870 (http://l2.espacenet.com/dips/viewer?PN=EP46870&CY=gb&LG=en&DB=EPD)
Abstract
Anhyd. RI were prepd. by treating R1CO2R (R = C1-4 alkyl; R1 = H, C1-8 alkyl or aryl) with iodine and H (and optionally CO) in the presence of a Pt metal compd. as catalyst and a quaternary heterocyclic N compd. or quaternary P compd. as promoter. Thus, 250 g AcOMe, 50 g AcOH, 60 g N,N-dimethylimidazolium iodide, 1.2 g [Rh(CO)2Cl]2 and 50 g iodine were pressurized with 2 bar CO and 4 bar H, then stirred 58 min at 373 K to give 99.6% MeI.
Hot aq. KI was continuously treated with a 3:2 mixt. of H2SO4 and MeOH, and MeI was gradually distd. in 90% yield.
oh my God! Is it true?
unfortunately, this patent (i guess, Poix also meant this one) is unavailable at Espacenet...
The thing that really confuses me is the reverse order of addition as well as usage of water. It's been always my impression that the more concentrated the hydrohalic acid is, the better is the conversion - and in this example we have an essentially small concentration of acid all the time...
Of course, that would bee good for not oxidizing HI formed into iodine - but if MeI formation is possible w/such low conc. aq. HI, then - why noone ever just did it w/MeOH and aqueous HI???
Anyone has any thoughts on this?
Antoncho
P.S. Foxy2 rulez! Thanks a lot!