Ok, this thread is hereby changed into the photoamination of propenylbenzenes thread.
I read the patents at the bottom of the document, and am convinced that this is a wonderful process. Here are some interesting notes.
1.This process works to use ammonia or a primary or secondary amine, in conjunction with an olefin, to produce aliphatic, cycloaliphatic, heterocyclic aliphatic, or aromatic mono-, di-, and tri- amines. That is a huge spectrum of possibilities!
2.Patent number 2,749,287 deals with the addition of ammonia to aromatics, specifically benzene, toluene, and xylene, to produce aniline, toluidine, and xylidine plus hydrogen. This is not addition across the double bond, but a substitution for tacking on an amine.
3.Technically speaking, catalysts are optional. They do greatly increase yields, but the reactions proceed without their use. You really need to read the second patent, the catalyst list is huge. (thats good, for those here that dont know)
4.The wavelength of light is said to be preferrably 1600-2200A (Angstroms?) and to use other wavelengths, a photocatalyst must be employed. At this wavelength, no catalyst is needed for the reaction to take place, but it is recommended.
5.This frequency range presents a minor issue on glassware. Quartz glass does not allow too much radiation of those wavelengths to pass through, but siliate glass works perfectly. Specifically types: Corning #7940, Suprasil
(R). No prob, who uses quartz glassware??? Boro
silicate pyrex should be fine.
6.Examples of lamps that produce light with the desired wavelengths are: Deuterium Lamps, Mercury Argon Lamps, and Xenon Flash Lamps. They say the xenon lamps are by far the best. Keep in mind this is for optimum wavelength.
7.Here's the good stuff! A list of organocatalysts used in these reactions. These are so simple! Examples: Ketones (they outright said they preferred acetone), Diacetone alcohol, Pyridine, Several Phosphines (read the patent), Benzene, and M-Xylene! Meta-xylene and acetone are what really caught my eye. Over the counter xylene is mostly the meta isomer, and the three isomers can actually be seperated if you want to.
8.Optimum temperature range is -10°C to 40°C, and I quote, "...but any convenient temperature may be used." Sheesh, "ya do whatever you want it'll work" Sounds good to me.
9.Ratios of amine to olefin: can range from 1:1 to 20:1. They say preferred ratios are 5:1 through 15:1. I'd agree, not just to get the reaction to proceed, but to minimize multiple additions of your newly formed amine to another propenylbenzene.
It says that the catalysts only need be present in catalytic amounts (no fucking shit) but is generally limited by the properties of solubility of the catalysts and reactants.
This patent seems to deal with the same concept drone discussed, but makes no mention of p-DCB or acetonitrile, makiing me wonder if the reaction is indeed not so specific to those reactants.
Personally, I'd think that using an organocatalyst as a solvent would do wonderful, such as acetone or m-xylene, or a solution thereof.
So really the only question I cansee as to which catalytic solvent you use, would be to use the one that offers the highest solubility for amonia or methylamine, so you can saturate it as much as possible.
I have one question that I'd really really
really like someone smarter than me to answer, if you don't mind. Would it be feasible to prepare a solution of methylamine in a nonpolar solvent by reaction of methylamine salt with base IN THE NONPOLAR.
I know thatthese compounds are not soluble in nonpolars, but the reaction should proceed, as by basic rules anyway. It will produce water. So for example, specifically, if SWIPP had some acetone with MgO crystals in it, and added some methylamine sulfate, would it react to form methylamine gas and magnesium sulfate, which will suck up the water and crystallize? You could then filter your nonpolar to remove the solids, and use it for immediate reaction.
The point is not to prepare a mere methylamine solution, it is to prepare a solution beyond the saturation point. (I assume it'd just start fuming)
PrimoPyro
Vivent Longtemps la Ruche!