I've looked at several synthesis for allyl alcohol, and they all use chemicals I dont want to waste, don't have, and have fairly low yields. One option I thought of is reducing acrolein to allyl alcohol. Acrolein is essentially allyl aldehyde.


Acrolein is toxic, volatile, and extremely easy to make using glycerin, sodium bisulfate and heat. I'm mostly focusing on the later, since I will first try this in a small scale, and I have the equipment to deal with fairly toxic compounds (fumehood, etc) and I will also attempt to destroy any that will escape.

I'm not to sure how to go about this however. How could I reduce the aldehyde to an alcohol while leaving the double bonded carbon?

I'm afraid most of the typical reductions - HCl/Fe, etc will also mess with the alkene part of the molecule. Do you know of any reaction that could turn acrolein into allyl alcohol with out significant by product of N-propanol?


I eventually plan to turn this into allyl bromide, and so if there is perhaps a method to go straight to that, it would be welcomed as well

Or maybe you'd like to go with some tasty cadmium?

US patent 3109865

Abstract
Acrolein (I) was reduced in aq. acid soln. to allyl alcohol (II) by Cd in good yield without H evolution.  Thus 10 ml. 0.5 mole-% soln. of I, contg. 8 moles H2SO4 and 0.1 mole HI/mole I, held in contact with 10 g. Cd chips 30 min. at 80 gave 82.5% II and 18.2% propionaldehyde.  Other strong acids proved less effective.  Methacrolein was similarly reduced to methallyl alcohol (78.7%) and isobutyraldehyde (17.4%) while crotonaldehyde gave crotyl alcohol (29.8%) and butyraldehyde (7.0%), both using 0.94 mole-% solns. of aldehyde contg. 4.71 mole-% HBr and a contact time of 10 min. in a continuous process at 80°C.

...File attached...

Abstract
Acrolein was reduced homogeneously to allyl alc. over aluminum isopropoxide with isopropanol as the hydrogen transfer agent.  The effect of technol. conditions such as reaction temp., reaction time, the ratio of isopropanol to acrolein and the amt. of catalyst was studied systematically.  It was found that the conversion and the selectivity to allyl alc. could reach to 90.4% and 91.2%, resp., when the reaction was carried out for 60 min at 50°C, the mole ratio of isopropanol to acrolein and aluminum isopropoxide to acrolein being 3:1 and 0.07:1, resp.

Very interesting. I also searched for Meervein-Ponndorf applications for acrolein to find smth for Vesp, but found a bit different results. Most sources used high temperatures, gas phase or sometimes pressure to keep the reagents in liquid phase, large ratios IPA/acrolein (like 25), special catalysts.  Why they were struggling like that then, to make reaction heterogenous and industrially applicable? Maybe yes, but still chinese guy's results seem to be suspicious. Though it is a 2007 year paper, but the conditions they used are typical, used by Meerwein when he investigated this reaction. Maybe that is really because of difference between industrial and laboratory requirements to a process
 
 

Cadium oxide is easily bought from ceramic stores used to make red glazes.

It depends on what is done - if the glycerin is mixed with something such as sulfuric acid or potassium bisulfate it and heated, it produces acrolien. You are correct that allyl aclohol is produced by mixing oxalic acid and glycerin though - I was just thinking this might be an interesting route if it were easy and oxalic acid was not the easiest or most convenient of chemicals to acquire or use.

I wonder if oxalic acid has the ability to react with triglycerides to produce allyl alcohol, without any major issues with formation of other compounds?

I will check it out. It sounds familiar. Though both are so so cheap, i don't think it was an impressive yield at all - was it?
eh I will just check.

Acrolein is detectable at concentrations before it is significantly harmful, correct?

Yeah, it's what's responsible for that nasty odor when you scorch cooking oil. Obviously if you get a sudden lungful out of nowhere you're still toast.

Acrolein formation can be minimized with the proper technique 

I thought distilling glycerine and oxalic acid produced allyl alcohol and a byproduct was acrolein...iirc I once ran a tube into an NaOH solution to neutralize the poisonous acrolein gas.

From:

http://parazite.nn.fi/hiveboard/chemistrydiscourse/000353665.html

EXPERIMENTAL.
Preparation of Allyl Alcohol, Allyl Formate, and Formic Acid.
Pure, hydrated, finely divided oxalic acid (500 grams) and anhydrous glycerol (250 grams) are mixed in a litre flask which is connected with a condenser and receiver. The latter is connected with a water-pump and exhausted to about 120-100 mm. The flask is then gently warmed. At about 60° (thermometer in the liquid) the mixture boils vigorously, becomes homogeneous, and water (more than 100 grains) distils. This is the first stage of the reaction, the formation of the oxalins, and usually takes one hour. The pressure then rapidly rises to 480 mm and the thermometer remains stationary at 105-110° for some time. The vigorous ebullition ceases, a rapid effervescence of carbon dioxide sets in, and formic acid distils over with more water. There is no frothing if pure materials are used and the, pressure is maintained below 500 mm. After one to one and a half hours, the pressure in the apparatus slowly falls to about 120 mm; this indicates the end of the second stage, namely, the production of formins from the oxalins by loss of carbon dioxide and their subsequent decomposition into oxalins and formic acid by excess of oxalic acid. The temperature also rises to 190°, when distillation and evolution of gas almost cease. Quite suddenly, at 195-200°, the pressure increases rapidly. The receiver is then changed and the distillation carried on at the ordinary pressure. Carbon dioxide is again rapidly evolved, contaminated with some carbon monoxide and à negligible quantity of allyl formate. Allyl alcohol and allyl formate distil over together and the temperature remains stationary at 226° until distillation ceases, showing the end of the third stage of the reaction. The temperature then rises to 240°, when there is a rapid evolution of almost pure carbon monoxide. The last reaction ceases abruptly after about five minutes, and the colourless residue (80 grains) consists of glycerol. During the last two stages of the reaction the apparratus should be connected with a wash-bottle containing water, and the gases led into; in efficient draught-chamber. If the rate of decomposition is allowed to become too rapid, a large amount of glycerol is liable to distil over. It will be seen from the above description that the changes on the manometer and the thermometer are accurate criteria of the transitions between the various stages of the reaction.
To obtain pure allyl alcohol, the crude allyl alcohol-formate mixture (160 grams) is boiled under reflux with 750 c.c. of 10 per cent sodium hydroxide solution for one hour and fractionated through à long column. All the allyl alcohol passes over below 98° and the distillate is dried with small quantities of anhydrous potassium carbonate. It is then distilled and should give 100 grams of pure allyl alcohol, b. p. 95-97°.
To obtain allyl formate, the crude allyl alcohol formate mixture is washed several times with small quantities (20 c.c.) of water to remove allyl alcohol, and the insoluble ester dried over anhydrous calcium chloride. This on distillation gives à yield of pure ester, b. p. 82-83°, corresponding with 70 per cent of the crude alcohol-formate mixture. The washings may be worked up for allyl alcohol in the usual manner.
Allyl formate may also be obtained by fractionating the crude product several times, but in this case only a 50 per cent yield can be obtained. The formic acid in the first aqueous distillate (stages I and II) may be recovered either as a formate or as formic acid in the usual manner.
Thus, in one operation, 40 grams of formic acid and 100 grams of pure allyl formate, or about 100 grams of allyl alcohol, can be obtained from 250 grams of glycerol and 500 grams of hydrated oxalic acid. The residue of glycerol (80 grams) is quite suitable for further use.
The experiments were performed exactly as described with different initial concentrations of glycerol and oxalic acid. It can be seen that these results are in complete accord with those required by the above reaction scheme, and may be summarised as follows.
1. The yield of allyl alcohol calculated on the glycerol actually used is always nearly theoretical.
2. As the amount of oxalic acid increases, the yield of allyl formate in comparison with allyl alcohol also increases. This is to be expected, because the larger amounts of oxalic acid are favourable to the production of dioxalin hydrogen oxalate, às is readily shown by à comparison of the amount of the alcohol-formate mixture with the yield of allyl formate. This was actually proved by isolating the allyl formate.
3. With increase of oxalic acid, the amount of free formic acid increases.
4. With increase of oxalic acid, the amount lost as carbon monoxide is diminished. This passes through a minimum in experiment 4, as in experiment 5 the loss increase; again. 1n this experiment the amount of oxalic acid is relatively very large, and no doubt di- and tri-hydrogen oxalins would he produced in appreciable quantities, giving the corresponding formins and ultimately glycerol and carbon monoxide. There is no necessity to use anhydrous oxalic acid in the above preparation (see Chattaway, loc. ca.), as all the water of crystallisation distils over during stages I and II. This effects a saving of several hours in the duration of the experiment.
The amount of carbon monoxide was relatively much larger with smaller amounts of oxalic acid. The quantitative results are not given, but it may be stated that in experiment 3 the ratio CO : CO2, rapidly exceeded unity, whilst in experiment 4 this ratio was not reached until all the allyl alcohol had distilled. In experiment 5 the amount of carbon monoxide was larger for the reason already given.
Preparation of Allyl Chloride.
The best results were obtained as follows
Allyl alcohol (46 grams) and anhydrous zinc chloride (20 grams) were mixed in a distillation flask immersed in a water-bath at 75-82°, and hydrogen chloride was passed into the mixture. The gas was rapidly absorbed and a fluid distilled. The end of the reaction was indicated by hydrogen chloride issuing from the end of the condenser. The crude distillate gave on fractionation: allyl chloride (35 grams) corresponding with à 60 per cent yield, and 10 grams of diallyl ether, b. p. 90-95°. The experiment required only half an hour. With aluminium chloride (anhydrous) alone, allyl alcohol reacts very vigorously, giving very little allyl chloride and a large tar-like residue.
When calcium chloride and allyl alcohol are mixed, an additive compound is obtained, which, when heated at 80-90° in a stream of hydrogen chloride, gives a product boiling at 30-32°. This is probably diallyl ether, and contains only à trace of chloride.
Aschan's method (loc. cit.) for the formation of allyl chloride was tried, but although the yield on the ester actually used is 80 per cent, the reaction is extremely slow, and it is advantageous to prepare the alcohol and then use gíven method given first in this paper. An experiment was made by saturating allyl alcohol in the cold with hydrogen chloride in the presence of zinc chloride. The yield was not improved, however, and the reaction required a long period for completion.