Synthesis of allyl alcohol

Preparation of allyl alcohol (2-propen-1-ol)

Preparation of allyl alcohol from glycerol and oxalic acid

Allyl alcohol is prepared  from glycerine and oxalic acid according to a following equation:

Preparation of allyl alcohol from glycerol and oxalic acid

Preparation of allyl alcohol from glycerol and oxalic acid

In a 3000 ml reaction flask equipped with condenser for distillation 1400 g of glycerine were mixed with 700 g of oxalic acid and to this mixture was added 3 g of ammonium chloride to aid in the reaction. The reaction mixture is heated and at 150° C, carbon dioxide begins to be evolved energetically and the liquid remains at that temperature for some time. The gas evolution diminishes as the temperature reaches 180° C. At 195° the distillate contains a large percentage of formic acid and this fraction up to 215° is collected in separate flask. At 200-210° C  the carbon dioxide evolution begins again, and the second stage of the reaction begins – the formation of allyl alcohol from the 1-monoacylglycerol. About 215° C a yellow oily substance condensed which is allyl alcohol. The temperature is kept at 220-230° C as long as possible. When finally the temperature reaches 240° C, which is after several hours heating, the distillation was interrupted. The contents of the flask was allowed to cool and 420 g more of oxalic acid were added. The distillation was repeated as above, only letting the temperature rise finally to 260° C. The mixture was again cooled and 140 g of oxalic acid was added and the temperature run up to 260° C. The mixture in the reaction flask was much diminished in volume, although the reaction is by no means a quantitative one. The collected distillates above 195° contained besides allyl alcohol, some allyl formate, glycerine, and acrolein. The distillation is kept up until a portion on saturation with solid potassium carbonate gave no oily drops. It began to distill at 80° C, most passing over at 115-120° C. The temperature was allowed to rise however to 150° C. The allyl alcohol was obtained by salting out with solid potassium carbonate and separating the two layers, water and allyl alcohol, with the separatory funnel. The crude allyl alcohol was treated with 12% of dry potassium hydroxide and left to stand 24 hours in order to completely remove acrolein. The allyl alcohol became very dark-colored. After separating from the alkaline layer at the bottom of the flask the allyl alcohol was distilled until the temperature reached 110° C. The resultant distillate was slightly yellow. It was dried by removing water by solid potassium carbonate and redistilled. The distillation began at 90.5° C and rose to 110° C, remaining mostly below 90.5° C, the boiling point of the pure substance. The resultant liquid is perfectly colorless and has a slight sharp odor.

The synthesis of amino acids, by B. B. Wilcox, 20-21, 1904

Preparation of allyl alcohol from glycerol and formic acid

Preparation of allyl alcohol from glycerol and formic acid

Preparation of allyl alcohol from glycerol and formic acid

In a 5 liter flask are placed 2000 g of pure glycerin and 575 g of 85% formic acid. In the stopper is fitted a condenser set for downward distillation and a thermometer the bulb of which is immersed in the reaction mixture. It is advisable to use as a receiver a boiling flask attached tightly to the lower end of the condenser. A tube is then run from the side arm of the boiling flask to a bottle of strong caustic soda to dissolve and decompose any acrolein which may form. A few pieces of clay plate are added to the distillation flask in order to prevent bumping and it is then heated rapidly over a good ring burner. The first runnings should come over within 15 min and a temperature of 195° C should be reached within 30-45 min. Slow heating causes charring and formation of much acrolein, thus giving a very low yield of allyl alcohol. The distillate collected up to the point where the thermometer registers 195° C is discarded. The heating of the reaction mixture is continued until the temperature reaches 200° C, the main reaction taking place at 225-235° C. At this point, when the heating should be stopped, a white smoke appears and decomposition apparently starts. The distillate (about 750 ml) coming over between the thermometer readings of 195-260° C is saved. For this operation 4-5 hous are requared. The contents of the reaction mixture flask are now cooled to about 100-125° C and 500 g more of the technical 85% formic acid are added. The distillation is then repeated in exactly the same manner as described and again 500 ml of distillate are collected between the temperatures of 195-260° C. The reaction mixtun1 is allowed to cool again and a third portion of 500 g of formic acid are added. Upon this distillation not more than 350 ml of the desired fraction is obtained, indicating that the glycerin is used up and that further addition of formic acid is unnecessary; moreover, the residue left behind, is now small, amounting only to from 100-200 ml.

The 195-260° C fractions of the distillates are treated with potassium carbonate to salt out the allyl alcohol and to neutralize a little formic acid present. This allyl alcohol is then distilled and the fraction boiling up to about 103° C is collected. In this way, 845 g of an allyl alcohol is obtained, which by a bromine titration shows a purity of about 70%. This is equivalent to 590 g of pure allyl alcohol (47% theory).

The alcohol may be made completely anhydrous by refluxing with successive portions of fused potassium carbonate until no further action is observed. The carbonate will remain finely divided and not become sticky when water is absent. A considerable amount of allyl alcohol is lost mechanically during the drying in this way, so that the potassium carbonate which is used here should be employed for the salting out of fresh portions of allyl alcohol in the first part of subsequent preparations. The allyl alcohol thus produced is dry enough for all practical purposes and it is unnecessary to dry with lime or barium oxide as advised in the literature in order to remove all of the water. The allyl alcohol obtained by this process boils 94-97° C and by the bromine titration shows practically 100% purity.

Organic Chemical Reagents, by A. Roger, 73-75, 1919

IUPAC Name

prop-2-en-1-ol

InChI

InChI=1S/C3H6O/c1-2-3-4/h2,4H,1,3H2

InChI Key

XXROGKLTLUQVRX-UHFFFAOYSA-N

Canonical SMILES

C=CCO

MeSH Synonyms

1-propen-3-ol, allyl alcohol, allylic alcohol

Depositor-Supplied Synonyms

ALLYL ALCOHOL, 2-Propen-1-ol, PROP-2-EN-1-OL, 2-Propenol, Vinylcarbinol, 2-Propenyl alcohol, 107-18-6, 3-Hydroxypropene, Allylic alcohol, 1-Propen-3-ol, Weed drench, Propenyl alcohol, 1-Propenol-3, Allylalkohol, Propenol, Propen-1-ol-3, Vinyl carbinol, Alcool allylique, Allilowy alkohol, Shell unkrautted A, Alcool allilco, Allyl al, RCRA waste number P005, Shell Unkrauttod A, 2-Propene-1-ol, 1-hydroxy-2-propene, 3-Hydroxy-1-propene, Allylalkohol [German], Caswell No. 026, NSC 6526, Alcool allilco [Italian], Alcool allylique [French], Allilowy alkohol [Polish], RCRA waste no. P005, CCRIS 747, HSDB 192, UNII-3W678R12M0, CHEBI:16605, XXROGKLTLUQVRX-UHFFFAOYSA-N, EINECS 203-470-7, UN1098, EPA Pesticide Chemical Code 068401, DSSTox_CID_44, AI3-14312, DSSTox_RID_75335, DSSTox_GSID_20044, CAS-107-18-6, allylalcohol, Orvinylcarbinol, Hydroxypropylene, Aaalcool allilco, AllOH, Propenol-3, 2-propen-1ol, 1-Propenol-3-ol, prop-2-en-I-ol, ALLYL-ALCOHOL, AC1L1PPO, CH2=CHCH2OH, AC1Q2AG8, AC1Q7BU7, WLN: Q2U1, 442445U_SUPELCO, 240532_ALDRICH, 453021_ALDRICH, 459798_ALDRICH, CHEMBL234926, Jsp000642, CTK0H5235, NSC6526, MolPort-001-779-684, 240532_SIAL, 453021_SIAL, NSC-6526, Tox21_200200, Tox21_303507, Allyl alcohol [UN1098] [Poison], AR-1C5554, LS-433, AKOS000118796, Allyl alcohol [UN1098] [Poison], 3W678R12M0, MCULE-2145308838, RP18243, UN 1098, NCGC00091428-01, NCGC00091428-02, NCGC00091428-03, NCGC00257474-01, NCGC00257754-01, AN-22470, BC201967, BP-21152, KB-47197, TX-012229, A0218, FT-0613372, LT01409768, 6025-EP0930075A1, 6025-EP2274983A1, 6025-EP2275401A1, 6025-EP2275411A2, 6025-EP2275417A2, 6025-EP2284157A1, 6025-EP2284162A2, 6025-EP2284163A2, 6025-EP2305684A1, 6025-EP2308861A1, 6025-EP2308877A1, 6025-EP2311815A1, 6025-EP2311823A1, 6025-EP2374783A1, 6025-EP2377841A1, 6025-EP2380568A1, A15097, C02001, InChI=1/C3H6O/c1-2-3-4/h2,4H,1,3H, 3B4-3749, I14-7436, ALLYL ALCOHOL (ALLYL ACETATE (591-87-7)), 62309-52-8

Removed Synonyms

CID7858, C006463, 108383-58-0, AA

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