Here's another angle on the Eugenol swing donated by the Wizard.
This is a bit of cool cat chemistry if I do say so. May you notice pretty much all of the chems can be easily obtained. Hydriodic acid can be made, check Rhod's site plus old message board for some kick ass OTC methods.
Also the lustful lack of any serious work up until the very end (nice huh).
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SYNTHESIS OF ISOSAFROLE FROM EUGENOL
Eugenol, M.W = 164.20 gr/mol; density @ 20 degC = 1.067 gr/cm3
PROCEDURE
Obtain pure eugenol from clove oil which has a boiling point of 255 degC at 760mmHg. With vacuum distillation the boiling point is 123 degC at 12-13mmHg, and 110-111 degC at 5mmHg.
In a 500 ml round bottom flask, cool in ice to 0-2 degC, 100 mls of 57% HI SOLUTION (HYDRIODIC ACID, M.W = 127.93) = 99 grams of HI = 0.774 moles of HI. (B.p 125.5-126.5 deg C/760mm Hg ; Density 1.70 gr/ml ; 55-57% w/w HI is 0.936 to 0.99 grams of HI per ml).
Add 32.8 grams, ~ 35.0 mls (0.2 moles) of Eugenol to the 100 mls of 57% HI, while the flask is still in the ice. Swirl gently, stopper, place back in the ice and insulate the container holding the ice and place in the fridge compartment for a period of 12 hours. Every 2 hours swirl gently again.
After the 12 hours period, add 1.0 grams of hydroquinone (a polyerisation inhibitor)[NOTE1] and swirl, stopper, remove from the ice to allow it to obtain room temperature. Attach a long reflux condenser and reflux for 2½ hours between 120-130 degC, perfect temperature is 128 degC. After refluxing for the time period allow to cool to room temperature. Dilute with 1 liter of ice cold distilled water and solvent extract with 3 x 100 mls of diethyl ether or petroleum ether and wash once with minimum distilled water 50 mls. Distill the solvent off and the methyl iodide, CH3I, Bp 42.4 degC.[NOTE2] Crystals will form, however some oily residue may or will persist.
In a 1 liter round bottom, reflux reaction flask, add the following.
A volume of 300 mls of ethanol is added to the crystal residue of 3,4-dihydroxy-1-propenylbenzene, 3,4(HO-)C6H3-CH=CH-CH3 and the 3,4-dihydroxy-1-(1-iodo)phenylpropane, 3,4(HO-)C6H3-CHI-CH2-CH3 and hydroquinone. Another 1.0 grams of hydroquinone is added and mixed together.[NOTE1] A solution of 22.44 grams (0.4 moles) of potassium hydroxide, KOH, in 200 mls of 50/50 distilled water/ethanol is made. The potassium hydroxide solution is then added with stirring to the above 3,4-dihydroxy-1-propenylbenzene, 3,4(HO-)C6H3-CH=CH-CH3 and the 3,4-dihydroxy-1-(1-iodo)phenylpropane, 3,4(HO-)C6H3-CHI-CH2-CH3 residue-ethanol solution. The combined mixture is then gently refluxed with stirring on a hot-water bath or steam bath for 1 hour.[NOTE3]
Add a solution of 53.58 grams (0.2 moles) of diiodomethane, ICH2I (M.W = 267.9 gr/mol), in 150 mls of ethanol and continue refluxing for 2 hours.[NOTE4] Strip all ethanol solvent under vacuum distillation, and add 400 mls of distilled water. Solvent extract with ether 2 x 100 mls. Keep the water layer as it contains unreacted 3,4-dipotassiumoxy-1-propenylbenzene, 3,4(KO-)C6H3-CH=CH-CH3.[NOTE5] The ether/isosafrole solution mixture is washed once with distilled water, and under careful vacuum distillation the isosafrole is distilled at 179.5 degC at 100 mmHg or 135.6 degC at 20 mmHg.
[NOTE6]
[NOTE1] hydroquinone oxidizes in air and in solutions exposed to air rapidly. Keep the flask well closed and protected from light.
[NOTE2] the solution contains a mixture of methyl iodide, CH3I ;
3,4-dihydroxy-1-propenylbenzene, 3,4(HO-)C6H3-CH=CH-CH3 and the
3,4-dihydroxy-1-(1-iodo)phenylpropane, 3,4(HO-)C6H3-CHI-CH2-CH3 and hydroquinone.
[NOTE3] at this stage the 3,4-dihydroxy-1-(1-iodo)phenylpropane, 3,4(HO-)C6H3-CHI-CH2-CH3 will be converted to 3,4-dihydroxy-1-propenylbenzene, 3,4(HO-)C6H3-CH=CH-CH3 and 3,4-dipotassiumoxy-1-propenylbenzene, 3,4(KO-)C6H3-CH=CH-CH3.
[NOTE4] methanol can be used in all cases, instead of ethanol. At this stage the main product is isosafrole. Dibromomethane, BrCH2Br can also be used.
[NOTE5] add dilute HCl until slightly acidic and solvent extract to obtain the 3,4-dihydroxy-1-propenylbenzene, 3,4(HO-)C6H3-CH=CH-CH3.
[NOTE6] propenylbenzene, C6H5-CH=CH-CH3, are susceptible to polyerisation, influenced by acids. Both isosafrole and safrole can be steam distilled.
TESTS
3,4-dihydroxy-1-propenylbenzene; 3,4(HO-)C6H3-CH=CH-CH3, in an alcoholic solution develops a deep green-blue colour on treatment with 2 % alcoholic ferric chloride solution.
Eugenol : In a cold saturated aqueous solution of ferric chloride, gives a turbid grayish-yellow colour. With 2 % alcoholic ferric chloride solution, a blue colour, which fades to grey-yellow colour in 15 minutes. An intense purple-black colour develops when reacted with 48 % hydrobromic acid at 2 degC.
Safrole and Isosafrole : an intense red to scarlet red colour develops when dissolved in concentrated sulphuric acid.