Brucine Butyl alcohol

CAS 64-17-5. Ethanol to which another liquid has been added to make it unfit to use as a beverage (chiefly for tax reasons). In the U.S., it may be either Completely Denatured (CDA) or Specially Denatured (SDA). At least 50 formulations are officially authorized for making denatured alcohol. They include the following denaturants SDA 40B must contain brucine, brucine sulfate, or quassin plus tert-butanol SDA 40A must contain sucrose octaacetate plus tert-butyl alcohol SDA 40B must contain Bi-trex [Macfarlan] and tert-butyl alcohol SDA40C must contain only rm-butyl alcohol. For exact formulas, consult 27CFR Part 21 and the Alcohol and Tobacco Tax Division of IRS, Washington D.C. Properties See ethanol. 

Classification Specially denatured alcohol Definition Ethyl alcohol (100 gal) denatured with t-butyl alcohol (1/8 gal) and 1.5 oz of either brucine alkaloid, brucine sulfate NF, quassin, or combination thereof... 

Acid Sulfates. Pasteur 6 and also Le Bel4 fractionated the cinchonine salts of the mixture of amyl hydrogen sulfates derived from fusel oil and effected a partial separation of the structurally isomeric alcohols. Krtiger 41 failed to resolve the alkaloid salts of the hydrogen sulfate of ethyl-n-propylcarbinol but Meth,42 after failures in other instances, finally effected a partial resolution of a-butyl hydrogen sulfate as the brucine salt. The method has proved to be impracticable for most alcohols 48 because the majority of alkyl hydrogen sulfates are unstable and inconvenient to handle. 

Working in this way it is possible to obtain fairly readily about 50-55% of the calculated amount of pure brucine d-s-butyl phthalate the yield depends on how long the fractionation is continued and how the mother liquors are handled (see below). When large quantities of alcohol are to be resolved it is convenient to unite the material from several runs at this stage. 

The d-s-butyl hydrogen phthalate and the corresponding pure alcohol may be obtained from the brucine salt by the general procedure previously described for the octyl hydrogen phthalates (p. 402). Pure d-s-butyl hydrogen phthalate has [a]D + 38.5° (c = 4, 95% ethanol). Alternatively, the process may be shortened considerably by treating the brucine salt directly with a small excess of dilute sodium hydroxide and distilling the alcohol with steam.138 The alcohol is extracted or is salted out with potassium carbonate, dried, and distilled b.p. 98°/750 mm. [ ]d + 10.83° (without solvent). 

The Worm of the alcohol can be obtained in 85-90% purity from the combined acetone and final methanol mother liquors by a rather laborious process of fractional crystallization aided by mechanical separation.137 140 Thus on long standing the acetone solution may deposit characteristic nodular aggregates of leaflets of nearly pure brucine 1-8-butyl phthalate, [a]n — 18.0° these are separated by filtration or decantation. The solution, upon concentration, may then yield more of the crude d-salt and then again the 1-salt. The method is tedious but gives rather good yields, especially when large quantities of material may be worked up in a leisurely fashion. 

The 1-alcohol also can be purified by fractionation of the cinchonidine salts of the hydrogen succinate.63 For this purpose the alcohol is recovered from the mother liquors of the brucine salt and converted to the hydrogen succinate by the general procedures previously outlined (p. 393). The oily succinate is oombined with one molecular proportion of cinchonidine in acetone. The very soluble cinchonidine Z-s-butyl succinate is purified by five or six crystallizations and then has m.p. 54-55° [a]D — 85° (c = 5, 95% ethanol). The alcohol is recovered from the pure salt in the usual way. 

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