DESTRUCTIVE DISTILLATION OF MANILA COPAL. 209 



THE LIQUID PRODUCTS GIVEN OFF DURING THE DISTILLATION OF MANILA 



COPAL. 



Water is evolved continually and smoothly below 330° and appears 

 to result from chemical decomposition. Powdered samples dried over 

 phosphorus pentoxide or in vacuo over sulphuric acid readily yield water 

 on heating. The aqueous solution' obtained from the distillation of 

 1,500 grams of resin weighed 46 grams. The substances soluble in water 

 which were found dissolved in the aqueous layer weighed about 9 grams, 

 leaving 37 grams for water, or 2.4 per cent of the weight of resin taken. 



The volatile acids detected in the aqueous layer were formic and acetic acids. 

 The aqueous solution was drawn off and the oil washed three times with water, 

 the washings being added to the original aqueous solution. The solution was 

 then diluted to 500 cubic centimeters. Formic acid was detected by the ferric 

 chloride test 21 and determined quantitatively in an aliquot part of the solution 

 by the mercuric chloride method." 2 From the amount found the total was cal- 

 culated to be 4.6 grams. The remainder of the acidity due to volatile acids, when 

 calculated as acetic acid, was equivalent to 3.1 grams. 



Formaldehyde was shown to be present by the well-known reaction with milk 

 and sulphuric acid containing a trace of ferric chloride. A previous distillation 

 had shown that all the formaldehyde, was condensed with the water, so that a 

 quantitative determination of it was made in an aliquot part of the solution by 

 the ammonia method as described by Williams. 2 " The amount found corresponded 

 to a total of 1.13 grams. 



The aqueous solution remaining after the acids and formaldehyde had been 

 determined amounted to 250 cubic centimeters. This was treated in the cold 

 with 1 cubic centimeter of phenylhydrazine dissolved in water and the mixture 

 allowed to stand in an ice chest over night. The light, crystalline precipitate 

 which separated was filtered, washed with a little cold alcohol, and dried over 

 sulphuric acid. The crude crystals weighed 0.22 gram and melted at 135°. 

 After recrystallization once from hot alcohol and once from benzene, the substance 

 melted at 143° to 144°. A combustion was also made on the body; 0.1515 gram 

 substance gave 0.3960 gram C0 2 and 0.0855 gram ELO. 





Calculated for 







C 15 H 16 N 4 . 



Found 





Per cent. 



per cent 



H 



6.34 



6.27 



C 



71.42 



71.28 



The crystalline substance is therefore the osazone of acetyl formaldehyde recently 

 described by Dennis. 24 



Furfuraldehyde was detected in the aqueous solution by its reaction with 

 metaxylidene acetate. 25 From the work of Aschan 2C on the distillation of wood 

 turpentine, diacetyl and some of its homologues were expected, but were not found. 



Small traces of other aldehydes are probably present, as an oil is formed in 



21 Smith, Journ. Am. Chem. Soc. (1907), 29, 1236. 



22 Merl. Ztschr. f. Untersuch. d. Nahrungs-u. Gennssmittel. (1908), 16, 385. 



-'Journ. Am. Chem. Soc. (1905), 27, 597. 



24 Am. Chem. Journ. (1907), 38, 583. 



26 Schiff. Ann. d. Chem. (Lieoig) (1887), 239, 380. 



"Ztschr. f. ang. Chem. (1907), 20, 1811. 



