INDUSTRIAL A N D ENGl'NEERING CHEMISTRY
1032
by a smooth curve and from this the following table was constructed. The temperature correction table was constructed by taking the specific gravities of the alcohol-water mixtures at 15'/4', 20'/4', and 25"/4" C. TABLE I-SPECIFIC GRAVITY OF SECONDARY BUTYLALCOHOL-WATER MIXTURES AT
Per cent by Weight
Per cent by Volume 0 0 1 1.24 2 2.47 3 3.70 4 4.92 6.14 7.36 8.58 8 9.79 9 11.00 12.21 11 lo 13.41 12 14.61 13 15.80 14 16.99 15 18.18 16 19.36 17 20.54 17.85 21.55 Immiscible 64.17 69.97 65 70.74 66 71.67 67 72.59 68 73.51 69 74.42 70 75.32 71 76.21 72 77.10
-!
Specific Gravity 0,9982 0.9968 0.9954 0.9940 0.9926 0.9912 0.9898 0 9884 0.9870 0.9856 0.9842 0.9828 0.9814 0.9800 0.9786 0.9772 0.9758 0.9744 0.9732 0.8792 0.8775 0.8756 0.8737 0.8716 0.8696 0.8675 0.8655 0.8634
20'14' c. Per cent Per cent b y Weight by Volurn 73 77.99 74 78.87 75 79.75 80.63 ' 76 81.50 77 82.36 78 83.22 79 84.07 80 81 84.92 82 85.76 83 86.60 84 87.44 85 88.27 86 89.09 87 89.90 88 90.71 89 91.51 92.31 90 91 93.10 92 93.89 93 94.67 95.45 94 95 96.22 96 96.99 97.76 97 98.52 98 99 99.27 100 100.00
.
Specific Gravity 0.8614 0.8594 0.8574 0.8554 0,8534 0.8514 0.8493 0.8473 0.8453, 0.8433 0.8413 0.8393 0.8373 0.8352 0.8332 0.8311 0,8291 0.8270 0.8249 0.8229 0.8208 0.8188 0.8167 0.8147 0.8127 0.8106 0.8085 0.8063
TABLE11-TEMPERATURECORRECTION (Change in specific gravity per degree centigrade) Strength Alcohol Per cent Correction 10 0.00035 16 0.00044 Immiscible 65 0.00077 70 0,00077 80 0.00077 90 0 00077 100 0,00077
Vol. 15, No. 10
At 20' C., 100 grams of secondary amyl alcohol dissolved 11.2 grams of water and 100 grams of water dissolved 4.2 grams of the alcohol. TABLE 111-SPECIFIC GRAVITYOF SECONDARY MIXTURESAT 20 O/4O C. Per cent Per cent by Weight b y Volume 89.8 91.67 90 91.76 91 92.59 92 93.43 93 94.26 94 95.09 95 95.92 96 96.75 97 97.57 98 98.38 99 99. I 9 100 100.00
AMYLALCOHOL-WATER Specific Gravity 0,8299 0.8295 0.8275 0.8255 0.8235 0.8214 0.8193 0.8172 0.8151 0.8130 0,8109 0.8088
SECONDARY AMYL CHLORIDE,2-CHLORPENTAh%-This compound was made in the same manner as isopropyl chloride and secondary butyl chloride. It boiled at 96' C.9 at 760 mm. It also had a sweet odor and was a good solvent for fats and waxes. SECONDARY HEXYLALCOHOL, 2-HEXANOL This alcohol was fractionated from a mixture of higher alcohols. A boiling point of 139.4' to 139.6' C.l0 was obtained. This is within 0.5 degree of the boiling points given in two of the three papers referred to. The alcohol had a specific gravity of 0.8159 a t 20'/4" C . ALCOHOLS HIGHER THAN HEXYL After the removal of all the alcohols up to and including secondary hexyl from the mixture obtained in the alcohol process, there remains an oily liquid which containE alcohols still higher than those already described. From this residual liquid have been isolated two alcohols with the characteristics of secondary heptyl (2-heptanol), and Eecondary octyl alcohol (2-octanol). The properties of these two alcohols have not yet been definitely determined and further work is in progress.
SECONDARY BUTYLACETATE-This compound was made by refluxing 1 mol of secondary butyl alcohol with 1 mol of acetic anhydride until the reaction was complete. After washing with water, neutralizing with sodium carbonate, HIGHER ALCOHOLS I N ORGANIC SYNTHESES and drying over calcium chloride, the ester distilled a t 112.2' C. and 760 mm. Norris and Green report a boiling point All the alcohols described here are now available in comof this ester at 111.5" to 112" C. a t 744 mm. The specific mercial quantities, with the exception of the hexyl, heptyl, gravity of the ester obtained by the writers was 0.8701 at and octyl. While they may be used as solvents, it is apparent 20'/4" C. to the organic chemist that the availability of these hitherto AZEOTROPI~ MIXTUREOF SECONDARY BUTYLALCOHOL very rare alcohols opens up an extensive field for their use AND SECONDARY BUTYLACETATE-The mixture boiled a t in organic syntheses. While only a few derivatives have been 99.60' C. at 758 mm. and consisted of 86.3 per cent of sec- mentioned in this paper, several others have been prepared. ondary butyl alcohol and 13.7 per cent of the ester by weight. It is probable that some of these alcohols or their derivatives Its specific gravity at 2Oo/4O C. was 0.8137. It possessed may find use in cosmetics and pharmaceutical preparations. a characteristic ester odor. 0 Przewalski, Chem. Zentv., 1909, 11, 793; Wagner and Saizew, Ann., SECONDARY BUTYL CHLORIDE,~-CHLORBUTANE-T~~S 179, 321 (1875). 10 Ponzio, Gaze. chim. ital., 31, I , 404 (1901); Sabatier and Senderens, compound was made in the same manner as isopropyl chloride rend., 137, 302 (1903); Zelinsky and Przewalski, Chem. Zenh., and the reaction proceeded very easily. The boiling point Compl. 1908, 11, 1855. of the chloride was 68' Ce17a t 760 mm. It had a pleasant odor and was a good solvent for fats and waxes. Registration at Milwaukee SECONDARY AMYLALCOHOL, 2-PENTANOL This was fractionqted from a mixture containing the amyl alcohol together with some water and other alcohols. I n this way a large fraction boiling between 118" and 120" C. was collected. This was refractionated until a constant boiling point of 119.2' C.8 at 760 mm. was attained. This alcohol had a specific gravity of 0.8088 at 20°/4'
c.
Estreicher, Ber., 83, 438 (1901); Norris and Green, A m . Chem. J., 16, 307 (1901). Bietohoubek, Be?., 9, 8 Wagner and Saizew, Ann., 179, 319 (1875); 925 (1876). 7
Arkansas Connecticut California Colorado Delaware Georgia Illinois Indiana Iowa Kansas Kentucky Louisiana Maryland Minnesota
4 8 5 4 5 3 179 83 27 3 2 6 6
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32 Guests TOTALREGISTRATION
34 29 1 17 1 1 6 20 1 59 2
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