Download (direct link):
anhydride of 6-nitro-i-ammo-2-naphthol-4-sulfonic acid).7 The present
procedure is more convenient than any of the earlier methods.
1 Miller, Ann. 208, 223 (1881); Huisinga, Rec. trav. chim. 27, 261
2 Levy and Stephen, J. Chem. Soc. 1931, 79.
3 Culhane and Woodward, Org. Syn. Coll. Vol. I, 399.
1 Bogert and Boroschek, J. Am. Chem. Soc. 23, 752 (1901).
s Cohen, Woodroffe and Anderson, J. Chem. Soc. 109, 232 (1916).
• Lawrance, J. Am. Chem. Soc. 42, 1872 (1920).
7 Ruggli, Knapp, Merz, and Zimmerman, Helv. Chim. Acta 12, 1043
>NH + HN03
¦I\ I I -|- H20
Submitted by E. H. Huntress, E. L. Shloss, Jr., and P.
Ehklich. Checked by W. W. Hartman and G. W. Sawdev.
To 1400 cc. of concentrated c.p. sulfuric acid (sp. gr. 1.84) in a 3-
I. beaker is added 240 cc. (5.7 moles) of c.p. fuming nitric add (sp. gr.
1.50), and the mixture is cooled to io°. The beaker is placed in an ice-
water bath, and 200 g. (1.36 moles) of com-merdal phthalimide is stirred
in rapidly (Note 1). The solution is allowed to stand at a temperature
not above 20° for five hours (Note 2).
The dear, pale yellow solution is poured slowly with vigorous
stirring onto 4500 g. of cracked ice (Note 3) and the crude nitration
product filtered through doth on a 20-cm. Buchner funnel with suction.
The paste is pressed as dry as possible and washed several times with
cold water (Note 4). Without being dried the moist cake is transferred to
a 5-I. flask and recrystallized from 31. of boiling 95 per cent alcohol
(Notes 5 and 6). The pale yellow 4-nitrophthalimide is filtered with
suction, washed with cold alcohol, and dried in the air. The product mdts
at 197-198° and weighs 157-173 g. (60-67 per cent of the theoretical
1. Care must be taken that the nitrating mixture is brought to
10-15° prior to the addition of the phthalimide. If a higher temperature
is used, the reaction mixture tends to heat up spon-
taneously, temperature control becomes difficult, and the yield is
2. Since the phthalimide dissolves readily, motor stirring is
unnecessary. Five hours' standing for the solution is sufficient, but if
convenient it may be left overnight and diluted the next day with
considerable saving of time. The solution may stand as long as twenty-
eight hours without deleterious effect, but leaving it for several days
decreases the yield.
3. This dilution may be done conveniently in a 3-gal. crock or by
dividing the material between two 4-I. beakers. Care must be exercised to
avoid local heating with resultant hydrolysis of the imide.
4. It is important to wash all nitric acid from the crude
5. If the crude material is dried at this point, the yield is 60-
70 per cent of the theoretical and the product melts at 180-185°. Such
drying is not recommended since the physical state of the product changes
to a hard form not readily soluble in the recrystallizing medium.
6. If the 4-nitrophthalimide is to be used for the preparation of
4-nitrophthalic acid, an entirely satisfactory product is obtained by
digesting with 1500 cc. of boiling alcohol, cooling, and filtering the
solid with suction. This process extracts the impurities and leaves a
yellowish white product which melts at the same point as the
recrystallized material (197-198°). In this way the use of the larger
volume of alcohol may be avoided.
3. Methods of Preparation
4-Nitrophthalimide has been prepared from 4-nitrophthalic acid,1 and
by nitrating phthalimide.2 The present procedure is a modification of the
method of Levy and Stephen.2
1 Seidel, Ber. 34, 4351 (1901); Seidel and Bittner, Monatsh. 23, 420
(1902); Bogert and Renshaw, J. Am. Chem. Soc. 30, 1137 (1908).
2 Levy and Stephen, J. Chem. Soc. 1931, 79.
PELARGONIC ACID (n-Nonoic Acid)
CH2(C02C2He)2 + C7Hi5Br -f C4H9ONa
-----> C7H15CH (CO2C2H5) 2 C4H9OH NaBr
C7Hi5CH(C02C2Hs)2 + 2H2O
^5 C7HioCH(C02H)2 + 2C2H5OH C7Hi6CH(C02H)2---------).
C7H15CH2CO2H + co2
Submitted by E. Emmet Reid and John R. Ruhoff.
Checked by W. W. Hartman and G. W. Sawdey.
A 5-I. three-necked flask is fitted with a liquid-sealed mechanical
stirrer, reflux condenser, dropping funnel, and thermometer. In the flask
is placed 2.5 1. of anhydrous butyl alcohol (Note 1), and 115 g. (5 gram
atoms) of clean, bright sodium cut in small pieces is added at one time.
Solution of the sodium may be facilitated by stirring, but heating is
unnecessary. After the sodium has dissolved completely, the solution is
allowed to cool to 70-80°, and then 800 g. (760 cc., 5 moles) of