1790 NOTES VOL.

24

sodium salt NS~S then obtained by precipitation A New Technique i n Preparing 2,4-Dinitro-
with alkali. phenylhydrazones. 111. Two Examples of
For the preparation of sodium perbutyrate, Hitherto Unobtainable Simple Derivatives :
perbutyric acid was prepared from butyric acid
and 90% hydrogen peroxide6 and the salt was pre- Diacetone Alcohol and Methyl Vinyl Ketone
pared as in the case of sodium peracetate.
The salts so obtained were found to contain one HENRYJ. SHINE
atom of active oxygen which could be analyzed
Received M a y 4,1959
iodometrically .
In the analysis of the active oxygen content, it
Recently' the convenient use of diglyme (di-
was found that on treating with acidified potas-
methylether of diethylene glycol) solutions of 2,4-
sium iodide solution, in neither case was liberation
dinitrophenylhydrazine for preparing 2,4-dinitro-
of iodine instantaneous; thus in the case of sodium
phenylhydrazones was described. It was suggested
peracetate, iodine liberation was complete only
a t that time that the new technique might be
after 30 min. a t room temperature and in the ab-
usable for preparing 2,4-dinitrophenylhydrazoiies
sence of light while sodium perbutyrate required
of sensitive compounds. This suggestion has now
75 mill. under the same conditions.
been found to be valid, and in view of the interest
Sodium peracetate decomposes a t 55' leaving a that has been shown in the earlier publication'"
residue which contains no active oxygen. On stand- we are prompted to illustrate the further useful-
ing at room temperature for 3 days in a moist ness of the new technique with two examples.
atmosphere, a sample of sodium peracetate lost all We have been able t o prepare for the first time the
of its active oxygen content and when a sample true derivative of diacetone alcohol and the deriva-
mas stored in vacuo a t room temperature, the tive of methyl vinyl ketone.
active oxygen content had decreased by 66% after Diacetone alcohol. The 2,4-dinitrophenylhydra-
24 hr. and by 93% after 7 days. zone, melting point 203", that is everywhere listed
as the derivative of diacetone alcohol, is really the
EXPERIMENTAL derivative of mesityl oxide. The conventional
Note: The use of a. safety shield is recommended in carry-
methods of preparation'" of the 2,i-dinitrophenyl-
ing out, the following reactions. hydrazone cause the acid-catalyzed dehydration
Sodium Peracetnte. A saturated solution of sodium car- of the keto1 to mesityl oxide.
bonate was added with constant stirring to "Becco" per- If a solution of diacetone alcohol in a diglyme
acetic acid3(50 ml.) a t 8-10' until a pH of 8.0 was obtained solution of 2,4-dinitrophenylhydrazineis acidified
as indicated by a pH meter. The resulting mixture was with acetic acid, however, the orange derivative,
extracted with ether (5 X 50 ml.) and the extracts dried
over magnesium sulfate. Analysis of an aliquot showed that I, formed is that of diacetone alcohol and has a
the combined extracts contained 5.94 g., of peracetic acid. melting point of 157-159". If, instead of acetic
To the ethereal solution was added a t O", sodium hydroxide acid, hydrochloric acid is used, or if I is dissolved
(3.13 g.) dissolved in water (5 ml.) and 95% ethanol (70 ml.), in ethanol and acidified with hydrochloric acid,
causing an immediate precipitate. It was allowed to stand
for 15 min. The salt was separated by filtration, washed with the dark red derivative of mesityl oxide is obtained.
ethanol, then with ether and dried i n vacuo a t room tem- Methyl Vinyl Ketone. The only report of the re-
perature. action of 2,4-dinitrophenylhydrazine with this
The sodium peracetate was analyzed for active oxygen simple ketone is that of I. N. Kazarov and co-
iodometrically and for sodium gravimetrically as the sul- workers.2 These authors report a compound with
fate.7 Found: active 0, 16.42; Xa, 24.31% CH3C03Na re-
quires: active 0, 16.32; Na, 23.467,.
a melting point of 217", the carbon analysis of
Sodium perbutyrate. To an aqueous solution of perbutyric which was 2.3% low for the expected derivative.
acid a t 0" was added a saturated solution of sodium car- They do not appear to have accepted their deriva-
bonate until a pH of 8.0 was obtained as indicated by a pH tive as authentic. We have prepared the authentic
meter. To the pure peracid (2.7 gm.) in ethyl acetate was derivative of this ketone; it has a melting point of
added a t O", sodium hydroxide (1.05 gm.) dissolved in 95y0
alcohol. On standing a t 0' for 2 hr., sodium perbutyrate 139.5-140.5'. It was prepared first in these labora-
precipitated. It was filtered off, washed and dried in vacuo tories by the diglyme technique using hydrochloric
a t room temperature and analyzed for active oxygen iodo- acid for catalysis. If attempts were made to pre-
metrically. Found: active 0, 12.80y0 C4H?O3Narequires: pare this derivative by conventional methods,
active 0, 12.687,. using ethanol as solvent, the derivative was not
SHAWINIGAN RESEARCH LABORATORIES obtained, but one of the products obtained was the
SHAWINIGAN, QUEBEC,CANADA. derivative of 4-ethoxybutanone-2, melting point
92-93". If methanol were used a b a solvent, the
derivative of 4-methoxybutanone-2 was obtained,
(6) J. D'$ns and W. Frey, Ber., 45, 1845 (1912).
(7) A similar preparation of several grams of dry sodium (1) (a) H. J. Shine, J. Org. Chern., 24, 252 (1950); (b)
peracetate exploded violently, while sitting in a flask at H. J. Shine, J . Chem. Ed., 3 6 , 5 7 5 (1959).
room temperature. Caution is recommended in handling (2) I. N. Nasarov, L. A. Kazitsyna and I. I. Zaretskaj-a,
this compound. Zhur. Obshchei Khim., 27, 606 (1957).
NOVEMBER 1959 NOTES 1791

melting point 88-90'. Thus, it is apparent that the orange crystals, m.p. 92-3"; (literature: 89-90°4; 10O-lo5);
solvent used is important in determining the Am,, (CHC13): 362 mmp; Am,, (ligroin): 344 mmp; emax
(CHCls): 21, 570.
final products of reaction. We found, indeed, that Anal. Calcd. for C12H16N406:C, 48.65; H, 5.44; N,18.90.
the derivative of methyl vinyl ketone can also be Founda: C, 48.38; H, 5.30; N, 18.80.
obtained if tetrahydrofuran and tert-butyl alcohol 4-Methoxybutanone-2 2,Q-dinitrophenylhydruzone.The pro-
are used as solvents. In the latter case the deriva- cedure described above was used. Again, the solution pre-
cipitated a yellow orange solid, m.p. 208-210". Treatment
tive precipitates quickly and addition of the of the filtrate as above gave a yellow product, m.p. 97-100".
alcohol to the double bond does not take place. Several crystallizations from methanol gave blunt, dark
I n the former case, as in the diglyme solutions, J ellow needles, m.p. 88-90'; (literature5: S5-S6') Amax
the solvent, cannot react with the ketone or its (CHClp): 364 mmp; A,, (ligroin): 345 mmp; Emax (CHCla):
derivative. Our work with methyl vinyl ketone 21,520.
Anal. Calcd. for CllH&405: C, 46.81; H, 5.00; K j 19.84.
has led us i,o begin investigating in some detail the Found:4 C, 46.64; H, 4.89; Tu', 19.70.
products that are formed from the derivative of Ultraviolet spectra. A Beckman DK-2 instrument was
methyl vinyl ketone and of the alkoxybutanones in used. The ligroin used was Eastman Kodak's permanganate
acidic solutions. We shall report on this investiga- purified, b.p. 66-75". Because of the unexpectedly high
values of Amex of the diacetone alcohol derivative the corre-
tion a t a later date. It is quite apparent to us a t this sponding A,, of mesityl oxide were determined. They were
stage that attempts to make the derivatives of 383 mmp (CHC13) and 365 mmp (ligroin). The Am,, (iso-
these ketones by conventional methods very often octane) given2 for mesityl oxide was 364 mmp; while the
lead t o products that are not the expected deriva- A,, (isooctane) calculated2 for methyl vinyl ketone was
tives. 354 mmp.
TECHNOLOGICAL
TEXAS COLLEGE
EXPERIXENTAL TEXAS
LUBBOCK,
Diacetone alcohol 2,4-di?~ztrophenylhydrazone.One milli- (4) K . A. Milas, et al., J. Am. Chem. SOC.,70, 1597
liter of vacuum distilled diacetone alcohol was added to 20 (1948).
ml. of a diglyme solution containing 0.8 g. of 2,4-dinitro- (5) I. N. Nazarov, S. G. Matsoyan, and V. N.Zhama-
phenylhydraiine. To this mas added 3 nil. of acetic acid. gortsyan, Zhur. Obshchei Khim., 23, 1986 (1053).
The solution was allon ed to stand a t room temperature for (6) Geller Laboratories, Bardonia, N. Y.
2 hr. and WBS then placed in the refrigerator for 24 hr.
R a t e r was added to the cold solution until it became
turbid and the solution was again refrigerated until crys-
tallization occurred. The orange product, m.p. 137-147', Isomeric Bis(trimethylsily1)xylylenes
was recrystallized twice from ethanol and then tuice from
benzene, giving glistening orange plates, m.p. 157-9";
Am,, (CHCl,): 370 mmp; Amax (ligroin): 351 mmp; enlax GLEN?;R. WILSONA K D GRETCHEN
M. HUTZEL
(CHCla): 23,250.
Anal. Calcd. for ClpHlsNaOa: C, 48.65; H, 5.44; N, 18.9. Received M a y 11, 1959
Founda: C, 48.59; H, 5.36; K,18.69.
A small amount of the derivative was dissolved in ethanol
and acidified s i t h concentrated hydrochloric acid. A red I n a recent article' we described the synthesis of
precipitate formed overnight. Crystallization from diglyme m- and p-bis(trimethylsily1)xylylenes from cou-
gave m.p. 203". The melting point of the derivative of pling the respective xylylene dihalides and trimethyl-
mesityl oxide was 203". chlorosilane with magnesium in tetrahydrofuran.
Methyl vinyl ketone 2,4-dinitrophenylhydrazone. To a We wish to report the successful preparation of the
solution of 0.2 ml. of methyl vinyl ketone (Matheson,
Coleman and Bell, technical, used without purification) in remaining isomer, bis(trimethylsily1)-o-xylylene, to
10 ml. of the diglyme reagent solution was added 3 drops of complete the series and an additional dichloro-derir-
concentrated hydrochloric acid. The solution stood over- ative of the p-isomer, bis(dimethylchlorosily1)-p-
night a t room temperature. Addition of water gave an orange xylylene. The physical properties of the three iso-
product, m.p 137-8". Several recrystallizations from etha-
nol gave loiig orange needles, m.p. 139.5-140.5"; Amax meric compounds are summarized in Table I and
(CHC1,): 3i0 mnip; A,", (ligroin): 352 mmp; emax (CHCl,): the infrared absorption spectrum of the o-isomer is
24,670. reproduced in Fig. 1.
Anal. Calcd. for CloHloN,04: C, 48.00; H, 4.03; N, 22.38.
Found3: C, 48.07; H, 4.24; X, 22.62. loor
&-Ethoxybutanone-2 2,4-dinztrophenylhydrazone. This was
obtained first when attempting to make the 217" product
from methyl vinyl ketone by the described2 procedure. A
solution n a s made by boiling 1 g. of 2,4-dinitrophenylhy-
&azine in a mixture of 45 ml. of ethanol, 5 ml. of dioxane
(freshly purified) and 1 ml. of concentrated hydrochloric
acid. The cool solution vias filtered from solid that had crys-
tallized and 4 as added to a solution of 1 ml. of methyl vinyl
ketone in 2 inl. of ethanol. A small amount of an orange L - I __ I 1 --L-
3 4 5 6 7 E Q c ' I3 4 3
yellow solid precipitated, m.p. 202-8". Dilution of the fil-
h A \ ELENG-H (h" C R C N S l
trate with water gave a flocculent yellow precipitate, m.p.
84-87", Several cry3tallizations from ethanol gave light Fig. 1. Bis( trimethylsily1)-o-xylylene
(3) Schwarzkopf Microanalytical Laboratories, Wood- ( 1 ) G. R. Wilson, G. M. Hutzel, and A. G. Smith, J .
side, S Y. Org. Chem., 24,381 (1959).