Synthesis and chemical transformations of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic hydrazide

Article abstract of DOI:10.1023/A:1012391720685

A method for synthesis of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic hydrazide. Certain chemical properties of the product were studied. It was found that β-(3,5-di-ter-butyl-4-hydroxyphenyl)-propionic β-(3,5-di-tert-butl-4-hydroxyphenyl)hydrazide is highly susceptible to oxidation.

Full text of DOI:10.1023/A:1012391720685

Russian Journal of General Chemistry, Vol. 71, No. 6, 2001, pp. 931 933. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 6, 2001,
pp. 991 993.
Original Russian Text Copyright
2001 by Ismagilov, Moskva, Lebedev, Mosunova.
Synthesis and Chemical Transformations
of -(3,5-Di-tert-butyl-4-hydroxyphenyl)propionic Hydrazide
R. K. Ismagilov, V. V. Moskva, Yu. V. Lebedev, and L. Yu. Mosunova
Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk, Russia
Received January 10, 2000
Abstract A method for synthesis of -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic hydrazide. Certain
chemical properties of the product were studied. It was found that -(3,5-di-ter-butyl-4-hydroxyphenyl)-
propionic -(3,5-di-tert-butl-4-hydroxyphenyl)hydrazide is highly susceptible to oxidation.
-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionic
hydrazide (I) is an efficient antioxidant for polymeric
materials [1, 2]. The polyfunctional chemical nature of
this compound explains researcher’s interest in its
synthesis and chemical properties [3 8].
We found that hydrazide I can be prepared by
hydrazinolysis of the full ester of pentaerythrol and
-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid
which is a known commercial stabilizer Irganox 1010
[9].
t-Bu
Bu-t
CH2CH2C(O)NHNH2
HO
t-Bu
C[CH2OC(O)CH2CH2
OH]4 + 4NH2NH2
Bu-t
I
The reaction was performed under the action of
excess anhydrous hydrazide in a sealed ampule at
130 140 C.
the latter converted to the starting compound IV, as
evidenced by the yellow color, IR spectrum, and
melting point of the product. The low stability of
compound V is consistent with the characteristic
behavior of 4-aminophenols, and the presence of
two tert-butyl radicals ortho to the carbonyl group
additionally favors the quinoid structure [10].
We performed certain chemical transformations of
hydrazide I and revealed a high nucleophilic activity
of its hydrazine moiety.
Oxidation of hydrazide I with iodine in boiling
alcohol gave 1,2-bis[ -(3,5-di-tert-butyl-4-hydroxy-
phenylpropionyl)hydrazine (II) in a good yield even
with about half the stoichiometric amount of iodine.
With all iodine, compound II was difficult to isolate.
EXPERIMENTAL
The IR spectra were recorded on a Specord M-80
spectrometer for suspensions in mineral oil.
As the full ester of pentaerythrol and -(3,5-di-tert-
butyl-4-hydroxyphenyl)propionic acid we used com-
mercial stabilizer Irganox 1010 (as received) as a
colorless powder, mp 115 125 C {published data [9]:
mp 118 125 C [9]}. 3,5-Di-tert-butyl-4-hydroxy-
benzaldehyde and 2,6-di-tert-butylbenzoquinone were
synthesized by the procedures described in [11, 12],
3,5-Di-tert-butyl-4-hydroxybenzaldehyde and 2,6-
di-tert-butylbenzoquinone -(3,5-di-tert-butyl-4-hydr-
oxyphenyl)propionylhydrazones (III, IV) were ob-
tained by boiling alcoholic solutions of the reactants
with catalytic amounts of hydrochloric acid. Com-
pound IV was reduced with zinc in acetic acid to ob-
tain a colorless unstable product V. On attempted
recrystallization from ethanol and on handling in air respectively.
1070-3632/01/7106-0931$25.00 2001 MAIK Nauka/Interperiodica

932
ISMAGILOV et al.
Bu-t
OH
Bu-t
t-Bu
HO
[O]
CH2CH2C(O)NHNHC(O)CH2CH2
II
t-Bu
t-Bu
t-Bu
Bu-t
OH
Bu-t
HO
t-Bu
C(O)H
CH2CH2C(O)NHN=CH
HO
I
III
t-Bu
t-Bu
t-Bu
Bu-t
O
O
t-Bu
O
CH2CH2C(O)NHN=
HO
IV
t-Bu
Bu-t
[H]
O2
Bu-t
OH
Bu-t
t-Bu
CH2CH2C(O)NHNH
HO
t-Bu
V
-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionic
hydrazide (I). A mixture of 5.88 g of the full ester of
pentaerythrol and -(3,5-di-tert-butyl-4-hydroxy-
of hydrochloric acid were refluxed for 2 h. The sol-
vent was removed in a vacuum to obtain 1.02 g (81%)
of an almost colorless compound III, mp 242 243 C
(ethanol water, 5:1). IR spectrum, , cm : 3620
(OH), 3340 (NH), 1690 (C=O), 1614 (C=N). Found,
%: N 5.12, 5.22. C32H48N2O3. Calculated, %: N 5.52.
1
phenyl)propionic acid and 3 ml of anhydrous hydra-
zine were heated for 2 h at 130 140 C. On cooling, a
crystalline product precipitated and was filtered off
and washed on the filter with a cold aqueous-alcoholic
mixture to obtain 4.96 g (85%) of compound I, mp
153 155 C (alcohol water, 5:1) {published data [2]:
mp 157 8 C). Found, %: N 9.51, 9.45. C17H28N2O2.
Calculated, %: N 9.59.
2,6-Di-tert-butylbenzoquinone -(3,5-di-tert-
butyl-4-hydroxyphenyl)propionylhydrazone (IV).
Hydrochloric acid, 3 drops, was added to a boiling
solution of 1.46 g of hydrazide I and 1.10 g of 2,6-di-
tert-butylbenzoquinone in 30 ml of ethanol. Abundant
yellow crystals formed. The mixture was refluxed for
30 min to obtain 2.29 g (93%) of compound IV, mp
1,2-Bis[ -(3,5-di-tert-butyl-4-hydroxyphenyl)-
propionylhydrazine (II). A solution of 1.27 g of
iodine in 6 ml of ethanol was added dropwise to a
solution of 1.46 g of hydrazide I in 10 ml of ethanol
until the reaction mixture no longer decolorized and
nitrogen no longer evolved. Therewith, about half the
calculated volume of iodine had been consumed. The
mixture was allowed to stand at room temperature for
24 h. The alcohol was removed in a vacuum, and the
residue was recrystallized to obtain 0.68 g (49%) of
compound II, mp 223 5 C (alcohol water, 10:1)
{published data [3]: mp 225 227 C). Found, %: N
5.35, 5.70. C34H52N2O4. Calculated, %: N 5.08.
1
262 5 C (dioxane). IR spectrum, , cm : 3640 br
(OH), 3150, 3080 (NH), 1670 (C=O), 1610 (C=N).
Found, %: N 5.83, 6.10. C31H46N2O3. Calculated, %:
N 5.67.
-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionic
(3,6-di-tert-butyl-4-hydroxyphenyl)hydrazide (V).
Zinc powder, 1.95 g, was added with stirring at
70 80 C over the course of 1 h to a solution of
1.48 g of compound IV in 25 ml of acetic acid. The
reaction mixture quickly decolorized. After that it was
refluxed for 30 min and left to stand at room tempera-
ture for 16 h. Volatiles were distilled off in a vacuum,
and the residue was mixed with 50 ml of cold water.
Colorless crystals formed and were washed with water
and dried in a vacuum over P2O5 to obtain 1.33 g
(89%) of compound V, mp 78 85 C. IR spectrum, ,
3,5-Di-tert-butyl-4-hydroxybenzaldehyde -(3,5-
di-tert-butyl-4-hydroxyphenyl)propionylhydrazone
(III). A mixture of solutions of 0.73 g of hydrazide I
in 6 ml of ethanol and of 0.58 g of 3,5-di-tert-butyl-4-
hydroxybenzaldehyde in 18 ml ethanol, and 3 drops
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 6 2001

SYNTHESIS AND CHEMICAL TRANSFORMATIONS
933
1
cm : 3645 br (OH), 3270 (NH), 1680 (C=O). Found,
%: N 5.17, 5.40. C31H48N2O3. Calculated, %: N 5.65.
4. US Patent 4520146, Ref. Zh. Khim., 1986, 5N135P.
5. US Patent 4233209, Ref. Zh. Khim., 1981, 21N147P.
Recrystallization from ethanol was accompanied by
coloration of the solution and formation of light
yellow crystals, mp 261 263 C. The melting point
and IR spectrum were the same as those of compound
IV.
6. Glushkova, L.V., Iofis, L.I., Belova, S.Yu., Egi-
dis, F.M., Ushakova, R.S., and Efimov, A.A., USSR
Inventor’s Certificate no. 737394, Byull. Izobret.,
1980, no. 20.
7. Jpn. Patent 52-2881, Ref. Zh. Khim., 1978, 7N111P.
8. Glushkova, L.V., Belov, S.Yu., and Babayan, V.G.,
USSR Inventor’s Certificate no. 566836, Byull. Izo-
bret., 1977, no. 28.
9. Khimicheskie dobavki k polimeram: Spravochnik
(Chemical Polymer Additives), Moscow: Khimiya,
1973, p. 117.
REFERENCES
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