New method of preparation of alkoxyacetic acids

Full text of DOI:10.1134/S0012500815050079

ISSN 0012ꢀ5008, Doklady Chemistry, 2015, Vol. 462, Part 1, pp. 127–129. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © G.Z. Raskil’dina, Yu.V. Legostaeva, L.R. Garifullina, R.M. Sultanova, G.Yu. Ishmuratov, S.S. Zlotskii, 2015, published in Doklady Akademii Nauk, 2015,
Vol. 462, No. 3, pp. 307–309.
CHEMISTRY
New Method of Preparation of Alkoxyacetic Acids
a
b
b
b
G. Z. Raskil’dina , Yu. V. Legostaeva , L. R. Garifullina , R. M. Sultanova ,
b
a
G. Yu. Ishmuratov , and S. S. Zlotskii
Presented by Academician A.A. Berlin November 5, 2014
Received November 5, 2014
DOI: 10.1134/S0012500815050079
Alkoxyacetic acids and their derivatives are known in the presence of alkali at –65
to be widely used in organic synthesis and as chemical –78
followed by the treatment of intermediate perꢀ
weed and pest killers [1, 2]. Their preparation is based oxide products with semicarbazide hydrochloride.
°C or in methanol at
°C
on the transformations of monochloroacetic acid
whose manufacture causes a large quantity of toxic
byproducts [3].
The ozonolysis of benzyl and phenyl allyl ethers Ia and
Ib in the presence of NaOH was found to lead in high
yield and selectivity to esters IIa and IIb, respectively.
In this work, we report the results of lowꢀtemperaꢀ Byproducts formed in small amounts are the correꢀ
ture ozonolysis of benzyl and phenyl allyl ethers for sponding alkoxyacetic aldehydes IIIa and IIIb. At the
the preparation of methyl benzylꢀ and phenoxyaceꢀ
tates.
same time, the treatment of primary ozonation prodꢀ
ucts (peroxides) with semicarbazide hydrochloride
The esters of arylacetic acids were prepared by two gives a mixture of esters IIa and IIb and acetals IVa
methods: in the methanol–methylene chloride system and IVb (Table 1).
O , NaOH–CH Cl –MeOH, –65°C
3
2
2
ROCH CO Me + ROCH CHO
2
2
2
IIa
,
IIb
IIIa,IIIb
1
. O , MeOH, –78°C
3
ROCH CH=CH
2
2
2
. NH C(O)NHNH · HCl
2
2
Ia
,Ib
ROCH CO Me + ROCH CH(OMe)
2
2
2
2
IIa,IIb
IVa,IVb
[
R = C H CH (Ia
,
IIa
,
IIIa),
6
5
2
R = C H (Ib, IIb, IIIb)]
6
5
As was shown previously [4], the lowꢀtemperature venient method for the synthesis of the corresponding
ozonolysis of terminal linear olefins leads to acids in alkoxycarbonyl compounds.
yields larger than 90%. Nonetheless, the ozonolysis of
allyloxy derivatives was not reported previously,
although the products of these reactions may be
EXPERIMENTAL
Equipment of the “Chemistry” Shared Facility
Center, Institute of Organic Chemistry, Ufa Research
Center, Russian Academy of Sciences was used in the
extremely promising for further chemical transformaꢀ
tions and synthesis on their basis of compounds showꢀ
ing biological activity.
1
13
work. H and C NMR spectra were recorded on a
Thus, the obtained results allows one to consider
the lowꢀtemperature ozonolysis of allyl ethers a conꢀ
1
Bruker AMꢀ300 spectrometer operating at 300.13 ( H)
13
and 75.47 MHz ( C) using Me Si as an internal referꢀ
4
ence. IR spectra were recorded on a Shimadzu IR
Prestigeꢀ21 spectrometer in thin film. Mass spectra
were obtained on a Thermo Finnigan MAT 95 XP
highꢀresolution chromatograph–mass spectrometer
at ionizing voltage 70 eV (ionization chamber temperꢀ
ature 250°C, direct injection at 50–270°C, heating
rate 10 K/min). GLC study was performed on a
a
Ufa State Oil Technical University,
ul. Kosmonavtov 1, Ufa, 450062 Russia
b
Institute of Organic Chemistry, Ufa Research Center,
Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, 450054 Russia
eꢀmail: graskildina444@mail.ru
127

128
RASKIL’DINA et al.
Table 1. The result of ozonolysis of allyl ethers Ia and Ib
Compound
Reaction conditions
Product (yield, %)
Iа
O /2.5 М NaOH–МеОН–CH Cl ,
3
–
65
°
C
IIa (60%) : IIIa (32%)
IIa (42%) : IVа (56%)
2
2
1
. O /МеОН, –78
°
C
3
. NH C(O)NHNH · HCl
2
2 2
Ib
O /2.5М NaOH–МеОН–CH Cl , –65
3
°
C
IIb (80%) : IIIb (12%)
IIb (24%) : IVb (63%)
2
2
1
. O /МеОН,
–
. NH C(O)NHNH · HCl
78°C
3
2
2
2
–
1
Table 2. Major signals (CDCl , δ, ppm) and absorption bands (ν, cm ) in NMR and IR spectra of ozonolysis products of
3
ethers Ia and Ib
Compound
13С, ppm
1Н, ppm
IR, cm–1 Reference
IIa
170.38; 137.40; 128.03; 127.94; 3.70 (s); 4.15(s); 4.65 (s); 7.30–7.60 (m)
1739; 1360
1739; 1377
1754
[5]
[6]
1
27.66; 73.01; 71.84; 51.28
169.08; 157.43; 129.09; 121.36; 3.82 (s); 4.64 (s); 6.95 (m); 7.20–7.40 (m)
14.23; 65.25; 51.73
199.96; 137.49; 128.08; 127.56; 4.15 (s); 4.65 (s); 7.30–7.40 (m); 10.0 (s)
27.38; 72.76; 72.04
198.82; 157.43; 128.34; 121.09; 4.51 (s); 6.99 (m); 7.05–7.30 (m); 9.80 (s)
14.23; 69.85
137.64; 128.09; 127.72; 127.54; 3.38 (s); 3.53 (d,
02.41; 73.10; 69.27; 53.46 (t, = 10.4, 5.1 Hz); 4.59 (s); 7.20–7.40 (m)
158.11; 129.10; 120.94; 114.23; 3.47 (s); 4.02 (d, = 5.2 Hz); 4.73
01.78; 67.05; 53.63 (t, = 10.4, 5.2 Hz); 6.95 (m); 7.20–7.40 (m)
IIb
1
IIIа
IIIb
IVа
IVb
[7]
1
1761
[8]
1
J
= 5.3 Hz); 4.55
1114
[9]
1
J
J
1246
This work
1
J
Chromꢀ5 chromatograph (column 1.2 m long), SEꢀ30 tography (SiО2, PE, PE : MTBE = 5 : 1, 4 : 1) gave
(
(
5%) stationary phase on Chromaton NꢀAWꢀDMCS 1.07 g (60%) of ester IIa and 0.47 g (32%) of aldeꢀ
0.16–0.20 mm), working temperature 50–300°C,
hyde IIIа. After evaporation, ether Ib produced 1.61 g
of a mixture of compound IIb and IIIb in 88 : 12 ratio
(according to GLC and NMR), column chromatograꢀ
phy (SiО2, PE, PE : MTBE = 5 : 1, 4 : 1) resulted in
helium as a carrier gas. TLC monitoring was perꢀ
formed using Sorbfil SiO2 (Russia), hexane–MTBE
(
methyl tertꢀbutyl ether) as eluent, anisic aldehyde
solution in sulfuric acid was used for visualization.
Column chromatography was carried out with a Lanꢀ
caster SiO2 (70–230) (Great Britain). Ozonator perꢀ
formance was 40 mmol О3/h.
1
.34 g (80%) of ester IIb and 0.16 g (12%) of aldeꢀ
hyde IIIb
.
(2) An ozone–oxygen mixture was bubbled
through a solution of 10.00 mmol of ethers Ia or Ib in
5
0 mL of MeOH at –78
The reaction mixture was purged with argon, 3.88 g
35.00 mmol) of NH C(O)NHNH2 HCl. HCl was
°C until blue color appeared.
Ozonation of Allyl Aryl Ethers Ia and Ib
(General Procedure)
(
⋅
2
added at –50°C. The mixture was stirred at ambient
temperature for 24 h. The reaction mixture was evapꢀ
(
1) An ozone–oxygen mixture was bubbled
through a solution of 10.00 mmol of ethers Ia or Ib in
a mixture of 20 mL of 2.5 M NaOH in MeOH and
orated, the residue was dissolved in 100 mL of CHCl3
,
washed with Н О (to pH ), and dried with Na SO4.
≈
7
8
0 mL of CH Cl at –65
°
C
until blue color appeared.
The reaction mixture was purged with argon, MTBE
70 mL) and water (30 mL) were added, stirred for 1 h
2
2
2
2
After evaporation, ether Iа produced 1.86 g of a mixꢀ
ture of compounds IIа and IVа in 40 : 60 ratio
(
(
according to GLC and NMR), column chromatograꢀ
at ambient temperature. The organic layer was sepaꢀ
rated, the aqueous layer was extracted with MTBE.
phy (SiО2, PE, PE : MTBE = 5 : 1, 4 : 1) afforded
The combined organic extracts were dried with 0.74 g (42%) of ester IIa and 1.09 g (56%) of acetal IVа
.
Na SO4. After evaporation, ether Iа produced 1.66 g After evaporation, ether Ib produced 1.64 g of a mixꢀ
2
of mixture of compounds IIа and IIIа in 72 : 28 ratio ture of compounds IIb and IVb in 25 : 75 ratio (accordꢀ
(
according to GLC and NMR data), column chromaꢀ ing to GLC and NMR data), column chromatography
DOKLADY CHEMISTRY Vol. 462
Part 1
2015

NEW METHOD OF PREPARATION OF ALKOXYACETIC ACIDS
129
(
SiО2, PE, PE : MTBE = 5 : 1, 4 : 1) gave 0.40 g (24%)
2. Ikrina, M.A. and Kolbin, A.M., Regulyatory rosta i razꢀ
vitiya rastenii (Plant Growth and Development Regulaꢀ
tors), Moscow: Khimiya, 2005, vol. 2.
of ester IIb and 1.15 g (63%) of acetal IVb
.
IR and 13C NMR spectra were the most informaꢀ
tive methods to establish the structure of the obtained
3
. Kuznetsov, V.M., Khimikoꢀtekhnologicheskie osnovy
razrabotki i sovershenstvovaniya gerbitsidnykh preparaꢀ
tivnykh form (Chemical and Technological Foundaꢀ
tions of Development and Improvement of Herbiꢀ
cides), Moscow: Khimiya, 2006.
compounds (IIa
chromatography (Table 2). The obtained spectral and
physicochemical characteristics of esters IIa IIb and
aldehydes IIIa IIIb agree well with the literature data
5–9].
, IIb–IVa, IVb) isolated by column
,
4
. Ishmuratov, G.Yu., Legostavea, Yu.V., Garifullina, L.R.,
Botsman, L.P., Muslukhov, R.R., Ishmuratova, N.M.,
and Tolstikov, G.A., Zh. Org. Chem., 2014, vol. 50,
no. 7, pp. 948–953.
,
[
5
. DesageꢀEl Murr, M., Nowaczyk, S., Le Gall, T., and
Mioskowski, C., Eur. J. Org. Chem., 2006, pp. 1489–
ACKNOWLEDGMENTS
This work was supported by the Ministry of Educaꢀ
tion and Science of the Russian Federation (in the
framework of the basic part of State Assignment,
project no. 1180).
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Translated by I. Kudryavtsev
DOKLADY CHEMISTRY Vol. 462
Part 1
2015