New Synthesis of Known Herbicides Based on Aryloxyalkanoic Acids

Article abstract of DOI:10.1134/S1070428018090075

A new version has been proposed for the synthesis of analogs of the known herbicides mecoprop (MCPP) and dichlorprop (2,4-DP) by ozonolysis of chloro derivatives of (pent-3-en-2-yloxy)benzene.

Full text of DOI:10.1134/S1070428018090075

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2018, Vol. 54, No. 9, pp. 1313–1318. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © L.R. Latypova, Sh.M. Salikhov, Yu.V. Legostaeva, R.N. Khusnitdinov, G.Yu. Ishmuratov, I.B. Abdrakhmanov, 2018, published in
Zhurnal Organicheskoi Khimii, 2018, Vol. 54, No. 9, pp. 1302–1306.
New Synthesis of Known Herbicides
Based on Aryloxyalkanoic Acids
L. R. Latypovaa, Sh. M. Salikhova,* Yu. V. Legostaevaa, R. N. Khusnitdinova,
G. Yu. Ishmuratova, and I. B. Abdrakhmanova
a Institute of Chemistry, Ufa Federal Research Center, Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, 450054 Bashkortostan, Russia
*e-mail: Salikhov@anrb.ru
Received April 9, 2018
Abstract—A new version has been proposed for the synthesis of analogs of the known herbicides mecoprop
(MCPP) and dichlorprop (2,4-DP) by ozonolysis of chloro derivatives of (pent-3-en-2-yloxy)benzene.
DOI: 10.1134/S1070428018090075
Selective herbicides based on aryloxyalkanoic acids
have been thoroughly studied, and they have been
widely used for plant protection, especially for the
protection of crops [1–4]. However, their preparation is
fairly difficult due to multistep procedures of synthesis
and low accessibility of required components [5, 6].
This prompted us to study the synthesis of chloro
derivatives of (pent-3-en-2-yloxy)benzene and their
transformations under ozonolysis conditions with the
goal of obtaining the known herbicides mecoprop
(MCPP) and dichlorprop (2,4-DP), as well as their
analogs [7].
o-(pent-3-en-2-yl)chlorophenols 9‒11 were formed
(Scheme 1).
Ozonolysis of olefins provides efficient highly
selective introduction of oxygen-containing function-
alities into organic molecules [10]; intermediate ozon-
olysis products (peroxides) are commonly decomposed
by treatment with H2O2–SeO2 [11], NH2C(O)NHNH2·
HCl [12], Me2S [13], or NaBH4 [11].
The ozonolysis of 5‒8 was carried out in the system
methylene chloride–acetic acid at 0°C with subsequent
oxidation with hydrogen peroxide in the presence of
a catalytic amount of selenium dioxide or treatment of
peroxides with semicarbazide hydrochloride. We thus
obtained 2-(chloroaryloxy)propanoic acids 12‒15 in
39–86% yield (Scheme 2). When the peroxide
ozonolysis products of compounds 5‒8 were reduced
with NaBH4 in methanol at 0°C, we isolated from the
reaction mixtures alcohols 16‒19, while the reduction
with dimethyl sulfide afforded aldehydes 20‒23
(Scheme 2).
Chlorinated (pent-3-en-2-yloxy)benzenes 5–8 were
synthesized by heating 4-chloropent-2-ene with the
corresponding chlorophenol in the presence of
0.1 equiv of tetrabutylammonium bromide and 2 equiv
of potassium carbonate in boiling acetone [8] or
3 equiv of potassium hydroxide in propan-2-ol [9]. The
reaction in the presence of KOH was accompanied by
Claisen rearrangement, so that mixtures of 5‒8 and
Scheme 1.
Cl
Cl
Me
Me
2'
2
5
4'
Me
Me
Me
R
R
R
K2CO3, Bu4NBr
Me2CO, 56°C
O
OH
OH
1'
3
4
KOH, i-PrOH
1
6
3'
5–8
+
Me5'
Me
Me
5–8
1–4
9–11
1, 5, R = 2,4,6-Cl3; 2, 6, 9, R = 2-Me-4-Cl; 3, 7, 10, R = 2,4-Cl2; 4, 8, 11, R = 3,5-Cl2.
1313

LATYPOVA et al.
1314
Scheme 2.
(1) O3, CH2Cl2–AcOH, 0°C
(2) H2O2, SeO2 or H2NC(O)NHNH2·HCl
R
O
COOH
5–8
Me
12–15
R
R
O
O
CHO
(1) O3, MeOH, 0°C
(2) NaBH4
(1) O3, MeOH, 0°C
(2) Me2S
OH
Me
5–8
Me
20–23
16–19
12, 16, 20, R = 2,4,6-Cl3; 13, 17, 21, R = 2-Me-4-Cl; 14, 18, 22, R = 2,4-Cl2; 15, 19, 23, R = 3,5-Cl2.
The proposed scheme of synthesis of 2-phenoxy-
propanoic acid derivatives 12‒15 can be regarded as
an alternative approach to such known crop-selective
herbicides as mecoprop (13, MCCP) and dichlorprop
(14, 2,4-DP).
10 min, and 3.8 g (36.8 mmol) of 4-chloropent-2-ene
was slowly added. When the reaction was complete
(TLC), the precipitate was filtered off, the filtrate was
evaporated, and the residue was subjected to column
chromatography on Al2O3 using petroleum ether as
eluent.
EXPERIMENTAL
2,4,6-Trichloro-1-[(3E)-pent-3-en-2-yloxy]ben-
zene (5). Yield 1.10 g (55%) (a), 1.06 g (53%) (b); oily
material, Rf 0.57 (petroleum ether–EtOAc, 5:1). IR
spectrum, ν, cm–1: 2983, 1589, 1442, 1255, 831, 671.
1H NMR spectrum, δ, ppm (J, Hz): 1.47 d (3H, 5′-H,
The NMR spectra were recorded at the Khimiya
Joint Center (Ufa Institute of Chemistry, Russian
Academy of Sciences) on a Bruker Avance III spec-
1
trometer at 500 MHz for H and 125.47 MHz for 13C;
3
4
3J = 6.3), 1.60 d.d (3H, 4′-H, J = 6.3, J = 1.0),
CDCl3 was used as solvent. Analytical thin-layer
chromatography was performed on Sorbfil PTSKh-
AF-A plates manufactured by Sorbpolimer closed
corporation (Krasnodar, Russia). The IR spectra were
recorded in the range from 4000 to 200 cm–1 on
a Specord M80 spectrometer; samples were prepared
as films. The mass spectra (electron impact, 70 eV)
were obtained on a Thermo Finnigan MAT-95-XP
instrument (ion source temperature 200°C). The
melting points were measured on a Boetius PHMK 05
melting point apparatus. The elemental compositions
were determined using a Euro 2000 CHNS(O)
analyzer. The ozonizer efficiency was 40 mmol of O3
per hour.
3
4.68 quint (1H, 1′-H, J = 6.3), 5.49 m (1H, 2′-H),
5.61 m (1H, 3′-H), 7.26 s (2H, 3-H, 5-H). 13C NMR
spectrum, δC, ppm: 17.49 (C4′), 21.11 (C5′), 81.62 (C1′),
128.53 (C3, C5), 128.71 (C4), 129.75 (C2′), 130.68
(C2, C6), 131.11 (C3′), 149.19 (C1). Mass spectrum:
m/z 266.5 [M + H]+. Found, %: C 49.71; H 4.22.
C11H11Cl3O. Calculated, %: C 49.75; H 4.18.
M 265.5625.
4-Chloro-2-methyl-1-[(3E)-pent-3-en-2-yloxy]-
benzene (6). Yield 1.20 g (60%) (a), 0.74 g (37%) (b);
oily material, Rf 0.57 (petroleum ether– EtOAc, 5:1).
IR spectrum, ν, cm–1: 2979, 1488, 1244, 869, 661.
1H NMR spectrum, δ, ppm (J, Hz): 1.42 d (3H, 5′-H,
3J = 6.3), 1.69 d.d (3H, 4′-H, 3J = 6.4, 4J = 0.9), 2.20 s
(3H, CH3), 4.68 quint (1H, 1′-H, 3J = 6.3), 5.28 m (1H,
O-Alkylation of phenols (general procedure).
a. 4-Chloropent-2-ene, 1.50 g (14.0 mmol), and
potassium carbonate, 3.9 g (28.0 mmol), were added to
a mixture of 2.0 g (14.0 mmol) of phenol 1‒4 and
0.50 g (1.4 mmol) of Bu4NBr in acetone. The mixture
was refluxed until the reaction was complete (TLC)
and cooled, and the precipitate was filtered off. The
filtrate was evaporated, and the residue was purified by
column chromatography on Al2O3 using petroleum
ether as eluent.
3
2′-H), 5.68 m (1H, 3′-H), 6.75 d (1H, 6-H, J = 8.6),
7.05 d.d (1H, 5-H, 3J = 8.6, 4J = 2.6), 7.11 d (1H, 3-H,
4J = 2.6). 13C NMR spectrum, δC, ppm: 16.35 (CH3),
17.71 (C4′), 21.66 (C5′), 70.84 (C1′), 114.81 (C6),
124.86 (C4), 126.07 (C5), 127.23 (C3′), 129.64 (C2),
130.35 (C3), 132.14 (C2′), 154.85 (C1). Mass spectrum:
m/z 211.7 [M + H]+. Found, %: C 68.45; H 7.20.
C12H15ClO. Calculated, %: C 68.40; H 7.18.
M 210.6996.
b. A mixture of 2.0 g (14.0 mmol) of phenol 1‒4
and 2.1 g (36.8 mmol) of potassium hydroxide in
50 mL of propan-2-ol was vigorously stirred for
2,4-Dichloro-1-[(3E)-pent-3-en-2-yloxy]benzene
(7). Yield 1.14 g (57%) (a), 0.66 g (33%) (b); oily
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 9 2018

NEW SYNTHESIS OF KNOWN HERBICIDES
1315
material, Rf 0.54 (petroleum ether–EtOAc, 5:1).
IR spectrum, ν, cm–1: 2982, 1475, 1258, 803, 667.
1H NMR spectrum, δ, ppm (J, Hz): 1.46 d (3H, 5′-H,
132.94 (C1′), 133.38 (C2), 133.35 (C3), 135.45 (C5),
153.59 (C1). Mass spectrum: m/z 232.1 [M + H]+.
Found, %: C 57.19; H 5.20. C11H12Cl2O. Calculated,
%: C 57.16; H 5.23. M 231.1178.
3
4
3J = 6.3), 1.69 d.d (3H, 4′-H, J = 6.4, J = 1.0),
3
4.71 quint (1H, 1′-H, J = 6.3), 5.52 m (1H, 2′-H),
3,5-Dichloro-2-[(3E)-pent-3-en-2-yl]phenol (11).
Yield 0.40 g (20%), oily material, Rf 0.48 (petroleum
ether–EtOAc, 10:1). IR spectrum, ν, cm–1: 3479, 2929,
5.68 m (1H, 3′-H), 6.68 d (1H, 6-H, 3J = 8.8), 7.12 d.d
(1H, 5-H, 3J = 8.8, 4J = 2.6), 7.35 d (1H, 3-H, 4J = 2.6).
13C NMR spectrum, δC, ppm: 18.05 (C4′), 21.52 (C5′),
76.98 (C1′), 117.41 (C6), 124.95 (C2), 125.81 (C4),
127.27 (C5), 128.24 (C3′), 129.89 (C3), 131.37 (C2′),
152.55 (C1). Mass spectrum: m/z 232.1 [M + H]+.
Found, %: C 57.19; H 5.29. C11H12Cl2O. Calculated,
%: C 57.16; H 5.23. M 231.1178.
1
1427, 1267, 985, 721. H NMR spectrum, δ, ppm
(J, Hz): 1.31 d (3H, 5′-H, 3J = 6.9), 1.69 d.d (3H, 4′-H,
4
3
3J = 5.9, J = 1.0), 3.78 quint (1H, 1′-H, J = 6.8),
4
5.57 m (2H, 2′-H, 3′-H), 7.03 d (1H, 5-H, J = 2.5),
7.18 d (1H, 3-H, J = 2.5). 13C NMR spectrum, δC,
4
ppm: 17.95 (C4′), 19.77 (C5′), 36.07 (C1′), 120.41 (C4),
125.19 (C2′), 125.19 (C3), 126.52 (C5), 126.65 (C2),
133.82 (C3′), 135.22 (C6), 147.55 (C1). Mass spectrum:
m/z 232.1 [M + H]+. Found, %: C 57.21; H 5.22.
C11H12Cl2O. Calculated, %: C 57.16; H 5.23.
M 231.1178.
3,5-Dichloro-1-[(3E)-pent-3-en-2-yloxy]benzene
(8). Yield 1.10 g (55%) (a), 0.76 g (38%) (b); oily
material, Rf 0.51 (petroleum ether–EtOAc, 5:1).
IR spectrum, ν, cm–1: 2979, 1589, 1444, 965, 855, 670.
1H NMR spectrum, δ, ppm (J, Hz): 1.41 d (3H, 5′-H,
3
4
3J = 6.3), 1.72 d.d (3H, 4′-H, J = 6.4, J = 1.0),
Treatment of peroxide ozonolysis products of
compounds 5‒8 (general procedure). a. An ozone–
oxygen mixture was bubbled through a solution of
0.4 mmol of compound 5‒8 in a mixture of 10 mL of
methylene chloride and 0.2 mL of acetic acid, cooled
to 0°C, until 0.5 mmol of ozone was absorbed. The
mixture was purged with argon, 0.1 mL of hydrogen
peroxide and 0.01 g (0.09 mmol) of selenium dioxide
were added with stirring at 0°C, and the mixture was
stirred for 48 h at room temperature. The mixture was
diluted with 30 mL of methylene chloride, washed
with brine (2 × 15 mL), dried over MgSO4, and
evaporated, and the residue was subjected to silica gel
chromatography using petroleum ether–ethyl acetate
(3:1) as eluent.
3
4.72 quint (1H, 1′-H, J = 6.3), 5.51 m (1H, 2′-H),
4
5.72 m (1H, 3′-H), 6.81 d (2H, 2-H, 6-H, J = 1.7),
6.93 t (1H, 4-H, J = 1.7). 13C NMR spectrum, δC,
4
ppm: 17.73 (C4′), 21.45 (C5′), 75.28 (C1′), 114.98 (C2,
C6), 120.74 (C4), 128.18 (C2′), 131.15 (C3′), 135.13 (C3,
C5), 159.17 (C1). Mass spectrum: m/z 232.1 [M + H]+.
Found, %: C 57.18; H 5.28. C11H12Cl2O. Calculated,
%: C 57.16; H 5.23. M 231.1178.
4-Chloro-2-methyl-6-[(3E)-pent-3-en-2-yl]phenol
(9). Yield 0.38 g (19%), oily material, Rf 0.58
(petroleum ether–EtOAc, 10:1). IR spectrum, ν, cm–1:
1
3488, 2967, 1457, 1190, 971, 741. H NMR spectrum,
3
δ, ppm (J, Hz): 1.37 d (3H, 5′-H, J = 6.9), 1.74 d.d
3
4
(3H, 4′-H, J = 5.9, J = 1.0), 2.21 s (3H, CH3),
3
3.52 quint (1H, 1′-H, J = 6.8), 5.67 m (2H, 2′-H,
b. An ozone–oxygen mixture was bubbled through
a solution of 0.4 mmol of compound 5‒8 in a mixture
of 10 mL of methylene chloride and 2.9 mL of acetic
acid, cooled to 0°C, until 0.5 mmol of ozone was
absorbed. The mixture was purged with argon, 0.2 g
(1.4 mmol) of semicarbazide hydrochloride was added
with stirring at 0°C, and the mixture was stirred at
room temperature until peroxide compounds disap-
peared (starch–iodine test). The mixture was diluted
with 30 mL of methylene chloride, washed with water
(3×15 mL), dried over MgSO4, and evaporated, and
the residue was subjected to silica gel chromatography
using petroleum ether–ethyl acetate (3:1) as eluent.
3′-H), 6.95 d (1H, 5-H, 4J = 2.5), 6.99 d (1H, 3-H, 4J =
2.5). 13C NMR spectrum, δC, ppm: 15.89 (CH3), 17.88
(C4′), 19.21 (C5′), 37.45 (C1′), 124.85 (C4), 125.10 (C5),
126.40 (C3′), 126.54 (C2), 128.54 (C3), 131.51 (C6),
134.48 (C2′), 150.88 (C1). Mass spectrum: m/z 211.7
[M + H]+. Found, %: C 68.45; H 7.20. C12H15ClO.
Calculated, %: C 68.40; H 7.18. M 210.6996.
4,6-Dichloro-2-[(3E)-pent-3-en-2-yl]phenol (10).
Yield 0.34 g (17%), oily material, Rf 0.41 (petroleum
ether–EtOAc, 10:1). IR spectrum, ν, cm–1: 3495, 2982,
1
1476, 1220, 987, 739. H NMR spectrum, δ, ppm
(J, Hz): 1.43 d (3H, 5′-H, 3J = 6.9), 1.68 d.d (3H, 4′-H,
4
3
3J = 5.9, J = 1.0), 4.31 quint (1H, 1′-H, J = 6.8),
5.48 m (1H, 2′-H), 5.86 m (1H, 3′-H), 6.80 m (2H,
4-H, 6-H). 13C NMR spectrum, δC, ppm: 17.91 (C4′),
17.99 (C5′), 38.13 (C1′), 116.59 (C6, C4), 125.01 (C2′),
2-(2,4,6-Trichlorophenoxy)propanoic acid (12).
Yield 0.06 g (60%) (a), 0.05 g (56%) (b); yellow
crystals, mp 179‒180°C, Rf 0.24 (petroleum ether–
EtOAc, 2:1). IR spectrum, ν, cm–1: 3518, 3081, 1717,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 9 2018

LATYPOVA et al.
1316
1
1569, 1471, 1256, 856, 732, 579. H NMR spectrum,
ture was bubbled through a solution of 0.45 mmol of
compound 5‒8 in 10 mL of anhydrous methanol,
cooled to 0°C, until 0.5 mmol of ozone was absorbed.
The mixture was purged with argon, 0.04 g (1.0 mmol)
of NaBH4 was added at 0°C, and the mixture was
stirred at room temperature until peroxide compounds
disappeared (starch–iodine test). The mixture was then
treated with 1 mL of 10% acetic acid, the aqueous
layer was extracted with chloroform (3×10 mL), the
extract was dried over MgSO4 and evaporated, and the
residue was subjected to silica gel chromatography
using petroleum ether–ethyl acetate (7:1) as eluent.
δ, ppm (J, Hz): 1.63 d (3H, 3′-H, 3J = 6.9), 4.92 q (1H,
2′-H, J = 6.9), 7.27 s (2H, 3-H, 5-H). 13C NMR spec-
3
trum, δC, ppm: 17.96 (C3′), 77.48 (C2′), 121.61 (C2, C6),
121.31 (C4), 128.08 (C3, C5), 146.92 (C1), 175.07
(C=O). Mass spectrum, m/z: 270.5 [M + H]+. Found,
%: C 40.14; H 2.65. C9H7Cl3O3. Calculated, %:
C 40.11; H 2.62. M 269.5082.
2-(4-Chloro-2-methylphenoxy)propanoic acid
(13). Yield 0.06 g (58%) (a), 0.04 g (39%) (b); light
brown crystals, mp 93‒94°C, Rf 0.21 (petroleum
ether–EtOAc, 2:1). IR spectrum, ν, cm–1: 3508, 2946,
1
1705, 1493, 1245, 792. H NMR spectrum, δ, ppm
2-(2,4,6-Trichlorophenoxy)propan-1-ol (16).
Yield 0.09 g (98%), oily material, Rf 0.34 (petroleum
ether–EtOAc, 3:1). IR spectrum, ν, cm–1: 3385, 2935,
3
(J, Hz): 1.67 d (3H, 3′-H, J = 6.8), 2.25 s (3H, CH3),
4.74 q (1H, 2′-H, J = 6.8), 6.64 d (1H, 6-H, 3J = 8.7),
3
7.07 d.d (1H, 5-H, 3J = 8.7, 4J = 2.4), 7.13 d (1H, 3-H,
4J = 2.4). 13C NMR spectrum, δC, ppm: 16.15 (CH3),
18.45 (C3′), 72.65 (C2′), 113.14 (C6), 126.37 (C4),
126.37 (C5), 129.54 (C2), 130.91 (C3), 154.14 (C1),
176.85 (C=O). Mass spectrum: m/z 215.6 [M + H]+.
Found, %: C 55.98; H 5.20. C10H11ClO3. Calculated,
%: C 55.96; H 5.17. M 214.6452.
1
1551, 1446, 1257, 1046, 575. H NMR spectrum, δ,
3
ppm (J, Hz): 1.32 d (3H, CH3, J = 6.5), 3.71 d.d (1H,
1′-H, 2J = 12.0, 3J = 5.0), 3.82 d.d (1H, 1′-H, 2J = 12.0,
3J = 3.0), 4.57 m (1H, 2′-H), 7.34 s (2H, 3-H, 5-H).
13C NMR spectrum, δC, ppm: 16.18 (C3′), 66.05 (C1′),
81.07 (C2′), 128.29 (C3, C5), 129.22 (C4), 130.11 (C2,
C6), 148.96 (C1). Mass spectrum: m/z 256.5 [M + H]+.
Found, %: C 42.35; H 3.57. C9H9Cl3O2. Calculated, %:
C 42.30; H 3.55. M 255.5247.
2-(2,4-Dichlorophenoxy)propanoic acid (14).
Yield 0.05 g (46%) (a), 0.04 g (44%) (b); light yellow
crystals, mp 116‒117°C, Rf 0.24 (petroleum ether–
EtOAc, 2:1). IR spectrum, ν, cm–1: 2955, 1713, 1458,
2-(4-Chloro-2-methylphenoxy)propan-1-ol (17).
Yield 0.08 g (88%), oily material, Rf 0.31 (petroleum
ether–EtOAc, 3:1). IR spectrum, ν, cm–1: 3383, 2930,
1
1243, 798. H NMR spectrum, δ, ppm (J, Hz): 1.72 d
(3H, 3′-H, 3J = 6.8), 4.78 q (1H, 2′-H, 3J = 6.8), 6.84 d
1
1485, 1246, 1050, 661. H NMR spectrum, δ, ppm
3
3
4
3
(1H, 6-H, J = 8.8), 7.17 d.d (1H, 5-H, J = 8.8, J =
(J, Hz): 1.25 d (3H, 3′-H, J = 6.2), 2.19 s (3H, CH3),
2.5), 7.40 d (1H, 3-H, J = 2.5). 13C NMR spectrum,
4
2
3
3.73 d.d (1H, 1′-H, J = 11.7, J = 6.4), 3.77 d.d (1H,
δC, ppm: 18.23 (C3′), 74.01 (C2′), 116.50 (C6), 124.98
(C2), 127.66 (C5), 127.67 (C4), 130.43 (C3), 151.80
(C1), 175.83 (C=O). Mass spectrum: m/z 236.1
[M + H]+. Found, %: C 46.01; H 3.46. C9H8Cl2O3. Cal-
culated, %: C 45.99; H 3.43. M 235.0634.
2
3
1′-H, J = 11.7, J = 4.1), 4.44 m (1H, 2′-H), 6.81 d
3
3
4
(1H, 3-H, J = 8.6), 7.08 d.d (1H, 5-H, J = 8.6, J =
2.6), 7.12 d (1H, 3-H, J = 2.6). 13C NMR spectrum,
4
δC, ppm: 15.91 (CH3), 16.30 (C3′), 66.37 (C1′), 75.54
(C2′), 114.63 (C6), 125.63 (C4), 126.43 (C5), 129.84
(C2), 130.71 (C3), 154.37 (C1). Mass spectrum:
m/z 200.7 [M + H]+. Found, %: C 59.91; H 6.55.
C10H13ClO2. Calculated, %: C 59.86; H 6.53.
M 200.6617.
2-(3,5-Dichlorophenoxy)propanoic acid (15).
Yield 0.09 g (86%) (a), 0.05 g (54%) (b); dark yellow
crystals, mp 184‒185°C, Rf 0.26 (petroleum ether–
EtOAc, 2:1). IR spectrum, ν, cm–1: 3520, 2991, 1724,
1
1574, 1442, 1257, 1093, 802, 670. H NMR spectrum,
2-(2,4-Dichlorophenoxy)propan-1-ol (18). Yield
0.09 g (98%), oily material, Rf 0.31 (petroleum ether–
EtOAc, 3:1). IR spectrum, ν, cm–1: 3374, 2932, 1478,
δ, ppm (J, Hz): 1.67 d (3H, 3′-H, 3J = 6.8), 4.77 q (1H,
3
4
2′-H, J = 6.8), 6.80 d (2H, 2-H, 6-H, J = 1.6), 7.01 t
(1H, 4-H, J = 1.6). 13C NMR spectrum, δC, ppm:
4
1
1261, 1059, 654. H NMR spectrum, δ, ppm (J, Hz):
18.26 (C3′), 72.35 (C2′), 114.24 (C2, C6), 122.27 (C4),
135.60 (C3, C5), 158.28 (C1), 176.47 (C=O). Mass
spectrum: m/z 236.1 [M + H]+. Found, %: C 46.03;
H 3.43. C9H8Cl2O3. Calculated, %: C 45.99; H 3.43.
M 235.0634.
3
1.31 d (3H, 3′-H, J = 6.2), 3.75 m (2H, 1′-H), 4.44 m
3
(1H, 2′-H), 6.93 d (1H, 6-H, J = 8.8), 7.18 d.d (1H,
3
4
4
5-H, J = 8.8, J = 2.5), 7.37 d (1H, 3-H, J = 2.5).
13C NMR spectrum, δC, ppm: 15.91 (C3′), 66.09 (C1′),
77.79 (C2′), 117.31 (C6), 125.2 (C4), 126.65 (C2),
127.69 (C5), 130.13 (C3), 152.33 (C1). Mass spectrum:
m/z 222.1 [M + H]+. Found, %: C 48.91; H 4.58.
Reduction of peroxide ozonolysis products with
NaBH4 (general procedure). An ozone–oxygen mix-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 9 2018

NEW SYNTHESIS OF KNOWN HERBICIDES
1317
C9H10Cl2O2. Calculated, %: C 48.89; H 4.56.
M 221.0799.
113.20 (C6), 126.32 (C2), 126.44 (C5), 129.45 (C4),
131.03 (C3), 154.07 (C1), 201.93 (CHO). Mass spec-
trum: m/z 199.6 [M + H]+. Found, %: C 60.49; H 5.60.
C10H11ClO2. Calculated, %: C 60.46; H 5.58.
M 198.6458.
2-(3,5-Dichlorophenoxy)propan-1-ol (19). Yield
0.09 g (98%), oily material, Rf 0.34 (petroleum ether–
EtOAc, 3:1). IR spectrum, ν, cm–1: 3373, 2935, 1589,
1
2-(2,4-Dichlorophenoxy)propanal (22). Yield
0.09 g (94%), oily material, Rf 0.38 (petroleum ether–
EtOAc, 5:1). IR spectrum, ν, cm–1: 3346, 2939, 1740,
1440, 1259, 1054, 833, 671. H NMR spectrum, δ,
3
ppm (J, Hz): 1.25 d (3H, 3′-H, J = 6.3), 3.65 m (2H,
1′-H), 4.43 m (1H, 2′-H), 6.81 s (2H, 2-H, 6-H), 6.93 s
(1H, 4-H). 13C NMR spectrum (125.47 MHz, CDCl3),
δC, ppm: 15.59 (C3′), 65.80 (C1′), 75.64 (C2′), 114.84
(C2, C6), 121.27 (C4), 135.35 (C3, C5), 158.85 (C1).
Mass spectrum: m/z 222.1 [M + H]+. Found, %:
C 48.90; H 4.59. C9H10Cl2O2. Calculated, %: C 48.89;
H 4.56. M 221.0799.
1
1478, 1263, 1060, 655. H NMR spectrum, δ, ppm
(J, Hz): 1.51 d (3H, 3′-H, 3J = 6.9), 4.61 d.q (1H, 2′-H,
3
3J = 6.9, 1.6), 6.79 d (1H, 6-H, J = 8.8), 7.15 d.d
(1H, 5-H, 3J = 8.8, 4J = 2.5), 7.39 d (1H, 3-H, 4J = 2.5),
3
9.74 d (1H, CHO, J = 1.6). 13C NMR spectrum, δC,
ppm: 15.79 (C3′), 79.93 (C2′), 116.55 (C6), 125.01 (C2),
127.49 (C4), 127.71 (C5), 130.49 (C3), 151.88 (C1),
201.88 (CHO). Mass spectrum: m/z 220.1 [M + H]+.
Found, %: C 49.36; H 3.69. C9H8Cl2O2. Calculated, %:
C 49.34; H 3.68. M 219.064.
Treatment of peroxide ozonolysis products with
dimethyl sulfide (general procedure). An ozone–
oxygen mixture was bubbled through a solution of
0.45 mmol of compound 5‒8 in 10 mL of anhydrous
methanol, cooled to 0°C, until 0.5 mmol of ozone was
absorbed. The mixture was purged with argon,
0.05 mL of dimethyl sulfide was added with stirring at
0°C, and the mixture was stirred at room temperature
until peroxide compounds disappeared (starch–iodine
test). The solvent was distilled off, the residue was
dissolved in 10 mL of chloroform, the solution was
washed with a saturated aqueous solution of sodium
hydrogen carbonate (2 ×5 mL) and with brine (2×
5 mL), dried over MgSO4, and evaporated, and the
residue was subjected to silica gel chromatography
using petroleum ether–ethyl acetate (6:1).
2-(3,5-Dichlorophenoxy)propanal (23). Yield
0.08 g (81%), oily material, Rf 0.5 (petroleum ether–
EtOAc, 3:1). IR spectrum, ν, cm–1: 3394, 2937, 1739,
1
1572, 1443, 1258, 1078, 670. H NMR spectrum, δ,
ppm (J, Hz): 1.50 d (3H, 3′-H, 3J = 6.9), 4.62 d.q (1H,
3
3
4
2′-H, J = 6.9, J = 1.3), 6.79 d (2H, 2-H, 6-H, J =
1.6), 7.01 t (1H, 4-H, 4J = 1.6), 9.68 d (1H, CHO, 3J =
1.3). 13C NMR spectrum, δC, ppm: 15.28 (C3′), 78.28
(C2′), 114.36 (C2, C6), 122.24 (C4), 135.72 (C3, C5),
158.23 (C1), 200.46 (CHO). Mass spectrum: m/z 220.1
[M + H]+. Found, %: C 49.37; H 3.68. C9H8Cl2O2.
Calculated, %: C 49.34; H 3.68. M 219.064.
This study was performed in the framework of state
assignment (project nos. AAAA-A17-117011910024-
9, AAAA-A17-117011910027-0).
2-(2,4,6-Trichlorophenoxy)propanal (20). Yield
0.09 g (88%), oily material, Rf 0.37 (petroleum ether–
EtOAc, 5:1). IR spectrum, ν, cm–1: 3298, 2939, 1733,
1
1435, 1258, 1054, 577. H NMR spectrum, δ, ppm
REFERENCES
(J, Hz): 1.48 d (3H, 3′-H, 3J = 7.0), 4.59 m (1H, 2′-H),
3
7.24 s (2H, 3-H, 5-H), 9.98 d (1H, CHO, J = 1.5).
1. Kulikova, N.A. and Lebedeva, G.F., Gerbitsidy
i
13C NMR spectrum, δC, ppm: 17.45 (C3′), 83.89 (C2′),
129.01 (C3, C5), 129.89 (C2, C6), 131.08 (C4), 148.94
(C1), 200.83 (CHO). Mass spectrum: m/z 254.5
[M + H]+. Found, %: C 42.66; H 2.79. C9H7Cl3O2.
Calculated, %: C 42.64; H 2.78. M 253.5088.
ekologicheskie aspekty ikh primeneniya (Herbicides and
Environmental Aspects of Their Application), Moscow:
LIBROKOM, 2010.
2. Zinchenko, V.A., Khimicheskaya zashchita rastenii:
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ekologicheskaya bezopas-
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Yield 0.08 g (80%), oily material, Rf 0.25 (petroleum
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1739, 1489, 1245, 1081, 663. H NMR spectrum, δ,
3
ppm (J, Hz): 1.49 d (3H, 3′-H, J = 6.9), 2.26 s (3H,
3
CH3), 4.59 m (1H, 2′-H), 6.61 d (1H, 6-H, J = 8.7),
7.08 d.d (1H, 5-H, 3J = 8.7, 4J = 2.4), 7.16 d (1H, 3-H,
3
13
4J = 2.4), 9.71 d (1H, CHO, J = 1.8). C NMR spec-
trum, δC, ppm: 15.56 (C3′), 16.21 (CH3), 78.34 (C2′),
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 9 2018