Reactions of aroxy- and arylsulfanylacetic acids and their esters with N-(2,2,2-trichloro-1-hydroxyethyl)sulfonamides and -carboxamides

Article abstract of DOI:10.1023/B:RUJO.0000019739.80215.e2

C-Amidoalkylation of aroxy- and arylsulfanylacetic acids and their methyl esters was effected by reaction with N-(2,2,2-trichloro-1-hydroxyethyl) sulfonamides and -carboxamides in the presence of methane-or trifluoromethanesulfonic acids as catalyst and s

Full text of DOI:10.1023/B:RUJO.0000019739.80215.e2

Russian Journal of Organic Chemistry, Vol. 39, No. 12, 2003, pp. 1753 1759. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 12, 2003,
pp. 1826 1832.
Original Russian Text Copyright
2003 by Rudyakova, Levkovskaya, Rozentsveig, Mirskova, Albanov.
Reactions of Aroxy- and Arylsulfanylacetic Acids and Their
Esters with N-(2,2,2-Trichloro-1-hydroxyethyl)sulfonamides
and -carboxamides
E. V. Rudyakova, G. G. Levkovskaya, I. B. Rozentsveig,
A. N. Mirskova, and A. I. Albanov
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
fax (3952)396046; e-mail: ggl@irioch.irk.ru
Received April 12, 2003
Abstract C-Amidoalkylation of aroxy- and arylsulfanylacetic acids and their methyl esters was effected by
reaction with N-(2,2,2-trichloro-1-hydroxyethyl)sulfonamides and -carboxamides in the presence of methane-
or trifluoromethanesulfonic acids as catalyst and solvent. The process is regioselective, and the substitution
occurs at the para-position with respect to the heteroelement-containing group.
Introduction of additional pharmacophoric groups
into molecules of aroxy- and arylsulfanylacetic acids
and their derivatives may be very promising, for these
compounds are known as plant growth regulators,
herbicides, fungicides, and antiphlogistic and im-
munostimulating agents [1 6]. While studying the
reactivity of CH N groups having strong electron-
acceptor substutuents [7], we have shown that aroxy-
(arylsulfanyl)acetic acid esters readily react with
accessible N-(2,2,2-trichloroethylidene)arenesulfon-
amides in the presence of oleum or (in some cases)
boron trifluoride diethyl ether complex [8] to give in
good yields the corresponding 4-(1-arylsulfonylamino-
2,2,2-trichloroethyl) derivatives at the aromatic ring.
The synthesis of analogous products with the use of
N-(polyhaloalkylidene)carboxamide was difficult, for
these reagents are unstable and less accessible [7].
It is known that N-(2,2,2-trichloro-1-hydroxy)-
arenesulfonamides, -carboxamides, and -carbamates,
which are readily available from the corresponding
amides and trichloroacetaldehyde (or via addition of
water to N-trichloroethylidene derivatives), are effec-
tive C-amidoalkylating agents with respect to arenes
in the presence of concentrated sulfuric acid [9 13].
We also found [8] that N-(2,2,2-trichloro-1-hydroxy-
ethyl)arenesulfonamides do not react in such a way
with methyl aroxy- and arylsulfanylacetates under the
same conditions.
acetic acids together with polychloromethyl and amide
groups, we examined reactions of accessible N-(2,2,2-
trichloro-1-hydroxy)arenesulfonamides, -carbox-
amides, and -carbamates Ia Id with aroxy- and aryl-
sulfanylacetic acids and their methyl esters in the
presence of sulfuric, methanesulfonic, and trifluoro-
methanesulfonic acids (Scheme 1). We failed to obtain
the desired products by reactions of N-(2,2,2-trichloro-
1-hydroxyethyl) derivatives Ia Id with acids and
esters IIa IIg in the presence of sulfuric acid under
the conditions ensuring successful amidoalkylation of
arenes [9 11], including those having functional
substituents [12, 13]. Presumably, this is explained by
the poor solubility of aroxy(arylsulfanyl)acetic acid
derivatives in sulfuric acid.
We have found that N-(2,2,2-trichloro-1-hydroxy-
ethyl) amides Ia Id readily react with acids and esters
IIa IIg in methane- or trifluoromethanesulfonic acid
to give the corresponding 4-[2,2,2-trichloro-1-arylsul-
fonyl(acetyl, benzoyl, or ethoxycarbonyl)aminoethyl]-
phenoxy(phenylsulfanyl)acetic acids and esters III
XVII (Scheme 1). We also examined the effect of
temperature, reaction time, and amount and nature of
the sulfonic acid on the reactions of acids and esters
IIa IIg with amides Ia Id. The reactions were carried
out with equimolar amounts of the reactants at 20 C
or on heating to 50 C, and the reaction time was
varied from 3 h to 3 days. We used catalytic amounts
(10 60 mol %) of methanesulfonic and trifluoro-
methanesulfonic acids in chloroform or these com-
With the goal of obtaining compounds whose
molecules contain fragments of aroxy- or arylsulfanyl-
1070-4280/03/3912-1753$25.00 2003 MAIK Nauka/Interperiodica

1754
RUDYAKOVA et al.
Scheme 1.
R = Me, CF3; I, R1 = 4-ClC6H4SO2 (a), EtOC(O) (b), MeC(O) (c), PhC(O) (d); II, X = O, R2 = R3 = H (a); X = O, R2 = H,
R3 = Me (b); X = O, R2 = R3 = Me (c); X = O, R2 = Cl, R3 = Me (d); X = S, R2 = R3 = H (e); X = S, R2 = H, R3 = Me (f);
X = S, R2 = R3 = Me (g); III, X = O, R1 = 4-ClC6H4SO2, R2 = H, R3 = Me; IV, X = O, R1 = EtOC(O), R2 = H, R3 = Me;
V, X = O, R1 = MeC(O), R2 = H, R3 = Me; VI, X = O, R1 = PhC(O), R2 = H, R3 = Me; VII, X = O, R1 = EtOC(O), R2 =
R3 = Me; VIII, X = O, R1 = PhC(O), R2 = R3 = Me; IX, X = O, R1 = PhC(O), R2 = Cl, R3 = Me; X, X = O, R1 = 4-ClC6H4SO2,
R2 = R3 = H; XI, X = O, R1 = EtOC(O), R2 = R3 = H; XII, X = S, R1 = 4-ClC6H4SO2, R2 = H, R3 = Me; XIII, X = S, R1 =
EtOC(O), R2 = H, R3 = Me; XIV, X = S, R1 = MeC(O), R2 = H, R3 = Me; XV, X = S, R1 = PhC(O), R2 = H, R3 = Me;
XVI, X = S, R1 = EtOC(O), R2 = R3 = Me; XVII, X = S, R1 = 4-ClC6H4SO2, R2 = R3 = H.
pounds were taken in a 3 6-fold excess with respect
to I and II, so that they played the role of solvent.
Also a mixture of sulfonic acid (100 to 200 mol %
relative to I and II) with chloroform at a volume ratio
of 1:1 was used.
A considerable success was reached by carrying out
the reaction in methanesulfonic acid, the molar ratio
II MeSO3H being 1:6 (20 C, 3 10 h). In this case,
products III XVII were formed in 75 93% yield
(method A). The use of trifluoromethanesulfonic acid
as solvent (molar ratio II CF3SO3H 1:1 4; 20 to
50 C; 3 to 72 h) did not increase the yield of III
XVII, but the corresponding amides XVIIIa XVIIId
were obtained in 5 80% yield. We succeeded in
effecting successful amidoalkylation of compounds
IIa IIg with amides Ia Id in a mixture of trifluoro-
methanesulfonic acid with chloroform. The maximal
yields of compounds III XVII (75 94%) and the
minimal yields (0.5 5%) of amides XVIIIa XVIIId
were attained when the reaction was carried out at
20 C (3 5 h) in a mixture of equal volumes of tri-
fluoromethanesulfonic acid (molar ratio CF3SO3H II
2 3:1) and chloroform (method B).
Amides Ia Id failed to react with compounds
IIa IIg in chloroform in the presence of 10 60 mol %
of methane- or trifluoromethanesulfonic acid both at
20 and at 50 C even when the reaction was prolonged
to 3 days. Apart from the initial reactants, we isolated
products of decomposition of N-(2,2,2-trichloro-1-
hydroxyethyl) derivatives Ia Id, the corresponding
unsubstituted amides: 4-chlorobenzenesulfonamide
(XVIIIa), ethyl carbamate (XVIIIb), acetamide
(XVIIIc), and benzamide (XVIIId). The fraction of
amides XVIII increased with rise in temperature and
reaction time: at 20 C (72 h), the yield of XVIII was
5 10%, and at 50 C (5 72 h), 50%.
Thus, using methane- or trifluoromethanesulfonic
acid as solvent or co-solvent in the reactions of
N-(2,2,2-trichloro-1-hydroxyethyl)amides Ia Id with
aroxy(arylsulfanyl)acetic acids or their esters IIa IIg
we succeeded in developing a preparative procedure
for synthesizing difficultly accessible functionalized
aroxy- and arylsulfanylacetic acid derivatives III
XVII in 75 94% yield. We believe that these reac-
tions are favored by homogeneous reaction medium
(acids and esters II are readily soluble in methane-
and trifluoromethanesulfonic acids [14]), as well as by
the strong protonating ability of these sulfonic acids.
In fact, trifluoromethanesulfonic acid (H0 = 14.1) is
When the reaction was carried out in a 1:1 (by
volume) mixture of methanesulfonic acid and chloro-
form at a MeSO3H-to-I(II) molar ratio of 1:1 to
1:3 4 (20 C, 10 20 h), target products III XVII
were formed in up to 50% yield. Also, up to 10% of
amides XVIIIa XVIIId and up to 5% of initial
reactants (hydroxyethyl amides I and esters or acids
II) were isolated. Increase of the reaction time to 72 h
favored formation of amides XVIIIa XVIIId.
Heating of the reaction mixture to 50 C resulted in
formation of up to 50% of amides XVIIIa XVIIId,
while the yield of target products III XVII did not
exceed 50%.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 12 2003

REACTIONS OF AROXY- AND ARYLSULFANYLACETIC ACIDS
1755
Scheme 2.
X, Z = O; XVII, Z = S.
stronger than sulfuric acid (H0 12.1) and 3:1 H2SO4
SO3 mixture (H0 = 13.6) [15], and the acididty of
anhydrous methanesulfonic acid is likely to be com-
parable with that of aqueous sulfuric acid [16].
Compounds X and XVII were also obtained in
up to 70% yield by reaction of N-(2,2,2-trichloro-
ethylidene)-4-chlorobenzenesulfonamide with acids
IIa and IIe, respectively, under the conditions ana-
logous to those reported in [8] (Scheme 2, method C).
Here, no products of nucleophilic addition of acids
IIa and IIe at the C N bond were detected.
spectrum as an AB quartet at 3.81 and 3.72 ppm,
JAB = 14.9 Hz). Presumably, the reason is restricted
rotation about the C S bond due to steric interactions
between the MeOC(O)CH2CS group and o-methyl
group and the presence of an asymmetric center
(CHCCl3) in the para-position of the aromatic ring.
No such effect is observed for oxygen analog VII.
Thus, using methane- or trifluoromethanesulfonic
acid as solvent and catalyst, we succeeded in effecting
regioselective C-amidoalkylation of aroxy- and aryl-
thioacetic acids and their methyl esters with N-(2,2,2-
trichloro-1-hydroxyethyl) derivatives of carboxamides,
sulfonamides, and ethyl carbamate.
Products III XVII are crystalline substances with
no odor. They are readily soluble in alcohol, acetone,
and DMSO, sparingly soluble in chloroform and
ether, and insoluble in water. Their structure was
EXPERIMENTAL
1
confirmed by elemental analysis (Table 1) and H
1
The H and 13C NMR spectra were recorded on
NMR and IR spectroscopy (Table 2). The properties
of previously known compounds III and XII were
consistent with published data [8].
Bruker DPX-400 (400 and 100.6 MHz, respectively)
and Jeol FX-90Q spectrometers (90 and 84 MHz,
respectively); samples were examined as 5 10% solu-
tions containing HMDS as internal reference. The IR
spectra were measured in KBr using a Specord IR75
spectrometer.
N-(2,2,2-Trichloro-1-hydroxyethyl) amides Ia Id
were synthesized from the corresponding amides and
trichloroacetaldehyde [17] or by addition of water to
Schiff bases derived from trichloroacetaldehyde [7].
N-(2,2,2-Trichloroethylidene)-4-chlorobenzenesulfon-
amide was obtained from 4,N,N-trichlorobenzenesul-
fonamide and trichloroethylene [18].
General procedure for the preparation of com-
pounds III XVII. Method A. Compound Ia Id,
0.01 mol, was dissolved at 10 15 C under stirring
in 4 ml (0.06 mol) of methanesulfonic acid. After
5 10 min, 0.01 mol of compound IIa IIg was added.
The mixture was stirred for 15 min at 10 15 C and
for 5 h at room temperature. When the reaction was
complete, 100 ml of water was added, and the precip-
itate was filtered off, washed with water until neutral
washings, and dried in air.
The IR spectra of III XVII contain strong absorp-
tion bands due to vibrations of the NH, SO2, and
COOH groups (compound X, XII, and XVII),
COOMe groups (III IX and XII XVI), aromatic
C C and C H bonds, and aliphatic C H bonds
(Table 2). Compounds III XVII characteristically
1
show in the H NMR spectra doublet signals from the
NH and CH protons (J = 10 11 Hz) and singlets from
protons of the XCH2 and COOCH3 groups (Table 2).
Aromatic protons in III VI and X XVII give rise
to an AA BB spin system, which indicates formation
of para-substituted products. The presence of a singlet
and two doublets from aromatic protons in the spectra
of compounds VII IX and XVI suggests o,p-substitu-
1
tion pattern in their molecules. The H NMR spectra
of V and XIV contain singlets from the methyl group,
and compounds IV, VII, X, XIII, XVI give rise to
a characteristic triplet quartet system from the ethoxy
group in the carbamate fragment. In the spectra of
V, VIII, and XV, signals from aromatic protons of
the benzoylamino group were also present.
Method B. Compound Ia Id, 0.01 mol, was dis-
solved under stirring in 2 ml of chloroform. The solu-
The SCH2 protons in molecule XVI are magnetic-
1
ally nonequivalent, and they appear in the H NMR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 12 2003

1756
RUDYAKOVA et al.
Table 1. Yields, melting points, and elemental analyses of compounds III XVII
Yield, %
Found, %
Cl
Calculated, %
Cl
Comp.
no.
mp,
C
Formula
A
B
C
H
N
S
C
H
N
S
III
92 90 152 155 41.73 3.21 28.72 2.76 7.28 C17H15Cl4NO5S 41.91 3.10 29.11 2.88 6.58
IV
V
VI
VII
VIII
IX
89 91 116 117 44.12 4.25 26.99 3.56
85 88 138 142 43.98 4.03 29.19 4.06
87 83 126 128 52.17 3.91 24.97 3.16
78 77 126 131 45.61 4.43 25.97 3.42
80 83 150 154 53.09 4.12 24.19 3.36
78 80 120 124 47.78 3.43 31.04 3.01
C14H16Cl3NO5
C13H14Cl3NO4
C18H16Cl3NO4
C15H18Cl3NO5
C19H18Cl3NO4
C18H15Cl4NO4
43.72 4.19 27.65 3.64
44.03 3.98 29.99 3.95
51.88 3.87 25.52 3.36
45.19 4.55 26.68 3.51
52.98 4.21 24.69 3.25
47.92 3.35 31.43 3.10
X
XI
90 94 165 171 40.54 2.97 29.68 3.09 7.07 C16H13Cl4NO5S 40.62 2.77 29.97 2.96 6.78
93 91 120 122 41.95 3.69 28.07 3.67 C13H14Cl3NO5 42.13 3.81 28.70 3.78
89 90 114 118 40.08 3.05 27.99 2.67 13.05 C17H15Cl4NO4S2 40.57 3.00 28.18 2.78 12.74
87 87 98 102 41.79 3.92 26.05 3.46 8.19 C14H16Cl3NO4S 41.96 4.02 26.54 3.50 8.00
82 84 155 156 42.43 3.92 28.48 3.80 8.96 C13H14Cl3NO3S 42.12 3.81 28.69 3.78 8.65
83 80 118 122 50.09 3.67 24.15 3.44 7.84 C18H16Cl3NO3S 49.96 3.73 24.58 3.24 7.41
75 78 163 166 43.00 4.39 25.65 3.35 7.70 C15H18Cl3NO4S 43.44 4.37 25.65 3.38 7.73
90 94 150 154 39.23 2.86 28.87 2.69 13.41 C16H13Cl4NO4S2 39.28 2.68 28.99 2.86 13.11
XII
XIII
XIV
XV
XVI
XVII
tion was cooled to 10 15 C, 2 ml (0.02 mol) of tri-
fluoromethanesulfonic acid was added, the mixture
was stirred for 5 10 min, and 0.01 mol of compound
IIb was added. The mixture was stirred for 15 min at
10 15 C and for 5 h at room temperature. Chloroform
was evaporated, 200 ml of water was added to the
residue, and the precipitate was filtered off, washed
with water until neutral washings, and dried in air.
according to methods A and B from 2.36 g (0.01 mol)
of compound Ib and 1.66 g (0.01 mol) of methyl
phenoxyacetate (IIb). Yield 3.43 g (A), 3.50 g (B).
Methyl 4-(1-acetylamino-2,2,2-trichloroethyl)-
phenoxyacetate (V) was synthesized according to
methods A and B from 2.06 g (0.01 mol) of com-
pound Ic and 1.66 g (0.01 mol) of ester IIb. Yield
3 g (A), 3.12 g (B).
Method C. N-(2,2,2-Trichloroethylidene)-4-chloro-
benzenesulfonamide, 3.21 g (0.01 mol) (prepared from
4,N,N-trichlorobenzenesulfonamide and trichloro-
ethylene as described in [17]), was dissolved in 8 ml
of dry chloroform, and 0.01 mol of compound IIa or
IIe was added to the solution in a stream of dry argon.
The mixture was cooled to 10 C, and 1 ml of oleum
(2 to 20% of SO3) was added dropwise under vigorous
stirring. The mixture was stirred for 15 min at 10 C
and for 3 h at room temperature. The oily material
was separated from the mixture by decanting, washed
with water (3 20 ml) and diethyl ether (3 10 ml),
and dried in air.
Methyl 4-[2,2,2-trichloro-1-(4-chlorophenylsul-
fonylamino)ethyl]phenoxyacetate (III) was obtained
according to methods A and B from 3.39 g (0.01 mol)
of compound Ia and 1.66 g (0.01 mol) of methyl
phenoxyacetate (IIb). Yield 4.48 g (A), 4.38 g (B).
Methyl 4-[2,2,2-trichloro-1-(ethoxycarbonyl-
amino)ethyl]phenoxyacetate (IV) was synthesized
Methyl 4-(1-benzoylamino-2,2,2-trichloroethyl)-
phenoxyacetate (VI) was synthesized according to
methods A and B from 2.68 g (0.01 mol) of compound
Id and 1.66 g (0.01 mol) of ester IIb. Yield 3.63 g
(A), 3.46 g (B).
Methyl 4-[2,2,2-trichloro-1-(ethoxycarbonyl-
amino)ethyl]-2-methylphenoxyacetate (VII) was
synthesized according to methods A and B from
2.36 g (0.01 mol) of compound Ib and 1.8 g
(0.01 mol) of methyl 2-methylphenoxyacetate (IIc).
Yield 3.11 g (A), 3.07 g (B).
Methyl 4-(1-benzoylamino-2,2,2-trichloroethyl)-
2-methylphenoxyacetate (VIII) was synthesized
according to methods A and B from 2.68 g (0.01 mol)
of compound Id and 1.8 g (0.01 mol) of ester IIc.
Yield 3.44 g (A), 3.57 g (B).
Methyl 4-(1-benzoylamino-2,2,2-trichloroethyl)-
2-chlorophenoxyacetate (IX) was obtained according
to methods A and B from 2.68 g (0.01 mol) of com-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 12 2003

REACTIONS OF AROXY- AND ARYLSULFANYLACETIC ACIDS
Table 2. IR and 1H NMR spectra of compounds III XVII
1757
1
IR spectrum, , cm
1H NMR spectrum,a , ppm (J, Hz)
Comp.
no.
C H
aliph. arom.
C H
XCH2
(s)
CH
(d)
NH
(d)
R3
(s)
COC C C C O
N H
Harom
R1
III
IV
V
1160,b 1430, 1760
1330b 1510,
1610
2930, 3060, 3270
2970 3090
4.76
4.80
4.81
4.80
5.21 7.42 d, 6.76 d 9.25
7.60 d, 3.74
(10.5) (6.9)
(10.5) 7.39 d
(6.8)
1180, 1510, 1720
2950, 3070
2990
3340
5.52 7.62 d, 6.92 d 8.62
1.18 t,
3.69
3.69
3.75
1250
1610
(10.2) (8.8)
(10.2) 4.08 q
(7.1)
1190, 1520, 1750
1230, 1610,
2910, 3040, 3350
2940, 3070
2960
5.84 7.58 d, 6.94 d 9.04
(10.0) (8.3) (10.0)
1.97 s
1250
1680
VI
1200, 1520, 1760, 2860
1260 1630 1770
3060, 3300
3080
6.27 7.81 d, 7.00 d 9.04
7.91 d
(15.3) (8.7)
(15.3) (7.3),
7.57 m,
7.47 m
VII
VIII
IX
1160, 1500, 1720, 2950, 3060, 3250
4.83
4.85
4.97
5.49 7.59 s (2-H),
(10.0) 7.47 d (5-H),
6.82 d (6-H,
8.6), 2.20 s
(CH3)
6.09 7.66 s (2-H),
(9.9) 7.50 d (5-H,
8.5), 6.86 d
(6-H), 2.22 s
(CH3)
6.18 8.09 s (2-H),
(9.8) 7.72 d (5-H,
8.7), 7.09 d
8.56
(10.0) 4.07 q
(7.1)
1.18 t,
3.70
1250
1510, 1760
1610
2980
3090
1140, 1520, 1740
1260 1640
2860, 3050, 3310
2920, 3090
2950
9.26
(9.9)
7.84 d, 3.69
7.57 m,
7.48 m
1080, 1500, 1740
1220, 1520,
2930, 3060, 3310
9.35
(9.8)
7.84 d, 3.71
7.59 t,
7.50 t
2950
3090
1280
1610
(6-H, 8.7)
X
1170,b 1510, 1740
1340,b 1590,
2920, 3070, 3250
2950 3090
4.68
4.72
3.93
3.93
5.22 7.44 d, 6.77 d 7.92
(10.6) (8.8)
7.57 d,
(10.6) 7.44 d
1240
1610
(6.8)
XI
1170, 1510, 1700
2920, 3070
2950,
2980
3410
3245
3300
5.62 7.67 d, 6.97 d 7.59
(10.4) (11.9)
1.17 t,
(10.4) 4.07 q
1240
1590,
1610
(7.1)
XII
XIII
1170,b 1470, 1710
2850, 3090
2950
5.23 7.43 d, 7.07 d 9.26
(10.3) (8.1)
7.65 d, 3.66
(10.3) 7.41 d
1330b 1590
(8.5)
1150, 1510, 1710
2850, 3030
2920
5.62 7.70 d, 7.34 d 8.67
(10.5) (8.4)
1.19 t,
(10.5) 4.10 q
(7.1)
3.63
3.69
1240
1540
XIV
XV
1160, 1530, 1760
1270 1610
1150, 1480, 1740a 2850, 3050
2860, 3050
2900
3310
3300
3.92
4.02
6.05 7.60 d, 7.51 d 9.09
(10.3) (8.4) (10.3)
6.22 7.81 d, 7.36 d 9.41
(10.3) (8.3) (10.3) 7.57 t,
1.98 s
7.85 d, 3.68
7.50 m
1280
1510,
1580
2910,
2950
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 12 2003

1758
RUDYAKOVA et al.
Table 2. (Contd.)
1
IR spectrum, , cm
C H
1H NMR spectrum,a , ppm (J, Hz)
Comp.
no.
C H
aliph. arom.
XCH2
(s)
CH
(d)
NH
(d)
R3
(s)
COC C C C O
N H
Harom
R1
XVI
1250
1520
1730
2950, 3030, 3330
3.81,c 6.58 7.84 s (2-H),
3.72c (10.3) 7.51 d (6-H),
7.23 d (5-H),
8.57
(10.3) 4.09 q
(7.1)
1.22 t,
3.59
2970
2900
3050
2.33 s (CH3)
XVII 1170,b 1470, 1710
3060, 3250
3090
3.78
5.24 7.46 d, 7.22 d 7.98
7.58 d,
(10.7) 7.33 d
(8.6)
1350b 1580,
1590,
(10.7) (8.3)
1600
a
1
The H NMR spectra of compounds VI, X, XI, and XVII were recorded in acetone-d6, and of the others, in DMSO-d6.
b
c
SO2.
AB-quartet, J = 14.9 Hz.
pound Id and 2.0 g (0.01 mol) of methyl 2-chloro-
phenoxyacetate (IId). Yield 3.52 g (A), 3.60 g (B).
Methyl 4-(1-benzoylamino-2,2,2-trichloroethyl)-
phenylsulfanylacetate (XV) was synthesized accord-
ing to methods A and B from 2.68 g (0.01 mol) of
compound Id and 1.82 g (0.01 mol) of ester IIf. Yield
3.58 g (A), 3.46 g (B).
Methyl 4-[2,2,2-trichloro-1-(ethoxycarbonyl-
amino)ethyl]-2-methylphenylsulfanylacetate (XVI)
was synthesized according to methods A and B from
2.36 g (0.01 mol) of compound Ib and 1.96 g
(0.01 mol) of methyl 2-methylphenylsulfanylacetate
(IIg). Yield 3.10 g (A), 3.23 g (B).
4-[2,2,2-Trichloro-1-(4-chlorophenylsulfonyl-
amino)ethyl]phenylsulfanylacetic acid (XVII) was
synthesized according to methods A and B from
3.39 g (0.01 mol) of compound Ia and 1.68 g
(0.01 mol) of phenylsulfanylacetic acid (IIe) or
according to method C from 3.21 g (0.01 mol) of
N-(2,2,2-trichloroethylidene)-4-chlorobenzenesulfon-
amide. Yield 3.96 g (A), 3.96 g (B), 4.20 g (C).
4-[2,2,2-Trichloro-1-(4-chlorophenylsulfonyl-
amino)ethyl]phenoxyacetic acid (X) was synthesized
according to methods A and B from 3.39 g (0.01 mol)
of compound Ia and 1.52 g (0.01 mol) of phenoxy-
acetic acid (IIa) or according to method C from
3.21 g (0.01 mol) of N-(2,2,2-trichloroethylidene)-4-
chlorobenzenesulfonamide. Yield 4.26 g (A), 4.44 g
(B), 4.25 g (C).
4-[2,2,2-Trichloro-1-(ethoxycarbonylamino)-
ethyl]phenoxyacetic acid (XI) was synthesized
according to methods A and B from 2.36 g (0.01 mol)
of compound Ib and 1.52 g (0.01 mol) of acid IIa.
Yield 3.44 g (A), 3.36 g (B).
Methyl 4-[2,2,2-trichloro-1-(4-chlorophenylsul-
fonylamino)ethyl]phenylsulfanylacetate (XII) was
synthesized according to methods A and B from 3.39 g
(0.01 mol) of compound Ia and 1.82 g (0.01 mol) of
methyl phenylsulfanylacetate (IIf). Yield 4.47 g (A),
4.52 g (B).
REFERENCES
Methyl 4-[2,2,2-trichloro-1-(ethoxycarbonyl-
amino)ethyl]phenylsulfanylacetate (XIII) was syn-
thesized according to methods A and B from 2.36 g
(0.01 mol) of compound Ib and 1.82 g (0.01 mol) of
methyl phenylsulfanylacetate (IIf). Yield 3.48 g (A),
3.48 g (B).
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