Polychloroethyltrifluoromethylsulfonamides from N,N-dichlorotrifluoromethylsulfonamide and dichloroethenes

Article abstract of DOI:10.1070/mc2003v013n01abeh001569

The interaction of trifluoromethylsulfonic acid N,N-dichloroamide with 1,1- and 1,2-dichloroethenes is a convenient way to N-(2,2,2-trichloroethyl)trifluoromethylsulfonamide, N-(2,2-dichloroethylidene)amide of trifluoromethylsulfonic acid and its derivatives.

Full text of DOI:10.1070/mc2003v013n01abeh001569

, 2003, 13(1), 25–26
Polychloroethyltrifluoromethylsulfonamides from
N,N-dichlorotrifluoromethylsulfonamide and dichloroethenes
Evgenii V. Kondrashov, Igor B. Rozentsveig,* Galina G. Levkovskaya and Anna N. Mirskova
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 664033 Irkutsk,
Russian Federation. Fax: +7 3952 39 6046; e-mail: i_roz@irioch.irk.ru
10.1070/MC2003v013n01ABEH001569
The interaction of trifluoromethylsulfonic acid N,N-dichloroamide with 1,1- and 1,2-dichloroethenes is a convenient way to
N-(2,2,2-trichloroethyl)trifluoromethylsulfonamide, N-(2,2-dichloroethylidene)amide of trifluoromethylsulfonic acid and its
derivatives.
The interaction of N,N-dichloroamides with 1,2-polychloro-
ethenes offers convenient ways to polyfunctional polyhaloethyl-
amides.1 We studied the reactions of N,N-dichlorotrifluoro-
methylsulfonamide2 1 with 1,1- and 1,2-dichloroethenes to
synthesise polychloroethyltrifluoromethylsulfonamides con-
taning pharmacophoric and synthetically attractive fragments.
We found that dichloroamide 1 reacts with 1,1-dichloroethene
with a strong exothermic effect to form N-(2,2,2-trichloro-
ethyl)amide of trifluoromethylsulfonic acid 3; the reaction was
accompanied by chloroethene polymerization.† At the first
stage, N-chloro-N-(2,2,2-trichloroethyl)amide 2 was probably
formed, and it was then reduced under the reaction conditions
to give amide 3 (Scheme 1).
1 + ClCH=CHCl
CF3SO2N=CHCHCl2
– Cl2CHCHCl2
CF3SO2NH2
4
CF3SO2NHCH(OH)CHCl2
[CF3SO2NHCH(OMe)CHCl2]
5
6
H2O
MeOH
X
H2NR
4
CF3SO2NHCHCHCl2
oleum
NHR
BF3OEt2
7a–c
CF3SO2NCl2 + Cl2C=CH2
CF3SO2NClCH2CCl3
CF3SO2NHCH
CHCl2
8a–c
X
S
1
2
R–H
CF3SO2NHCH2CCl3
CF3SO2NHCH
3
R–H = polymer, traces of H2O, traces of HCl
Scheme 1
S
CHCl2
8d
a R = C(O)NHPh, X = H
b R = SO2Ph, X = Me
c R = C(S)Me, X = Cl
A similar process was described for N,N-dichloroarylsulfon-
amides;3 however, the corresponding N-chloro-N-(2,2,2-tri-
chloroethyl)arylsulfonamides are more stable.
Recently,4 we found that the interaction of compound 1 with
1,2-dichloroethylene follows only one direction and results in
N-(2,2-dichloroethylidene)amide of trifluoromethylsulfonic
acid 4 without trichloroethylamide and diamidopolychloro-
ethane impurities in contrast to the reaction of N,N-dichloro-
arylsulfonamides with 1,2-dichloroethylene.1,5
Scheme 2
causes a strong exothermic effect. The product of water addi-
tion, N-(1-hydroxy-2,2-dichloroethyl)trifluoromethylsulfonamide
5, was identified by its spectrum. However, we failed to purify 5
and to determine methoxy derivative 6. The reactions were
accompanied by the formation of trifluoromethylsulfonamide
and unidentified dichloroacetaldehyde oligomers.
We improved the synthesis of imine 4 and studied it in the
reactions with O-, N-nucleophiles and aromatics.
Dichloroamide 1 reacts with cis-, trans- or a mixture of
1,2-dichloroethylene isomers to produce 4 under exposure to
visible light. Other kinds of initiation are not necessary in the
process in contrast to an analogous N,N-dichloroarylsulfon-
amide reaction.1,5
The isolation of pure compound 4 form is difficult because
of its high activity. Therefore a solution of 4 was used for
synthetic purposes (Scheme 2).‡
Amide addition products 7a–c are stable. The reaction of 1
with phenylurea or phenylsulfonamide occurs exothermally to
give expected 1,1-diamido-2,2-dichloroethane 7a,b.
Thioamides are well-known S-nucleophiles in reactions with
the acylimines of polyhaloaldehydes.6 The addition of thio-
acetamide to 4 involves the NH2 group to give N-(1-trifluoro-
methylsulfonamido-2,2-dichloroethyl)thioacetamide 7c.
The C-amidoalkylation of benzene, toluene and chlorobenzene
with imine 4 takes place in the presence of oleum as a catalyst
to form N-(1-aryl-2,2-dichloroethyl)trifluoromethylsulfon-
amides 8a–c. The reaction was unsuccessful with Lewis acids
or sulfuric acid instead of oleum or without a catalyst. However,
the C-amidoalkylation of thiophene occurs easily in the pres-
ence of BF3 etherate with substitution at the α-position of a
thienyl ring (compound 8d).
Imine 4 reacts with phenol in an unusual manner. Instead
of expected O-addition product 9, 1,1-bis(4-hydroxyphenyl)-
2,2-dichloroethane 11 was isolated (Scheme 3). Intermediate
structures 9 and 10 were not found.
In contrast to imine 4, the arenesulfonylimines of polyhalo-
aldehydes interact with phenol to give N-(1-phenoxy-2-poly-
chloroethyl)amides,7 whereas N-[1-(4-hydroxyphenyl)ethyl]-
amides are produced in the presence of oleum.8 No diaryl-
ethanes like 11 were found.7,8
Compound 4 reacts with water even in contact with moist
air. The addition of water or an alcohol to the solution of 4
†
NMR spectra were measured on a Bruker DPX-400 spectrometer.
1H (400.13 MHz) and 13C NMR (101.61 MHz) in [2H6]DMSO.
3: A solution of 1,1-dichloroethylene (0.81 ml, 10 mmol) in 2 ml of
CCl4 was added dropwise to a solution of N,N-dichlorotrifluoromethyl-
sulfonamide 14 (2.18 g, 10 mmol) in 2 ml of CCl4 at –10 °C with stirring
for 10 min. The mixture was heated to room temperature for 1 h and
then evaporated in a vacuum (80–100 Torr). Yield 2.38 g (85 %),
mp 112–113 °C (hexane, sublimated). 1H NMR, d: 4.23 (s, 2H, CH2),
8.9 (br. s, 1H, NH). 13C NMR, d: 60.50 (CH2), 97.18 (CCl3), 119.51 (q,
CF3, JC–F 322.1 Hz). IR (KBr, n/cm–1): 3290 (NH), 1460, 1380, 1240,
1200 (CF3SO2). MS, m/z (%): 121 (5), 119 (23), 117 (43) [CCl3]+, 98
(12), 96 (63) [M+ – CF3SO2NH – Cl], 79 (30) [M+ – CF3 – CH2CCl3],
69 (100) [CF3]+, 64 (40) [SO2]+. Found (%): C, 12.70; H, 1.07; Cl,
38.21; N, 5.02; S, 11.49. Calc. for C3H3Cl3F3NO2S (%): C, 12.85; H,
1.08; Cl, 37.92; N, 4.99; S, 11.43.
– 25 –

, 2003, 13(1), 25–26
A comparison of the reactivity of N-sulfonylimines of poly-
halogenated aldehydes1 and compound 4 indicates that the
latter is more active in the reaction with O-, N-nucleophiles and
aromatics. Moreover, it is suggested that the trifluoromethyl-
sulfonamide group is an easier leaving group than the arylsul-
fonamide group.
OH
CF3SO2NHCH
CHCl2
O
4
+
9
OH
‡
4: A solution of N,N-dichloroamide 14 (2.18 g, 10 mmol) in 7.7 ml
(100 mmol) of 1,2-dichloroethene was allowed to stand for 12 h in sun-
light under continuous bubbling of argon, avoiding spontaneous heating
over 20 °C. The obtained mixture was used in the syntheses given below.
1H NMR (in a mixture of cis- and trans-1,2-dichloroethenes), d: 8.57 (d,
1H, HC=N, J 6.4 Hz), 6.24 (d, 1H, CHCl2, J 6.4 Hz), 5.95 (s, 2H,
Cl2HC–CHCl2). IR (microlayer, n/cm–1): 3095 (=CH), 1660 (C=N),
1150, 1200, 1240, 1360 (CF3SO2).
CF3SO2NHCH
OH
– CF3SO2NH2
CHCl2
10
5: A solution of imine 4 was allowed to stand in air for 24 h to give
a mixture (3.89 g) of amide 5 (unstable) and 1,1,2,2-tetrachloroethane.
1H NMR, d: 5.95 (s, 2H, 1,1,2,2-tetrachloroethane), 5.01 (d, 1H, CH–N,
J 4.9 Hz), 6.05 (d, 1H, CHCl2, J 4.9 Hz), 10.49 (br. s, 1H, NH). IR (KBr,
n/cm–1): 3520 (OH), 3300 (NH), 1360, 1240, 1200, 1150 (CF3SO2).
General procedure for the preparation of 7a–c. 10 mmol of an amide
was added to the solution of imine 4. The mixture was stirred for 1 h,
avoiding spontaneous heating above 20 °C, and allowed to stand for 24 h;
then, it was evaporated in a vacuum. The solid residue was recrystallised
from hexane.
OH
HO
CH
CHCl2
11
Scheme 3
References
1 G. G. Levkovskaya, T. I. Drozdova, I. B. Rozentsveig and A. N. Mirskova,
Usp. Khim., 1999, 68, 638 (Russ. Chem. Rev., 1999, 68, 581).
2 V. P. Nazaretyan, O. A. Radchenko and L. M. Yagupolskii, Zh. Org.
Khim., 1974, 10, 2460 [J. Org. Chem. USSR (Engl. Transl.), 1974, 10,
2477].
3 N. A. Ribakova, V. I. Dostavalova, A. A. Slepushkina, V. I. Robas and
R. H. Freidlina, Izv. Akad. Nauk SSSR, Ser. Khim., 1973, 359 (Bull.
Acad. Sci. USSR, Div. Chem. Sci., 1973, 22, 342).
4 I. B. Rozentsveig, E. V. Kondrashov, G. G. Levkovskaya and A. N.
Mirskova, Zh. Org. Khim., 2001, 37, 775 (Russ. J. Org. Chem., 2001, 37,
739).
5 I. B. Rozentsveig, I. T. Evstaf’eva, G. G. Levkovskaya, A. N. Mirskova
and A. I. Albanov, Zh. Org. Khim., 2000, 36, 847 (Russ. J. Org. Chem.,
2000, 36, 813).
6 N. G. Zabirov and R. A. Cherkasov, Zh. Obshch. Khim., 1990, 60, 1251
[J. Gen. Chem. USSR (Engl. Transl.), 1990, 60, 1116].
7 A. N. Mirskova, T. I. Drozdova, G. G. Levkovskaya, O. B. Bannikova,
I. D. Kalihman and M. G. Voronkov, Zh. Org. Khim., 1982, 18, 1407 [J.
Gen. Chem. USSR (Engl. Transl.), 1982, 18, 1223].
8 E. V. Rudyakova, G. G. Levkovskaya, I. B. Rozentsveig, A. N. Mirskova
and A. I. Albanov, Zh. Org. Khim., 2001, 37, 106 (Russ. J. Org. Chem.,
2001, 37, 96).
7a: yield 3.34 g (88%), mp 207 °C (decomp.). 1H NMR (room tempe-
rature) d: 5.77 (dd, 1H, CHN, JCH–CHCl 3.9 Hz, JCH–NH 9.6 Hz), 6.42 (d,
2
1H, CHCl2, J 3.9 Hz), 6.94–7.45 (m, 6H, Ph + CNHC=O), 9.01 (s, 1H,
1
NHPh), 10.60 (br. s, 1H, SO2NH). H NMR (at 60 °C) d: 5.76 (dd, 1H,
CHN, J
3.9 Hz, JCH–NH 9.6 Hz), 6.42 (d, 1H, CHCl2, J 3.9 Hz),
CH–CHCl2
6.88 (d, 1H, CNHC=O, J 9.6 Hz), 6.95–7.45 (m, 5H, Ph), 8.55 (s, 1H,
NHPh), 9.80 (br. s, 1H, SO2NH). 13C NMR, d: 65.77 (NCH), 74.16
(CHCl2), 119.43 (q, CF3, JC–F 321.9 Hz), 118.16, 122.22, 128.96, 139.54
(Ph), 153.18 (C=O). IR (KBr, n/cm–1): 3335 (NH), 3280 (NH), 1650
(C=O), 1380, 1230, 1200, 1140 (CF3SO2). MS, m/z (%): 92 (85)
[PhNH]+, 85 (20), 83 (43) [CHCl2]+, 77 (14) [Ph]+, 69 (100) [CF3]+, 64
(22) [SO2]+. Found (%): C, 31.40; H, 2.63; Cl, 18.56; N, 11.11; S, 8.47.
Calc. for C10H10Cl2F3N3O3S (%): C, 31.59; H, 2.65; Cl, 18.65; N, 11.05;
S, 8.43.
1
7b: yield 2.52 g (63%), mp 175 °C. H NMR, d: 5.05 (dd, 1H, CHN,
JCH–CHCl 4.2 Hz, JCH–NH 9.0 Hz), 5.97 (d, 1H, CHCl2, J 4.2 Hz), 7.62
2
and 7.86 (m, 5H, ArH), 8.65 (d, 1H, NHSO2Ph, JCH–NH 9.0 Hz), 10.2
(br. s, 1H, NHSO2CF3). IR (KBr, n/cm–1): 3250 (NH), 1380, 1350, 1225,
1200, 1170 (CF3, SO2). MS, m/z (%): 156 (11) [PhSO2NH]+, 85 (12), 83
(23) [CHCl2]+, 77 (7) [Ph]+, 69 (100) [CF3]+, 64 (33) [SO2]+. Found (%):
C, 26.54; H, 2.30; Cl, 17.21; N, 6.78; S, 15.79. Calc. for C9H9Cl2F3N2O4S2
(%): C, 26.94; H, 2.26; Cl, 17.67; N, 6.98; S, 15.98.
1
7c: yield 2.65 g (83%), mp 97–98 °C. H NMR, d: 2.53 (s, 3H, Me),
6.36 (dd, 1H, CHN, JCH–CHCl 5.0 Hz, JCH–NH 7.3 Hz), 6.38 (d, 1H,
2
CHCl2, J 5.0 Hz), 10.95 [d, 1H, NHC(S), JCH–NH 7.34 Hz]. 13C NMR, d:
32.77 (Me), 69.70 (NCH), 70.86 (CHCl2), 119.26 (q, CF3, JC–F 321.7 Hz),
202.73 (C=S). IR (KBr, n/cm–1): 3350 (NH), 3250 (NH), 1380, 1225,
1200, 1130 (CF3SO2). Found (%): C, 18.54; H, 2.20; Cl, 22.10; N, 8.83;
S, 20.19. Calc. for C5H7Cl2F3N2O2S2 (%): C, 18.82; H, 2.21; Cl, 22.22;
N, 8.78; S, 20.09.
Received: 28th February 2002; Com. 02/1895
8c: yeild 1.42 g (40%), mp 105–107 °C. 1H NMR, d: 5.17 (d, 1H, CHN,
J 5.38 Hz), 6.50 (d, 1H, CHCl2, J 5.38 Hz), 7.49–7.61 (AA'BB' spin
system, C6H4, J 8.4 Hz), 10.98 (br. s, 1H, NH). 13C NMR, d: 64.73
(CHN), 74.68 (CHCl2), 119.33 (q, CF3, JC–F 321.7 Hz), 128.65, 129.67,
133.85, 135.14 (C6H4). IR (KBr, n/cm–1): 3300 (NH), 1380, 1230, 1200,
1140 (CF3SO2). MS, m/z (%): 272 (100) [M+ – CHCl2], 139 (12) [M+ –
– CHCl2 – CF3SO2], 138 (19) [M+ – CHCl2 – CF3SO2 – H], 83 (5)
[CHCl2]+, 69 (26) [CF3]+. Found (%): C, 30.17; H, 1.96; Cl, 29.69;
N, 3.95; S, 9.03. Calc. for C9H7Cl3F3NO2S (%): C, 30.32; H, 1.98; Cl,
29.83; N, 3.93; S, 8.99.
8d: Thiophene (2.38 ml, 30 mmol) and 3–5 drops of BF3OEt2 were
added to the solution of imine 4. The mixture was stirred for 30 h and
evaporated in a vacuum. Yeild 1.48 g (45%), mp 82 °C (hexane). 1H NMR,
d: 5.36 (d, 1H, CHN, J 4.5 Hz), 6.47 (d, 1H, CHCl2, J 4.5 Hz), 7.05 (dd,
1H, C4Hthienyl, J 3.5, J 5.0 Hz), 7.33 (d, 1H, C3Hthienyl, J 3.5 Hz), 7.54 (d,
1H, C5Hthienyl, J 5.0 Hz), 10.90 (br. s, 1H, NH). 13C NMR, d: 61.50
(CHN), 74.73 (CHCl2), 119.41 (q, CF3, JC–F 321.7 Hz), 127.06, 127.22,
128.00, 137.76 (thienyl). IR (KBr, n/cm–1): 3280 (NH), 1373, 1230,
1200, 1147 (CF3SO2). Found (%): C, 25.52; H, 1.83; Cl, 21.50; N, 4.30;
S, 19.62. Calc. for C7H6Cl2F3NO2S2 (%): C, 25.62; H, 1.84; Cl, 21.61;
N, 4.27; S, 19.54.
General procedure for the preparation of N-(1-aryl-2,2-dichloro-
ethyl)trifluoromethylsulfonamides 8a–c. An arene (50 mmol) and 3–5
drops of oleum (5–22% SO3) were added to the solution of imine 4. The
mixture was stirred for 3 h and evaporated in a vacuum (80–100 Torr).
The residue was dissolved in an ammonia liquor (5% NH3) and filtered;
the rate was neutralised with hydrochloric acid (10%). The resulting
precipitate was separated, dried and recrystallised from hexane.
8a: yield 1.51 g (47%), mp 102–103 °C. 1H NMR, d: 5.10 (d, 1H,
CHN, J 5.0 Hz), 6.50 (d, 1H, CHCl2, J 5.0 Hz), 7.34–7.57 (m, 5H, Ph),
10.77 (br. s, 1H, NH). 13C NMR, d: 65.55 (CHN), 74.92 (CHCl2), 119.33
(q, JC–F 321.7 Hz), 127.69, 128.58, 128.85, 136.12 (Ph). IR (KBr, n/cm–1):
3290 (NH), 1380, 1230, 1200, 1140 (CF3SO2). MS, m/z (%): 238 (100)
[M+ – CHCl2], 173 (12) [M+ – CF3SO2NH], 104 (43) [M+ – CHCl2 –
– CF3SO2 – H], 83 (3) [CHCl2]+, 77 (30) [Ph]+, 69 (32) [CF3]+, 51 (17)
[Ph+ – C2H2]. Found (%): C, 33.60; H, 2.48; Cl, 22.12; N, 4.37; S, 10.01.
Calc. for C9H8Cl2F3NO2S (%): C, 33.56; H, 2.50; Cl, 22.01; N, 4.35;
S, 9.95.
8b: yeild 1.41 g (42%), mp 93 °C. 1H NMR, d: 2.29 (s, 3H, Me), 5.01
(d, 1H, CHN, J 5.0 Hz), 6.44 (d, 1H, CHCl2, J 5.0 Hz), 7.19–7.41
(AA'BB' spin system, 4H, C6H4, J 8.0 Hz), 10.69 (br. s, 1H, NH). 13C
NMR, d: 20.73 (Me), 65.22 (CHN), 74.99 (CHCl2), 119.23 (q, JC–F
321.7 Hz, CF3), 127.48, 129.07, 133.03, 138.21 (C6H4). IR (KBr, n/cm–1):
3290 (NH), 1385, 1230, 1200, 1145 (CF3SO2). Found (%): C, 35.61;
H, 3.00; Cl, 20.93; N, 4.20; S, 9.58. Calc. for C10H10Cl2F3NO2S (%):
C, 35.73; H, 3.00; Cl, 21.09; N, 4.17; S, 9.54.
11: Phenol (0.94 g, 10 mmol) was added to the solution of imine 4.
The mixture was stirred for 100 h and evaporated in a vacuum. The
residue was washed sequentially with CHCl3 and water. Yield 0.43 g
1
(23%), mp 173 °C. H NMR, d: 4.37 (d, 1H, C1H, J 9.7 Hz), 6.65–7.22
(AA'BB' spin system, 8H, 2C6H4, J 7.6 Hz), 7.04 (d, 1H, CHCl2, J 9.7 Hz),
9.28 (s, 2H, 2OH). 13C NMR, d: 61.17 (C1), 76.42 (CHCl2), 115.09,
128.9, 131.89, 156.15 (C6H4). Found (%): C, 59.33; H, 4.25; Cl, 24.91.
Calc. for C14H12Cl2O2 (%): C, 59.39; H, 4.27; Cl, 25.04.
– 26 –