New synthesis of polyfluoroalkanesulfonylureas

Article abstract of DOI:10.1016/j.jfluchem.2007.05.022

This study describes a new synthesis of F-alkanesulfonyl ureas by reaction of the sodium salt of perfluoroalkane sulfonamide (R_F = C₄F₉, C₆F₁₃) with some isocyanates in anhydrous THF. The perfluorinated sulfonylureas are obtained, in one step, from moderate to good yields.

Full text of DOI:10.1016/j.jfluchem.2007.05.022

Journal of Fluorine Chemistry 128 (2007) 1353–1358
www.elsevier.com/locate/fluor
New synthesis of polyfluoroalkanesulfonylureas
*
Z. Benfodda, L. Delon, F. Guillen, H. Blancou
´ ´
Institut des Biomolecules Max Mousseron (IBMM), UMR CNRS 5247, Universite de Montpellier I et de Montpellier II,
´ `
Universite de Montpellier II CC 1706, Place Eugene Bataillon 34095, Montpellier Cedex 05, France
Received 20 March 2007; received in revised form 29 May 2007; accepted 30 May 2007
Available online 13 June 2007
Abstract
This study describes a new synthesis of F-alkanesulfonyl ureas by reaction of the sodium salt of perfluoroalkane sulfonamide (RF = C4F9,
C6F13) with some isocyanates in anhydrous THF. The perfluorinated sulfonylureas are obtained, in one step, from moderate to good yields.
# 2007 Elsevier B.V. All rights reserved.
Keywords: F-alkanesulfonyl ureas; Sodium salt of perfluoroalkane sulfonamide; Isocyanates
1. Introduction
We describe here a new preparation of perfluoroalkane-
sulfonyl ureas derivatives starting from salts of sodium of F-
alkane sulfonamides with different isocyanates, which is a very
effective and new pathway to synthesize these derivatives.
The first sulfonylurea VK 57 was tested in 1942 by Marcel
Janbon in a hospital in Montpellier France and a few years
`
later, his colleague Auguste Loubatieres demonstrated that the
compound caused the neoformation of insulin granules in rat
beta cells. Since then, the sulfonylureas have been used for the
treatment of non insulin-dependent diabetes mellitus
(NIDDM) because of their reliable efficiency in many newly
diagnosed diabetic patients and their limited side effects and
low cost [1–3].
2. Results and discussion
Perfluoroalkanesulfonyl fluorides were prepared from
perfluoroalkane iodides, in three steps, in good yields
according to a method developed in our laboratory (Scheme
1) [10,11].
In addition to their biological properties, sulfonylureas are a
relatively new class of herbicide used for selective pre and post
emergence controls of broad-leaved weeds in croplands. Such
molecules are considered of negligible environmental impact
because of their low application rates, their very low toxicity
towards animals and their short lifetime [4,5].
The reaction of perfluoroalkane iodide with Na2S2O4 in the
presence of Ca(OH)2 in a mixture of CH3CN/H2O gave the
sodium perfluoroalkanesulfinate in good yields. The reaction of
perfluoroalkanesulfinate with chlorine in water at 50 8C leads to
the formation of perfluoroalkanesulfonyl chloride correspond-
ing in good yields; the product was easily separated by a simple
decantation without any purification. The perfluoroalkanesul-
fonyl fluoride, used in this study, was synthesized from
previously prepared perfluoroalkanesulfonyl chloride and a
fluorination reagent (NH4FHF, TEA, H2O) in CH2Cl2 at 30 8C;
the product was easily separated by a simple decantation
without any purification.
However, in spite of this important interest related to this
family of compounds, there are few examples that describe the
synthesis of F-alkanesulfonyl ureas. They involve a reaction of
F-alkanesulfonyl isocyanate with amines [6,7] or a Curtius
rearrangement of carboximidoyl chlorides [8] or a reaction of
N-bis-(methylthio)methylene-trifluoromethanesulfonylamide
via chloroformamidine intermediate [9].
We do not use commercially available perfluoroalkanesul-
fonyl fluoride, manufactured by electrochemical fluorination of
the corresponding alkanesulfonyl fluoride, because of the
presence of byproducts [12].
The perfluoroalkanesulfonamides may be synthesized from
perfluoroalkanesulfonyl azide intermediates [13,14] or from
* Corresponding author. Tel.: +33 4 67 14 39 19; fax: +33 4 67 63 10 46.
E-mail address: hubert.blancou@univ-montp2.fr (H. Blancou).
0022-1139/$ – see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2007.05.022

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Z. Benfodda et al. / Journal of Fluorine Chemistry 128 (2007) 1353–1358
Scheme 1.
Scheme 2.
perfluoroalkanesulfonyl fluoride by reaction with ammonia,
suitable primary or secondary amine [15,16].
In this study, the perfluoroalkanesulfonamides (1) were
prepared, in good yields, by reaction of perfluoroalkanesulfonyl
fluoride which were placed in a dried stainless steel bomb with
an excess of ammonia without any solvent at room temperature
(Scheme 2). The perfluoroalkanesulfonamides were easily
purified by recrystallisation in ethanol/water media.
Scheme 3.
amines lead exclusively perfluoroalkanesulfinates and not to
perfluoroalkanesulfonamides [16].
It is interesting to note that the synthesis of perfluoroalk-
anesulfonamides does not occur by reaction of ammonia with
perfluoroalkanesulfonyle chloride as it is the case for the
perhydrogenated equivalents. Indeed it had been already shown
that perfluoroalkanesufonyle chloride in presence with primary
Then, the perfluoroalkanesulfonamides underwent a reac-
tion with sodium methylate to give the corresponding sodium
sulfonamides in excellent yields in a Et2O/CH3OH media (2 as
described in Scheme 2). These compounds were characterized
by 19F NMR spectroscopy and HRMS.
It is interesting to note that unlike their hydrogenated
counterparts, these sodium sulfonamides have a great stability
in particular with respect to the hydrolysis. The electron-
attracting effect of the fluorinated chain is responsible for this
high stability of these intermediates whatever the length of the
F-alkylated chain studied (C4F9, C8F17). However, the
stabilizing effect of these F-alkylated chain of sodium
perfluoroalkanesulfonamides does not prevent their reaction
with highly electrophilic compounds such as isocyanates.
In this context, highly fluorinated sulfonylurea were
obtained by the reaction of sodium F-alkane sulfonamide with
some commercially available isocyanates in anhydrous THF (3
as described in Scheme 3). In each case, an excellent conversion
of the sodium sulfonamides to sulfonylureas was observed by
NMR 19F spectroscopy.
Table 1
Preparation of polyfluoroalkanesulfonyl ureas
Entry
RF–
R–
Conversiona (%)
Yieldb (%)
83
3a
C4F9
98
3b
3c
3d
3e
3f
C8F17
C4F9
93
98
95
94
90
75
79
80
79
75
C8F17
C4F9
Recrystallisation of these compounds in ethanol/water
media gave corresponding sulfonylurea with high purity from
moderate to good yields (Table 1).
C8F17
3g
3h
3i
C4F9
C8F17
C4F9
C8F17
C4F9
C8F17
CH3(CH2)2–
CH3(CH2)2–
CH3(CH2)5–
CH3(CH2)5–
(CH3)3C–
99
93
99
94
99
95
84
62
79
49
81
75
3. Conclusion
In summary, we have developed a new and efficient method
for the synthesis of polyfluoroalkane sulfonylureas starting
from sodium sulfonamide salts and alkyl–aryl isocyanate.
The sodium sulfonamides salts were suitable intermediates
to synthetize the F-alkane sulfonylureas. The electron-
attracting effect of the fluorinated chain is responsible for its
high stability of these compounds. Further research will study
their biological properties.
3j
3k
3l
(CH3)3C–
a
The conversions were determined by 19F NMR spectroscopy (Me2SO) by
the relative integration of the functional CF2 signal of 1 compared with that of
the functional CF2 signal of 3.
b
All these compounds were crystallised in a mixture of ethanol/water.

Z. Benfodda et al. / Journal of Fluorine Chemistry 128 (2007) 1353–1358
1355
4. Experimental
from EtOH/H2O mixture to give pure product (39.8 g, yield
80%).
4.1. General
mp: 154.6 8C. 1H NMR (300.13 MHz, d6-acetone): d 8.2 (m,
2H, SO2NH2); 19F NMR (282.37 MHz, d6-acetone): d ꢀ125.8
(m, 2F, CF3CF2(CF2)6), ꢀ122.3 (m, 2F, CF3CF2CF2(CF2)5),
ꢀ121.4 (m, 6F, CF3(CF2)2(CF2)3(CF2)2), ꢀ119.9 (m, 2F,
CF3(CF2)5CF2CF2), ꢀ113.5 (m, 2F, CF3(CF2)6CF2), ꢀ80.7 (m,
3F, CF3(CF2)7); MS (FABꢀ, NBA): [MꢀH+] = 498; HRMS
calcd. for C8HO2NF17S: 497.9457; found: 497.9455.
Moisture sensitive reactions were carried out under dry
nitrogen. All isocyanate reagents were purchased from Aldrich.
Perfluoroalkane iodides were purchased from Elf Atochem.
Solvents were distilled from the appropriate drying agents
immediately prior to use.
1H, 19F, and 13C NMR spectra were recorded at 300.13 MHz,
282.37 MHz and 75.46 MHz, respectively, with a Brucker
Avance 300 spectrometer; chemical shifts are given in d ppm
relative to Me4Si, CCl3F, respectively, as internal standards.
Coupling constants are given in Hz. IR spectra were obtained
using a Nicolet 205 FT-IR instrument (n cmꢀ1). Mass spectra
and HRMS are recorded on a JEOL SX 102 spectrometer.
Melting points are recorded at atmospheric pressure unless
otherwise stated on a Stuart scientific SMP3 apparatus and were
remained without any correction.
4.3. General procedure for the synthesis of sodium
perfluoroalkane sulfonamides (2a, 2b)
A solution of perfluoroalkanesulfonamides (1 equiv.),
dissolved in anhydrous diethyl ether was added dropwise to
a suspension of sodium methylate (95%) in anhydrous
methanol (0.9 equiv.). The mixture was refluxed for 3–5 h
and then filtered. The filtrate was evaporated in vacuo and the
residue was washed three times with diethyl ether to remove the
excess of perfluoroalkanesulfonamide and then dried under
vacuum.
4.2. Synthesis of perfluoroalkanesulfonamides 1a and 1b
A typical procedure for perfluoroalkanesulfonamides 1a and
1b is described. In a 100 mL dried stainless steel bomb,
perfluoroalkanesulfonyl fluoride (1 equiv.) was placed with
magnetic stirrer, at 25 8C. Then ammonia (3 equiv.) was
transferred into the bomb through the vacuum line within 1 h.
The excess of ammonia was then removed with a flow of dry
N2. The solid product (RFSO2NHNH4 and NH4F) was acidified
with HCl followed by the addition of Et2O. The organic layer
was dried over anhydrous Na2SO4 and concentrated under
reduced pressure. The crude product was purified by
recrystallisation from EtOH/H2O (90/10) to give white crystals
of the corresponding sulfonamides.
4.3.1. Synthesis of sodium 1,1,2,2,3,3,4,4,4 nonafluoro-n-
butane sulfonamide 2a
A mixture of 20 g of perfluorobutanesulfonamide 1a
(66.8 mmol) and 3.42 g of sodium methylate (63.37 mmol)
dissolved, respectively, in anhydrous diethyl ether (100 mL)
and methanol 10 mL was refluxed for 3 h. A 21 g of 2a were
obtained (98%).
19F NMR (282.37 MHz, d6-acetone): d ꢀ125.8 (m, 2F,
CF3CF2(CF2)2), ꢀ121.0 (m, 2F, CF3CF2CF2CF2), ꢀ113.7 (m,
2F, CF3(CF2)2CF2), ꢀ80.8 (m, 3F, CF3(CF2)3); MS (FABꢀ) m/
z: 298; HRMS calcd. for C4HO2NF9S: 297.9584; found
297.9594.
4.2.1. Synthesis of 1,1,2,2,3,3,4,4,4 nonafluoro-n-
butanesulfonamide 1a
4.3.2. Synthesis of sodium 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8
heptadecafluoro-n-octane sulfonamide 2b
25 g of 1,1,2,2,3,3,4,4,4 nonafluoro-n-butanesulfonyl fluor-
ide (82.78 mmol) were placed with 0.25 mol of ammonia, then
the solid product (C4F9SO2NHNH4 and NH4F) was acidified
with HCl (3 M) (40 mL) followed by addition of Et2O (50 mL).
The product was crystallized from EtOH/H2O mixture to give
pure product (19 g, yield 77%).
mp: 67.5 8C; 1H NMR (300.13 MHz, d6-acetone): d 8.2 (m,
2H, SO2NH2); 19F NMR (282.37 MHz, d6-acetone): d ꢀ125.8
(m, 2F, CF3CF2(CF2)2), ꢀ121.0 (m, 2F, CF3CF2CF2CF2),
ꢀ113.7 (m, 2F, CF3(CF2)2CF2), ꢀ80.8 (m, 3F, CF3(CF2)3); MS
(FABꢀ, NBA): [MꢀH+] = 298; HRMS calcd. for C4HO2NF9S:
297.9584; found: 297.9572.
A mixture of 40 g of perfluorooctanesulfonamide 1b
(80.16 mmol) and 4.10 g of sodium methylate (75.94 mmol)
dissolved, respectively, in anhydrous diethyl ether (170 mL)
and methanol (12 mL) was refluxed for 5 h. A 39.4 g of 2b were
obtained (94%).
19F NMR (282.37 MHz, d6-acetone): d ꢀ125.9 (m, 2F,
CF3CF2(CF2)6), ꢀ122.4 (m, 2F, CF3CF2CF2(CF2)5), ꢀ121.5
(m, 6F, CF3(CF2)2(CF2)3(CF2)2), ꢀ120.0 (m, 2F, CF3(CF2)5
CF2CF2), ꢀ113.5 (m, 2F, CF3(CF2)6CF2), ꢀ80.8 (m, 3F,
CF3(CF2)7); MS (FABꢀ): 498; HRMS calcd. for C8HO2NF17S:
497.9457; found 497.9423.
4.4. General procedure for the synthesis of
perfluoroalkanesulfonyl urea (3a–g)
4.2.2. Synthesis of 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8
heptadecafluoro-n-octane sulfonamide 1b
50 g of 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8 heptadecafluoro-n-
octanesulfonyl fluoride (99.6 mmol) were placed with 0.3 mol
of ammonia. Then the solid product (C8F17SO2NHNH4 and
NH4F) was acidified with HCl (3 M) (80 mL), followed by
the addition of Et2O (100 mL). The product was crystallized
A solution of alkyl/aryl isocyanates (1.1 equiv.) was added
dropwise for 5–10 min to a stirred mixture of sodium
perfluoroalkanesulfonamide (1 equiv.) in anhydrous THF.
The reaction mixture was refluxed for 4–6 h. After cooling,
all volatile parts of the mixture were removed in vacuo. The

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Z. Benfodda et al. / Journal of Fluorine Chemistry 128 (2007) 1353–1358
residue was dissolved in EtOAc and washed with 1 M HCl and
water. The organic layer was dried over anhydrous Na2SO4 and
concentrated under reduced pressure. The crude product was
purified by crystallization from EtOH/H2O (90/10) to give
white crystals of the corresponding sulfonylureas.
4.4.3. Synthesis of N-phenyl, N0-(perfluorobutanesulfonyl
urea) 3c
2a (2 g, 6.23 mmol) and phenylisocyanate (0.745 mL,
6.85 mmol) in anhydrous THF (10 mL) were refluxed for
4 h. The product was crystallized from EtOH/H2O mixture to
give pure product (2 g, yield 79%).
4.4.1. Synthesis of N-cyclohexyl, N0-
(perfluorobutanesulfonyl urea) 3a
2a (2 g, 6.23 mmol) and cyclohexylisocyanate (0.875 mL,
6.85 mmol) in anhydrous THF (10 mL) were refluxed for 4 h.
The crude product was crystallized from EtOH/H2O mixture to
give pure product (2.2 g, yield 83%).
mp: 171.3 8C; IR (KBr): 3379 (nNH), 1621 (nC O), 1205
(nSO ), 1143 (nC–F); 1H NMR (300.13 MHz, d6-DMSO): d 6.9 (t,
2
J = 7.3, 1H, HAr), 7.2 (m, 2H, HAr), 7.5 (m, 2H, HAr); 19F NMR
(282.37 MHz, d6-DMSO): d ꢀ125.5 (m, 2F, CF3CF2(CF2)2),
ꢀ121.2 (m, 2F, CF3CF2CF2CF2), 112.3 (m, 2F, CF3(CF2)2CF2),
ꢀ80.3 (m, 3F, CF3(CF2)3); 13C NMR (75.46 MHz, d6-DMSO): d
107–118(C4F9), 118.1(2CAr), 121.3(CAr), 128.3(2CAr), 139.7
(CAr); 152.5 (CO); MS (FABꢀ) m/z: (MꢀH+): 417; HRMS
calcd. for C11H6O3N2F9S: 416.9955; found: 416.9939.
mp: 170.9 8C; IR (KBr): 3361 (nNH), 1687 (nC O), 1195
(nSO ), 1142 (nC–F); H NMR (300.13 MHz, d6-DMSO): d 1.1
1
2
(m, 1H, H4a), 1.3 (m, 4H, H3a, H5a, H2a, H6a), 1.5 (m, 1H, H4e),
1.6 (m, 2H, H3e and H5e), 1.7 (m, 2H, H2e and H6e), 3.4 (m, 1H,
H1), 7.2 (m, 1H, NH), 11.5 (m, 1H, NH), with ‘e’ representing
equatorial and ‘a’ axial; 19F NMR (282.37 MHz, d6-DMSO): d
ꢀ125.8 (m, 2F, CF3CF2(CF2)2), ꢀ121.4 (m, 2F, CF3CF2CF2
CF2), ꢀ111.9 (m, 2F, CF3(CF2)2CF2), ꢀ80.6 (m, 3F, CF3
(CF2)3); 13C NMR (75.46 MHz, d6-DMSO): d 24.1 (C4); 24.8
(C3 and C5); 31.7 (C2 and C6); 49.3 (C1), 107.8–118.64 (C4F9);
151.2 (C O); MS (FAB+) m/z: (M+H+): 425; HRMS calcd. for
C11H14O3N2F9S: 425.0581; found: 425.0583 (Scheme 4).
4.4.4. Synthesis of N-phenyl, N0-(perfluorooctanesulfonyl
urea) 3d
2b (4 g, 7.68 mmol) and phenylisocyanate (0.92 mL,
8.44 mmol) in anhydrous THF (20 mL) were refluxed for
6 h. The product was crystallized from EtOH/H2O mixture to
give pure product (3.8 g, yield 80%).
mp: 254.9 8C; IR (KBr): 3379 (nNH), 1621 (nC O), 1205
(nSO ), 1149 (nC–F); 1H NMR (300.13 MHz, d6-DMSO): d 6.8 (t,
2
J = 7.2, 1H, HAr), 7.2(m, 2H, HAr), 7.5(m, 2H, HAr), 7.8(m, 2H,
NH, NH); 19F NMR (282.37 MHz, d6-DMSO): d ꢀ125.8 (m, 2F,
CF3CF2(CF2)6), ꢀ122.5(m, 2F, CF3CF2CF2(CF2)5), ꢀ121.7(m,
6F, CF3(CF2)2(CF2)3(CF2)2), ꢀ120.3 (m, 2F, CF3(CF2)5
CF2CF2), ꢀ112.4 (m, 2F, CF3(CF2)6CF2), ꢀ80.3 (m, 3F,
CF3(CF2)7); 13C NMR (75.46 MHz, d6-DMSO): d 106.5–117.9
(C8F17), 117.4 (2 CAr), 120.2 (CAr), 127.6 (2 CAr), 140.7 (CAr),
156.4 (CO); MS (FABꢀ) m/z: (MꢀH+): 617; HRMS calcd. for
C15H6O3N2F17S: 616.9828; found: 616.9829.
4.4.2. Synthesis of N-cyclohexyl, N0-
(perfluorooctanesulfonyl urea) 3b
2b (1 g, 1.92 mmol) and cyclohexylisocyanate (0.27 mL,
2.11 mmol) in anhydrous THF (10 mL) were refluxed for 4 h.
The crude product was crystallized from EtOH/H2O mixture to
give pure product (0.9 g, yield 75%).
mp: 169.8 8C; IR (KBr): 3365 (nNH), 1687 (nC O), 1203
(nSO ), 1149 (nC–F); H NMR (300.13 MHz, d6-DMSO): d 1.1
1
2
(m, 1H, H4a); 1.3 (m, 4H, H3a, H5a, H2a, H6a); 1.5 (m, 1H, H4e);
1.6 (m, 2H, H3e and H5e); 1.7 (m, 2H, H2e and H6e); 3.5 (m, 1H,
H1); 7.0 (m, 1H, NH); 8.9 (m, 1H, NH), with ‘e’ representing
equatorial and ‘a’ axial; 19F NMR (282.37 MHz, d6-DMSO): d
4.4.5. Synthesis of N-benzyl, N0-(perfluorobutanesulfonyl
urea) 3e
2a (1.5 g, 4.67 mmol) and benzylisocyanate (0.745 mL,
5.14 mmol) in anhydrous THF (10 mL) were refluxed for 4 h.
The product was crystallized from EtOH/H2O mixture to give
pure product (2 g, yield 79%).
ꢀ126.3 (m, 2F, CF CF ðCF2Þ ), ꢀ122.9 (m, 2F, CF CF
ꢀ
3
2
3
2
6
CF ðCF2Þ ), ꢀ122.0 (m, 6F, CF (CF ) (CF ) (CF ) ), ꢀ120.6
ꢀ
2
3
2 2
2 3
2 2
5
(m, 2F, CF3(CF2)5CF2CF2), ꢀ112.0 (m, 2F, CF3(CF2)6CF2),
ꢀ80.9 (m, 3F, CF3(CF2)7); 13C NMR (75.46 MHz, d6-DMSO): d
24.0 (C4); 24.8 (C3 and C5); 31.7 (C2 and C6); 49.2 (C1), 106.8–
118.1 (C8F17); 151.2 (C O); MS (FAB+) m/z: (M+H+): 625;
HRMS calcd. for C15H14O3N2F17S: 625.0454; found: 625.0461
(Scheme 5).
mp: 171.3 8C; IR (KBr): 3336 (nNH), 1690 (nC O), 1208
(nSO ), 1141 (nC–F); H NMR (300.13 MHz, d6-DMSO): d 4.3
1
2
(s, 2H, NCH2), 7.2 (m, 3H, HAr), 7.3 (m, 2H, HAr), 10 (m, 2H,
NH); 19F NMR (282.37 MHz, d6-DMSO): d ꢀ125.64 (m, 2F,
CF3CF2(CF2)2), ꢀ121.23 (m, 2F, CF3CF2CF2CF2), 111.86 (m,
2F, CF3(CF2)2CF2), ꢀ80.34 (m, 3F, CF3(CF2)3); 13C NMR
(75.46 MHz, d6-DMSO): d 43.6 (CH2), 107–118 (C4F9), 126.9
(CAr), 126.9 (2 CAr), 128.2 (2 CAr), 138.8 (CAr), 152 (CO); MS
(FAB+) m/z: (M+H+): 433; HRMS calcd. for C12H10O3N2F9S:
433.0268; found: 433.0264.
Scheme 4.
4.4.6. Synthesis of N-benzyl, N0-(perfluorooctanesulfonyl
urea) 3f
2b (4 g, 7.68 mmol) and benzylisocyanate (0.92 mL,
8.44 mmol) in anhydrous THF (20 mL) were refluxed for
6 h. The product was crystallized from EtOH/H2O mixture to
give pure product (3.64 g, yield 75%).
Scheme 5.

Z. Benfodda et al. / Journal of Fluorine Chemistry 128 (2007) 1353–1358
1357
mp: 182.2 8C; IR (KBr): 3336 (nNH), 1687 (nC O), 1203
(nSO ), 1151 (nC–F); H NMR (300.13 MHz, d6-DMSO): d 4.3
J = 6.6, 3H, CH3), 1.2 (m, 6H, (CH2)2(CH2)3CH3), 1.4 (m, 2H,
CH2CH2(CH2)3CH3), 3.1 (m, 2H, CH2(CH2)4CH3), 7.2 (m, 1H,
NH), 11.5 (m, 1H, NH); 19F NMR (282.37 MHz, d6-DMSO): d
ꢀ125.8 (m, 2F, CF3CF2(CF2)2), ꢀ121.4 (m, 2F, CF3CF2
CF2CF2), 112.1 (m, 2F, CF3(CF2)2CF2), ꢀ80.5 (m, 3F,
CF3(CF2)3); 13C NMR (75.46 MHz, d6-DMSO): d 13.7
(CH3), 21.9 (CH2CH3), 25.6 (CH2(CH2)2CH3), 28.7 (CH2CH2
CH3), 30.8 (NCH2CH2), 40.1 (NCH2), 107–119 (C4F9), 153.10
(CO); MS (FAB+) m/z: (M+H+): 427; HRMS calcd. for
C11H16O3N2F9S: 427.0738; found: 427.0734.
1
2
(s, 2H, NCH2), 7.2 (m, 3H, HAr), 7.3 (m, 2H, HAr), 7.7 (m, 2H,
NH, NH); 19F NMR (282.37 MHz, d6-DMSO): d ꢀ125.7 (m,
ꢀ
2F, CF3CF2(CF2)6), ꢀ122.4 (m, 2F, CF3CF2 CF2(CF2)5),
ꢀ121.6 (m, 6F, CF3(CF2)2(CF2)3(CF2)2), ꢀ120.2 (m, 2F,
CF3(CF2)5CF2CF2), ꢀ111.8 (m, 2F, CF3(CF2)6CF2), ꢀ80.2 (m,
3F, CF3(CF2)7); 13C NMR (75.46 MHz, d6-DMSO): d 43.6
(CH2), 107.2–118 (C8F17), 126.81 (CAr), 126.9 (2 CAr), 128.2
(2 CAr), 138.9 (CAr), 153.1 (CO); MS (FAB+) m/z: (M+H+):
633; HRMS calcd. for C16H10O3N2F17S: 633.0141; found:
633.0121.
4.4.10. Synthesis of N-hexyl, N0-(perfluorooctanesulfonyl
urea) 3j
2b (4 g, 7.68 mmol) and n-hexylisocyanate (1.22 mL,
8.44 mmol) in anhydrous THF (20 mL) were refluxed for
6 h. The product was crystallized from EtOH/H2O mixture to
give pure product (2.36 g, yield 49%).
4.4.7. Synthesis of N-propyl, N0-(perfluorobutanesulfonyl
urea) 3g
2a (2 g, 6.23 mmol) and n-propylisocyanate (0.64 mL,
6.85 mmol) in anhydrous THF (10 mL) were refluxed for
4 h. The product was crystallized from EtOH/H2O mixture to
give pure product (2 g, yield 84%).
mp: 157.9 8C; IR (KBr): 3358 (nNH), 1686 (nC O), 1220
(nSO ), 1150 (nC–F); 1H NMR (300.13 MHz, d6-DMSO): d 0.8 (t,
2
mp: 162.5 8C; IR (KBr): 3351 (nNH), 1693 (nC O), 1202
J = 6.6, 3H, CH3), 1.2 (m, 6H, (CH2)2(CH2)3CH3), 1.4 (m, 2H,
CH2CH2(CH2)3CH3), 3.1 (m, 2H, CH2(CH2)4CH3), 5.2 (m, 1H,
NH), 7 (m, 1H, NH); 19F NMR (282.37 MHz, d6-DMSO): d
ꢀ125.8 (m, 2F, CF3CF2(CF2)6), ꢀ122.5 (m, 2F, CF3CF2
CF2(CF2)5), ꢀ121.5 (m, 6F, CF3(CF2)2(CF2)3(CF2)2), ꢀ120.2
(m, 2F, CF3(CF2)5CF2CF2), ꢀ112 (m, 2F, CF3(CF2)6CF2),
ꢀ80.2 (m, 3F, CF3(CF2)7); 13C NMR (75.46 MHz, d6-DMSO): d
13.7 (CH3), 21.9 (CH2CH3), 25.7 (CH2(CH2)2CH3), 28.8
(nSO ), 1154 (nC–F); 1H NMR (300.13 MHz, d6-DMSO): d 0.8 (t,
J = 7.4, 3H, CH3), 1.4 (m, 2H, CH2CH3), 3.05 (t, J = 7, 2H,
2
NHCH2CH2 ), 7.5 (m, 1H, NH), 11.7 (m, 1H, NH); 19F NMR
ꢀ
(282.37 MHz, d6-DMSO): d ꢀ125.7 (m, 2F, CF3CF2(CF2)2),
ꢀ121.3 (m, 2F, CF3CF2CF2CF2), ꢀ112.1 (m, 2F, CF3(CF2)
2CF2), ꢀ80.4 (m, 3F, CF3(CF2)3); 13C NMR (75.46 MHz, d6-
DMSO): d 10.8 (CH3), 22.0 (CH2CH3), 41.9 (CH2CH2), 107–
119 (C4F9), 153.0 (CO); MS (FAB+) m/z: (M+H+): 385; HRMS
calcd. for C8H10O3N2F9S: 385.0268; found: 385.0268.
ꢀ
(CH2CH2CH3), 30.8 (NCH2CH2), 40.1 (NCH2 ), 106–122
(C8F17), 153.1 (CO); MS (FAB+) m/z: (M+H+): 627; HRMS
calcd. for C15H16O3N2F17S: 627.0610; found: 627.0618.
4.4.8. Synthesis of N-propyl, N0-(perfluorooctanesulfonyl
urea) 3h
2b (1 g, 1.92 mmol) and n-propylisocyanate (0.2 mL,
2.11 mmol) in anhydrous THF (20 mL) were refluxed for
6 h. The product was crystallized from EtOH/H2O mixture to
give pure product (0.7 g, yield 62%).
4.4.11. Synthesis of N-tertbutyl, N0-
(perfluorobutanesulfonyl urea) 3k
2a (1 g, 3.11 mmol) and tertbutyl isocyanate (0.39 mL,
3.42 mmol) in anhydrous THF (5 mL) were refluxed for 4 h.
The product was crystallized from EtOH/H2O mixture to give
pure product (1 g, yield 81%).
mp: 150.8 8C; IR (KBr): 3351 (nNH), 1688 (nC O), 1202
(nSO ), 1142 (nC–F); H NMR (300.13 MHz, d6-DMSO): d 0.8
1
mp: 104.8 8C; IR (KBr): 3396 (nNH), 1698 (nC O), 1188
2
(t, J = 7.4, 3H, CH3), 1.4 (m, 2H, CH2CH3), 3 (t, J = 6.9, 2H,
NHCH2CH2), 5.9 (m, 1H, NH), 7.2 (m, 1H, NH); 19F NMR
(282.37 MHz, d6-DMSO): d ꢀ125.9 (m, 2F, CF3CF2(CF2)6),
ꢀ122.6 (m, 2F, CF3CF2CF2(CF2)5), ꢀ121.7 (m, 6F,
CF3(CF2)2(CF2)3(CF2)2), ꢀ120.3 (m, 2F, CF3(CF2)5CF2CF2),
(nSO ), 1139 (nC–F); 1H NMR (300.13 MHz, d6-DMSO): d 1.25
2
(s, 9H, (CH3)3), 6.8 (m, 1H, NH), 8.7 (m, 1H, NH); 19F NMR
(282.37 MHz, d6-DMSO): d ꢀ125.9 (m, 2F, CF3CF2(CF2)2),
ꢀ121.5 (m, 2F, CF3CF2CF2CF2), ꢀ111.8 (m, 2F, CF3(CF2)2
CF2), ꢀ80.6 (m, 3F, CF3(CF2)3); NMR 13C (75.46 MHz, d6-
DMSO): d 27.9 (CH3)3, 50.9 (C(CH3)3), 107–119 (C4F9), 149.2
(C O); MS (FAB+) m/z: (M+H+): 399; HRMS calcd. for
C9H12O3N2F9S: 399.0425; found: 399.0428.
ꢀ112 (m, 2F, CF3(CF2)6CF2), ꢀ80.3 (m, 3F, CF3(CF2)7); 13
C
NMR (75.46 MHz, d6-DMSO): d 10.5 (CH3), 21.9 (CH2CH3),
41.8 (CH2CH2), 107.5–117.9 (C8F17), 152.7 (CO); MS (FAB+)
m/z: (M+H+): 585; HRMS calcd. for C12H10O3N2F17S:
585.0141; found: 585.0126.
4.4.12. Synthesis of N-tertbutyl, N0-
(perfluorooctanesulfonyl urea) 3l
2b (4 g, 7.68 mmol) and tertbutylisocyanate (0.96 mL,
8.44 mmol) in anhydrous THF (20 mL) were refluxed for
6 h. The product was crystallized from EtOH/H2O mixture to
give pure product (3.4 g, yield 75%).
4.4.9. Synthesis of N-hexyl, N0-(perfluorobutanesulfonyl
urea) 3i
2a (2 g, 6.23 mmol) and n-hexylisocyanate (0.99 mL,
6.85 mmol) in anhydrous THF (10 mL) were refluxed for
4 h. The product was crystallized from EtOH/H2O mixture to
give pure product (2.1 g, yield 79%).
mp: 119 8C; IR (KBr): 3396 (nNH), 1704 (nC ), 1204 (nSO2 ),
O
1
1151 (nC–F); H NMR (300.13 MHz, d6-DMSO): d 1.2 (s, 9H,
mp: 134.9 8C; IR (KBr): 3340 (nNH), 1690 (nC O), 1206
(CH3)3), 6.7 (m, 1H, NH), 8.9 (m, 1H, NH); 19F NMR
(282.37 MHz, d6-DMSO): d ꢀ126.6 (m, 2F, CF3CF2(CF2)6),
(nSO ), 1137 (nC–F); 1H NMR (300.13 MHz, d6-DMSO): d 0.8 (t,
2

1358
Z. Benfodda et al. / Journal of Fluorine Chemistry 128 (2007) 1353–1358
[7] M.R.C. Gerstenberger, A. Haas, H. Pauling, Helv. Chim. Acta 65 (1982)
490–494.
ꢀ123.1(m, 2F, CF3CF2CF2(CF2)5), ꢀ122.2 (m, 6F, CF3(CF2)2
(CF2)3(CF2)2), ꢀ120.7 (m, 2F, CF3(CF2)5CF2CF2), ꢀ112 (m,
2F, CF3(CF2)6CF2), ꢀ81.3 (m, 3F, CF3(CF2)7); 13C NMR
(75.46 MHz, d6-DMSO): d 27.7 (CH3)3, 50.8 (C(CH3)3), 106–
122 (C8F17), 149.3 (C O); MS (FAB+) m/z: (M+H+): 599;
HRMS calcd. for C13H12O3N2F17S: 599.0297; found: 599.0314.
[8] L.M. Yagupolskii, S.V. Shelyazhenko, I.I. Maletina, V.N. Petrik, E.B.
Rusanov, A.N. Chernega, Eur. J. Org. Chem. (2001) 1225–1233.
[9] V.N. Petrik, N.V. Kondratenko, L.M. Yagupolskii, J. Fluorine Chem. 124
(2003) 151–158.
[10] H.J. Blancou, F.D. Guillen, WO 2002081431 (Chem. Abstr. 137:
294708).
[11] H.J. Blancou, F.D. Guillen, WO 2002081081 (Chem. Abstr. 137:296564).
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[13] H.J. Lehmler, V.V.V.N.S. Rama Rao, D. Nauduri, J.D. Vargo, S. Parkin, J.
Fluorine Chem. 128 (2007) 595–607.
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