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Synthesis of F-alkyl bis(N-aroxy or alkoxysulfonyl)dicarbamates
Journal of Fluorine Chemistry 105 (2000) 103±105
Synthesis of F-alkyl bis(N-aroxy or alkoxysulfonyl)dicarbamates H. Sbihi, M. Beji, A. Baklouti* Laboratoire de Chimie Structurale Organique, Faculte des Sciences de Tunis, Campus Universitaire, 1060 Tunis, Tunisia Received 29 February 2000; accepted 11 April 2000
Abstract The synthesis of F-alkyl bis(N-aroxy or alkoxysulfonyl)dicarbamates has been achieved at room temperature by the action of Falkyldiols on aroxy or alkoxysulfonyl isocyanates. # 2000 Elsevier Science S.A. All rights reserved. Keywords: F-alkyl; Aroxysulfonyl isocyanate; Aroxy or alkoxysulfonyl dicarbamates
1. Introduction The action of diols on simple isocyanates has been described as one of the ways to prepare diurethanes and polyurethanes [1,2]. In the case of aroxysulfonyl isocyanates which react readily with ¯uorinated alcohols, thiols and amines as we have reported previously [3±5], we extend the addition reaction to the F-alkyldiol HOCH2-(CF2)3-CH2OH and C6F13-CHOH-CH2OH. 2. Results Generally, the addition of hydroxylated compounds to simple isocyanates may be achieved at high temperature. This reaction takes place with the more reactive alkoxy and aroxysulfonyl isocyanates at room temperature. As shown in Scheme 1, the synthesis of compounds 4a±d and 5a±d was realized in ether at 258C. The yields of the reactions do not exceed 40% for the starting aroxysulfonyl isocyanates bearing electrodonor substituents on the aromatic ring and are higher with electronattracting groups. In all cases, mono adducts were not isolated; each of the two hydroxy groups of the diols react with one aroxysulfonyl isocyanate molecule to furnish the corresponding F-alkyl bis(N-aroxy or alkoxysulfonyl)dicarbamates (Table 1). A herbicidal activity study of these new compounds is in progress.
300 apparatus at 300 MHz for 1H and 282 MHz for 19F. Chemical shifts are reported in ppm from internal TMS for 1 H and from CFCl3 for 19F. HRMS spectra were obtained with a MAT SBE spectrometer. Alkoxy and aroxysulfonyl isocyanates [6,7] (1a±d) and diols 1 and 2 [8,9] were prepared according to literature methods. 3.1. Synthesis of F-alkyl bis(N-aroxy or alkoxysulfonyl)dicarbamates 4a±d A solution of F-alkyldiols (5 mmol) in anhydrous ether was added under argon to 10 mmol of alkoxy or aroxysulfonyl isocyanate dissolved in the same solvent. The mixture was stirred for 60±90 min. The solid product was obtained after evaporation of the solvent and was recrystallized from CCl4.
mp, 1008C. IR (n, cmÿ1): 3428 (NH); 1775 (C=O); 1377 and 1176 (SO2); 1100±1300 (C±F). 19F NMR (d ppm): ÿ122.3, ÿ122.2 (4F, 2(CF2)); ÿ127 (2F, CF2). 1H NMR (d ppm): 7.03 (6H, aromatic); 4.7 (4H, 2(O-CH2-CF2)); 2.37 (12H, 4(CH3-Ar)). HRMS: Calcd. for C23H24N2O10S2F6: 666.0776; found: 666.0789.
3. Experimental IR spectra were obtained by using a Perkin-Elmer FTPARAGON. NMR spectra were recorded on a Bruker AC *
Corresponding author. Fax: 216-1-871-666.
mp, 1128C. IR (n, cmÿ1): 3369 (NH); 1778 (C=O); 1376 and 1166 (SO2); 1100±1300 (C±F). 19F NMR (d ppm): ÿ117,
0022-1139/00/$ ± see front matter # 2000 Elsevier Science S.A. All rights reserved. PII: S 0 0 2 2 - 1 1 3 9 ( 0 0 ) 0 0 2 8 2 - 7
104
H. Sbihi et al. / Journal of Fluorine Chemistry 105 (2000) 103±105
Scheme 1.
ÿ116.8 (4F, 2(CF2)); ÿ122.7 (2F, CF2). 1H NMR (d ppm): 6.86 (4H, aromatic); 4.7 (4H, 2(O-CH2-CF2)); 2.3 (12H, 4(CH3-Ar)); 2.2 (6H, 2(CH3-Ar)). HRMS: Calcd. for C25H28N2O10S2F6: 694.1089; found: 694.1045.
NMR (d ppm): 7.43, ÿ7.24 (8H, aromatic); 4.8 (4H, 2(OCH2-CF2)). HRMS: Calcd. for C19H14N2O10S2F6Cl2: 677.9371; found: 677.9354.
mp, 1428C. IR (n, cmÿ1): 3374 (NH); 1771 (C=O); 1402 and 1162 (SO2); 1100±1300 (C±F). 19F NMR (d ppm): ÿ119.8, ÿ119.6 (4F, 2(CF2)); ÿ125.6 (2F, CF2). 1H NMR (d ppm): 4.98 (4H, 2(CCl3-CH2)); 4.76 (4H, 2(O-CH2-CF2)). HRMS:
ÿ1
mp, 1358C. IR (n, cm ): 3366 (NH); 1776.6 (C=O); 1402 and 1171 (SO2); 1100±1300 (C±F). 19F NMR (d ppm): ÿ117.1, ÿ116.8 (4F, 2(CF2)); ÿ122.8 (2F, CF2). 1H Table 1 Prepared F-alkyl dicarbamates Dicarbamates
Yield (%)
Time (min)
40
85
40
90
60
70
60
68
40
78
38
82
5c
80
60
5d
70
60
4a
4b
4c 4d
5a
5b
H. Sbihi et al. / Journal of Fluorine Chemistry 105 (2000) 103±105
105
found:
CH2). HRMS: Calcd. for C22H13N2O10S2F13Cl2: 845.9181; found: 845.9159.
mp, 1088C. IR (n, cmÿ1): 3366 (NH); 1769 (C=O); 1396 and 1173 (SO2); 1100±1300 (C±F). 19F NMR (d ppm): ÿ80.76 (3F, CF3); ÿ120.6 (2F, CF2); ÿ121.7 (4F, 2(CF2)); ÿ122.7 (2F, CF2); ÿ126 (2F, CF2). 1H NMR (d ppm): 7.1ÿ6.9 (6H, aromatic); 4.56 (1H, CH); 4.4 (2H, CH2); 2.39 (6H, 2(CH3Ar)); 2.28 (6H, 2(CH3-Ar)). HRMS: Calcd. for C26H23N2O10S2F13: 834.0586; found: 834.0589.
mp, 1278C. IR (n, cmÿ1): 3347 (NH); 1767 (C=O); 1401 and 1182 (SO2); 1100±1300 (C±F). 19F NMR (d ppm): ÿ81 (3F, CF3); ÿ119.3 (2F, CF2); ÿ121.8 (4F, 2(CF2)); ÿ122.3 (2F, CF2); ÿ126.2 (2F, CF2). 1H NMR (d ppm): 5 (2H, CCl3CH2); 4.9 (2H, CCl3-CH2); 4.6 (1H, CH); 4.4 (2H, CH2). HRMS: Calcd. for C26H23N2O10S2F13: 834.0586; found: 834.0589.
Calcd. for 717.7869.
C11H10N2O10S2F6Cl6:
717.7812;
Acknowledgements mp, 1048C. IR (n, cmÿ1): 3368 (NH); 1768 (C=O); 1400 and 1172 (SO2); 1100±1300 (C±F). 19F NMR (d ppm): ÿ80.76 (3F, CF3); ÿ118.5 (2F, CF2); ÿ121.7 (4F, 2(CF2)); ÿ123 (2F, CF2); ÿ126 (2F, CF2). 1H NMR (d ppm): 7.2±6.86 (4H, aromatic); 4.6 (1H, CH); 4.4 (2H, CH2); 2.42 (6H, 2(CH3Ar)); 2.39 (6H, 2(CH3-Ar)); 2.24 (3H, CH3-Ar); 2.2 (3H, CH3-Ar). HRMS: Calcd. for C28H27N2O10S2F13: 862.0899; found: 862.0854.
mp, 1208C. IR (n, cmÿ1): 3353 (NH); 1769 (C=O); 1383 and 1176 (SO2); 1100±1300 (C±F). 19F NMR (d ppm): ÿ80.73 (3F, CF3); ÿ119.5 (2F, CF2); ÿ121.2 (4F, 2(CF2)); ÿ122.5 (2F, CF2); ÿ125.9 (2F, CF2). 1H NMR (d ppm): 11.2 (2H, NH); 7.43±7.27 (8H, aromatic); 4.9 (1H, CH); 4.5 (2H,
We thank Prof. J. Courtieu and F. Perez for HRMS measurements. References [1] M.N. Belgacem, J. Quilleron, A. Gandini, Eur. Polym. J. 29 (1993) 1217. [2] E. Orthmann, A. Warmuth, W. Goyert, H.G. Hoppe, H.G. Wussow, (Bayer A-G) Ger. Offen. DE 4,113,891 (Cl. CO8L 75/00), 29 October 1992; Appl. 27 April 1991, 14 pp. [3] M. Beji, H. Sbihi, A. Baklouti, A. Cambon, J. Fluorine Chem. 99 (1999) 17. [4] M. El Kateb, M. Beji, A. Baklouti, J. Fluorine Chem. 81 (1997) 139. [5] M. El Kateb, M. Beji, A. Baklouti, J. Fluorine Chem. 94 (1999) 119. [6] G. Lohaus, Chem. Ber. 105 (1972) 2791. [7] M. Hedayatullah, J.F. Brault, C.R. Acad. Sci., C 285 (1977) 153. [8] D.A. Rausch, A.M. Lovelace, L.E. Coleman Jr., J. Org. Chem. 21 (1956) 1328. [9] E.T. McBee, T.M. Burton, J. Am. Chem. Soc. 74 (1952) 3022.
Synthesis of F-alkyl bis(N-aroxy or alkoxysulfonyl)dicarbamates H. Sbihi, M. Beji, A. Baklouti* Laboratoire de Chimie Structurale Organique, Faculte des Sciences de Tunis, Campus Universitaire, 1060 Tunis, Tunisia Received 29 February 2000; accepted 11 April 2000
Abstract The synthesis of F-alkyl bis(N-aroxy or alkoxysulfonyl)dicarbamates has been achieved at room temperature by the action of Falkyldiols on aroxy or alkoxysulfonyl isocyanates. # 2000 Elsevier Science S.A. All rights reserved. Keywords: F-alkyl; Aroxysulfonyl isocyanate; Aroxy or alkoxysulfonyl dicarbamates
1. Introduction The action of diols on simple isocyanates has been described as one of the ways to prepare diurethanes and polyurethanes [1,2]. In the case of aroxysulfonyl isocyanates which react readily with ¯uorinated alcohols, thiols and amines as we have reported previously [3±5], we extend the addition reaction to the F-alkyldiol HOCH2-(CF2)3-CH2OH and C6F13-CHOH-CH2OH. 2. Results Generally, the addition of hydroxylated compounds to simple isocyanates may be achieved at high temperature. This reaction takes place with the more reactive alkoxy and aroxysulfonyl isocyanates at room temperature. As shown in Scheme 1, the synthesis of compounds 4a±d and 5a±d was realized in ether at 258C. The yields of the reactions do not exceed 40% for the starting aroxysulfonyl isocyanates bearing electrodonor substituents on the aromatic ring and are higher with electronattracting groups. In all cases, mono adducts were not isolated; each of the two hydroxy groups of the diols react with one aroxysulfonyl isocyanate molecule to furnish the corresponding F-alkyl bis(N-aroxy or alkoxysulfonyl)dicarbamates (Table 1). A herbicidal activity study of these new compounds is in progress.
300 apparatus at 300 MHz for 1H and 282 MHz for 19F. Chemical shifts are reported in ppm from internal TMS for 1 H and from CFCl3 for 19F. HRMS spectra were obtained with a MAT SBE spectrometer. Alkoxy and aroxysulfonyl isocyanates [6,7] (1a±d) and diols 1 and 2 [8,9] were prepared according to literature methods. 3.1. Synthesis of F-alkyl bis(N-aroxy or alkoxysulfonyl)dicarbamates 4a±d A solution of F-alkyldiols (5 mmol) in anhydrous ether was added under argon to 10 mmol of alkoxy or aroxysulfonyl isocyanate dissolved in the same solvent. The mixture was stirred for 60±90 min. The solid product was obtained after evaporation of the solvent and was recrystallized from CCl4.
mp, 1008C. IR (n, cmÿ1): 3428 (NH); 1775 (C=O); 1377 and 1176 (SO2); 1100±1300 (C±F). 19F NMR (d ppm): ÿ122.3, ÿ122.2 (4F, 2(CF2)); ÿ127 (2F, CF2). 1H NMR (d ppm): 7.03 (6H, aromatic); 4.7 (4H, 2(O-CH2-CF2)); 2.37 (12H, 4(CH3-Ar)). HRMS: Calcd. for C23H24N2O10S2F6: 666.0776; found: 666.0789.
3. Experimental IR spectra were obtained by using a Perkin-Elmer FTPARAGON. NMR spectra were recorded on a Bruker AC *
Corresponding author. Fax: 216-1-871-666.
mp, 1128C. IR (n, cmÿ1): 3369 (NH); 1778 (C=O); 1376 and 1166 (SO2); 1100±1300 (C±F). 19F NMR (d ppm): ÿ117,
0022-1139/00/$ ± see front matter # 2000 Elsevier Science S.A. All rights reserved. PII: S 0 0 2 2 - 1 1 3 9 ( 0 0 ) 0 0 2 8 2 - 7
104
H. Sbihi et al. / Journal of Fluorine Chemistry 105 (2000) 103±105
Scheme 1.
ÿ116.8 (4F, 2(CF2)); ÿ122.7 (2F, CF2). 1H NMR (d ppm): 6.86 (4H, aromatic); 4.7 (4H, 2(O-CH2-CF2)); 2.3 (12H, 4(CH3-Ar)); 2.2 (6H, 2(CH3-Ar)). HRMS: Calcd. for C25H28N2O10S2F6: 694.1089; found: 694.1045.
NMR (d ppm): 7.43, ÿ7.24 (8H, aromatic); 4.8 (4H, 2(OCH2-CF2)). HRMS: Calcd. for C19H14N2O10S2F6Cl2: 677.9371; found: 677.9354.
mp, 1428C. IR (n, cmÿ1): 3374 (NH); 1771 (C=O); 1402 and 1162 (SO2); 1100±1300 (C±F). 19F NMR (d ppm): ÿ119.8, ÿ119.6 (4F, 2(CF2)); ÿ125.6 (2F, CF2). 1H NMR (d ppm): 4.98 (4H, 2(CCl3-CH2)); 4.76 (4H, 2(O-CH2-CF2)). HRMS:
ÿ1
mp, 1358C. IR (n, cm ): 3366 (NH); 1776.6 (C=O); 1402 and 1171 (SO2); 1100±1300 (C±F). 19F NMR (d ppm): ÿ117.1, ÿ116.8 (4F, 2(CF2)); ÿ122.8 (2F, CF2). 1H Table 1 Prepared F-alkyl dicarbamates Dicarbamates
Yield (%)
Time (min)
40
85
40
90
60
70
60
68
40
78
38
82
5c
80
60
5d
70
60
4a
4b
4c 4d
5a
5b
H. Sbihi et al. / Journal of Fluorine Chemistry 105 (2000) 103±105
105
found:
CH2). HRMS: Calcd. for C22H13N2O10S2F13Cl2: 845.9181; found: 845.9159.
mp, 1088C. IR (n, cmÿ1): 3366 (NH); 1769 (C=O); 1396 and 1173 (SO2); 1100±1300 (C±F). 19F NMR (d ppm): ÿ80.76 (3F, CF3); ÿ120.6 (2F, CF2); ÿ121.7 (4F, 2(CF2)); ÿ122.7 (2F, CF2); ÿ126 (2F, CF2). 1H NMR (d ppm): 7.1ÿ6.9 (6H, aromatic); 4.56 (1H, CH); 4.4 (2H, CH2); 2.39 (6H, 2(CH3Ar)); 2.28 (6H, 2(CH3-Ar)). HRMS: Calcd. for C26H23N2O10S2F13: 834.0586; found: 834.0589.
mp, 1278C. IR (n, cmÿ1): 3347 (NH); 1767 (C=O); 1401 and 1182 (SO2); 1100±1300 (C±F). 19F NMR (d ppm): ÿ81 (3F, CF3); ÿ119.3 (2F, CF2); ÿ121.8 (4F, 2(CF2)); ÿ122.3 (2F, CF2); ÿ126.2 (2F, CF2). 1H NMR (d ppm): 5 (2H, CCl3CH2); 4.9 (2H, CCl3-CH2); 4.6 (1H, CH); 4.4 (2H, CH2). HRMS: Calcd. for C26H23N2O10S2F13: 834.0586; found: 834.0589.
Calcd. for 717.7869.
C11H10N2O10S2F6Cl6:
717.7812;
Acknowledgements mp, 1048C. IR (n, cmÿ1): 3368 (NH); 1768 (C=O); 1400 and 1172 (SO2); 1100±1300 (C±F). 19F NMR (d ppm): ÿ80.76 (3F, CF3); ÿ118.5 (2F, CF2); ÿ121.7 (4F, 2(CF2)); ÿ123 (2F, CF2); ÿ126 (2F, CF2). 1H NMR (d ppm): 7.2±6.86 (4H, aromatic); 4.6 (1H, CH); 4.4 (2H, CH2); 2.42 (6H, 2(CH3Ar)); 2.39 (6H, 2(CH3-Ar)); 2.24 (3H, CH3-Ar); 2.2 (3H, CH3-Ar). HRMS: Calcd. for C28H27N2O10S2F13: 862.0899; found: 862.0854.
mp, 1208C. IR (n, cmÿ1): 3353 (NH); 1769 (C=O); 1383 and 1176 (SO2); 1100±1300 (C±F). 19F NMR (d ppm): ÿ80.73 (3F, CF3); ÿ119.5 (2F, CF2); ÿ121.2 (4F, 2(CF2)); ÿ122.5 (2F, CF2); ÿ125.9 (2F, CF2). 1H NMR (d ppm): 11.2 (2H, NH); 7.43±7.27 (8H, aromatic); 4.9 (1H, CH); 4.5 (2H,
We thank Prof. J. Courtieu and F. Perez for HRMS measurements. References [1] M.N. Belgacem, J. Quilleron, A. Gandini, Eur. Polym. J. 29 (1993) 1217. [2] E. Orthmann, A. Warmuth, W. Goyert, H.G. Hoppe, H.G. Wussow, (Bayer A-G) Ger. Offen. DE 4,113,891 (Cl. CO8L 75/00), 29 October 1992; Appl. 27 April 1991, 14 pp. [3] M. Beji, H. Sbihi, A. Baklouti, A. Cambon, J. Fluorine Chem. 99 (1999) 17. [4] M. El Kateb, M. Beji, A. Baklouti, J. Fluorine Chem. 81 (1997) 139. [5] M. El Kateb, M. Beji, A. Baklouti, J. Fluorine Chem. 94 (1999) 119. [6] G. Lohaus, Chem. Ber. 105 (1972) 2791. [7] M. Hedayatullah, J.F. Brault, C.R. Acad. Sci., C 285 (1977) 153. [8] D.A. Rausch, A.M. Lovelace, L.E. Coleman Jr., J. Org. Chem. 21 (1956) 1328. [9] E.T. McBee, T.M. Burton, J. Am. Chem. Soc. 74 (1952) 3022.