One-Step Synthesis of New Anionic Gemini Surface Active Azoinitiators

Miloš Sedlák; Klaus Tauer

doi:10.1055/s-2003-45006

LETTER

One-Step Synthesis of New Anionic Gemini Surface Active Azoinitiators

Miloš Sedlák*^a, Klaus Tauer^b
^a Department of Organic Chemistry, University of Pardubice, Nám. Č s. Legií 565, 53210 Pardubice, Czech Republic
Fax: +42(466)037068; e-Mail: Milos.Sedlak@upce.cz;
^b Max-Planck-Institute of Colloids and Interfaces, Research Campus Golm, 14424 Potsdam, Germany

Abstract

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Abstract

A one-step reaction of AIBN, sulfuric oxide and the respective alkene (1-octene, 1-decene, 1-tetradecene, and 1-hexadecene) in the medium of trifluoroacetic acid and 1,2-dichloroethane and subsequent neutralisation provided sodium salts of 2,2′-azobis(N-2′-methylpropanoyl-2-amino-alkyl-1)-sulfonates. The sulfonates obtained are anionic gemini surfactants, which simultaneously act as initiators of emulsion polymerisations (INISURFs).

Key words

surface-active initiator - gemini surfactants - Ritter reaction - sulfonates - ion-exchange chromatography

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References

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Sodium salt of 2,2′-azobis(N-2′-methylpropanoyl-2-amino-octyl)-1-sulfonate (1a, n = 5): Yield: 52%. ¹H NMR (400 MHz, DMSO-d ₆): d = 0.89 (m, 3 H), 1.28-1.36 (m, 11 H), 1.40 (m, 3 H), 1.52 (m, 1 H), 1.67 (m, 1 H); 3.25 (m, 1 H), 3.46 (m, 1 H), 4.58 (m, 1 H), 7.59 (m, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): d = 14.1, 22.3, 25.1, 28.9, 29.3, 36.4, 39.1-40.2, 57.5, 71.9, 172.1. Anal. Calcd for C₂₄H₄₆N₄Na₂O₈S₂ (628.3): C, 45.85; H, 7.37; N, 8.91; S, 10.20. Found: C, 45.89; H, 7.48; N, 8.87; S, 10.38.

Sodium salt of 2,2′-azobis(N-2′-methylpropanoyl-2-amino-decyl)-1-sulfonate (1b, n = 7): Yield: 47%. ¹H NMR (400 MHz, DMSO-d ₆): d = 0.89 (m, 3 H), 1.28-1.36 (m, 15 H), 1.40 (m, 3 H), 1.53 (m, 1 H), 1.67 (m, 1 H), 3.25 (m, 1 H), 3.47 (m, 1 H), 4.59 (m, 1 H), 7.60 (m, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): d:= 14.1, 22.3, 25.1, 28.8, 29.2, 29.3, 36.4, 39.1-40.2, 57.5, 71.9, 172.1. Anal. Calcd for C₂₈H₅₄N₄Na₂O₈S₂ (684.9): C, 49.10; H, 7.95; N, 8.18; S, 9.36. Found: C, 48.89; H, 7.88; N, 8.27; S, 9.48.

Sodium salt of 2,2′-azobis(N-2′-methylpropanoyl-2-amino-tetradecyl)-1-sulfonate (1c, n = 11): Yield: 41%. ¹H NMR (400 MHz, DMSO-d ₆): d = 0.89 (m, 3 H), 1.28-1.36 (m, 23 H), 1.40 (m, 3 H), 1.53 (m, 1 H), 1.68 (m, 1 H), 3.25 (m, 1 H), 3.46 (m, 1 H), 4.58 (m, 1 H), 7.61 (m, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): d = 14.1, 22.3, 25.1, 28.8-29.0, 29.2, 29.3, 36.4, 39.1-40.2, 57.5, 71.9, 172.2. Anal. Calcd for C₃₆H₇₀N₄Na₂O₈S₂ (797.1): C, 54.25; H, 8.85; N, 7.03; S, 8.08. Found: C, 54.34; H, 8.88; N, 7.17; S, 8.13.

Sodium salt of 2,2′-azobis(N-2′-methylpropanoyl-2-amino-hexadecyl)-1-sulfonate (1d, n = 13): Yield 39%. ¹H NMR (400 MHz, DMSO-d ₆): d = 0.89 (m, 3 H), 1.28-1.40 (m, 30 H), 1.52 (m, 1 H), 1.67 (m, 1 H), 3.24 (m, 1 H), 3.46 (m, 1 H), 4.58 (m, 1 H), 7.60 (m, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): d = 14.1, 22.3, 25.1, 28.8-29.0, 29.2, 29.3, 36.4, 39.1-40.2, 57.5, 71.8, 172.2. Anal. Calcd. for C₄₀H₇₈N₄Na₂O₈S₂ (853.2): C, 56.31; H, 9.21, N, 6.57; S, 7.25. Found: C, 56.44; H, 9.15, N, 6.69; S, 7.63.

As a product of mono-N-alkylation was isolated and characterised only sodium salt of 2-{2-[(cyano-dimethyl-methy)-azo]-2-methyl-propionylamino}-decane-1-sufonate (2b, n = 7): Yield: 11%. ¹H NMR (400 MHz, DMSO-d ₆):
d = 0.89 (m, 3 H), 1.28-1.36 (m, 21 H), 1.40 (m, 3 H), 1.52 (m, 1 H), 1.68 (m, 1 H), 3.26 (m, 1 H), 3.47 (m, 1 H), 4.58 (m, 1 H), 7.60 (m, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆):
d = 14.1, 22.3, 25.1, 28.9, 29.3, 36.4, 39.1-40.2, 57.5, 71.9, 120.1, 171.8. Anal. Calcd for C₁₈H₃₃N₄NaO₄S (424.5): C, 50.92; H, 7.83; N, 13.20; S, 7.55 Found: C, 50.84; H, 7.98; N, 13.17; S, 7.63.