Syntheses, structures, and stabilities of aliphatic and aromatic fluorous iodine(I) and iodine(III) compounds

the role of iodine Lewis basicity

Tathagata Mukherjee, Soumik Biswas, Andreas Ehnbom, Subrata K. Ghosh, Ibrahim El-Zoghbi, Nattamai Bhuvanesh, Hassan S. Bazzi, John A. Gladysz

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The title molecules are sought in connection with various synthetic applications. The aliphatic fluorous alcohols RfnCH2OH (Rfn = CF3(CF2)n-1; n = 11, 13, 15) are converted to the triflates RfnCH2OTf (Tf2O, pyridine; 22-61%) and then to RfnCH2I (NaI, acetone; 58-69%). Subsequent reactions with NaOCl/HCl give iodine(III) dichlorides RfnCH2ICl2 (n = 11, 13; 33-81%), which slowly evolve Cl2. The ethereal fluorous alcohols CF3CF2CF2O(CF(CF3)CF2O)xCF(CF3)CH2OH (x = 2-5) are similarly converted to triflates and then to iodides, but efforts to generate the corresponding dichlorides fail. Substrates lacking a methylene group, RfnI, are also inert, but additions of TMSCl to bis(trifluoroacetates) RfnI(OCOCF3)2 appear to generate RfnICl2, which rapidly evolve Cl2. The aromatic fluorous iodides 1, 3-Rf6C6H4I, 1, 4-Rf6C6H4I, and 1, 3-Rf10C6H4I are prepared from the corresponding diiodides, copper, and RfnI (110-130 °C, 50-60%), and afford quite stable RfnC6H4ICl2 species upon reaction with NaOCl/HCl (80-89%). Iodinations of 1, 3-(Rf6)2C6H4 and 1, 3-(Rf8CH2CH2)2C6H4 (NIS or I2/H5IO6) give 1, 3, 5-(Rf6)2C6H3I and 1, 2, 4-(Rf8CH2CH2)2C6H3I (77-93%). The former, the crystal structure of which is determined, reacts with Cl2 to give a 75:25 ArICl2/ArI mixture, but partial Cl2 evolution occurs upon work-up. The latter gives the easily isolated dichloride 1, 2, 4-(Rf8CH2CH2)2C6H3ICl2 (89%). The relative thermodynamic ease of dichlorination of these and other iodine(I) compounds is probed by DFT calculations.

Original languageEnglish
Pages (from-to)2486-2501
Number of pages16
JournalBeilstein Journal of Organic Chemistry
Volume13
DOIs
Publication statusPublished - 23 Nov 2017

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Iodine Compounds
Alkalinity
Iodine
Iodides
Alcohols
Trifluoroacetic Acid
Acetone
Discrete Fourier transforms
Copper
Crystal structure
Thermodynamics
Molecules
Substrates

Keywords

  • Chlorination
  • Copper mediated perfluoroalkylation
  • Crystal structure
  • DFT calculations
  • Fluorous
  • Hypervalent iodine
  • Nucleophilic substitution
  • Polar space group

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Syntheses, structures, and stabilities of aliphatic and aromatic fluorous iodine(I) and iodine(III) compounds : the role of iodine Lewis basicity. / Mukherjee, Tathagata; Biswas, Soumik; Ehnbom, Andreas; Ghosh, Subrata K.; El-Zoghbi, Ibrahim; Bhuvanesh, Nattamai; Bazzi, Hassan S.; Gladysz, John A.

In: Beilstein Journal of Organic Chemistry, Vol. 13, 23.11.2017, p. 2486-2501.

Research output: Contribution to journalArticle

Mukherjee, Tathagata ; Biswas, Soumik ; Ehnbom, Andreas ; Ghosh, Subrata K. ; El-Zoghbi, Ibrahim ; Bhuvanesh, Nattamai ; Bazzi, Hassan S. ; Gladysz, John A. / Syntheses, structures, and stabilities of aliphatic and aromatic fluorous iodine(I) and iodine(III) compounds : the role of iodine Lewis basicity. In: Beilstein Journal of Organic Chemistry. 2017 ; Vol. 13. pp. 2486-2501.
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abstract = "The title molecules are sought in connection with various synthetic applications. The aliphatic fluorous alcohols RfnCH2OH (Rfn = CF3(CF2)n-1; n = 11, 13, 15) are converted to the triflates RfnCH2OTf (Tf2O, pyridine; 22-61{\%}) and then to RfnCH2I (NaI, acetone; 58-69{\%}). Subsequent reactions with NaOCl/HCl give iodine(III) dichlorides RfnCH2ICl2 (n = 11, 13; 33-81{\%}), which slowly evolve Cl2. The ethereal fluorous alcohols CF3CF2CF2O(CF(CF3)CF2O)xCF(CF3)CH2OH (x = 2-5) are similarly converted to triflates and then to iodides, but efforts to generate the corresponding dichlorides fail. Substrates lacking a methylene group, RfnI, are also inert, but additions of TMSCl to bis(trifluoroacetates) RfnI(OCOCF3)2 appear to generate RfnICl2, which rapidly evolve Cl2. The aromatic fluorous iodides 1, 3-Rf6C6H4I, 1, 4-Rf6C6H4I, and 1, 3-Rf10C6H4I are prepared from the corresponding diiodides, copper, and RfnI (110-130 °C, 50-60{\%}), and afford quite stable RfnC6H4ICl2 species upon reaction with NaOCl/HCl (80-89{\%}). Iodinations of 1, 3-(Rf6)2C6H4 and 1, 3-(Rf8CH2CH2)2C6H4 (NIS or I2/H5IO6) give 1, 3, 5-(Rf6)2C6H3I and 1, 2, 4-(Rf8CH2CH2)2C6H3I (77-93{\%}). The former, the crystal structure of which is determined, reacts with Cl2 to give a 75:25 ArICl2/ArI mixture, but partial Cl2 evolution occurs upon work-up. The latter gives the easily isolated dichloride 1, 2, 4-(Rf8CH2CH2)2C6H3ICl2 (89{\%}). The relative thermodynamic ease of dichlorination of these and other iodine(I) compounds is probed by DFT calculations.",
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T1 - Syntheses, structures, and stabilities of aliphatic and aromatic fluorous iodine(I) and iodine(III) compounds

T2 - the role of iodine Lewis basicity

AU - Mukherjee, Tathagata

AU - Biswas, Soumik

AU - Ehnbom, Andreas

AU - Ghosh, Subrata K.

AU - El-Zoghbi, Ibrahim

AU - Bhuvanesh, Nattamai

AU - Bazzi, Hassan S.

AU - Gladysz, John A.

PY - 2017/11/23

Y1 - 2017/11/23

N2 - The title molecules are sought in connection with various synthetic applications. The aliphatic fluorous alcohols RfnCH2OH (Rfn = CF3(CF2)n-1; n = 11, 13, 15) are converted to the triflates RfnCH2OTf (Tf2O, pyridine; 22-61%) and then to RfnCH2I (NaI, acetone; 58-69%). Subsequent reactions with NaOCl/HCl give iodine(III) dichlorides RfnCH2ICl2 (n = 11, 13; 33-81%), which slowly evolve Cl2. The ethereal fluorous alcohols CF3CF2CF2O(CF(CF3)CF2O)xCF(CF3)CH2OH (x = 2-5) are similarly converted to triflates and then to iodides, but efforts to generate the corresponding dichlorides fail. Substrates lacking a methylene group, RfnI, are also inert, but additions of TMSCl to bis(trifluoroacetates) RfnI(OCOCF3)2 appear to generate RfnICl2, which rapidly evolve Cl2. The aromatic fluorous iodides 1, 3-Rf6C6H4I, 1, 4-Rf6C6H4I, and 1, 3-Rf10C6H4I are prepared from the corresponding diiodides, copper, and RfnI (110-130 °C, 50-60%), and afford quite stable RfnC6H4ICl2 species upon reaction with NaOCl/HCl (80-89%). Iodinations of 1, 3-(Rf6)2C6H4 and 1, 3-(Rf8CH2CH2)2C6H4 (NIS or I2/H5IO6) give 1, 3, 5-(Rf6)2C6H3I and 1, 2, 4-(Rf8CH2CH2)2C6H3I (77-93%). The former, the crystal structure of which is determined, reacts with Cl2 to give a 75:25 ArICl2/ArI mixture, but partial Cl2 evolution occurs upon work-up. The latter gives the easily isolated dichloride 1, 2, 4-(Rf8CH2CH2)2C6H3ICl2 (89%). The relative thermodynamic ease of dichlorination of these and other iodine(I) compounds is probed by DFT calculations.

AB - The title molecules are sought in connection with various synthetic applications. The aliphatic fluorous alcohols RfnCH2OH (Rfn = CF3(CF2)n-1; n = 11, 13, 15) are converted to the triflates RfnCH2OTf (Tf2O, pyridine; 22-61%) and then to RfnCH2I (NaI, acetone; 58-69%). Subsequent reactions with NaOCl/HCl give iodine(III) dichlorides RfnCH2ICl2 (n = 11, 13; 33-81%), which slowly evolve Cl2. The ethereal fluorous alcohols CF3CF2CF2O(CF(CF3)CF2O)xCF(CF3)CH2OH (x = 2-5) are similarly converted to triflates and then to iodides, but efforts to generate the corresponding dichlorides fail. Substrates lacking a methylene group, RfnI, are also inert, but additions of TMSCl to bis(trifluoroacetates) RfnI(OCOCF3)2 appear to generate RfnICl2, which rapidly evolve Cl2. The aromatic fluorous iodides 1, 3-Rf6C6H4I, 1, 4-Rf6C6H4I, and 1, 3-Rf10C6H4I are prepared from the corresponding diiodides, copper, and RfnI (110-130 °C, 50-60%), and afford quite stable RfnC6H4ICl2 species upon reaction with NaOCl/HCl (80-89%). Iodinations of 1, 3-(Rf6)2C6H4 and 1, 3-(Rf8CH2CH2)2C6H4 (NIS or I2/H5IO6) give 1, 3, 5-(Rf6)2C6H3I and 1, 2, 4-(Rf8CH2CH2)2C6H3I (77-93%). The former, the crystal structure of which is determined, reacts with Cl2 to give a 75:25 ArICl2/ArI mixture, but partial Cl2 evolution occurs upon work-up. The latter gives the easily isolated dichloride 1, 2, 4-(Rf8CH2CH2)2C6H3ICl2 (89%). The relative thermodynamic ease of dichlorination of these and other iodine(I) compounds is probed by DFT calculations.

KW - Chlorination

KW - Copper mediated perfluoroalkylation

KW - Crystal structure

KW - DFT calculations

KW - Fluorous

KW - Hypervalent iodine

KW - Nucleophilic substitution

KW - Polar space group

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