EP0647224A1 - Ion-sensitive calixarenes - Google Patents

Ion-sensitive calixarenes

Info

Publication number
EP0647224A1
EP0647224A1 EP94914394A EP94914394A EP0647224A1 EP 0647224 A1 EP0647224 A1 EP 0647224A1 EP 94914394 A EP94914394 A EP 94914394A EP 94914394 A EP94914394 A EP 94914394A EP 0647224 A1 EP0647224 A1 EP 0647224A1
Authority
EP
European Patent Office
Prior art keywords
group
anion
substituted
receptor
independently
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP94914394A
Other languages
German (de)
French (fr)
Inventor
Trevor John Wear
Christopher Peter Moore
Alistair J. Goulden
Paul D. Beer
Nicholas C. Fletcher
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kodak Ltd
Eastman Kodak Co
Original Assignee
Kodak Ltd
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kodak Ltd, Eastman Kodak Co filed Critical Kodak Ltd
Publication of EP0647224A1 publication Critical patent/EP0647224A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/20—Quaternary compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C07F15/0053—Ruthenium compounds without a metal-carbon linkage
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators

Definitions

  • the invention relates to ion-sensitive compounds. More particularly, the invention relates to ion-sensitive compounds comprising a receptor designed to bind anionic species by the formation of a receptor-substrate complex.
  • Anion receptors comprising a plurality of quaternary amine groups are known. Examples of such compounds may be seen in P.G. Potvin and J-M Lehn, Prog. Macrocyclic Chern . , 1987, 3, 214.
  • the ion-sensitive compounds of the invention have the formula A ⁇ +B ⁇ - wherein A represents a cation capable of forming a receptor-substrate complex with an anion, and B represents one or more counter anions. characterised in that the cation is an anion receptor represented by the formula I
  • R 1 , R2, R3 and R 4 are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkylamido group, an arylamido group, an alkylsulfonamido group, an arylsulfonamido group or a nitro group;
  • R5 and R ⁇ are each independently H or a lower alkyl group having from 1 to 4 carbon atoms, or R5 and R ⁇ taken together represent an ethylene bridging group; and, n is 0 or 1.
  • the invention also provides a method of sensing an anion in solution by contacting the anion with a compound comprising a cation which is a receptor for the anion to form a receptor-substrate complex and sensing a detectable change which results from the formation of the complex characterised in that the compound is a compound of the invention.
  • the compounds of the invention show selectivity to anions and are useful for the electrochemical and/or optical detection of anions, especially halides and particularly chlorides.
  • Fig. 1 is a graphical representation of the observed ⁇ H NMR response of the compound of Example 1 on addition of a chloride ion source.
  • Fig. 2 is a graphical representation of the observed ⁇ H NMR response of the compound of Example 2 on addition of a chloride ion source. Detailed description of the Invention
  • R 1 , R 2 , R 3 and-R 4 are each independently H, a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms e.g. methyl, ethyl, propyl, butyl, pentyl, hexyl and eicosyl.
  • Tertiary alkyl groups are particularly preferred e.g. t-butyl.
  • Suitable substituents include alkylamido, arylamido, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonamido, arylsulfonamido, alkylcarbonyl, alkoxy, cyano and nitro.
  • R 1 , R 2 ' R 3 and R 4 are each independently a substituted or unsubstituted phenyl group.
  • Suitable substituents include alkyloxy, aryloxy, alkylamido, arylamido, alkylsulfonamido, arylsulfonamido, alkyloxycarbonyl, aryloxycarbonyl and nitro.
  • R 5 and R 6 are each methyl groups.
  • B 2- represents any suitable anions which together with A 2+ are capable of forming a stable compound. Examples of such anions include sulphate, nitrate, phosphate, borate and halide e.g. iodide.
  • B 2 ⁇ represents weakly coordinating anions such as hexafluorophosphate and tetrafluoroborate.
  • Compounds of the invention can be prepared via the condensation reaction of the 1,3 diacid chloride of an unsubstituted or 4-substituted calix[4]arene and an appropriate pyridine compound e.g. two moles of 4-aminopyridine or 4- aminomethylpyridine. Quaternisation of the pyridine nitrogen atoms of the resulting dipyridyl derivative provides compounds having the structure I. Alternatively, reaction of the resulting dipyridyl derivative with ruthenium dipyridyl dichloride dihydrate provides compounds having the structure II.
  • the compounds of the invention can be used in a method of sensing anions as indicated above. The detectable change resulting from formation of the complex can be measured by any suitable means such as NMR measurement, electrochemical measurement e.g. cyclic voltammetry, or optical measurement e.g. fluorescence spectroscopy.
  • the p-tert-butylcalix[4]arene used was recrystallised from hot toluene/ethanol and dried under vacuum. Acetone was dried by standing over calcium sulphate overnight then distilled from fresh calcium sulphate.
  • 1,3 diacid Diester (5.24g, 6.4mmol) was taken up in approximately 1.51 of warm ethanol before 80ml sodium hydroxide was added and the solution refluxed for 12 hours. The ethanol was removed to leave a white solid which was dried under vacuum. Water was added to this solid to form a brown slurry which was acidified to pHl using concentrated hydrochloric acid. A colour change was noted during acidification from brown to cream and then the organic components of this slurry were extracted into chloroform. The organic extract was washed with IxHClaq and IxNaCl, dried using MgS04 and the chloroform removed to leave 5.07g of a yellow solid. Yield 100%. 1,3 diacid chloride (in situ)
  • Diacid (0.80g, l.Ommol) was taken up in dry toluene, thionyl chloride (1.0ml, 8.4mmol) was added at room temperature in an inert atmosphere and then the reactants were refluxed for 12 hours. Excess thionyl chloride and toluene were removed by vacuum distillation to leave a brown gum (crude acid chloride) . Dry dichloromethane can be used in place of toluene.
  • the diacid chloride of Example 1 was taken up in dichloromethane and added via a cannula to a stirring solution of 4-aminomethylpyridine (0.16ml, 1.25mmol) and triethylamine (0.12ml, 1.25mmol) in dichloromethane under an inert atmosphere. An immediate colour change was observed from yellow to red and the reactants were stirred for a further 16 hours at room temperature. Solvents were removed to leave a brown crude product which was purified using a silica column (mesh 60-200) . Solvents ethyl acetate : ethanol 5:1 Rf 0.16. Yield 20%.
  • Example 3 indicated the formation of a 1:1 complex with the chloride ion.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Molecular Biology (AREA)
  • Biophysics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Pyridine Compounds (AREA)

Abstract

An ion-sensitive compound has the formula A2+B2- wherein A represents a cation capable of forming a receptor-substrate complex with an anion, and B represents one or more counter anions, characterised in that the cation is an anion receptor represented by formula (I) or formula (II) wherein R?1, R2, R3 and R4¿ are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkylamido group, an arylamido group, an alkylsulfonamido group, an arylsulfonamido group or a nitro group; R?5 and R6¿ are each independently H or a lower alkyl group having from 1 to 4 carbon atoms, or R?5 and R6¿ taken together represent an ethylene bridging group; and n is 0 or 1. Such compounds can be used for sensing anions.

Description

Ion-sens1t1ve callxarenes Field of the Invention
The invention relates to ion-sensitive compounds. More particularly, the invention relates to ion-sensitive compounds comprising a receptor designed to bind anionic species by the formation of a receptor-substrate complex. Background of the Invention
Anion receptors comprising a plurality of quaternary amine groups are known. Examples of such compounds may be seen in P.G. Potvin and J-M Lehn, Prog. Macrocyclic Chern . , 1987, 3, 214.
L.A. Summers, "The Bipyridinium Herbicides", Academic Press, New York, 1980, describes the use of certain compounds comprising, diquaternary 2,2'- bipyridinium moieties in herbicidal applications.
Metal ion centres have also been utilised in systems for the recognition of anions as described in D.N. Reinhoudt, J.Am. Chem . Soc. 1992, 114, 9671-9673. Problem to be solved by the Invention
There is a continuing need to provide new receptor compounds for a variety of applications. For example, there is a need for compounds which can be incorporated in electrochemical or optical sensors for anion determination. There is also a need for compounds which can be used in removal devices where levels of a given anion need to be kept low.
It is also desirable to provide receptor compounds which can be readily synthesised. Summary of the Invention
The ion-sensitive compounds of the invention have the formula A^+B^- wherein A represents a cation capable of forming a receptor-substrate complex with an anion, and B represents one or more counter anions. characterised in that the cation is an anion receptor represented by the formula I
CH2CONH CH2CONH n
or by the formula II
CH-CONH CH2CONH
wherein
R1, R2, R3 and R4 are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkylamido group, an arylamido group, an alkylsulfonamido group, an arylsulfonamido group or a nitro group; R5 and R^ are each independently H or a lower alkyl group having from 1 to 4 carbon atoms, or R5 and R^ taken together represent an ethylene bridging group; and, n is 0 or 1. The invention also provides a method of sensing an anion in solution by contacting the anion with a compound comprising a cation which is a receptor for the anion to form a receptor-substrate complex and sensing a detectable change which results from the formation of the complex characterised in that the compound is a compound of the invention. Advantageous effect of the Invention
The compounds of the invention show selectivity to anions and are useful for the electrochemical and/or optical detection of anions, especially halides and particularly chlorides. Brief description of the drawings
Fig. 1 is a graphical representation of the observed ^H NMR response of the compound of Example 1 on addition of a chloride ion source.
Fig. 2 is a graphical representation of the observed ^H NMR response of the compound of Example 2 on addition of a chloride ion source. Detailed description of the Invention
Preferably, R1, R2, R3 and-R4 are each independently H, a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms e.g. methyl, ethyl, propyl, butyl, pentyl, hexyl and eicosyl. Tertiary alkyl groups are particularly preferred e.g. t-butyl. Suitable substituents include alkylamido, arylamido, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonamido, arylsulfonamido, alkylcarbonyl, alkoxy, cyano and nitro.
Preferably, R1, R2' R3 and R4 are each independently a substituted or unsubstituted phenyl group. Suitable substituents include alkyloxy, aryloxy, alkylamido, arylamido, alkylsulfonamido, arylsulfonamido, alkyloxycarbonyl, aryloxycarbonyl and nitro.
Preferably, R5 and R6 are each methyl groups. B2- represents any suitable anions which together with A2+ are capable of forming a stable compound. Examples of such anions include sulphate, nitrate, phosphate, borate and halide e.g. iodide. Preferably, B2~ represents weakly coordinating anions such as hexafluorophosphate and tetrafluoroborate.
The synthesis of unsubstituted and substituted calixarenes is well documented. By way of example, reference is made to Calixarenes by C. David Gutsche, Royal Society of Chemistry, 1989.
Compounds of the invention can be prepared via the condensation reaction of the 1,3 diacid chloride of an unsubstituted or 4-substituted calix[4]arene and an appropriate pyridine compound e.g. two moles of 4-aminopyridine or 4- aminomethylpyridine. Quaternisation of the pyridine nitrogen atoms of the resulting dipyridyl derivative provides compounds having the structure I. Alternatively, reaction of the resulting dipyridyl derivative with ruthenium dipyridyl dichloride dihydrate provides compounds having the structure II. The compounds of the invention can be used in a method of sensing anions as indicated above. The detectable change resulting from formation of the complex can be measured by any suitable means such as NMR measurement, electrochemical measurement e.g. cyclic voltammetry, or optical measurement e.g. fluorescence spectroscopy.
Specific examples of the preparation of compounds of the invention are given as follows. E ample 1 1,3 diester
The p-tert-butylcalix[4]arene used was recrystallised from hot toluene/ethanol and dried under vacuum. Acetone was dried by standing over calcium sulphate overnight then distilled from fresh calcium sulphate.
A slurry of p-tert-butylcalix[4]arene (β.OOg, δ.lOmmol) and anhydrous potassium carbonate (2.24g, 16.2mmol) were stirred in dry acetone (200ml) at room temperature for lOmins. Bromoethylacetate (1.81ml, 16.2mmol) was added and the reactants stirred for 18 hours at room temperature. Salt precipitated was removed by filtration and acetone removed to leave the crude product. This was taken up in dichloromethane, washed with water to leave the desired product as a white powder. No further purification was required. Yield 100%. 1,3 diacid Diester (5.24g, 6.4mmol) was taken up in approximately 1.51 of warm ethanol before 80ml sodium hydroxide was added and the solution refluxed for 12 hours. The ethanol was removed to leave a white solid which was dried under vacuum. Water was added to this solid to form a brown slurry which was acidified to pHl using concentrated hydrochloric acid. A colour change was noted during acidification from brown to cream and then the organic components of this slurry were extracted into chloroform. The organic extract was washed with IxHClaq and IxNaCl, dried using MgS04 and the chloroform removed to leave 5.07g of a yellow solid. Yield 100%. 1,3 diacid chloride (in situ)
Diacid (0.80g, l.Ommol) was taken up in dry toluene, thionyl chloride (1.0ml, 8.4mmol) was added at room temperature in an inert atmosphere and then the reactants were refluxed for 12 hours. Excess thionyl chloride and toluene were removed by vacuum distillation to leave a brown gum (crude acid chloride) . Dry dichloromethane can be used in place of toluene.
1,3 dipyridyl derivative
This gum was taken up in dry dichloromethane then added via a cannula to a stirring solution of 4- aminopyridine (0.24g, 2.4mmol) and triethylamine (0.19ml, 2.4mmol) in dry acetonitrile at room temperature. A brown precipitate was deposited on stirring. This was removed by filtration and the solvents removed to leave 0.83g of a brown crude product. Recrystallization from dichloromethane: petroleum ether furnished 0.44g of the cream coloured product. Yield 52%. 1,3 quaternised dipyridyl derivative The 1,3 dipyridyl derivative (0.09g, lm ol) was refluxed in methyliodide (25ml, excess) for 18 hours. A colour change was observed for the reaction solution from colourless to orange. The methyliodide was removed by distillation to leave 0.12g of an orange solid. Yield 100%. Example 2 1,3 Ruthenium bipyridyl complex
The 1,3 dipyridyl derivative of Example 1 (0.20g, 0.26mmol) and ruthenium dipryidyl dichloride dihydrate were taken up in ethanol and refluxed for 5 days. Ethanol was removed and the sample was dried under vacuum before the crude reaction mixture was taken up in water and the purple product precipitated out as the PF^-salt using ammonium hexafluorophosphate. Yield 25%.
Example 3
The diacid chloride of Example 1 was taken up in dichloromethane and added via a cannula to a stirring solution of 4-aminomethylpyridine (0.16ml, 1.25mmol) and triethylamine (0.12ml, 1.25mmol) in dichloromethane under an inert atmosphere. An immediate colour change was observed from yellow to red and the reactants were stirred for a further 16 hours at room temperature. Solvents were removed to leave a brown crude product which was purified using a silica column (mesh 60-200) . Solvents ethyl acetate : ethanol 5:1 Rf 0.16. Yield 20%.
The bis 4-methylaminopyridine derivative so formed (O.lg) was refluxed in methyl iodide (lOmls, excess) for 16 hours. The excess methyl iodide was removed by distillation to leave the quaternised product as a yellow solid. Yield 100%. Example 4
1H NMR proton titrations were performed on the compounds of Examples 1, 2 and 3. The titrations were carried out using a Bruker 300 MHz spectrometer. The molecular hosts were dissolved in deuteriochloroform and tetrabutylammonium chloride was added to concentrations of 0.25, 0.50, 1.0 and 5.0 mole equivalents and the NMR spectra recorded. The samples were run sequentially in order to keep conditions constant. The change in chemical shift of the NH proton at the recognition site was recorded and plotted against equivalency of chloride. The plots for the compounds of Examples 1 and 2 are shown in Figures 1 and 2, respectively, and indicate complex formation in each case. In Figure 1, the compound of the invention is compared with a model compound in which the pyridine groups are unquaternised. The titration results for the compound of
Example 3 indicated the formation of a 1:1 complex with the chloride ion.

Claims

Claims
1. An ion-sensitive compound having the formula wherein A represents a cation capable of forming a receptor-substrate complex with an anion, and B represents one or more counter anions, characterised in that the cation is an anion receptor represented by the formula
CH CH2CONH
or
CH-CONH CH2CONH
wherein
R , R2, R3 and R4 are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkylamido group, an arylamido group, an alkylsulfonamido group, an arylsulfonamido group or a nitro group;
R5 and R^ are each independently H or a lower alkyl group having from 1 to 4 carbon atoms, or R5 and R^ taken together represent an ethylene bridging group; and, n is 0 or 1.
2. A compound according to claim 1 wherein R1, R2, R3 and R4 are each independently a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms.
3. A compound according to claim 2 wherein R1, R2, R3 and R4 are each independently a tertiary alkyl group
4. A compound according to claim 1 wherein R1, R2, R3 and R4 are each independently a substituted or unsubstituted phenyl group.
5. A compound according to any one of the preceding claims wherein R3 and R4 are each methyl groups.
6. A method of sensing an anion in solution by contacting the anion with a compound comprising a cation which is a receptor for the anion to form a receptor-substrate complex and sensing a detectable change which results from the formation of the complex characterised in that the compound is a compound according to any one of the preceding claims.
EP94914394A 1993-04-21 1994-04-18 Ion-sensitive calixarenes Withdrawn EP0647224A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9308214 1993-04-21
GB939308214A GB9308214D0 (en) 1993-04-21 1993-04-21 Ion-sensitive compounds
PCT/EP1994/001192 WO1994024126A1 (en) 1993-04-21 1994-04-18 Ion-sensitive calixarenes

Publications (1)

Publication Number Publication Date
EP0647224A1 true EP0647224A1 (en) 1995-04-12

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Country Link
EP (1) EP0647224A1 (en)
JP (1) JPH07508538A (en)
CA (1) CA2136017A1 (en)
GB (1) GB9308214D0 (en)
WO (1) WO1994024126A1 (en)

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Publication number Priority date Publication date Assignee Title
FR2727415A1 (en) * 1994-11-30 1996-05-31 Commissariat Energie Atomique New bi:functional ruthenium complexes
US6576192B1 (en) * 1996-04-18 2003-06-10 Novartis Ag Fluoroionophores and their use in optical ion sensors
JP4303595B2 (en) * 2001-12-21 2009-07-29 透 小池 Zinc complexes capable of trapping substances with anionic substituents
CN105523979B (en) * 2015-12-07 2017-08-08 江汉大学 Azo Thiourea anion receptor and preparation method thereof, application

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Publication number Priority date Publication date Assignee Title
US5043415A (en) * 1987-09-24 1991-08-27 Loctite (Ireland) Ltd. Nitrogen-containing oxacalixarene and calixarene derivatives, polymers including groups related to such derivatives, and use of such compounds

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Title
See references of WO9424126A1 *

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JPH07508538A (en) 1995-09-21
CA2136017A1 (en) 1994-10-27
WO1994024126A1 (en) 1994-10-27
GB9308214D0 (en) 1993-06-02

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