EP0000219B1 - Macrocyclic polyether complexes and a process for the isolation of macrocyclic polyethers - Google Patents

Macrocyclic polyether complexes and a process for the isolation of macrocyclic polyethers Download PDF

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Publication number
EP0000219B1
EP0000219B1 EP78200038A EP78200038A EP0000219B1 EP 0000219 B1 EP0000219 B1 EP 0000219B1 EP 78200038 A EP78200038 A EP 78200038A EP 78200038 A EP78200038 A EP 78200038A EP 0000219 B1 EP0000219 B1 EP 0000219B1
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EP
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Prior art keywords
polyether
macrocyclic
carbon atoms
ring
complex
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Expired
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EP78200038A
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German (de)
English (en)
French (fr)
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EP0000219A1 (en
Inventor
Feike De Jong
David Nicolaas Reinhoudt
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms

Definitions

  • the invention relates to novel complexes of macrocyclic polyethers and to a process for the isolation of these macrocyclic polyethers from a mixture containing the said macrocyclic polyethers with the aid of such complexes.
  • Macrocyclic polyethers are defined as heterocyclic compounds containing a ring made up of carbon atoms and at least three oxygen atoms, in which each of the oxygen atoms is bound to two carbon atoms.
  • An example of a macrocyclic polyether is 1,4,7,10,13,16-hexaoxacyclo-octadecane. Hereinafter this compound will also be referred to by its trivial name "18-crown-6". Its structural formula is shown on the Formula page (compound 1).
  • 18-Crown-6 can be prepared by heating tetraethylene glycol and bis(2-chloroethyl) ether in the presence of tetrahydrofuran as a solvent and potassium hydroxide, see "Synthesis" 1976, 515-516.
  • the reaction mixture thus formed contains 18-crown-6, potassium chloride, water and by-products, i.a. macrocyclic polyethers having a ring of larger size than 18-crown-6.
  • the solvent was evaporated from the reaction mixture to give a brown slurry to which dichloromethane was added.
  • the present invention provides complexes formed between (1) a disulphonate of the general formula wherein X represents a barium or strontium atom and R' represents a bivalent group derived from an alkane by removal of two hydrogen atoms, and (2) a macrocyclic polyether compatible with the ion derived from the atom X.
  • R 1 has preferably fewer than ten and particularly fewer than six carbon atoms. Groups R 1 having fewer than three carbon atoms are most preferred.
  • the group R 1 may be derived from an alkane by removal of two hydrogen atoms from one carbon atom or of one hydrogen atom from two carbon atoms. Examples of groups R' are methylene, ethylidene, isopropylidene, dimethylene, trimethylene, tetramethylene and propylene groups.
  • the groups R 1 having fewer than three carbon atoms the groups ⁇ (CH 2 ) n ⁇ , n being an integer of less than 3, are preferred, i.e. methylene and dimethylene groups. Methylene groups are most preferred.
  • the disulphonate of formula I may be water-free or may contain water of crystallization.
  • the macrocyclic polyether present in the novel complexes should be compatible with a barium and/or a strontium ion, that is such an ion and the macrocyclic polyether must be stereo-chemically compatible with regard to the size of the hole in the polyether ring and the diameter of the ion.
  • the hole in the polyether ring should be capable of accommodating a barium or a strontium ion.
  • preferred macrocyclic polyethers are those consisting of 4 to 10. units where Y represents the group each of R I and R 3 representing a hydrogen atom or an alkyl group having from one to four carbon atoms.
  • R 2 and R 3 in formula III may represent.
  • both R 2 and R 3 represent a hydrogen atom.
  • Preferred complexes are those between barium methanedisulphonate and 1,4,7,10,1.3,16-hexaoxacyclooctadecane, between barium methanedisulphonate and 1,4,7,10,13-pentaoxacydopentadecane, between barium 1,2-ethanedisulphonate and 1,4,7,10,13,16-hexaoxacyclooctadecane, and between strontium methanedisulphonate and 1,4,7,10,13,16-hexaoxacyclooctadecane.
  • macrocyclic polyethers consist of compounds in which the polyether ring in the macrocyclic polyether contains 4 to 10 oxygen atoms and in which
  • the aromatic ring present in the macrocyclic polyether may be a carbocyclic or a hetero-aromatic ring.
  • the preferred carbocyclic aromatic ring is the o-phenylene ring.
  • the carbocyclic aromatic rings may be fused, as is the case in, for example, 1,2- and 2,3-naphthylene groups and 1,2- and 2,3- anthrylene groups.
  • Hetero-aromatic rings are derived from hetero-aromatic compounds which are defined as in Kirk-Othmer, "Encyclopedia of Chemical Technology", Second Edition, Volume 2 (1963), page 702: obtained by replacement of one or more carbon atoms of a carbocyclic aromatic compound by hetero-atom - for example pyridine, pyrimidine, pyrazine, quinoline and isoquinoline - and also include those heterocyclic compounds having five-membered rings which show aromatic character-. istics and are mentioned on page 703 of the said volume, for example thiophene, pyrrole, furan, indole and benzothiophene.
  • hetero-aromatic rings examples include 2,3-furylene, 2,3-thienylene, 3,4-furylene and .3,4-thienylene rings.
  • the aromatic ring or rings and the rings obtained by saturation of such aromatic rings may carry substituents, for example halogen atoms or alkyl, nitro or cyano groups.
  • Preferably only one pair of vicinal carbon atoms of the polyether ring also forms part of an aromatic ring or of an ring obtained by saturation of such an aromatic ring.
  • the preferred ring obtained by saturation of an aromatic ring is the 1,2-cyclohexylene ring.
  • Methyl and ethyl groups are preferred among the alkyl groups bound to the carbon atoms of the polyether ring only forming part of the polyether ring.
  • each of the latter carbon atoms is bonded to two hydrogen atoms.
  • Preferred complexes are those between barium methanedisulphonate and 2,3-benzo-1,4,7,10,13,16-hexaoxacyclooctadeca-2-ene, between barium methanedisulphonate and 2,3-benzo-1,4,7,1:0,13,16,19-heptaoxacycloheneicosa-2-ene and between barium methanedisulphonate and 2,5,8,15,18,21-hexaoxatricyclo[20.4.0.0 9 ' 14 ]-hexacosane.
  • the complexes according to the invention are very suitable for use in a process for the isolation of macrocyclic polyethers from a mixture containing them.
  • the macrocyclic polyethers can thus be obtained in high yield and need not be distilled, thus avoiding the explosions mentioned hereinbefore. Moreover, the use of very low temperatures is avoided.
  • the present invention also provides a process for the isolation of a macrocyclic polyether compatible with a barium or strontium ion from a solution containing the said macrocyclic polyether, which process comprises contacting the said solution with a disulphonate of the general formula wherein X represents a barium 6r strontium atom and R 1 represents a bivalent group derived from an alkane by removal of two hydrogen atoms, to form a solid complex of the said disulphonate and the said macrocyclic polyether, separating the solid complex from the mixture containing the complex and extracting the separated complex with a solvent for the macrocyclic polyether.
  • the complex formed between a disulphonate of formula I and a compatible macrocyclic polyether contains one molecule of the disulphonate per molecule of macrocyclic polyether. Accordingly, the starting solution containing the macrocyclic polyether is preferably contacted with the disulphonate of formula I using a molar ratio of disulphonate to rnacrocyclic polyether of at least 1.
  • the reaction mixture formed by contacting the starting solution with such a disulphonate contains as solid materials the complex and any stoichiometric excess of disulphonate. To reduce the excess of disulphonate in the reaction mixture the molar ratio of disulphonate to macrocyclic polyether is preferably not higher than 2.
  • Molar ratios of disulphonate to macrocyclic polyether higher than 2, for example up to 5, may be used, if desired, but usually will not be of further advantage.
  • the use of a molar ratio of disulphonate to macrocyclic polyether of less than 1 gives a complex containing only very little non-complexed disulphonate, if any at all. In view of these considerations this molar ratio is preferably near to 1.0, for example between 1.0 and 1.1
  • the solution containing the macrocyclic polyether may be contacted with the disulphonate of formula I by adding the disulphonate to the solution and stirring the suspension thus formed for, for example, 0.5 to 10 hours, to form the solid complex.
  • the macrocyclic polyether present in the mixture obtained upon this reaction partly resides in the complex and the balance is dissolved non-complexed in the solution obtained.
  • the proportion of the macrocyclic polyether residing in the complex is particularly high, for example more than 97%, when the macrocyclic polyether is 18-crown-6. This proportion is considerably higher than in the case of the 18-crown-6-acetonitrile complex; hence, the 18-crown-6 can be isolated in a correspondingly higher yield.
  • the macrocyclic polyether need not be reacted with the disulphonate of formula I at a very low temperature.
  • the solution containing the macrocyclic polyether is preferably contacted with the disulphonate at a temperature in the range of from -30°C to +50°C and particularly in the range of from 15°C to 30°C. Ambient temperature is very suitable.
  • solvents may be present in the starting solution containing the macrocyclic polyether to be isolated.
  • Very suitable solvents are alkanols, nitroalkanes, dialkyl sulphoxides, dialkyl ketones, alkanenitriles and dialkyl ethers; all of these solvents preferably have fewer than six carbon atoms per molecule.
  • Particularly preferred are methanol, nitromethane, dimethyl sulphoxide, acetone and acetonitrile.
  • suitable solvents are tetrahydrothiophene 1,1-dioxide and N-methylpyrrolidone.
  • the macrocyclic polyether in the starting mixture may have been formed by any known process. Very good results have been obtained with 18-crown-6 formed by reacting tetraethylene glycol with a bis(2-haloethyl) ether, halo representing chloro, bromo or iodo, in the presence of a alkali metal. hydroxide, as described in "Synthesis" 1976, 515-516. If desired, alkali metal halide formed may be removed from the reaction mixture obtained, leaving the 18-crown-6-containing starting solution.
  • the disulphonates of formula I are selective in that, when contacted with a mixture containing 18- crown-6 and one or more other compatible macrocyclic polyethers, they preferentially form complexes with 18-crown-6.
  • 18-crown-6-containing starting mixtures containing one or more other compatible macrocyclic polyethers are very suitable starting materials, particularly those obtained by catalytic oligomerization of ethylene oxide, as described in German Offenlegungsschrift 2,401,126.
  • the suspended complex can easily be separated from the solution obtained, for example by filtration, centrifugation or decantation.
  • the complex can simply be extracted with such a solvent, thus giving a solution of the macrocyclic polyether and leaving the solid disulphonate.
  • the temperature at which this extraction is carried out is not critical and is preferably in the range of from 50°C to 125°C.
  • Suitable solvents are, for example, nitromethane, acetonitrile and tetrahydrofuran. Evaporation of the solvent from the solution of the macrocyclic polyether at sub-atmospheric pressure leaves the macrocyclic polyether.
  • This macrocyclic polyether is very pure and need not be distilled.
  • nitromethane is used as the solvent and 18-crown-6 as the macrocyclic polyether, a residue of the 18-crown-6-nitromethane complex is first formed.
  • the latter complex is described in European Patent Application No. 78200037.6 (Publication No. 0 J00 218).
  • acetonitrile is used as the solvent and 18-crown-6 as the macrocyclic polyether, a residue of the 18-crown-6-acetonitrile complex is first formed.
  • the 18-crown-6-nitromethane complex is decomposed into 18-crown-6 and nitromethane and the 18-crown-6-acetonitrile complex into 18-crown-6 and acetonitrile.
  • the disulphonate of formula I left after the extraction with the solvent for the macrocyclic polyether, may be reused for complexing further quantities of compatible macrocyclic polyether.
  • the barium methanedisulphonate used was water-free.
  • a suspension obtained by addition of barium methanedisulphonate (0.104 mmol) to a solution in methanol (1.5 ml) of 0.10 mmol of 18-crown-6 and 0.10 mmol of macrocyclic polyether 3 of the formula page was stirred for six hours at 20°C.
  • the molar ratio of macrocyclic polyether 3 to 18-crown-6 in the filtrate obtained by filtration of the reaction mixture was 7:1, indicating that 18-crown-6 is preferentially complexed.
  • the 18-crown-6-barium methanedisulphonate complex (1 mmol) was continuously extracted for 16 hours in a Soxhlet apparatus. At the end of this period the percentage of the 18-crown-6 extracted- from the complex was determined. Two solvents were tested. Table VI presents the results.
  • the complex was kept for 30 minutes at 70°C and a pressure of 13 Pa, leaving 18-crown-6 in a yield of 34% calculated on starting tetraethylene glycol, or 79%, calculated on 18-crown-6 in the crude 18- crown-6.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
EP78200038A 1977-06-23 1978-06-12 Macrocyclic polyether complexes and a process for the isolation of macrocyclic polyethers Expired EP0000219B1 (en)

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US (1) US4199513A (enrdf_load_stackoverflow)
EP (1) EP0000219B1 (enrdf_load_stackoverflow)
JP (1) JPS549292A (enrdf_load_stackoverflow)
AU (1) AU516439B2 (enrdf_load_stackoverflow)
CA (1) CA1111050A (enrdf_load_stackoverflow)
DE (1) DE2861109D1 (enrdf_load_stackoverflow)
IT (1) IT1096597B (enrdf_load_stackoverflow)

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DE3132906A1 (de) * 1980-03-28 1983-03-03 Berthold H. Dr. 5630 Remscheid Daimler Verfahren und vorrichtung zur speicherung von fliessfaehigen stoffen zwecks druckfoerderung, insbesondere spraydosen, spritzgeraete und dosiervorrichtungen
JPS6089026A (ja) * 1983-10-21 1985-05-18 松下電器産業株式会社 スイツチング装置
US4607110A (en) * 1985-03-11 1986-08-19 Armstrong World Industries, Inc. Novel polyacrylic esters bearing pendant macrocyclic ethers and electrically conducting compositions comprised thereof
JPH02158392A (ja) * 1988-12-12 1990-06-18 Toppan Printing Co Ltd 印刷インキ転写体及びその製造方法並びにその成形機
US5393892A (en) * 1993-05-07 1995-02-28 Ibc Advanced Technologies, Inc. Processes for removing, separating and concentrating lead, thallium, alkali metals, alkaline earth metals from concentrated matrices using macrocyclic polyether cryptand ligands bonded to inorganic supports
US7091338B2 (en) 2001-11-15 2006-08-15 Pg Research Foundation Purification of 4,4′(5′)- di-t-butylcyclohexano-18-crown-6
FR2899895B1 (fr) * 2006-04-12 2010-09-17 Servier Lab Nouveaux sels de strontium d'acides sulfoniques, leur procede de preparation et les compositions pharmaceutiques qui les contiennent
US8124793B2 (en) * 2007-11-27 2012-02-28 Gail Marie Cronyn, legal representative Derivatives of ethylene methanedisulfonate as cancer chemotherapeutic agents
NO333172B1 (no) * 2011-06-06 2013-03-25 Inst Energiteknik Radioaktivt merket organisk sporstoff, dets bruk og fremgangsmate for dets produksjon

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US3814700A (en) * 1972-08-03 1974-06-04 Ibm Method for controllably varying the electrical properties of nematic liquids and dopants therefor

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DE2861109D1 (en) 1981-12-10
US4199513A (en) 1980-04-22
JPS6246548B2 (enrdf_load_stackoverflow) 1987-10-02
AU3728278A (en) 1980-01-03
JPS549292A (en) 1979-01-24
IT1096597B (it) 1985-08-26
AU516439B2 (en) 1981-06-04
EP0000219A1 (en) 1979-01-10
CA1111050A (en) 1981-10-20
IT7824812A0 (it) 1978-06-21

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