EP0000218B1 - Verfahren zur Isolierung von 1,4,7,10,13,16-Hexaoxacycloocta-decan - Google Patents

Verfahren zur Isolierung von 1,4,7,10,13,16-Hexaoxacycloocta-decan Download PDF

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Publication number
EP0000218B1
EP0000218B1 EP78200037A EP78200037A EP0000218B1 EP 0000218 B1 EP0000218 B1 EP 0000218B1 EP 78200037 A EP78200037 A EP 78200037A EP 78200037 A EP78200037 A EP 78200037A EP 0000218 B1 EP0000218 B1 EP 0000218B1
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EP
European Patent Office
Prior art keywords
crown
nitromethane
complex
ether
hexaoxacyclooctadecane
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Expired
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EP78200037A
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English (en)
French (fr)
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EP0000218A1 (de
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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms

Definitions

  • the invention relates to a process for the isolation of 1,4,7,10,13,16-hexaoxacydooctadecane from a mixture also containing one or more other macrocyclic polyethers.
  • 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 invention provides a process for the isolation of 1,4,7,10,13,16-hexaoxacyclooctadecane from a mixture also containing one or more other macrocyclic polyethers containing rings of more than 7 carbon atoms, characterized by reacting the 1,4,7,10,13,16-hexaoxacyctooctadecane with nitromethane in the presence of a solvent for the said macrocyclic polyethers, to precipitate a complex of 1,4,7,10,13,16-hexaoxacyclooctadecane and nitromethane, separating precipitated complex from the mixture containing the complex, dissociating separated complex and separating the components from each other.
  • nitromethane is selective in that, when contacted with a mixture containing 18- crown-6 and one or more other macrocyclic polyethers, it only forms a complex with 18-crown-6.
  • the 18-crown-6-nitromethane complex obtained according to the invention does not, or hardly contains any macrocyclic polyethers other than 18-crown-6.
  • the complex can simply be dissociated into 18-crown-6 and nitromethane by allowing it to stand in the open air.
  • the complex is rapidly dissociated by heating it at sub-atmospheric pressure and removing the nitromethane vapour formed, leaving pure or almost pure 18-crown-6. Heating may take place at a temperature of, for example, 35°C to 125°C at a pressure of, for example, 5 to 1500 Pa.
  • the process according to the invention must be carried out in a solvent for macrocyclic polyethers in which the 18-crown-6-nitromethane complex can be precipitated.
  • a solvent may substantially consist of nitromethane.
  • a solvent is taken to consist substantially of a specified compound when the content of this specified compound in the solvent is higher than 50%w.
  • the solvent substantially consists of an ether (other than a macrocyclic polyester having more than 7 carbon atoms in the ring).
  • Preferred ethers are dialkyl ethers and cyclic ethers.
  • dialkyl ethers are diethyl ether, di-n-butyl ether and di-n-hexylether.
  • the 18-crown-6-nitromethane complex is considerably less soluble in diethyl ether than in nitromethane at the same temperature, so that a considerably larger part of the 18-crown-6 present in the starting mixture can be isolated.
  • Attractive examples of the cyclic ethers are 1,4-dioxane and tetrahydrofuran.
  • the solvent substantially consists of an alkanol, a hydrocarbon (or a mixture of hydrocarbons) or water.
  • suitable alkanols are those having in the range of from one to five carbon atoms, for example methanol, ethanol, 2-propanol and tert- butanol.
  • suitable hydrocarbons are benzene, toluene, the three xylenes and heptane.
  • Particularly attractive solvents are methanol and benzene.
  • 18-Crown-6 dissolved in water may be removed therefrom by reaction with nitromethane to form a precipitate of the 18-crown-6-nitromethane complex in nitromethane-containing water. Mixtures of solvents may be used, for example of diethyl ether and ethanol.
  • the 18-crown-6-acetonitrile complex is very difficult to precipitate from the solvents mentioned in the last three paragraphs, if at all, as this complex is too highly soluble in these solvents.
  • the reaction between 18-crown-6 and nitromethane is preferably carried out at a temperature in the range of from -25°C to +35°C, and, when the solvent substantially consists of nitromethane, of from 0°C to -25°C, so as to enable a very large part of the 18-crown-6 to be isolated.
  • the solvent substantially consists of an ether, an alkanol, a hydrocarbon (or a mixture of hydrocarbons) or water
  • the reaction between 18-crown-6 and nitromethane is very suitably carried out at a temperature in the range of from 0°C to +35°C.
  • Ambient Temperature for example, a temperature between 15°C and 25°, is very suitable.
  • the 18-crown-6-nitromethane complex can easily be separated from the mixture containing the complex, for example by filtration, centrifugation or decantation.
  • the 18-crown-6-nitromethane complex contains two molecules of nitromethane per molecule of 18-crown-6. Accordingly, the 18-crown-6 is reacted with nitromethane using a molar ratio of nitromethane to 18-crown-6 of at least 2:1. Preferably, this molar ratio is not higher than 20:1. This range is not critical, molar ratios of nitromethane to 18-crown-6 outside this range may be used, if desired.
  • the 18-crown-6-nitromethane complex may be precipitated in any suitable manner, for example by adding nitromethane to the starting mixture and, if desired, cooling the mixture thus obtained to a suitable temperature, or by dissolving the starting mixture in diethyl ether and adding nitromethane at ambient temperature to the solution obtained, or by dissolving the starting mixture in any other of the above-mentioned solvents, for example methanol, adding nitromethane and, if desired, cooling the mixture obtained to a suitable temperature.
  • the starting mixture may be solid or liquid at the temperature at which the 18-crown-6 is reacted with nitromethane.
  • the 18-crown-6 in the starting mixture may have been formed by any process. Very good results have been obtained by reacting tetraethylene glycol with a bis(2-haloethyl)ether, halo representing chloro, bromo or iodo, in the presence of an alkali metal hydroxide. If desired, the alkali metal halide formed and solvent, if present, may be removed from the reaction mixture obtained, leaving the 18-crown-6-containing starting mixture.
  • Other examples of processes for the preparation of 18-crown-6 are:
  • Acetonitrile (1.48 mmol) was added to a solution of 18-crown-6 (0.19 mmol) and macrocyclic polyether No. 3 of the formula page (0.19 mmol) in diethyl ether (1 ml) at 25°C.
  • the 18-crown-6-acetonitrile complex crystallized out immediately and was filtered off. It contained 40% of the starting amount of 18-crown-6.
  • Comparison with Example VI shows that nitromethane had complexed a much larger part of the 18-crown-6 than acetonitrile. The purity of the 18-crown-6 was more than 99%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (17)

1. Verfahren zur Isolierung von 1,4,7,10,13,16-Hexaoxacyclooctadecan aus einem Gemisch, das auch einen oder mehrere andere makrocyclische Polyäther enthält, die Ringe mit mehr als 7 Kohlenstoffatome enthalten, dadurch gekennzeichnet, dass man das 1,4,7,10,13,16-Hexaoxacyclooctadecan mit Nitromethan in Gegenwart eines Lösungsmittels für die makrocyclischen Polyäther mischt, um einen Komplex von 1,4,7,10,13,16-Hexaoxacyclooctadecan und Nitromethan auszufällen, den ausgefällten Komplex von dem den Komplex enthaltenden Gemisch abtrennt, den abgetrennten Komplex aufspaltet und die Komponenten voneinander trennt.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Lösungsmittel mehr als 50 Gew.-% Nitromethan enthält.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Lösungsmittel mehr als 50 Gew.-% eines Äthers (der nicht ein makrocyclischer Polyäther mit mehr als 7 Kohlenstoffatomen im Ring ist) enthält.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass der Äther ein Dialkyläther ist.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass der Dialkyläther Diäthyläther ist.
6. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass der Äther ein cycIischer Äther ist.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass der cyclische Äther 1,4-Dioxan ist.
8. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass der cyclische Äther Tetrahydrofuran ist.
9. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Lösungsmittel mehr als 50 Gew.-% eines Alkanols enthält.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass der Alkanol Methanol ist.
11. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Lösungsmittel mehr als 50 Gew.-% eines Kohlenwasserstoffs oder Gemisches von Kohlenwasserstoffen enthält.
12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, dass der Kohlenwasserstoff Benzol ist.
13. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Lösungsmittel mehr als 50 Gew.-% Wasser enthält.
14. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Reaktion zwischen 1,4,7,10,13,16-Hexaoxacyclooctadecan und Nitromethan bei einer Temperatur im Bereich von -25°C bis +35°C durchgeführt wird.
15. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass die Reaktion zwischen 1,4,7,10,13,16-Hexaoxacyciooctadecan und Nitromethan bei einer Temperatur im Bereich von 0°C bis -25°C durchgeführt wird.
16. Verfahren nach einem der Ansprüche 3 bis 13, dadurch gekennzeichnet, dass die Reaktion zwischen 1,4,7,10,13,16-Hexaoxacyclooctadecan und Nitromethan bei einer Temperatur im Bereich von 0°C bis +35°C durchgeführt wird.
17. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das 1,4,7,10,13,16-Hexaoxacyclooctadecan in dem Ausgangsgemisch erhalten worden ist durch Umsetzung von Tetraäthylenglykol mit einem Bis(2-halogenäthyl)äther in Gegenwart eines Alkalimetallhydroxids.
EP78200037A 1977-06-23 1978-06-12 Verfahren zur Isolierung von 1,4,7,10,13,16-Hexaoxacycloocta-decan Expired EP0000218B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB2633377 1977-06-23
GB2633377 1977-06-23

Publications (2)

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EP0000218A1 EP0000218A1 (de) 1979-01-10
EP0000218B1 true EP0000218B1 (de) 1981-11-11

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EP78200037A Expired EP0000218B1 (de) 1977-06-23 1978-06-12 Verfahren zur Isolierung von 1,4,7,10,13,16-Hexaoxacycloocta-decan

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EP (1) EP0000218B1 (de)
JP (1) JPS6034955B2 (de)
CA (1) CA1095922A (de)
DE (1) DE2861306D1 (de)
IT (1) IT1096598B (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY128673A (en) * 1997-10-30 2007-02-28 Shell Int Research Catalytic hydrolysis of alkylene oxides
WO2017062398A1 (en) * 2015-10-08 2017-04-13 Novelis Inc. A process for warm forming an age hardenable aluminum alloy in t4 temper

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EP0000218A1 (de) 1979-01-10
IT1096598B (it) 1985-08-26
IT7824811A0 (it) 1978-06-21
JPS549291A (en) 1979-01-24
CA1095922A (en) 1981-02-17
JPS6034955B2 (ja) 1985-08-12
DE2861306D1 (en) 1982-01-14

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