EP0378574A1 - Fluorination d'orthocarbonates et de polyalkoxypropanes - Google Patents

Fluorination d'orthocarbonates et de polyalkoxypropanes

Info

Publication number
EP0378574A1
EP0378574A1 EP88908555A EP88908555A EP0378574A1 EP 0378574 A1 EP0378574 A1 EP 0378574A1 EP 88908555 A EP88908555 A EP 88908555A EP 88908555 A EP88908555 A EP 88908555A EP 0378574 A1 EP0378574 A1 EP 0378574A1
Authority
EP
European Patent Office
Prior art keywords
hydrogen fluoride
orthocarbonate
polyalkoxypropane
fluorine
fluorination
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Withdrawn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
EP88908555A
Other languages
German (de)
English (en)
Inventor
Richard J. Lagow
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.)
Exfluor Research Corp
Original Assignee
Exfluor Research Corp
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 Exfluor Research Corp filed Critical Exfluor Research Corp
Publication of EP0378574A1 publication Critical patent/EP0378574A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/60—Preparation of compounds having groups or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/30—Compounds having groups
    • C07C43/313—Compounds having groups containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/32—Compounds having groups or groups

Definitions

  • This invention pertains to perfluoroalkyl orthocarbonates and perfluoropolyalkoxypropanes and to methods of producing these perfluorinated compounds.
  • the perfluoroalkyoorthocarbonates are represented by the formula:
  • R f1 , R f2 , R f3 and R f4 are the same or different short, straight or branched chain perfluoroalkyl radicals.
  • R f1 , R f2 , R f3 and R f4 are the same or different and are selected from -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF(CF 3 ) CF 2 CF 3 , -CF 2 CF(CF 3 ) 2 , and -C(CF 3 ) 3 .
  • the perfluoroalkoxypropanes are represented by the formula: f2 f4 wherein R f1 , R f2 , R f3 and R f4 are short, straight or branched chain perfluoroalkyl radicals.
  • R f ⁇ , R f2 , R f3 and R f4 are the same or different and are selected from -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 ,
  • the perfluoroalkylorthocarbonates and perfluoroalkoxypropanes of this invention are produced by direct fluorination with elemental fluorine.
  • the perfluoro compounds are more volatile than perfluoropolyethers of the same molecular weight. They are unaffected by concentrated sulfuri ⁇ acid and nitric acid, but decompose in hydrogen fluoride solution and concentrated hydrochloric acid. They are stable at 150°C and above.
  • the perfluoro compounds of this invention are useful as lubricants, heat exchangers, solvents, vapor phase soldering fluids and oxygen carriers.
  • Figure 1 shows the reactions of elemental fluorine in the production of perfluoroalkylorthocarbonates and perfluoroalkyoxypropanes.
  • the perfluoroalkylorthocarbonate of this invention are represented by the formula: wherein R f1 , R f2 , R f3 and R f4 are the same or different and are selected from short, straight or branched chain perfluoroalkyl radicals.
  • R f1 , R f2 , R f3 and R f4 are selected from -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF(CF 3 )CF 2 CF 3 , -CF 2 CF(CF 3 ) 2 , and -C(CF 3 ) 3 .
  • Especially preferred perfluoroalkylorthocarbonates are represented by the formula:
  • R f is selected from -CF 3 , -CF 2 CF 3 , CF 2 CF 2 CF 3 and CF(CF 3 ) 2 .
  • the perfluoroalkyoxypropanes of this invention are represented by the formula:
  • R f1 , R f2 , R f3 and R f4 are shortr straight or branched chain perfluoroalkyl radicals.
  • R f1 , R f2 , R f3 and R f4 are selected from -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , and -CF 2 CF 2 CF 2 CF 3 , -CF(CF 3 )CF 2 CF 3 , -CF(CF 3 )CF 2 CF 3 , -CF 2 CF(CF 3 ) , -C(CF 3 ) 3 .
  • Especially preferred perfluoroalkyoxypropanes are represented by the formula:
  • R f is selected from -CF 3 , -CF CF 3 , CF 2 CF 2 CF 3 and -CF(CF 3 ) 2 .
  • fluorination procedures for production of perfluoroalkoxy propanes can yield novel compounds of the formula:
  • R f is as defined above.
  • the perfluoro compounds of this invention are produced by the direct fluorination technique of Lagow and Margrave, Prog, of Org. Chem. 26, 161: (1979).
  • Appropriate orthocarbonate or polyalkoxy- propane starting materials are selected.
  • orthocarbonates can be selected from compounds of the formula:
  • R 1 , R 2 , R 3 and R 4 can be the same or different and are selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 1 , -CH(CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -CH(CH 3 )CH 2 CH 3 , -CH 2 CH(CH 3 ) 2 , and -C(CH 3 ) 3 .
  • Polyalkoxypropanes can be selected from compounds of the formula: 2 4 wherein R 1 , R 2 , R 3 can be the same different and are selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -CH(CH 3 ) CH 2 CH 3 , -CH 2 CH(CH 3 ) 2 , and -C(CH 3 ) 3 .
  • the starting material is placed in a fluorine reactor such as the reactor described by Lagow and Margrave , supra.
  • the reactor is cooled and flushed with an inert gas such as helium or nitrogen after which the fluorine is initiated under controlled conditions.
  • low fluorine concentrations between about one and about ten percent are used initially.
  • the dilute fluorine is passed over the material to be fluorinated.
  • the fluorination reaction proceeds the fluorine concentration and flow rate of the gas are gradually increased until pure fluorine conditions are achieved and the material is perfluorinated.
  • the yield and quality of the perfluoropolyether product is improved when fluorination is conducted in the presence of a hydrogen fluoride scavenger.
  • the scavenger is believed to prevent the formation of ether-HF acid base complexes during the fluorination reaction.
  • Fluorination in the presence of a hydrogen fluoride scavenger can be performed in several ways.
  • the hydrogen fluoride scavenger in powdered or pellet form
  • the orthocarbonate or polyalkoxypropane is mixed with the orthocarbonate or polyalkoxypropane.
  • the blend is placed in a suitable fluorination reactor and fluorinated by exposure to gradually increasing concentrations of fluorine gas.
  • the orthocarbonate or polyalkoxypropane may be coated onto the scavenger and fluorinated in this form.
  • the perfluoroalkyorthocarbonates and perfluoroalkoxypropanes of this invention are useful as lubricants, heat exchangers, vapor phase soldering fluids, solvents and oxygen carriers.
  • the oils are useful as vacuum pump oils and oils for diffusion pumps.
  • the more volatile orthocarbonates and alkoxypropanes are used to cool electronic devices such as computers.
  • the perfluoro compounds are also useful as perfluorocarbon solvents, as oxygen carriers in biomedical applications and as oxygen carriers for organic oxidation reactions. This invention is illustrated further by the following examples.
  • Tetramethyl orthocarbonate, tetraethyl orthocarbonate, tetra-i-propyl orthocarbonate, 1,1,3,3- tetramethoxypropane, and 1,1,3,3-tetraethoxypropane were used as received from Aldrich Chemicals. Fluorine was research grade and obtained from air Products and Chemicals, Inc. Elemental analyses were performed by E+R Mecroanalytical Laboratory, Inc., Corona, New York. 19F nmr spectra were recorded on a Varian EM 390 spectrometer operating at 84.67 MHz. Chemical shifts were reported relative to CFCl 3 . Negative shifts refer to high field of the reference.
  • Mass spectra were measured in a gas phase on a Bell & Howell Model 21-490 mass spectrometer. A Bendix 2300-gas chromatograph equipped with a cryogenic controller and a thermalconductivity detector was used for separation. Infrared spectra were recorded on a Beckman Acculab 8 spectrometer utilizing a gas cell with KBr windows.
  • a 1.82 g of 1,1,3,3-tetraethoxypropane was fluorinated using the same conditions as those for 1 , 1,3 ,3-tetramethoxypropane. After fractionation 2.72 grams of crude products were collected. From GC separation at 25 °C were isolated perfluoro 1 ,1,3,3-tetraethoxypropane (a), perfluoro-1 ,1,3-triethoxypropane (b), perfIuoro-1 ,3-diethoxypropane (c), and perfluoro-1 ,1-diethoxypropane (d). The yields were 13.0%, 23.4%, 20.0%, and 9.3% respectively, based on the starting 1, 1,3,3-tetraethoxy propane. GC retention time increased in the order: d ⁇ c ⁇ b ⁇ a.
  • Tetramethyl orthocarbonate was introduced into the reactor in different manner. Inside the cryogenic reactor the first two zones were packed with a mixture of NaF and copper turnings, and the last two zones were packed with fluorinated copper turnings. Tetramethyl orthocarbonate (2.04 g) was slowly injected into the evaporator and condensed in the first zone by the passage of 60 cc/min of helium flow, while zones 2, 3, 4 were cooled to -100 °C. The reactor was then cooled to
  • Tetraethyl orthocarbonate (1.6 g) was handled in an usual way and fluorinated from -100 °C to room temperature (see Table 3). A 2.6 g of perfluoro tetraethyl orthocarbonate was isolated from 2.86 g of crude products. The yield was 56.5% based on the starting tetraethyl orthocarbonate.
  • the FNMR spectrum consisted of two peaks at -88.3 ppm (-CF 3 ) and -91.0 ppm (-CF 2 -). The relative ratio was 2 : 1.
  • Fluorination of tetra-i-propyl orthocarbonate Tetra-i-propyl orthocarbonate (1.4 g) was fluorinated using the similar conditions as those for tetraethyl orthocarbonate, except the reaction was initiated at -120 °C (see Table 4). Large amounts of lowboiling products passed to -131 °C on a vacuum-line separation.
  • the GC assay indicated the presence of a number of components, which were inseparable.
  • the -78 °C fraction contained the desired products, from which a mixture of perfluoro tetra-n-propyl orthocarbonate and perfluoro tetra-i-propyl orthocarbonate was isolated in an amount of 0.55 grams. The total yield was 12.8%.
  • PCT/US88/02966 81) Designated States: AT (European patent), AU, BE ( ropean patent), BR, CH (European patent), DE (E
  • Perfluoroalkylorthocarbonates and perfluoropolyalkoxypropanes are disclosed.
  • the perfluoro compounds are syn thesized by direct fluorination procedures.
  • the perfluoro compounds are useful lubricants, heat exchangers, vapor phas soldering fluids, solvents, and oxygen carriers.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

On décrit des perfluoroalkylorthocarbonates et des perfluoropolyalkoxypropanes. Les composés perfluoro sont synthétisés par des procédés de fluorination directe. Les composés perfluoro sont utiles en tant que lubrifiants, échangeurs thermiques, fluides de soudage en phase de vapeur, solvants et porteurs d'oxygène.
EP88908555A 1987-08-28 1988-08-26 Fluorination d'orthocarbonates et de polyalkoxypropanes Withdrawn EP0378574A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US9065887A 1987-08-28 1987-08-28
US90658 1998-06-04

Publications (1)

Publication Number Publication Date
EP0378574A1 true EP0378574A1 (fr) 1990-07-25

Family

ID=22223721

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88908555A Withdrawn EP0378574A1 (fr) 1987-08-28 1988-08-26 Fluorination d'orthocarbonates et de polyalkoxypropanes

Country Status (5)

Country Link
EP (1) EP0378574A1 (fr)
JP (1) JPH03500172A (fr)
KR (1) KR950004893B1 (fr)
CA (1) CA1325219C (fr)
WO (1) WO1989001929A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5300683A (en) * 1988-09-28 1994-04-05 Exfluor Research Corporation Fluorination of acetals, ketals and orthoesters
US5053536A (en) * 1988-09-28 1991-10-01 Exfluor Research Corporation Fluorination of acetals, ketals and orthoesters

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415847A (en) * 1965-10-18 1968-12-10 Minnesota Mining & Mfg Fluorocarbon orthoesters
US4113435A (en) * 1973-07-16 1978-09-12 Massachusetts Institute Of Technology Cryogenically controlled direct fluorination apparatus
US4755567A (en) * 1985-11-08 1988-07-05 Exfluor Research Corporation Perfluorination of ethers in the presence of hydrogen fluoride scavengers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8901929A2 *

Also Published As

Publication number Publication date
JPH03500172A (ja) 1991-01-17
CA1325219C (fr) 1993-12-14
KR950004893B1 (ko) 1995-05-15
KR890701523A (ko) 1989-12-20
WO1989001929A3 (fr) 1989-06-01
WO1989001929A2 (fr) 1989-03-09

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