GB1560842A - Process for preparing perfluoro - 4 - oxo - 2,5 - dimethyl - 2 - fluorocarbonyl - 1,3 - dioxolane - Google Patents

Process for preparing perfluoro - 4 - oxo - 2,5 - dimethyl - 2 - fluorocarbonyl - 1,3 - dioxolane Download PDF

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GB1560842A
GB1560842A GB2130877A GB2130877A GB1560842A GB 1560842 A GB1560842 A GB 1560842A GB 2130877 A GB2130877 A GB 2130877A GB 2130877 A GB2130877 A GB 2130877A GB 1560842 A GB1560842 A GB 1560842A
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temperature
dimethyl
dioxolane
hfpo
mole
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/06—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals
    • C07D295/067—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals with the ring nitrogen atoms and the substituents attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/42—Halogen atoms or nitro radicals

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Description

(54) PROCESS FOR PREPARING PERFLUORO-4-OXO-2,5 DIMETHYL- 2-FLUOROCARBONYL- 1,3-DIOXOLANE (71) We, HOECHST ARTIENGESELLSCHAFT, a body corporate organised according to the laws of the Federal Republic of Germany, of 6230 Frankfurt/Main 80, Postfach 80 03 20, Federal Republic of Germany, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to a process for the preparation of perfluoto-4-oxo-2,S- dimethyl-2-íluorocarbonyl- 1,3 -dioxolane .
The reaction of ketones and aldehydes with hexafluoropropene-oxide (HFPO) at 100 to 3000C is described in US Patent No. 3,450,716, and to the formation of perfiuoro-pyruvoyl fluoride or its cyclic dimer, períluoro-4-oxo-2,5-dimethyl-2-fluoro- carbonyl-1,34ioxolane.
This cyclic compound can be used, as described in US Patent No. 3,450,716, as a soil disinfectant and an insecticide and as a valuable intermediate product.
This cyclic compound may be hydrolyzed, for example to perfuoro-pyruvic acid which is also an insecticidal agent.
However, this known one-step process for preparing the periluorinated dioxolane requires the reaction to be carried out under elevated pressure.
The present invention seeks to provide a process for preparing perfluoro-4- oxo-2,5-dimethyl-fluorocarbonyl-1,3-dioxolane which avoids the disadvantages of the known process and especially which can be carried out under normal pressure and at low temperatures.
The present invention provides a process for preparing perfluoro-4-oxo-2,5- dimethyl-2-fluorocarbonyl- 1,3-dioxolane which comprises reacting hexafluoropropene oxide with an N-formylated secondary amine free from active hydrogen atoms, at a temperature of from -50 to +20or, removing unreacted hexafluoropropene oxide and isolating the perfluorinated dioxolane from the reaction mixture.
When dimethyl formarnide is used as the N-formylated secondary amine, the process according to the invention can be illustrated as follows:
This shows that 2 moles of a fluorine-containing tertiary amine are formed for each mole of the desired perfluorinated dioxolane (PODF).
An excess of HFPO may be easily removed after completion of the reaction by distillation or by blowing off with an inert gas. The easiest way to isolate PODF is by fractional distillation. However, it is also possible to separate the reaction mixture into two liquid phases by the addition of a perfluorinated solvent, for example a perfluorinated ether or ketone preferably having a boiling point above 200or. The phase containing the perfluorinated solvent contains also the desired PODF (I) without the simultaneously formed fluorine-containing tertiary amine (11). Subsequently it is easy to separate the PODF from the solvent by distillation.
presence of an inert solvent. Aprotic polar solvents, especially ethers such as The process according to the present invention may also be carried out in the diethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether are especially suitable; there may also be used nitriles such as acetonitrile or propionitrile. The quantity of solvent is not critical but is preferably from 0.15 to 1.0 parts by volume per part by volume of N-formylated secondary amino.
HFPO may be used alone or in admixture with hexafluoropropene (HFP). The amount of HFPO is nor critical, although it is preferred to use an equimolar quantity calculated on the N-formylated secondary amine, or a slight excess, for example of 10 mole %. If HFPO is present in excess, then the excess is distilled off during workup of the reaction mixture and may be used for further subsequent reactions. When a deficient amount of HFPO is used, part of the N-formylated secondary amine is not reacted and remains in the residue after work-up. This unreacted N-formylated amine may also be used for furrher subsequent reactions.
Although reaction temperatures above +200C, for example up to 500C, are possible, they bring about the risks of decomposition and lower yields. Reaction temperatures below --500C reduce considerably the reaction speeds.
The reaction products PODF and ffuorine-containing tertiary amine may be separated by fractional distillation under normal pressure. In order to avoid decoy position, fractionating is most usefully carried out under reduced pressure so that the head and sump temperatures-especially prior to elimination of the fluorine- containing amine-do not exceed 200C, preferably ooC. Moreover, it is advantageous to add to the distillation mixture a HF-binding agent, preferably an alkali metal fluoride such as sodium fluoride or potassium fluoride; the fluoride may be used in an amount of from 0 to 50, especially from 2 to 40, and preferably from 10 to 25 g per 100 g of distillation mixture.
The structure of the N-formylated secondary amine is not critical. However, the N-formyl compound must not contain any active hydrogen, i.e. it should be free from hydroxy groups, carboxy groups and sulfonic acid groups. Especially good results are obtained when the free secondary amine from which the N-formyl compound is derived has a basic nature, and especially a pK value above 6, preferably above 7.
There may be used for example, N-formyl compounds of secondary aliphatic or heterocyclic amines having the general formula
in which each of R1 and R2 is a straight-chained or branched alkyl group having from 1 to 13 carbon atoms or a cydoalayl group having from 3 to 8 carbon atoms. Alkyl groups having from I to 4 carbon atoms and cycloalkyl groups having 5 and 6 carbon atoms are preferred. However, R1 and R2 may also form together a bivalent group, preferably a bivalent saturated group, in which case the bivalent group together with the N-formyl group forms a heterocycle having from 5 to 7 members. The bivalent group may be, for example, an alkylene group having from 4 to 6 carbon atoms, for example the group -CH2CH2CH(CH3)CH2CH2- or a polymethylene group having from 3 to 6 carbon atoms, for example a (CH2)4 or (CH2) group.
The alkylene groups may also be interrupted by hetero atoms or groups preferably by one hetero atom or group Such hetero atoms and groups include for example oxygen, > N--(C-C)alkyl and > N-CHO.
There may be used, for example, the N-formyl compound of pyrrolidine, piperidine, hexamethylene-imine, morpholine, piperazine, N-methyl-piperazine, Nmethyl-imidazolidine and oxazolidine. It is evident that stoichiometrically the use of a compound with two N-formyl groups in the molecule for each example, N,N'diformyl-piperazine, requires only half a mole per mole of HFPO.
When using a low molecular weight or high molecular weight N-formyl compound for example, dimethylformamide (DMF) or bis-decyl-formamide, the fluorinecontaining tert.amines formed as by-products have boiling points which differ sub stantially from the boiling point of the desired compound. This favours easydisnilative separation of the reaction mixture. When the N-formyl compound is a derivative of a long-chain secondary aliphatic amine, it may happen in some cases, especially upon addition of a solvent, that the reaction mixture decomposes spontaneously into two phases, one of them essentially containing the desired PODF.
The following Examples illustrate the present invention EXAMPLE 1 Períluoro4-oxo-2,5-dimethyl-2-uorocarbonyl-1,3Zioxolane and aHr difluorotrimethylamine 216 g of DMF (2.96 mole) are introduced into a three-necked flask equipped with an agitator, a thermometer, a cooling device and a gas inlet pipe, and subsequently at a temperature of from -20 to --100C and at a rate of 25 1 per hour there are introduced 850 g of a picture of HFPO and HFP (weight ratio 60:40)- corresponding to 3.07 mole of epoxide. This is followed by 6 hours of agitation at --15 to 1000. The temperature is then allowed to rise to +15 to +200C, while 319 g of a gaseous mixture of HFP and HFPO (weight ratio 70:30) escape. The residue is distilled in vacua (up to +400C/70 mm). In two cooling traps in series (CH2CIJCO2) there are obtained 579 g of a mixture of compounds (I) and (II) leaving a residue of 34 g of unreacted DMF. By distillation over KF there are obtained 246 g of compound (II) (bp 490 to 520C) and 145 g of compound (I) (bp. 700 to 72 CC).
The structures of compounds (I) and (II) are confirmed by IR and NMR spectroscopy and elemental analysis.
EXAMPLE 2 The apparatus used in Example 1 is charged with 48.5 g (0.5 mole) of N-formylpyrrolidine and 60 ml of tetraethylene glycol-dimethyl ether. At a temperature from -300C there are introduced 150 g of a mixture of HFPO/HFP (weight ratio 80:20).
Agitation is continued for two hours at this temperature. Subsequently the temperature is allowed to rise to ambient temperature. Unreacted HFPO and dissolved HFP escape and are collected in a cooling trap. The rernsin ng residue separates into two phases. The lower phase is distilled to provide 45 g of the desired dioxolane (bp. 70 to 720C).
EXAMPLE 3 150 g of 80% hexafluoropropene epoxide are added art 2300 to a solution of 27.5 g of N-formyl-morpholine (0.5 mole) in 50 ml of tetraethylene glycol dimethyl ether. At this temperature agitation is continued for 16 hours. The temperature is then allowed to rise to +20 C, while unreacted epoxide escapes and is collected in a cooling trap. The two phases which had formed upon reaction are separated and the low-boiling portions of the upper phase are condensed in a cooling trap at 250C and 1 mm Hg. The material obtained is distilled together with the lower phase (72 g). There are obtained 55 g (76.4%) of PODF having a boiling point of 7072 C.
Distillation of the residue of the upper phase yields 22 g of N-difluoromerhyl morpholine (bp. 23270C/3 mm) and 50 g of tetraglyme.
WHAT WE CLAIM IS: 1. A process for preparing perfluoroloxo-2,5-dimethyl-2-fìuorocarbonyl-1,3- dioxolane which comprises reacting hexafluoropropene oxide with an N-formylated secondary amine free from active hydrogen atoms, at a temperature of from -30 to f200C, removing unreacted hexafluoropropene oxide and isolating perfluoro-4-oxo 2,5-dimethyl-2-Suorocarbonyl-1,34ioxolane from the reaction mixture.
2. A process according to claim 1 carried out substantially as described in any one of Examples 1 to 3 herein.
3. Perfluoro4oxo-2,3 Aimethyl-2-fluorocarbonyl- 1,3 dioxolane whenever prepared by a process according to claim 1 or claim 2.
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (3)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    a long-chain secondary aliphatic amine, it may happen in some cases, especially upon addition of a solvent, that the reaction mixture decomposes spontaneously into two phases, one of them essentially containing the desired PODF.
    The following Examples illustrate the present invention EXAMPLE 1 Períluoro4-oxo-2,5-dimethyl-2-uorocarbonyl-1,3Zioxolane and aHr difluorotrimethylamine
    216 g of DMF (2.96 mole) are introduced into a three-necked flask equipped with an agitator, a thermometer, a cooling device and a gas inlet pipe, and subsequently at a temperature of from -20 to --100C and at a rate of 25 1 per hour there are introduced 850 g of a picture of HFPO and HFP (weight ratio 60:40)- corresponding to 3.07 mole of epoxide. This is followed by 6 hours of agitation at --15 to 1000. The temperature is then allowed to rise to +15 to +200C, while 319 g of a gaseous mixture of HFP and HFPO (weight ratio 70:30) escape. The residue is distilled in vacua (up to +400C/70 mm). In two cooling traps in series (CH2CIJCO2) there are obtained 579 g of a mixture of compounds (I) and (II) leaving a residue of 34 g of unreacted DMF. By distillation over KF there are obtained 246 g of compound (II) (bp 490 to 520C) and 145 g of compound (I) (bp. 700 to 72 CC).
    The structures of compounds (I) and (II) are confirmed by IR and NMR spectroscopy and elemental analysis.
    EXAMPLE 2 The apparatus used in Example 1 is charged with 48.5 g (0.5 mole) of N-formylpyrrolidine and 60 ml of tetraethylene glycol-dimethyl ether. At a temperature from -300C there are introduced 150 g of a mixture of HFPO/HFP (weight ratio 80:20).
    Agitation is continued for two hours at this temperature. Subsequently the temperature is allowed to rise to ambient temperature. Unreacted HFPO and dissolved HFP escape and are collected in a cooling trap. The rernsin ng residue separates into two phases. The lower phase is distilled to provide 45 g of the desired dioxolane (bp. 70 to 720C).
    EXAMPLE 3
    150 g of 80% hexafluoropropene epoxide are added art 2300 to a solution of 27.5 g of N-formyl-morpholine (0.5 mole) in 50 ml of tetraethylene glycol dimethyl ether. At this temperature agitation is continued for 16 hours. The temperature is then allowed to rise to +20 C, while unreacted epoxide escapes and is collected in a cooling trap. The two phases which had formed upon reaction are separated and the low-boiling portions of the upper phase are condensed in a cooling trap at 250C and 1 mm Hg. The material obtained is distilled together with the lower phase (72 g). There are obtained 55 g (76.4%) of PODF having a boiling point of 7072 C.
    Distillation of the residue of the upper phase yields 22 g of N-difluoromerhyl morpholine (bp. 23270C/3 mm) and 50 g of tetraglyme.
    WHAT WE CLAIM IS: 1. A process for preparing perfluoroloxo-2,5-dimethyl-2-fìuorocarbonyl-1,3- dioxolane which comprises reacting hexafluoropropene oxide with an N-formylated secondary amine free from active hydrogen atoms, at a temperature of from -30 to f200C, removing unreacted hexafluoropropene oxide and isolating perfluoro-4-oxo 2,5-dimethyl-2-Suorocarbonyl-1,34ioxolane from the reaction mixture.
  2. 2. A process according to claim 1 carried out substantially as described in any one of Examples 1 to 3 herein.
  3. 3. Perfluoro4oxo-2,3 Aimethyl-2-fluorocarbonyl- 1,3 dioxolane whenever prepared by a process according to claim 1 or claim 2.
GB2130877A 1976-05-22 1977-05-20 Process for preparing perfluoro - 4 - oxo - 2,5 - dimethyl - 2 - fluorocarbonyl - 1,3 - dioxolane Expired GB1560842A (en)

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DE19762623089 DE2623089A1 (en) 1976-05-22 1976-05-22 PROCESS FOR THE PREPARATION OF PERFLUORINE-4-OXO-2,5-DIMETHYL-2-FLUOROCARBONYL-1,3-DIOXOLANE

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JP (1) JPS52142072A (en)
BE (1) BE854912A (en)
CA (1) CA1087618A (en)
DE (1) DE2623089A1 (en)
FR (1) FR2351975A1 (en)
GB (1) GB1560842A (en)
IT (1) IT1074841B (en)
NL (1) NL7705444A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114555576A (en) * 2019-10-04 2022-05-27 公益财团法人相模中央化学研究所 Method for producing perfluoro (2, 4-dimethyl-2-fluoroformyl-1, 3-dioxolane)

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JP7307586B2 (en) * 2019-04-26 2023-07-12 東ソー株式会社 Method for producing perfluoro(2,4-dimethyl-2-fluoroformyl-1,3-dioxolane)
EP3848359A4 (en) * 2018-09-03 2022-06-01 Tosoh Corporation Aldehyde adduct to hexafluoropropylene oxide, method for producing trifluoropyruvate fluoride dimer, and method for producing perfluoro(2,4-dimethyl-2-fluoroformyl-1,3-dioxolane)
JP7307587B2 (en) * 2018-09-03 2023-07-12 東ソー株式会社 Method for producing aldehyde adduct to hexafluoropropylene oxide and trifluoropyruvic acid fluoride dimer
CN112638891A (en) 2018-09-03 2021-04-09 东曹株式会社 Aldehyde adduct of hexafluoropropylene oxide, method for producing trifluoroacetylacyl fluoride dimer, and method for producing perfluoro (2, 4-dimethyl-2-fluoroformyl-1, 3-dioxolane)

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FR1422169A (en) * 1964-10-21 1965-12-24 Du Pont Perfluorohydrocarbon products
US3962279A (en) * 1975-06-06 1976-06-08 E. I. Du Pont De Nemours And Company Synthesis of perfluoropyruvyl fluoride dimer
DE2623090A1 (en) * 1976-05-22 1977-12-08 Hoechst Ag PROCESS FOR PRODUCING PERFLUORALPHA (3,6-DIMETHYL-1,4-DIOXANYL-2-OXY) -PROPIONIC ACID FLUORIDE

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114555576A (en) * 2019-10-04 2022-05-27 公益财团法人相模中央化学研究所 Method for producing perfluoro (2, 4-dimethyl-2-fluoroformyl-1, 3-dioxolane)

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BE854912A (en) 1977-11-23
JPS52142072A (en) 1977-11-26
IT1074841B (en) 1985-04-20
FR2351975A1 (en) 1977-12-16
DE2623089A1 (en) 1977-12-08
NL7705444A (en) 1977-11-24
FR2351975B1 (en) 1982-10-22
CA1087618A (en) 1980-10-14

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