NO157816B - PROCEDURE FOR THE PREPARATION OF ISOBUTYRYL FLUORIDE. - Google Patents
PROCEDURE FOR THE PREPARATION OF ISOBUTYRYL FLUORIDE. Download PDFInfo
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- NO157816B NO157816B NO841549A NO841549A NO157816B NO 157816 B NO157816 B NO 157816B NO 841549 A NO841549 A NO 841549A NO 841549 A NO841549 A NO 841549A NO 157816 B NO157816 B NO 157816B
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- NO
- Norway
- Prior art keywords
- fluoride
- reactor
- reaction
- carbon monoxide
- isopropyl
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 13
- FSQOYWQCIXSBNP-UHFFFAOYSA-N 2-methylpropanoyl fluoride Chemical compound CC(C)C(F)=O FSQOYWQCIXSBNP-UHFFFAOYSA-N 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 14
- PRNZBCYBKGCOFI-UHFFFAOYSA-N 2-fluoropropane Chemical compound CC(C)F PRNZBCYBKGCOFI-UHFFFAOYSA-N 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 10
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 150000001265 acyl fluorides Chemical class 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SDTXSEXYPROZSZ-UHFFFAOYSA-N 1,2-dibromo-2-methylpropane Chemical compound CC(C)(Br)CBr SDTXSEXYPROZSZ-UHFFFAOYSA-N 0.000 description 1
- OQPNDCHKFIHPBY-UHFFFAOYSA-N 1,2-dichloro-2-methylpropane Chemical compound CC(C)(Cl)CCl OQPNDCHKFIHPBY-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 150000002510 isobutyric acid esters Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- -1 pivalyl fluoride Chemical compound 0.000 description 1
- WMFABESKCHGSRC-UHFFFAOYSA-N propanoyl fluoride Chemical compound CCC(F)=O WMFABESKCHGSRC-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003797 solvolysis reaction Methods 0.000 description 1
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
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- Saccharide Compounds (AREA)
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Description
Denne oppfinnelse angår en fremgangsmåte til fremstilling This invention relates to a method for production
av isobutyrylfluorid ved karbonylering av isopropylfluorid• of isobutyryl fluoride by carbonylation of isopropyl fluoride•
Isopropylfluorid er et velkjent stoff som er egnet til mange formål som er velkjente for fagmenn på området. Iso-propylf luorid kan fremstilles ut fra propylen og hydrogenfluorid som vist i US-patent nr. 2 917 559, for eksempel. Isopropyl fluoride is a well-known substance suitable for many purposes well known to those skilled in the art. Iso-propyl fluoride can be prepared from propylene and hydrogen fluoride as shown in US Patent No. 2,917,559, for example.
Fremstillingen av visse acylfluorider ved omsetting The preparation of certain acyl fluorides by reaction
av acylklorider med visse uorganiske fluorider er kjent. En annen fremgangsmåte til fremstilling av visse acylfluorider er å omsette visse sekundære organiske klorider eller bromider med karbonmonoksyd i nærvær av bortrifluorid som katalysator, og hydrogenfluorid som vist i US-patent nr. 2 570 793. Tertiære klorider og bromider er blitt omsatt med karbonmonoksyd i nærvær av en katalysator såsom bortrifluorid og hydrogenfluorid under oppnåelse av acylfluorider som beskrevet i US-patent nr. 2 580 070. ^of acyl chlorides with certain inorganic fluorides is known. Another method for the preparation of certain acyl fluorides is to react certain secondary organic chlorides or bromides with carbon monoxide in the presence of boron trifluoride as a catalyst, and hydrogen fluoride as shown in US Patent No. 2,570,793. Tertiary chlorides and bromides have been reacted with carbon monoxide in presence of a catalyst such as boron trifluoride and hydrogen fluoride while obtaining acyl fluorides as described in US Patent No. 2,580,070. ^
US-patent nr. 3 414 612 beskriver en fremgangsmåte til omdannelse av visse klor- eller brom-substituerte hydrokar-boner såsom tertiært butylklorid, tertiært butylbromid, l,2-diklor-2-metylpropan eller l,2-dibrom-2-metylpropan til det tilsvarende pivalyl-fluorid ved omsetting av disse stoffer med karbonmonoksyd under anvendelse av vannfritt hydrogenf luorid som katalysator (og selvfølgelig som reaktant) . Den fremgangsmåte som er beskrevet i dette patent, utføres fortrinnsvis ved et trykk på minst 53 kg/cm 2, og de beste resultater (90+% utbytter) oppnås ved trykk på over 105 US Patent No. 3,414,612 describes a process for converting certain chlorine- or bromine-substituted hydrocarbons such as tertiary butyl chloride, tertiary butyl bromide, 1,2-dichloro-2-methylpropane or 1,2-dibromo-2-methylpropane to the corresponding pivalyl fluoride by reacting these substances with carbon monoxide using anhydrous hydrogen fluoride as catalyst (and of course as reactant). The process described in this patent is preferably carried out at a pressure of at least 53 kg/cm 2 , and the best results (90+% yields) are obtained at pressures above 105
2 2
kg/cm^. kg/cm^.
Kanbara et al, Bull, Jap. Pet. Inst., 11, sider 48-53 Kanbara et al, Bull, Jap. Pet. Inst., 11, pages 48-53
(1969) beskriver omsetning av etylfluorid med karbonmonoksyd (1969) describes the reaction of ethyl fluoride with carbon monoxide
og vannfritt hydrogenfluorid ved høyt trykk fulgt av vann-behandling under oppnåelse av propionsyre. Kanbara et al. angir på side 51: "i autoklaven må det virkelige produkt være propionylfluorid, men dette hydrolyseres lett under dannelse av propionsyre når det helles i vann". Fremgangsmåten ifølge Kanbara et al utføres ved en temperatur på 100°C eller høyere and anhydrous hydrogen fluoride at high pressure followed by water treatment to yield propionic acid. Kanbara et al. states on page 51: "in the autoclave the real product must be propionyl fluoride, but this readily hydrolyzes to form propionic acid when poured into water". The method according to Kanbara et al is carried out at a temperature of 100°C or higher
og ved trykk på 177 kg/cm<2> eller større. De høyere tempe-raturer og trykk gir betydelig forbedring i utbyttet ved fremgangsmåten ifølge Kanbara et al. and at pressures of 177 kg/cm<2> or greater. The higher temperatures and pressures give a significant improvement in the yield in the method according to Kanbara et al.
Det er et formål med denne oppfinnelse å tilveiebringe en fremgangsmåte til fremstilling av isobutyrylfluorid ved den forholdsvis milde reaksjon mellom isopropylfluorid og karbonmonoksyd. Isobutyrylfluoridet kan lett omdannes til isosmør-syre og/eller isosmørsyreestere ved at det behandles med vann og/eller alkoholer. It is an object of this invention to provide a method for producing isobutyryl fluoride by the relatively mild reaction between isopropyl fluoride and carbon monoxide. The isobutyryl fluoride can easily be converted into isobutyric acid and/or isobutyric acid esters by treating it with water and/or alcohols.
Oppfinnelsen angår således en fremgangsmåte til fremstilling av isobutyrylfluorid, karakterisert ved at man bringer isopropylfluorid, karbonmonoksyd og vannfritt hydrogenfluorid i kontakt med hverandre ved en temperatur i området fra 0 til 80°C og ved et trykk i området fra 10,5 til 49 kg/cm<2>, under anvendelse av et molforhold mellom vannfritt hydrogenfluorid og isopropylfluorid på fra 4,5:1 til 40:1. The invention thus relates to a method for producing isobutyryl fluoride, characterized by bringing isopropyl fluoride, carbon monoxide and anhydrous hydrogen fluoride into contact with each other at a temperature in the range from 0 to 80°C and at a pressure in the range from 10.5 to 49 kg/ cm<2>, using a molar ratio of anhydrous hydrogen fluoride to isopropyl fluoride of from 4.5:1 to 40:1.
Mengden av vannfritt hydrogenfluorid som anvendes ved fremgangsmåten ifølge oppfinnelsen, uttrykt som mol pr. mol av isopropylfluoridet, er fortrinnsvis fra 9:1 til 20:1. The amount of anhydrous hydrogen fluoride used in the method according to the invention, expressed as moles per mol of the isopropyl fluoride is preferably from 9:1 to 20:1.
Karbonyleringsreaksjonen utføres fortrinnsvis i temperatur-området fra 20 til 80°C. Reaksjonstemperaturer høyere enn 80°C resulterer i et betydelig redusert utbytte av isobutyrylfluorid. The carbonylation reaction is preferably carried out in the temperature range from 20 to 80°C. Reaction temperatures higher than 80°C result in a significantly reduced yield of isobutyryl fluoride.
Det trykk som anvendes ved fremgangsmåten ifølge oppfinnelsen, holdes fortrinnsvis i området fra 28 t^l 42 kg/cm<2>. The pressure used in the method according to the invention is preferably kept in the range from 28 to 42 kg/cm<2>.
Reaksjonstiden er i alminnelighet i området 30-50 minutter, men lengre tidsrom kan anvendes. The reaction time is generally in the range of 30-50 minutes, but longer periods can be used.
Hovedproduktet fra reaksjonen er isobutyrylfluorid i utbytter på 89 % eller bedre. The main product from the reaction is isobutyryl fluoride in yields of 89% or better.
En hvilken som helst egnet fremgangsmåte til isolering Any suitable method of isolation
av isobutyrylfluorid fra reaksjonsblandingen kan anvendes ved vår fremgangsmåte. Videre kan fremgangsmåten utføres enten chargevis eller kontinuerlig. For eksempel kan overskudd av hydrogenfluorid og karbonmonoksyd i reaksjons-utløps-strømmen resirkuleres til reaksjonen. of isobutyryl fluoride from the reaction mixture can be used in our method. Furthermore, the method can be carried out either batchwise or continuously. For example, excess hydrogen fluoride and carbon monoxide in the reaction outlet stream can be recycled to the reaction.
Som tidligere angitt kan isobutyrylfluorid-produktet, som er ganske reaktivt, lett omdannes ved solvolyse til den tilsvarende isosmørsyre, estere eller amider. As previously indicated, the isobutyryl fluoride product, which is quite reactive, can easily be converted by solvolysis to the corresponding isobutyric acid, esters or amides.
Vår oppfinnelse er ytterligere illustrert ved de følgende eksempler. Our invention is further illustrated by the following examples.
EKSEMPEL 1 EXAMPLE 1
Reaksjonen ble utført i en reaktor av typen Hasteloy C Magnedrive med kapasitet 300 cm^. I reaktoren ble det anbrakt 92 g vannfritt hydrogenfluorid, og det ble dannet overtrykk i reaktoren ved hjelp av karbonmonoksyd til ca. 34 ato. Isopropylfluorid (under anvendelse av nitrogen-partialtrykk for å opprettholde væskeform) ble pumpet fra en annen sylin-der inn i damprommet i reaktoren i løpet av et tidsrom på 26 minutter mens man opprettholdt et trykk av karbonmonoksyd på 32-38 ato. Etter ca. 33 minutters reaksjonstid (innbe-fattende tilsetningstid) ved en reaksjonstemperatur på 50°C ble trykket i reaktoren stabilisert, hvilket anga hovedsake-lig fullstendig reaksjon. Etter ytterligere 26 minutter under disse betingelser ble reaktor-innholdet avkjølt, 39 g vann (2,2 mol) ble tilsatt i reaktoren og det gassformige materiale ble ventilert ut av reaktoren, hvilket brakte innholdet til et trykk som var omtrent likt atmosfæretrykket. Væsken i reaktoren ble overført og ytterligere fortynnet The reaction was carried out in a reactor of the Hasteloy C Magnedrive type with a capacity of 300 cm 2 . 92 g of anhydrous hydrogen fluoride were placed in the reactor, and overpressure was created in the reactor using carbon monoxide to approx. 34 ato. Isopropyl fluoride (using nitrogen partial pressure to maintain liquid form) was pumped from another cylinder into the vapor space of the reactor over a period of 26 minutes while maintaining a carbon monoxide pressure of 32-38 ato. After approx. After a reaction time of 33 minutes (including addition time) at a reaction temperature of 50°C, the pressure in the reactor was stabilized, which indicated essentially complete reaction. After a further 26 minutes under these conditions, the reactor contents were cooled, 39 g of water (2.2 moles) was added to the reactor and the gaseous material was vented out of the reactor, bringing the contents to a pressure approximately equal to atmospheric pressure. The liquid in the reactor was transferred and further diluted
med vann til en 10-15% HF/H20-oppløsning som inneholdt de hydrolyserte karbonyleringsprodukter. 400 g natriumsulfat ble tilsatt, og den resulterende blanding ble behandlet med cykloheksan under ekstraksjon av isosmørsyre fra vannfasen. GC-analyse viste at det var oppnådd 94% utbytte av isosmør-syre. with water to a 10-15% HF/H 2 O solution containing the hydrolysed carbonylation products. 400 g of sodium sulfate was added and the resulting mixture was treated with cyclohexane extracting isobutyric acid from the aqueous phase. GC analysis showed that a 94% yield of isobutyric acid had been achieved.
EKSEMPEL 2 EXAMPLE 2
Apparaturen og deler av fremgangsmåten som er beskrevet The apparatus and parts of the method described
i Eksempel 1, ble anvendt i dette Eksempel. I reaktoren ble det anbrakt 91 g vannfritt hydrogenfluorid, og det ble deretter dannet et overtrykk i reaktoren på ca. 34 ato. in Example 1, was used in this Example. 91 g of anhydrous hydrogen fluoride was placed in the reactor, and an overpressure of approx. 34 ato.
med karbonmonoksyd ved 50°C. Deretter ble 30,6 g (0,49 mol) isopropylfluorid tilført til reaktoren ved at det ble pumpet inn som en væske under nitrogentrykk gjennom en nål med dimen-sjon 20 (0,508 mm ID) anbrakt i en inngangsåpning som befant with carbon monoxide at 50°C. Next, 30.6 g (0.49 mol) of isopropyl fluoride was added to the reactor by being pumped in as a liquid under nitrogen pressure through a 20 gauge needle (0.508 mm ID) placed in an inlet port containing
seg under overflaten av det vannfrie hydrogenfluorid i reaktoren. Den totale mengde isopropylfluorid ble pumpet til reaktoren som ble holdt ved 50°C i løpet av et tidsrom på ca. 25 minutter. Trykket, som ble holdt på fra ca. 32 til 39 ato. med karbonmonoksyd inne i reaktoren, ble stabilisert i løpet av ca. 33 minutter etterat isopropylfluoridet første gang ble innført. Reaksjonsblandingen ble opparbei-det som beskrevet i Eksempel 1 under oppnåelse av et utbytte på 93% av isosmørsyre. below the surface of the anhydrous hydrogen fluoride in the reactor. The total amount of isopropyl fluoride was pumped to the reactor which was maintained at 50°C over a period of approx. 25 minutes. The pressure, which was maintained from approx. 32 to 39 ato. with carbon monoxide inside the reactor, was stabilized during approx. 33 minutes after the isopropyl fluoride was first introduced. The reaction mixture was worked up as described in Example 1, obtaining a yield of 93% of isobutyric acid.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO841549A NO157816C (en) | 1984-04-17 | 1984-04-17 | PROCEDURE FOR THE PREPARATION OF ISOBUTYRYL FLUORIDE. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO841549A NO157816C (en) | 1984-04-17 | 1984-04-17 | PROCEDURE FOR THE PREPARATION OF ISOBUTYRYL FLUORIDE. |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO841549L NO841549L (en) | 1985-10-18 |
| NO157816B true NO157816B (en) | 1988-02-15 |
| NO157816C NO157816C (en) | 1988-05-25 |
Family
ID=19887610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO841549A NO157816C (en) | 1984-04-17 | 1984-04-17 | PROCEDURE FOR THE PREPARATION OF ISOBUTYRYL FLUORIDE. |
Country Status (1)
| Country | Link |
|---|---|
| NO (1) | NO157816C (en) |
-
1984
- 1984-04-17 NO NO841549A patent/NO157816C/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO841549L (en) | 1985-10-18 |
| NO157816C (en) | 1988-05-25 |
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