NO137235B - PROCEDURE FOR THE PREPARATION OF 3,4-EPOXY-4-METHYL-PENTANON-2 - Google Patents
PROCEDURE FOR THE PREPARATION OF 3,4-EPOXY-4-METHYL-PENTANON-2 Download PDFInfo
- Publication number
- NO137235B NO137235B NO1678/72A NO167872A NO137235B NO 137235 B NO137235 B NO 137235B NO 1678/72 A NO1678/72 A NO 1678/72A NO 167872 A NO167872 A NO 167872A NO 137235 B NO137235 B NO 137235B
- Authority
- NO
- Norway
- Prior art keywords
- epoxy
- methyl
- preparation
- pentanon
- procedure
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- KFIKRXHVTJQQTB-UHFFFAOYSA-M chlorocopper;pyridine Chemical class [Cu]Cl.C1=CC=NC=C1 KFIKRXHVTJQQTB-UHFFFAOYSA-M 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical class [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- -1 dipyridyls Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 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
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- OUULRIDHGPHMNQ-UHFFFAOYSA-N stibane Chemical class [SbH3] OUULRIDHGPHMNQ-UHFFFAOYSA-N 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/32—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by aldehydo- or ketonic radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Plural Heterocyclic Compounds (AREA)
- Catalysts (AREA)
Description
Foreliggende oppfinnelse angår en fremgangsmåte for fremstilling The present invention relates to a method for production
av 3,4-epoksy-4-m.etyl - pentanon -2. of 3,4-epoxy-4-m.ethyl - pentanone -2.
Det er kjent fremgangsmåter for fremstilling av substituerte eller ikke-substituerte epoksy-forbindelser. Disse er basert på flertrinnsreaksjoner, og anvender vanskelig tilgjengelige reagenser som merkbart influerer på prosessens Skonomi. There are known methods for producing substituted or unsubstituted epoxy compounds. These are based on multi-step reactions, and use hard-to-find reagents that noticeably influence the economy of the process.
Det er nå funnet at det er mulig å syntetisere en substituert, epoksy-forbindelse på en enkel og billig måte i henhold til en fremgangsmåte som er meget interessant ut fra et industrielt synspunkt. It has now been found that it is possible to synthesize a substituted epoxy compound in a simple and cheap way according to a method which is very interesting from an industrial point of view.
Oppfinnelsen vedrbrer således en fremgangsmåte for fremstilling The invention thus relates to a method for production
av 3, 4-epoks:y-4-metylpentanon-2 med formel of 3,4-epoxy:γ-4-methylpentanone-2 with formula
og det særegne ved fremgangsmåten i henhold til oppfinnelsen er at en alkohol.med formel. oiksyderes i væskefase med molekylært oksygen i nærvær av kobber(I)-klorid som katalysator. Reaksjonen forer til dannelse av det substituerte epoksyd etter fblgende skjema and the peculiarity of the method according to the invention is that an alcohol.with formula. is oxidized in the liquid phase with molecular oxygen in the presence of copper(I) chloride as a catalyst. The reaction leads to the formation of the substituted epoxide according to the following scheme
For oppnåelse av en bedre løselighet og følgelighbyere reaksjons-hastighet kan kuprokloridet fordelaktig anvendes i komplekser med en koordinerende base som kan være enkel eller substituert og valgt fra fenantroliner, dipyridylér, pyridiner, dimetylsulfoksyd (DMSO), dimetylformamid (DMF), fosfiner, arsiner, stibiner, imidazol, piperidin osv. Fortrinnsvis anvendes kuprokloridet i form av et kuproklorid-pyridinkompleks. To achieve a better solubility and consequently a higher reaction rate, the cupric chloride can advantageously be used in complexes with a coordinating base which can be simple or substituted and selected from phenanthrolines, dipyridyls, pyridines, dimethylsulfoxide (DMSO), dimethylformamide (DMF), phosphines, arsines, stibines, imidazole, piperidine, etc. The cupric chloride is preferably used in the form of a cupric chloride-pyridine complex.
En fordel ved fremgangsmåten i henhold til oppfinnelsen består i muligheten av ved slutten av oksydasjonsreaksjonen å gjennvinne kobber-utgangsforbindelsen som kan brukes om igjen, og den katalytiske cyklus gjennomfbres uten vesentlig tap av katalysatoren. An advantage of the method according to the invention consists in the possibility of recovering the starting copper compound at the end of the oxidation reaction, which can be used again, and the catalytic cycle is carried out without significant loss of the catalyst.
Oksydasjonen i henhold til oppfinnelsen kan utfores på en enkel måte, den gir gode utbytter og kan gjennomfbres innen et bredt område av trykk og temperatur. Det er mulig å operere både i nærvær og i fravær av losningsmidler eller fortynningsmidler. The oxidation according to the invention can be carried out in a simple way, it gives good yields and can be carried out within a wide range of pressure and temperature. It is possible to operate both in the presence and in the absence of solvents or diluents.
I sistnevnte tilfelle tjener alkoholen selv som reaksjonsmedium. In the latter case, the alcohol itself serves as the reaction medium.
På den annen side kan det i fbrstnevnte tilfelle gjbres bruk av løsningsmidler valgt fra enkle eller substituerte alkyl-, aromatiske og cykloalifatiske hydrokarboner, etere og andre, eller fra de foran nevnte baser. On the other hand, in the first-mentioned case, it is possible to use solvents selected from simple or substituted alkyl, aromatic and cycloaliphatic hydrocarbons, ethers and others, or from the aforementioned bases.
Reaksjonstemperaturen kan variere innen et bredt område. Med hensyn til arbeidstrykket må dette sbrge for opprettholdelse 'av en flytende fase. Anvendbare områder for temperatur er fra 15°C til 150°c og for trykk fra 1 til 30 atmosfærer. The reaction temperature can vary within a wide range. With regard to the working pressure, this must ensure the maintenance of a liquid phase. Usable ranges for temperature are from 15°C to 150°c and for pressure from 1 to 30 atmospheres.
Hvis kuprokloridet anvendes i form av et kuproklorid-pyridinkompleks, fremstilles dette ved kjent teknikk og kan innfores som sådant i reaktoren, eller fremstilles fra CuCl og pyridin under selve oksydasjonsreaksjonen. If the cuprochloride is used in the form of a cuprochloride-pyridine complex, this is produced by known techniques and can be introduced as such into the reactor, or produced from CuCl and pyridine during the oxidation reaction itself.
Noen andre spesielle arbeidsbetingelser vil bli nevnt i det fblgende eksempel som skal illustrere oppfinnelsen. Some other special working conditions will be mentioned in the following example to illustrate the invention.
Eksempel - Fremstilling av 4-me:tyl -3/4-epoksy-pentanpn-2 Example - Preparation of 4-methyl-3/4-epoxy-pentanpn-2
fra diaceton (4-hydroksy-4-me-tyl- pentarion-2) . from diacetone (4-hydroxy-4-methylpentarion-2).
Det ble fremstilt en blanding bestående av 48 gram diacetonalkohol og 3,5 gram pyridin. Deri ble lost 2 gram CuCl og det hele ble underkastet oksydasjon ved gjennombobling av oksygen (2 l/h) ved 70°C. A mixture consisting of 48 grams of diacetone alcohol and 3.5 grams of pyridine was prepared. 2 grams of CuCl were dissolved in it and the whole was subjected to oxidation by bubbling through oxygen (2 l/h) at 70°C.
Etter 12 timer ble 2,5 gram CuCl-pyridin fraskilt ved filtrering After 12 hours, 2.5 grams of CuCl-pyridine were separated by filtration
i nitrogenatmosfære. Reaksjonsproduktene ble analysert i lbsningen ved gasskromatografi. Omdannelsen av diacetonalkohol var 28% ved en selektivitet av 95% til epoksyd og 5% til aceton. in a nitrogen atmosphere. The reaction products were analyzed in the solution by gas chromatography. The conversion of diacetone alcohol was 28% at a selectivity of 95% to epoxide and 5% to acetone.
Det ble oppnådd 12,5 gram epoksyd og 0,7 gram aceton. 12.5 grams of epoxide and 0.7 grams of acetone were obtained.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2449971 | 1971-05-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NO137235B true NO137235B (en) | 1977-10-17 |
| NO137235C NO137235C (en) | 1978-01-25 |
Family
ID=11213758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO1678/72A NO137235C (en) | 1971-05-13 | 1972-05-10 | PROCEDURE FOR THE PREPARATION OF 3,4-EPOXY-4-METHYL-PENTANON-2 |
Country Status (15)
| Country | Link |
|---|---|
| AT (1) | AT316574B (en) |
| AU (1) | AU466536B2 (en) |
| BE (1) | BE783339A (en) |
| CA (1) | CA996125A (en) |
| CH (1) | CH553774A (en) |
| DD (1) | DD97883A5 (en) |
| DE (1) | DE2223299C3 (en) |
| DK (1) | DK132274C (en) |
| FR (1) | FR2147922B1 (en) |
| GB (1) | GB1381012A (en) |
| LU (1) | LU65336A1 (en) |
| NL (1) | NL144270B (en) |
| NO (1) | NO137235C (en) |
| SE (1) | SE386176B (en) |
| ZA (1) | ZA722962B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8516744D0 (en) * | 1985-07-02 | 1985-08-07 | British Petroleum Co Plc | Preparation of epoxides |
-
1972
- 1972-04-27 AU AU41628/72A patent/AU466536B2/en not_active Expired
- 1972-05-01 CA CA141,020A patent/CA996125A/en not_active Expired
- 1972-05-02 ZA ZA722962A patent/ZA722962B/en unknown
- 1972-05-09 DK DK229772A patent/DK132274C/en active
- 1972-05-10 NO NO1678/72A patent/NO137235C/en unknown
- 1972-05-10 FR FR7216676A patent/FR2147922B1/fr not_active Expired
- 1972-05-10 SE SE7206242A patent/SE386176B/en unknown
- 1972-05-11 GB GB2223572A patent/GB1381012A/en not_active Expired
- 1972-05-12 BE BE783339A patent/BE783339A/en unknown
- 1972-05-12 DD DD162931A patent/DD97883A5/xx unknown
- 1972-05-12 AT AT416472A patent/AT316574B/en not_active IP Right Cessation
- 1972-05-12 LU LU65336D patent/LU65336A1/xx unknown
- 1972-05-12 CH CH703472A patent/CH553774A/en not_active IP Right Cessation
- 1972-05-12 DE DE2223299A patent/DE2223299C3/en not_active Expired
- 1972-05-15 NL NL727206500A patent/NL144270B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO137235C (en) | 1978-01-25 |
| CH553774A (en) | 1974-09-13 |
| DK132274C (en) | 1976-05-10 |
| DE2223299B2 (en) | 1974-02-14 |
| SE386176B (en) | 1976-08-02 |
| FR2147922A1 (en) | 1973-03-11 |
| FR2147922B1 (en) | 1974-09-27 |
| LU65336A1 (en) | 1972-08-23 |
| CA996125A (en) | 1976-08-31 |
| AU4162872A (en) | 1973-11-01 |
| AU466536B2 (en) | 1975-10-30 |
| DE2223299A1 (en) | 1972-11-23 |
| GB1381012A (en) | 1975-01-22 |
| AT316574B (en) | 1974-07-25 |
| DD97883A5 (en) | 1973-05-20 |
| NL7206500A (en) | 1972-11-15 |
| BE783339A (en) | 1972-09-01 |
| ZA722962B (en) | 1973-02-28 |
| NL144270B (en) | 1974-12-16 |
| DK132274B (en) | 1975-11-17 |
| DE2223299C3 (en) | 1974-10-03 |
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