DE1643668C - Process for the preparation of 2 methyl-2-hepten-6-one - Google Patents
Process for the preparation of 2 methyl-2-hepten-6-oneInfo
- Publication number
- DE1643668C DE1643668C DE1643668C DE 1643668 C DE1643668 C DE 1643668C DE 1643668 C DE1643668 C DE 1643668C
- Authority
- DE
- Germany
- Prior art keywords
- methyl
- hepten
- isomerization
- preparation
- reaction
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 3
- UHEPJGULSIKKTP-UHFFFAOYSA-N sulcatone Chemical compound CC(C)=CCCC(C)=O UHEPJGULSIKKTP-UHFFFAOYSA-N 0.000 title description 10
- 238000006317 isomerization reaction Methods 0.000 claims description 10
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 5
- FMCHGBFGIKQNCT-UHFFFAOYSA-N 6-methylhept-6-en-2-one Chemical compound CC(=C)CCCC(C)=O FMCHGBFGIKQNCT-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical compound N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001717 carbocyclic compounds Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- MQIKJSYMMJWAMP-UHFFFAOYSA-N dicobalt octacarbonyl Chemical group [Co+2].[Co+2].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] MQIKJSYMMJWAMP-UHFFFAOYSA-N 0.000 description 1
- -1 diplomatic ethers Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- JPTOCTSNXXKSSN-UHFFFAOYSA-N methylheptenone Chemical class CCCC=CC(=O)CC JPTOCTSNXXKSSN-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
Es ist allgemein bekannt, olefinisch ungesättigte Carbonylverbindungen durch Verschiebung der C- C-Doppelbindungen unter Verwendung verschiedenartiger katalytisch wirksamei Verbindungen oder auch thermisch zu isomerisieren.It is well known to displace olefinically unsaturated carbonyl compounds C-C double bonds using different types catalytically active compounds or can also be isomerized thermally.
Die bisherigen Versuche:, 2-MethyI-l-h-pten-fi-on (II) zu 2-Methyl-2-heptan-6-on (I) zu isomerisieren \ erliefen jedoch wegen zahlreicher Nebenreaktionen sehr unbefriedigend. So erhält man z. B. bei der Isomerisierung von II mit Schwefelsäure an Stelle des .gewünschten Isomeren I vorwiegend carbocyclische Verbindungen (vgl. J. Am. Chem. Soc, Band 80 (l')58). S. 5266).The previous attempts :, 2-MethyI-l-h-pten-fi-on Isomerize (II) to 2-methyl-2-heptan-6-one (I), however, because of numerous side reactions very unsatisfactory. So you get z. B. in the isomerization of II with sulfuric acid in place of the .desired isomers I predominantly carbocyclic compounds (cf. J. Am. Chem. Soc, Volume 80 (l ') 58). P. 5266).
Es wurde nun unerwarteiervveise ein Verfahren zur Herstellung von 2-Methyl-2-hepten-6-on durch Isomerisierung von 2-Methyl-l-hepten-6-on mit Hilfe eines Isomerisierungskatalysators gefunden, das dadurch gekennzeichnet ist, daß man das 2-Methyll-hepten-6-on bei Temperaturen von K)O bis 250° C mit Drücken von 1 bis 50 at mit 0,1 bis 20 Gewichtsprozent. bezogen auf das 2-Methyl-l-hepten-6-on einer Carbonylverbindung eines nullweitigen Elements der 6. bis 8. Nebengruppe des Periodensystems umsetzt, wobei ein Teil der Carbonylgruppen des Isomerisierungskatalysators durch andere neutrale Ligandcn ersetzt sein kann. Besonders bevorzugt werden unter diesen definitionsgemäßen Carbonylverbindungen Dicobaltoctacarbonyl, Nickeltetracarbonyl und vor allem Fiscnpentacarbonyl. Daneben kommen jedoch auch Carhonylverbindungcn in Betracht, die an Stelle einer oder mehrerer Kohlcnmonoxidmoleküle I.igandcii mit tertiären basischen N- oder P-Atomcn tragen. /. B. Bis-lriphenylphosphin-eiscntricarbonyl (»!er Tripyridin-dieiscntetracarbonyl.There has now been unexpectedly a method for Production of 2-methyl-2-hepten-6-one by isomerization of 2-methyl-l-hepten-6-one found with the help of an isomerization catalyst, which thereby is characterized in that the 2-methyll-hepten-6-one at temperatures from K) 0 to 250 ° C with pressures from 1 to 50 at with 0.1 to 20 percent by weight. based on the 2-methyl-l-hepten-6-one of a carbonyl compound of a zero-second element the 6th to 8th subgroup of the periodic table converts, with some of the carbonyl groups of the isomerization catalyst can be replaced by other neutral ligands. Are particularly preferred among these carbonyl compounds according to the definition, dicobalt octacarbonyl, nickel tetracarbonyl and especially fish pentacarbonyl. In addition, however, come Carbonyl compounds can also be used which replace one or more carbon monoxide molecules I.igandcii with tertiary basic N or P atoms carry. /. B. Bis-triphenylphosphine-ice tricarbonyl ("! Er tripyridine di-tetracarbonyl.
Die für die Isomerisierung benotigte Menge an ilen Carbonylverbindungen kann vorzugsweise 1 bis 5 Gewichtsprozent, bezogen auf die Menge von II bei ragen. Es ist jedoch auch ohne weiteres möglich, größere oder geringere Mengen dieser Katalysatoren zu verwenden, wodurch die Isomerisierung beschleunigt bzw. verlangsamt wird.The amount of ilen carbonyl compounds required for the isomerization can preferably be 1 to 5 percent by weight, based on the amount of II at ragen. However, it is also easily possible Use greater or lesser amounts of these catalysts, thereby preventing isomerization is accelerated or decelerated.
Man kann die Reaktion auch vorzugsweise bei temperatur«.·!! von 140 bis 200" C sowie mit oder ohne Lösungsmittel diskontinuierlich oder kontinuierlich vornehmen.The reaction can also preferably be carried out at temperature «. · !! from 140 to 200 "C as well as with or Carry out discontinuously or continuously without solvents.
Als Lösungsmittel eignen sich vor allem KohlenwasscrstolTc. die unter ilen jeweiligen ReaktionsliedingimgcM llüssig sind, also beispielsweise Hexan, Heptan, Petroläthcr. Benzol. Toluol oder Xylol. Weiterhin kommen höhersiedcndc Äther wie Dipliciiyliilhcr, 2,2'-Dimclhoxydiätliyläther und 2,2' Diiilhoxydiälhyläther in Betracht.Particularly suitable solvents are hydrocarbons. the respective reaction links under ilen are liquid, for example hexane, heptane, petroleum ether. Benzene. Toluene or xylene. Furthermore, there are higher-boiling ethers such as diplomatic ethers, 2,2'-Dimclhoxydietliyläther and 2,2'-Diilhoxydietliyläther into consideration.
Da die Methylheptenone I und Il als 0IeHtIe oxydalionseinpfindlieb sind, empfiehlt sich das Arbeit'-n Ausschluß von Sauurstolf, ulwa unter Stickstof- oder Argonaimosphäre, wenn man besonders reine Verfahrensprodukte herstellen will.Since the methylheptenones I and II are oxydalionseinpfindlieb as OIeHtIe are, it is advisable to work'-n Exclusion of Sauurstolf, ulwa under nitrogen or argona atmosphere, if you want to manufacture particularly pure process products.
Nach beendeter Isomerisierung kann das Reaktionsgemisch wie üblich, vorzugsweise destillativ, aufgearbeitet werden.After the isomerization has ended, the reaction mixture can be worked up as usual, preferably by distillation will.
Das Verfahrensprodukt I ist ein wertvolles Zwischenprodukt für organische Synthesen, insbesondere für die Herstellung von Verbindungen derCarotinoidreihe und von Duftstoffen.Process product I is a valuable intermediate for organic syntheses, in particular for the preparation of compounds of the carotenoid series and of fragrances.
Man erhitzt ein Gemisch aus 500 g 2-Methyll-hepten-6-on und 10 g Eisenpentacarbonyl bei 20 at Stunden lang auf 1800C und arbeitet das Gemisch anschließend in üblicher Weise auf.Heating a mixture of 500 g of 2-Methyll-hepten-6-one and 10 g of iron pentacarbonyl in 20 hours at 0 to 180 C, and then working the mixture up in the usual manner.
Man erhält das reine 2-MethyI-2-hepten-6-on in 93,7"/oiger Ausbeute; Kp. = 171° C/760 Torr; 11% = 1,4387.Pure 2-methyl-2-hepten-6-one is obtained in 93.7% yield; bp = 171 ° C. / 760 torr; 11% = 1.4387.
Man erhitzt ein Gemisch aus 500 g 2-MethyI-l-hepten-6-on und 5 g Molybdänhexacarbonyl bei at 2 Stunden auf 180° C und arbeitet danach in üblicher Weise auf. Man erhält das reine 2-Methyl-2-hepten-6-on in 85%iger Ausbeute.A mixture of 500 g of 2-methyl-1-hepten-6-one is heated and 5 g of molybdenum hexacarbonyl at 2 hours at 180 ° C and then works in usual way. Pure 2-methyl-2-hepten-6-one is obtained in 85% yield.
Man erhitzt ein Gemisch aus 250 g 2-Methyll-hepten-6-on und 5 g der CarbonylverbindungA mixture of 250 g of 2-methyll-hepten-6-one is heated and 5 g of the carbonyl compound
[Co(CO)3 ■ P(CH3)3]2 [Co (CO) 3 ■ P (CH 3 ) 3 ] 2
Stunden auf 180 C und arbeitet das Gemisch anschließend in üblicher Weise auf. Das reine 2-Methyi-2-hepten-6-on wird in 71n/nigcr Ausbeute erhalten.Hours at 180 ° C. and then the mixture is worked up in the usual way. The pure 2-methyl-2-hepten-6-one is obtained n / nigcr yield in 71st
Claims (3)
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