DE1015782B - Process for the production of epoxies - Google Patents
Process for the production of epoxiesInfo
- Publication number
- DE1015782B DE1015782B DEF20096A DEF0020096A DE1015782B DE 1015782 B DE1015782 B DE 1015782B DE F20096 A DEF20096 A DE F20096A DE F0020096 A DEF0020096 A DE F0020096A DE 1015782 B DE1015782 B DE 1015782B
- Authority
- DE
- Germany
- Prior art keywords
- epoxies
- reaction mixture
- yield
- sodium acetate
- acid
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 6
- 239000004593 Epoxy Substances 0.000 title description 5
- 125000003700 epoxy group Chemical group 0.000 title description 5
- 229920000647 polyepoxide Polymers 0.000 title description 5
- 238000004519 manufacturing process Methods 0.000 title description 3
- -1 aliphatic peracids Chemical class 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 239000000337 buffer salt Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 150000002118 epoxides Chemical class 0.000 claims 1
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 5
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 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
- 238000006243 chemical reaction Methods 0.000 description 3
- ODGBRFFGIINVHG-UHFFFAOYSA-N 1-[2-(cyclohexen-1-yl)propan-2-yl]cyclohexene Chemical compound C=1CCCCC=1C(C)(C)C1=CCCCC1 ODGBRFFGIINVHG-UHFFFAOYSA-N 0.000 description 2
- MRXPNWXSFCODDY-UHFFFAOYSA-N 2-methyl-2-phenyloxirane Chemical compound C=1C=CC=CC=1C1(C)CO1 MRXPNWXSFCODDY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- LBAYFEDWGHXMSM-UHFFFAOYSA-N butaneperoxoic acid Chemical compound CCCC(=O)OO LBAYFEDWGHXMSM-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- XXVUOMFVRJIVLH-UHFFFAOYSA-N 2-(3-methylbutyl)oxirane Chemical compound CC(C)CCC1CO1 XXVUOMFVRJIVLH-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- JIUFYGIESXPUPL-UHFFFAOYSA-N 5-methylhex-1-ene Chemical compound CC(C)CCC=C JIUFYGIESXPUPL-UHFFFAOYSA-N 0.000 description 1
- DFVOXRAAHOJJBN-UHFFFAOYSA-N 6-methylhept-1-ene Chemical compound CC(C)CCCC=C DFVOXRAAHOJJBN-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241001481828 Glyptocephalus cynoglossus Species 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 239000002253 acid Substances 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
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- GMDNUWQNDQDBNQ-UHFFFAOYSA-L magnesium;diformate Chemical compound [Mg+2].[O-]C=O.[O-]C=O GMDNUWQNDQDBNQ-UHFFFAOYSA-L 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- KYKFCSHPTAVNJD-UHFFFAOYSA-L sodium adipate Chemical compound [Na+].[Na+].[O-]C(=O)CCCCC([O-])=O KYKFCSHPTAVNJD-UHFFFAOYSA-L 0.000 description 1
- 235000011049 sodium adipate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
-
- 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
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
Description
Verfahren zur Herstellung von Epoxyden Zur Herstellung von Epoxyden von olefinischen Kohlenwasserstoffen mit isolierten Doppelbindungen durch Anlagerung von Sauerstoff werden diese Kohlenwasserstoffe mit organischen Persäuren umgesetzt. Bei diesem als Prileshajewsche Reaktion bekannten Verfahren werden vorwiegend aromatische Persäuren, insbesondere Benzopersäure, verwendet. Die wesentlich leichter zugänglichen aliphatischen Persäuren, insbesondere die Peressigsäure, liefern unter gleichen Bedingungen nur schlechte Ausbeuten an Epoxyden. Daneben entstehen Glykole bzw. Glykolmonocarbonsäureester. In manchen Fällen, insbesondere bei Kohlenw.asserstoffen mit mehr als einer isolierten Doppelbindung, werden in der Regel Harze erhalten.Process for the production of epoxies For the production of epoxies of olefinic hydrocarbons with isolated double bonds by addition These hydrocarbons are converted by oxygen with organic peracids. This process, known as the Prileshajew reaction, produces predominantly aromatic substances Peracids, in particular benzoperacid, are used. The more accessible ones aliphatic peracids, especially peracetic acid, deliver among the same Conditions only poor yields of epoxides. In addition, glycols or Glycol monocarboxylic acid ester. In some cases, especially with hydrocarbons with more than one isolated double bond, resins are usually obtained.
Es wurde nun gefunden, daß man mono- und polyfunktionelle Olefine mit isolierten Doppelbindungen mit aliphatischen Persäuren, insbesondere Peressigsäure, mit guten Ausbeuten dadurch in Epoxyde überführen kann, ,daß man dem Reaktionsgemisch Puffersalze zusetzt. Die Puffersalze können gegebenenfalls auch erst im Reaktionsgemisch erzeugt werden.It has now been found that one can use monofunctional and polyfunctional olefins with isolated double bonds with aliphatic peracids, especially peracetic acid, can be converted into epoxides in good yields by adding to the reaction mixture Adds buffer salts. The buffer salts can optionally also only be added to the reaction mixture be generated.
Der dadurch erreichte Effekt ist weitgehend unabhängig von der Art der gegebenenfalls mitverwendeten Lösungsmittel und überraschenderweise nicht an die An- oder Abwesenheit von Wasser im Reaktionsgemisch gebunden.The effect achieved in this way is largely independent of the species any solvents used and surprisingly not the presence or absence of water in the reaction mixture.
Mono- und polyfunktionelle Olefine, die erfindungsgemäß in Epoxyde übergeführt werden können, sind z. B. Penten, Isopenten, Hexen, Isohexen, Hepten, Isohepten, Octen, Isoocten, Diallyl, Cyclohexen, Cyclohepten, Cycloocten, 2, 2-Dicyclohexenyl-propan, 2, 2-Dicyclohexenyl=butan, 2, 2-Dicyclohexenylpentan, 1, 1-Dicyclohexenyl-äthan, 1, 1-Dicyclohexenyl-butan, Dipenten, Styrol, a-Methylstyrol und Stilben.Mono- and polyfunctional olefins, according to the invention in epoxies can be transferred, are z. B. pentene, isopentene, witches, isohexene, heptene, Isoheptene, octene, isooctene, diallyl, cyclohexene, cycloheptene, cyclooctene, 2,2-dicyclohexenyl propane, 2,2-dicyclohexenyl = butane, 2,2-dicyclohexenylpentane, 1,1-dicyclohexenylethane, 1,1-dicyclohexenyl-butane, dipentene, styrene, α-methylstyrene and stilbene.
Aliphatische Persäuren im Sinne der Erfindung sind z. B. Perameisensäure, Peressigsäure, Perpropionsäure, Perbuttersäure und Adipindipersäure.Aliphatic peracids for the purposes of the invention are, for. B. performic acid, Peracetic acid, perpropionic acid, perbutyric acid and adipic diperic acid.
Als Lösungsmittel können z. B. Wasser, Methylenchlo-rid, Chloroform, Tetrachlorkohlenstoff, Ät er, Benzol und Toluol verwendet werden.As a solvent, for. B. water, methylene chloride, chloroform, Carbon tetrachloride, ethers, benzene and toluene can be used.
An Puffersalzen seien beispielsweise genannt: Natrium-, Kalium-, Calcium-, Magnesiumformiat, -acetat, -butyrat, Dinatriumadipinat, Dinatriumphthalat und Natriumdihydrogenphosphat.Examples of buffer salts are: sodium, potassium, calcium, Magnesium formate, acetate, butyrate, disodium adipate, disodium phthalate and sodium dihydrogen phosphate.
An deren Stelle können gegebenenfalls Natrium-, Kalium-, Calciurn-, Magnesiumoxyd, -hydroxyd, -carbonat und -bicarbonat verwendet werden, aus denen die entsprechenden Puffersalze im Reaktionsgemisch entstehen.In their place, sodium, potassium, calcium, Magnesium oxide, hydroxide, carbonate and bicarbonate are used, from which the corresponding buffer salts are formed in the reaction mixture.
Die Menge der zuzusetzenden Puffersalze richtet sich nach dem pH, das sich bei Anwesenheit von Wasser im Reaktionsgemisch einstellt oder nach Zusatz von Wasser zum Reaktionsgemisch einstellen würde, und läßt sich von Fall zu Fall durch Vorversuche leicht ermitteln. Der günstigste pA-Bereich liegt im allgemeinen bei etwa 4 bis 6,5.The amount of buffer salts to be added depends on the pH, which occurs in the presence of water in the reaction mixture or after addition of water would adjust to the reaction mixture, and can be varied on a case-by-case basis easily determined by preliminary tests. The most favorable pA range is generally at about 4 to 6.5.
Bei höherem pH sind zwar unerwünschte Folgereaktionen ebenfalls ausgeschlossen, doch sinken dann die Ausbeuten infolge der mehr und mehr in den Vordergrund tretenden Zersetzung der Persäuren ab.At a higher pH, undesirable secondary reactions are also excluded, but then the yields decrease as a result of the more and more coming to the fore Decomposition of the peracids.
Es ist ein besonderer Vorteil des Verfahrens, daß in vielen Fällen die Reaktionstemperatur innerhalb weiter Grenzen nur von geringem Einfluß auf die Ausbeute ist. So kann die Reaktionstemperatur zwischen etwa -20 und -I-100°, vorzugsweise zwischen etwa 0 und 70° liegen.It is a particular advantage of the procedure that in many cases the reaction temperature, within wide limits, has little influence on the Yield is. Thus, the reaction temperature can be between about -20 and -I-100 °, preferably lie between about 0 and 70 °.
Bei der Aufarbeitung erübrigen sich besondere Vorsichtsmaßnahmen, da selbst empfindliche Epoxyde, wie z. B. die des Styrols oder des a-Methylstyrols, ,die von verdünnter Essigsäure schon in der Kälte rasch angegriffen werden, im angegebenen pH-Bereich stabil sind.Special precautionary measures are not necessary during processing, because even sensitive epoxies such. B. that of styrene or a-methylstyrene, which are quickly attacked by dilute acetic acid even in the cold, in the specified pH range are stable.
Beispiel 1 Zu einer Lösung von 59 g (0,5 Mal) a-Methylstyrol in 100
ccm Methylenchlorid läßt man nach Zusatz von 50 g wasserfreiem Natriumacetat innerhalb
2 Stunden bei 24 bis 27° 47 g einer 89,5%igen Peressigsäure (0,55 Mol) zutropfen.
Man läßt anschließend die Temperatur noch bis etwa 30° ansteigen und hält weitere
3 Stunden auf Zimmertemperatur. Dann schüttelt man mit Wasser aus, neutralisiert
mit Sodalösung und trocknet über wasserfreiem Kaliumcarbonat. Man erhält so bei
60 bis 62°/6 mm Hg 62 g a-Methylstyroloxyd. Ausbeute: 92,5% der Theorie.
Beispiel 2' Zu einer Lösung von 59 g (0,5 Mol) a-Methylstyrol in 100 ccm Methylenchlorid läßt man nach Zusatz von 40 g wasserfreiem Natriumacetat und 20 g wasserfreiem Kaliumcarbonat bei 0° innerhalb 2 Stunden 57 g einer 80,5a/oigen Peressigsäure (0,6 1M1) zutropfen. Nach 4stündiger Reaktionszeit bei Zimmertemperatur schüttelt man mit Wasser aus, wäscht mit Sodalösung neutral und trocknet über wasserfreiem Käliumcarbonat. Man erhält so bei 54 bis 66°/5 mm Hg 57 g a-Methylstyroloxyd. Ausbeute: 85% der Theorie.Example 2 'To a solution of 59 g (0.5 mol) of α-methylstyrene in 100 ccm of methylene chloride is left after the addition of 40 g of anhydrous sodium acetate and 20 g of anhydrous potassium carbonate at 0 ° within 2 hours 57 g of an 80.5% Add peracetic acid (0.6 1M1) dropwise. After a reaction time of 4 hours at room temperature it is shaken out with water, washed neutral with soda solution and dried over anhydrous Potassium carbonate. 57 g of α-methylstyrene oxide are obtained at 54 to 66 ° / 5 mm Hg. Yield: 85% of theory.
Beispiel 3 Zu einer Lösung von 98 g (1 Mol) Isohepten vom Siedepunkt
84 bis 85° in 200 ccm Methylenchlorid läßt man nach Zusatz von 110g wasserfreiem
Natriumacetat bei 25° innerhalb von 1 Stunde 127 g einer 89,5%igen Perbuttersäure
(1,1 11ol) zutropfen. Nach 10stündigem Stehen bei Zimmertemperatur schüttelt man
mit Wasser aus, wäscht mit Sodalösung neutral und trocknet über wasserfreiem Kaliumcarbonat.
Nach Abdestillieren des Lösungsmittels erhält man 96 g Isoheptenoxyd vom Siedepunkt
112 bis 120°. Ausbeute: 84% der Theorie.
Beispiel 4 Zu einer Lösung von 51 g (0,25 Mol) 2, 2-Dicyclohexenylpropan
in 250 ccm Methylenchlorid läßt man nach Zusatz von 60 g wasserfreiem Natriumacetat
bei 25° innerhalb 2 Stunden 52,5 g einer 80%igen Peressigsäure (0,55 Mol) zutropfen.
Nach 2tägigem Stehen bei Raumtemperatur schüttelt man mit Wasser aus, wäscht mit
Sodalösung neutral und trocknet über wasserfreiem Kaliumcarbonat. Nach Abdestillieren
des Lösungsmittels erhält man bei 140 bis 155°/1 mm Hg 56 g 2, 2-(Dicyclohexenyl)-p-ropan-dioxyd.
Ausbeute: 95 % der Theorie.
Verwendet man nur ein Viertel der oben angegebenen Menge N atriumacetat, dann beträgt die Ausbeute unter sonst gleichen Bedingungen 47°/o der Theorie.If only a quarter of the amount of sodium acetate given above is used, then, under otherwise identical conditions, the yield is 47% of theory.
Beispiel 5 Zu einem Gemisch von 102 g (0,5 Mol) 2, 2-Dicyclohexenylpropan, 200 ccm Wasser und 109g wasserfreiem Natriumacetat läßt man unter starkem Rühren bei 40° 110 g einer 85%igen Peressigsäure (1,3 Mol) zutropfen. Anschließend erwärmt man noch 2 Stunden auf 60°, bis die Peressigsäure verbraucht ist. Die wäßrige Schicht wird abgetrennt, die organische Schicht mit Methylenchlorid aufgenommen, mit Sadalösung neutral geschüttelt und über wasserfreiem Kaliumcarbonat getrocknet. Nach Abdestillieren des Lösungsmittels erhält man bei 138 bis 155"/1 mm Hg 96g 2, 2-Dicyclohexenyl-propandioxyd. Ausbeute: 81% der Theorie.Example 5 To a mixture of 102 g (0.5 mol) of 2,2-dicyclohexenylpropane, 200 cc of water and 109 g of anhydrous sodium acetate are left with vigorous stirring at 40 ° 110 g of an 85% strength peracetic acid (1.3 mol) are added dropwise. Then warmed up one another 2 hours at 60 ° until the peracetic acid is consumed. The aqueous layer is separated off, the organic layer is taken up with methylene chloride, with Sado solution Shaken neutral and dried over anhydrous potassium carbonate. After distilling off of the solvent is obtained at 138 to 155 "/ 1 mm Hg 96g of 2,2-dicyclohexenyl propanedioxide. Yield: 81% of theory.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF20096A DE1015782B (en) | 1956-04-20 | 1956-04-20 | Process for the production of epoxies |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF20096A DE1015782B (en) | 1956-04-20 | 1956-04-20 | Process for the production of epoxies |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1015782B true DE1015782B (en) | 1957-09-19 |
Family
ID=7089553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF20096A Pending DE1015782B (en) | 1956-04-20 | 1956-04-20 | Process for the production of epoxies |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1015782B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1240515B (en) * | 1964-10-22 | 1967-05-18 | Knapsack Ag | Process for the continuous production of epoxy compounds |
| US4083856A (en) * | 1969-08-18 | 1978-04-11 | Union Carbide Corporation | Addition of unsaturated epoxy monomer to Si-H with chloroplatinic acid and HCl-acceptor |
| EP0090239A1 (en) * | 1982-03-26 | 1983-10-05 | Bayer Ag | Process for the preparation of 2,2-bis-(3-cyclohexenyl)-propane diepoxide |
| EP0300163A1 (en) * | 1987-07-18 | 1989-01-25 | Degussa Aktiengesellschaft | Process for the preparation of epoxides |
| US5101051A (en) * | 1990-06-13 | 1992-03-31 | Eka Nobel | Process for the production of epoxides |
-
1956
- 1956-04-20 DE DEF20096A patent/DE1015782B/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1240515B (en) * | 1964-10-22 | 1967-05-18 | Knapsack Ag | Process for the continuous production of epoxy compounds |
| US4083856A (en) * | 1969-08-18 | 1978-04-11 | Union Carbide Corporation | Addition of unsaturated epoxy monomer to Si-H with chloroplatinic acid and HCl-acceptor |
| EP0090239A1 (en) * | 1982-03-26 | 1983-10-05 | Bayer Ag | Process for the preparation of 2,2-bis-(3-cyclohexenyl)-propane diepoxide |
| EP0300163A1 (en) * | 1987-07-18 | 1989-01-25 | Degussa Aktiengesellschaft | Process for the preparation of epoxides |
| US5101051A (en) * | 1990-06-13 | 1992-03-31 | Eka Nobel | Process for the production of epoxides |
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