DE1291741B - Process for the addition of alcohols to the bicyclo [2, 2, 1] -hepten system - Google Patents
Process for the addition of alcohols to the bicyclo [2, 2, 1] -hepten systemInfo
- Publication number
- DE1291741B DE1291741B DEC28364A DEC0028364A DE1291741B DE 1291741 B DE1291741 B DE 1291741B DE C28364 A DEC28364 A DE C28364A DE C0028364 A DEC0028364 A DE C0028364A DE 1291741 B DE1291741 B DE 1291741B
- Authority
- DE
- Germany
- Prior art keywords
- bicyclo
- alcohols
- hepten
- addition
- hept
- 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
- 150000001298 alcohols Chemical class 0.000 title claims description 5
- 238000000034 method Methods 0.000 title claims description 5
- VGUXWSJVGWCTEC-UHFFFAOYSA-N bicyclo[2.2.1]hept-3-ene Chemical compound C1C(C2)CCC2=C1 VGUXWSJVGWCTEC-UHFFFAOYSA-N 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 3
- 238000004061 bleaching Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- -1 bicyclo- [2 Chemical class 0.000 description 3
- QYCGBAJADAGLLK-UHFFFAOYSA-N 1-(cyclohepten-1-yl)cycloheptene Chemical compound C1CCCCC=C1C1=CCCCCC1 QYCGBAJADAGLLK-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QHDHNVFIKWGRJR-UHFFFAOYSA-N 1-cyclohexenol Chemical compound OC1=CCCCC1 QHDHNVFIKWGRJR-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- PQANGXXSEABURG-UHFFFAOYSA-N cyclohexenol Natural products OC1CCCC=C1 PQANGXXSEABURG-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
In der Patentanmeldung P 1 278 431.5-42 ist ein Verfahren zur Anlagerung von Alkoholen an Dicyclopentadien in Gegenwart von Katalysatoren beschrieben, das dadurch gekennzeichnet ist, daß bei Temperaturen von 60 bis 1300C gearbeitet wird und als Katalysatoren nach den üblichen Methoden aktivierte Bleicherden verwendet werden. Die Alkohole lagern sich dabei an die Doppelbindung des Bicyclo-[2,2,1]-heptensystems an. In the patent application P 1 278 431.5-42 there is a method for addition of alcohols on dicyclopentadiene in the presence of catalysts described that is characterized in that temperatures of 60 to 1300C are used and activated bleaching earths used as catalysts by the customary methods will. The alcohols are deposited on the double bond of the bicyclo- [2,2,1] -hepten system at.
Es wurde nun gefunden, daß an Stelle von Dicyclopentadien andere das Bicyclo- [2,2,1]-heptensystem enthaltende Verbindungen oder Bicyclo-[2,2,1]-hepten selbst verwendet werden können. It has now been found that instead of dicyclopentadiene, other compounds containing the bicyclo- [2,2,1] -heptene system or bicyclo- [2,2,1] -heptene can be used by yourself.
Solche Derivate sind Verbindungen wie Bicyclo-[2,2,11-heptadien, Ester des Bicyclo-[2,2,1]-hept-2-en-6-ols mit gesättigten und ungesättigten Carbonsäuren, wie z. B. Essig-, Laurin-, Stearin-, Acryl- und Ölsäure, Äther jenes Alkohols mit gesättigten und ungesättigten Alkoholen, wie z. B. Äthanol, Butanol, Cyclohexanol, Vinylalkohol, Cyclohexenol, Bicyclo- [2,2,1]-heptanol, ferner das Bicycloheptensystem enthaltende Verbindungen, wie 1,4, 6,9-Dimethano-1 4,5, 6,9,10-hexa--hydronaphthalin und 6-(Bicyclo- 2, 1]-hept-2-en-6-yl)-bicyclo-[2,2,1]-hept-2-en. Such derivatives are compounds such as bicyclo- [2,2,11-heptadiene, Esters of bicyclo- [2,2,1] -hept-2-en-6-ol with saturated and unsaturated carboxylic acids, such as B. acetic, lauric, stearic, acrylic and oleic acid, ether of that alcohol with saturated and unsaturated alcohols, such as. B. ethanol, butanol, cyclohexanol, Vinyl alcohol, cyclohexenol, bicyclo- [2,2,1] -heptanol, and also the bicycloheptene system containing compounds, such as 1,4, 6,9-dimethano-1 4,5, 6,9,10-hexa - hydronaphthalene and 6- (Bicyclo-2,1] -hept-2-en-6-yl) -bicyclo- [2,2,1] -hept-2-ene.
Solche, das Bicycloheptensystem enthaltende Verbindungen lassen sich durch Diels-Alder-Addition ungesättigter Verbindungen an Cyclopentadien und gegebenenfalls weitere Umsetzungen der erhaltenen Addukte herstellen. Such compounds containing the bicycloheptene system can be by Diels-Alder addition of unsaturated compounds to cyclopentadiene and optionally produce further reactions of the adducts obtained.
Die Reaktionsbedingungen für die Anlagerung von hydroxylhaltigen Verbindungen an die Doppelbindung des Bicycloheptensystems entsprechen denen der Hauptpatentanmeldung. The reaction conditions for the addition of hydroxyl-containing Connections to the double bond of the bicycloheptic system correspond to those of Main patent application.
Die erhaltenen Produkte sind unter anderem als Rohstoffe zur Herstellung von Epoxydharzen geeignet. The products obtained are, among other things, used as raw materials for manufacture suitable for epoxy resins.
Beispiel 1 9,3 g Allylalkohol (0,16 Mol) wurden mit 15,0 g Bicyclo-[2,2,1]-hepten (0,16 Mol), 2,4 g aktivierter Bleicherde, welche unter der Handelsbezeichnung K 10 der Firma Süd-Chemie bekannt ist, und 50mg Hydrochinon 2 Stunden in einem geschüttelten Bom- benrohr auf 100°C erhitzt. Nach dem Abkühlen wurde filtriert und das Filtrat (22,5 g) im Vakuum destilliert. Das Destillat wurde über eine kurze Kolonne fraktioniert und dabei 17,5 g Bicyclo-[2,2,1]-hept-2-yl-allyläther vom Kr.12 = 70 bis 71"C und einer Reinheit von 96°/o erhalten (Reinausbeute, bezogen auf die eingesetzten Reaktionspartner: 750/o). n2o0 = 1,4687, Jodzahl = 159, 4 (berechnet 166). Example 1 9.3 g of allyl alcohol (0.16 mol) was mixed with 15.0 g of bicyclo- [2.2.1] -heptene (0.16 mol), 2.4 g of activated fuller's earth, which is available under the trade name K 10 from the company Süd-Chemie is known, and 50mg hydroquinone for 2 hours in a shaken Bomb ben tube heated to 100 ° C. After cooling, it was filtered and the filtrate (22.5 g) distilled in vacuo. The distillate was fractionated over a short column and thereby 17.5 g of bicyclo- [2,2,1] -hept-2-yl-allyl ether of Kr.12 = 70 to 71 "C and a purity of 96% obtained (pure yield, based on the reactants used: 750 / o). n2o0 = 1.4687, iodine number = 159.4 (calculated 166).
Das IR-Spektrum zeigte keine OH-Absorption im Bereich von 3500 cm-1, wohl aber die der Allylgruppe zuzuordnenden Banden bei 3990, 1630 und 910 cm-1, ferner die C -0 - C-Schwingung bei 1090 cm-1. The IR spectrum showed no OH absorption in the range of 3500 cm-1, but the bands at 3990, 1630 and 910 cm-1 that can be assigned to the allyl group, also the C -0 - C oscillation at 1090 cm-1.
CloHl6O (MG 152): Berechnet .... C 78,9, H 10,5, 0 10,5; gefunden .... C78,3, H 10,9, 0 11,1.CloHl60 (MW 152): Calculated .... C 78.9, H 10.5, 0 10.5; found .... C78.3, H 10.9, 0 11.1.
Beispiel 2 30 g Allylalkohol (0,52 Mol) wurden mit 90 g 6-(Cyclohex-3-enyl)-bicyclo- [2,2,11-hept-2en (0, 52 Mol) und 12 g aktivierter Bleicherde, welche unter der Handelsbezeichnung K10 der Fa. Süd-Chemie bekannt ist, während 21/2 Stunden unter Rühren auf 100"C erhitzt. Nach dem Abkühlen wurde filtriert und der Katalysator mit etwas Äther extrahiert. Die Fraktionierung ergab 75 g 6-(Cyclo-hex-3-enyl)-bicyclo-[2,2,1]-hept-2-yl-allyläther. (630/0, bezogen auf die eingesetzten Reaktionspartner vom Kp. o 5 = 90 bis 95"C. Jodzahl = 212 (berechnet 220). Example 2 30 g of allyl alcohol (0.52 mol) were mixed with 90 g of 6- (cyclohex-3-enyl) -bicyclo- [2,2,11-hept-2en (0.52 mol) and 12 g of activated fuller's earth, which is available under the trade name K10 from Süd-Chemie is known, while stirring at 100 ° C. for 21/2 hours heated. After cooling, it was filtered and the catalyst was extracted with a little ether. Fractionation gave 75 g of 6- (cyclo-hex-3-enyl) -bicyclo- [2,2,1] -hept-2-yl-allyl ether. (630/0, based on the reactants used with a boiling point of 5 = 90 to 95 ° C. Iodine number = 212 (calculated 220).
Das IR-Spektrum zeigte wiederum keine OH-Absorption, wohl aber die der Allylgruppe zuzuordnenden Banden und die 0-0- 0-Schwingung bei den im Beispiel 1 beschriebenen Frequenzen. The IR spectrum again showed no OH absorption, but it did the bands to be assigned to the allyl group and the 0-0-0 oscillation in the example 1 described frequencies.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC28364A DE1291741B (en) | 1962-11-08 | 1962-11-08 | Process for the addition of alcohols to the bicyclo [2, 2, 1] -hepten system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC28364A DE1291741B (en) | 1962-11-08 | 1962-11-08 | Process for the addition of alcohols to the bicyclo [2, 2, 1] -hepten system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1291741B true DE1291741B (en) | 1969-04-03 |
Family
ID=7018617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEC28364A Pending DE1291741B (en) | 1962-11-08 | 1962-11-08 | Process for the addition of alcohols to the bicyclo [2, 2, 1] -hepten system |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1291741B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2596279A (en) * | 1950-12-30 | 1952-05-13 | Interchem Corp | Process for the condensation of an allylic alcohol and a conjugated diene |
| DE1092010B (en) * | 1959-04-10 | 1960-11-03 | Bayer Ag | Process for the preparation of cyclopentenylphenols |
-
1962
- 1962-11-08 DE DEC28364A patent/DE1291741B/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2596279A (en) * | 1950-12-30 | 1952-05-13 | Interchem Corp | Process for the condensation of an allylic alcohol and a conjugated diene |
| DE1092010B (en) * | 1959-04-10 | 1960-11-03 | Bayer Ag | Process for the preparation of cyclopentenylphenols |
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