DE1227894B - Process for the condensation of 1-vinylcyclohex-3-ene with dicyclopentadiene - Google Patents
Process for the condensation of 1-vinylcyclohex-3-ene with dicyclopentadieneInfo
- Publication number
- DE1227894B DE1227894B DEC30194A DEC0030194A DE1227894B DE 1227894 B DE1227894 B DE 1227894B DE C30194 A DEC30194 A DE C30194A DE C0030194 A DEC0030194 A DE C0030194A DE 1227894 B DE1227894 B DE 1227894B
- Authority
- DE
- Germany
- Prior art keywords
- dicyclopentadiene
- condensation
- vinylcyclohexene
- found
- diene
- 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
- 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 title claims description 16
- 238000009833 condensation Methods 0.000 title claims description 9
- 230000005494 condensation Effects 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 5
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 title description 2
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 claims description 16
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 description 13
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 6
- 239000007859 condensation product Substances 0.000 description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009102 absorption Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- QYCGBAJADAGLLK-UHFFFAOYSA-N 1-(cyclohepten-1-yl)cycloheptene Chemical group C1CCCCC=C1C1=CCCCCC1 QYCGBAJADAGLLK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- -1 ethylene, propylene Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 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
- 230000003637 steroidlike Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/50—Diels-Alder conversion
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/86—Ring systems containing bridged rings containing four rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Kondensation von 1-Vinylcyclohex-3-en mit Dicyclopentadien 6-(Cyclohex-3'-en-1'-yl)- bicyclo- [2,2,1]-hept-2-en, im folgenden als »Dien 1< bezeichnet, wurde schon durch Kondensation von Vinylcyclohexen und Cyclopentadien im Molverhältnis 1 : 1 während 15 Stunden bei 180 bis 190"C hergestellt. Bei der fraktionierten Destillation dieses Kondensationsproduktes erhielt man jedoch neben viel unverändertem Vinylcyclohexen das »Dien I« nur in einer Ausbeute von 11O/o, bezogen auf eingesetztes Cyclopentadien. Außerdem wurden 330/, des eingesetzten Cyclopentadiens als Tricyclopentadien und höhere Polymere erhalten (K. Alder, H. F. Rickert, Ber. dtsch. chem.Process for the condensation of 1-vinylcyclohex-3-ene with dicyclopentadiene 6- (Cyclohex-3'-en-1'-yl) -bicyclo- [2,2,1] -hept-2-en, hereinafter referred to as "diene 1" has already been designated by the condensation of vinylcyclohexene and cyclopentadiene in a molar ratio of 1: 1 for 15 hours at 180 to 190 "C. In the fractional distillation of this condensation product was obtained in addition to much unchanged vinylcyclohexene the "diene I" only in a yield of 110 / o, based on cyclopentadiene used. In addition, 330 /, of the were used Cyclopentadiene obtained as tricyclopentadiene and higher polymers (K. Alder, H. F. Rickert, Ber. German chem.
Ges., 71, S. 373, 1938). Weiterhin ist es nach der USA.-Patentschrift 2 340 908 bekannt, Bicyclo-[2,2,1]-hepten-(2)-Homologe aus Dicyclopentadien und Äthylen, Propylen oder anderen olefinisch ungesättigten Kohlenwasserstoffen herzustellen.Ges., 71, p. 373, 1938). Furthermore it is according to the USA patent specification 2,340,908 known, bicyclo- [2,2,1] -hepten- (2) -homologe from dicyclopentadiene and To produce ethylene, propylene or other olefinically unsaturated hydrocarbons.
Es wurde nun ein Verfahren zur Kondensation von Vinylcyclohexen mit Dicyclopentadien gefunden, welches dadurch gekennzeichnet ist, daß man zur Herstellung von 6-(Cyclohex-3'-en-1'-yl)-bicyclo-[2,2,1]-hept-2-en 1-Vinylcyclohexen-(3) mit Dicyclopentadien im Molverhältnis von 20 bis 30 : 1 während 2 bis 4 Stunden auf 230 bis 260"C erhitzt. Ferner wurde festgestellt, daß man wesentliche Anteile der bisher nicht beschriebenen 3-(Cyclohex-3'-en-l '-yl)-tetracyclo [4,4,0,12,5,1,7,10]-dodec-8-en im folgenden als »Dien II« bezeichnet, erhalten kann, wenn man die Kondensation von Vinylcyclohexen mit Dicyclopentadien wie oben angegeben führt, jedoch das Molverhältnis auf 2 bis 6 : 1 hält.A process for the condensation of vinylcyclohexene with dicyclopentadiene has now been found, which is characterized in that 6- (cyclohex-3'-en-1'-yl) -bicyclo- [2,2,1] -hept is used -2-ene 1-vinylcyclohexene (3) with dicyclopentadiene in a molar ratio of 20 to 30: 1 for 2 to 4 hours at 230 to 260 ° C. It was also found that significant proportions of the previously not described 3- (cyclohex -3'-en-l'-yl) -tetracyclo [4,4,0,12,5,1,7,10] -dodec-8-en hereinafter referred to as "diene II", can be obtained if the condensation of vinylcyclohexene with dicyclopentadiene is carried out as indicated above, but the molar ratio is kept at 2 to 6: 1.
Es hat sich gezeigt, daß sich mit steigendem Molverhältnis von Vinylcyclohexen zu Dicyclopentadien im Ansatz der Anteil des »Dien I« im Kondensationsprodukt gegenüber dem des »Dien II« erhöht und bei einem Molverhältnis von 30 : 1 über 80O/o, bezogen auf das eingesetzte Dicyclopentadien, beträgt (Ab b. 1). It has been shown that with increasing molar ratio of vinylcyclohexene to dicyclopentadiene in the approach the proportion of "diene I" in the condensation product compared that of "diene II" is increased and, at a molar ratio of 30: 1, over 80% on the dicyclopentadiene used is (Ab b. 1).
Die Reaktionstemperatur und die Dauer der Kondensation haben einen erheblichen Einfluß auf die Ausbeute an »Dien I«, »Dien 11<' und schwerflüchtigen Kondensationsprodukten. The reaction temperature and the duration of the condensation have one considerable influence on the yield of "Dien I", "Dien 11" and less volatile Condensation products.
Bei gegebenem Molverhältnis und gegebener Temperatur durchläuft die Ausbeute an den Dienen, insbesondere an »Dien 1«, ein Optimum, das durch die Dauer des Erhitzens bestimmt ist. Es liegt z. B. für »Dien 1« beim Molverhältnis 6 Vinylcyclohexen zu 1 Dicyclopentadien bei 250"C und einer Erhitzungsdauer von etwa 3 Stunden (A b b. 2). For a given molar ratio and a given temperature, the Yield of the servants, especially of "Dien 1", an optimum that is achieved by the duration of heating is intended. It is z. B. for "diene 1" with a molar ratio of 6 vinylcyclohexene to 1 dicyclopentadiene at 250 "C and a heating time of about 3 hours (A b b. 2).
Bei kürzerer Reaktionszeit ist, abgesehen von einem geringeren Umsatz, die Ausbeute an »Dien f« und »Dien II« durch die Bildung von durch fraktionierte Destillation schwer abtrennbarem Tricyclopentadien beeinträchtigt; bei längerer Reaktionszeit verwandeln sich »Dien 1< und »Dien II« rasch in schwerflüchtige hochmolekulare Kondensationsprodukte (Abb. 2 und 2a). With a shorter reaction time, apart from a lower conversion, the yield of "diene f" and "diene II" through the formation of fractionated Distillation of difficult to separate tricyclopentadiene impaired; for longer Reaction times quickly transform "Dien 1" and "Dien II" into non-volatile ones high molecular weight condensation products (Fig. 2 and 2a).
Durch Wahl der Reaktionsbedingungen läßt sich also erfindungsgemäß Ausbeute und Verhältnis von »Dien I« zu »Dien II« als Hauptprodukt der Reaktion in gewünschter Weise einstellen. Thus, according to the invention, the choice of reaction conditions allows Yield and ratio of "diene I" to "diene II" as the main product of the reaction set in the desired manner.
Die beschriebenen Diene sind einzeln oder in Mischung Rohstoffe für vielseitige Anwendungsgebiete, z. B. für Polymere, Copolymere, Lacke, Epoxyde und daraus herstellbare Kunststoffe. The dienes described are raw materials for singly or in a mixture versatile areas of application, e.g. B. for polymers, copolymers, paints, epoxies and plastics that can be produced therefrom.
Beispiel 1 3240 g (30 Mol) Vinylcyclohexen wurden mit 132 g (1 Mol) Dicyclopentadien 6 Stunden (einschließlich etwa 11/2 Stunden Aufheizzeit des Autoklavs) unter Stickstoffatmosphäre auf 230"C erhitzt, hierauf durch einen Kühler abgelassen und fraktioniert destilliert. Example 1 3240 g (30 mol) of vinylcyclohexene were mixed with 132 g (1 mol) Dicyclopentadiene 6 hours (including about 11/2 hours of heating up the autoclave) Heated to 230 ° C. under a nitrogen atmosphere, then drained through a cooler and fractionally distilled.
Nach Abdestillieren von 2979 g reinem Vinylcyclohexen wurden 284 g (81,6 0/o der Theorie) »Dien 1< (Kp.12 112"C) und 68 g höhersiedende Anteile, welche zu 750/o aus »Dien II« bestanden, erhalten.After distilling off 2979 g of pure vinylcyclohexene, 284 g were obtained (81.6% of the theory) »Dien 1 <(Kp.12 112" C) and 68 g higher-boiling fractions, of which 750 / o consisted of "Dien II".
Beispiel 2 1944 g (18 Mol) Vinylcyclohexen wurden mit 396 g (3 Mol) Dicyclopentadien 3 Stunden (einschließlich etwa 1 Stunde Aufheizzeit des Autoklavs) unter Stickstoff auf 2500 C erhitzt. Hierauf wurde das Reaktionsprodukt sofort durch einen Kühler abgelassen und durch fraktionierte Destillation aufgearbeitet. Neben 1297 g unverändertem Vinylcyclohexen wurden 605 g »Dien Ia (58°/o der Theorie, bezogen auf das eingesetzte Dicyclopentadien) sowie 259 g )>DienII« (180/o der Theorie, bezogen auf das eingesetzte Dicyclopentadien) vom Kr.,'5 142 bis 147"C erhalten. Als Destillationsrückstand hinterblieben 150 g der schwerflüchtigen Kondensationsprodukte. Example 2 1944 g (18 mol) of vinylcyclohexene were mixed with 396 g (3 mol) Dicyclopentadiene 3 hours (including approx. 1 hour heating time of the autoclave) heated to 2500 C under nitrogen. Thereupon the reaction product was immediately through drained a condenser and worked up by fractional distillation. Next to 1297 g of unchanged vinylcyclohexene were obtained from 605 g of diene Ia (58% of theory on the dicyclopentadiene used) and 259 g)> DienII "(180 / o of the theory, based on the dicyclopentadiene used) from Kr., '5 142 to 147 "C. 150 g of the non-volatile condensation products remained as the distillation residue.
Das »DienII« kann theoretisch in insgesamt acht ster oisomeren Formen auftreten und ist eine farblose, bei längerem Stehen teilweise erstarrende Flüssigkeit. The "diene II" can theoretically be in a total of eight steroidal isomeric forms occur and is a colorless liquid that partially solidifies when standing for a long time.
Die Konstitution folgt aus dem IR-Spektrum. Bei 3055 und 3020 cm-l finden sich die für die Olefin-H-Atome des Cyclohexen- bzw. Bicycloheptenringes charakteristischen Absorptionen. Ebenso treten die für die beiden Ringsysteme charakteristischen C Absorptionen bei 1650 bzw. 1570 cm-l auf.The constitution follows from the IR spectrum. At 3055 and 3020 cm-l are found for the olefin H atoms of the cyclohexene or bicycloheptene ring characteristic absorptions. The characteristic of the two ring systems also occur C absorptions at 1650 and 1570 cm-l.
Die kryoskopische Molekulargewichtshestimmung in Benzol ergab 241 (Theorie 240). Als Jodzahl wurde 225 (Theorie 212) ermittelt. Cryoscopic molecular weight determination in benzene gave 241 (Theory 240). The iodine number was determined to be 225 (theory 212).
Durch Kristallisation aus Alkohol wurde aus dem Isomerengemisch eines der Stereoisomeren in reiner kristalliner Form abgetrennt (Fp. 82 bis 82,5°C). Das IR-Spektrum entsprach der in Spalte 1 angegebenen Formel. Crystallization from alcohol turned the mixture of isomers into one the stereoisomers separated off in pure crystalline form (melting point 82 to 82.5 ° C.). That The IR spectrum corresponded to the formula given in column 1.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC30194A DE1227894B (en) | 1963-06-14 | 1963-06-14 | Process for the condensation of 1-vinylcyclohex-3-ene with dicyclopentadiene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC30194A DE1227894B (en) | 1963-06-14 | 1963-06-14 | Process for the condensation of 1-vinylcyclohex-3-ene with dicyclopentadiene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1227894B true DE1227894B (en) | 1966-11-03 |
Family
ID=7019238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEC30194A Pending DE1227894B (en) | 1963-06-14 | 1963-06-14 | Process for the condensation of 1-vinylcyclohex-3-ene with dicyclopentadiene |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1227894B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5095082A (en) * | 1991-06-10 | 1992-03-10 | Shell Oil Company | Polymerization process employing mixture of Diels-Alder adducts of 4-vinylcyclohexene and cyclopentadiene |
| WO1993014050A1 (en) * | 1992-01-10 | 1993-07-22 | Shell Oil Company | Diels-alder process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2340908A (en) * | 1942-11-25 | 1944-02-08 | Universal Oil Prod Co | Hydrocarbon synthesis |
-
1963
- 1963-06-14 DE DEC30194A patent/DE1227894B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2340908A (en) * | 1942-11-25 | 1944-02-08 | Universal Oil Prod Co | Hydrocarbon synthesis |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5095082A (en) * | 1991-06-10 | 1992-03-10 | Shell Oil Company | Polymerization process employing mixture of Diels-Alder adducts of 4-vinylcyclohexene and cyclopentadiene |
| WO1992022597A1 (en) * | 1991-06-10 | 1992-12-23 | Shell Oil Company | Polymerization process and products |
| WO1993014050A1 (en) * | 1992-01-10 | 1993-07-22 | Shell Oil Company | Diels-alder process |
| US5260498A (en) * | 1992-01-10 | 1993-11-09 | Shell Oil Company | Diels-Alder process |
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