CH533068A - Preparation of olefins from heterocyclic bases and - Google Patents
Preparation of olefins from heterocyclic bases andInfo
- Publication number
- CH533068A CH533068A CH1301267A CH1301267A CH533068A CH 533068 A CH533068 A CH 533068A CH 1301267 A CH1301267 A CH 1301267A CH 1301267 A CH1301267 A CH 1301267A CH 533068 A CH533068 A CH 533068A
- Authority
- CH
- Switzerland
- Prior art keywords
- parts
- weight
- halogen
- preparation
- heterocyclic bases
- Prior art date
Links
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title claims description 4
- 150000001336 alkenes Chemical class 0.000 title 1
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000002896 organic halogen compounds Chemical class 0.000 claims 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000009835 boiling Methods 0.000 abstract description 6
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 abstract description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- AQNQQHJNRPDOQV-UHFFFAOYSA-N bromocyclohexane Chemical compound BrC1CCCCC1 AQNQQHJNRPDOQV-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 abstract 1
- 150000007824 aliphatic compounds Chemical class 0.000 abstract 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 12
- GODQTWKZSBLTIU-UHFFFAOYSA-N 1,2,6,7,8,9,10,10a-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2C=CCNC21 GODQTWKZSBLTIU-UHFFFAOYSA-N 0.000 description 7
- 150000002366 halogen compounds Chemical class 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- -1 aliphatic halogen compounds Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- XGINAUQXFXVBND-UHFFFAOYSA-N 1,2,6,7,8,8a-hexahydropyrrolo[1,2-a]pyrimidine Chemical compound N1CC=CN2CCCC21 XGINAUQXFXVBND-UHFFFAOYSA-N 0.000 description 1
- HLAUCEOFCOXKNF-UHFFFAOYSA-N 2-bromoheptane Chemical compound CCCCCC(C)Br HLAUCEOFCOXKNF-UHFFFAOYSA-N 0.000 description 1
- FTJHYGJLHCGQHQ-UHFFFAOYSA-N 2-bromooctane Chemical compound CCCCCCC(C)Br FTJHYGJLHCGQHQ-UHFFFAOYSA-N 0.000 description 1
- BNUTXEKPXPZAIT-UHFFFAOYSA-N 4-bromoheptane Chemical compound CCCC(Br)CCC BNUTXEKPXPZAIT-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
- C07C1/30—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms by splitting-off the elements of hydrogen halide from a single molecule
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Olefines are produced by treating a secondary or tertiary halogen-containing aliphatic compound with a heterocyclic base (I) R1, R2, R3, R4 are H or a C1 to 5 alkyl; n is 2 to 7 and m is 2 to 4. The principal patent (1, 364, 173) claimed only halogeno compounds where the halogen was in the alpha or beta position to an activating group. This addition increases the range of reactants. 80g of cyclohexyl bromide, 40 cc of dimethyl sulphoxide and 83 g of 1,5-diaza-bicyclo-(4,5,0)-undecene-5 were heated to 95 deg.C when a vigorous reaction started. Distillation of the products gave 38.8g of cyclohexene, boiling point 82 deg.C. Yield was 95%.
Description
Verfahren zur Herstellung von olefinisch ungesättigten Verbindungen
Gegenstand des Hauptpatentes Nr. 428 703 ist ein Verfahren zur Herstellung von ungesättigten Verbindungen unter Abspaltung von Chlor, Brom- oder Jodwasserstoff, dadurch gekennzeichnet, dass man aus entsprechenden Halogenverbindungen, deren Halogenatom sich in a- oderss-Stellung zu einer Carbonylgruppe, Äthylen-, Acetylen- oder Cyanogruppierung befindet, oder deren Halogenatome in a- und ss-Stellung zu den genannten Gruppierungen stehen, mit heterocyclischen Basen der allgemeinen Formel
EMI1.1
in der R1, R2, R3, R4 Wasserstoff oder niedere Alkylgruppen mit 1 bis 5 Kohlenstoffatomen darstellen, n die Werte von 2 bis 7 und m die Werte von 2 bis 4 bedeuten, Halogenwasserstoff abspaltet.
Bei der weiteren Bearbeitung des Erfindungsgedankens, der dem Hauptpatent Nr. 428 703 zugrunde liegt, wurde gefunden, dass sich überraschenderweise auch sekundäre oder tertiäre Halogenverbindungen, deren Halogenatom sich nicht in a- oder ,B-Stellung zu einer aktivierenden Gruppe, wie eine Carbonyl-, Carboxy-, Nitril-, Äthylen- oder Acetylengruppe, befindet, mit Hilfe der genannten heterocyclischen Basen in die entsprechenden ungesättigten Verbindungen überführen lassen.
Als Halogenverbindungen können geradkettige oder verzweigte sekundäre oder tertiäre aliphatische Halogenverbindungen oder auch cycloaliphatische Halogenverbindungen verwendet werden. Die genannten Verbindungen können darüber hinaus in X-, b- oder ±-Stellung andere funktionelle Gruppen, die keinen aktivierenden Einfluss mehr auf das Halogenatom ausüben, besitzen, wie Nitril-, Carboxy-, Carbonyl-, Äthylen- oder Acetylengruppen.
Die Halogene in den oben angeführten Halogenverbindungen können Chlor oder Brom aber auch Jod sein.
Als Dehydrohalogenierungsmittel der obigen allgemeinen Formel eignen sich z. B. 1,5-Diaza-bicyclo-(4, 3, O)-nonen (5) oder 1,5-Diaza-bicyclo-(4, 5, 0)-undecen-(5). Im übrigen verfährt man nach den Angaben im Hauptpatent Nummer 428 703.
In den folgenden beschriebenen Ausführungsbeispielen verhalten sich Volumteile zu Gewichtsteilen wie Liter zu Kilogramm.
Beispiel 1
Man erwärmt 82 Gewichtsteile Cyclohexylbromid, 40 Vo lumteile Dimethylsulfoxyd und 83 Gewichtsteile 1,5-Diazabicyclo-(4, 5, 0)-undecen-(5) auf 95" C, wobei eine heftige Reaktion eintritt, und destilliert das entstandene Reaktionsprodukt ab.
Ausbeute: 38,8 Gewichtsteile (95 % der Theorie) Cyclohexen vom Siedepunkt 82" C.
Beispiel 2
Man verfährt wie im Beispiel 1 beschrieben, ersetzt jedoch die Base durch 70 Gewichtsteile 1,5-Diaza-bicyclo-(4, 3, 0)nonen-(5) und erhält 38 Gewichtsteile (93 % der Theorie) Cyclohexen vom Siedepunkt 82" C.
Beispiel 3
Man erwärmt 36 Gewichtsteile 4-Bromheptan, 45 Gewichtsteile 1,5-Diaza-bicyclo-(4, 5, 0)-undecen-(5) und 15 Volumteile Dimethylsulfoxyd auf 95" C, wobei das Reaktionsprodukt entsteht, das aus dem Ansatz destilliert wird.
Ausbeute: 17,9 Gewichtsteile (91% der Theorie) Hepten (3) vom Siedepunkt 96 bis 97" C.
Beispiel 4
Man erwärmt 36 Gewichtsteile 2-Bromheptan und 33,4 Gewichtsteile 1,5-Diaza-bicyclo-(4, 5, 0)-undecen-(5) bis zur Reaktionstemperatur von 80" C und destilliert das Reaktionsprodukt ab.
Ausbeute: 15,3 Gewichtsteile (78 % der Theorie) Heptene vom Siedepunkt 960 C mit einem Gehalt von 79% Hepten (2) und 19% Hepten-(l).
Beispiel 5
Man verfährt wie im Beispiel 4 beschrieben, setzt jedoch als Halogenverbindung 2-Bromoctan ein. Man erhält 18,9 Gewichtsteile (84% der Theorie) Octene vom Siedepunkt 1220 C mit einem Gehalt von 7864 Octen-(2) und 21% Octen-(l).
Process for the preparation of olefinically unsaturated compounds
The subject of the main patent No. 428 703 is a process for the preparation of unsaturated compounds with elimination of chlorine, bromine or hydrogen iodide, characterized in that, from corresponding halogen compounds, the halogen atom of which is in a- or a-position to a carbonyl group, ethylene, Acetylene or cyano grouping, or the halogen atoms of which are in a- and ss-position to the groupings mentioned, with heterocyclic bases of the general formula
EMI1.1
in which R1, R2, R3, R4 represent hydrogen or lower alkyl groups having 1 to 5 carbon atoms, n the values from 2 to 7 and m the values from 2 to 4, splitting off hydrogen halide.
In the further processing of the idea of the invention on which the main patent No. 428 703 is based, it was found that, surprisingly, secondary or tertiary halogen compounds whose halogen atom is not in a- or B-position to an activating group, such as a carbonyl , Carboxy, nitrile, ethylene or acetylene group, can be converted into the corresponding unsaturated compounds with the aid of the heterocyclic bases mentioned.
Straight-chain or branched secondary or tertiary aliphatic halogen compounds or else cycloaliphatic halogen compounds can be used as halogen compounds. The compounds mentioned can also have other functional groups in the X, b or ± position which no longer exert an activating influence on the halogen atom, such as nitrile, carboxy, carbonyl, ethylene or acetylene groups.
The halogens in the halogen compounds listed above can be chlorine or bromine, but also iodine.
Suitable dehydrohalogenating agents of the above general formula are, for. B. 1,5-diaza-bicyclo- (4, 3, O) -nonen (5) or 1,5-diaza-bicyclo- (4, 5, 0) -undecen- (5). Otherwise one proceeds according to the information in main patent number 428 703.
In the exemplary embodiments described below, parts by volume are related to parts by weight as liters are related to kilograms.
example 1
82 parts by weight of cyclohexyl bromide, 40 parts by weight of dimethyl sulfoxide and 83 parts by weight of 1,5-diazabicyclo- (4,5,0) -undecene (5) are heated to 95 ° C., a vigorous reaction occurs, and the resulting reaction product is distilled off.
Yield: 38.8 parts by weight (95% of theory) of cyclohexene with a boiling point of 82 "C.
Example 2
The procedure described in Example 1 is followed, but the base is replaced by 70 parts by weight of 1,5-diaza-bicyclo- (4, 3, 0) nonene (5) and 38 parts by weight (93% of theory) of cyclohexene with a boiling point of 82 "are obtained. C.
Example 3
36 parts by weight of 4-bromoheptane, 45 parts by weight of 1,5-diaza-bicyclo- (4, 5, 0) -undecene (5) and 15 parts by volume of dimethyl sulfoxide are heated to 95 ° C., the reaction product being formed, which distills from the batch becomes.
Yield: 17.9 parts by weight (91% of theory) of heptene (3) with a boiling point of 96 to 97 "C.
Example 4
36 parts by weight of 2-bromoheptane and 33.4 parts by weight of 1,5-diaza-bicyclo- (4, 5, 0) -undecene (5) are heated to the reaction temperature of 80 ° C. and the reaction product is distilled off.
Yield: 15.3 parts by weight (78% of theory) of heptene with a boiling point of 960 ° C. with a content of 79% heptene (2) and 19% heptene (1).
Example 5
The procedure described in Example 4 is followed, but 2-bromooctane is used as the halogen compound. 18.9 parts by weight (84% of theory) of octenes with a boiling point of 1220 ° C. with a content of 7864 octene (2) and 21% octene (1) are obtained.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF36803A DE1186063B (en) | 1962-05-15 | 1962-05-15 | Process for the preparation of olefinically unsaturated compounds |
| DEF50559A DE1279679B (en) | 1966-10-28 | 1966-10-28 | Process for the preparation of olefinically unsaturated compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH533068A true CH533068A (en) | 1973-01-31 |
Family
ID=25975324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1301267A CH533068A (en) | 1962-05-15 | 1967-09-18 | Preparation of olefins from heterocyclic bases and |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH533068A (en) |
-
1967
- 1967-09-18 CH CH1301267A patent/CH533068A/en unknown
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PLZ | Patent of addition ceased |