US3676511A - Polyene hydrocarbons containing two conjugated double bonds and process for obtaining same - Google Patents

Polyene hydrocarbons containing two conjugated double bonds and process for obtaining same Download PDF

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US3676511A
US3676511A US109009A US3676511DA US3676511A US 3676511 A US3676511 A US 3676511A US 109009 A US109009 A US 109009A US 3676511D A US3676511D A US 3676511DA US 3676511 A US3676511 A US 3676511A
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double bonds
conjugated double
polyene hydrocarbons
hydrocarbons containing
obtaining same
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US109009A
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Sergio Arrighetti
Eugenio Vajna
Sebastiano Cesca
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SnamProgetti SpA
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SnamProgetti SpA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
    • C07C35/23—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings
    • C07C35/28—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings the condensed ring system containing seven carbon atoms
    • C07C35/29—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings the condensed ring system containing seven carbon atoms being a (2.2.1) system
    • 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
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
    • C07C1/326—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom the hetero-atom being a magnesium atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/39—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing seven carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/39—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing seven carbon atoms
    • C07C13/42—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing seven carbon atoms with a bicycloheptene ring structure
    • C07C13/43—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing seven carbon atoms with a bicycloheptene ring structure substituted by unsaturated acyclic hydrocarbon
    • 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
    • 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
    • C07C2/52—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

Definitions

  • R is hydrogen or an alkyl radical
  • R,, R R R R R R" and R may be hydrogen, alkyl or aryl radicals.
  • hydrocarbons are obtained by reacting a substituted or unsubstituted norbornene carbonyl derivative with a Grignard alkenyl derivative, for example according to the fol lowing scheme:
  • R R R R R, R', R" and R have the aforesaid meanings and X is a halogen as Br, C1 or I.
  • R C C Cal I 1 R! R!!! Its- All the above reactions are carried out at a temperature ranging from 0 to C, and preferably in the presence of a solvent which may be selected from ethers as tetrahydrofuran, dioxane, ethyl ether, butyl ether, and the like, from aromatic hydrocarbons as benzene, toluene, xylenes or mixtures of these solvents.
  • a solvent which may be selected from ethers as tetrahydrofuran, dioxane, ethyl ether, butyl ether, and the like, from aromatic hydrocarbons as benzene, toluene, xylenes or mixtures of these solvents.
  • Typical unrestrictive examples of triene derivatives according to the present invention are the following ones:
  • reaction mass was allowed to reflow for 2 hours: then the magnesium salts were dissolved by an excess of a watery CH COOH (1:1 by volume), the organic phase was washed up to neutrality, dried on Ne so and the tetrahydrofuran was removed by distillation.
  • R is hydrogen or an alkyl radical
  • R,, R R R R, R" and R' are hydrogen, alkyl or aryl radicals.
  • a process for preparing polyene hydrocarbons as claimed in claim 1 characterized in that said hydrocarbons are obtained by reacting a Grignard derivative as:
  • R, R R R R R, R", R and X have the aforesaid meanings.
  • a process for preparing polyene hydrocarbons as claimed in claim 1 characterized in that cyclopentadiene is allowed to react with an acetylene derivative containing at least a double bond conjugated with the triple bond.

Abstract

There are provided novel polyene hydrocarbons containing two conjugated double bonds and having the following general formula

WHEREIN R is hydrogen or alkyl and R1, R2, R3, R4, R'', R'''' and R'''''' are hydrogen, alkyl or aryl.

Description

United States Patent Arrighetti et al.
[ 51 July 11, 1972 [54] POLYENE HYDROCARBONS CONTAINING TWO CONJUGATED DOUBLE BONDS AND PROCESS FOR OBTAINING SAME [72] Inventors: Sergio Arrighetti, Milan; Eugenio Vajna; Sebastiano Cesca, both of San Donato Milanese, all of Italy [73] Assignee: Snam Progetti S.p.A., Milan, Italy [22] Filed: Jan. 22, 1971 [2]] Appl. No.: 109,009
[5 l Int. Cl. C07c 5/24 [58] Field of Search ..260/666 A, 666 FY [56] References Cited UNITED STATES PATENTS 3,347,875 10/1967 Foster ..260/666 PY 3,565,961 2/1971 Nagase et al ..260/666 PY 2,966,527 12/1960 Schmerling ..260/666 PY Primary Examiner-Delbert E. Gantz Assistant Examiner-Veronica OKeefe Attorney-Ralph M. Watson [57] ABSTRACT There are provided novel polyene hydrocarbons containing two conjugated double bonds and having the following general formula wherein R is hydrogen or alkyl and R,, R R R,, R, R" and R' are hydrogen, alkyl or aryl.
4 Claims, No Drawings in which R is hydrogen or an alkyl radical; R,, R R R R R" and R may be hydrogen, alkyl or aryl radicals.
These hydrocarbons are obtained by reacting a substituted or unsubstituted norbornene carbonyl derivative with a Grignard alkenyl derivative, for example according to the fol lowing scheme:
wherein R R R R R, R', R" and R have the aforesaid meanings and X is a halogen as Br, C1 or I.
It is also possible to react a substituted or unsubstituted Grignard compound of the norbomadiene halogen derivative with a ketone and then to dehydrate the corresponding alcohol, according to the scheme wherein R R R R R, R, R, R'" and X have the known meanings. Another unrestri'ctive example of the invention is the Diels-Alder reaction between the substituted or unsubstituted cyclopentadiene and an acetylene derivative containing at least a double bond adjacent to the triple bond:
R C=C Cal I 1 R! R!!! Its- All the above reactions are carried out at a temperature ranging from 0 to C, and preferably in the presence of a solvent which may be selected from ethers as tetrahydrofuran, dioxane, ethyl ether, butyl ether, and the like, from aromatic hydrocarbons as benzene, toluene, xylenes or mixtures of these solvents.
Typical unrestrictive examples of triene derivatives according to the present invention are the following ones:
2-propenyl-norbor-2,5-dieue II C H;
l :0 H--C H3 t C H: 2-(butenyl-2) 3-methyl-norbor-2, fi-dlene III CH! lsopropyliden-norbomadienyl-methane The invention is now illustrated by the following unrestrictive examples.
EXAMPLE I In a three neck flask provided with a reflux condenser and a mechanical stirrer, a tetrahydrofuran solution of decahydronorcanfor was added to a tetrahydrofuran 2M solution of the Gringard derivative of l-bromo-l-propene.
After a prudent mixing of the reactants, the reaction mass was allowed to reflow for 2 hours: then the magnesium salts were dissolved by an excess of a watery CH COOH (1:1 by volume), the organic phase was washed up to neutrality, dried on Ne so and the tetrahydrofuran was removed by distillation.
The remaining alcohol was already dehydrated during the distillation at reduced pressure (0.5 mmHg); in such a way the product I was obtained, having a b.p. 45 C/lO mmHg and a MW 132 (mass spectometry).
EXAMPLE [I The condensation product of cyclopentadiene with alphabromo-acrolein was dehydroalogenated into formylnorbornadiene. This compound was prudently treated with an excess of the Grignard reactant of Z-bromo-propane. The alcohol, obtained from the reaction mass according to the preceding example, was dehydrated on 01 A1 0, at 230 C and a product was obtained having a boiling point of 55 C at 10 mmI-IG, a molecular weight equal to 146 (mass spectrometry), it being in agreement with the structure III.
EXAMPLE II] By employing suitable catalyst [according to Dt. Botz, C. Bucur, J. Primus, L. Stanescu, D. Sandulescu-Rev. Chimi (Budarest) 12, 503 (1961) CA. 56 5848 g (1962) and to RP. 1,364,969] cyclopentadiene was allowed to react with 3- methyl-2-esen-4-ino at 144 C: the obtained produce was rectified and the compound II was obtained showing a well agreement with the proposed structure at the physical-chemical investigation.
What we claim is:
1. Polyene hydrocarbons containing two conjugated double bonds and having the following general formula:
in which R is hydrogen or an alkyl radical; R,, R R R R, R" and R' are hydrogen, alkyl or aryl radicals.
2. A process for preparing polyene hydrocarbons as claimed in claim 1 characterized in that a carbonyl derivative as:
is allowed to react with an alkenyl Grignard derivative as:
4 IR! Ila/I XMg-C=CR wherein R R,, R R, R, R, R" and R' have the aforesaid meanings; and X is a halogen as Cl, Br or I.
3. A process for preparing polyene hydrocarbons as claimed in claim 1 characterized in that said hydrocarbons are obtained by reacting a Grignard derivative as:
wherein R, R R R R R, R", R and X have the aforesaid meanings.
4. A process for preparing polyene hydrocarbons as claimed in claim 1 characterized in that cyclopentadiene is allowed to react with an acetylene derivative containing at least a double bond conjugated with the triple bond.
mg UNITED STATES PATM 0mm @E'NFMATE @F QQRREWWN Patent No. 3,676,511 Dated July 11 197 Inventor) Sergio Arrighetti, et a].
It is certified that error appears in the above-identified patent and that said Letters Patent are hereby correctco ao shown below:
Column 1, line 45, correct the second formula as follows:
iv I HC I o c R" Colman 2, line 7 4, change "produce" to --product--='.
Column 4, line 4, after "R correct "R", first occurrence,
Signed and sealed this 19th day of February 197M.
(SEAL) Attest:
EDWARD M.FLETCHER,JR. Q MARSHALL DANN Attesting Officer Commissioner of Patents

Claims (3)

  1. 2. A process for preparing polyene hydrocarbons as claimed in claim 1 characterized in that a carbonyl derivative as:
  2. 3. A process for preparing polyene hydrocarbons as claimed in claim 1 characterized in that said hydrocarbons are obtained by reacting a Grignard derivative as:
  3. 4. A process for preparing polyene hydrocarbons as claimed in claim 1 characterized in that cyclopentadiene is allowed to react with an acetylene derivative containing at least a double bond conjugated with the triple bond.
US109009A 1970-01-22 1971-01-22 Polyene hydrocarbons containing two conjugated double bonds and process for obtaining same Expired - Lifetime US3676511A (en)

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JP (1) JPS5242792B1 (en)
AT (3) AT310717B (en)
BE (1) BE761745A (en)
CA (1) CA976989A (en)
CH (1) CH534645A (en)
DE (1) DE2102972A1 (en)
FR (1) FR2075697A5 (en)
GB (1) GB1337074A (en)
LU (1) LU62467A1 (en)
NL (1) NL7100918A (en)
ZA (1) ZA71424B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2966527A (en) * 1956-10-09 1960-12-27 Universal Oil Prod Co Preparation of bicycloalkadienes
US3347875A (en) * 1965-02-19 1967-10-17 Union Carbide Corp Acetylenic epoxides and dienes
US3565961A (en) * 1969-05-15 1971-02-23 Sumitomo Chemical Co Process for producing 5-(1'-alkenyl)-2-norbornene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2966527A (en) * 1956-10-09 1960-12-27 Universal Oil Prod Co Preparation of bicycloalkadienes
US3347875A (en) * 1965-02-19 1967-10-17 Union Carbide Corp Acetylenic epoxides and dienes
US3565961A (en) * 1969-05-15 1971-02-23 Sumitomo Chemical Co Process for producing 5-(1'-alkenyl)-2-norbornene

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BE761745A (en) 1971-07-01
NL7100918A (en) 1971-07-26
JPS5242792B1 (en) 1977-10-26
DE2102972A1 (en) 1972-02-17
AT310717B (en) 1973-10-10
CA976989A (en) 1975-10-28
ZA71424B (en) 1971-10-27
FR2075697A5 (en) 1971-10-08
LU62467A1 (en) 1971-09-02
CH534645A (en) 1973-03-15
GB1337074A (en) 1973-11-14
AT314496B (en) 1974-04-10
AT305969B (en) 1973-03-26

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