US3562316A - Process for the cyclization of unsaturated organic compounds - Google Patents

Process for the cyclization of unsaturated organic compounds Download PDF

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Publication number
US3562316A
US3562316A US643389A US3562316DA US3562316A US 3562316 A US3562316 A US 3562316A US 643389 A US643389 A US 643389A US 3562316D A US3562316D A US 3562316DA US 3562316 A US3562316 A US 3562316A
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acid
mixture
mol
cyclization
double bonds
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Marc Julia
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Rhone Poulenc SA
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Rhone Poulenc SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • 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
    • C07C2601/14—The ring being saturated
    • 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
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/12—One of the condensed rings being a six-membered aromatic ring the other ring being at least seven-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/14—All rings being cycloaliphatic
    • C07C2602/22—All rings being cycloaliphatic the ring system containing eight carbon atoms, e.g. pentalene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes

Definitions

  • the invention accordingly provides a process for the cyclization of an organic compound having two carboncarbon double bonds in the 1,5- or 1,6-position, which comprises mixing the said compound with a mercuric salt in an amount such as to provide one Hg++ ion for each pair of double bonds, adding a proton acid the anion of which is only slightly nucleophilic or a Lewis acid, and heating the mixture so obtained.
  • the unit which carries the two double bonds may be substituted and one or both of the double bonds may belong to a ring. However, it is essential that the carbon atoms of the double bonds in question should not be entirely substituted. With this reservation, any organic compound containing a pair of 1,5- or 1,6- carbon-carbon double bonds may be cyclized by the new process.
  • the following may be cyclized: purely aliphatic compounds such as diallyl, 2,5-dimethyl-diallyl, and 2- methyl-2,6-heptadiene; compounds in which one of the double bonds is part of an aliphatic or aromatic ring which may optionally be substituted, for example 4-phenyl-1- butene and S-phenyl-l-pentene; compounds in which both the double bonds are in rings, each belonging to a different ring, for example 3-[2-(3-methoxyphenyl)ethyl] cyclohexene and 3 [2-(3,4-dimethoxyphenyl)ethyl1cyclohexene; compounds having the two double bonds in a single ring, for example 1,5-cyclooctadiene.
  • compounds in which one of the double bonds is part of an aliphatic or aromatic ring which may optionally be substituted, for example 4-phenyl-1- butene and S-phenyl-l-pentene
  • the ring formed may have 5, 6 or 7 carbon atoms.
  • the anionic part of the mercuric salt used may, after addition to one of the double bonds, remain as a substituent in the resulting ring.
  • the cyclization may also take place so that no new substituents appear in the resulting ring; this is so when the bond to the expected substituent is too weak to withstand the working conditions, particularly when the substituent would be carried by a tertiary carbon atom.
  • the ring obtained under these conditions is thus necessarily an unsaturated ring. If the starting materials employed and the working conditions are such that the cyclization results in a cyclohexadiene group, the latter has a greater or less tendency to aromatise into a benzene ring.
  • the mercuric salt may in general be any salt of an organic carboxylic acid, especially a salt of a lower alkanoic acid, and more particlarly mercuric acetate.
  • the mercuric salt corresponding to the proton acid may also be used.
  • the amount of the mercuric salt is 1 Hg++ per unit with 1,5- or 1,6-double bonds and per mol of organic compound containing this unit.
  • the amount of proton acid may be a small molar fraction of the starting material or an equimolar proportion.
  • a proportion of mol per mol of 1,5- or 1,6-diene is generally sufiicient.
  • the reaction may be carried out in an anhydrous organic medium, especially in a lower alkanoic acid or in a compound such as nitromethane. It may equally be carried out in an aqueous organic medium or even in a purely aqueous medium.
  • the reaction may take place rapidly at ambient temperature (for example 20 C.) or may, conversely, require heating to a more or less elevated temperature, possibly in an autoclave. It is generally not necessary to exceed 150 C. and most frequently it is possible to work satisfactorily at a temperature of 6090 C.
  • a particularly valuable method of working consists of mixing a mercuric salt of a lower alkanoic acid and a diene compound, as defined above, in a liquid organic carboxylic acid, which may be acetic acid, and then, after dissolving the salt, adding the proton acid and heating, generally to 6090 C.
  • a liquid organic carboxylic acid which may be acetic acid
  • the mercury metal produced is removed, and the organic compound formed is isolated by known methods; for example, water is added to the product which has been freed of the mercury metal, the mixture is extracted with an organic solvent which is inert under the working conditions, the solution obtained is washed until neutral and dried, the solvent is evaporated, and the residue is fractionally distilled. In this way a main fraction consisting of a cyclic ester, and subsidiary fractions containing unconverted diene and secondary reaction products, are obtained.
  • the cyclization product may optionally be converted into other compounds either after isolation or by directly treating the crude cyclization product.
  • the products resulting from a cyclization with fixation of an acyloxy radical may be saponified to alcohols.
  • EXAMPLE 1 41 g. (0.5 mol) of diallyl are added to a suspension of 160 g. (0.5 mol) of mercuric acetate in 1250 cm. of acetic acid. After dissolving the salt, g. (0.5 mol) of 60% perchloric acid are added, and the mixture heated at 70 C. for 30 minutes. g. (0.5 gram atom) of mercury are produced and separated. The liquid portion is poured into 1 l. of water, and extracted with benzene. The extract is successively washed with sodium carbonate solution and water, and dried. The solvent is evaporated and the residue then distilled under reduced pressure. In this way two fractions of the following properties are obtained:
  • EXAMPLE 2 21.6 g. (0.1 mol) of mercuric oxide, 200 cm. of water, and sufficient concentrated aqueous perchloric acid solution to dissolve all the mercuric oxide are introduced into a flask fitted with a cooling unit and a condenser cooled with a mixture of solid carbon dioxide and acetone. 8.2 g. (0.1 mol) of diallyl are then added and the mixture heated under reflux overnight. During the reaction a gas is evolved which is condensed in the condenser cooled by the solid carbon dioxide-acetone mixture. The mixture obtained at the end of the reaction is filtered to remove the mercury formed. The filter is washed with diethyl ether which is then added to the aqueous phase.
  • EXAMPLE 5 11 g. (0.1 mol) of 2-methyl-2,6-heptadiene are added to a solution of 32 g. of mercuric acetate in 300 cm. of acetic acid. 1.8 g. of 60% perchloric acid are added, and the mixture is heated to 70 C. After 40 minutes, the portion which has been separated from the 20 g. of mercury formed is poured into 300 cm. of water, and extracted with benzene. The extract is washed as described above and dried, the solvent is evaporated, and the residue distilled. In this way 3.4 g. of a product, B.P. 130 C./ 40 mm. Hg, identified as 3-isopropylidene-cyclopentyl acetate, are obtained.
  • B.P. -91 C./l 0 mm. Hg, 9' g., whose composition, by vapour phase chromatography, is as follows:
  • EXAMPLE 8 2.5 g. (0.01 mol) of 3-[2-(3,4-dimethoxyphenyl)ethyl]- cyclohexene, 3.2 g. of mercuric acetate and 20 cm. of acetic acid are introduced into a flask which is equipped as in the preceding examples. When the whole of the mercuric salt has dissolved, 1 cm. of a 60% aqueous solution of perchloric acid is added, and the mixture is heated to 80 C. After three hours heating at this tem perature, the mixture is cooled and filtered, and filtrate is poured into cm. of water, and the product is neutralised by adding 2 N caustic soda solution and extracted with chloroform.
  • the chloroform extract is evaporated, and the residue is saponified by adding 250 cm. of methanol containing 4 g. of potassium hydroxide and heating under reflux for 3 hours.
  • the product from this saponification is evaporated to drive olf the alcohol and then, after adding 150 cm. of Water, the residue is neutralised by adding 3 N aqueous hydrochloric acid.
  • the mixture is extracted with chloroform and 0.9 g. (40% yield) of a product, melting at 142-143 C. and identified as 4 hydroxy 6,7 dimethoxy 1,2,3,4,4a,9,10,10a octahydrophenanthrene, is isolated.
  • the 3-[2-(3-methoxyphenyl)ethyl] cyclohexene used as the starting material was prepared in the following manner.
  • the magnesium derivative of 1-bromo-2(3-methoxyphenyl)ethane is prepared and is then reacted with 3- bromocyclohexene.
  • 3-[2-(3-methoxyphenyl)ethyl]cyclohexene, B.P. 120-l33 C./1 mm. Hg is obtained.
  • EXAMPLE 10 10.8 g. (0.1 mol) of cyclooctadiene are added to a suspension of 32 g. of mercuric acetate '(0.1 mol) in 300 cm. of acetic acid. The mixture is heated to 85 C., and 18 g. (0.1 mol) of concentrated perchloric acid are added. After about 1 hour the mixture is allowed to cool, and decanted, and the precipitate is washed with benzene. 500 cm. of water are added to the acetic acid solution and the mixture is extracted with benzene (initially with the benzene with which the precipitate has been washed).
  • the benzene extract is first washed with aqueous sodium bicarbonate solution, and then with water, and dried over anhydrous sodium sulphate.
  • the solution is evaporated in vacuo and the residue then distilled. This yields:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US643389A 1966-06-08 1967-06-05 Process for the cyclization of unsaturated organic compounds Expired - Lifetime US3562316A (en)

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Application Number Priority Date Filing Date Title
FR64698A FR1490605A (fr) 1966-06-08 1966-06-08 Procédé de cyclisation de composés organiques non saturés

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US (1) US3562316A (fr)
CH (1) CH520086A (fr)
DE (1) DE1618831B1 (fr)
FR (1) FR1490605A (fr)
GB (1) GB1153375A (fr)
NL (1) NL6707851A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4159989A (en) * 1977-05-02 1979-07-03 Standard Oil Company (Indiana) Process for preparing ethylene glycol diacylate
US4609491A (en) * 1982-06-03 1986-09-02 Givaudan Corporation Tri- and tetra-substituted cyclohexen-1-methyl acetates as odorants

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE560018A (fr) * 1956-08-14

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4159989A (en) * 1977-05-02 1979-07-03 Standard Oil Company (Indiana) Process for preparing ethylene glycol diacylate
US4609491A (en) * 1982-06-03 1986-09-02 Givaudan Corporation Tri- and tetra-substituted cyclohexen-1-methyl acetates as odorants

Also Published As

Publication number Publication date
CH520086A (fr) 1972-03-15
FR1490605A (fr) 1967-08-04
DE1618831B1 (de) 1972-01-05
NL6707851A (fr) 1967-12-11
GB1153375A (en) 1969-05-29

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