Process for the production of 4,4,8,8,10-pentamethyl-10-cyano-bicyclo[4.4.0]-dec-1,6-en-2-one

Information

  • Patent Grant
  • 4788318
  • Patent Number
    4,788,318
  • Date Filed
    Tuesday, August 25, 1987
    37 years ago
  • Date Issued
    Tuesday, November 29, 1988
    36 years ago
Abstract
A process for the production of the bicyclic compound 4,4,8,8,10-pentamethyl-10-cyano-bicyclo[4.4.0]-dec-1,6-en-2-one which comprises the steps of (a) reacting a ketone fraction comprising ##STR1## or mixtures thereof, (b) by adding HCN to the ketone fraction the presence of a base, at a temperature of 50.degree.-200.degree. C. to obtain an addition product comprising the bicyclic compound, and(c) isolating the addition product.
Description

BACKGROUND OF THE INVENTION
1. Field of the Invention:
The invention relates to a process for the production of 4,4,8,8,10-pentamethyl-10-cyano-bicyclo[4.4.0]-dec-1,6-en-2-one [A] from a C15 ketone mixture, as it is obtained by fractionation of the sump product which occurs in the production of isophorone at 1 to 100 mbar with an approximately 30% yield, by the addition of hydrogen cyanide. ##STR2##
2. Discussion of Background:
Compound A is an excellent precursor for the synthesis of amines, diamines, heterocycles and a large number of other substances.
In the production of isophorone by the condensation of acetone, up to 10% condensation products with a higher molecular weight are formed, and at the present time, these are burned. Therefore, a need exists for processes to separate or convert this mixture into products which can be utilized synthetically.
The state of the art of isophorone production may be ascertained by reference to the Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Edition, Vol. 13 (1982), pages 918-922, particularly page 920 and U.S. Pat. Nos. 3,337,423 and 3,337,633, the disclosures of which are incorporated herein by reference.
SUMMARY OF THE INVENTION
Accordingly, one object of the present invention is to provide a method of producing 4,4,8,8,10-pentamethyl-10-cyano-bicyclo [4.4.0]-dec-1,6-en-2-one in an economical manner without using expensive reagents.
A further object of the invention is to provide a method of utilizing the sump product which occurs in the production of isophorone to produce useful chemical products.
These and other objects of the present invention which will become apparent from the following specification have been achieved by the present process for the production of the bicyclic compound 4,4,8,8,10-pentamethyl-10-cyano-bicyclo[4.4.0]-dec-1,6-en-2-one, comprising the steps of: producing a ketone fraction comprising ##STR3## or mixtures thereof, adding HCN to the ketone fraction in the presence of a base, at a temperature of 50.degree.-200.degree. C., to produce an addition product comprising said bicyclic compound, and
isolating the addition product.





DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Surprisingly, it was found that compound A can be obtained with a good yield and in excellent purity with process steps that are easy to carry out technically, by adding hydrogen cyanide to a special fraction of the isophorone sump product.
By fractionation of the isophorone sump product at 1 to 100 mbar, preferably at 10 to 30 mbar, a ketone fraction which consists essentially of C15 compounds is obtained. This ketone fraction, which is obtained with a yield of approximately 30%, boils at 125.degree. to 145.degree. C. at a pressure of 13 mbar. As the main components, this fraction contains the isomers B and C ##STR4##
The position of the double bonds in B and C is not completely certain. Additionally, the ratio of the two isomers B and C to one another is not constant. Also, the content of both substances in the C15 fraction can differ. The total of both isomers in the C15 fraction is generally 75 to 90%.
The base-catalyzed addition of hydrogen cyanide to the C15 ketone fraction (Michael addition) surprisingly results in the same nitrile A from isomers B and C. It is furthermore surprising that hydrogen cyanide does not add to other compounds of the C15 ketone fraction and also that, no bis-HCN adduct with the structure D occurs. ##STR5##
General basic substances are suitable as the basic catalyst. Preferably, alkali cyanides, alkali carbonates, alkali phenolates, alkali alcoholates, particularly the sodium salts are used, and the use of sodium methoxide is particularly preferred.
Base-catalyzed addition of hydrogen cyanide is carried out at temperatures from 50.degree. to 200.degree. C., preferably from 150.degree. to 170.degree. C.
Hydrogen cyanide is generally used in amounts of 5 to 10 wt. %, relative to the ketone fraction.
Instead of adding hydrogen cyanide to the C15 ketone sections with the isomers B and C obtained from the sump product of isophorone production, it can, of course be added to B and/or C which have been produced by any other suitable process.
The addition of hydrogen cyanide can be carried out continuously or batchwise. The addition can also be carried out in the presence of solvent.
The conversion mixture is diluted with light gasoline or a hydrocarbon such as hexane and distilled by fractionation after being washed with 1% acid, preferably nitric acid/water solution. Fractionation preferably takes place in a vacuum.
Other features of the invention will become apparent in the course of the following description of an exemplary embodiment which is given for illustration of the invention and is not intended to be limiting thereof.
EXAMPLE
The sump product of isophorone synthesis (by condensation of acetone) is fractionated at a pressure of 13 mbar. This results in a ketone fraction in a 30% yield (b.p. 125.degree. to 145.degree. C.), which consists essentially of C15 compounds, with the main components being compounds B and C.
100 g C15 ketone mixture (total B, C=89%) and 0.5 ml 30% methanolic NaOCH.sub.3 solution were filled into a 1-liter stirring apparatus with a bottom valve, equipped with a dropping funnel and reflux condenser with a connected bubbler. At 170.degree. C., a 30% methanolic NaOCH.sub.3 solution was fed in through a metering pump, at a rate of 0.9 ml/h. At the same time, a solution of 420 g C15 ketone mixture (total B, C=89%) and 49.2 g HCN was dripped in. The HCN mixture was added as rapidly as the HCN reacted. With increasing reaction time, the conversion rate increased because of the increasing reaction volume. After 4.5 h, the entire solution had been added. The addition of catalyst was discontinued and the mixture was stirred at 170.degree. C. for one hour. After it had cooled to 60.degree. C., 350 ml hexane were added, and the mixture was washed once with 100 ml 1.5% nitric acid and once with 100 ml water. The n-hexane was drawn off and the residue (576 g) was distilled through a 60 cm packed column (b.p. 82.degree. C.).
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
__________________________________________________________________________ Amount of Temperature .degree.C. Pressure Distillate Analytical Composition in %Fraction sump mantle head (mbar) (g) % .SIGMA.BC .SIGMA.U C.sub.16 --Nitrile__________________________________________________________________________ A1 153-193 70-80 72-78 0.25 118.8 20.6 60 40 02 193-202 80-120 78-132 0.25 32.2 5.6 15 68.3 16.73 202-240 120-125 132-139 0.25-0.3 378.2 65.7 -- -- 1004 (240-260) 125-160 139-148 0.3 31.6 5.5 -- 0.7 99.3residue 2.6 0.5 n.a. n.a. n.a.cooling 9.8 1.7 n.a. n.a. n.a.trap__________________________________________________________________________ Yield = 92% of theory calculated for HCN 79% of theory calculated for total B and C U = unidentified products n.a. -- not applicable
Claims
  • 1. A process for the production of the bicyclic compound 4,4,8,8,10-pentamethyl-10-cyanobicyclo[4.4.0]-dec-1,6-en-2-one, comprising the steps of:
  • reacting a ketone fraction comprising ##STR6## or mixtures thereof, by adding HCN to said ketone fraction in the presence of a base, at a temperature of 150.degree.-200.degree. C. to obtain an addition product comprising said bicyclic compound, and
  • isolating said addition product.
  • 2. The method of claim 1, wherein said isolating step comprises washing said addition product with aqueous acid and isolating said addition product by distillation.
  • 3. The process of claim 1, wherein said base is selected from a group consisting of alkali cyanides, akali carbonates, alkali phenolates, alkali alcoholates and mixtures thereof.
  • 4. The process of claim 3, wherein said base is selected from a group consisting of sodium cyanides, sodium carbonates, sodium phenolates, sodium alcoholates and mixtures thereof.
  • 5. The process of claim 1, wherein said base is sodium methoxide.
  • 6. The process of claim 1, wherein said adding step occurs at a temperature of from 150.degree.-170.degree. C.
  • 7. The process of claim 1, wherein said ketone fraction comprises 75-90% of ##STR7## or mixtures thereof.
  • 8. The process of claim 1, wherein said HCN is added in an amount of 5-10 wt. % relative to said ketone fraction.
  • 9. The process of claim 1, wherein said ketone fraction is obtained by fractionating the sump product, which occurs during the production of isophorone by the condensation of acetone, at 1-100 mbar to produce said ketone fraction.
  • 10. The process of claim 2, wherein said aqueous acid is aqueous nitric acid.
Priority Claims (1)
Number Date Country Kind
3640306 Nov 1986 DEX
US Referenced Citations (5)
Number Name Date Kind
2188340 Dykstra Jan 1940
3337423 Schmitt et al. Aug 1967
3337633 Schmitt et al. Aug 1967
3341554 Murray et al. Sep 1967
4299775 Dubreux Nov 1981
Foreign Referenced Citations (4)
Number Date Country
632600 Dec 1961 CAX
685034 Apr 1964 CAX
887411 Jan 1962 GBX
1047920 Nov 1966 GBX
Non-Patent Literature Citations (2)
Entry
Noller, "Chemistry of Organic Compounds", 3rd ed., (1965), W. B. Saunders Co. (Philadelphia), p. 98.
Kirk-Othmer, "Encyclopedia of Chemical Technology", 3rd ed., vol. 13, (1981); pp. 918, 919, 920, 921, 922.