DE1618145A1 - Process for the preparation of 2,3-dehydronorbornyl ketones - Google Patents

Description

BADISCHE ANILIN- & SODA-FABRIK AG

Our reference: O. Z. 24 851 WS / D Ludwigshafen am Rhein, April 27, 1967

Process for the preparation of 2,3-dehydronorbornyl ketones

The invention is a process for the production of 2,3-dehydronorbornyl ketones by reacting 3-oxo alcohols with cyclopentadiene.

It is known from the Bulletin de l'Academie des Sciences de I ¹ URSS, Classe, des Sciences Chimiques 1947, pages 219 ff., To produce 2,3-dehydronorhornyl methyl ketone by reacting cyclopentadiene with methyl vinyl ketone. Cyclopentadiene is produced by distilling dicyclopentadiene or by pyrolysis of hydrocarbons (Ulimann's Encyclopedia of Technical Chemistry, Volume 5, ^r -> lte 701). Methyl vinyl ketone is obtained by the addition of water to monovinylacetylene (Johnson, the Acetylenic Alcohols, 19 ^ 6 * page 56) or by condensation of acetone and paraformaldehyde (Journal of the Chemical Society 1943, page 30).

It has now been found that 2,3-dehydronorborny! Ketones can be used Conversion of cyclopentadiene and vinyl ketones at elevated temperature advantageous if the vinyl ketone is obtained in the course of the reaction from the corresponding β ^ hydroxy-alkyl-ketone and optionally which gives rise to cyclopentadiene from such resulting substances. You can use the process in the presence of "dehydration

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perform catalysts.

The implementation can be carried out in the case of the use of "dicyclopentadiene and 3-oxobutanol represented by the following formulas:

OH 0
+ 2CH ₂ -CH ₂ -C- CH ₃ »2 | W ~~ ^C0 ~ ^CH 3 +

In comparison to the known method, the method follows the invention from more easily accessible starting materials and provides numerous 2,3-dehydronorbornyl ketones in a 1 τstufenverfahren in good yield. The easy implementation of dicyclopentadiene is surprising because this starting material leads to polymerisation and formation of polycyclopentadienes at elevated temperature inclines [Liebigs Annalen der Chemie, Volume 44γ, page 99 (1926)},

The starting materials used are cyclopentadiene or substances that give cyclopentadiene under the reaction conditions, such as tr! Cyclopentadiene, Tetrapentadiene or preferably dicyclopentadiene and ß-Hydroxy-alkyl-ketones used .. The used as starting material or cyclopentadiene resulting from the starting material is usually mixed with the starting ketone in a molar ratio of 1 to 10 to 1, preferably 2 to 1, implemented. The end products that can be produced can, depending on the starting material and reaction conditions, exo, endo compounds or mixtures of the two configurations.

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ο.ζ. 24 851 1618146

Preferred final substances are spicke of the general formula

^ HG, - '■. ■ ". ■■■■■ - ■. I HG - CO ^ R

HC

ti

in which M denotes an Alxphatisshen ^ #palip ||, atlBG & en _# cyoloaliphatic ^ en or aromatic radical. Preferred S-hydroxy-alkyl-ketones are those of the general Föpnel.

OH O
- ■ - ■; CH ₂ -GH ₂ -CH p, ■ · ■. . '

in, the R the aforementioned meaning 'tiat.

Particularly preferred starting materials II and accordingly more particularly PREFERRED end products I are splehe ^ in deiPeii formula ϊϊ Η an Alskyl residue with 1 to "8 Eoliienstoffafcomen, an Araliqrlrest with 7 t> is 12 carbon atomsi a CfGLo # .lil £ yli? eiSt with 6 to Means 10 carbon atoms or an aryl pass with 6 to 10 carbon atoms.

So z. B, the following ß-hydroxy-alkyl-icetones are used as starting materials: 3-oxo-butanol, -pentanol, -n-deeyl alcohol, 3-oxo-4, 4-dimethylpentanol, 3-Οχο-Ψ-phenyl- butanol., 3- oxo-3-pheny 1-propyl alcohol, ^ -oxo-IS-phenyl-lauryl alcohol, 3-0x0-4-naphthylbutanol, 3-oxo-3-toluyl-propyl alcohol.

The reaction is ⁱⁿ * & ^er preferably at elevated temperature usually at a temperature between 100 and 30O ⁰ C between 150 and:> they durchgeführtj place at normal pressure or at elevated

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Di ^ üök takes place and can be carried out continuously or discontinuously * It is advantageous to use dehydration catalysts in the reaction, such as aluminum oxide, silica gel, kaolin, fuller's earth or bauxite; - they are usually in a lot up to 5% by weight, based on the amount by weight of 3-oxo alcohol, used »

The reaction can be carried out as follows: A mixture of the Starting materials and optionally a dehydration catalyst is kept for 1/2 hour to 4 hours at the aforementioned temperature »During the reaction, what is formed is left Waters, irt d @ r sails in a mixture with proportions of cyclopentadiene, äbdestilliefeh and condense in a template. From the condensate Min separates the cyclopentadiene layer formed from the water towards Söheht and thus leads continuously escaping cyclopentadiene Reaction Again to »Mäeh termination of the reaction one submits the Reäktiönsggmiseh a fractional distillation and separates Overjoyed dloyclopentadiene that can be reused. " and the Behydronorbornyiketon from *

The connections that can be made according to the process are valuable Solvents for dyes and serve as stabilizers for dye solutions in hydrocarbons *

The parts given in the examples are parts by weight.

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Example 1 : . ·

In a stirring apparatus, a mixture of 800 parts of dicyclopentadiene, 'J55 O parts of 3-oxo-butähol and 10 parts of neutral alumina (in 4-mm pellets) for 30 minutes is kept at 170 ⁰ C while allowing continuously atdestillieren the water formed. Cyclopentadiene components exiting with the water in the mixture are returned to the reaction after separation from the water. The end product is now separated from the reaction mixture by fractional distillation. 481 parts of dehydronorbornyl methyl ketone are obtained at bp ₁₅ 79 to 81 ° C. (corresponds to 89 % of theory, based on 5-oxobutanol used). ~

Example 2 ''

In a stirred apparatus bringing a mixture of 264 parts of dicyclopentadiene and 176 Teilenj5-0xo-butanol at 200 ⁰ C for reaction. The reaction has ended after 4 hours. The reaction product is discharged and worked up as in Example T. In addition to unreacted Dloyclopentadien 189 parts are obtained of a mixture of endo- and exo-2,3-Dehydronorbornylmethylketon from Kp ₁₅ 80 to 82 ⁰ C and n ^ ° 1.4828. (69.9 % of theory, based on 3-oxobutanol used). ,

Example 3

300 parts of hydroxyethyl-phenyl-ketone and 450 parts Dicyolop & ^nfca-: are used in the presence of 1.5 parts of aluminum oxide at 200 ⁰ C analogously to Example 1 and worked up, the reaction mixture accordingly. 184.5 parts of dehydronorbornyl-phenyl-

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ketone with a bp _{Q of} 112 to 114 ° C and n ^ ° 1.5677 (corresponds to 93.5 % of theory, based on the phenyl hydroxyethyl ketone used)

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ORIGINAL IHSPECTED - 7 -

Claims (1)

-τ- latent claims 1, expire? Manufacture vöh 2 _§ 3-06 ^ 3ΓίΐΓοηοί · ΐΐΘΓηγί ^ θΐοη6η by converting dyclößeiitädieh und Ifinytkgtöfteri at elevated 'temperature * thereby kji1rigjiij3hatfe i that ffiäfl the vinyl ketone in the course of the conversion out of the corresponding! gives rise n äüsi sölöhes resulting Stoffeh \ 2 *! Method according to claim 1 * characterized in that it is rec ^ nnz ^ iöhnet j that it is carried out in the presence of dehydration risk treatment " BADiSCHE ANiLII ^ & SÖiSÄ- ^ ÄBRIE AG 10 98 137 IB31