DE2023687A1 - New 2-alkylidene-norbornane derivatives and processes for their preparation - Google Patents

Description

"New 2-alkylidene-norbornane derivatives and methods for their Manufacture "

Priority: May 16, 1969, Japan, No. 38 18/69

The invention relates to new 2-alkylidene-norbornane derivatives of the general formula

t = C ■ - OH

(D

in which R ^{1 is} a hydrogen atom or an alkyl radical having 1 to 8 carbon atoms and E ^{2 is} a hydrogen atom, a lower alkyl radical or a lower acyl radical. The alkyl or acyl radicals preferably have 1 to 6 carbon atoms.

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The invention also relates to a method for producing these Compounds, which is characterized in that one is a 1-alkenyl-nortricyclen the general formula

Λ ■ "" V / - Oxirj

in which R has the meaning given above, with a

2 2

Proton donor of the general formula R OH, in which R has the meaning given above, in the presence of a catalyst implements.

The above procedure can be followed by the reaction scheme below illustrate:

R ² OH

Catalyst Z- ^ V / ^ C -

Ή. -C = OHn

The method according to the invention is preferably carried out in such a way that that 1-alkenyl-nortricyclene is mixed with the proton donor, such as water, a lower aliphatic alcohol, or a lower carboxylic acid, in the presence of a catalyst vigorously stirs at a temperature of -20 ° C to the boiling point.

This reaction seems to be as follows? The rearrangement of the Side chain occurs when the cyclopropane ring opens. You get a carbonization - see this with the anion of the proton donor connects. .

* As a proton donor one can use water, an alcohol such as methanol

Ethanol, propanol or butanol, or a carboxylic acid such as formic acid, Use acetic acid or propionic acid.

The catalysts used in the process according to the invention are, for example, palladium-on-charcoal, which is generally used as the hydrogenation catalyst is used, also inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid or their aqueous Solutions, or organic sulfonic acids such as p-toluenesulfonic acid or naphthalenesulfonic acid is used. The amount of to use Catalyst is not critical. In the case of palladium on charcoal, however, an amount of 1/10 to 1/10 © becomes equivalent preferred.

The reaction proceeds quantitatively with vigorous stirring of the Reactants at a temperature from -20 C to the boiling point of the reaction mixture for a few 10 minutes to several hours regardless of the pressure. The final product can be made in the usual way to be isolated.

The method according to the invention can also be carried out in this case if the compound (II) is present as a mixture with its isomers, i.e. 5-alkylidene-2-norbomene with 5-alkenyl-2-norbornene, which cannot be separated from one another by fractional distillation. In this case only the reacts Compound (II) so that the reaction to separation and removal of the compound (II) of its isomers can be used.

The new 2-alcylidene-norbornene derivatives are available as starting

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compounds for the production of organic intermediates, Medicinal and agricultural chemicals can be used. They can also be used for the production and purification of 5-alkylidene-2-norbornenes used, in turn, as a diene component of ethylene-propylene-diene terpolymers can be used.

The examples illustrate the invention.

example 1

3 * ® g of 1-isopropenylnortricyclene, 1.41 g of 10% palladium on charcoal and 30 ml of glacial acetic acid are placed in a 5 ml glass vessel. The mixture is stirred vigorously at room temperature in a nitrogen atmosphere. After 10 hours, the catalyst is filtered off and 90 ml of water are added to the filtrate and the mixture is then extracted with ether. The ether extract is neutralized with sodium carbonate, dried, the ether is evaporated, and 4.2 g of 6-acetoxy-2-isopropylidene-norbornane are obtained. Kp. ^ 116 Ci n _D ° 1.4830.

The structure of the product is indicated by the IR, mass and NMR spectra confirmed.

H
found s 73 * 88; 9.55.

C ₁₂ H ₁₈ O ₃ : calc .: 74.19j 9.34;

Example 2

1. O g of 1-isopropenylnortricyclene are added to a 20 ml glass vessel. 0.5 g of 1% palladium-on-charcoal and 10 ml Ethanol. The mixture is stirred vigorously at room temperature a nitrogen atmosphere »The reaction device becomes gas-sensitive

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20236 & 7

matographically analyzed. It has the following composition:

Response time, starting material, end product, mine fo%

30 60.0 40.0

360 2.0 98.0

Yield of 6-ethoxy-2-isopropylidene-norbornane: 1.3 g. _{Bp 14} 92 ⁰ C] n ² ^ 1.4790.

the

The structure of the final product is defined by / infrared, mass and NMR spectra confirmed.

CH
C ₁₂ H ₂₀ O: Calculated: 79.94; 11.18; Found: 80.05; 11.31.

Example 3

In a JO ml equipped with a magnetic stirrer Erlenmeyer flask is given 2.0 g of 1-isopropenyl-nortrieyclen, 20 ml of ethanol and 0.1 g of concentrated sulfuric acid. The mixture is stirred vigorously at room temperature in a nitrogen fatmosphere. After 3 hours, water is added to the reaction mixture, which is neutralized and extracted with ether. The ether extract it is washed with water, dried and the ether is evaporated. 2.5 g of 6-ethoxy-2-isopropylidene-norbornane are obtained.

Example 4

In a 30 ml capacity equipped with a magnetic stirrer Brlenmeyer flask is given 2.0 g of 1-isopropenyl-nortricyclen, 15 g glacial acetic acid and 0.1 g concentrated sulfuric acid. The mixture stir vigorously at room temperature under a nitrogen atmosphere. After 30 minutes, ice cream * is added to the reaction mixture.

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water, neutralized and extracted with ether «, Ben ether extract is washed with water, dried and the ether evaporated. 2.60 g of 6-acetoxy-2-isopropylidene-norbornane are obtained.

Example 5

In a 1 liter / Zrlenmeyer flask equipped with a magnetic stirrer a mixture of 275 g of 5-isopropylidene-2-norbornene is added and 24 g of l-isopropenyl-nortricyclenj 240 g of ethanol and 18 g of $ 50 sulfuric acid. The mixture is stirred vigorously 5 hours at room temperature in a nitrogen atmosphere.

The reaction mixture is poured into ice water, neutralized and extracted with ether. The ether extract is washed with water, dried and evaporated the ether from "This gives 260 g of 5-isopropylidene-2-norbornenj, Kp. G _Q 90 ⁰ C and 32 g of 6-Ätfroxy-2-isopropylidene-norbornanj Kp" · «104 ⁰ C

Example 6

A mixture of 4.0 g of 5-isopropylidene-2-norbornene and 1.0 g of 1-isopropenylnortricyclene and 14 ml of 20% aqueous sulfuric acid are placed in a 50 ml separating funnel. The mixture is stirred vigorously at room temperature -in one stickst offatmosphäre "Kach neutralized 5 hours, the mixture and extracted it with ether ,, ΏβΆ ether extract is washed with water, dried ihnj, and evaporated from the ether" is obtained 4.1 g of a mixture with a Kp _{0 0} ^ 85 to 8JQ ₃ the 95 $ from 5 ~ isopropylidene-2-norbornene and 5 $ l-isopropenyl-nortricyclene as well as from 0.7 g 6-hydroxy-2 ~ isopropylidene-norbornane of the bp. ₁₉ 118 ⁰ G i η ² _Ώ 1, 5O6o ₈ consists of "

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Analysis of the latter compound

C. 89; H ber .: 78 23; 10.59; found s 78 10.95.

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Claims (1)

Patent claims 1/2-alkylidene-norbornane derivatives of the general formula in which R is a hydrogen atom or an alkyl radical with 1 to Is 8 carbon atoms and R is a hydrogen atom _? means a lower alkyl radical or a lower acyl radical. 2t 6-acetoxy-2-isopropylidene-norbornane. 3. 6-ethoxy-2-isopropylidene-norbornane. 4. G-Hydroxy - ^ - isopropylidene-norbornane, 5. Process for the preparation of the compounds according to Claims 1 to 4f, characterized in that that one is a 1-alkenyl-nortricyclen of the general formula R ¹ - C <= CH ₂ in which R has the meaning given in claim 1, with a proton donor of the general formula R ² OH in which R has the meaning given in claim 1, in Presence of a catalyst unisetzt. 00 9 8 49/2043 6. The method according to claim 5, characterized in that g e k e η η draw ty that the catalyst used is palladium-on-carbon, an inorganic acid, an aqueous solution of an inorganic acid or an organic sulfonic acid is used. 7. The method according to claim 5 »characterized in that the proton donor is water, methanol, Ethanol, propanols, butanols, formic acid, acetic acid or propionic acid are used. 8. The method according to claim 5, dad u rehgekisiert that the reaction is carried out at a temperature of -2O ⁰ C to the boiling point of the reaction system for a few 10 minutes to several hours. 9. The method according to claim 5, characterized in ^ draws that the reaction is carried out in the presence of 5-alkylidene-2-norbornene and 5-alkenyl-2-norbornene and the 2-alkylidene-norbornane derivative produced from the unreacted Separates norbornenes. 10. The method according to one or more of claims 5 to 9 » characterized in that compounds are used as starting materials whose lower alkyl radicals or lower acyl radicals have 1 to 6 carbon atoms. 0 0 9849/20 43