DE2022550C - - Google Patents

Description

r- *

- C

--C-! - C

C-X C-X '

.1

in a manner known per se with an acyclic conjugated diolefin of the structure

- C = CC = C- Norborneiulchlorid is an R-action participant. hot O b \ -, ISO C is condensed.

l: i The literature reports that unsaturated

ic, pohcxclic hydrocarbons, such as bicyclo (2.2.l | - 2.5-hepiadiene. cannot be obtained by splitting off hydrochloride or water from the corresponding s.ch! or- or iH> drox \ der _: '. data (see German Auslegeschriften 1 124488.1 02630'-,

ι * and German patent specification 977 582). As a result it was previously necessary to make such products Aceulen. z. B by Diels-Alder condensation with To produce cyclopentadiene in spite of the known Disadvantages of using Acer ien. i.e. the Risk of explosion.

A method has now been developed by which the cleavage reaction can be carried out successfully in such a way that the doubly unsaturated products from readily available and

easily handleable substances such as vinyl chloride and vinyl acetate can be obtained.

The invention relates to a process for the production of polycyclic hydrocarbons the structure

35 - C

I! —C

\ / T

is condensed and XX 'subsequently from the intermediate compound thus obtained with the aid of the door Formation of different double bonds known working methods is split off, with the remaining Valences of the substituted cyclic hydrocarbon and the acyclic conjugated Diolefins by hydrogen or chlorine or bromine, phenyl or lower alkyl with up to 6 carbon atoms are saturated as substituents and X is hydrogen or a halogen and X ' represents a halogen, preferably chlorine, or a hydroxyl, carboxyl or ester group.

2. The method according to claim 1, characterized in that that X 'is a halogen, preferably chlorine, and that XX' is a hydrogen halide by means of an alkali or Erdaikalalkoxyds, which is preferably from an alcohol with 4 to 20 carbon atoms originates, is split off.

3. The method according to claim 2, characterized in that the elimination of the hydrogen halide in the alcohol from which the alkoxide originates at 50 to 270 ⁰ C or in dimethyl sulfoxide, an ether, an ester, an amide or tetramethylene sulfone at 50 to 150 ⁰ C is performed.

4. The method according to claim 1 to 3, characterized in that the substituted cyclic hydrocarbon with the acyclic conjugated hydrocarbon at a pressure of 1 to 50 atmospheres and 0 to 300 ⁰ C or, if

\!
c

he-I - | -c

C-

C-

wherein / 1 denotes zero or 1, characterized in that that a substituted cyclic hydrocarbon of the formula

-C

II-

-C

-I-

C-X

C-X '

in a manner known per se with an acyclic conjugated diolefin of the structure

- C = C-C = C-

is condensed and XX 'subsequently from the s (obtained intermediate connection with the help of dii Formation of different double bonds known procedures is split off, with the rest Valences of the substituted cyclic hydrocarbons and the acyclic conjugated diolefin

tireh hydrogen or chlorine or bromine. Pheinl Jer lower alkyl with up to 6 carbon atoms is substituents are saturated and X is hydrogen which is a halogen and X 'is a halogen, preferably chlorine. or a hydroxyl. Carboxyl or "ester" group represents.

The substituted i: \ clic carbon used as starting materials for the present invention : nHydrogen are partly already known! German aislegeschrift 1 124 48S. Dutch exposition 206 724). They can be produced by using cyclopentadiene with a normal <> Run the formula

-C

C-X

Ii -c -— c 1 c-x ·

imsetzt and that one cyclopentadiene with a cyclic unsubstituted olefin of the formula

i i
X-C = C-X '

implements. The value of η in the substituted cyclic hydrocarbon then depends on the molar ratio of the cyclopemadiene to the norbornene compound or to the olefin. To beis; lelsweise to produce a substituted cyclic hydrocarbon in which a substantial proportion has the value η = 1. a molar ratio of cyclopentadiene to norbornene compound in the range from 0.75: 1 to 1.25: 1 or a molar ratio of cyclopentadiene to acyclic substituted olefin in the range from 1.75: 1 to 2.25: 1 is suitable. If, on the other hand, a substituted cyclic hydrocarbon is to be prepared in which η is zero, at least 1.5 mol of acyclic substituted olefin per mole of cyclopentadiene, in particular at least 2.0 mol per mole of cyclopentadiene, is preferably used. It is expedient to use 1.5 to 4 moles per mole of cyclopentadiene. In these reactions, dicyclopentadiene can be used in place of cyclopentadiene, provided that the reaction temperature is kept high enough that the dissociation of the dicyclopentadiene to cyclopentadiene occurs more quickly than vice versa.

If X is a hydrogen atom, then X 'may conveniently be a halogen atom, such as e.g. B. a chlorine atom, represent. Or else X can represent a hydrogen atom and X 'a hydroxyl group, where the double bond is formed by dehydration. Preferably X is a hydrogen aiom and X ' an ester group, especially one derived from a lower alkanoic acid having up to 6 carbon atoms Ester group such as B. an acetate group, or X is hydrogen and X 'is a halogen atom, such as Chlorine. Particularly effective substituted acyclic olefins are Vin>! Derivatives, such as. B. vinyl acetate or Vinyl chloride, in which X 'denotes acetate or chlorine, that from the intermediate compound as acetic acid or hydrogen chloride is eliminated. X and X 'can also be part of an acid anhydride group form as it is obtained ζ B. when maleic anhydride is the substituted olefin. The removal of XX 'can be carried out in various ways. z. B. by P \ rol \ se at a temperature of up to 700 C. catalytically with z. B. a platinum, chrome. Mohbdän-. Tungsten or yanadium catalv.aior. chemically, e.g. B. by removing hydrogen halide m: t of a base, such as El. K.alium-tert.-huio \\ d.

ίο or by removing neighboring halogen atoms with a metal such as B. Zinc: or electro-1 \ lisch, for example by removing neighboring carboxyl groups as carbon dioxide Electrolysis of the dipotassium salt of the dibasic

■ 5 acid. Optionally, X and X 'can be present in the reaction participant to more easily removable atoms b / w. Groups are implemented after the intermediate \ connection has been formed. For example, X can be a hydrogen atom and X 'can be an ester group in the substituted cyclic hydrocarbon: in the intermediate compound, however, the ester group may be converted to a hydroxyl group, which is then removed by dehydration. When a hydrogen halide is eliminated with a base.

² S so the base is preferably an alkali or alkaline earth alkoxide. especially a sodium or potassium alkoxide. Preferred is an alkoxide. Alcohol, especially an alkanol having 4 to 20, preferably 4 to 10 carbon atoms, e.g. B. Sodium iso-octoxide. although the alkali or alkaline earth salt of a di- or trihydric alkanol having up to 20 carbon atoms can also be used. If an alkoxide is used in the elimination reaction, the reaction can be carried out in the alcohol from which the alkoxide is derived. In this case, the temperature is expediently from 100 to 350.degree. C., preferably from 150 to 270.degree. C., in particular from 180 to 250.degree. But it is also possible that an inert solvent, especially a polar solvent such as dimethyl sulfoxide. an ether, e.g. B. diethyl ether or tetrahydrofuran, an ester, e.g. B. dinonyl phthalate, an amide, e.g. B. acetamide. Dimethylacetamide or dimethylformamide, or tetramethylenesulfone may be present, and the elimination reaction may then with a base in the presence of such a solvent at a temperature of 50 to 150 ^{r 1} C are performed. For the elimination of hydrogen halide by means of a base, the pressure expediently has the value that arises in a closed system at the reaction temperature, e.g. B. up to 100 atmospheres, mostly up to 50 atmospheres.

The remaining valences of the substituted cyclic hydrocarbon as well as the acyclic conjugated Diolefins can be formed by hydrogen or by lower alkyl groups with up to 6 carbon atoms, z. B. methyl or ethyl groups, be saturated by chlorine or bromine.

Preferred reactants are 6-chloro-b / w o-acetoxynorbornene- ^. The preferred acyclic conjugated diolefin is isoprene because this leads to the production of a particularly valuable product when reacted with norbornene substituted in the 6-position or disubstituted in the 5- and 6-positions; but other conjugated "diolefins, z. B. butadiene and 2,3-dimethylbutadiene can be used.
The reaction of substituted cyclic carbons

Hydrogen with the acyclic conjugated diolefin can be carried out at an elevated temperature and pressure depending on the kind of the cyclic hydrocarbon as well as the diolefin. Temperatures from 0 to 300 C., preferably from 50 to 250 C. and autogenous pressures, e.g. B. up to 100 atm. preferably from 1 to 50 atm. be used. If norbornyl chloride is a reactant or a product, the preferred temperature is 0 to 180 ° C. for isomerization to give the nortricyclyl derivative. which takes place at higher temperatures should be avoided or reduced to a minimum. The reaction between the substituted cyclic hydrocarbon and the acyclic conjugated diolefin can be carried out in excess of the substituted cyclic hydrocarbon, e.g. B. be carried out with a 2 to S-fold excess of this hydrocarbon over the conjugated acyclic diolefin, or an inert solvent can be present. Appropriately, an aprotic solvent, e.g. B. an ether such as diethyl ether or tetrahydrofuran, an ester such as dinonyl phthalate, an aromatic hydrocarbon such as benzene or xylene, an alcohol such as ethanol, or a cycloparaffin or paraffin such as cyclohexane or n-octane, can be used.

The Diels-Alder reaction can, if appropriate, be carried out in the presence of a catalyst. Suitable catalysts are, for example, strong acids, e.g. B. trichloroacetic acid, nitrogenous bases, ζ. B. trimethylamine and dimethylaniline. Compounds such as 1,3,5-trinitrobenzene and transition metals and transition metal complexes, especially monovalent rhodium complexes, as described, for example, in British patent specification 1 121 642 are written.

With the method described here, cyclic compounds of the general formula

-C

ü
-c

--C — I -hc—

c—

40

45

50

from easily accessible substances such as norbornonyl chloride and an acyclic conjugated diolefin getting produced. The products from the process are useful as termonomers in ethylene-propylene copolymers.

Optionally, mixtures of acyclic conjugated diolefins, e.g., isoprene and 1,3-dimethylbutadiene, as e.g. B. incurred as a refinery distillation stream, can also be used, wherein a mixed product is obtained which is suitable as a comonomer. On the other hand, a similar refinery distillation stream, e.g. B. contains hydrocarbons with 4 to 8 carbon atoms, are treated so that all conjugate contained therein greed servants are removed except for one, whereupon the remaining mixture with one conjugated lhen without further. Cleaning can be used.

the remaining paraffins and / or mono-olefins not interfering with the reaction. For example, such a “concentrated” Raffinsriestrom can contain isoprene as div's only conjugated diene and be suitable for the present invention.

The polycyclic products of the process generally have structures in which the cyclohexene ring in the exo position to the neighboring Norborny I-speaking endo-compound can also be generated. If a norbornene is produced in such a way that vinyl chloride is reacted with cyclopentadiene, and if the norbornene is then reacted with isoprene, an intermediate product is obtained in which the caclohexene ring is almost exclusively in the exo position: the corresponding exo-1,4-endomethylene - 6 - methyllAS.SQlO-hexahydronaphthalene, which is produced by the elimination of HCl from the product , is a particularly valuable polymer intermediate as it has been found that the exo configuration is easier to incorporate into the polymer than the eniio configuration .

The invention is explained in more detail below on the basis of exemplary embodiments.

example 1

Vinyl acetate can be mixed with cyclopentadiene to form norbornenyl acetate according to the method described in the book »Organic Reactions «Vol. IV, p. 92, described processes are implemented.

Isoprene (90 g) and norbornenyl acetate (194 g) were heated ^{to 170 ° C. in an autoclave for 2 hours.} The product was distilled under a pressure of 10 mm, collecting the fraction boiling at 140 to 148 ° C.

This intermediate product was passed through a stainless steel tube at 600 ° C and the product obtained contained 1-4-endomethylene-o-methyl-1,4,5,8,9,10-hexahydronaphthalene (4-methyltricyclo- (6.2 , l, 0 ^{2 "7)} -undecadien-4,9). the composition of the product was determined by nuclear magnetic resonance, mass spectrometry and gas liquid chromatography.

Example 2

Norbornenylchlorid (bp. 50 to 6O ⁰ C at 10 mm pressure) was prepared by 320 g of vinyl chloride and 175 g of dicyclopentadiene were reacted for 3 hours in an autoclave at 190 ⁰ C.

Isoprene (50 ml) and norbornenyl chloride (80 ml) were heated to 170 ° C. in an autoclave for 3 hours. Then became

removed by distillation; Bp 100 ° C / 0.5 mm. The product obtained with the formula

CI

ie
in
Is
ie

ig ic ; n

r- Ά. m ie

nl) he-

(26 g) was treated with potassium tert-butoxide (13.4 g) for 15 minutes heated under reflux at 190 to 200 ° C. and then cooled.

Water was added to the solution and the mixture was extracted with ether. The essential Solution was washed with water, dried and evaporated. The evaporation residue was fractionated distilled. This gave 1,4-endomethylene-6-methyl-1,4,5,8,9,10-hexahydronaphthalene, 80 to 85'C / IOTorr. Through nuclear magnetic resonance it was possible to establish that this product only contained the isomer in which the cyclohexene ring cxo to the norbornean structure. Further fractions, which are at 85 to 1 10 ° C / 10 Torr and 1 10 to 120 C / 10 Torr boiled were also preserved. The latter fraction contained

(49 pieces). Bp 140 to 148 ° C / 15 torr. In the alembic 13.5 parts of deslination residue remained.

A stainless steel autoclave was purged with nitrogen and filled with 224 parts

Ii ',!

example

2-chloro-6-methyl-1,4-endomethylcn-1.3.4,5,8.9.10-hcptahydronaphthalene was made according to the procedure according to the first Tci! of Example 2 made.

Ethylene glycol (30 ml). Sodium hydroxide (10 g) and 20 g of the Hcptahydronaphthalins were in one with Condenser and stirrer-equipped vessel are introduced and heated there for 24 hours Stirred at reflux. After cooling, the contents of the jar were diluted with water and 3 times extracted with ether. The ethereal solution was dried and evaporated. An oil was thus obtained {9 g). 70% of M-endomethylene-ö-methyl-1,4.5.8,9,10-hexahydronaphthalene duration.

Example 4

The parts given are parts by weight.

A stainless steel autoclave was flushed through with nitrogen and filled with 186 parts of dicyclopentadiene and 325 parts of vinyl chloride. The autoclave was then closed and heated to 190 ° C. and held at this temperature for 3 hours. The autoclave was then allowed to cool to room temperature and opened. The unreacted vinyl chloride was allowed to evaporate.

The contents of the autoclave were then introduced into a still and distilled through a metalized, approximately 61 cm long, vacuum jacketed column filled with glass spirals. A first fraction distilled at temperatures up to 5C C, 15 mm Torr and was discarded. Two further fractions were collected, namely norbornenyl chloride (70.5 parts). Bp. 52 C 15 Torr, and

and 40 parts isoprene filled. The autoclave was closed and heated to a temperature of 170 "C and kept at this temperature for 3 hours. Then the autoclave was allowed to cool to room temperature, whereupon its contents are introduced into a still and then through one with glass spirals filled metalized, about 61 cm long column with vacuum jacket was distilled.

13 parts of a temperature up to 118 C / 7 Torr The boiling first fraction was discarded and three more fractions were collected, viz 117 parts of unreacted compound of the formula

/ Y-

egg

Bp. 118 to 135 C / 7 mm (mainly 125 C). 30 parts of a fraction boiling at 135 to 162C7 Torr and 465 parts of a compound of the formula

Mc

wherein one of the groups X and X 'is hydrogen and the other is chlorine. Bp. 162 to 195 C 7 tone (mainly 192 C). 44 parts of the compound of formula

where one of the groups X and X 'is hydrogen and the other is a chlorine atom, were in ei Introduced with a condenser and stirrer provided vessel and under reflux aui a Temperati

heated from 20ffC. 16 parts of potassium tert-butox) were gradually added to the GeR over a period of 30 minutes. When the addition was complete, the contents of the vessel were allowed to cool. The mixture was then poured into water and extracted three times with ether. D.

6s essential extract was made by standing over vnsst free sodium sulfate for 2 hours eetrockn The ether was then evaporated, and the Rüc A vigret was about 61 cm long

10

column distilled. Thus, 13 parts of a were obtained Faction from

Me

Bp. I uO to 190 ° C / 8 torr.

Example 5

Isoprene was made with norbomenyl acetate as in Example 1 implemented. The intermediate product thus obtained was in a nitrogen stream through a ii-clay cream layer passed at 300 "C. The volume of the layer was 30 ecm, the flow rate of nitrogen was 20 l / h, and the contact time of the Acetates in the shift was about 5 seconds. Approximately 20 g of acetate were through the column in 50 to 90 minutes passed through. The composition of the product was determined by nuclear magnetic resonance turbomctric, Mass spectrometric and gas-liquid chromatography determined. Sales of Acetate to M-endomethylene-o-methyl-1,4,5,8,9,10-hydroxahydronaphthalene was 21.8%.

Example 6

ratio Tcmp. Norborncnyl chloride too S isoprene 170 4: 190 ίο ₄ . 210 4: 170 2: 210 2: 170 • 5 4:

time Sld.

Yield to sales volume EMHN *> - Norbornenyl chluiiü, related chlorinated on implemented β / Norborncnyl / · chloride 14.9 94.6 19.5 82.0 23.1 57.4 22.2 95.2 35.8 46.7 23.8 95.0

*) ^ -hcptiihydronaphlhalin.

Example 7

2-chloro-6-methy I-1,4-endomethylcn-1,3,4,5,8,9,10-heplahydronaphthalene was produced as in Example 2.

0.5 mol of the heptahydronaphthalene was heated ^{to 2 (X) 1} C with 1 mol of sodium tert-butoxide in tert-butanol. After 2 hours, 77% of the 2-chlorohydronaphthalene had been converted to 1,4-endomethylene-6-methyl-1, 4,5,8,9,10-hexahydronaphthalene.

Examples 8 to K)

Norbornyl chloride and isoprene were placed in a l-l "Inconei" aulokiav type AE at one temperature

between 170 and 210 C under autogenous pressure In the following examples, norbornenyl-

implemented together. The products were bayed by chloride with the indicated services magnetic resonance and gas-liquid heating are implemented in an autoclave, whereupon the

Analyzed by chromatography. The results obtained reaction product isolated in each case by distillation

were as follows: was.

Bci-
picl Norborncn \ l-
chlond Service reaction time
and temperature C. product Yield*! Sdp.
C. Torr SId 170 8th 256 g (2 months!) 2: 3-dimethyl /
Butadiene. 41 g
(0.5 moles) 20th 170 57.5 g
(55.6%) 161 to 165/6 9 512 g (4MoI) Piperylene. 136 g
(2 moles) 24 170 140 g
(36%) 116 to 130/10 10 256 g (2Moi) Butadiene. 54 g
(I mole) 20th α
(X / 112g
(62%) 120 to 122/10

Eüminienmg of HCl from the Norbornenyl chloride / diene adduct

3.45 g of sodium were mixed with 150 ml of teft-butanol Reacted for 3 hours in a vibrating autoclave at 160 ° C. The autoclave was then cooled and opened, whereupon the norbornenyl chloride / Dier Adduct was entered. Then the autoclave was operated under those given in the table below Conditions reheated. The products were each isolated by distillation.

at
game Adducl Adduct
cinwaagc reaction time
and temperature "C product yield Sdp.
^o C / Torr G Hours. 200 8th 26.8 2 200 14.7 g
(66%) 60 to 70/1 9 <V 20th 2 200 12g
(73.5%) 90 to 95/20 10 Cl
CÄf 46 2 \ / V 23.5 g
(63%) 80 to 82/12

Claims (1)

Piitentan claims: 1. Method of making pol \ cy: hsdien Hydrocarbons of the structure -C C- -C- in which η denotes zero or 1, characterized in that a substituted cyclic hydrocarbon of the formula