DD211549A1 - MOUNTING OF MONO ALCOHOLS ON COMPOUNDS WITH BICYCLO (2.2.1) -HEPTEN- (2) STRUCTURE - Google Patents

Abstract

Process for the addition of monoalcohols on compounds with bicyclo (2.2.1) -hepten- (2) structure in the presence of acidic catalysts at 320-400 K. The aim of the invention is the reduction of side reactions and the improvement of the work-up of the reaction products. This is achieved by attaching the monoalcohols to compounds with a bicyclio- (2.2.1) -hepten- (2) structure in the presence of strongly acidic cation exchangers.

Description

VBB Leuna Works "Leuna, 2. 11. 1982

"Walter Ulbricht"

LP 8295 Title of the invention

Addition of monoalcohols to compounds with bicyclo / 2.2.17 heptene (2) structure

Field of application of the invention

The invention relates to a process for the addition of monoalcohols on compounds with 3icyclo / 2.2.1 / hept'en- (2) structure.

Characteristic of the known technical solutions

The addition of alcohols to olefinic double bonds by means of strong acids, such as concentrated sulfuric acid, is known; when attached to cyclic olefins with Bicycle- / 2.2.1 _ / - hepten- (2) structure, monoethers are readily formed. "However, the processes using sulfuric acid have serious disadvantages: lifting reactions occur, and product recovery from an acidic two-phase system is complex, corrosion problems are to solve au and in the wastewater treatment are difficult to cope.

It is further described, alcohols in the presence of solid catalysts such as ζ · 3 · activated bleaching earths at temperatures of 333 to 403 K of dicyclopentadiene / DE-AS 1278431 / or in general on compounds with 3icyclo - / 2.2,1J ⁷ -hepten- (2 )

--System / DE-AS 1291741 / accumulate. These catalysts rapidly lose their catalytic activity. It is expressly pointed out in the literature that in the addition of alcohols to compounds having a bicyclo / 2.2 × 1 / heptene (2) structure, acidic cation exchangers are used instead of catalysts concentrated sulfuric acid are not catalytically active ·

Object of the invention

The aim of the invention is to develop an economically advantageous process for the addition of monoalcohols on compounds with bicyclo / 2.2 "1 / -hepten- (2) structure *

Explanation of the essence of the invention

It was therefore the object of the invention to develop a process which allows monoalcohols to be attached to compounds having a bicyclo / 2.2, i7-heptene (2) structure at high conversion and yields in such a way that no side reactions occur to a greater extent and the work-up the reaction products can be carried out in the simplest way.

This object is achieved by a method for the addition of monoalcohols to compounds with 3icyclo- / 2.2.1_7-hepten- (2) structure in the presence of acidic catalysts at 32O-4OC K according to the invention in that the addition of monoalcohols to monoethers by heterogeneous catalysis in the presence of strongly acidic cation exchangers, wherein the alcohol is used in the reaction with an excess of 2 to 20: 1 moles compared to the compound having bicyclo / 2,2,1-heptene (2) structure *

The cation exchanger used is preferably a styrene-divinylbenzene copolymer having a channel structure which contains, as active groups, sulfonic acid groups in the H.sup. ⁺ -Fo.rm having a total weight capacity of more than 4.sup.-4 meq / g.

The reaction is conveniently carried out so that the cation exchanger in amounts of 3 to 20 %, based

is used on the entire reaction mixture. The mixture of the monoalcohol with a compound having bicyclo / 2.2... 17-epi-2-structure is maintained in the reaction zone in the presence of the cation exchanger at / K to 300 K for a period of at least 5 hours, the reaction being discontinuous can be carried out in the stirring process or continuously in the reaction tube.

Examples

1. In a 2-liter three-necked flask equipped with an intensive condenser, stirrer and dropping funnel, 64Og of methanol (20 moles), 396 g of tricyclo- / 5.2.1.0 ^2-6 -7-decadiene- (3,8) ( 3 moles) and 150 g of Wofatit OK 80. The mixture was refluxed with good stirring for 20 hours.

After cooling, the composition of the reaction mixture was analyzed by capillary gas chromatography. The mixture contained reaction products (except methanol):

2 6

6.9 % unreacted tricyclo- / 5,2,1,0'-7-decadiene- (3,8)

87.2 % 8 (9) -methoxytricyclo- / 5 2.1 2.1.0 ^{2 # 6} 7-dece.ne- (3), (3 components and as lifting products 5.0 % 8 (9) -hydroxytricyclo- / 5.2. 1.0 ² * ⁶ 7-decene (3).

The reaction mixture was worked up by distillation after separating the ion exchanger. After driving off the methanol through a 30 cm column filled with Raschig rings, 304 g of distillate were obtained in the range from 343 to 375 K at 2 mm pressure. In a further distillation of this fraction 273 g of distillate were obtained at 350 to 355 K under 3 mm pressure, corresponding to 54 % yield. The distillate received 97.64 % 8 (9) -methoxytricyclo- / 5.2.1.0 ^{2 #} ^ 7-decene- (3); n _D ²⁵ = 1.4949, d ₄ ²⁰ = 1.009.

2. In a manner analogous to that described in Example 1, 15 moles of ethanol, isopropanol and allyl alcohol were reacted with one mole of tricyclo- / 5.2.1.0 ² · v-decadiene- (3,8). Bs become those shown in the table below Results achieved:

Tricycle "r Destil- oc ολ pure yield

/5.2.1.0^ ^# V- la t ions- η. ° d ^ ^u hey it

decen- (3) experiment in ^ '°

_N G / mm f &

G ₂ H ₅ -O- 87.91 / 4 1.4931 1.002 85 170 32 CH 1 CH-O-105-108 / 10 1.4824 0.976 83 96 25

GH ₂ = CH-CH ₂ -O108-1IO / IO 1.4870 89 194 52

In a 4-liter three-necked flask equipped with an intensive condenser, stirrer and dropping funnel were each 282 g Bicyclo- / 2.2.1. Hepten- (2) (3 moles) with 25 moles of different alcohols in the presence of 200 g of wofatite OK 80 heated for 20 hours under reflux with good stirring, After cooling the reaction mixture and separation of the ion exchanger, a distillative workup was carried out on a filled with Raschig rings 30 cm column. Ea were the from the table below. achieved results:

Bicyclo- Destil- _? r _9f) pure yield

/2.2.17- lations- n _D ° d. ^{υ unit} ^

hepten area in % ^ώ '"

oc / mm

2-methoxy 1 2-ethoxy- 60-62 / 25 1 , 4552 0 , 9420 99 , 47 236 62 2-allyloxy 52-155 / 766 71-72 / 22 1 , 4520 0 919 86 48 196 46 68-70 / 11 1 , 4680 97 10 281 62

Under the conditions given in Example 3, in each case 3 moles of Tetra eye Io - / "6.2.1 ¹ ' ⁸ Q ² ' ⁷ 1 ³ '^ / - dodecene (4) or pentacyclo = / 9.2.1 ^{1 # 11} 0 ^{2 # 10} 1 ^{3 # 9} 0 ⁴ * ^ 7-pentadecadiene- (5.12) with 10 moles each over a period of 25 hours. The results to be seen from the following table were obtained:

distillation range

C / mm

20

¹ D

Purity in

yield

4 (5) methoxy

dodecane 123-127 / 5 1.5109

12 (13) Methoxypentadecen- (5)

161-171 / 8 1,5397

1.0410 99.0

198

1,087 94.0

(4 main components)

Claims (5)

invention claim 1 · A method for the addition of monoalcohols to compounds with bicyclo [2.2.iJ-heptene (2) structure in the presence of acidic catalysts at 320 K to 400 K, characterized in that the addition of the monoalcohols to mono-ethers by heterogeneous catalysis is carried out in the presence of strongly acidic cation exchangers, wherein the alcohol is used in the reaction with an excess of 2 to 20: 1 moles compared to the compound with bicyclo 2.2 2.2 "ij-h.epten (2) structure. 2. The method according to item 1, characterized in that a styrene-divinylbenzene copolymer having a channel structure ange¬; andt is used as the cation exchanger, the active groups sulfonic acid groups in the H ⁺ -form having a total weight capacity of more than 4.4 meq / g having, 3. The method according to item 1 and 2, characterized in that the cation exchanger in amounts of 3 to 20 %, based on the total reaction mixture is used « 4. The method according to item 1 and 2, characterized in that a mixture of a HOnoalkohols with a compound having Bicyclo-f2,2.i] -hepten- (2) structure in the presence of a KatIonenaustauschers at 320 K to 400 K on a Period of at least Held in the reaction zone for 5 hours, wherein the reaction is carried out batchwise in the stirring process or continuously in the reaction tube.