US3014928A

US3014928A - Wilke

Info

Publication number: US3014928A
Authority: US
Priority date: 1957-04-26
Filing date: 1958-04-23
Publication date: 1961-12-26
Anticipated expiration: 1978-12-26
Also published as: DE1058987B; DE1058987C2

Description

1961 G. WILKE 3,014,928

CYCLODODECADIENE MONOEPOXIDE, AND ITS PRODUCTION FROM CYCLODODECATRIENES Filed April 25, 1958 INVENTOR GUI/THEE WILKE Sta Filed Apr. 23, 1958, Ser. No. 730,339 Claims priority, application Germany Apr. 26, 1957 11 Claims. (Cl. 260-348) This invention relates to cyclododecadiene monoepoxide, and its production from cyclododecatriene.

Belgian patent specification No. 555,180 describes a process which is concerned with the production of cyclododecatri-(l,S,9)-enes concurrently with other cyclic hydrocarbons from butadiene and other diolefines. With the aid of organometallic mixed catalysts, such as have been developed by K. Ziegler and collaborators for the polymerisation of ethylene, it is possible by means of this process to obtain cyclododecatri-(1,5,9)-enes in various configurations and with high yields (namely 8090%) from butadiene, for example. -It has been pointed out in said Belgian patent that these cyclododecatrienes are valuable starting materials for organic syntheses, especially for the production of a,w-difunctional derivatives of n-dodecane.

It is known that cyclic hydrocarbons can be converted by oxidation into difunctional open-chain compounds with the same number of carbon atoms. Such a process has for example been achieved in the oxidation of cyclooctane to suberic acid. These ring-splitting reactions can however only be carried out with good yields if it is possible for the cyclic hydrocarbon to be converted, prior to the splitting reaction proper, into a monofunctional or 1,2-difunctional oxidation product, for example into an alcohol or a glycol, since in this case the splitting reaction takes place preferentially on the carbon atoms already combined with oxygen. Thus, suberic acid is obtained in a high yield from cyclooctanol by means of nitric acid.

Consequently, in the conversion of cyclododecatriene into the a,w-difl.InCiiOI1fll derivatives of n-dodecane, an attempt must be made to convert the triply unsaturated ring in the first reaction stage into a definite derivative with only one oxygen function in the molecule. At first sight the simplest method seems to be the selective hydro genation to cyclododecene, which can then be converted in known manner into cyclododecanol. This process would correspond to the reaction sequence with cyclooctatetraene, which, as indicated by W. Reppe and collaborators, can easily be converted into cyclooctene by selective hydrogenation.

The selective hydrogenation cannot however be carried out with cyclododecatriene, since the latter differs very substantially from cyclooctatetraene by the fact that the double bonds in the molecule are not conjugated double bonds, an arrangement which is essential for the hydrogenation to form a monoolefine, for it is only in this case that the last double bond of the polyoleiine is hydrogenated very much more slowly than the others. When cyclododecatri(1,5,9)-ene is hydrogenated, a mixture of cyclododecene With cyclododecane and cyclododecadiene is always obtained, since the double bonds do not differ, or only differ slightly, in their hydrogenation capacity.

It has now been found that cyclododecatriene can be converted simply with high yields into the desired monofunctional derivative by converting the cyclododccatriene into cyclododecadiene monoepoxide. In accordance with the invention, cyclododecatrienes of any desired configuration, but specially the trans-trans-cis-configuration and the trans-trans-trans-configuration, are oxidised with or- 3,014,928 Patented Dec. 26, 1961 ice when no excess of per compounds is used, the formation velocity of this monoepoxide clearly being very much greater than the formation velocity of the diepoxides or triepoxides. As per compounds, it is possible to use per acids, such as performic acid, peracetic acid, trilluoroperacetic acid, perbenzoic acid or acetaldehyde peracetate.

It is particularly advantageous to use acetaldehyde peracetate, which is formed under certain conditions when acetaldehyde is oxidised and can be utilised in accordance with British Patent No. 735,974 for epoxidation purposes. By using this per-compound, the cyclododecadiene monoepoxide is obtained with a yield higher than and in addition acetaldehyde and acetic acid are recovered. This process can be carried out continuously particularly smoothly.

It is advisable to avoid an excess of per-compounds. The best results are produced when a deficiency of percompounds is used. The oxidation is advantageously carried out at temperatures from 0 to 0, preferably from 20 to 50 C., in a solvent which is inert with respect to per-compounds. Aliphatic or aromatic hydrocarbons, or their halogen or oxygen derivatives, can for example be used as such inert solvents. v

In the process of the invention, high yields of cyclododecadiene monoepoxide are obtained as well as small proportions of the monoacylates of cyclododecadienediol, which are formed due to conversion of the initially formed epoxide by the acid which is present or which is formed. These by-products are however also valuable, since they can easily be converted into the cyclododecanediol, which can be used with equal success for the ring-splitting reaction.

The cyclododecadiene monoepoxide obtained by the process of the invention can be hydrogenated selectively to cyclododecane epoxide or completely to cyclododecanol. The cyclododecanol can be oxidised to cyclododecanone. The cyclododecanone can'in its turn be converted in known manner into its oxime and the latter by Beckmann transformation into the lactarn of w-aminododecane carboxylic acid. It is known that the'lactam is an important initial material for the production of polyamide plastics.

The cyclododecanol can also be split, for example with nitric acid, to form dodecane-1,12-carboxylic acid, which also is an important material for the production of polyamides and polyesters.

The following examples further illustrate the invention.

Example 1 44 g. of 68% peracetic acid are added dropwise over a period of 1 /2 hours to a solution of 134 g. of cyclododecatriene in 462 g. of chloroform, the temperature being kept between 25 and30 C. by cooling. After the dropwise addition is complete, almost the whole of the peracetic acid has reacted. After the reaction mixture has been washed with a bicarbonate solution and the solvent removed, distillation of the residue yields 45.6 g. of cyclododecadiene epoxide, RP. 05 mm, 68-71 C., n 1.5060, as well as unmodified cyclododecatriene. The yield is 97% of the theoretical, based on reacted cyclododecatriene, and 64% of the theoretical, based on peracetic acid.

Example 2 The procedure is as set out in Example 1, but a mixture of glacial acetic acid and acetic acid anhydride (5:1) is used as solvent. The yield is 93% of the theoretical, based on reacted cyclododecatriene, and 72% of the theoretical, based on peracetic acid.

Example 3 8.5 g.=(0.05 mol) of cyclododecatriene, dissolved in 10 cc. of chlorobenzene, are mixed at C. with 250 cc. of a solution of perbenzoic acid in chlorobenzene which titres 14.1 cc. of N/ 10 Na S O per 10 00., this corresponding to 0.35 mol of perbenzoic acid. The solution is slowly heated to room temperature and left to stand for 2 hours, after which it is no longer possible to detect any peracid. The chlorobenzene is distilled oil in vacuo and the residue is fractionated. 3.9 g. of cyclododecadiene epoxide are obtained, this corresponding to a yield of 65% of the theoretical.

Example 4 45.2 g. of acetaldehyde mono-peracetate, dissolved in 140 g. of glacial acetic acid, are added dropwise over a period of 50 minutes to 120 g. of trans-trans-cis-cyclododecatri-(1,5,9)-ene. The temperature is kept below 10 C. The reaction mixture is stirred for another 3 hours and thereafter the solvent is distilled off in vacuo. Fractionation of the residue through a highly effective column at 13 mm. Hg yields 44.4 g. of cyclododecadiene epoxide, RP 13 mm 133.8-1342" C.; i7 :1.5060. The yield is 83% of the reacted cyclododecatriene, or 66.5% based on the acetaldehyde mono-peracetate.

The infra-red spectrum of the epoxide produced is shown on the left hand side of the accompanying drawmg.

Example 5 The procedure is as set out in Example 4, except that trans-trans-trans-cyclododecatri-(1,5,9,)-ene, dissolved in glacial acetic acid, is used for the epoxidation. A similar yield of cyclododecadiene epoxide is obtained; the infrared spectrum of the product, as shown on the right hand side of the accompanying drawing, still gives an indication of the absorption due to a cis-double bond only in the middle position. B.P. mm 71-73" C.; 11 1.4995; M.P. 26-27 C.

Example 6 The procedure set out in Example 4 is used, but ethyl acetate is used as solvent, and the reaction temperature is kept between 25 and 30 C. The reaction is complete after only 1 hour. The yield is 92%, based on reacted cyclododecatriene, and 78% of the theoretical, based on acetaldehyde monoperacetate.

Example 7 The continuous epoxidation of cyclododecatri-(1,5,9)- ene with acetaldehyde peracetate is carried out as follows: A solution of acetaldehyde monoperacetate in ethyl acetate is continuously mixed at 5 to C. with a solution of cyclododecatriene in acetic ester (molar ratio between cyclododecatriene and peracetate 2:1). The cold mixture is introduced by suction into a separating column which is kept at 40-50" C. and which is under a vacuum of 30 to 50 mm. Hg. The separating column serves as reactor. Acetaldehyde, ethyl acetate and the glacial acetic acid which is formed are drawn off through the head of the column. The reaction product and unreacted cyclododecatriene are withdrawn from the lower part of the column and are separated from one another by being re-distilled in vacuo.

This procedure gives the cyclododecadiene epoxide in yields higher than 90% of the theoretical, based on reacted cyclododecatriene. The unreacted cyclododecatriene, and the ethyl acetate and the acetaldehyde are returned to the cycle.

Example 8 The procedure followed is that set out in Example 3, but hexane is used instead of chlorobenzene as solvent. The yield of cyclododecadiene epoxide is 85% of the theoretical, based on reacted cyclododecatriene, and 70% of the theoretical based on perbenzoic acid.

Example 9 215 g. of formic acid are run into vigorously stirred mixture of 1,300 g. of cyclododecatriene and 1,350 g. of 25% hydrogen peroxide. After a time, the internal temperature rises and the temperature is kept below 35 C. by cooling with ice and later with water. The mixture is stirred for 48 hours, whereupon the resulting two layers are separated and the organic layer is washed with water, dilute sodium hydroxide solution and bisulphite solution and dried over CaCl Distillation by means of an efiicient column yields 520 g. of unreacted cyclododecatriene, 846 g. of 1,Z-epoxycyclododecadi-S,9-ene and 12 g. of residue, i.e. a yield of 98% of the theoretical is obtained, with a conversion of 60%.

What I claim is:

1. 1,Z-monoepoxycyclododeca-di-(5,9)-ene.

2. Process for the production of 1,2 monoepoxycyclododeca-di-(5,9)-ene which comprises oxidizing cyclododecatri-(l,5,9)-ene at a temperature between about 0 and 100 degrees C. with an oxidizing agent selected from the group consisting of acetaldehyde, monoperacetate, performic acid, perbenzoic acid and peracetic acid.

3. Process according to claim 2 in which said cyclododecatri-(1,5,9)-ene is in the form of the trans-transsis-isomer.

4. Process according to claim 2 in which said cyclododecatri(l,5,9)-ene is in the form of the trans-transtrans-isomer.

5. Process according to claim 2 in which said oxidizing agent is performic acid.

6. Process according to claim 2 in which said oxidizing agent is peracetic acid.

7. Process according to claim 2 in which said oxidizing agent is trifiuoroperacetic acid.

8. Process according to claim 2 in which said oxidizing agent is perbenzoic acid.

9. Process according to claim 2 in which said oxidation is effected at a temperature between about 20-50 degrees C.

10. Process according to claim 2 in which said oxida tion is effected in the presence of an inert organic solvent.

11. Process according to claim 2 in which said cyclododecatri-(1,5,9)-ene in solution in ethylacetate is mixed with acetaldehyde peracetate at a temperature below about 0 degree C. and thereafter oxidation is elfected by raising the temperature of the mixture to between about 40-50 degrees C.

References Cited in the file of this patent UNITED STATES PATENTS 2,201,200 Pinkey May 21, 1940 2,221,369 Cass Nov. 12, 1940 2,250,445 Bruson July 29, 1941 2,281,253 Susie Apr. 28, 1942 2,351,352 McAllister June 13, 1944 2,359,935 Nudenberg Oct. 10, 1944 2,426,224 Kharasch Aug. 26, 1947 2,438,485 Henne Mar. 23, 1948 2,500,599 Bergsteinsson et al Mar. 14, 1950 2,524,432 Dorough Oct. 3, 1950 2,541,670 Segall Feb. 13, 1951 2,752,376 Julian et al. June 26, 1956 FOREIGN PATENTS 192,907 Austria Nov. 11, 1957 OTHER REFERENCES Findley et al.: JACS, vol. 67, pages 412-414 (1945). Swern: JACS, vol. 69, pages 1692-1698 (1947). Swern: Chem. Reviews, vol. 45, pages 1-68 (1949). Prolog: Helv. Chim. Acta 38, 1955, pp. 1786-94.

Claims

1. 1,2-MONOEPOXYCYCLODODECA-DI-(5,9)-ENE