SU355795A1 - - Google Patents

Description

METHOD OF OBTAINING MACROCYCLIC COMPOUNDS

This invention relates to a process for the preparation of macrocyclic compounds.

A known method for the preparation of macroscopic compounds by decomposition. When heated above 100 ° C di-or tri-peroxide cyclic ketones of the general formula

.0 (about

where a is 2 or 3;

b is greater than 3, and one of the CI2 groups can be substituted with hydroxyl, halo, alkoxy, acyloxy, carboxy, oxyalkyl, haloalkyl, alkoxyalkyl, carboxyalkyl, hydroxyaryl, haloaryl, alkoxyaryl, acyloxyaryl, carboxyaryl.

However, these peroxides explode spontaneously.

The output of macrocyclic compounds 29-44%.

The purpose of the invention is to reduce the explosion hazard of the process and increase the yield of the target product is achieved by carrying out the process in the presence of an organic solvent, such as benzene, at a 1: 1 -1: 100000 ratio of peroxide to solvent.

The process is preferably carried out at 100-350 ° C and the ratio between the peroxide and solvent is 1: 4-1: 8.

The starting peroxides are dimeric and trimeric type peroxides, for example, dicycloalkylndene and tricyloalkylidene nerexides, and have the general formula

0-0

ten

(SNg) p 5

0-0

or

SDS4 about%

1.l

CS4

where m and n are positive integers from

4 to 17 and above.

They are saturated hydrocarbon cyclic compounds, or peroxides, which can be substituted with alkyl, alkoxy, carbonyl, hydroxyl, halo,

Cyclic peroxides are typically formed by cyclic ketone treatment with hydrogen peroxide and acid. Some dicycloalkylidene peroxides are obtained by treating the corresponding olefin with ozone. The cyclic components can be the same or different molecules, which makes it possible to obtain unmixed and mixed so-called dimensional or dimeric peroxides.

Dicycloalkylidene peroxides in a hydrocarbon solvent decompose when heated to form hydrocarbons and lactones of the general formulas

(Ng) gg1t1

(SNg)

while tricycloalkylidene peroxides decompose, forming the hydrocarbons and lactones of the following General formulas

xc

(SNGNp something

f

(CHg / gn-m

The original peroxides are dissolved in appropriate amounts in a suitable hydrocarbon solvent, for example, decane, benzene, dodecane or nonane.,

The resulting macrocyclic lactones are used as musk or dusty substances in the perfume industry.

Example 1. A solution of 40 g of dicyclohexylidenecyclopentylidane peroxide in 180 ml of decane is heated for 3 hours under reflux at 180 ° C and kept at room temperature overnight. A small amount of the heavy oil was separated by decantation, and the decane was distilled off in a molecular distillation column. Distillation of the product yields 4.22 g (17.2%) of cyclotetradecane, t. Bales. 77-78 ° C / 0.4 LJ, and 6.17 g (22.2%) of cyclopentadecanolide, t. Bale. 114 ° C / 0.5 mm. Both products are identified using IR and NMR spectroscopy and mass spectrometry.

Example 2. A solution of 700 mg of dicyclohexylidene cyclopentylidene peroxide in 10 ml of decane is heated for 2.1 hours with a reflux condenser. The mixture is analyzed and the products are isolated by preparative gas chromatography.

The product yield is determined by calibrating the detector response when using solutions of known authentic substances.

Table 1

Tricyclopentylidene

(Dicyclopentylcyclohexylidene

(,) Dicyclopentylcycloheptylidene

(,) Dicyclohexylidene-3 - methicyclohexylidene

(, 3-methyl in ring B) Dii, iclohexylidene-4 - methicyclohexylidene

(5, 4-methyl in ring B) Dicycloheptylidenecyclopentylidene

(,) Dicycloheptylideclohexylidene

(,) Tricycloheptylidene

() Dicycloheptylide cyclododecanolidene

(, t 11) Tricyclo-octylidene

The output of cyclohexadecane 25%, cycloheptadecanolide-lactone 20%. The identity of the products is proved as in example 1.

In tab. 1 lists the peroxides used, the reaction conditions and the hydrocarbons and lactones produced.

Example 3. A solution of 3.0 g of di- (2-methylcyclohexylidene), so pl. 105-106 ° C, in 60 ml of benzene is heated under reflux in a 200 ml glass vessel designed for high pressure operation of the node to 80 ° C, immediately sealed, heated to 180 ° C and maintained at this temperature 1 hour After cooling, the reaction mixture is a11alized and the products are isolated with preparative gas chromatography.

The yield of 1,2-dimethylcyclodecane is 26.8%, dimethylcycloundecanolide 3%, 6-methylcyclohexanolide 26.4% and 2-methylcyclohexanolide 13.5%. The structure of the products is determined as in Example 2.

Example 4. Pyrolysis of 4 g of tri- (4-methylcyclohexylidene) peroxide, mp. 85 ° C, carried out under the conditions of Example 3 and obtain the products listed in table. 2

table 2

Example 5. Using the same procedures as in example 1, pyrolysis of 580 mg of dicycloheptylidene peroxide in 10 ml of decane was carried out for 1.33 hours.

The yield of cyclodecade is 15%, cyclotridecanolide-lactone is 25% (according to gas chromatography).

Example 6. A solution of 50 g of tricyclohexylidene peroxide in 785 ml of undecaia is heated under reflux for 3 hours at 194 ° C, cooled, washed three times with a saturated solution of carbonate and water, and dried over anhydrous sodium sulfate.

After vacuum distillation of the mixture in a ring Teflon apparatus, 5 g (16.3%) of cyclopentade a, t. Cues are obtained. 84 ° C / 0.5 mm, and 7.12 g (18.4%) of cyclohexadecanolide lactone (dihydroambretolide), t. Bale. 120 ° C / 0.15 mm. The structure of the products is examined as in Example 2. The resulting lactone is very

valuable musk compound for perfumery.

Example 7. The results of the pyrolysis of tricyclohexylide peroxide in various conditions are given in Table. 3

Table 3

ten

20

From the table. 3 data shows that under different conditions the yield of lactone, which is a very valuable musky compound, is quite high.

Example 8. A solution of 43 g of dicyclohexylidene peroxide in 1075 ml of benzene is slowly added dropwise to a column (diameter 1 inch) filled with glass beads (diameter about 1/8 inch) and heated to 233 ° C. During the reaction, nitrogen gas was passed through the column at a rate of 5 ml / min. The temperature of the column is maintained at 230-24U ° C for 3 hours. The pyrolysis product and the solvent are collected in a cold trap placed at the bottom of the column.

A small amount of benzene is removed in a rotary evaporator, the product is distilled in a ring evaporator for distillation, and 5.6 g (237 °) cyclodecane is obtained, t. Bale. 40-48 ° C / 0.5 mm, and 3.5 g (10%) of cycloundecane, t. 58-64 C / 0.5 mm.

The identity of the product is proved as in example 2.

According to the proposed method, macrocyclic dialactones can be obtained from tricycloalkylidene peroxides as mixtures of isomers.

Tricycloalkylidene peroxides are decomposed according to the following scheme:

The resulting products are used as musk compounds. During hydrolysis, they form difunctional alcoholic acids, suitable as monomers in the preparation of polyesters. The subject of the invention is 1. A method for producing macrocyclic compounds by thermal decomposition of diyl or triperoxide cyclic ketones of the general 10 formula where a is 2 or 3; b - more than 3, and one of the groups of LNG can be substituted for hydroxy, halogen, alkoxy.

Example 9. The experiment was carried out as in Example 1.

The yield of products obtained by the decomposition of peroxides tricycloalkedine listed in the table. four.

Table 4 15 acyloxy, car, boxy, o xyalkyl, haloalkyl, alkoxyalkyl, carboxyalkyl, 0 xyaryl, haloaryl, alkoxyaryl, acyloxyaryl, carboxyaryl, at a temperature above 100 ° C, characterized in that the target yield is increased the product, the process is carried out in the presence of an organic solvent, for example, Be1Nzol, taken in relation to the peroxide 1: 1-1: 100000. 2. The method according to claim 1, characterized in that the process is carried out at 100-350 ° C and the ratio between the peroxide and solvent 1: 4-1: 8.