SU301916A1 - - Google Patents

Description

A method for producing dimers and oligomers of halide-containing bis (cyclopentadienyl) The proposed method relates to the preparation of dimers and oligomers of halo-containing bis (cyclopentadienyl) compounds of the general formula

Wn

where X is chlorine, fluorine, bromine,

R, -H, CH3

RI-CH3, H,. The method consists in the compounds of the general formula

(N) ,,. G,

CH-Y

Y-chj

CONNECTIONS

subjected to interaction with the compounds of Grignard or alkali metal of cyclopentadiene or methylcyclopentadiene when heated to 130 ° C with isolation of the target product by a known technique.

Example 1. Oligomeric a, a - bis (cyclopentadienyl) -2,3,5,6 -tetrachloro-l - xylene. 23 parts of metallic sodium are melted in 220 parts of toluene, finely dispersed and cooled. 3 parts of tertiary butyl alcohol are added and then 72.6 parts of monomeric cyclopentadiene are added dropwise with stirring and external cooling at 40-45 ° C. Stand 4 hours at

20 ° C in nitrogen atmosphere. At 90 ° C, a solution consisting of 149 parts of a, a-2,3,5,6-hexachloro-d-xylene in 500 parts of toluene is introduced at 60 ° C for 2 hours and stirred for the next hour at 90 ° C. Determination of the concentration of chlorine ions by titration indicates the quantitative exchange of nitrogen of chlorine standing in the a-position.

pressure at last for 3 hours at 60 ° C and a pressure of 0.01 Torr. Obtain 124 parts of a light yellow solid resin with m. 135 ° C

Calculated,%: C 58,10; H 3.79; C1 38.11. Found,%: C 57.96; H 3.84; C1 38.18. Molecular weight 950 (average value corresponding to a mixture of dimers and trimers).

For the preparation of the above a, a2, 3,5,6-hexachloro-p-xylene, 500 parts of 2,3,5,6-tetrachloro-i-xylene are dissolved in 4800 parts of carbon tetrachloride. When refluxed (under reflux) and irradiated with ultraviolet light, chlorine is injected until a theoretical amount of PS1 is released. Cool and filter the precipitated crystals; m.p. 177-178 ° C.

Example 2. Oligomeric a, a-bis- (cyclopentadienyl) -2,4,5,6-tetrachloro-z-xylene.

The test was carried out as in Example 1, except that instead of 149 parts a, a-2,3,5,6-hexachloro-p-xylene, 149 parts a, a-2, 4,5,6-hexachloro- m-xylene; m.p. 139 ° C

Obtain 138 parts of a light yellow solid resin with m. 115 ° C.

Calculated,%: C 58,10; P 3.79; C1 38.11. Found,%: C 56.58; H 3.83; C1 38.50. Molecular weight 1150.

For the preparation of a, a-2,4,5,6-hexachloro-jsylene used in this example, the procedure is the same as in example 1, but instead of 2,3,5,6-tert-chloro-l-xylene, they take 2.4 , 5,6-tetrachloro-L4-xylene.

Example 3. Dimeric a, a-bis- (cyclopentadienyl) -3,4,5,6-tetrachloro-o-xylene.

The test was carried out according to Example 1, but instead of 149 parts a, a-2,3,5,6-hexachloro- / g-xylene, 149 parts a were used, a-3,4,5,6-hexachloro-o-xylene. ; m.p. 76-78 ° C. 160 parts of a brown solid resin are obtained with mp. 60 ° C.

Calculated,%: C 58,10; H 3.79; C1 38.11. Found,%: C 56.68; H 3.64; C1 39.9. Molecular weight was found 623. To prepare the applied a, a-3,4,5, 6-hexachloro-o-xylene, all operations were repeated as in Example 1, only instead of 2,3,5,6 tetrachloro-1- xylene take 3,4,5,6-tetrachloro-oxylol.

Example 4. Oligomeric a, a-bis- (cycloheptadienyl) -2-bromo-p-xylene.

The experiment was carried out according to Example 1, but instead of 72.6 parts of cyclopentadiene, 69.5 parts are used, or instead of 149 parts of a, a-2,3,5,6 hexachloro-l-xylene, take 163 parts) a, a-2 tribre-p xylene. 98 parts of a dark-brown solid resin with a softening point of 115 ° C are obtained.

Calculated,%: Br 25.4. Found,%: Br 24.9.

To 92.5 parts of bromine-xylene, 160 parts of bromine are slowly ripped at a bath temperature of 130 ° C and irradiated with ultraviolet light. Upon cooling, a crystalline mass is formed, which, after recrystallization from light gasoline (90-120 ° C), gives colorless crystals of a, a-2-tribre- "- xylene, melting at 90-91 ° C.

Example 5. Oligomeric a, a-bis- (cyclopentadienyl) -2,3,5-trichloro-p-xylene.

The experiment was carried out according to Example 1, but instead of 149 parts of a, a-2,3,5,6-hexachloro-p-xylene, 132.5 parts of a, a-2,3,5-pentachloro-x-xylene were used; m.p. 82-84 ° C. A PO of parts of a light yellow solid resin with a softening point of 107 ° C is obtained.

Calculated,%: C 64.03; H 4.48; C1 31.50. Found,%: C 63.31; H 4.60; C1 31.18. Molecular weight 1140.

Example 6. Oligomeric a, a-bis- (methylcyclopentadienyl) -2,3,5,6-tetrachloro - "- xylene. The experiment was carried out according to Example 1, but instead of 72.6 parts of monomeric cyclopentadiene, 88 parts of monomeric methylcyclopentadiene with a bale were used. 70 ° C (technical mixture consisting predominantly of 2 methyl cyclopentadiene and a smaller fraction of 1 methyl cyclopentadiene). 156 parts of a light yellow solid resin with a softening point are obtained.

Calculated,%: C 60.03; H 4.53; C1 35.44. Found,%: C 59.81; H 4.68; C1 35.22. Molecular Weight 980.

Example 7. Oligomer a, a-bis- (cyclopentadienyl) -2,5-difluoro-p-xylene.

A suspension of cyclopentadiene sodium is prepared according to the proposed method in example 1 from 23 g (1 mol) of sodium, 3 g of tertiary butyl alcohol and 72.6 g (1.1 mol) of monomeric cyclopentadiene. On a glass suction filter, the suspension is washed with 500 ml of toluene from dimeric cyclopentadiene and tertiary butyl alcohol. The sodium cyclopentadiene is dissolved in such an amount of tetrahydrofuran to give 1N solution.

0.615 g (2.91 mmol) a, a-dichloro 2,5-difluoro-xylene is mixed in a 50 ml round flask in a nitrogen atmosphere at room temperature with 6.11 lbl of 1N. solution of cyclopentadiene in tetrahydrofuran. Dichloride immediately reacts and causes a temperature rise of about 8 ° C. The dark violet solution is allowed to stand for 1 hour at room temperature. The solution is slightly acidified with 0.3 ml of glacial acetic acid, and the color changes to light yellow. It is placed in 50 ml of benzene, shaken with 20 ml of water, separated and washed with a solution of benzene twice more, each time with help, and 20 ml of a saturated solution of common salt. The organic phase is dried with calcium chloride and concentrated under reduced pressure at 20 ° C. After 24 hours under vacuum at 20 ° C and 0.1 toro, 0.638 g of a highly viscous brown resin (81% of the theoretical yield) is obtained, which is an oligomer a, a-bis (cyclopentadienyl) -2,5-difluorop-xylene . Found with the help of analysis, the elementary composition of this resin is close to the calculated one.

The resin is converted to a rubber product within 30 minutes at 80 ° C.

If the resin is cured without air for 1 hour at 200 ° C, it is non-melting and solid.

The a, a-dichlor2, 5-difluoro-p-xylene used in this example was prepared as follows.

A. a, a-dihydroxy-2,5-difluoro - - - xylene.

63.2 g (0.265 mol) of 2,3,5,6-tetrafluoroterephthalic acid with mp. 268-271 ° C, dissolved in 450 ml of tetrahydrofuran, is introduced into the solution under ice cooling within 1 hour

40.3 g (1.06 mol) of lithium aluminum hydride in 1200 ml of tetrahydrofuran. Heat and maintain the reaction mixture for

24 hours at return temperature. It is cooled to 10 ° C and carefully mixed with 40 ml of water, then with 40 ml of a 15% sodium hydroxide solution and finally with 120 ml of water. The white precipitate is removed by filtration, washed with 500 ml of tetrahydrofuran and the clear filtrate is concentrated at 60 ° C in vacuo. 37.9 of slightly yellow crystals are obtained. Thin layer chromatography shows a mixture of but less than three substances. In order to isolate one uniform substance, it is introduced into 500 ml of ether, 2.8 g of insoluble portions are removed by filtration and the ether solution is concentrated to объема volume, mixed with 35 ml of pentane and cooled to 10 ° C. And white needles fall out. After double recrystallization from ether-pentane, 3.4 g of fine needles are obtained, mp. 107-109 ° C.

For CaHP2O2.

Calculated,%: C 55.17; H 4.63; F 21.82.

Found,%: C 55.38; H 4.69; F 21.5.

The nuclear resonance spectrum of the obtained compound shows a structure characteristic of a, (x-ligidroxy-2,5-difluoro-p-xylene.

B. a, a-Dichloro-2,5-difluoro-d-xylene. Into the mix

25 g of phosphorus pentachloride and 25 g of phosphorus oxychloride are introduced under ice cooling, 3 g

triethylamine. Then a solution of 2.2 g of a, a-dihydroxy-2,5-difluoro-p-xylene in 10 ml of carbon tetrachloride is added. Within 2 hours, heated to 70 ° C. It is cooled, poured onto ice and introduced into benzene. The benzene solution is washed with an aqueous solution of sodium carbonate and then dried with calcium chloride. After evaporation of the solvent, the residue is repeatedly recrystallized from methanol water. 1.85 g of thin, colorless needles are obtained, mp. 62.5-64.5 ° C.

For SvbSyRa.

Calculated,%: C 45.51; H 2.87; F 18.00.

Found,%: C 45.31; H 3.13; F 17.1.

Subject invention

The method of producing dimers and oligomers of halo-containing bis (cyclopentadienyl) 20 compounds of the general formula

(HI

25

where X is chlorine, fluorine, bromine;

RI is H, CH3;

Rl-CH3, H;

/ g 1-4,

characterized in that the halide compounds of the general formula

(N) 4.n

.r.jl- / H a Y

f bJTir, Y

 Nc-i - /

(3C) n

where X is chlorine, fluorine, bromine;

45 Y is chlorine or bromine,

subjected to interaction with the compounds of the Grignard or alkali metal cyclopentadiene or methylcyclopentadiene when heated to 130 ° C with the release of the target

50 product known reception.