SU642318A1 - Method of obtaining bis-(p-enyl)palladium - Google Patents

Description

one

The invention relates to the field of organomylene organic chemistry, namely to an improved method for producing bis (R.-env) palladium of the general formula I

(VA,

Going - alkyl, metal.

Bis (t-yl) palladium finds use as a catalyst for the oligomerization of 1,3-butadiene, as well as in the preparation of supported catalysts.

The method of producing bis (1C-yl) -yl-yl) palladium of formula I i is that the corresponding alkenylmapichlo d is reduced to interaction with the yenyl palladium chloride in an organic solvent, iprmer, and sulfuric ether Sh.

nj compliance with the optimum yield of bis (f-yl) palladium by the atom method reaches 81%. Used in the synthesis, α-phenyl palladium chloride is obtained by known methods from PdCE2.

The disadvantage of this method for the synthesis of bis (yl) palladium is a two-step process for converting RiCBg to (1-yl) -laladium bns.

The closest to the invention to the technical essence and the achieved result is the method of obtaining bis (it-phenyl) palladium of formula (l), concluded that the corresponding alkenyl magnesium chloride is subjected to interaction with palladium chloride in the medium; sulfuric acid for 6 hours at (-4O) - (-78) C. &) the Bis- (6-yl) palladium run reaches 46% | d |.

The advantage of this method is the one-step production of the target product, but the pellet product is small.

The aim of the invention is to increase the yield of the target product.

This goal is achieved by the described method of obtaining bis (41 ennl) palladium of formula (l), which implies that the corresponding alkenelmagnevyllorvd is reacted with palladium chloride at (7p) - (9O) C, mainly (-7ОV-8O) С in sulfuric medium ether and liquid proanleva. The hc content of propylene in the reversed mixture is 255% v / v.

Synthesis of e "c (ft) palladium is carried out in the following manner,

in a glass reactor equipped with a magnetic stirrer, in an atmosphere of argon, greedy propylene or an ether solution of propylene and palladium chloride is introduced. The reaction mixture is kept for 0.5 h at a given temperature (-7 °) - (-90) C, then with intensive while stirring, an ethereal solution of an alkeneamine nichloride is added to the reaction mixture in small portions over a minute. The reaction mixture becomes dark (dark brown to black). After completion of the reaction, ether and propylene are distilled off from the reactor under vacuum. N-Pentane is introduced into the solution and the suspension of products insoluble in H-Pentane is intensively stirred at room temperature for 5 minutes. The light yellow solution is filtered through a porous filter into a vacuumized ampoule and H-pentane is distilled off under a pony vacuum. temperature. The dry residue is light yellow bis (-ecl) palladium crystals.

The difference between the described method and the known one is that 25-5% by volume of propylene is introduced into the reaction mixture and the reaction is carried out at (-7O) (-90) ° C, preferably (-70) (-80) ° C.

Example. A glass reactor filled with argon, equipped with a stirrer H, thermostatically controlled at (-78) C

is С, - 5.0 g (28.2 mmol) of palladium chloride, 30 ml of sulfuric ether, 5 O ml (25 vol.%) of liquid propylene are introduced and the reaction mixture is stirred for 0.5 h at (-78) С . Then, over 10 minutes, 12 ml are added.

O, 47 N. (56.4 mHEQ) of the ethereal solution of allylmagnesium chloride, stirred for another 4 min, and distilled off the sulfur and ether. H-Pentane (in the calculation of 1OO ml / 5 h of the residue), cooled to (-79) C, was added to the dry residue, and the reaction mixture was vigorously stirred at (-78) C for 20 minutes, the pentane solution was filtered through a porous glass N 4 filter (under argon atmosphere), then N-pentane is distilled off under vacuum of 1O mm Hg. Art. at (-15) C.

The dry residue (3.6 g) is bis (yl) palladium. In the synthesis using propylene with the content of the main product of 99.9%, ether and N -pentane, dried over sodium wire. The yield of the target product is 68% of theoretical, the degree of purity is 99%.

Example 2. A glass reactor filled with argon, equipped with a stirrer and thermostatically controlled at (-8 O) - (-9 o) C (vibrations - temperature in a thermostat (-85)), was introduced 7.08 (40.0 mmol) chloride palladium and 1OO ml of liquid propylene in (5O vol.%) the reaction mixture is stirred for 0.5 h, then 1OO ml (80, O mEq.) O, 8N, ethereal metallic magnesium chloride and stir further for 1 hour. The reaction mixture thus becomes light. 1. color. To the reaction mixture, 20 O ml of N-Pentane cooled to (-78) C is added, the mixture is stirred and cooled to (-78) C and filtered (under argon atmosphere) through a 4-gauge glass filter into a special glass ampoule l The vial is distilled from the ampoule under vacuum, sulfuric ether and H-pentane as in Example 1. The dry residue (7.2 g is the target product. &Amp; Target product flow is 81% of theoretical, purity 99%.

Thus, the proposed synthesis method makes it possible to obtain BCS (L-yl) palladium in one stage with high ylohods of the target product.

Claims (1)

Invention Formula The method of obtaining bis (I-yl) palladium of the general formula I (ft - Rl2Pd, where T is allyl, metal, by reacting the corresponding alkenyl magnesium chloride with anhydrous palladium chloride in the medium ethyl ether at a low temperature, due to the fact that, in order to achieve the yield of the target product, 25-5 O% by volume are introduced into the reaction mixture 5642318b propylene is used at (-7O) -1. Angora testimony of the USSR . (- 90) S.№ 525413,1si. C 07 P 15/00. 1973. Source of .form. The first issues are 2.Kheim, D “seHation. echni attention when examining 6che HochsohuEe fachem.Wbd.s.iQT.