DE2257787B2 - Uranium allyl hooks and processes for their production - Google Patents

Description

IUC-CH-CH.

with a compound of the formula HX or X ₂ . wherein X has the meanings given in claim 1.

In the Italian patent specification 869 752, the preparation of uranium-lctraallyl derivatives of the formula

R, R, R ₄

R ₁ - C C - C - R ₅

35

described, wherein R ₁ . R ₂ . Rj, R ₄ and R ₅ , which can be the same or different. Hydrogen atoms, alkyl radicals with 1 to 10 carbon atoms, aryl radicals with 4 to 10 carbon atoms and alkaryl radicals and the dashed line connecting the three carbon atoms indicates the possible delocalization of the valences of the double bond.

A process has now been found for the synthesis of new uranium allyl compounds which themselves have one represent further the subject of the invention and which the formula

H ₂ C-CH

CH ₂ UX ,,

- 4 Il

exhibit. Herein, XCl "or I and mean 11 1 or 2.

The compounds according to the invention can be prepared according to «The following reactions are produced:

(.7-AlIyI) ₄ U -I- ηHX

♦ (.7-AHyI) ₄ "UX" \ - iKAllyl - H)

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2. (.7-AlIyD ₄ U + _Λ X ₂

fto

'(.7-AlIyI) ₄ "UX" -l · H (AlIyD

where HX or X ₂ HCI. HI. Mean Cl ₂ or I ₂ .

The above reactions can be carried out by dissolving the starting uranium tetra-.7-allyl in aliphatic, aromatic and cyclic ethers. Diethylallier. Dibiilylether. Diphenyl ether. Tetrahydrofuran or tetrahydropyran and by adding the amount of HX or X ₂ calculated according to the above reaction equations 1 and 2, dissolved in the same solvent, can be carried out.

The reaction temperature is kept in the range from -78 to +50.degree. The product is filtered through obtained and washed in the filter with solvent still at low temperature.

The isolated compounds are insta tii in air and in moisture and must be handled and stored in an inert gas atmosphere.

The compounds according to the invention can advantageously be used as catalysts in the polymerization or Oligomerization of unsaturated compounds and especially for stereospecific polymerization by Diolefincn. as described in German Patent 2 257 786 can be used.

example 1

8 g (20 mmol) of tetra (. 7-allyl) uranium were dissolved in 100 cm ^{1 of} diethyl ether at -40 ° C. and slowly mixed with 20 mmol of HCl. dissolved in 150αη ^{Λ of} the same solvent, added.

The addition was carried out in about 4 hours at -40 ° C. At the end of the addition the suspension was via a glass frit. which are at the same temperature was cooled, filtered. The precipitate obtained was precooled on the filter three times with about 20 cm 'each Ether washed.

The precipitate was dried in a high vacuum, again at a temperature of -40 C., and a dark-violet crystalline solid was obtained. The yield, calculated on uranium, was 85 "".

Analysis for (C ₁ II ₅ J ₁ UCI:

Calculated ... U 60. C 27.20. H 3.88. Cl 8.92 ",,: found .... U 58.90. C 27.50. II 4.01. Cl 8.85V".

Example 2

The procedure was as in the previous example: 6.03 g (15 mmol) of tetra (. 7-allyl) uranium in 100 cm × ¹ ethyl ether with 15 mmol of Hl were dissolved in 150 cm ^{1 of} ether at a temperature of -35 ° C implemented. After filtration and drying, a black-violet solid was obtained in a yield of 90%.

Analysis for (C ₁ IU) ₁ UI:

Calculated ... U 48.74. C 22.20. H 3.05. 126.01 "/ ,,: found .... LJ 47.50. C 24.00. H 3.20. I 25.60 '! ·;,.

Example 3

The same compound as in Example 2 was prepared starting from U (C ₁ H _{5 I 4} and I ₂ in place of III. 6.8 g (17 mmol) of tetra-allyl urane with the stoichiometric amount of I ₂ implemented in ethyl ether.

After filtration, washing and drying, a solid was isolated which gave the following analysis:

Found ... U 47.30. I 25.80%.

Example 4

It was prepared (.7-C ₁ H ₅ I ₂ UCI _2. In this case the reaction was carried out in tetrahydrofuran in order to reduce the insolubility of the intermediate / u

avoid. 9.5 mmoles of Tclra-allyl-urane, dissolved in 100 cm ^{3 of} THF, were at -60 ° C. with 19 mm of Mo! UCI, dissolved in 90 cm ^{3 of} the same solvent, reacted.

At the end of the addition, 50 cm ^{3 of} chilled ethyl ether was added to the reaction mixture to facilitate the overall discharge of the product.

Ils was filtered, washed with Äthylälher and anschlieiknd with cold pentane and under high vacuum at - dried 30 ^L C.

The yield was 6.5 mmol (nC ₃ H ₅ ), UCl ₂ , which crystallized with 2 molecules of THF.

Analysis for (C ₃ H ₅ ) ₂ UC1 ₂ · 2C ₄ H ₈ O:

Calculated ... U 44.6, C 31.50, H 4.87, Cl 13.30%; found .... U 43.30, C 29.80, H 4.30. Cl 13.4%.

Claims (2)

Patent claims: I. Uranium allyl halides of the formula
~ H, C -CH-CH ₂ ] UX ,, wherein the dashed line representing the three carbon atoms connects, indicating the possible delocalization of the valence electrons, ΧΟΓ or I ~ is and π represents 1 or 2. 2. Process for the preparation of the compounds according to claim 1, characterized in that a uranium tetraallyl derivative is used in a known manner the formula