DE1190939B - Process for the preparation of new pi-allyl compounds of metals of III. to VIII. subgroup - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C07f

German class: 12 ο -26/03

Number: 1190 939

File number: St 19116 IVb / 12 ο

Filing date: April 18, 1962

Opening day: April 15, 1965

It was not known and could not be foreseen that it would be possible to create compounds of the transition metals produce in which only one or more π-allyl groups on the transition metal are bound. This was all the more surprising since the transition metals are generally not stable able to form organometallic compounds in which the ligands exclusively over C atoms are bound to the transition metal.

It has now been found that new n- allyl ίο compounds of the metals of the III. to VIII. Subgroup of the Periodic System (transition metals), which exclusively contain one or more allyl groups of the general formula

Method of manufacturing new
π-AUyl compounds of metals
the III. to VIII. subgroup

Applicant:

Study Society Coal m. B. H.,

Mülheim / Ruhr, Kaiser-Wilhelm-Platz 1

Named as inventor:

Dipl.-Chem. Dr. Günther Wilke, Mülheim / Ruhr

R ₁ R3 R ₄

R ₂ -C —C —C -

included bound to the transition metal in the following manner

R ₁ R ₃ R ₄

R <> - O - O - C * -

where in these formulas Me is the transition metal, η is an integer from 1 to the highest valency of the transition metal in question and R ₁ to R _{5 are} identical or different radicals and are hydrogen, alkyl, cycloalkyl, aralkyl or aryl radicals, where R ₁ and R _{1 can} also be closed to form a ring system, can be produced by using anhydrous, partially soluble compounds of the transition metals of III. to VIII. Subgroup of the periodic system in the presence of a liquid, inert reaction medium with exclusion of water and under protective gas at temperatures between -100 and + 100 ° C, preferably at temperatures below 0 ° C, with allyl compounds of main group metals or metals of the II. subgroup of the periodic System implemented, which are optionally generated in situ in a known manner.

Correspondingly, the transition metal compounds used are those which are present in the reaction medium are at least somewhat soluble, although the solubility can be very low. Particularly proven have the halides or acetylacetonates of the transition metals, but can also be any other connections can be used. As organometallic components for the introduction of the allyl radical In particular, the compounds of the alkali and alkaline earth metals come into consideration, but can (I) the corresponding compounds in the same way

of tin or lead as well as boron or aluminum

ao miniums are used. It has also been shown that the organometallic compounds of the last elements in the ranks of the transition metals for the implementation according to the invention suitable, d. i.e., the corresponding metal-Me (II) as organic compounds of zinc or mercury can be used.

The organometallic compounds of the elements mentioned are obtained by known processes, in the simplest case z. B. the allyl magnesium chloride from allyl chloride and magnesium. However, it has been found that in many cases it is not necessary to use the organometallic component to be prepared separately before the conversion with the transition metal compound, rather succeeds desired reaction also if you z. B. crotyl chloride in the presence of the transition metal compound with z. B. Magnesium converts. The necessary magnesium compound is formed intermediately, which, however, reacts directly with the transition metal compound.

Depending on the stability of those produced according to the invention Connection works at temperatures between -100 to + 100 ° C, but come mostly temperatures below 0 ° C in question.

The novel compounds of the transition metals are mostly sensitive to oxygen and moisture Substances, so that all work must be carried out under protective gas. Most of the new ones Compounds are very volatile, this is especially true for the compounds with lower Hydrocarbon residues. Isolation can thus be carried out by distillation or sublimation

509 539/405

3 4

will. In other cases it is advisable to distill off the known bis-methallylnickel of the composition and the desired products with z. B. carbon NiC ₈ H ₁₄ in the form of yellow crystals. Extract the hydrocarbons from the residue. The bond is sensitive to air and must then be stored in the cold as salts accumulating as by-products.
back unsolved. In most cases these are example 4
new compounds well crystallized.

The technical significance of the In 300 cm ^{3 of} absolute ether according to the invention are 12 g =

Transition metal compounds lies in the fact that they = 0.09 moles of anhydrous nickel bromide and 24 g

consistently presented highly effective catalysts for reac- io 1 g-atom magnesium shavings. To this

tions of unsaturated hydrocarbons, in particular the mixture is added dropwise over the course of 6 hours

special 1,3-diolefins and acetylenes represent. 30 g = 0.33 mol of metalallyl chloride in 200 cm ^{3 of} absolute

This is how z. B. the inventively produced lutem ether. A yellow-colored ethereal

Bis-allylnickel very smoothly with butadiene forming a solution from which according to Example 2 or 3 the

of cyclododecatriene- (1,5,9). 15 bis-metallylnickel is isolated. Yield 50 to

60% of theory.
example 1

40 g = 0.18 mol of anhydrous nickel bromide

suspended in 250 cm ^{3 of} absolute ether. The 575 cm ^{3 of} a 0.46 molar solution of AlIyI mixture is cooled to -20 to -25 ° C and 20 magnesium chloride (0.264MoI) in ether are cooled to -80 ° C with stirring over the course of 30 minutes and in the course of of 2 hours with 700 cm ^{s of} a saturated solution (0.6 normal) of a solution of 14 g = 0.087 mol of iron (III) -chlovon allyl magnesium chloride in ether (0.42 mol of rid in 150 cm ^{3 of} ether. The ethereal C ₃ H ₃ MgQ). The reaction starts immediately. The solution turns deep yellow-brown. When done and the solution turns deep yellow. The reaction is warmed to the ether at -30 to -50.degree. C. to 0.degree. C. and the ether is distilled and the reac vacuum is removed. The residue is extracted tion product in vacuo boiled down to -8O ⁰ C in an at - 30 ⁰ C with pentane. The deep brown colored pen cooled template. Last play the Nickelverbin- tanextrakt is on - cooled to 80 ° C, manure separate in this case be deducted from 0.1 to 1 Torr, it is gold-colored crystals from that in a high vacuum heated to the distillation flask in a water bath 30 at - 8O ⁰ C of the last Remains of the solvent at about 40 ° C. The ether will be freed from the reaction product. The crystals are volatile in a high vacuum duct by distillation over a low temperature at 0 ° C. The hitherto unknown column (bp. _20o 0 to 5 ° C) is separated. In the back Tris-allyle iron of the composition FeC ₉ H ₁₅ before. a yellow nickel compound accumulates, yield 10 to 20% of theory.
the last traces of traces at -80 ° C in a high vacuum. The ether can only be freed at a low temperature. The product can be stored for cleaning. At room temperature, they decompose explosively in a high vacuum at 0 to -10 ° C into an explosion on the crystals. The connection is

- 80 ° C cooled template can be sublimated. !insensitive.

A very pure product is also obtained by re-Example 6
crystallize from pentane - 8O ⁰ C. The long 40

yellow needles correspond to the composition

NiC ₆ H ₁₀ and represent the previously unknown iron (III) acetylacetonate. Yield 20% of the

Bis-tt-allylnickel. Yield 40 to 50% of theory.

Theory. The compound ignites immediately in example 7
the air, and is expediently at temperature 45

Doors stored below - 20 ⁰ C, since they are 7.12 g = 0.02MoI cobalt (III) acetylacetonate

slowly decomposes at room temperature. suspended in 100 cm ^{3 of} absolute ether. the

The suspension is cooled to -80 ° C. and set

Example 2 _then Jg _{0 cm} 3 _e j _ner solution (0.5 molar) of AHyI-

20 g = 0.09 mol of anhydrous nickel bromide are added 50 magnesium chloride (0.09 mol). You get one

suspended in 150 cm ^{3 of} absolute ether and a deep orange-colored solution. The green acetylaceto

- 20 ° C with 700 cm ^{3 of} a solution (0.5 normal) of nat slowly disappears. When the reaction is complete, crotyl magnesium chloride (0.35 mol) in ether is removed from the ether at 0.1 to 1 torr and set at -60 ° C. The ethereal solution turns deep yellow. After starting. The residue is at -6O ⁰ C with pentane 4 hours, the ether is extracted at 200 Torr over a 55 and cooled the extract to -8O ⁰ C. Distilled off low-temperature column. Reddish gold-colored crystals are deposited in a high vacuum and 10.7 g of a nickel compound, freed from the last residues of pentane nickel compound in the form of yellow crystals and _{corresponding to the composition of CoC 9} H ₁₅ , sublime in a high vacuum Composition NiC ₈ H ₁₄ and represents the previously unknown tris-allylcobalt and the previously unknown bis-crotyl-60 len. Yield 45 to 50% of theory.

nickel represents. Yield 70% of theory. The connection must also be made at low temperatures

this compound is extremely sensitive to air and must be stored because it decomposes at 0 ° C.

must be stored in the cold. The connection is sensitive to air and

Example ^ vacuum volatile.

The procedure is as in Example 2, except that eispie is used

the nickel compound with a solution of Me- Man works as in Example 6, but one sets

thallyl magnesium chloride. A cobalt (II) chloride is obtained in aus for reaction. During a

Tris-allylcobalt is obtained from the disproportionation reaction next to elemental cobalt. Yield 20% of theory.

Example 9

A suspension of allyl magnesium chloride is produced at 0 ° C. from 20 g = 0.82 g atom of magnesium shavings, 350 cm »of ether and 60 g = 0.79 mol of allyl chloride in 100 cm ^{3 of ether.} The suspension is cooled to -30 ° C. and 28.4 g = 0.18 mol of anhydrous chromium (III) chloride, which has been ground in 150 cm ^{3 of} ether to form a fine suspension, is then added. The chromium (III) chloride disappears and a deep red solution is obtained. The ether is distilled off at low temperature in vacuo and the residue is extracted at 0 ° C. with pentane. The combined pentane extracts are cooled to −80 ° C., deep red, shiny crystals separate out, which after repeated recrystallization _{correspond to the composition CrC 9} O ₁₅ and represent tris-allyl chromium. The compound is sensitive to air and volatile in a vacuum. Yield 50 to 60% of theory.

Example 10

11 g = 0.05 mol of anhydrous nickel bromide are ^{suspended in 50 cm 3 of absolute ether and 500 cm 3 of} a 0.29 n Grignard solution obtained from tin amyl chloride and magnesium are slowly added at -80 ° C. After the reaction pulling the ether in vacuo at a bath temperature of - 30 ° C and then the residue is extracted at -2O ⁰ C with absolute pentane. The yellow-red colored pentane solution is cooled to -80 ° C. 8 g of reddish yellow crystals precipitate. The composition of these crystals corresponds to (C ₆ H ₅ -C ₃ H ₄ ) ₂ Ni.

Example 11

8 g = 0.036 mol of anhydrous nickel bromide are suspended in 20 cm ³ of absolute ether and at - 8O ⁰ C and 250 cm ³ of a 0.44 n-Grignard solution prepared from 3-bromo-octadiene (l, 7) and magnesium is produced, implemented. It is worked up as in Example 10 and after 3 days 1.5 g of yellow crystals which correspond to _{the composition (C 8} H ₁₃ ) _{2 Ni are obtained from the pentane solution at -80 ° C.} From booty: 14% of theory. "

Example 12

6 g = 0.027 mol of anhydrous nickel bromide are ^{suspended in 30 cm 3 of} absolute ether and at -130 ° C with 300 cm ^{3 of} a 0.35 n-Grignard solution made from 3-chlorocyclohexene and magnesium and pre-cooled to - 80 ° C was transferred. The solution turns deep dark. After 10 hours, pulling the ether at 10 ^-3 to 10 ^-4 Torr and a temperature of -8O ⁰ C from. The dark-colored residue is extracted with pentane at -80 ° C. and the pentane solution is then concentrated. After 2 days yellowish crystals can be isolated, which decompose and already at -30 to 4O ⁰ C of the composition (C ₆ H _9), "Ni correspond. The yield of bis - ^ - cyclohexenylnickel is low.

Example 13

6 g = 0.034 mol of palladium chloride are ^{suspended in 30 cm 3 of} absolute ether and 400 cm ^{3 of} a 0.35 n-allyl magnesium chloride solution are added at -80 ° C. After 6 to 10 hours pulling the ether at -8O ⁰ C and 10 ~ ³ to ΙΟ ^"4 Torr from., By sublimation at 10 ~ ⁴ Torr 3.2 g of bis-ji-allylpalladium from the residue in the form of light yellow crystals Yield: about 50% of theory.

Example 14

3g = 0.017 mol of palladium chloride are ^{suspended in 20 cm 3 of} absolute ether and 140 cm ^{3 of} a 0.5 n-methallyl magnesium chloride solution are added at -80 ° C. The procedure is as in Example 13 and 0.36 g of bis-jr-methallylpalladine is obtained in the form of yellow crystals. Yield: 10% of theory.

Example 15

3.6 g = 0.014 mol of anhydrous platinum chloride are ^{suspended in 20 cm 3 of} absolute ether and 140 cm ^{3 of} a 0.42 η solution of allyl magnesium chloride are added at -60 ° C. The ether solution turns reddish yellow. The procedure is as in Example 13 and small amounts of bis -.-z-allylplatinum are obtained in the form of pale yellow crystals.

Example 16

A solution of 22 g = 0.08 mol of molybdenum pentachloride in 550 cm ^{3 of} absolute ether is added dropwise at 20 ° C. to a solution of 0.52 mol of allyl magnesium chloride in 11 ether. The mixture is stirred for 25 hours. Then precipitated magnesium chloride is filtered off and washed with ether until the solution is colorless. The filtrate is freed from ether in vacuo and the residue is ^{extracted with 500 cm 3 of} pentane. The filtered pentane solution is cooled to -80 ° C. and 4 g of black-green colored crystals of the composition (Mo [C ₃ H _g ] ₂ ) _{2 are obtained} . According to the molecular weight determination, the bis-? R ~ allyl molybdenum is dimeric. Yield: 20% of theory.

Example 17

9.85 g = 16.9 mmol of tungsten tabromide are dissolved in 350 cm ^{3 of} absolute ether and added dropwise at 20 ° C. to a solution of 87 mmol of allyl magnesium chloride in 150 cm ^{3 of} ether. The mixture is stirred for 18 hours and then freed from ether in vacuo. The residue is extracted with 300 cm ^{3 of} pentane. The filtered pentane solution is concentrated and the residue at 10 ~ ⁴ Torr and 70 to 75 ° C bath temperature sublimates. 1.2 g of pale brown crystals of composition (C ₃ Hj) ₄ W are obtained. Yield: 20% of theory.

Example 18

1.6 g = 6.24 mmol of nickel acetylacetonate are ^{suspended in 100 cm 3 of} absolute ether. The mixture is stirred at - 8O ⁰ C are slowly added under stirring with a solution of 1.2 g = 25 mmol lithiumallyl in 36 cm ³ of ether. (The lithium allyl solution was prepared by cleaving allyl phenyl ether with lithium, it therefore contained equimolecular amounts of lithium phenolate; see J. Org. Chem., 28, p. 2145 [1963].) A deep yellow colored solution is obtained.

After the reaction has ended, all volatile products are distilled off in a high vacuum. That Distillate contains 0.65 g = 4.65 mmol bis-rc-allylnickel. Yield: 75% of theory.

Example 19

0.5 = 1.95 mmol of nickel acetylacetonate are dissolved in 5 cm ^{s of} benzene and then 1.2 g = 10 mmol of boron triallyl are added. The mixture remains at 20 ° C for 24 hours. A yellow-brown solution is obtained. All volatile products are then distilled off in a high vacuum. The distillate contains 20.4 mg bis-rc-allylnickel. Yield: 7.4% of theory.

Example 20

1.25 g = 8.4 mmol Zinkdiallyl are dissolved in 150 cm ^s ether and then ³ ether added to a suspension of 1.84 g = 0.84 mmol nickel bromide in 50 cm. The solution turns yellow, and once the nickel has been dissolved, distilling all volatile products from at 10 ~ ⁴ Torr. The distillate contains the yellow colored bis-jr-allylnickel. The yield is 10 to 20% of theory.

Example 21

closing dried at 10 ~ ⁴ Torr. The tris-yr-allylvanadin ignites in air and evaporates immediately under inert gas at temperatures from -40 to -30 ⁰ C.

Example 23

4.4 g = 12.5 mmol of manganese (III) acetylacetonate are ^{suspended in 50 cm 3 of} absolute ether and 200 cm ^{3 of} a 0.19 molar solution of magnesium diallyl (38 mmol) at 20 ° C. are added. The suspended manganese acetylacetonate dissolves in the course of the reaction, and a brown-colored reaction solution is obtained. The ether is suctioned off at 1 Torr and the residue is taken up in toluene. Small amounts of insoluble products are removed by filtration. The clear brown-red colored solution contains the π-allyl compound of manganese, which, however, is bound to the magnesium compounds present in the solution at the same time, so that it cannot be separated in pure crystallized form. The presence of a ^ -allyl compound can be seen from the fact that no metallic manganese is deposited during the reaction, as is the case with reactions of Manas ganverbindungen with normal metal alkyls.

23.3 g = 0.1 mol of zirconium tetrachloride are suspended in absolute ether and finely ground in a ball mill. The resulting fine suspension is filled up with absolute ether to 500 cm ^3, at - 80 ° C and then cooled in a mixture of 50 g = 0.5 mol of allyl magnesium chloride and 800 cm "ether, which is also cooled to -80 ⁰ C, added in portions with stirring. The mixture is for 12 hours at - 80 ° C was stirred, filtered at -80 ⁰ C and stripped at 10 ~ ⁴ Torr and -80 ⁰ C from ether. The residue is extracted three times at -40 ° C. with 600 cm ^{3 of} absolute pentane each time. The extracts are also at - 40 ⁰ C and filtered then concentrated in vacuo to about 300 cm ^3. The remaining solution is cooled to - 80 ° C, during which the zircon tetra-Tr-allyl separates out in the form of black-red crystals. The first fraction obtained is 10.2 g = 40% of the theory of an analytically pure product. A further 7 g of zirconium tetra-ti-allyl can be obtained from the mother liquor. Overall yield: 17.3 g = 67.5% of theory.

Example 22

Slowly 8O ⁰ C under vigorous stirring, a solution of 13.55 g = 0.07 mol of vanadium tetrachloride, in 200 cm ³ of absolute pentane dissolved to - to 1400 cm ³ of a solution of allylmagnesium 0,5molaren (0,7MoI), about at so that while the temperature of the mixture - not exceeding 70 ⁰ C. After about 2 hours the mixture is filtered at -8O ⁰ C and then distilled under -6O ⁰ C at 10 ~ ⁴ Torr the ether from. The dry brown residue is extracted with 300 cm ³ of absolute, cooled to ⁰ C -6O pentane four times and the extracts are again at - 6O ⁰ C filtered. The deep dark colored filtrate is halogen-free. It is concentrated at -8O ⁰ C and 10 Torr * to about 100 cm ^3. The tris-ra-allylvanadine separates out in the form of a very finely divided brown crystal powder. The product is washed on the frit with little at -8O ⁰ C chilled pentane and

Claims (4)

Patent claims: 1. Process for the preparation of new π-allyl compounds of the metals of III. until VIII. Subgroup of the Periodic System (transition metals), which exclusively contain one or several allyl groups of the general formula R ₁ R ₃ R ₄ R ₂ -CCCR ₅ I. included bound to the transition metal in the following manner R ₁ R ₃ R ₄
- C- - C- - C- - i \ c Me where in these formulas Me is the transition metal, η is an integer from 1 to the highest valency of the transition metal in question and R ₁ to R _{5 are} identical or different radicals and are hydrogen, alkyl, cycloalkyl, aralkyl or aryl radicals, where R ₁ and i? _{4 can} also be closed to form a ring system, characterized in that anhydrous, partially soluble compounds of the transition metals of III. to VIII. Subgroup of the periodic system in the presence of a liquid inert reaction medium with exclusion of water under protective gas at temperatures between -100 and + 100 ° C, preferably at temperatures below 0 ° C, reacted with allyl compounds of main group metals or metals of the II. subgroup of the periodic system which are optionally generated in situ in a manner known per se. 2. The method according to claim 1, characterized in that the liquid inert reaction 9 10 medium aliphatic, cyclic or aromatic ionic component allyl compounds of the alkali ethers be used. or alkaline earth metals, of zinc or mercury 3. The method according to claim 1 and 2, that silver can be used. characterized in that as connections the Transition metals their halides or acetyl 5 acetonate can be used. Considered publications: 4. The method according to claim 1 to 3, characterized in German Auslegeschrift K 22285 IVb / 12o (marked that as organometallic reac- made known on 25.10.1956). 509 539/405 4.65 © Bundesdruckerei Berlin