Method for producing metal organyls

• US 10,640,519 B2
• Filed: 10/30/2018
• Issued: 05/05/2020
• Est. Priority Date: 04/02/2015
• Status: Active Grant

• Current Assignee: Albemarle Germany GmbH (Albemarle Corporation)
• Original Assignee: Albemarle Germany GmbH (Albemarle Corporation)
• Inventors: Wietelmann, Ulrich, Kurth, Christopher, Scherer, Stefan, Rittmeyer, Peter, Stoll, Armin
• Primary Examiner(s): Zucker, Paul A
• Application Number:
  US16/175,243
• Publication Number:
  US 20190062347A1
• Time in Patent Office: 553 Days
• CPC Class Codes: C01B 6/04 Hydrides of alkali metals, alkaline earth metals, beryllium or magnesium; Addition complexes thereof
• CPC Class Codes: C07F 1/00 Compounds containing elements of Groups 1 or 11 of the Periodic Table
• CPC Class Codes: C07F 1/02 Lithium compounds
• CPC Class Codes: C07F 1/04 Sodium compounds
• CPC Class Codes: C07F 3/00 Compounds containing elements of Groups 2 or 12 of the Periodic Table
• CPC Class Codes: C07F 3/02 Magnesium compounds
• CPC Class Codes: C07F 5/066 compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)

Abstract

This invention provides a method for producing organometallic compounds R_nM (M=alkali or alkaline earth element, R=alkyl residue) where n=valence of the metal M- and R=alkyl residue with 2 to 18 C atoms. In the method of this invention, an olefin is hydrometalated in an alkyl methyl ether, or in a solvent mixture containing an alkyl methyl ether, by means of the metal M and in the presence of a hydrogen source and in the presence of a transition metal catalyst, wherein the molar ratio between alkyl methyl ether and metal M is at least 0.01:1 and at most 50:1.

Claims

1. A method for producing organometallic compounds R_nM of the alkali or alkaline earth elements, where R=alkyl residue with 2 to 18 C atoms, characterized in that an α

-olefin is hydrometalated in an aprotic and anhydrous liquid phase comprising an alkyl methyl ether wherein said alkyl methyl ether is selected from the group consisting of dimethyl ether, methyl ethyl ether, methyl propyl ether, methyl butyl ether, methyl pentyl ether, methyl cyclopentyl ether, methyl hexyl ether, by means of (i) the metal M, wherein M=Li, and in the presence of a hydrogen source for providing hydrogen, or (ii) by means of active metal hydrides MH_n in the presence of a halogen or alkoxy compound of the 4^th and 5^th sub group of the periodic table of elements as catalyst, wherein the molar ratio between alkyl methyl ether and metal M is at least 0.01;

1 and at most 50;

1, characterized in that the active metal hydrides MH_n are produced in situ and in the presence of finely dispersed metal M² with a mean particle size D₅₀ of 0.01 to 100 μ

m and a source for hydrogen, wherein

M²=an element of the 3rd main group of the periodic table of elements selected from the group consisting of B, Al, Ga, In;

n=1 or 2, corresponding to the valence of the metal M.

3. The method according to claim 1, characterized in that M² is aluminum.

7. The method according to claim 1, characterized in that the formation of the active metal hydrides occurs in situ at −

20 to 150°

C.

8. The method according to claim 1, characterized in that the formation of the active metal hydrides occurs under an H₂ atmosphere in the pressure range 1-300 bar.

9. The method according to claim 1, characterized in that the metal M is Li.

10. The method according to claim 1, characterized in that the alkyl methyl ether is dimethyl ether.

2. A method for producing organometallic compounds R_nM of the alkali or alkaline earth elements, where an R=alkyl residue with 2 to 18 C atoms, characterized in that an α

-olefin is hydrometalated in an aprotic and anhydrous liquid phase comprising an alkyl methyl ether wherein said alkyl methyl ether is selected from the group consisting of dimethyl ether, methyl ethyl ether, methyl propyl ether, methyl butyl ether, methyl pentyl ether, methyl cyclopentyl ether, methyl hexyl ether, by means of (i) the metal M, wherein M=Li, and in the presence of a hydrogen source for providing hydrogen, or (ii) by means of active metal hydrides in the presence of a halogen or alkoxy compound of the 4th and 5th sub group of the periodic table of elements as catalyst, wherein the molar ratio between alkyl methyl ether and metal M is at least 0.01;

1 and at most 50;

1, characterized in that the active metal hydrides are produced in situ and in the presence of a compound having the general formula M¹_x[M²(A¹_yA²_z)_3+x]b, wherein

M¹=an alkali metal selected from the group consisting of Li, Na, K, Rb, Cs;

an alkaline earth metal selected from the group consisting of Be, Mg, Ca, Sr, Ba, or an element from the group of the rare earths selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu;

x=0 or 1;

M²=an element of the 3rd main group of the periodic table of elements selected from the group consisting of B, Al, Ga, In;

A¹=H or an alkyl group, branched or unbranched, containing 1-18 C atoms, wherein the up to four A groups can be identical or different;

A²=an alkoxy residue OR where R=alkyl with 1-8 C atoms, dialkylamino residue —

NR₂ where R=alkyl with 1-8 C atoms or a halogen from Cl, Br, I;

y=1, 2 or 3, and wherein y+z=3;

b=the valence of M¹;

n=1 or 2, corresponding to the valence of the metal M.

4. The method according to claim 2, characterized in that the compound M¹_x[M²(A¹_yA²_z)_3+x]_b is selected from the group consisting of complex aluminum hydrides, alkylaluminum hydrides, alkylaluminum compounds, aluminum chloride or metal halogen aluminates.

5. The method according to claim 4, characterized in that the complex aluminum hydrides are selected from the group consisting of LiAlH₄, NaAlH₄, Na[H₂AlEt₂];

the alkylaluminum hydrides are diisobutylaluminum hydride;

the alkylaluminum compounds are selected from the group consisting of Me₃Al, Et₃Al or Bu₃Al, and the metal halogen aluminates are selected from the group consisting of LiAlCl₄ or NaAlCl₄.

6. The method according to claim 2, characterized in that the compound M¹_x[M²(A¹_yA²_z)_3+x]_b is used in stoichiometric quantities or in the presence of a source for hydrogen in at least catalytic quantities, wherein the molar ratio of catalyst to M or the active metal hydrides is at least 0.0001:

1 and at most 0.5;

1.

11. The method according to claim 2, characterized in that the metal M is Li.

12. The method according to claim 2, characterized in that the alkyl methyl ether is dimethyl ether.