Lithium alkyl aluminates as alkyl transfer reagents

Patent metadata

Field	Value
Publication number	US-11384102-B2
Application number	US-201917312761-A
Country	US
Kind code	B2
Filing date	Nov 28, 2019
Priority date	Dec 11, 2018
Publication date	Jul 12, 2022
Grant date	Jul 12, 2022

Abstract

The invention relates to lithium alkyl aluminates according to the general formula Li[AlR4] and to a method for preparing same, starting from LiAlH4 and RLi in an aprotic solvent. The invention also relates to compounds according to the general formula Li[AlR4] which can be obtained using the claimed method, and to the use thereof. The invention also relates to the use of a lithium alkyl aluminate Li[AlR4] as a transfer reagent for transferring at least one radical R to an element halide or metal halide and to a method for transferring at least one radical R to a compound E(X)q for preparing a compound according to the general formula E(X)q-pRp, where E=aluminium, gallium, indium, thallium, germanium, tin, lead, antimony, bismuth, zinc, cadmium, mercury, or phosphorus, X=halogen, q=2, 3 or 4, and p=1, 2, 3 or 4. The invention also relates to compounds which can be obtained using such a method, to the use thereof, and to a substrate which has an aluminium layer or a layer containing aluminium on one surface.

First claim

The invention claimed is:

1. A method for preparing lithium alkyl aluminates according to the general formula
Li[AlR 4 ]  (I)

wherein
R is selected from the group consisting of a (C1-C10) alkyl radical, a partially or fully halogenated (C1-C10) alkyl radical, a (trialkylsilyl) alkyl radical R A —Si(R B ) 3 , a benzyl radical, a partially or fully substituted benzyl radical, a mononuclear or polynuclear arene, a partially or fully substituted mononuclear or polynuclear arene, a mononuclear or polynuclear heteroarene and a partially or fully substituted mononuclear or polynuclear heteroarene,
wherein
R A is selected from the group consisting of a (C1-C6) alkylene radical and a partially or fully halogenated (C1-C6) alkylene radical,
R B radicals are selected independently of one another from the group consisting of a (C1-C10) alkyl radical, a partially or fully halogenated (C1-C10) alkyl radical and an O—R E alkyl ether radical,

wherein radicals R E are selected independently of one another from the group consisting of a (C1-C10) alkyl radical, a partially or fully halogenated (C1-C10) alkyl radical, a benzyl radical, a partially or fully substituted benzyl radical, a mononuclear or polynuclear arene, a partially or fully substituted mononuclear or polynuclear arene, a mononuclear or polynuclear heteroarene and a partially or fully substituted mononuclear or polynuclear heteroarene,
comprising the step of:
Reacting LiAlH 4 with a compound according to the general formula RLi,
wherein
R is selected from the group consisting of a (C1-C10) alkyl radical, a partially or fully halogenated (C1-C10) alkyl radical, a (trialkylsilyl) alkyl radical R A —Si(R B ) 3 , a benzyl radical, a partially or fully substituted benzyl radical, a mononuclear or polynuclear arene, a partially or fully substituted mononuclear or polynuclear arene, a mononuclear or polynuclear heteroarene and a partially or fully substituted mononuclear or polynuclear heteroarene,
wherein
R A is selected from the group consisting of a (C1-C6) alkylene radical and a partially or fully halogenated (C1-C6) alkylene radical,
R B radicals are selected independently of one another from the group consisting of a (C1-C10) alkyl radical, a partially or fully halogenated (C1-C10) alkyl radical and an O—R E alkyl ether radical,

wherein radicals R E are selected independently of one another from the group consisting of a (C1-C10) alkyl radical, a partially or fully halogenated (C1-C10) alkyl radical, a benzyl radical, a partially or fully substituted benzyl radical, a mononuclear or polynuclear arene, a partially or fully substituted mononuclear or polynuclear arene, a mononuclear or polynuclear heteroarene and a partially or fully substituted mononuclear or polynuclear heteroarene,
in at least one aprotic solvent in a reaction vessel,
wherein a molar ratio LiAlH 4 :RLi is ≥0.25.

2. The method according to claim 1 , wherein R is selected from the group consisting of Me, Et, nPr, iPr, nBu, tBu, sBu, iBu, CH(Me)(iPr), CH(Me)(nPr), CH(Et) 2 , CH(Et)(Me) 2 , CH 2 C 6 H 5 , C 6 H 5 , CH 2 SiMe 3 , CH 2 SiEt 3 , CH 2 Si(Me) 2 (OMe), CH 2 Si(Et) 2 (OEt), CH 2 Si(Me)(tBu)(OMe), CH 2 Si(tBu)(C 6 H 5 )(OtBu) and CH 2 Si(iPr) 2 (OiPr).

3. The method according to claim 1 , wherein the reaction of LiAlH 4 with compound RLi comprises the steps of:
i) providing a solution or a suspension of LiAlH 4 in a first solvent S1,
ii) adding the compound RLi,
wherein during and/or after the addition of RLi, a reaction of LiAlH 4 with the compound RLi takes place.

4. The method according to claim 1 , wherein the compound RLi is added in a form suspended or dissolved in a second solvent S2.

5. The method according to claim 4 , wherein the second solvent S2 is miscible with or identical to the first solvent S1.

6. The method according to claim 4 , wherein the first solvent S1 and the second solvent S2 are selected independently of one another from the group consisting of hydrocarbons, benzene and benzene derivatives.

7. The method according to claim 1 , wherein the reaction of LiAlH 4 with the compound RLi is carried out at an internal temperature T U of the reaction vessel, the internal temperature T U being between −30° C. and 100° C.

8. The method according to claim 3 , wherein an internal temperature T H of the reaction vessel during and/or after the addition of the compound RLi is between −40° C. and 80° C.

9. The method according to claim 1 , wherein the step comprising the reaction of LiAlH 4 with compound RLi is followed by a further step comprising the isolation of Li[AlR 4 ]:
i) as a solution,
comprising Li[AlR 4 ] (I) and the at least one aprotic solvent,
or
ii) as a solid.

10. The method according to claim 1 , wherein isolation comprises a filtration step.

11. A method for preparing compounds according to the general formula
(R)EH 2 (III),
using
a lithium alkyl aluminate according to the general formula Li[AlR 4 ] (I),
wherein
R is selected from the group consisting of a (C1-C10) alkyl radical, a partially or fully halogenated (C1-C10) alkyl radical, a (trialkylsilyl) alkyl radical R A —Si(R B ) 3 , a benzyl radical, a partially or fully substituted benzyl radical, a mononuclear or polynuclear arene, a partially or fully substituted mononuclear or polynuclear arene, a mononuclear or polynuclear heteroarene and a partially or fully substituted mononuclear or polynuclear heteroarene,
wherein
R A is selected from the group consisting of a (C1-C6) alkylene radical and a partially or fully halogenated (C1-C6) alkylene radical,
R B radicals are selected independently of one another from the group consisting of a (C1-C10) alkyl radical, a partially or fully halogenated (C1-C10) alkyl radical and an O—R E alkyl ether radical,

wherein radicals R E are selected independently of one another from the group consisting of a (C1-C10) alkyl radical, a partially or fully halogenated (C1-C10) alkyl radical, a benzyl radical, a partially or fully substituted benzyl radical, a mononuclear or polynuclear arene, a partially or fully substituted mononuclear or polynuclear arene, a mononuclear or polynuclear heteroarene and a partially or fully substituted mononuclear or polynuclear heteroarene,
comprising the steps of:
a) providing a solution of lithium alkyl aluminate according to the general formula Li[AlR 4 ] (I) in at least one aprotic solvent,
b) reacting the solution from step a) with a compound EX3 in a reaction vessel,
wherein
E is selected from the group consisting of phosphorus, antimony and bismuth

and
X=halogen,

and
c) adding a solution or a suspension comprising a hydridic reducing agent in an aprotic solvent S Z ,
wherein
a molar ratio EX 3 :Li[AIR 4 ] (I) is ≥4

and
a molar ratio EX 3 :reducing agent is ≤1.

12. The method according to claim 11 , wherein the hydridic reducing agent is prepared in situ by reacting NaAlH 4 with a glycol ether,
wherein a molar ratio NaAlH 4 :glycol ether is 0.5.

13. The method according to claim 12 , wherein the glycol ether is selected from the group consisting of a monoethylene glycol monoether, a diethylene glycol monoether, a triethylene glycol monoether, a monopropylene glycol monoether, a dipropylene glycol monoether and a tripropylene glycol monoether.

Assignees

• Umicore Ag & Co Kg

Inventors

• Herritsch Susanne
• Sundermeyer Joerg

Classifications

• C07F5/062 Primary

  Al linked exclusively to C · CPC title

• C23C16/20

  Deposition of aluminium only · CPC title

• C07F9/5004

  Acyclic saturated phosphines · CPC title

• C07F19/00

  Metal compounds according to more than one of main groups C07F1/00 - C07F17/00 · CPC title

• C07F9/5068 Primary

  from starting materials having the structure >P-Hal · CPC title