Hydrocarbon-soluble halogen and thiolate/magnesium exchange reagents

Patent metadata

Field	Value
Publication number	US-11236113-B2
Application number	US-201816651790-A
Country	US
Kind code	B2
Filing date	Sep 20, 2018
Priority date	Sep 27, 2017
Publication date	Feb 1, 2022
Grant date	Feb 1, 2022

Abstract

The invention relates to hydrocarbon-soluble halogen or thiolate/magnesium exchange reagents of the general formulaR1MgR11-n(OR3)n.LiOR2.(1−n)LiOR3.aDonorin which: R1 is a C1-C8 alkyl and OR2 as well as OR3 are same or different and represent primary, secondary, or tertiary alkoxide residues having 3 to 18 carbon atoms, wherein R2 and/or R3 can for their part contain an alkoxy substituent OR4; a assumes a value of 0 to 2, n assumes a value between 0 and 1, and the donor is an organic molecule containing at least 2 nitrogen atoms.

First claim

The invention claimed is:

1. Hydrocarbon-soluble exchange reagents of the general formula:
R 1 MgR 1 1-n (OR 3 ) n .LiOR 2 .(1 −n )LiOR 3 .a Donor
wherein R 1 is selected from the group consisting of isopropyl (i-Pr), n-butyl (n-Bu), sec-butyl (s-Bu), tert-butyl (t-Bu) and n-hexyl (n-Hex) and OR 2 and OR 3 are each independently selected from the group consisting of:
a) tert-alkoxy,
b) sec-alkoxy,
c) primary alkoxy OCH 2 CHR 4 R 5 , having 3 to 12 carbon atoms, wherein the alkoxy residue has a branch at position 2 relative to the O-function and R 4 and R 5 independently represent alkyl radicals having 1 to 8 carbon atoms, and
d) alkoxy, containing another alkoxy function, of the general formula O(CHR 6 ) b OR 7 wherein R 6 =H or an alkyl radical having 1 to 6 carbon atoms, which is either linear or has a branch at position 3 or higher relative to the O-function, R 7 is a linear or branched alkyl radical having 2 to 12 carbon atoms, and b=an integer from 1 to 4;
wherein R 2 and/or R 3 contain an alkoxy substituent OR 4 , a has a value of 0 to 2, n has a value from 0 to 1, and the Donor is an organic molecule containing at least 2 nitrogen atoms.

2. The hydrocarbon-soluble exchange reagents according to claim 1 , characterized in that the donor is a diamine or a triamine, wherein a has a value between 0.5 and 1.5 and n has a value of 0 or 1.

3. The hydrocarbon-soluble exchange reagents according to claim 1 , characterized in that the hydrocarbon-soluble exchange reagents are present as solutions having a concentration of at least 0.5 mol/kg in relation to Mg in a hydrocarbon or hydrocarbon mixture, wherein the solution contains 1 wt % or less of an ethereal solvent.

4. The hydrocarbon-soluble exchange reagents according to claim 1 , characterized in that the hydrocarbons are selected from the group consisting of aromatics and aliphates.

5. The hydrocarbon-soluble exchange reagents according to claim 1 , characterized in that R 1 is exchanged for the aromatic residue Ar or HetAr by reacting with electron-rich halogen aromatics (Hal-Ar), or halogen heteroaromatics (Hal-HetAr), wherein Hal=Cl, Br, or I, or aryl thiolates R 8 S—Ar, or hetero aryl thiolates R 8 S-HetAr, wherein R 8 =alkyl, aryl, or phenyl.

6. A method for preparing the hydrocarbon-soluble exchange reagents according to claim 1 , characterized in that a dialkoxy magnesium compound R 2 O—Mg—OR 3 is reacted with (n+1) equivalents of an alkyl lithium compound R 1 Li in a hydrocarbon-containing solvent or solvent mixture, wherein: R 1 is selected from the group consisting of isopropyl (i-Pr), n-butyl (n-Bu), sec-butyl (s-Bu), tert-butyl (t-Bu) and n-hexyl (n-Hex),
n has a value of 1 or 0, and
OR 2 and OR 3 are each independently selected from the group consisting of:
a) tert-alkoxy,
b) sec-alkoxy,
c) primary alkoxy OCH 2 CHR 4 R 5 having 3 to 12 carbon atoms, wherein the alkoxy residue has a branch at position 2 relative to the O-function and R 4 and R 5 independently represent alkyl radicals having 1 to 8 carbon atoms, and
d) alkoxy residue, containing another alkoxy function, of the general formula O(CHR 6 ) b OR 7 wherein R 6 =H or an alkyl radical having 1 to 6 carbon atoms, which is either linear or has a branch at position 3 or higher relative to the O-function, R 7 is a linear or branched alkyl radical having 2 to 12 carbon atoms, and b is an integer from 1 to 4.

7. A method for preparing hydrocarbon-soluble exchange reagents according to claim 1 , characterized in that a dialkyl magnesium compound R 1 —Mg—R 9 is reacted, for n=1, with one equivalent alcohol R 3 OH and one equivalent of a lithium alkoxide compound R 2 OLi, or, for n=0, with a total of two equivalents of the lithium alkoxide compounds R 2 OLi and/or R 3 OLi in a hydrocarbon-soluble solvent or solvent mixture, wherein:
R 1 is selected from the group consisting of isopropyl (i-Pr), n-butyl (n-Bu), sec-butyl (s-Bu), tert-butyl (t-Bu) and n-hexyl (n-Hex), and
OR 2 and OR 3 each are independently selected from the group consisting of:
a) tert-alkoxy,
b) sec-alkoxy,
c) primary alkoxy OCH 2 CHR 4 R 5 , having 3 to 12 carbon atoms, wherein the alkoxy residue has a branch at position 2 relative to the O-function and R 4 and R 5 independently represent alkyl radicals having 1 to 8 carbon atoms,
d) alkoxy residue, containing another alkoxy function, of the general formula O(CHR 6 ) b OR 7 wherein R 6 =H or an alkyl radical having 1 to 6 carbon atoms, which is either linear or has a branch at position 3 or higher relative to the O-function, R 7 is a linear or branched alkyl radical having 2 to 12 carbon atoms, and b is an integer from 1 to 4, and

R 9 is any alkyl group having 1 to 8 carbon atoms and R 9 is either the same as, or different from, R 1 .

8. A method for preparing hydrocarbon-soluble exchange reagents according to claim 1 , characterized in that a dialkyl magnesium compound R 1 —Mg—R 9 is reacted with one equivalent of a dialkoxy magnesium compound R 5 O—Mg—OR 3 in a hydrocarbon-containing solvent or solvent mixture, and 0.5 to 1.5 equivalents of an alkyl lithium compound R 2 OLi are added to this reaction mixture, wherein:
R 1 is selected from the group consisting of isopropyl (i-Pr), n-butyl (n-Bu), sec-butyl (s-Bu), tert-butyl (t-Bu) and n-hexyl (n-Hex), and
OR 2 and OR 3 each are independently selected from the group consisting of:
a) tert-alkoxy,
b) sec-alkoxy,
c) primary alkoxy OCH 2 CHR 4 R 5 , having 3 to 12 carbon atoms, wherein the alkoxy residue has a branch at position 2 relative to the O-function and R 4 and R 5 independently represent alkyl radicals having 1 to 8 carbon atoms, and
d) alkoxy residue, containing another alkoxy function, of the general formula O(CHR 6 ) b OR 7 wherein R 6 =H or an alkyl radical having 1 to 6 carbon atoms, which is either linear or has a branch at position 3 or higher relative to the O-function, R 7 is a linear or branched alkyl radical having 2 to 12 carbon atoms, and b is an integer from 1 to 4.

9. The method for preparing hydrocarbon-soluble exchange reagents according to claim 6 , characterized in that equivalents of a donor are added to the reaction mixture from synthesis a in relation to Mg, wherein the donor is a diamine or a triamine and a has a value of 0.5 to 1.5.

10. The method for preparing hydrocarbon-soluble exchange reagents according to claim 6 , characterized in that only hydrocarbon-based solvents are used.

11. A process comprising reacting the hydrocarbon-soluble exchange reagents according to claim 1 with halogenated or thiolate-functionalized aromatics or heteroaromatics of the general formulas Hal-Ar, Hal-HetAr, R 9 S—Ar, or R 9 S-HetAr wherein R 9 =alkyl or aryl and reacting electrophiles with the metalated intermediates Ar—Mg—OR 3 .LiOR 2 .aDonor, HetAr—Mg—OR 3 .LiOR 2 .aDonor, Ar 2 Mg.LiOR 2 .LiOR 3 .aDonor and HetAr 2 Mg.LiOR 2 .LiOR 3 .aDonor for CC or CN coupling reactions or addition reactions.

12. The process of claim 11 wherein the halogenated or thiolate-functionalized aromatics or heteroaromatics have one or several functional groups selected from the group consisting of F, Cl, Br, CN, CO 2 R, OR, OH, NR 2 , NHR, NH 2 , PR 2 , P(O)R 2 , CONR 2 , CONHR, SR, SH, CF 3 , NO 2 .

13. A process comprising reacting the hydrocarbon-soluble exchange reagents according to claim 1 in exchange reactions with electron-rich aromatics.

14. The process of claim 12 wherein the electron-rich heteroaromatics are selected from the group consisting of pyrroles, furans, thiophenes, oxazoles, isoxazoles, thiazoles, isothiazoles, imidazoles, benzimidazoles, triazoles, indazoles, and

Assignees

• Albemarle Germany Gmbh
• Univ Muenchen Ludwig Maximilians

Inventors

• Knochel Paul
• Ziegler Dorothée
• Simon Meike

Classifications

• C07B49/00

  Grignard reactions · CPC title

• C07C41/22

  by introduction of halogens; by substitution of halogen atoms by other halogen atoms · CPC title

• C07F3/02 Primary

  Magnesium compounds · CPC title

• C07C41/14

  by exchange of organic parts on the ether-oxygen for other organic parts, e.g. by trans-etherification · CPC title

• C07F1/02

  Lithium compounds · CPC title