Title of Invention

"METHOD FOR THE PRODUCTION OF GRIGNARD COMPOUNDS"

Abstract A process for the production of at least one Grignard compound, characterized in that magnesium is reacted in a suitable liquid reaction mdium under a protective gas atmosphere with at least one halosubstituted organic compound with microwave irradiation, wherein microwave irradiation proceeds at a power of 100 to 1200 watt, the frequency of the irradiated microwaves is in the range of 850 to 22250 MHz, duration of the reaction amounts to no more than 60 minutes and the reaction proceeds at a temperature of up to at most the boiling temperature of the liquid reaction medium.
Full Text The present invention relates to a process for the production of Grignard compounds, according to which magnesium is reacted in a suitable liquid reaction medium under a protective gas atmosphere with halosubstituted -organic compounds with microwave irradiation.
Over the past few decades, organometallic compounds have proven to be an indispensable reaction component in the synthesis of organic compounds both in the laboratory and in large industrial scale production despite their sometimes high sensitivity to atmospheric oxygen and moisture.
Organomagnesium compounds, which also include so-called Grignard compounds, have gained particular significance. These Grignard compounds may be obtained by reacting magnesium with halosubstituted organic compounds under a protective gas atmosphere in a suitable reaction medium and comprise a strongly polarised magnesium-carbon bond, in which the carbon atom bears the negative charge density, see for example, "Grignard Reagents: New Developments", Herman G. Richey Jr., John Wiley and Sons Ltd, 2000, pages 185 to 275, "Organomagnesium Methods in Organic Synthesis", Basil J. Wakefield, Academic Press, London, 1995, pages 21 to 71 and "Handbook of Grignard Reagents", Gary S. Silverman, Philip E. Rakita, Marcel Dekker, Inc., New York, 1996, pages 53 to 77.
The Grignard compounds therefore readily react as nucleophilic reagents with electrophilic compounds with formation of a new carbon-carbon-bond and are thus suitable




We Claim:
1. A process for the production of at least one Grignard compound, characterized in that magnesium is reacted in a suitable liquid reaction mdium under a protective gas atmosphere with at least one halosubstituted organic compound with microwave irradiation, wherein microwave irradiation proceeds at a power of 100 to 1200 watt, the frequency of the irradiated microwaves is in the range of 850 to 22250 MHz, duration of the reaction amounts to no more than 60 minutes and the reaction proceeds at a temperature of up to at most the boiling temperature of the liquid reaction medium.
2. The process as claimed in claim 1, wherein the magnesium is present in the form of magnesium strip or in multiparticulate form, preferably in the form of chips or powder, particularly preferably in the form of chips.
3. The process as claimed in claim 1 or claim 2, wherein at least one ether compound or a mixture containing at least one ether compound is present as reaction medium.
4. The process as claimed in claim 3, wherein the ether compound is selected from the group consisting of aliphatic ethers, cyclic ethers and aliphatic polyethers.
5. The process as claimed in claim 4, wherein at least one dialkyl ether, preferably diethyl ether, dibutyl ether or a mixture thereof, is present as aliphatic ether.
6. The process as claimed in claim 4 or 5, wherein tetrahydrofuran, 1,4-dioxane or a mixture thereof is present as cyclic ether.
7. The process as claimed in any one of claims 4 to 6, wherein the aliphatic polyether is based on an alkylene glycol, preferably on ethylene glycol.
8. The process as claimed in claim 7, wherein the polyether is selected from the group consisting of ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether(diglyme), triethylene glycol dimethyl ether (triglyme) and mixtures containing at least two of these polyethers.

9. The process as claimed in any one of claims 1 to 8, wherein an aliphatic halogen compound, a cycloaliphatic halogen compound optionally comprising at least one heteroatom in the ring system or an aromatic halogen compound optionally comprising at least one heteroatom in the ring system is used as a halosubstituted organic compound.
10. The process as claimed in claim 9, wherein the aliphatic halogen compound comprises 1
to 10 carbon atoms, preferably 1 to 5 carbon atoms, particularly preferably 1 to 3 carbon
atoms.
11. The process as claimed in claim 9, wherein the cycloaliphatic halogen compound
comprises 3 to 8 carbon atoms.
12. A process as claimed in any one of claims 1 to 11, wherein the halogen compound is
substituted with fluorine, chlorine, bromine or iodine, preferably with chlorine, bromine
or iodine, particularly preferably with bromine or iodine.
13. The process as claimed in claim 9, wherein the aromatic halogen compound used is a
compound of the general formulae I or II,
(Formula Removed)
in which X in each case denotes F, C1, Br or I,
and the substituent R is selected from the group consisting of F, C1, Br, I, a C1-5 alkyl residue optionally at least mono-substituted with fluorine, a C1-5 alkoxy residue, an NO2 residue, and N(R1)2 residue, a CON(R1)2 residue, an SR1 residue, and SOR1 residue, an SO2R1 residue, an SO2N(R12 residue, a residue of the general formulae III to VI
(Formula Removed)
and an aryl or heteroaryl residue, which may optionally be at least mono-substituted with R1, wherein
A and B, identical or different, denote O, S or NH, and preferably both denote O,
the residue R1 in each case denotes a C1-6 alkyl residue, preferably a C1-3 alkyl residue, particularly preferably a methyl or ethyl residue
or - in the case of the general formula III - the two residues R1 as ring members mean the group CH2-CH2 or CH2-CH2-CH2,
the residues R2, R3, R4, R5, R6 and R7, in each case mutually independently, denote H, a C1-6 alkyl residue or an optionally substituted aryl residue and/or an aryl residue optionally comprising a heteroatom, and
the residue R1 is selected from the group consisting of F, C1, Br, I, a C1-5 alkyl residue optionally at least mono-substituted with fluorine, a C1-5 alkoxy residue, an NO2 residue, an N(R1)2 residue, a CONCR1)2 residue, an SR1 residue, an SOR1 residue, an SO2R1 residue, an SO2NCR1)2 residue and a residue of the above-stated general formulae III to VI.
14. The process as claimed in claim 13, wherein X denotes C1, Br or I, preferably Br or I.
15. The process as claimed in claim 13 or 14, wherein the residue R1 denotes a C1.3 alkyl residue, preferably a methyl or ethyl residue.
16. The process as claimed in any one of claims 13 to 15, wherein the residues R2, R3, R4, R5, R6 and R7, in each case mutually independently, denote a C1-3 alkyl residue preferably a methyl or ethyl residue, or an optionally substituted phenyl residue, preferably an unsubstituted phenyl residue.
17. The process as claimed in any one of claims 13 to 16, wherein A and B in each case denote 0.
18. The process as claimed in claim 13, wherein the compound of the general formula II is selected from the group consisting of o-bromoanisole, m-bromoanisole, p-bromoanisole, o-bromobenzotrifluoride, m-bromobenzotrifluoride and p-bromobenzotrifluoride, preferably m-bromoanisole.
19. The process as claimed in claim 13, wherein p-chlorobenzylchloride is used as compound of the general formula I.
20. The process as claimed in any one of claims 1 to 19, wherein the magnesium and the halosubstituted organic compound(s) are used in equimolar quantities.
21. The process as claimed in any one of claims 1 to 20, wherein the protective gas atmosphere is an atmosphere of argon and/or nitrogen.
22. The process as claimed in any one of claims 1 to 21, wherein microwave irradiation proceeds at a power particularly preferably 100 to 250 watt.
23. The process as claimed in any one of claims 1 to 22, wherein irradiation is performed with microwaves of a frequency in the range of 850 to 2250 MHz, preferably in the range 915 ±25 MHz, 2450 ± 13 MHz, 5800 ± 75 MHz or 22125 ± 125 MHz.
24. The process as claimed in any one of claims 1 to 23, wherein the duration of the reaction amounts to preferably no more than 45 minutes and particularly preferably no more than 30 minutes.
25. The process as claimed in claim 1, wherein the reaction proceeds with refluxing of the liquid reaction medium.

Documents:

1911-DELNP-2004-Abstract-(29-12-2010).pdf

1911-DELNP-2004-Claims-(29-12-2010).pdf

1911-DELNP-2004-Correspondence-Others-(04-05-2010).pdf

1911-DELNP-2004-Correspondence-Others-(29-12-2010).pdf

1911-DELNP-2004-Description (Complete)-(29-12-2010).pdf

1911-DELNP-2004-Form-3-(04-05-2010).pdf

1911-DELNP-2004-GPA-(29-12-2010).pdf

1911-DELNP-2004-Petition 137-(29-12-2010).pdf


Patent Number 249855
Indian Patent Application Number 1911/DELNP/2004
PG Journal Number 46/2011
Publication Date 18-Nov-2011
Grant Date 16-Nov-2011
Date of Filing 05-Jul-2004
Name of Patentee GRÜNENTHAL GMBH
Applicant Address ZIEGLERSTRASSE 6, D-52078 AACHEN, GERMANY
Inventors:
# Inventor's Name Inventor's Address
1 BETTINA THADEN, AM GINSTERBUSCH 15, D-52249 ESCHWEILER, GERMANY
2 HEIKE STOLLENWERK, HEIMBACHER STR. 69, D-52385 NIDEGGEN, GERMANY
3 UWE KREBBER, MONSCHAUER STR. 72, B-4700 EUPEN, BELGIUM
PCT International Classification Number C07F 3/02
PCT International Application Number PCT/EP2002/014790
PCT International Filing date 2002-12-28
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 102 00 149.9 2002-01-04 Germany