US2010144516A1PendingUtilityA1

Preparation and use of magnesium amides

Assignee: CLOSOSKI GIULIANO CESARPriority: Jan 18, 2006Filed: Jan 4, 2008Published: Jun 10, 2010

Est. expiryJan 18, 2026(expired)· nominal 20-yr term from priority

Inventors:Giuliano Cesar Clososki Christoph Josef Rohbogner Paul Knochel

C07F 3/02C07B 49/00C07F 3/003

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Claims

Abstract

The present application relates to mixed Mg/Li amides of the general formula R 1 R 2 N—Mg—NR 3 R 4 .zLiY (II) wherein R 1 , R 2 , R 3 , and R 4 are, independently, selected from H, substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or silyl derivatives thereof; and R 1 and R 2 together, or R 3 and R 4 together can be part of a cyclic or polymeric structure; and wherein at least one of R 1 and R 2 and at least one of R 3 and R 4 is other than H; Y is selected from the group consisting of F; Cl; Br; I; CN; SCN; NCO; HaIO n , wherein n=3 or 4 and Hal is selected from Ci, Br and I; NO 3 ; BF 4 ; PF 6 ; H; a carboxylate of the general formula R x CO 2 ; an alcoholate of the general formula OR x ; a thiolate of the general formula SR x ; R x P(O)O 2 ; or SCOR x ; or SCSR x ; O n SR x , wherein n=2 or 3; or NO n , wherein n=2 or 3; and a derivative thereof; wherein R X is a substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or derivatives thereof, or H; m is O or 1; and z>1; as well as a process for the preparation of the mixed Mg/Li amides and the use of these amides, e.g. as bases.

Claims

exact text as granted — not AI-modified

1 . A reagent of the general formula
   R 1 R 2 N—Mg—NR 3 R 4   .z LiY  (II)   wherein   R 1 , R 2 , R 3 , and R 4  are, independently, selected from H, substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or silyl derivatives thereof; and R 1  and R 2  together, or R 3  and R 4  together can be part of a cyclic or polymeric structure; and wherein at least one of R 1  and R 2  and at least one of R 3  and R 4  is other than H;   Y is selected from the group consisting of F; Cl; Br; I; CN; SCN; NCO; HalO n , wherein n=3 or 4 and Hal is selected from Cl, Br and I; NO 3 ; BF 4 ; PF 6 ; H; a carboxylate of the general formula R X CO 2 ; an alcoholate of the general formula OR X ; a thiolate of the general formula SR X ; R X P(O)O 2 ; or SCOR X ; or SCSR X ; O n SR X , wherein n=2 or 3; or NO R , wherein n=2 or 3; and a derivative thereof; wherein R X  is a substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or derivatives thereof, or H; and   z&gt;1;   or as adduct with a solvent.   
   
   
       2 . Solution of the reagent according to  claim 1  in a solvent. 
   
   
       3 . Solution according to  claim 2 , wherein the solvent is selected from cyclic, linear or branched mono or polyethers, thioethers, amines, phosphines, and derivatives thereof containing one or more additional heteroatoms selected from O, N, S and P, dibutyl ether, diethyl ether, tert-butylmethyl ether, dimethoxyethane, dioxanes, triethylamine, ethyldiisopropylamine, dimethylsulfide, dibutylsulfide; cyclic amides, cyclic, linear or branched alkanes and/or alkenes wherein one or more hydrogens are replaced by a halogen, urea derivatives, aromatic, heteroaromatic or aliphatic hydrocarbons, hexamethylphosphorus triamide (HMPA), CS 2 ; or combinations thereof. 
   
   
       4 . Solution according to  claim 3 , wherein the solvent is 1,4-dioxane. 
   
   
       5 . Solution according to  claim 3 , wherein the solvent is tetrahydrofuran (THF) or 2-methyltetrahydrofuran. 
   
   
       6 . Solution according to  claim 3 , wherein the solvent is N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), and/or N-butyl-2-pyrrolidone (NBP). 
   
   
       7 . Solution according to  claim 3 , wherein the solvent is N,N′-dimethylpropyleneurea (DMPU). 
   
   
       8 . Solution according to  claim 3 , wherein the solvent is dichloromethane, 1,2-dichloroethane, and/or CCl 4 . 
   
   
       9 . Solution according to  claim 3 , wherein the solvent is benzene, toluene, xylene, pyridine, pentane, cyclohexane, hexane, and/or heptane. 
   
   
       10 . Use of the reagent according to  claim 1  in a reaction with an electrophile. 
   
   
       11 . Use of the reagent according to  claim 1  for the deprotonation of any substrate which can form stabilized or unstabilized carbaniones. 
   
   
       12 . Process for the preparation of a mixed Mg/Li amide comprising reacting in a solvent a primary or secondary amine with a Grignard reagent in the presence of a lithium salt, or with a Grignard reagent complexed with a lithium salt, or reacting in a solvent a primary or secondary lithium amide with a magnesium salt. 
   
   
       13 . Process for the preparation of a reagent having the general formula
   R 1 R 2 N—Mg—NR 3 R 4   .z LiY  (II)   wherein   R 1 , R 2 , R 3 , and R 4  are, independently, selected from H, substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or silicon derivatives thereof; and R 1  and R 2  together, or R 3  and R 4  together can be part of a cyclic or polymeric structure; and wherein at least one of R 1  and R 2  and at least one of R 3  and R 4  is other than H;   Y is selected from the group consisting of F; Cl; Br; I; CN; SCN; NCO; HalO n , wherein n=3 or 4 and Hal is selected from Cl, Br and I; NO 3 ; BF 4 ; PF 6 ; H; a carboxylate of the general formula R X CO 2 ; an alcoholate of the general formula OR X ; a thiolate of the general formula SR X ; R X P(O)O 2 ; or SCOR X ; or SCSR X ; O n SR X  wherein n=2 or 3; or NO n  wherein n=2 or 3; and a derivative thereof; wherein Rx is a substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or derivatives thereof, or H; and   z&gt;1;   comprising   reacting in a solvent R 1 R 2 N—MgX or R 1 R 2 N—MgX.zLiY with R 3 R 4 NLi, or reacting R 1 R 2 NLi and R 3 R 4 NLi with MgX 2 ; and   X is defined as Y above.   
   
   
       14 . Process according to  claim 13 , wherein X and Y are independently or both Cl, Br or I. 
   
   
       15 . Process according to  claim 14 , wherein X and Y are independently or both Cl. 
   
   
       16 . Process according to  claim 13 , wherein z is in the range from 1-5. 
   
   
       17 . Process according to  claim 16 , wherein z is in the range from 1.5-2.5. 
   
   
       18 . Process according to  claim 16 , wherein z is in the range from 1.8-2.2. 
   
   
       19 . Process according to  claim 16 , wherein z is in the range from 1.9-2.1. 
   
   
       20 . Process according to  claim 16 , wherein z is in the range from 1.95-2.05. 
   
   
       21 . Process according to  claim 16 , wherein z is about 2. 
   
   
       22 . Process according to  claim 13 , wherein the Grignard reagent R′MgX.zLiY is iPrMgCl.LiCl. 
   
   
       23 . Process according to  claim 13 , wherein the solvent is selected from cyclic, linear or branched mono or polyethers, thioethers, amines, phosphines, and derivatives thereof containing one or more additional heteroatoms selected from O, N, S and P, dibutyl ether, diethyl ether, tert-butylmethyl ether, dimethoxyethane, dioxanes, triethylamine, ethyldiisopropylamine, dimethylsulfide, dibutylsulfide; cyclic amides; cyclic, linear or branched alkanes and/or alkenes wherein one or more hydrogens are replaced by a halogen; urea derivatives; aromatic, heteroaromatic or aliphatic hydrocarbons; hexamethylphosphorus triamide (HMPA), CS 2 ; or combinations thereof. 
   
   
       24 . Process according to  claim 13 , wherein the solvent is 1,4-dioxane. 
   
   
       25 . Process according to  claim 13 , wherein the solvent is tetrahydrofuran (THF) or 2-methyltetrahydrofuran. 
   
   
       26 . Process according to  claim 13 , wherein the solvent is N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), and/or N-butyl-2-pyrrolidone (NBP). 
   
   
       27 . Process according to  claim 13 , wherein the solvent is N,N′-dimethylpropyleneurea (DMPU). 
   
   
       28 . Process according to  claim 13 , wherein the solvent is benzene, toluene, xylene, pyridine, pentane, cyclohexane, hexane, and/or heptane. 
   
   
       29 . Process according to  claim 13 , wherein the solvent is dichloromethane, 1,2-dichloroethane, and/or CCl 4 .

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