US2006128996A1PendingUtilityA1
Compositions containing Ionic liquids and uses thereof, especially in organic synthesis
Est. expirySep 26, 2022(expired)· nominal 20-yr term from priority
B01J 31/0288C07B 37/02B01J 31/30C07B 37/12B01J 31/04C07C 67/347B01J 2231/4211B01J 2231/326B01J 31/0224C07C 2602/42C07C 67/03B01J 2231/341B01J 2231/4261C07B 37/04B01J 31/0239B01J 31/0281B01J 2231/4266C07C 67/343
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Claims
Abstract
The invention relates to the use of an ionic liquid as a matrix liquid for organic synthesis in a homogeneous phase on a soluble medium, said ionic liquid being present in the form of a liquid or solid at room temperature, having formula A 1 + X 1 − , 1 + representing a functional or non-functional cation or a mixture of cations wherein none of said cations are functional or at least one of the cations is functional, and X 1 − a functional or non-functional anion or a mixture of anions wherein none of the anions are functional or at least one of the anions is functional.
Claims
exact text as granted — not AI-modified1 - 32 . (canceled)
33 . A method of organic synthesis in homogeneous phase on soluble support, without volatile organic solvent, comprising the use of an ionic liquid, as liquid matrix, said ionic liquid being presented in liquid or solid form at ambient temperature, of formula A 1 + X 1 − , A 1 + representing a cation, functional or non-functional, or a mixture of cations in which either none of the cations is functional or at least one of the cations is functional, and X 1 − an anion, functional or non-functional, or a mixture of anions in which either none of the anions is functional or at least one of the anions is functional.
34 . The method of claim 33 , characterized in that A 1 + represents a non-functional cation or a mixture of non-functional cations and X 1 − a non-functional anion or a mixture of non-functional anions.
35 . The method of claim 33 , characterized in that
A 1 + represents a functional cation or a mixture of cations at least one of which is functional, and/or X 1 − represents a functional anion or a mixture of anions at least one of which is functional, said functional cations and functional anions corresponding to an ionic entity, namely cationic or anionic respectively, linked to at least one function F i , F i varying from F 0 to F n , n being an integer varying from 1 to 10.
36 . The method of claim 33 , for the preparation of a stable composition containing in solution:
at least said ionic liquid of formula A 1 + X 1 − , playing the role of liquid matrix and, at least one functionalized salt (salt with a dedicated task), in particular functionalized onium salt, of formula A 2 + X 2 − , as reaction support, the functionalized salt, in particular the functionalized onium salt, being dissolved in the liquid matrix, in order to form a homogeneous phase, A 1 + representing a non-functional cation or a mixture of cations in which none of the cations is functional, and X 1 − representing a non-functional anion or a mixture of anions in which none of the anions is functional, A 2 + representing a cation, functional or non-functional, or a mixture of cations in which none of the cations is functional or in which at least one of the cations is functional, and X 2 − representing an anion, functional or non-functional, or a mixture of anions in which none of the anions is functional or in which at least one of the anions is functional, provided that A 2 + and/or X 2 − represent(s) or comprise(s) a functional cation and a functional anion respectively, said functional cations and functional anions corresponding to an ionic entity Y—, namely cationic Y + — or anionic Y − — respectively, linked, optionally via an L arm, in particular an alkyl group comprising 1 to 20 carbon atoms, to at least one function F i , F i varying from F 0 to F n , n being an integer varying from 1 to 10, the functional cation being representable in the form Y + -L-F i , and the functional anion in the form Y − -(L) k -F i , k being equal to 0 or 1, and the functional anion possibly representing, when k is equal to 0, a single anion, corresponding to Y − —F i , in particular chosen from: OH − , F − , CN − , RO − or RS − , R representing an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms.
37 . The method of claim 35 , for the preparation of a stable composition containing in solution:
at least one first part of said ionic liquid of formula A 1 + X 1 − , the cation and/or the anion of which correspond(s) to an ionic entity linked to one or more initial functions F 0 , playing the role of liquid matrix, and at least one second part of said ionic liquid of formula A 1 + X 1 − , in which said initial function or functions Fo are converted into first novel functions, conferring upon said second part of said ionic liquid the role of functionalized salt and of reaction support, the functionalized salt and the liquid matrix forming a homogeneous phase, the abovementioned first novel functions of the second part of said ionic liquid being capable of being converted subsequently into other functions, without affecting the initial function or functions Fo of the first part of said ionic liquid.
38 . The method of claim 36 , characterized in that the A 2 + cation and/or the X 2 − anion of the functionalized salt or salts, corresponding to a Y— ionic entity linked to at least one function F i , are immobilized in the liquid matrix and cannot be extracted from the liquid matrix by standard extraction means, in particular by solvent, and in which the function(s) F i of the functionalized salt or salts can be converted at the end of at least one reaction resulting from the addition of at least one reagent to said composition.
39 . The method of claim 38 , characterized in that several functionalized salts are immobilized.
40 . The method of claim 36 , characterized in that the A 2 + cation is functional.
41 . The method of claim 36 , characterized in that the X 2 − anion is functional.
42 . The method of claim 36 , characterized in that A 2 + and X 2 − are functional.
43 . The method of claim 33 , characterized in that:
either the ionic liquid of formula A 1 + X 1 − is solid at ambient temperature and is liquefiable within a temperature range from approximately 25° C. to approximately 250° C., in particular from approximately 30° C. to approximately 150° C., and the A 2 + X 2 − functionalized salt is solid at ambient temperature and is soluble in the liquefied A 1 + X 1 − ionic liquid, in order to form a homogeneous phase, or the ionic liquid of formula A 1 + X 1 − is solid at ambient temperature and is liquefiable within a temperature range from approximately 25° C. to approximately 250° C., in particular from approximately 30° C. to approximately 150° C., and the A 2 + X 2 − functionalized salt is liquid at ambient temperature, and is miscible with the liquefied A 1 + X 1 − ionic liquid, in order to form a homogeneous phase, or the A 1 + X 1 − ionic liquid is liquid at ambient temperature and the A 2 + X 2 − functionalized salt is liquid at ambient temperature and miscible with the A 1 + X 1 − ionic liquid, in order to form a homogeneous phase, or the A 1 + X 1 − ionic liquid is liquid at ambient temperature and the A 2 + X 2 − functionalized salt is solid at ambient temperature and is soluble or partially soluble in the A 1 + X 1 − ionic liquid within a temperature range from approximately 25° C. to approximately 250° C., in particular from approximately 30° C. to approximately 150° C., in order to form a homogeneous phase.
44 . The method of claim 37 , characterized in that:
either the ionic liquid of formula A 1 + X 1 − is liquid at ambient temperature, or the ionic liquid of formula A 1 + X 1 − is solid at ambient temperature and is liquefiable within a temperature range from approximately 25° C. to approximately 250° C., in particular from approximately 30° C. to approximately 150° C.
45 . The method of claim 33 , characterized in that the ionic liquid of formula A 1 + X 1 − , playing the role of liquid matrix, has a viscosity less than or equal to approximately 1500 cp (15 N.s/m 2 ), in particular less than approximately 500 cp (5 N.s/m 2 ) and preferably less than approximately 200 cp (2 N.s/m 2 ).
46 . A stable composition containing in solution:
at least said ionic liquid of formula A 1 + X 1 − , playing the role of liquid matrix and, at least one functionalized salt (salt with a dedicated task), in particular functionalized onium salt, of formula A 2 + X 2 − , as reaction support, the functionalized salt, in particular the functionalized onium salt, being dissolved in the liquid matrix, in order to form a homogeneous phase, A 1 + representing a non-functional cation or a mixture of cations in which none of the cations is functional, and X 1 − representing a non-functional anion or a mixture of anions in which none of the anions is functional, A 2 + representing a cation, functional or non-functional, or a mixture of cations in which none of the cations is functional or in which at least one of the cations is functional, and X 2 − representing an anion, functional or non-functional, or a mixture of anions in which none of the anions is functional or in which at least one of the anions is functional, provided that A 2 + and/or X2 − represent(s) or comprise(s) a functional cation and a functional anion respectively, said functional cations and functional anions corresponding to an ionic entity Y—, namely cationic Y + — or anionic Y − — respectively, linked, optionally via an L arm, in particular an alkyl group comprising 1 to 20 carbon atoms, to at least one function F i , F i varying from F 0 to F n , n being an integer varying from 1 to 10, the functional cation being representable in the form Y + -L-F i , and the functional anion in the form Y − -(L) k -F i , k being equal to 0 or 1, and the functional anion possibly representing, when k is equal to 0, a single anion, corresponding to Y − —F i , in particular chosen from: OH − , F − , CN − , RO − or RS − , R representing an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms.
47 . A stable composition containing in solution:
at least one first part of said ionic liquid of formula A 1 + X 1 − , the cation and/or anion of which correspond(s) to an ionic entity linked to one or more initial functions F 0 , playing the role of liquid matrix, and at least one second part of said ionic liquid of formula A 1 + X 1 − , in which said initial function or functions F 0 are converted into first novel functions, conferring on said second part of said ionic liquid the role of functionalized salt and reaction support, the functionalized salt and the liquid matrix forming a homogeneous phase, the abovementioned first novel functions of the second part of said ionic liquid being capable of being subsequently converted to other functions, without affecting the initial function or functions F 0 of the first part of said ionic liquid.
48 . The composition of claim 46 , characterized in that the A 2 + cation and/or the X 2 − anion of the functionalized salt or salts, corresponding to a Y— ionic entity linked to at least one function F i , are immobilized in the liquid matrix and cannot be extracted from the liquid matrix by standard extraction means, in particular by solvent.
49 . The composition of claim 46 characterized in that the liquid matrix is non-reactive vis-à-vis the functionalized salt.
50 . The composition of claim 46 , characterized in that A 2 + is a functional cation.
51 . The composition of claim 50 , characterized in that the X 1 − and X 2 − anions are identical.
52 . The composition of claim 50 , characterized in that:
the X 1 − and X 2 − anions are chosen from the following two families: the non-complex anions, chosen in particular from the BF 4 − , PF 6 − , CF 3 SO 3 − , CH 3 COO −, CF 3 CO 2 − , − N(SO 2 CF 3 ) 2 (or NTf 2 − ) anion the halides, the BR 4 − , RCO 2 − or RSO 3 − anions, R being an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms, said R group also possibly representing a perfluorinated or partially fluorinated group, or the R′SO 4 − anions, R′ being a hydrogen atom, a methyl group or an ethyl group; the complex anions, resulting from the combination of a Lewis acid and a halide, preferably Cl − or F − , of general formula MXj, j being an integer comprised between 1 and 7, and M representing a metal, in particular chosen from aluminium, tin, zinc, bismuth, manganese, iron, copper, molybdenum, antimony, gallium or indium; the A 1 + and A 2 + cations are chosen from the onium cations, such as the substituted or non-substituted pyridinium, imidazolium, ammonium, phosphonium or sulphonium cations, and preferably ammonium or phosphonium.
53 . The composition of claim 46 , characterized in that the A 2 + functional cation corresponds to a Y + — cationic entity, linked, via an L arm, in particular an alkyl group comprising 1 to 20 carbon atoms, to a function F 0 , said function F 0 being chosen from the standard functions of organic chemistry, such as the hydroxyl, carboxylic, amide, sulphone, primary amine, secondary amine, aldehyde, ketone, ethenyl, ethynyl, dienyl, ether, epoxide, phosphine (primary, secondary or tertiary), azide, imine, ketene, cumulene, heterocumulene, thiol, thioether, sulphoxide, phosphorus-containing moieties, heterocycles, sulphonic acid, silane, stannane or functional aryl functions.
54 . The composition of claim 46 , characterized in that the ionic liquid is chosen from the following:
R a and R b representing linear or branched alkyl groups, comprising 1 to 20 carbon atoms, in particular an ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl group, or functional alkyl groups comprising 1 to 20 carbon atoms, or functional or non-functional aryl groups comprising 6 to 30 carbon atoms,
Bu 3 P + —Me, X 1 − ⊕ P(C 6 H 13 ) 3 C 14 H 29 , X 1 − (C 8 H 17 ) 3 N + Me, X 1 −
X 1 − being in particular chosen from: NTf 2 − , PF 6 − , BF 4 − or CF 3 SO 3 − .
55 . The composition of claim 46 , characterized in that the functionalized salt is chosen from the following:
X 2 − being chosen from: NTf 2 − , PF 6 − , BF 4 − , Cl − , Br − , I − , CF 3 SO 3 − , MeSO 4 − , EtSO 4 − , MeSO 3 − , C 6 H 5 SO 3 − , pMeC 6 H 4 SO 3 − ,
m being an integer comprised between 0 and 20,
R β representing a substituted or non-substituted vinyl group, functional aryl group comprising 1 to 20 carbon atoms, or functional alkyl group comprising 6 to 30 carbon atoms,
and R a representing a branched or non-branched alkyl group comprising 1 to 20 carbon atoms, in particular an ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl group.
56 . The composition of claim 46 , characterized in that X 2 − is a functional anion, corresponding in particular to an anion the pK A of the conjugated acid of which is less than 30, and is chosen in particular from the following anions:
OH − , F − , R c BZ 3 − , N 3 − , CN − , or W{overscore (C)}R c V Z representing an —F, —OH, —OR group, R representing an alkyl group comprising 1 to 20 carbon atoms, V and W representing, independently of each other, an electroattractive group, in particular a cyano, alkoxycarbonyl moiety comprising 2 to 20 carbon atoms, acyl moiety comprising 2 to 20 carbon atoms, benzoyl, alkyl sulphonyl moiety comprising 1 to 20 carbon atoms, aryl sulphonyl moiety comprising 6 to 30 carbon atoms, dialkoxyphosphonyl moiety comprising 2 to 20 carbon atoms, R c representing a branched or non-branched, cyclic or non-cyclic alkyl moiety, comprising 1 to 20 carbon atoms, or an aryl moiety comprising 6 to 30 carbon atoms, and in that the A 2 + cation is chosen from the ammonium and phosphonium cations, in particular from the following cations: Me 3 N + —R d Et 3 N + —R d Bu 4 P + —R d R d being an alkyl group comprising 1 to 20 carbon atoms.
57 . A method of continuous, discontinuous, combinatorial, or parallel organic synthesis, and/or for the preparation of libraries of products, comprising the use of the composition of claim 46 .
58 . A method for the implementation of the preparation of a molecule G, comprising the use of the composition of claim 46 , said molecule G having an initial function F 0 , linked, optionally via an L arm, in particular an alkyl group comprising 1 to 20 carbon atoms, to a Y + — ionic entity, forming part of the A 2 + cation of the A 2 + X 2 − , and/or Y − — functionalized salt, forming part of the X 2 − anion of the A 2 + X 2 − functionalized salt, the cation being in the form Y + -L-F 0 and/or the anion being in the form Y − -(L) k -F 0 , k being equal to 0 or 1, which method comprises the stages:
of a first addition of a reagent B 1 into the abovementioned composition and the reaction between said function F 0 , and the reagent B 1 , leading to a function F 1 , linked to the Y + — ionic entity, forming part of the A 2 + cation of the A 2 + X 2 − functionalized salt, and/or to the Y − — ionic entity, forming part of the X 2 − anion of the A 2 + X 2 − functionalized salt, according to one of the following reaction diagrams: of n-1 successive additions of B i reagents, 1<i≦n, n varying from 2 to 10, to the abovementioned composition, allowing, at each addition, the reaction between the reagent B i and a function F i-1 , leading to the obtaining of a function F i , the (n-1) th addition of the reagent B n to the function F n-1 leading to the obtaining of the function F n , the n-1 additions being representable according to one of the following reaction diagrams: of cleavage of the function F n , linked to the Y + — or Y − — ionic entity respectively of the A 2 + cation and/or of the X 2 − anion, making it possible to recover
on the one hand the A 2 + X 2 − functionalized salt in the form Y + -L-F 0 , X 2 − or
A 2 + , Y − -(L) k -F 0 , in solution in the A 1 + X 1 − ionic liquid matrix, or in the form Y + -L-F′ 0 , X 2 − or A 2 + , Y − -(L) k -F′ 0 , in which F′ 0 represents a function different from F 0 , and on the other hand the molecule G, according to one of the following reaction diagrams:
59 . The method of claim 58 for implementation of the Diels-Alder reaction, according to one of the following reaction diagrams:
p being an integer varying from 0 to 2,
Y + — representing an onium cation such as the substituted or non-substituted pyridinium, imidazolium, ammonium, phosphonium or sulphonium cations, and preferably ammonium or phosphonium of claim 52 , and preferably being a trimethylalkylammonium, triethylalkylammonium or tributylalkylphosphonium cation,
L representing an arm, in particular a linear or branched alkyl group comprising 1 to 20 carbon atoms, or an optionally functional aralkyl group, comprising 6 to 30 carbon atoms, and preferably being a linear alkyl group preferably a linear alkyl group of (CH2)r type, r varying from 1 to 20, and preferably from 3 to 6,
X 2 − being an anion, functional or non-functional, or a mixture of anions in which either none of the anions is functional or at least one of the anions is functional, and being in particular NTf 2 − , BF 4 − , PF 6 − , Cl − , Br − , CH 3 COO − , CF 3 CO 2 − , CF 3 SO 3 − , BR 4 − , R being an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms, said R group also possibly representing a perfluorinated or partially fluorinated group, or the R′SO 4 − anions, R′ being a hydrogen atom, a methyl group or an ethyl group,
the A 1 + X 1 − ionic liquid being in particular in the form:
R a and R b representing linear or branched alkyl groups, comprising 1 to 20 carbon atoms, in particular an ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl group, or functional alkyl groups comprising 1 to 20 carbon atoms, or functional or non-functional aryl groups comprising 6 to 30 carbon atoms, and preferably representing alkyl groups comprising 1 to 20 carbon atoms,
X 1 − being chosen from: BF 4 − , PF 6 − , NTf 2 − , Cl − , Br − , CH 3 COO − , CF 3 CO 2 − , CF 3 SO 3 − , BR 4 − , R being as defined in claim 20 ,
the functions F 0 , F 1 and F 2 being as defined below:
F 0 corresponds to a −χ 1 H group, in which χ 1 represents an oxygen atom or an —NR f group, R f corresponding to a linear or branched alkyl group, comprising 1 to 20 carbon atoms, or an aryl group comprising 6 to 30 carbon atoms,
F 1 corresponds to the following formula:
χ 1 being as defined above,
F 2 corresponds to the following formula:
χ 1 being as defined above,
G corresponding to the following formula:
in which χ 2 represents either an OR g group, R g representing a hydrogen atom or an alkyl group comprising 1 to 20 carbon atoms, or an —NR h R u group, R h and R u representing independently of each other a hydrogen atom, an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms,
Y + —, L, X 2 − and the A 1 + X 1 − ionic liquid being as defined previously,
the functions F 0 , F 1 and F 2 being as defined below:
F 0 represents any function making it possible to attach a 1,3-diene, and is in particular chosen from the carbonyl, amine, alkoxy, silane, stannane and borane functions, comprising 1 to 20 carbon atoms,
F 1 corresponds to the following formula:
p being an integer varying from 0 to 2,
F 2 corresponds to the following formula:
χ 3 representing an electroattractive group, in particular chosen from the cyano, alkoxycarbonyl groups, comprising 1 to 20 carbon atoms, acyl groups comprising 2 to 20 carbon atoms, benzoyl, sulphonyl, dialkoxyphosphonyl groups comprising 1 to 10 carbon atoms,
G corresponding to the following formula:
χ 3 being as defined above.
60 . The method of claim 58 for implementation of Heck's reaction, according to the following reaction diagram:
Y + — representing an onium cation as defined in claim 53 , and preferably being a trimethylalkylammonium, triethylalkylammonium or tributylalkylphosphonium cation,
L representing an arm, in particular a linear or branched alkyl group comprising 1 to 20 carbon atoms, or an optionally functional aralkyl group comprising 1 to 20 carbon atoms, and preferably being a linear alkyl group preferably a linear alkyl group of (CH 2 ) r type, r varying from 1 to 20, and preferably from 3 to 6,
X 2 − being an anion, functional or non-functional, or a mixture of anions in which either none of the anions is functional or at least one of the anions is functional, and being in particular BF 4 − , PF 6 − , NTf 2 − , CF 3 SO 3 − , Cl − , Br − , or I − ,
the A 1 + X 1 − ionic liquid being in particular in the form:
R a and R b representing linear or branched alkyl groups, comprising 1 to 20 carbon atoms, in particular an ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl group, or functional alkyl groups comprising 1 to 20 carbon atoms, or functional or non-functional aryl groups comprising 6 to 30 carbon atoms, and preferably representing alkyl groups comprising 1 to 20 carbon atoms,
X 1 − being chosen from: BF 4 − , PF 6 − , NTf 2 − , Cl − , Br — , CH 3 COO − , CF 3 CO 2 − , CF 3 SO 3 − , BR 4 − , R being as defined in claim 20 ,
the functions F 0 , F 1 , F′ 1 , F 2 and F′ 2 being as defined below:
F 0 corresponds to a −χ 1 H group, in which χ 1 represents an oxygen atom or an —NR f group, R f corresponding to a linear or branched alkyl group, comprising 1 to 20 carbon atoms, or an aryl group comprising 6 to 30 carbon atoms,
F 1 corresponds to the following formula:
χ 1 being as defined above,
F 2 corresponds to the following formula:
χ 1 being as defined above,
G corresponding to the following formula:
in which χ 2 represents either an —OR g group, R g representing a hydrogen atom or an alkyl group comprising 1 to 20 carbon atoms, or an —NR h R u group, R h and R u representing independently of each other a hydrogen atom, an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms,
χ 3 representing a leaving moiety, in particular chosen from the halides I, Cl and Br, the mesylate, tosylate, triflate, sulphonate, sulphate or phosphate groups,
T 1 , T 2 , T 3 , T 4 and T 5 representing independently of one another a hydrogen atom, a linear or branched alkyl group, comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms, or a functional group in particular chosen from NO 2 , CN, COOR, OR, COR, NHCOR, NRR″, SO 2 R, I, Br, R and R″ representing independently of each other an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms,
the entity
representing in particular the following groups:
F′ 1 corresponds to the following formula:
χ 1 and χ 3 being as defined above,
F′ 2 corresponds to the following formula:
χ 1 being as defined above,
G′ corresponding to the following formula:
χ 2 being as defined above.
61 . The method of claim 58 for implementation of the Baylis-Hillman reaction, according to the following reaction diagram:
Y + — representing an onium cation as defined in claim 53 , and preferably being a trimethylalkylammonium, triethylalkylammonium or tributylalkylphosphonium cation,
L representing an arm, in particular a linear or branched alkyl group comprising 1 to 20 carbon atoms, or an optionally functional aralkyl group, comprising 6 to 30 carbon atoms, and preferably being a linear alkyl group preferably a linear alkyl group of (CH 2 ) r type, r varying from 1 to 20, and preferably from 3 to 6,
X 2 − being an anion, functional or non-functional, or a mixture of anions in which either none of the anions is functional or at least one of the anions is functional, and being in particular BF 4 − , PF 6 − , NTf 2 − , CF 3 SO 3 — , Cl − , Br − , I − , CH 3 CO 2 − or CF 3 CO 2 − ,
the A 1 + X 1 − ionic liquid being in particular in the form:
R a and R b representing linear or branched alkyl groups, comprising 1 to 20 carbon atoms, in particular an ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl group, or functional alkyl groups comprising 1 to 20 carbon atoms, or functional or non-functional aryl groups comprising 6 to 30 carbon atoms, and preferably representing alkyl groups comprising 1 to 20 carbon atoms,
X 1 − being chosen from: BF 4 − , PF 6 − , NTf 2 − , Cl − , Br − , CH 3 COO − , CF 3 CO 2 − , CF 3 SO 3 − , BR 4 − , R an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms, said R group also possibly representing a perfluorinated or partially fluorinated group, or the R′SO 4 − anions, R′ being a hydrogen atom, a methyl group or an ethyl group,
the functions F 0 , F 1 and F 2 being as defined below:
F 0 represents an —OH group,
F 1 corresponds to the following formula:
F 2 corresponds to the following formula:
G corresponding to the following formula:
χ 1 representing an —OH group, or an —OR g group, R g representing a linear or branched alkyl group, comprising 1 to 20 carbon atoms,
Ar representing a substituted or non-substituted, aromatic or heteroaromatic group,
ArCHO being in particular chosen from:
62 . The method of claim 58 for implementation of Suzuki coupling, according to one of the following reaction diagrams:
R 3 being chosen from the substituted or non-substituted aryl, heteroaryl, ethenyl, dienyl, allyl, ethynyl groups, comprising 2 to 30 carbon atoms,
R 7 represents a branched or linear alkyl group or a cycloalkyl group comprising 1 to 12 carbon atoms,
Y + — representing an onium cation as defined in claim 53 , and preferably being a trimethylalkylammonium, triethylalkylammonium or tributylalkylphosphonium cation,
L representing an arm, in particular a linear or branched alkyl group comprising 1 to 20 carbon atoms, or an optionally functional aralkyl group comprising 6 to 30 carbon atoms, and preferably being a linear alkyl group preferably a linear alkyl group of (CH 2 ) r type, r varying from 1 to 20, and preferably from 3 to 6,
X 2 − being as an anion, functional or non-functional, or a mixture of anions in which either none of the anions is functional or at least one of the anions is functional, and being in particular NTf 2 − , BF 4 − , PF 6 − , Cl − , Br − , CH 3 COO − , CF 3 CO 2 − , CF 3 SO 3 − , BR 4 − , R being an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms, said R group also possibly representing a perfluorinated or partially fluorinated group, or the R′SO 4 − anions, R′ being a hydrogen atom, a methyl group or an ethyl group,
the A 1 + X 1 − ionic liquid being in particular in the form:
R a and R b being representing linear or branched alkyl groups, comprising 1 to 20 carbon atoms, in particular an ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl group, or functional alkyl groups comprising 1 to 20 carbon atoms, or functional or non-functional aryl groups comprising 6 to 30 carbon atoms, and preferably representing alkyl groups comprising 1 to 20 carbon atoms,
X 1 − being chosen from: BF 4 − , PF 6 − , NTf 2 − , Cl − , Br − , CH 3 COO − , CF 3 CO 2 − , CF 3 SO 3 − , BR 4 − , R being an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms, said R group also possibly representing a perfluorinated or partially fluorinated group, or the R′SO 4 − anions, R′ being a hydrogen atom, a methyl group or an ethyl group,
the functions F 0 , F 1 and F 2 being as defined below:
F 0 is in the form −χ 1 H, χ 1 representing an oxygen atom or an —NR f group, R f corresponding to a linear or branched alkyl group, comprising 1 to 20 carbon atoms, or an aryl group comprising 6 to 30 carbon atoms,
F 1 is in the form —R e -χ, R e representing an aromatic or heteroaromatic group comprising 6 to 30 carbon atoms, χ representing a leaving group preferably chosen from Cl, Br, I, OTf, O—CO 2 R 5 or OSO 3 —R 5 , R 5 representing an alkyl group comprising 1 to 10 carbon atoms or an aralkyl group comprising 6 to 30 carbon atoms, F 1 preferably corresponding to the following formula:
F 2 is in the form —R e —R 2 , R e being as defined above and R 2 being chosen from the substituted or non-substituted aryl, heteroaryl, ethenyl, dienyl, allyl, ethynyl groups, comprising 2 to 30 carbon atoms, F 2 preferably corresponding to the following formula:
Ar 1 representing an aromatic group preferably chosen from:
the G molecule being in the form R 2 —R 3 , R 2 and R 3 being as defined above, and corresponds in particular to the following formula:
in which χ 2 represents either an —OR g group, R g representing a hydrogen atom or an alkyl group comprising 1 to 20 carbon atoms, i.e. an —NR h R u group, R h and R u representing independently of each other a hydrogen atom, an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms,
Ar 1 is as defined above,
Y + —, L, X 2 − , A 1 + X 1 − and R 2 being as defined above, the functions F 0 , F 1 and F 2 being as defined below:
F 0 is in the form −χ 1 H, χ 1 being as defined above,
F 1 is in the form —R q —B(OR 7 ) 2 , R 7 being as defined above, and R q corresponding to an aryl group comprising 6 to 30 carbon atoms, heteroaryl group comprising 4 to 20 carbon atoms, ethenyl group comprising 2 to 20 carbon atoms, dienyl group comprising 3 to 20 carbon atoms, allyl group comprising 3 to 20 carbon atoms, ethynyl group comprising 2 to 20 carbon atoms, substituted or non-substituted, F, preferably corresponding to the following formula:
Ar 2 corresponding to a substituted or non-substituted aryl group comprising 6 to 30 carbon atoms,
F 2 is in the form —R q —R e , R q and R e being as defined above, F 2 preferably corresponding to the following formula:
Ar 1 representing an aromatic group preferably chosen from:
the G molecule being in the form R 2 —R 3 , R 2 and R 3 being as defined above, and corresponding in particular to the following formula:
in which χ 2 , Ar 1 and Ar 2 are as defined above,
Y + —, L, X 2 − , A 1 + X 1 − , R 2 and R 3 being as defined above, R 3 preferably being a phenyl group,
A 2 + being an (R a ) 3 N + R b ammonium or (R a ) 3 P + R b phosphonium cation, preferably tetrabutylammonium and tetramethylammonium, R a and R b being as defined above,
X 2 − being in particular chosen from OH − , F − , CN − , R a O −− , R a S − , preferably OH − or F − , R s representing an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms,
R 3 and R 4 being as defined above,
R 6 and R 7 representing independently of each other an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms,
the boronic molecule of formula R 3 R 7 R 6 B being a trialkyl or aryl borane, the alkyl group comprising 1 to 20 carbon atoms and the aryl group comprising 6 to 30 carbon atoms, a boronic acid or ester, preferably a boronic acid or ester chosen as being phenyl boronic acid,
R 2 and χ are as defined previously, R 2 χ preferably corresponding to an aryl halide chosen from:
63 . The method of claim 33 for the synthesis of molecule libraries according to the parallel synthesis technique, according to the following diagram:
characterized in that the Y + -L-F 1 , X 2 − functionalized salt in the A 1 + , X 1 − ionic liquid is separated into n approximately equal parts, n varying from 2 to 1024, and in that each of these parts is then converted according to an organic synthesis reaction, preferably a Heck or Suzuki coupling reaction, each using a different reagent B i in order to produce n solutions each containing a defined Y + -L-F 2 i , X 2 − compound, F 2 i representing a function chosen from the functions as defined in claim 53 , i varying from 1 to n, each solution being treated in order to release the G i molecules, i varying from 1 to n, which are each isolated and purified, constituting a molecule library.
64 . The method of claim 33 , for implementation of the synthesis of molecule libraries by the split-and-mix technique according to the following diagram:
characterized in that:
n fractions of the Y + -L-F 1 , X 2 − solution, obtained from the starting Y + -L-F 0 , X 2 − functionalized salt, in the A 1 + X 1 − ionic liquid are converted in parallel according to an organic chemistry reaction, preferably a Heck or Suzuki coupling reaction, each using a different reagent B i in order to produce n solutions each containing a defined Y + -L-F 2 i , X 2 − compound, i varying from 1 to n, n varying from 2 to 1024, preferably from 2 to 96, F 2 i representing a function chosen from the standard functions of organic chemistry, such as the hydroxyl, carboxylic, amide, sulphone, primary amine, secondary amine, aldehyde, ketone, ethenyl, ethynyl, dienyl, ether, epoxide, phosphine (primary, secondary or tertiary), azide, imine, ketene, cumulene, heterocumulene, thiol, thioether, sulphoxide, phosphorus-containing moieties, heterocycles, sulphonic acid, silane, stannane or functional aryl functions,
the n solutions obtained in the preceding stage are mixed in order to produce a solution in the A 1 + X 1 − ionic liquid containing the n Y + -L-F 2 i , X 2 − products, i varying from 1 to n, annotated
∑
i
=
1
i
=
n
Y
+
-
L
-
F
2
i
,
X 2 − , and this solution is subjected to a cleavage stage, preferably a transesterification or a transamidation, in order to obtain in solution in the A 1 + X 1 − ionic liquid, a mixture of the n G i molecules, i varying from 1 to n, and the starting Y + -L-F 0 , X 2 − functionalized salt
the mixture as obtained in the preceding stage is separated from the A 1 + X 1 − ionic liquid and from the starting Y + -L-F 0 , X 2 − functionalized salt by the usual separation methods, preferably by vacuum distillation, by extraction with a standard solvent such as heptane or toluene followed by evaporation of the solvent, by chromatography on a column, plates or under pressure, in order to obtain a library containing n G i molecules, this sequence of stages mentioned above being possibly repeated j times, j being comprised between 2 and 10, in order to obtain j different libraries of n products.Cited by (0)
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