Brønsted-acidic fluoroalkyl phosphonates

Patent metadata

Field	Value
Publication number	US-2018258115-A1
Application number	US-201615759987-A
Country	US
Kind code	A1
Filing date	Aug 30, 2016
Priority date	Sep 15, 2015
Publication date	Sep 13, 2018
Grant date	—

Abstract

The invention relates to Brønsted-acidic fluoroalkyl phosphonates as bifunctional catalysts and to processes for the preparation thereof.

First claim

1 . Compounds of the formula I
[Kt] z+ z [R f P(O)(OH)O] −   I,
where R f corresponds to the formula C n F (2n+1)−(m+k) H m X k , X denotes Cl, Br or I, n denotes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, m denotes 0, 1, 2, 3 or 4, k denotes 0, 1 or 2, with the proviso that, if n denotes 1, m denotes 0, 1 or 2 and/or k denotes 0, 1 or 2 and [Kt] z+ denotes a singly, doubly, triply or multiply positively charged metal atom.

2 . Compounds according to claim 1 , where R f denotes a linear or branched perfluoroalkyl group having 1 to 12 C atoms.

3 . Compounds according to claim 1 , where [Kt] z+ is selected from cations of the metals Li, Na, Ca, Mg, Ag, Fe, Co, Ni, Cu, Au, Al, In, Sn, Zn, Bi, Rh, Ru, Ir, Pd, Pt, Os, Cr, Mo, W, V, Nb, Ta, Ti, Zr, Hf, Y, Yb, La, Sc, Lu, Ce, Nd, Tb, Er, Eu or Sm.

4 . Process for the preparation of compounds of the formula I according to claim 1 , characterised in that a compound of the formula II
R f P(O)(OH) 2   II,
where R f has a meaning indicated in claim 1 , is reacted with a metal which forms the future metal cation [Kt] z+ , or a compound of the formula III
[Kt] z+ z/b [An] b−   III,

where [Kt] z+ has a meaning indicated in claim 1 , and [An] b− denotes [Cl] − , [OH] − , [CO 3 ] 2− or [O] 2− , where equimolar amounts of compounds of the formula II and of the formula III or of the metal are employed, which is determined by the valence of the cation [Kt] z+ in the compound of the formula I.

5 . Process according to claim 4 , characterised in that the reaction is carried out in the presence or without the presence of water or an organic solvent.

6 . Process for the preparation of the compounds of the formula I according to claim 1 , characterised in that a compound of the formula IV
[Kt] z+ z/ 2[R f P(O)O 2 ] 2−   IV,
is reacted in a disproportionation reaction with a compound of the formula II
R f P(O)(OH) 2   II,

where R f corresponds to the formula C n F (2n+1)−(m+k) H m X k , X denotes Cl, Br or I, n denotes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, m denotes 0, 1, 2, 3 or 4, k denotes 0, 1 or 2, with the proviso that, if n denotes 1, m denotes 0, 1 or 2 and/or k denotes 0, 1 or 2 and [Kt] z+ denotes a singly, doubly, triply or multiply positively charged metal atom.

7 . A method for performing catalysis which comprises using compounds of the formula I according to claim 1 as bifunctional catalysts.

8 . Bifunctional catalysts of the formula I according to claim 1 for use in organic synthesis.

9 . Bifunctional catalysts of the formula I according to claim 8 for use in Lewis acid-catalysed and/or Brønsted acid-catalysed reactions or domino reactions selected from a condensation reaction, alcoholysis, aldol reaction, Mukaiyama aldol reaction, Gattermann-Koch reaction, Beckmann and Fries rearrangement, Friedel-Crafts acylation, Friedel-Crafts alkylation, Mannich reaction, Diels-Alder reaction, aza-Diels-Alder reaction, Baylis-Hillman reaction, Reformatsky reaction, Claisen rearrangement, Prins cyclisation reaction, allylation of carbonyl compounds, cyanation of aldehydes and ketones, cyanosilylation of aldehydes and ketones, 1,3-dipolar cycloaddition, hydration of alkenes, cyclisation reaction, polymerisation, Michael reaction, oxidation and reduction reactions.

Assignees

• Merck Patent Gmbh

Inventors

• Ignatiev Nikolai (Mykola)
• Barthen Peter
• Bredenhagen Bernd
• Meyer Michaela Katharina
• Frank Walter

Classifications

• C07C67/00

  Preparation of carboxylic acid esters · CPC title

• C07C45/46

  Friedel-Crafts reactions · CPC title

• C07F9/4816 Primary

  Acyclic saturated acids or derivatices which can have further substituents on alkyl · CPC title

• B01J31/0261

  comprising phosphonous acid (-ester) groups (RP(OR')2) or the isomeric phosphinic acid (-ester) groups (R2(R'O)P=O), i.e. R= C, R'= C, H · CPC title

• C07C2601/14

  The ring being saturated · CPC title