Process for preparing cyclic carbonates

Patent metadata

Field	Value
Publication number	US-11292780-B2
Application number	US-201816634255-A
Country	US
Kind code	B2
Filing date	Aug 14, 2018
Priority date	Aug 14, 2017
Publication date	Apr 5, 2022
Grant date	Apr 5, 2022

Abstract

The present invention relates to a process for preparing cyclic carbonates of formula Ia or Ib or mixtures thereof (Ia) (Ib) comprising the process step: a) reacting a propargylic alcohol of formula II (II) with carbon dioxide in the presence of at least one transition metal catalyst TMC1, which comprises a transition metal selected from metals of groups 10, 11 and 12 of the periodic table of the elements according to IUPAC and at least one bulky ligand.

First claim

The invention claimed is:

1. A process for preparing a cyclic carbonate of formula Ia or Ib or a mixture thereof

wherein R 1 is hydrogen or an organic radical having from 1 to 40 carbon atoms, the process comprising:
a) reacting a propargylic alcohol of formula II

wherein R 1 is defined as in formula Ia or Ib,
with carbon dioxide in the presence of at least one transition metal catalyst TMC1, which comprises: a transition metal selected from metals of groups 10, 11 and 12 of the periodic table of the elements; and at least one bulky ligand selected from the group of ligands consisting of a compound of formula III and a compound of formula IV

wherein D is P, As or Sb,
R 2 , R 3 , R 4 and R 5 are each independently an organic radical having from 1 to 40 carbon atoms,
and
Z is a divalent bridging group selected from —CR 7 ═CR 8 —, —CR 7 ═N—, —CR 7 R 9 — CR 8 R 10 — and —CR 7 R 9 —CR 8 R 10 —CR 11 R 12 —, wherein R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen or an organic radical having from 1 to 40 carbon atoms or two adjacent radicals R 7 and R 8 and/or R 10 and R 11 together with the atoms connecting them form a monocyclic or polycyclic, substituted or un-substituted, aliphatic or aromatic ring system which has from 4 to 40 carbon atoms and optionally comprises at least one heteroatom selected from the group of elements consisting of Si, Ge, N, P, O and S
thereby obtaining the cyclic carbonate of formula Ia or Ib or the mixture thereof in a yield of from 2% to 99%.

2. The process of claim 1 , wherein R 1 is hydrogen, hydroxymethyl (—CH 2 OH), acetoxy-methylene (—CH 2 OC(O)CH 3 ), formyloxy-methylene (—CH 2 OC(O)H) or —CH 2 OC(O)OCH 3 .

3. The process of claim 1 , wherein the transition metal of the at least one transition metal catalyst TMC1 is Ag.

4. The process of claim 1 , wherein the at least one transition metal catalyst TMC1 is prepared in situ by using a transition metal compound, which does not comprise any bulky ligand, and the compound of formula III or the compound of formula IV as a bulky ligand or a protonated form of the compound of formula IV represented by formula V,

wherein R 2 , R 5 and Z are defined as in formulae III or IV and X − is an anion equivalent, together with a base.

5. The process of claim 4 , wherein the transition metal compound is selected from AgOAc, AgF, Ag 2 O and Ag 2 CO 3 .

6. The process of claim 1 , wherein the at least one bulky ligand is a compound of formula III.

7. The process of claim 1 , wherein the at least one bulky ligand is selected from a compound of the following formulae A to P and mixtures thereof

8. The process of claim 1 , wherein a molar ratio of the at least one bulky ligand to the transition metal of the at least one transition metal catalyst TMC1 is in a range of from 0.4 to 1.2.

9. The process of claim 1 , wherein an amount of the at least one transition metal catalyst TMC1 used in a) is in a range of from 0.005 to 5 mol %, based on an amount of the propargylic alcohol of formula II.

10. The process of claim 1 , wherein a) is performed at a pressure in a range of from 1 to 50 bar.

11. The process of claim 1 , wherein a) is performed at a temperature in a range of from 0° C. to 1° *C.

12. The process of claim 1 , wherein a) is carried out in the presence of a solvent selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, amides, ureas, nitriles, sulfoxides, sulfones, esters, carbonates, ethers, alcohols and mixtures thereof.

13. The process of claim 1 , wherein the cyclic carbonate of formula Ia or Ib or the mixture thereof is separated from the at least one transition metal catalyst TMC1 after a) via distillation.

14. The process of claim 1 , wherein the the at least one transition metal catalyst TMC1 is recycled to the reacting of a) after the cyclic carbonate of formula Ia or Ib or the mixture thereof is removed via distillation.

15. A process for preparing a cyclic carbonate of formula Ia or Ib or a mixture thereof

wherein R 1 is hydrogen or an organic radical having from 1 to 40 carbon atoms, the process comprising:
a) reacting a propargylic alcohol of formula II

wherein R 1 is defined as in formula Ia or Ib,
with carbon dioxide in the presence of at least one transition metal catalyst TMC1, which comprises: a transition metal selected from metals of groups 10, 11 and 12 of the periodic table of the elements; and at least one bulky ligand selected from the group of ligands consisting of a compound of formula III and a compound of formula IV

wherein D is P, As or Sb,
R 2 , R 3 , R 4 and R 5 are each independently an organic radical having from 1 to 40 carbon atoms,
and
Z is a divalent bridging group selected from —CR 7 ═CR 8 —, —CR 7 ═N—, —CR 7 R 9 — CR 8 R 10 — and —CR 7 R 9 —CR 8 R 10 —CR 11 R 12 —, wherein R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen or an organic radical having from 1 to 40 carbon atoms or two adjacent radicals R 7 and R 8 and/or R 10 and R 11 together with the atoms connecting them form a monocyclic or polycyclic, substituted or un-substituted, aliphatic or aromatic ring system which has from 4 to 40 carbon atoms and optionally comprises at least one heteroatom selected from the group of elements consisting of Si, Ge, N, P, O and S,
wherein the at least one transition metal catalyst TMC1 is prepared in situ by using a transition metal compound, which does not comprise any bulky ligand, and the compound of formula III or the compound of formula IV as a bulky ligand or a protonated form of the compound of formula IV represented by formula V,

wherein R 2 , R 5 and Z are defined as in formulae III or IV and X − is an anion equivalent, together with a base.

16. A process for preparing a cyclic carbonate of formula Ia or Ib or a mixture thereof

wherein R 1 is hydrogen or an organic radical having from 1 to 40 carbon atoms, the process comprising:
a) reacting a propargylic alcohol of formula II

wherein R 1 is defined as in formula Ia or Ib,
with carbon dioxide in the presence of at least one transi

Assignees

• Basf Se

Inventors

• Bayarmagnai Bilguun
• Schaub Thomas
• Mormul Verena
• Rudolf Peter

Classifications

• C08F124/00

  Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen (cyclic esters of polyfunctional acids C08F118/00; cyclic anhydrides of unsaturated acids C08F120/00, C08F122/00) · CPC title

• H01M2300/0025

  Organic electrolyte · CPC title

• B01J31/2282

  Unsaturated compounds used as ligands · CPC title

• C07D317/40 Primary

  Vinylene carbonate; Substituted vinylene carbonates · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title