Process for preparing cyclic carbonates with an exocyclic vinylidene group

Patent metadata

Field	Value
Publication number	US-12486243-B2
Application number	US-202117758683-A
Country	US
Kind code	B2
Filing date	Jan 5, 2021
Priority date	Jan 15, 2020
Publication date	Dec 2, 2025
Grant date	Dec 2, 2025

Abstract

A process can be used for preparing cyclic carbonates with an exocyclic vinylidene group by reacting a propargylic alcohol with CO 2 in the presence of a silver catalyst having at least one bulky ligand a lipophilic carboxylate ligand. After completion of the reaction, the catalyst is separated from the cyclic carbonate by the use of two organic solvents of different polarity and having a miscibility gap. The silver catalyst is enriched in the less polar solvent and the cyclic carbonate in the more polar solvent.

First claim

The invention claimed is:

1 . A process for preparing at least one cyclic carbonate I selected from the group consisting of
a compound of formula Ia, a compound of formula Ib, a mixture of the compound of formula Ia and the compound of formula Ib, and a compound of formula I-bis;

wherein
A is a bridging group selected from the group consisting of:
˜CH 2 —O—CH 2 -1,4-phenylene-CH 2 —O—CH 2 —; —CH 2 —O—C(═O)—NH—1,4-toluylene-NH—C(═O)—O—CH 2 —; —CH 2 —O—CH 2 —CH(OH)—CH 2 —O—(CH 2 )—O—CH—CH(OH)—CH 2 —O—CH 2 —; —CH 2 —O—CH 2 —CH(OH)—CH 2 —O-1,4-phenylene-C(CH 3 ) 2 -1,4-phenylene-O—CH 2 —CH(OH)—CH 2 —O—CH 2 —; and —CH 2 —(OCH 2 CH 2 ) 3 —O—CH 2 —; and

is —CH 2 —O—R 14 ,
wherein
R 14 is selected from the group consisting of hydrogen; C 1 -C 4 -alkyl carrying 1, 2, or 3 radicals R 15 ; —C(═O)R 16 , and C 3 -C 6 -cycloalkyl carrying 1, 2, or 3 radicals R 17 ;
wherein
R 15 is selected from the group consisting of OH, C 1 -C 4 -alkoxy, phenyl, and a 3-, 4-, 5-, or 6-membered saturated heterocyclic ring containing 1 or 2 oxygen atoms as ring member;
R 16 is selected from the group consisting of C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 1 -C 4 -alkoxy, and —NR 18 R 19 , wherein R 18 is hydrogen or C 1 -C 4 -alkyl and R 19 is selected from the group consisting of hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkyl substituted by a group R 20 , and phenyl which may carry 1, 2, 3, 4, or 5 substituents selected from the group consisting of C 1 -C 4 -alkyl and C 1 -C 4 -alkoxy;
wherein
R 20 is selected from the group consisting of —O—R 21 , —N(R 13 )—R 21 , —O—C(═O)—R 21 , —C(═O)—O—R 21 , —N(R 13 )—C(═O)—R 21 —C(═O)—N(R 13 )—R 21 , —O—C(═O)—O—R 21 , —O—C(═O)—N(R 13 )—R 21 —N(R 13 )—C(═O)—O—R 21 , and —N(R 13 )—C(═O)—N(R 13 )—R 21 , wherein each R 21 is independently hydrogen, C 1 -C 6 -alkyl, or C 2 -C 6 -alkenyl, and wherein each R 13 is independently hydrogen or C 1 -C 10 -alkyl; and

R 17 is selected from the group consisting of —O—R 21 , —N(R 13 )—R 21 —O—C(═O)—R 21 , —C(═O)—O—R 21 , —N(R 13 )—C(═O)—R 21 , —C(═O)—N(R 13 )—R 21 , —O—C(═O)—O—R 21 , —O—C(═O)—N(R 13 )—R 21 , —N(R 13 )—C(═O)—O—R 21 , and —N(R 13 )—C(═O)—N(R 13 )—R 21 , wherein each R 21 is independently hydrogen, C 1 -C 6 -alkyl, or C 2 -C 6 -alkenyl, and wherein each R 13 is independently hydrogen or C 1 -C 10 -alkyl; and

the process comprising;
a) reacting a proparoyl alcohol with carbon dioxide, to obtain a reaction mixture,
wherein, if the at least one cyclic carbonate I is the compound of formula Ia, the compound of formula Ib, or the mixture of the compound of formula Ia and the compound of formula Ib, the propargyl alcohol is a compound of formula II

wherein R 1 is as defined above,

or
if the at least one cyclic carbonate I is the compound of the formula I-bis,
the propargyl alcohol is the compound of the formula II, in which R 1 is —CH 2 —O—R 14 , wherein R 14 is as defined above, or the propargyl alcohol is a compound of the formula II-bis

wherein A is as defined above;
wherein the reaction is carried out in at least one organic solvent L1 or in a solvent mixture containing the at least one organic solvent L1 and at least one organic solvent L2; wherein the at least one organic solvent L1 has a higher polarity than the at least one organic solvent L2, and wherein the at least one organic solvent L1 and the at least one organic solvent L2 have a miscibility gap at least between 2° and 30° C.;
wherein the reaction is carried out in the presence of a silver catalyst Ag1 comprising at least one bulky ligand and a carboxylate ligand,
wherein the at least one bulky ligand is at least one selected from the group consisting of a compound of formulae A to W and a mixture thereof:

wherein Me is methyl, Cy is cyclohexyl, i-Pr is isopropyl, Ph is phenyl, and t-Bu is tert-butyl; and
wherein the carboxylate ligand is according to formula V

wherein
R 6 is selected from the group consisting of C 8 -C 18 -alkyl and C 2 -C 4 -alkyl carrying a cyclohexyl ring;

b1) in case that a) has not been carried out in the presence of the at least one solvent L2: adding the at least one solvent L2 to the reaction mixture obtained in a); or
b2) in case that a) has been carried out in the presence of the at least one solvent L2: optionally, adding an additional amount of the at least one solvent L2 to the reaction mixture obtained in a);
c) subjecting the reaction mixture obtained in a), b1), or b2) to a phase separation to obtain a product phase containing the at least one cyclic carbonate I and the at least one solvent L1, and a catalyst phase containing the silver catalyst and the at least one solvent L2; and
d) if desired, isolating the at least one cyclic carbonate I from the product phase.

2 . The process as claimed in claim 1 , wherein the at least one cyclic carbonate I is the compound of formula Ia, the compound of formula Ib, or the mixture thereof of the compound of formula Ia and the compound of formula Ib, in which R′ is —CH 2 —O—R 14 , wherein R 14 is —CH 2 —CH(OH)—CH 2 —O—C(CH 3 ) 3 ; and
wherein the propargyl alcohol is the compound of the formula II, in which R′ is —CH 2 —O—R 14 , wherein R 14 is —CH 2 —CH(OH)—CH 2 —O—C(CH 3 ) 3 .

3 . The process as claimed in claim 1 , wherein the silver catalyst Ag1 is used in a) in an amount of from 0.001 to 50 mol %, based on an amount of the propargylic alcohol of the formula II.

4 . The process as claimed in claim 1 , wherein the at least one solvent L1 is a polar aprotic solvent with a dipole moment of at least 10·10 −30 C·m; and the at least one solvent L2 is a non-polar solvent with a dipole moment of at most 2·10 −30 C·m.

5 . The process as claimed in claim 1 , wherein the at least one solvent L1 is at least one selected from the group consisting of an amide, a urea, a nitrile, a sulfoxide, a sulfone, a carbonate, a nitro compound, and a mixture thereof, and
wherein the at least one solvent L2 is at least one selected from the group consisting of an alkane, a cycloalkane, a C 1 -C 2 -alkyl ester of a C 12 -C 20 -fatty acid, and a mixture thereof.

6 . The process as claimed in claim 5 , wherein the at least one solvent L1 is acetonitrile and the at least one solvent L2 is at least one selected from the group consisting of a C 5 -C 14 -alkane, a C 5 -C 8 -cycloalkane which may carry a C 1 -C 2 -alkyl substituent, and a C 1 -C 2 -alkyl ester of a saturated C 12 -C 20 fatty acid; or
wherein the at least one solvent L1 is dimethylformamide and the at least one solvent L2 is at least one selected from the group consisting of a C 5 -C 14 -alkane, a C 5 -C 8 -cycloalkane which may carry a C 1 -C 2 -alkyl substituent, and a C 1 -C 2 -alkyl ester of a saturated C 12 -C 20 f

Assignees

• Basf Se

Inventors

• Schaub Thomas
• Rudolf Peter
• Licht Ulrike
• Hashmi A Stephen K
• Dabral Saumya
• Johnson Chloe

Classifications

• B01J2531/17

  Silver · CPC title

• B01J2231/49

  Esterification or transesterification · CPC title

• B01J31/2404

  Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring · CPC title

• B01J31/18

  containing nitrogen, phosphorus, arsenic or antimony {as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms (double metal cyanides B01J27/26; N-heterocyclic carbenes B01J31/2265)} · CPC title

• B01J31/04

  containing carboxylic acids or their salts {(B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226)} · CPC title