# US 9,434,665 B2 · Ruthenium complex and method for preparing methanol and diol

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- Number: US 9,434,665 B2
- Document ID: US9434665B2
- Status: Granted
- Kind: B2
- Application number: 14/436,842
- Filed: 2013-03-22
- Published: 2016-03-03
- Granted: 2016-09-06
- Earliest claimed: 2012-10-19
- Assignees: Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences
- Applicants: Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences
- Inventors: Kuiling Ding; Zhaobin Han
- Web page: https://patentgrep.com/patent/US9434665B2

## CPC

- C07C 29/136: of >C=O containing groups, e.g. —COOH
- B01J 31/189: {containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand}
- B01J 31/20: Carbonyls
- B01J 31/24: Phosphines {, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands}
- B01J 31/2476: {comprising aliphatic or saturated rings}
- C07C 41/26: by introduction of hydroxy or O-metal groups
- C07F 15/0046: {Ruthenium compounds}
- C07F 19/00: Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
- B01J 2231/64: Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J 2231/643: of R2C=O or R2C=NR (R= C, H)
- B01J 2531/0247: Tripodal ligands, e.g. comprising the tris(pyrazolyl)borate skeleton, "tpz", neutral analogues thereof by CH/BH exchange or anionic analogues of the latter by exchange of one of the pyrazolyl groups for an anionic complexing group such as carboxylate or -R-Cp
- B01J 2531/0258: Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
- B01J 2531/821: Ruthenium
- C07B 2200/05: Isotopically modified compounds, e.g. labelled
- Y02P 20/52: using catalysts, e.g. selective catalysts
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Provided is a method for preparing methanol and diol from cyclic carbonate, comprising: under a hydrogen atmosphere, in an organic solvent, and with the presence of a ruthenium complex (Ru(L)XYY′) and an alkali, conducting a hydrogenation reduction reaction on the cyclic carbonate or polycarbonate to obtain methanol and diol. Also provided is a ruthenium complex prepared from ruthenium and a tridentate amido diphosphine ligand. Also provided is a deuterated methanol and deuterated diol preparation method by substituting the hydrogen and ruthenium complex with deuterium.

## Claims

### Claim 1

A method for preparing methanol and diol, wherein said method comprises, under hydrogen atmosphere, subjecting a cyclic carbonate or polycarbonate to the following reaction under the action of a catalyst, so as to give methanol and diol,
in formula I and III:
n=0˜20, m=2˜1000000;
R1, R2, R3, R4, R5, R6 can be independently selected from a hydrogen, a C1˜C20 alkyl, a C4˜C24 aryl, a C5˜C25 aryl alkyl, —(C1˜C8)—OR7, —(C1˜C8)—SR8, or —(C1˜C8)—NR9R10;
R5, R6 may be further independently selected from a C4˜C10 cycloalkyl;
wherein R7, R8, R9, R10 are independently selected from a C1˜C10 alkyl, a C4˜C24 aryl or a C5˜C25 aryl alkyl, and R9, R10 may also be joined atom to form a cyclic amine group with the nitrogen;
when n=0, R1 and R3 may be joined to form an alicyclic group or aryl ring;
when n≧1, R1 and R5, R3 and R6 may be joined to form an alicyclic group or an aryl ring;
in formula II and IV:
R1′, R2′, R3′, R4′, R5′, R6′ may be independently selected from a hydrogen, a C1˜C20 alkyl, a C4˜C24 aryl, a C5˜C25 aryl alkyl, —(C1˜C8)—OR7′, —(C1˜C8)—SR8′ or —(C1˜C8)—NR9′R10′;
R5′, R6′ may be further independently selected from a C4˜C10 cycloalkyl;
wherein R7′, R8′, R9′, R10′ are independently selected from a C1˜C10 alkyl, a C4˜C24 aryl or a C5˜C25 aryl alkyl, R9′, R10′ may be further joined to form a cyclic amine group with the nitrogen atom;
when n=0, R1′ and R3′ may be joined to form an alicyclic group or aryl ring;
when n≧1, R1′ and R5′, R3′ and R6′ may be joined to form an alicyclic group or an aryl ring.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the catalyst is a compound of transition metal of Group VIIIB.

### Claim 3 (depends on 2)

The method according to claim 2, wherein the transition metal of Group VIIIB is selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir or Pt.

### Claim 4 (depends on 1, 2, 3)

The method according to any one of claims 1-3, wherein the method includes conducting the following reaction in the presence of an organic solvent and a base:
wherein the compounds of structural formula I, II, III and IV are defined as in claim 1, and the ruthenium complex V has the general structural formula V:
Ru(L)XYY′ (V);
in formula V:
X is carbon monoxide, triphenylphosphine, pyridine, tetrahydrofuran or dimethyl sulfoxide;
Y, Y′ are independently selected from: a hydride ion, a hydroxyl ion, a chloride ion, a bromide ion, an iodide ion and BH4−, BH3CN−, BH(Et)3−, BH(sec-Bu)3−, AlH4− or AlH2(OCH2CH2CH3)2−;
wherein L is a tridentate amino bisphosphorus ligand of general structural formula VI:
in general formula VI, n=0˜3;
R0 is H;
R1″, R2″ are independently selected from a C1˜C10 alkyl, a C3˜C10 cycloalkyl, a C4˜C24 aryl or an adamantyl, wherein the aryl includes an unsubstituted or substituted aryl;
R3″, R4″, R5″, R6″, R7″, R8″ are independently selected from a hydrogen, a C1˜C10 alkyl, a C3˜C10 cycloalkyl, a C1˜C10 alkoxy or a C4˜C36 aryl;
when n=0, R3″ and R7″, R4″ and R8″ may be joined to form an alicyclic group or an aryl ring;
when n≧1, R3″ and R5″, R4″ and R6″, R5″ and R7″ as well as R6″ and R8″ may be joined to form an alicyclic group or an aryl ring.

### Claim 5 (depends on 4)

The method according to claim 4, wherein the ruthenium complex V is shown in structural formula 1a:

### Claim 6 (depends on 4)

The method according to claim 4, wherein the molar ratio of the cyclic carbonate or polycarbonate to ruthenium complex is 100˜1000000:1.

### Claim 7 (depends on 4)

The method according to claim 4, wherein the base is an alkali metal salt of alcohol, an alkali metal carbonate, or an alkali metal hydroxide.

### Claim 8 (depends on 4)

The method according to claim 4, wherein the molar ratio of base to ruthenium complex is 1 to 100:1.

### Claim 9 (depends on 4)

The method according to claim 4, wherein the temperature for the reaction is 60-180° C.

### Claim 10 (depends on 4)

The method according to claim 4, wherein the reaction time for the reaction is 0.1-1000 hours.

### Claim 11 (depends on 4)

The method according to claim 4, wherein the hydrogen pressure for the reaction is 1-100 atmospheres.

### Claim 12

A ruthenium complex according to structural formula 1b-1e:

### Claim 13 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11)

A method for preparing deuterated methanol and deuterated diol, wherein the method includes performing the method according to any one of claims 1-11 by using deuterium D2 instead of hydrogen H2, so as to give deuterated methanol and deuterated diol.

### Claim 14

A method for preparing alcohol, wherein the method includes, in the presence of a ruthenium complex (V) and a base, reducing carbonate through hydrogenation in a organic solvent, so as to give alcohol, wherein the ruthenium complex is shown in formula V
Ru(L)XYY′ (V);
in formula V:
X is carbon monoxide, triphenylphosphine, pyridine, tetrahydrofuran or dimethyl sulfoxide;
Y, Y′ are independently selected from: a hydride ion, a hydroxyl ion, a chloride ion, a bromide ion, an iodide ion and BH4−, BH3CN−, BH(Et)3−, BH(sec-Bu)3−, AlH4− or AlH2(OCH2CH2CH3)2−;
wherein L is a tridentate amino bisphosphorus ligand of general structural formula VI:
in general formula VI, n=0˜3;
R0 is H;
R1″, R2″ are independently selected from a C1˜C10 alkyl, a C3˜C10 cycloalkyl, a C4˜C24 aryl or an adamantyl, wherein the aryl is an unsubstituted or substituted aryl;
R3″, R4″, R5″, R6″, R7″, R8″ are independently selected from a hydrogen, a C1˜C10 alkyl, a C3˜C10 cycloalkyl, a C1˜C10 alkoxy or a C4˜C36 aryl;
when n=0, R3″ and R7″, R4″ and R8″ may be joined to form an alicyclic group or an aryl ring;
when n≧1, R3″ and R5″, R4″ and R6″, R5″ and R7″ as well as R6″ and R8″ may be joined to form an alicyclic group or an aryl ring.