Novel ruthenium complex and method for preparing methanol and diol
AssigneeShanghai Institute od Organic Chemistry, Chinese Academy of Sciences
InventorsKuiling Ding, Zhaobin Han
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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.
Claims15
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)—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, 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.
A ruthenium complex of 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 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
- wherein, when all of R3″, R4″, R5″, R6″, R7″ and R8″ are H, R2″ is not a phenyl.
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.
Dependencies are inferred from the claim text.