Zinc complex

Patent metadata

Field	Value
Publication number	US-9611279-B2
Application number	US-201414769147-A
Country	US
Kind code	B2
Filing date	Mar 27, 2014
Priority date	Mar 27, 2013
Publication date	Apr 4, 2017
Grant date	Apr 4, 2017

Abstract

A zinc complex characterized in exhibiting an octahedral structure and being configured from repeating units represented by general formula (I):

wherein L represents a linker region, and R 1 represents a C1-4 alkyl group, which can have a halogen atom.

First claim

The invention claimed is:

1. A zinc complex with an octahedral geometry, comprising a repeating unit represented by general formula (I):

wherein L represents a linker moiety, and R 1 represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s).

2. A zinc complex obtained by reacting
a zinc carboxylate compound represented by general formula (III) or a zinc carboxylate compound represented by general formula (IV) with
a compound represented by general formula (V) in an amount of 2 mole equivalents to zinc atoms of the zinc carboxylate compound:
Zn(OCOR 1a ) 2 .x H 2 O  (III),

wherein R 1a represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and x represents any number of 0 or greater;
Zn 4 O(OCOR 1b ) 6 (R 1b COOH) n   (IV),

wherein R 1b represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and n represents 0 to 1; and

wherein L represents a linker moiety.

3. The zinc complex according to claim 2 , wherein
the linker L is represented by general formula (II):

wherein X represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryl group, an optionally substituted allyl group, or a substituted amino group.

4. A catalyst comprising the zinc complex according to claim 1 .

5. A method for acylating a hydroxy group, comprising
reacting a carboxylic acid or an ester thereof in the presence of the catalyst according to claim 4 .

6. A method for converting a hydroxy group to a carbonate, comprising
reacting a carbonate ester in the presence of the catalyst according to claim 4 .

7. A method for deacylating a carboxylate ester, comprising
deacylating the carboxylate ester in the presence of the catalyst according to claim 4 .

8. A method for acylating a hydroxy group with a carboxylic acid or an ester thereof, comprising
forming a catalyst by adding a zinc carboxylate compound represented by general formula (III) or a zinc carboxylate compound represented by general formula (IV) together with a compound represented by general formula (V) to an acylation reaction system:
Zn(OCOR 1a ) 2 .x H 2 O  (III),

wherein R 1a represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and x represents any number of 0 or greater;
Zn 4 O(OCOR 1b ) 6 (R 1b COOH) n   (IV),

wherein R 1b represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and n represents 0 to 1; and

wherein L represents a linker moiety.

9. A method for converting a hydroxy group to a carbonate with a carbonate ester, comprising
forming a catalyst by adding a zinc carboxylate compound represented by general formula (III) or a zinc carboxylate compound represented by general formula (IV) together with a compound represented by general formula (V) to a carbonate formation reaction system:
Zn(OCOR 1a ) 2 .x H 2 O  (III),

wherein R 1a represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and x represents any number of 0 or greater;
Zn 4 O(OCOR 1b ) 6 (R 1b COOH) n   (IV),

wherein R 1b represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and n represents 0 to 1; and

wherein L represents a linker moiety.

10. A method for deacylating a carboxylate ester, comprising
forming a catalyst by adding a zinc carboxylate compound represented by general formula (III) or a zinc carboxylate compound represented by general formula (IV) together with a compound represented by general formula (V) to a deacylation reaction system:
Zn(OCOR 1a ) 2 .x H 2 O  (III),

wherein R 1a represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and x represents any number of 0 or greater;
Zn 4 O(OCOR 1b ) 6 (R 1b COOH) n   (IV),

wherein R 1b represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and n represents 0 to 1; and

wherein L represents a linker moiety.

11. A method for producing a zinc complex represented by general formula (I), comprising
reacting a zinc carboxylate compound represented by general formula (III) or a zinc carboxylate compound represented by general formula (IV) with
a compound represented by general formula (V) in an amount of 2 mole equivalents to zinc atoms of the zinc carboxylate compound:

wherein L represents a linker moiety, and R 1 represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s);
Zn(OCOR 1a ) 2 .x H 2 O  (III),

wherein R 1a represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and x represents any number of 0 or greater;
Zn 4 O(OCOR 1b ) 6 (R 1b COOH) n   (IV),

wherein R 1b represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and n represents 0 to 1; and

wherein L represents a linker moiety.

12. The zinc complex according to claim 2 , wherein
the linker L is represented by general formula (II):

wherein X represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryl group, an optionally substituted allyl group, or a substituted amino group.

13. A catalyst comprising the zinc complex according to claim 2 .

14. A method for acylating a hydroxy group, comprising
reacting a carboxylic acid or an ester thereof in the presence of the catalyst according to claim 13 .

15. A method for converting a hydroxy group to a carbonate, comprising
reacting a carbonate ester in the presence of the catalyst according to claim 13 .

16. A method for deacylating a carboxylate ester, comprising
deacylating the carboxylate ester in the presence of the catalyst according to claim 13 .

Assignees

• Takasago Perfumery Co Ltd

Inventors

• Ohshima Takashi
• YAZAKI Ryo
• YOKOTE Yuki
• Matsushima Yoshimasa

Classifications

• B01J31/181

  Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine · CPC title

• C07C29/1285

  of esters of organic acids · CPC title

• B01J31/182

  comprising aliphatic or saturated rings · CPC title

• B01J2231/49

  Esterification or transesterification · CPC title

• C07C33/22

  Benzylalcohol; phenethyl alcohol · CPC title