Hydrophilic polymer derivative having cyclic benzylidene acetal linker

Patent metadata

Field	Value
Publication number	US-2017107325-A1
Application number	US-201515300699-A
Country	US
Kind code	A1
Filing date	Mar 30, 2015
Priority date	Mar 31, 2014
Publication date	Apr 20, 2017
Grant date	—

Abstract

A hydrophilic polymer derivative having a cyclic benzylidene acetal linker represented by the following formula (1):

wherein R 1 and R 6 are each independently a hydrogen atom or a hydrocarbon group; R 2 , R 3 , R 4 and R 5 are each independently an electron-withdrawing or electron-donating substituent or a hydrogen atom; X 1 is a chemically reactive functional group; P is a hydrophilic polymer, s is 1 or 2, t is 0 or 1, and s+t is 1 or 2; w is an integer of 1 to 8; and Z 1 and Z 2 are each independently a selected divalent spacer.

First claim

1 . A hydrophilic polymer derivative having a cyclic benzylidene acetal linker represented by formula (1):

wherein R 1 and R 6 are each independently a hydrogen atom or a hydrocarbon group; R 2 , R 3 , R 4 and R 5 are each independently an electron-withdrawing or electron-donating substituent or a hydrogen atom; X 1 is a chemically reactive functional group; P is a hydrophilic polymer, s is 1 or 2, t is 0 or 1, and s+t is 1 or 2; m is an integer of 1 to 8; and Z 1 and Z 2 are each independently a selected divalent spacer.

2 . The hydrophilic polymer derivative as claimed in claim 1 , wherein s is 1 and t is 0, R 2 and R 5 are each a hydrogen atom, and a sum (Σσ) of substituent constants (σ) in R 3 , R 4 and P—Z 1 satisfies −0.30≦Σσ≦1.05.

3 . The hydrophilic polymer derivative as claimed in claim 1 , wherein s is 1 and t is 0, at least one of R 2 and R 5 is the substituent, and a sum (Σσ) of substituent constants (σ) in R 3 , R 4 and P—Z 1 satisfies −1.71≦Σσ≦0.88.

4 . The hydrophilic polymer derivative as claimed in claim 1 , wherein s is 1 and t is 1, or s is 2 and t is 0, R 2 and R 5 are each a hydrogen atom, and a sum (Σσ) of substituent constants (σ) in R 3 , R 4 and P—Z 1 satisfies −0.19≦Σσ≦0.57.

5 . The hydrophilic polymer derivative as claimed in claim 1 , wherein s is 1 and t is 1, or s is 2 and t is 0, at least one of R 2 and R 5 is the substituent, and a sum (Σσ) of substituent constants (σ) in R 3 , R 4 and P—Z 1 satisfies −0.98≦Σσ≦0.48.

6 . The hydrophilic polymer derivative as claimed in claim 1 , wherein X 1 is selected from the group consisting of an active ester group, an active carbonate group, an aldehyde group, an isocyanate group, an isothiocyanate group, an epoxy group, a maleimide group, a vinyl sulfone group, an acryl group, a sulfonyloxy group, a carboxy group, a thiol group, a dithiopyridyl group, an α-haloacetyl group, an alkynyl group, an allyl group, a vinyl group, an amino group, an oxyamino group, a hydrazide group and an azide group.

7 . The hydrophilic polymer derivative as claimed in claim 1 , wherein X 1 is selected from the group consisting of formula (a), formula (b), formula (c), formula (d), formula (e), formula (f), formula (g), formula (h), formula (i), formula (j), formula (k), formula (l), formula (m) and formula (n):

wherein R 7 is a hydrogen atom or a sulfo group; R 8 and R 11 are each independently a hydrogen atom or a hydrocarbon group having from 1 to 5 carbon atoms; R 9 is a hydrocarbon group having from 1 to 10 carbon atoms which may contain a halogen atom; and R 10 is a halogen atom selected from a chlorine atom, a bromine atom and an iodine atom.

8 . The hydrophilic polymer derivative as claimed in claim 1 , wherein Z 1 and Z 2 are each independently an ether bond, an ester bond, a carbonate bond, a urethane bond, an amide bond, a secondary amino group, an alkylene group containing any of these bonds and group, a single bond or an alkylene group, and in a case where at least one of Z 1 and Z 2 is an ether bond, an ester bond, a carbonate bond, a urethane bond, an amide bond, a secondary amino group or an alkylene group containing any of these bonds and group and a plurality of identical structural units are connected, a number of the structural units is 2 or less.

9 . The hydrophilic polymer derivative as claimed in claim 1 , wherein P is a linear polyethylene glycol having a hydrocarbon group or a chemically reactive functional group at its terminal.

10 . The hydrophilic polymer derivative as claimed in claim 9 , wherein w is 1, and P is represented by formula (2):
Y—(OCH 2 CH 2 ) n —  (2)

wherein Y is a hydrocarbon group having from 1 to 24 carbon atoms; and n is an integer of 3 to 2,000.

11 . The hydrophilic polymer derivative as claimed in claim 9 , wherein w is 1, and P is represented by formula (3):
X 2 —Z 3 —(OCH 2 CH 2 ) n —  (3)

wherein X 2 is a chemically reactive functional group different from X 1 ; Z 3 is a divalent spacer, and n is an integer of 3 to 2,000.

12 . The hydrophilic polymer derivative as claimed in claim 1 , wherein P is a branched polyethylene glycol having a hydrocarbon group or a chemically reactive functional group different from X 1 at its terminal.

13 . The hydrophilic polymer derivative as claimed in claim 12 , wherein w is 1, and P is represented by formula (4):

wherein Y is a hydrocarbon group having from 1 to 24 carbon atoms; n is an integer of 3 to 1,000; and v is 0 or 2.

14 . The hydrophilic polymer derivative as claimed in claim 12 , wherein w is 1, and P is represented by formula (5):

wherein X 2 is a chemically reactive functional group different from X 1 ; Z 3 is a divalent spacer, n is an integer of 3 to 1,000; and v is 0 or 2.

15 . The hydrophilic polymer derivative as claimed in claim 12 , wherein w is v+2, and P is represented by formula (6):

wherein X 2 is a chemically reactive functional group different from X 1 ; Z 3 is a divalent spacer, n is an integer of 3 to 1,000; and v is 0 or 2.

16 . The hydrophilic polymer derivative as claimed in claim 11 , wherein X 2 is selected from the group consisting of an active ester group, an active carbonate group, an aldehyde group, an isocyanate group, an isothiocyanate group, an epoxy group, a maleimide group, a vinyl sulfone group, an acryl group, a sulfonyloxy group, a carboxy group, a thiol group, a dithiopyridyl group, an α-haloacetyl group, an alkynyl group, an allyl group, a vinyl group, an amino group, an oxyamino group, a hydrazide group and an azide group.

17 . The hydrophilic polymer derivative as claimed in claim 11 , wherein X 2 is selected from the group consisting of formula (a), formula (b), formula (c), formula (d), formula (e), formula (f), formula (g), formula (h), formula (i), formula (j), formula (k), formula (l), formula (m) and formula (n):

wherein R 7 is a hydrogen atom or a sulfo group; R 8 and R 11 are each independently a hydrogen atom or a hydrocarbon group having from 1 to 5 carbon atoms; R 9 is a hydrocarbon group having from 1 to 10 carbon atoms which may contain a halogen atom; and R 10 is a halogen atom selected from a chlorine atom, a bromine atom and an iodine atom.

18 . The hydrophilic polymer derivative as claimed in claim 11 , wherein Z 3 is an ether bond, an ester bond, a carbonate bond, a urethane bond, an amide bond, a secondary amino group, an alkylene group containing any of these bonds and group, a single bond or an alkylene group, and in a case where Z 3 is an ether bond, an ester bond, a carbonate bond, a urethane bond, an amide bond, a secondary amino group or an alkylene group containing any of these bonds and group and a plurality of identical structural units are connected, a number of the structural units is 2 or less.

19 . The hydrophilic polymer derivative as claimed in claim 1 , wherein P is polyethylene glycol having a

Assignees

• Nof Corp

Inventors

• TSUBUSAKI Takuma
• Yamamoto Yuji

Classifications

• C08G65/3346

  having sulfur bound to carbon and oxygen · CPC title

• C07D317/24

  esterified · CPC title

• C08G65/329

  with organic compounds · CPC title

• C07D317/22

  etherified · CPC title

• C08G65/333

  containing nitrogen · CPC title