Method for producing polyalkylene glycol derivative having amino group at end, polymerization initiator for use in the same, and alcohol compound as raw material for the polymerization initiator

Patent metadata

Field	Value
Publication number	US-2016159979-A1
Application number	US-201514959318-A
Country	US
Kind code	A1
Filing date	Dec 4, 2015
Priority date	Dec 4, 2014
Publication date	Jun 9, 2016
Grant date	—

Abstract

A method for producing a narrowly distributed and high-purity polyalkylene glycol derivative having an amino group at an end, a polymerization initiator for use in the method, and a precursor of the polymerization initiator are provided.
The present invention provides: a method for producing a polyalkylene glycol derivative having an amino group at an end, using, as a polymerization initiator, a compound represented by the general formula (I); a compound represented by the following general formula (I); and a precursor thereof:

wherein R A 1a and R A 1b each independently represent a protective group of the amino group, or one of R A 1a and R A 1b represents H and the other represents a protective group of the amino group, or R A 1a and R A 1b bind to each other to represent a cyclic protective group forming a ring; R A 2 represents a linear, branched, or cyclic hydrocarbon group having 1 to 6 carbon atoms; R A 3 represents a single bond, or a linear, branched, or cyclic hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain a heteroatom; the total number of carbon atoms (or the total number of carbon atoms and heteroatoms) of R A 2 and R A 3 is 4 or more; and M represents an alkali metal.

First claim

What is claimed is:

1 . A method for producing a polyalkylene glycol derivative having an amino group at an end, comprising at least a step of reacting a polymerization initiator represented by the following general formula (I) with an alkylene oxide:

wherein R A 1a and R A 1b each independently represent a protective group of the amino group, or one of R A 1a and R A 1b represents a hydrogen atom and the other represents a protective group of the amino group, or R A 1a and R A 1b bind to each other to represent a cyclic protective group forming a ring together with a nitrogen atom of the amino group;
R A 2 represents a linear divalent hydrocarbon group having 1 to 6 carbon atoms, or a branched or cyclic divalent hydrocarbon group having 3 to 6 carbon atoms;
R A 3 represents a single bond, or a linear divalent hydrocarbon group having 1 to 20 carbon atoms, or a branched or cyclic divalent hydrocarbon group having 3 to 20 carbon atoms, and the hydrocarbon group may comprise a heteroatom;
a total number of carbon atoms of R A 2 and R A 3 is 4 or more, or in a case in which R A 3 comprises a heteroatom, a total number of carbon atoms and heteroatoms of R A 2 and R A 3 is 4 or more; and
M represents an alkali metal.

2 . A method for producing a polyalkylene glycol derivative having an amino group at an end, comprising the following steps a) to step c):

wherein R A 1a and R A 1b each independently represent a protective group of the amino group, or one of R A 1a and R A 1b represents a hydrogen atom and the other represents a protective group of the amino group, or R A 1a and R A 1b bind to each other to represent a cyclic protective group forming a ring together with a nitrogen atom of the amino group;
R A 2 represents a linear divalent hydrocarbon group having 1 to 6 carbon atoms, or a branched or cyclic divalent hydrocarbon group having 3 to 6 carbon atoms;
R A 3 represents a single bond, or a linear divalent hydrocarbon group having 1 to 20 carbon atoms, or a branched or cyclic divalent hydrocarbon group having 3 to 20 carbon atoms, and the hydrocarbon group may comprise a heteroatom;
a total number of carbon atoms of R A 2 and R A 3 is 4 or more, or in a case in which R A 3 comprises a heteroatom, a total number of carbon atoms and heteroatoms of R A 2 and R A 3 is 4 or more;
R A 4 represents a hydrogen atom, or a linear, branched, or cyclic hydrocarbon group that may be substituted, the hydrocarbon group having 1 to 12 carbon atoms, and the hydrocarbon group may comprise a heteroatom;
R A 5 represents an alkylene group having 2 to 8 carbon atoms;
M represents an alkali metal; and
n represents an integer of 1 to 450;
Step a)
a step of reacting a polymerization initiator represented by the general formula (I) with an alkylene oxide in a polymerization solvent to obtain a compound represented by the following general formula (I-1):

wherein R A 1a , R A 1b , R A 2 , R A 3 and R A 5 are the same as defined in the general formula (II);
M represents an alkali metal and is the same as M in the general formula (I); and
r represents an integer of 1 to 445;
Step b)
a step of reacting the compound represented by the general formula (I-1) with a compound represented by the following general formula (I-2) to obtain a compound represented by the general formula (II):
R A 4 (OR A 5 ) k L  (1-2)

wherein R A 4 and R A 5 are the same as defined in the general formulas (II) and (III);
k represents an integer of 0 to 5; and
L represents a leaving group; and
Step c)
a step of deprotecting the compound represented by the general formula (II) to obtain a compound represented by the general formula (III).

3 . The method according to claim 2 , wherein R A 1a and R A 1b in the general formulas (I) to (III) each represent a protective group being deprotectable without using a heavy metal catalyst, and the compound represented by the general formula (II) is deprotected without using a heavy metal catalyst in the step c).

4 . The method according to claim 2 , further comprising a pre-step for synthesizing the polymerization initiator represented by the general formula (I) prior to the step a), the pre-step comprising at least a step of reacting a compound represented by the following general formula (i) with an alkali metal or an alkali metal compound selected from M, M + H − , R X − M + , [R Y ] •− M + and R Z O − M + (wherein M represents an alkali metal, R X represents an alkyl group that may have a substituent, the alkyl group having 1 or 20 carbon atoms, R Y represents an aromatic compound that may have a substituent, and R Z represents an alkyl group having 1 to 6 carbon atoms) to obtain the polymerization initiator represented by the general formula (I):

wherein R A 1a , R A 1b , R A 2 and R A 3 are the same as defined in the general formula (I).

5 . The method according to claim 2 , wherein the polymerization initiator represented by the formula (I) used in the step a) is a polymerization initiator represented by the following general formulas (1) and/or (2), and the compound represented by the general formula (III) obtained in the step c) is a compound represented by the following general formulas (3) and/or (4):

wherein R 1 each independently represent a linear monovalent hydrocarbon group having 1 to 6 carbon atoms, or a branched or cyclic monovalent hydrocarbon group having 3 to 6 carbon atoms, or R 1 may bind to each other to form a 3 to 6 membered ring together with a silicon atom having bonds with R′;
R 2 represents a linear divalent hydrocarbon group having 1 to 6 carbon atoms, or a branched or cyclic divalent hydrocarbon group having 3 to 6 carbon atoms; and
R 3 represents a linear divalent hydrocarbon group having 4 to 6 carbon atoms;
R 5 represents an alkylene group having 2 to 8 carbon atoms;
M represents an alkali metal; and
m represents an integer of 1 to 3;
H 2 NR 2 (OR 5 ) n+m OR 4   (3)

H 2 N—R 3 (OR 5 ) n —OR 4   (4)

wherein R 2 , R 3 , R 5 , and m are the same as defined in the general formulas (1) and (2);
R 4 represents a hydrogen atom, or a linear, branched, or cyclic hydrocarbon group that may be substituted, the hydrocarbon group having 1 to 12 carbon atoms and the hydrocarbon group may comprise a heteroatom; and
n represents an integer of 1 to 450.

6 . The method according to claim 5 , wherein the compound represented by the general formula (i) used in the pre-step is a compound represented by the following general formulas (6) and/or (7):

wherein R 1 , R 2 , R 3 , R 5 , and m are the same as defined in the general formulas (1) and (2).

7 . The method according to claim 4 , wherein, in the pre-step, the compound represented by the general formula (i) is reacted with an alkali metal or an alkali met

Assignees

• Shinetsu Chemical Co

Inventors

• Suka Yuki
• Harada Yuji
• Watanabe Takeru
• Nonaka Shiori

Classifications

• C08G65/2609

  containing aliphatic hydroxyl groups · CPC title

• Y02P20/55

  Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups · CPC title

• C07F7/10 Primary

  containing nitrogen {having a Si-N linkage} · CPC title

• C08G65/329

  with organic compounds · CPC title

• C08G65/2618

  the other compounds containing nitrogen · CPC title