METHOD FOR PRODUCING POLYALKYLENE GLYCOL DERIVATIVE HAVING AMINO GROUP AT END

• US 20190322688A1
• Filed: 06/27/2019
• Published: 10/24/2019
• Est. Priority Date: 12/04/2014
• Status: Active Grant

• Current Assignee: Shin-Etsu Chemical Company Limited
• Original Assignee: Shin-Etsu Chemical Company Limited
• Inventors: Suka, Yuki, Harada, Yuji, Watanabe, Takeru, Nonaka, Shiori
• Granted Patent: US 11,066,430 B2
• Time in Patent Office: Days
• CPC Class Codes: C07F 7/0892 Compounds with a Si-O-N linkage
• CPC Class Codes: C07F 7/10 containing nitrogen having a Si-N linkage
• CPC Class Codes: C08G 65/12 containing organo-metallic compounds or metal hydrides
• CPC Class Codes: C08G 65/2609 containing aliphatic hydroxyl groups
• CPC Class Codes: C08G 65/33303 containing amino group
• CPC Class Codes: C08G 65/33306 acyclic
• CPC Class Codes: Y02P 20/55 Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Abstract

A method simply produces a narrowly distributed and high-purity polyalkylene glycol derivative having an amino group at an end without using a heavy metal catalyst. A method for producing a polyalkylene glycol derivative having an amino group at the end by reacting a compound represented by the general formula (V) with an alkylene oxide, then reacting a reaction product with an electrophile represented by the general formula (I), and deprotecting the obtained product without using a heavy metal:

R_A³O(R_A⁴O)_k−1R_A⁴O⁻M⁺  (V)

• • wherein R_A³ represents a linear, branched, or cyclic hydrocarbon group having 1 to 20 carbon atoms; R_A⁴ represents an alkylene group having 2 to 8 carbon atoms; k represents an integer of 2 to 5; and M represents an alkali metal;

• • 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 form a cyclic protective group, and the protective group is deprotectable without using a heavy metal; R_A² represents a linear, branched, or cyclic hydrocarbon group having 1 to 6 carbon atoms; and X represents a leaving group.

Claims

1-22. -22. (canceled)

23. An electrophile of formula (I):

24. The electrophile according to claim 23, wherein X is p-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate.

25. An alcohol compound having silyl-protected amino group of formula (I-2-A):

26. A method for producing the alcohol compound having silyl-protected amino group of formula (I-2-A) according to claim 25, comprising:

protecting an amino group of an aminoalkyl compound of formula (I-0-A) with two trialkylsilyl groups of Si(R¹)₃, and protecting a hydroxyl group of the compound of formula (I-0-A) with a trialkylsilyl group of Si(R¹)₃ to obtain a trisilyl compound of formula (I-1-A);

HO—

R_A²—

NH₂ 

 

(I-0-A)

wherein R_A² is the same as R_A² in formula (I-2-A);

27. The method according to claim 26, wherein the group of Si(R¹)₃ is independently selected from a trimethylsilyl group, a triethylsilyl group, and a tert-butyldimethylsilyl group.

28. A method for producing the electrophile of formula (I):

29. The method according to claim 28, wherein the sulfonic halide is p-toluenesulfonyl chloride or methanesulfonyl chloride.