Salts of diamino acetals and diamino ketals, their synthesis and their conversion to diamino acetals and diamino ketals

文档序号:883666 发布日期:2021-03-19 浏览:9次 中文

阅读说明:本技术 二氨基缩醛和二氨基缩酮的盐及它们的合成及它们向二氨基缩醛和二氨基缩酮的转化 (Salts of diamino acetals and diamino ketals, their synthesis and their conversion to diamino acetals and diamino ketals ) 是由 S.科辛斯基 S.J.帕斯汀 U.巴特 于 2019-01-07 设计创作,主要内容包括:本申请部分涉及由下列式(1)的结构表示的新型盐及其制备方法:其中R~(1a)选自:氢、任选取代的烷基(例如,未取代的C-(1-6)烷基,例如,-CH-3);R~(1b)为任选取代的烷基(例如,未取代的C-(1-6)烷基,例如,-CH-3);R~2和R~3的每一种情况独立地选自:氢、任选取代的烷基、任选取代的环烷基、和任选取代的芳基;R~2和R~3可以彼此组合以形成任选取代的环烷基;各m和n独立地为1至20的整数(例如,m和n独立地为1至5的整数);且各和独立地为抗衡离子(例如,和各自独立地为选自以下的抗衡离子:氯离子、溴离子、氟离子、碘离子、醋酸根、羧酸根、硫酸氢根、硝酸根和苯酚根、以及磺酸根,例如,氯离子)。(The present application relates, in part, to novel salts represented by the structure of the following formula (1) and methods of making the same: wherein R is 1a Selected from: hydrogen, optionally substituted alkyl (e.g. unsubstituted C) 1‑6 Alkyl radicals, e.g., -CH 3 );R 1b Is optionally substituted alkyl (e.g., unsubstituted C) 1‑6 Alkyl radicals, e.g., -CH 3 );R 2 And R 3 Each instance of (a) is independently selected from: hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, and optionally substitutedA substituted aryl group; r 2 And R 3 May be combined with each other to form optionally substituted cycloalkyl; each m and n is independently an integer from 1 to 20 (e.g., m and n are independently an integer from 1 to 5); and each is And independently, a counter ion (e.g., and each independently a counterion selected from: chloride, bromide, fluoride, iodide, acetate, carboxylate, bisulfate, nitrate and phenolate, and sulfonate, e.g., chloride).)

1. A compound represented by the formula (2-a), and a salt thereof:

wherein:

R1aindependently selected from: hydrogen and optionally substituted alkyl;

R1bis optionally substituted alkyl; and is

R2cAnd R2dEach independently selected from optionally substituted alkyl.

2. The compound of claim 1, wherein R1aIs hydrogen and R1bIs unsubstituted C1-6An alkyl group.

3. The compound of claim 1, R1aAnd R1bEach independently selected from unsubstituted C1-6An alkyl group.

4. The compound of claim 1, wherein R2cAnd R2dEach independently selected from unsubstituted C1-6An alkyl group.

5. The compound of claim 1, wherein the compound is selected from the group consisting of a compound represented by formula (2-a-I) and a compound represented by formula (2-a-II):

6. the compound of claim 1, wherein the compound is selected from compounds represented by the formula (2-a-I):

7. the compound of claim 1, wherein the compound is selected from compounds represented by the formula (2-a-II):

8. the compound of claim 1, wherein the compound is selected from

9. The compound of claim 1, wherein the compound is selected from

10. The compound of claim 1, wherein the compound is selected from

11. The compound of claim 1, wherein the compound is selected from

12. A salt of the compound of claim 1.

13. The salt of claim 11, wherein the salt is a diammonium salt.

14. The salt of claim 11, wherein the salt is the dihydrochloride salt.

15. A salt of the compound of claim 8.

16. The salt of claim 11, wherein the salt is a diammonium salt.

17. The salt of claim 11, wherein the salt is the dihydrochloride salt.

18. A method for preparing a compound represented by formula (2):

wherein

R1aSelected from: hydrogen and optionally substituted alkyl;

R1bis optionally substituted alkyl;

R2and R3Each instance of (a) is independently selected from: hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, and optionally substituted aryl, or R2And R3May be combined with each other to form optionally substituted cycloalkyl; and is

Each m and n is independently an integer from 1 to 20,

the method comprises contacting a salt of a compound of formula (2) with a base to produce a compound of formula (2).

19. The method of claim 18, wherein the salt of the compound of formula (2) is a salt of formula (1):

wherein

R1aSelected from: hydrogen and optionally substituted alkyl;

R1bis optionally substituted alkyl;

R2and R3Each instance of (a) is independently selected from: hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl and optionally substituted aryl;

R2and R3May be combined with each other to form optionally substituted cycloalkyl;

each m and n is independently an integer from 1 to 20; and is

Andeach independently a counterion.

20. A method for producing a salt of a compound represented by formula (2-1):

wherein

R1aSelected from: hydrogen and optionally substituted alkyl;

R1bis optionally substituted alkyl;

R2and R3Each instance of (a) is independently selected from: hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, and optionally substituted aryl, or R2And R3May be combined with each other to form optionally substituted cycloalkyl; and is

Each instance of n is independently an integer from 1 to 20,

the method comprises reacting an aldehyde equivalent or a ketone equivalent with a salt represented by formula (3) to produce a salt of formula (1).

21. The method of claim 20, wherein each n is 2.

22. The method according to claim 20, wherein the salt of the compound represented by formula (2-1) is a salt represented by formula (1-1):

wherein

R1aSelected from: hydrogen and optionally substituted alkyl;

R1bis optionally substituted alkyl;

R2and R3Each instance of (a) is independently selected from: hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl and optionally substituted aryl;

R2and R3May be combined with each other to form optionally substituted cycloalkyl;

each n is independently an integer from 1 to 20; and is

Andeach independently a counterion.

23. The method of claim 22, whereinAndare all chloride ions.

24. The method of claim 20, wherein the salt represented by formula (1-1) is a salt of a compound represented by formula (1-a-II):

25. the method of claim 20, wherein the salt represented by formula (1-1) is a salt of a compound represented by formula (1-a-II):

wherein R is2Is unsubstituted C1-6Alkyl and R1aIndependently selected from hydrogen and-CH3

26. The process of claim 20, wherein the ketone equivalent is selected from the group consisting of 2, 2-dimethoxypropane, 2-methoxypropene, 2-diethoxypropane; and 2-ethoxypropene.

27. The process of claim 26, wherein the ketone equivalent is selected from the group consisting of 2, 2-dimethoxypropane and 2-methoxypropene.

28. The process of claim 27, wherein the ketone equivalent is 2, 2-dimethoxypropane.

29. The method of claim 27, wherein the ketone equivalent is 2-methoxypropene.

30. The method of claim 20, wherein the aldehyde equivalent is selected from the group consisting of 1,1 dimethoxyethane, methyl vinyl ether, 1-diethoxyethane, and ethyl vinyl ether.

31. The method of claim 20, wherein the salt of formula (3) is selected from the group consisting of:

32. the method of claim 20, further comprising contacting a salt of the compound of formula (1-1) with a base to react to produce the compound of formula (2).

33. The method of claim 25, wherein the compound of formula (2) is selected from the group consisting of:

34. the process of claim 20, wherein the reaction is carried out in the presence of a solvent.

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