JPS61249975A - Cyclic amine having omega-hydroxyalkyl group and production thereof - Google Patents

Abstract

NEW MATERIAL:A cyclic amine, having omega-hydroxyalkyl group and expressed by formula I (n is an integer >=4; m and l are 2 or 3). EXAMPLE:The compound expressed by formula II. USE:Capable of trapping molecular oxygen as an active species and useful as an oxygen catalyst. PREPARATION:An alpha-(omega-hydroxyalkyl)malonic acid diester expressed by formula III (R is lower alkyl) is condensed with a polyamine expressed by formula IV to give the aimed compound expressed by formula I. The condensation reaction is carried out by refluxing the reactants in a solvent, e.g. methanol, ethanol or propanol. The raw material compound expressed by formula III is synthesized by, for example brominating 1,4-butanediol, etherifying the resultant product with 3,4-dihydro-2H-pyran and reacting the product with a malonic acid dialkyl ether.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to a cyclic anone having an ω-hydroxyalkyl group and a method for producing the same. More specifically, the present invention relates to a cyclic amine having an ω-hydroxyalkyl group that can be pendant to various carboxylic acid dust polymers, and a method for producing the same.

[Prior Art] and [Problems to be Solved by the Invention] Cyclic amines can capture molecular oxygen as an active species, and therefore can be used as oxygen catalysts. The color also differs depending on whether it is present or not. These characteristics can be further enhanced by making the cyclic amine pendant in the polymer and exhibiting it in the polymer state.

and ζ, in the following general formula CI), n-2,! 1
A cyclic amine having a 2-hydroxyethyl group, which is 72, l''3, is already known as described in Tetrahedron Letters, 1977, Volume 12, pages 1049-1052. However, since this cyclic amine has a short alkyl group, it may be difficult to make it pendant to a sterically hindered polymer.

The present inventors have investigated the possibility of eliminating steric hindrance by increasing the chain length of the ω-hydroxyalkyl group of a cyclic amine to 4 or more carbon atoms, thereby obtaining a cyclic amine that can easily pendant into a polymer. I was able to achieve my goal.

[Means for Solving the Problems] and [Operation] Accordingly, the present invention relates to a cyclic amine having an ω-hydroxyalkyl group, which is represented by the following general formula (13).

n: an integer of 4 or more m: zt or 3 1: 2t or 3 The present invention also relates to a method for producing a cyclic amine having such an ω-hydroxyalkyl group. % (1) (wherein R is a lower alkyl group, n is an integer of 4 or more) and α-(ω-hydroxyalkyl)malonic acid diester and the general formula % ( (m and 1 are 2 or 3) are subjected to a condensation reaction.

α-(ω-H), which is one of the starting materials for cyclic amine synthesis
Oa xyalkyl) malonic acid diester [H] is 1,
4-butanediol, 1.6-hexanediol, 1.
One hydroxyl group of α,ω-flukanediol having carbon it4 or more such as 10-decanediol and 1,12-dodecanediol is brominated using hydrobromic acid etc., and the obtained ω-hydroxyalkyl bromide is 4-phydro-2M-bilane (see Helvetica Chimica Acta No. It is possible to create a compound that can be synthesized.

'HO(OHt)nOH+ HBr←HO(OH
z), B rThe other starting material polyamine (1)
as H,H'-bis(2-aminoethyl)-1,
3-propanediamine, M, M'-bis(2-aminoethyl)-1,2-ethanediamine, N, N'-(s-7
Minoprovir) -1,3-propanediamine, m, N
/ (3-aminopropyl)-1,2-ethanediamine is used.

The condensation reaction between these two starting materials is carried out by refluxing them in a solvent such as methanol, ethanol, propatool or the like.

〔Effect of the invention〕

By lengthening the alkyl group spacer of a cyclic amine having an ω-hydroxyalkyl group, a green amine that can be pendant to various carboxylic acid type polymers such as polyacrylic acid, polymethacrylic acid, and polyglutamic acid can be obtained. Obtained.

〔Example〕

Next, the present invention will be described with reference to one embodiment.

Example 1.6-h+'t on') Oh k 17a029 (
1,494#) and 47% hydrobromic acid 307.6
g (1,79 mol) with petroleum ether 100-
Reflux at 80°C for 8 hours, then distillation under reduced pressure to produce 6-hydroxyhexyl bromide (boiling point 105-106°C/sm
ag) was obtained in an amount of 136.90 (yield 51%).

[Infrared absorption spectrum]

-OH, 2850an-' 2930 cm-'-O
H3250-3480 cm Broad ('H-NM
R'1 δ1.48~Z15 I) pin 218 pieces -(O
H2) - Obtained 6-hydroxyhexyl bromide 6
3,4-dihydro-2H-bilane 39. L719 (0,346 mol) was placed on a water bath and, with stirring, 3,4-dihydro-2H-bilane 39.
009 (0,356 mol) was added dropwise. After the dripping is finished,
12N[010,175-] was added thereto, and the mixture was stirred overnight at room temperature. This was diluted with ether, washed with 2M NaOH and water using a separating funnel, dehydrated with anhydrous sodium sulfate, and then distilled under reduced pressure. 59.00 g (yield 64%) of an etherified product (boiling point 125°C/161101H) which was etherified at the 2-position of the pentamethylene oxide ring was obtained.

('H-NMR) δ 4.45 ppm) 1 ripple Oxide ring 2-40 two-tone 81.98-1.40 ppm
Multi 14 pieces 10H3-Ethanol 10 other than the above
5.19 (0.22 mol) of metallic sodium was dissolved in 0-, and 3 & 24 g (0.22 mol) of diethyl malonate was added to this.
, 22 mol) and stirred for 15 minutes, the entire amount of the above etherified product was added dropwise. - After refluxing at night, cool and filter sodium bromide through the suction port, then 30 m of ethanol.
1 g was added and stirred with 2N H, 50450- for 3 hours. The condensate 75- and Nichiru 100- were added and extracted using a separating funnel.

The ether extract layer was dehydrated with anhydrous sodium sulfate and then distilled under reduced pressure to obtain α-(6-hydroxyhexyl)malonic acid diethyl ester 1 point 134-135°C/&5v
21.199 mHg) (yield 37%) was obtained.

[Infrared absorption spectrum]

OH22850an 2930 cm-'-OH3
400-3600 pictures-1 broad) o-0 (outside nephew★)
1735oys-'1750an-'('H-M
MR) δ3.80~4.40X1prn multi 4 pieces Ethyl group - country, acceptable.

δ 1.15-1.34ppm) 6 rear frets
Echi 4-0H20H.

δ1.36-100% multi-hexyl ts central 4 pieces tv methylene group-(Qchi)4- α-(6-hydroxyhexyl) malonic acid diethyl ester 7.669 < 29.4 mmol) and H,H'-bis(2-aminoethyl)-1
4.959 (30.8 mmol) of 3-propanediamine were refluxed for 14 days in nitrogen gas with 50 - of ethanol. After the reaction, ethanol was distilled off, developed using a silica gel (Wako-0200) column in a methanol-fluoroform (1:1) mixed bath a, and a methanol-chloroform-aqueous ammonia (2:2:1) mixed solution Rf O, 88 ~ by thin layer chromatography using
A white solid obtained by chasing a spot of 0.93 and evaporating it to dryness was washed with ether while heating. As a result, 1.359 cyclic amines having a 6-hydroxyhexyl group were found to have the following structure (yield: 14%).
) obtained.

[Infrared absorption spectrum]

-OH3400~3600cm-' -NH3350 country-1

Claims (1)

[Claims] 1. ω represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] (where n is an integer of 4 or more, and m and 1 are 2 or 3) - A cyclic amine having a hydroxyalkyl group. 2. α-(ω-hydroxyalkyl)malonic acid represented by the general formula HO(CH_2)_nCH(COOR)_2[II] (where R is a lower alkyl group and n is an integer of 4 or more) Diester and general formula H_2N(CH_2)_
mNH(CH_2)_lNH(CH_2)_mNH_2
[III] (where m and 1 are 2 or 3) A general formula characterized by condensation reaction of polyamines ▲ There are mathematical formulas, chemical formulas, tables, etc. , m and l are as defined above).