JPH05194389A - Substituted glutaric ester compound - Google Patents

Abstract

PURPOSE:To obtain a new compound useful for a light stabilizer for organic material and an intermediate for medicines, agricultural chemicals, etc. CONSTITUTION:Compounds of formula I and formula II [A and B are group of formula III (R<1> is H, 1-4C alkyl or 7-11C aralkyl; R<2> is H or methyl)] such as di(2,2,6,6-tetramethyl-4-piperidinyl)=2-methyleneglutarate. The compounds of formula I and formula II are obtained by esterifying 2-methyleneglutaric acid, dimer of acrylic acid or 2-methylglutaric acid with a 4-hydroxypiperidine.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

The present invention relates to a substituted glutaric acid ester compound having a novel structure containing a piperidine group. More specifically, the present invention is useful as a light stabilizer for various organic materials or an intermediate thereof, and can also be used as an intermediate for medicines, agricultural chemicals, etc.
-A substituted glutaric acid ester compound containing a tetraalkylpiperidine skeleton.

[0002]

2. Description of the Related Art Conventionally, 2,2,6,6-tetraalkylpiperidine skeleton (so-called hindered amine skeleton)
It is known that the compound having is excellent in radical scavenging ability and is useful as a light stabilizer or an antioxidant for various organic materials including resins. Japanese Patent Laid-Open No. 1-155
Japanese Patent Publication No. 861 describes that a hindered amine derivative of itaconic acid represented by the following compound (a) is used as an antioxidant.

[0003]

[Chemical 2]

[0004]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of intensive investigations by the present inventors, a compound having higher performance as a light stabilizer and excellent reactivity as an intermediate thereof has been obtained.
Higher photostabilization effect and higher reactivity than compound (a),
The present invention has been completed by finding a substituted glutaric acid ester compound having a novel structure represented by the general formulas [I] and [II].

[Outline of Invention]

[Means for Solving the Problems]

<Summary> The substituted glutaric acid ester compound according to the present invention is represented by the following general formula [I] or [II].

[0006]

[In the formula, A and B may be the same or different and each represents a group represented by the following general formula [III].

[0008]

[Chemical 3]

(In the formula, R ¹ is a hydrogen atom or has 1 to 1 carbon atoms.
4 represents an alkyl group having 4 to 7 carbon atoms or an aralkyl group having 7 to 11 carbon atoms, and R ² represents a hydrogen atom or a methyl group. )]

<Effect> The compound of the present invention can be easily produced by an esterification reaction of 2-hydroxypiperidines with 2-methyleneglutaric acid or 2-methylglutaric acid, which is a dimer of acrylic acid. It is a compound showing a high light stabilizing effect on materials, particularly resins such as polyolefins.

Further, among the compounds of the present invention, a compound of the general formula [I]
The compound represented by has a double bond in the molecule and is rich in various reactivity such as Michael type addition reaction and Diels-Alder reaction. It also has an effect as an intermediate of the organic compound.

[Detailed Description of the Invention] <Substituted glutaric acid ester compound> The substituted glutaric acid ester compound of the present invention has the general formula [I] or the general formula [I]
I]. In the general formulas [I] and [II], A and B are groups represented by the general formula [III]. A
And B are usually the same.

Groups A and B representing a hindered amine moiety
In, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms.
Here, the alkyl group and the alkyl group in the aralkyl group may contain a double bond (the present invention shall be construed as such). Of these, R ¹ is preferably a hydrogen atom, a methyl group, an allyl group, a propyl group, a benzyl group or the like, and particularly preferably a hydrogen atom or a methyl group.

R ² is either a hydrogen atom or a methyl group, and in both cases, a similar light stabilizing effect is obtained.
From the viewpoint of production, a hydrogen atom is preferable.

The general formula [I] or the general formula [II] of the present invention
Representative examples of substituted glutaric acid ester compounds represented by
It is as follows. Note that these compounds will be referred to by the corresponding numbers below.

1) Di (2,2,6,6-tetramethyl-4-piperidinyl) = 2-methylene glutarate (Compound No. 1)

[0017]

[Chemical 4]

2) Di (1,2,2,6,6-pentamethyl-4-piperidinyl) = 2-methylene glutarate (Compound No. 2)

[0019]

[Chemical 5]

3) Di (1-allyl-2,2,6,6-
Tetramethyl-4-piperidinyl) = 2-methylene glutarate (Compound No. 3)

[0021]

[Chemical 6]

4) Di (1-benzyl-2,2,6,6)
-Tetramethyl-4-piperidinyl) = 2-methylene glutarate (Compound No. 4)

[0023]

[Chemical 7]

5) Di (2,6-diethyl-1,2,
3,6-Tetramethyl-4-piperidinyl) = 2-methylene glutarate (Compound No. 5)

[0025]

[Chemical 8]

6) Di (2,2,6,6-tetramethyl-4-piperidinyl) = 2-methylglutarate (Compound No. 6)

[0027]

[Chemical 9]

7) Di (1,2,2,6,6-pentamethyl-4-piperidinyl) = 2-methylglutarate (Compound No. 7)

[0029]

[Chemical 10]

8) Di (1-propyl-2,2,6,6
-Tetramethyl-4-piperidinyl) = 2-methyl glutarate (Compound No. 8)

[0031]

[Chemical 11]

9) Di (1-benzyl-2,2,6,6
-Tetramethyl-4-piperidinyl) = 2-methyl glutarate (Compound No. 9)

[0033]

[Chemical 12]

<Production of Compound> The substituted glutaric acid ester compound of the present invention can be produced by any method suitable for forming a bond and introducing or forming a substituent. One of the suitable manufacturing methods is, for example, the following manufacturing method.

[0035]

[Chemical 13]

The substituted glutaric acid ester compound [IV] (dimethyl = 2-methylene glutarate in this example) and the substituted glutaric acid of the present invention by a one-step or two-step transesterification reaction with the alcohol compounds A-OH and B-OH. Ester compounds [I] and [II] can be obtained.

In this reaction, as a catalyst, lithium amide,
It is usual to use a basic catalyst such as sodium methoxide and an organic solvent such as hexane, heptane, toluene and dioxane as a solvent. The reaction temperature is
A temperature in the range of 0 ° C to the solvent reflux temperature can be selected, but a preferable reaction temperature is 50 to 150 ° C.

<Usefulness of Compounds> The compounds [I] and [II] according to the present invention are useful as light stabilizers for various organic materials or intermediates for producing the same, and intermediates for pharmaceuticals, agricultural chemicals and the like. As described above, it is also useful as a body.

[0039]

EXAMPLES The following examples serve to illustrate the compounds according to the invention.

Example 1 [Production of di (2,2,6,6-tetramethyl-4-piperidinyl) = 2-methylene glutarate (Compound No. 1)]

In a 300 ml reactor equipped with a molecular sieve packed column, 2.58 g (15 mmol) of dimethyl 2-methylene glutarate, 4-hydroxy-
2,2,6,6-tetramethylpiperidine 5.19 g
(33 mmol), 0.10 g (4 mmol) of lithium amide and 200 ml of toluene were added, and at a solvent reflux temperature (reaction temperature of 107 ° C.), methanol azeotropic with toluene was adsorbed and removed with a molecular sieve.
Reacted for hours. After completion of the reaction, 150 ml of diethyl ether was added to the reaction solution, and this was washed twice with 50 ml of water. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated to give a white solid (6.44 g). This is n-
Recrystallized from hexane to give 5.58 g of the desired white crystal.
Was obtained (yield 88%).

The analytical values are as follows. (1) Melting point 73.6 ° C. (2) ¹ H-NMR (CDCl ₃ ) δ [ppm] (see FIG. 1) 0.72 (bs, 2H), 1.08-1.31 (m, 2)
8H), 1.86-2.02 (m, 4H), 2.45-
2.67 (m, 4H), 5.13-5.32 (m, 2
H), 5.58 (s, 1H), 6.17 (s, 1H)

(3) ¹³ C-NMR (CDCl ₃ ) δ
[Ppm] (see FIG. 2) 27.1, 28.8, 33.1, 34.6, 43.5,
43.6, 51.1, 68.6, 69.1, 125.
2, 139.1, 165.8, 171.9

(4) IR (KBr) wave number [cm ^-1 ] (see FIG. 3) 3446, 2964, 1725, 1711, 1636,
1375, 1366, 1327, 1250, 1162,
972

Example 2 [Di (1,2,2,6,6-pentamethyl-4-piperidinyl) = 2-methylene glutarate (Compound No. 2)
Manufacturing of〕

In Example 1, 4-hydroxy-2
Instead of 2,6,6-tetramethylpiperidine, 4-
Using 5.65 g (33 mmol) of hydroxy-1,2,2,6,6-pentamethylpiperidine, the same procedure as in Example 1 was carried out to obtain 6.76 g of a pale yellow viscous liquid. This was purified by alumina gel chromatography (n-hexane / ethyl acetate mixed solvent) to obtain 5.75 g of a slightly yellow viscous liquid which was a target substance (yield 85%).

The analytical values are as follows. (1) ¹ H-NMR (CDCl ₃ ) δ [ppm] 1.07 (s, 6H), 1.09 (s, 6H), 1.1
6 (s, 6H), 1.17 (s, 6H), 1.42-
1.60 (m, 4H), 1.79-1.92 (m, 4
H), 2.24 (s, 3H), 2.25 (s, 3H),
2.46-2.68 (m, 4H), 4.99-5.18
(M, 2H), 5.58 (s, 1H), 6.18 (s,
1H) (2) ¹³ C-NMR (CDCl ₃ ) δ [ppm] 20.7, 27.3, 28.0, 33.1, 45.8,
55.1, 67.8, 68.2, 125.4, 139.
3, 166.2, 172.3

Example 3 [Production of di (1,2,2,6,6-pentamethyl-4-piperidinyl) = 2-methylglutarate (Compound No. 7)]

In Example 1, 2.61 g (15 mmol) of dimethyl = 2-methylglutarate was replaced with 4-hydroxy-2,2,6,6-tetramethylpiperidine instead of dimethyl = 2-methyleneglutarate. By using 5.65 g (33 mmol) of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine in place of the above, 6.80 g of a pale yellow viscous liquid was obtained in the same manner as in Example 1. Obtained. This was purified by alumina gel chromatography (n-hexane / ethyl acetate mixed solvent) to obtain 5.91 g of a slightly yellow viscous liquid which was a target substance (yield 87%).

The analytical values are as follows. (1) ¹ H-NMR (CDCl ₃ ) δ [ppm] 1.05-1.20 (m, 24H), 1.47 (dd,
4H), 1.78-1.90 (m, 8H), 2.24.
(S, 6H), 2.32 (dd, 4H), 4.99-
5.12 (m, 2H) (2) ¹³ C-NMR (CDCl ₃ ) δ [ppm] 17.0, 20.6, 27.9, 28.6, 32.1,
33.1, 38.8, 45.7, 55.1, 67.6,
172.6, 175.6

Example 4 [Evaluation of Light Stabilizing Effect] The intrinsic viscosity measured in tetralin at 135 ° C. was 1.9, and the isotactic one was 98%.
100 parts by weight of polypropylene powder, tetrakis [3
0.1 parts by weight of-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane and 0.05 parts by weight of calcium stearate,
0.2 parts by weight of each of the compounds produced in Examples 1 to 3 was added as an additive compound to the mixture, thoroughly mixed with a mixer, melt-kneaded with a 20 mm diameter extruder at a cylinder temperature of 260 ° C., and granulated. The pellets obtained are 230 ° C.
Then, a test piece was prepared by compression molding into a sheet having a thickness of 0.5 mm. Of the composition of the test pieces, instead of the compounds produced in Examples 1 to 3, di (1,2,2,6,6)
-Pentamethyl-4-piperidinyl) itaconate (compound (a)) was used to form a sheet into a test piece for comparison in the same manner as the above-mentioned test piece.

These test pieces were manufactured by Atlas 65 / XW.
Using a -WR type xenon weatherometer, light irradiation was performed at a black panel temperature of 80 ° C., and light stabilization effects were compared by the time until each test piece deteriorates. The results obtained are
It was as shown in Table 1.

^{Table 1} Experiment No. Addition compound Photodegradation time [hr] 1 None 120 _2-di (1,2,2,6,6-pentamethyl-4-Piperi ₆₀₀ Jiniru) = itaconate (Compound (i)) _3-di (2,2,6,6-tetramethyl-4-piperidin ₇₆₀ Le) = 2-methylene glutarate (Compound No. 1) _4-di (1,2,2,6,6-pentamethyl-4-Piperi ₇₈₀ Jiniru) = 2-methylene glutarate (Compound No. 2) ₅ di (1,2,2,6,6-pentamethyl-4-piperidin ₇₆₀ dinyl) = 2-methyl glutarate (Compound No. 7)

[0054]

INDUSTRIAL APPLICABILITY The novel compound according to the present invention has a photostabilizing ability for organic compounds and is easy to manufacture, as described in the section of [Summary of the Invention].

[Brief description of drawings]

FIG. 1 is a ¹ H-NMR spectrum of di (2,2,6,6-tetramethyl-4-piperidinyl) = 2-methyleneglutarate (Compound No. 1) produced in Example 1.

FIG. 2 is a ¹³ C-NMR spectrum (proton decoupling method) of the same compound.

FIG. 3 is an IR absorption spectrum of the same compound.

Claims (1)

[Claims] 1. A substituted glutaric acid ester compound represented by the following general formula [I] or general formula [II]. [In the formula, A and B may be the same or different and each represents a group represented by the following general formula [III]. [Chemical 1] (In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms;
² represents a hydrogen atom or a methyl group. )]