JPH0532626A - Phenolic compound - Google Patents

Abstract

PURPOSE:To provide a novel phonolic compound having a piperidine skeleton and useful as a light stabilizer for various organic materials (especially resins such as polyolefins), as an intermediate thereof, or as an intermediate for medicines, agricultural chemicals, etc. CONSTITUTION:A phenolic compound of formula I (R<1>, R<2> are H, 1-5C alkyl; R<3>, R<4> together form =CHR<7>, or R<3> is H and R<4> is CH2R<7>; R<2> is phenyl or cyclohexyl which may be substituted; R<5> is H, CH3; R<6> is H, 1-4C alkyl; n is an integer of 0-3), e.g. [3-benzyl-2,2,6,6-tetramethylpiperidine-4-yl 3-(3,5-di-t- butyl-4-hydroxyphenyl) propanoate. The compound can be produced by transesterification of an ester compound of formula II with an alcohol compound. The compound of formula I can industrially be produced, is substantially not bled out from resins, and has high light stabilization effect and excellent hydrolysis resistance.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

TECHNICAL FIELD The present invention relates to a phenol compound having a novel structure containing a piperidine skeleton. 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. 2,2,6,6-tetraalkylpiperidine skeleton To a phenol compound containing

[0002]

2. Description of the Related Art Conventionally, 2,2,6,6-tetraalkylpiperidine skeleton (so-called hindered amine skeleton)
The compound having is excellent in radical scavenging ability and is particularly used as a light stabilizer for various organic materials including resins. Among the light stabilizers having such a hindered amine skeleton, those generally used as light stabilizers for resins include 2,2,6,6-tetramethylpiperidinol and a polyvalent carboxylic acid. There are many ester compounds,
Among them, bis (2,2,6,6-tetramethyl-4-
Piperidyl) sebacate (commercially available is Sanol LS770 manufactured by Sankyo Co., Ltd.) is often used.

Japanese Patent Publication No. 58-38471 discloses 3,5-dialkyl-4-hydroxybenzoic acid or 3,5-dialkyl-4-hydroxyphenylalkylcarboxylic acid and 2,2,6,6-tetracarboxylic acid. Ester compounds with methylpiperidinol are disclosed as light stabilizers.

[0004]

When these light stabilizers are used in the resin, the light stabilizing effect is high, but since the bleed-out from the resin is more severe, does it escape from the inside of the resin during the molding process? Alternatively, it has a drawback that when the resin is used, it is gradually deposited on the surface of the resin to impair the appearance. As a result of studying to solve such a drawback, the present inventors have found that the compound can be produced industrially, has less bleed-out from a resin, and has a high photostabilization effect. The present invention has been completed by discovering a phenol compound having a novel structure shown below.

[Outline of Invention]

[0006]

The phenol compound according to the present invention is represented by the following general formula [I].

[0007]

[Chemical 2] [In the formula, R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be the same or different.

R ³ and R ⁴ together are ═CH—
Is R ⁷ , or R ³ is a hydrogen atom and R ⁴ is-
CH ₂ —R ⁷ or either (provided that R ⁷
Represents a substituted or unsubstituted phenyl group or cyclohexyl group (wherein the substituent is an alkyl group having 1 to 4 carbon atoms).

R ⁵ represents a hydrogen atom or a methyl group.

R ^{6 represents a} hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

N represents an integer of 0 to 3. <Effects of the Invention> The compound according to the present invention can be easily produced by an esterification reaction between a hydroxyphenyl group-containing carboxylic acid and 4-hydroxypiperidines,
It is a compound showing a high light stabilizing effect on organic materials, particularly resins such as polyolefins.

In the compound [I] of the present invention, R
A compound having a substituent such as a benzyl group or a cyclohexylmethyl group in ³ or R ⁴ is excellent in compatibility with various organic materials including resins, particularly polyolefins such as polyethylene, polypropylene and polystyrene, so that bleed out is caused. It has a small effect of improving the appearance of the organic material to be added, and has a high light stabilizing effect. Further, the light stabilizer having a structure in which a substituent is introduced into R ³ or R ⁴ as described above is bis (2,2,6,6-
R ³ as found in most of conventional light stabilizers such as tetramethyl-4-piperidyl) sebacate [trade name Sanol LS770 manufactured by Sankyo Co., Ltd.]
Alternatively, it also has an effect of being excellent in hydrolysis resistance as compared with a structure in which R ⁴ has no substituent.

[Detailed Description of the Invention] <Phenol Compound> The phenol compound of the present invention is represented by the following general formula [I].

[0014]

[Chemical 3] Here, R ¹ and R ² can each be arbitrarily selected from a hydrogen atom or an alkyl group having 1 to 5 carbon atoms and may be the same or different. Among them, at least one of R ¹ and R ² is preferably an alkyl group having 3 to 5 carbon atoms, and particularly preferably a t-butyl group or a t-amyl group.

R ³ and R ⁴ together are a benzylidene group or a substituted benzylidene group, a cyclohexylmethylidene group or a substituted cyclohexylmethylidene group, or R ³ is a hydrogen atom and R ⁴ is a benzyl group. Or a substituted benzyl group, a cyclohexylmethyl group, or a substituted cyclohexylmethyl group. R ³ and R ⁴ together form a benzylidene group or a substituted benzylidene group, or a cyclohexylmethylidene group or a substituted cyclohexylmethylidene group in view of excellent compatibility with various organic materials, particularly polyolefins, and an effect of hydrolysis resistance. Or when R ³ is a hydrogen atom, R ⁴ is preferably a benzyl group or a substituted benzyl group, or a cyclohexylmethyl group or a substituted cyclohexylmethyl group, among which R ³ is a hydrogen atom, It is particularly preferable that R ⁴ is a benzyl group or a substituted benzyl group, or a cyclohexylmethyl group or a substituted cyclohexylmethyl group.

R ⁵ 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.

R ⁶ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and among them, a hydrogen atom or a methyl group is preferable.

N is an integer of 0 to 3, and preferably 1 or 2.

Typical examples of the phenol compound represented by the general formula [I] of the present invention include substituents R ^{1 to} R ⁶ and n.
Are those shown in Table 1. Note that these compounds will be referred to by the corresponding numbers below. -TC ₄ and H ₉ are t- butyl _group, -tC _{5 H 11} is a t- aluminum group, also, _-C 6 _{H 5} and _-C 6 _{H 11}
Each represents a phenyl group and a cyclohexyl group,
₆ H ₄ -CH ₃ and _-C 6 _H 10 -CH ₃ shows the corresponding ring-substituted bodies (para).

[0020]

[Table 1] <Production of Compound> The phenol compound of the present invention can be produced by any method that is purposeful for forming a bond and introducing or forming a substituent. One of the suitable production methods comprises, for example, the following reactions.

[0021]

[Chemical 4] The phenol compound [I] of the present invention is obtained by the transesterification reaction of the ester compound [II] and the alcohol compound [III].
Can be obtained. The definitions of R ^{1 to} R ⁶ and n in the ester compound [II] and the alcohol compound [III] are the same as those shown in the general formula [I].

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 can be selected in the range of 0 ° C to the solvent reflux temperature, but the preferable reaction temperature is 50 to 150 ° C. <Usefulness of Compounds> The compound [I] according to the present invention is useful as a light stabilizer for various organic materials or an intermediate for producing the same, and is also useful as an intermediate for pharmaceuticals, agricultural chemicals and the like. Is as described above.

[0023]

EXAMPLES The following examples serve to illustrate the compounds according to the invention. <Example 1> [3-benzyl-2,2,6,6-tetramethylpiperidin-4-yl 3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propanoate (Compound No. 1)
Manufacturing] 300 equipped with Dean-Stark cooling pipe
In a reactor of ml, 8.8 g of methyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propanoate
(30 mmol) 3-benzyl-2,2,6,6-tetramethyl-4-hydroxypiperidine 7.4 g (30
Mmol), 0.15 g (3 mmol) of sodium methoxide and 150 ml of n-heptane, and reacted at a solvent reflux temperature (reaction temperature 100 ° C.) for 6 hours while separating and removing methanol azeotroping with n-heptane. did. 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 obtain 14.8 g of a slightly yellow transparent viscous liquid. Silica gel chromatography (chloroform-ethyl acetate mixed solvent)
And purified to obtain 12.7 g of a colorless transparent viscous liquid which is the target. (Yield 84%) The physical properties are as follows. (1) ¹ H-NMR (CDCl ₃ ) δ [ppm] (see FIG. 1) 0.83-0.93 (m, 1H), 1.03-1.57
(M, 31H), 1.62-1.77 (m, 1H),
1.77-1.91 (m, 1H), 2.47-2.85
(M, 4H), 2.87-3.02 (m, 2H), 4.
90-5.05 (m, 1H), 5.07 (s, 1H),
6.95-7.30 (m, 7H) (2) ¹³ C-NMR (CDCl ₃ ) δ [ppm] (see FIG. 2) 26.8, 30.3, 30.4, 30.9, 32 .8,
33.2, 34.3, 34.4, 36.8, 40.6,
49.2, 49.9, 53.0, 69.9, 124.
8, 125.9, 128.4, 128.9, 130.
9, 135.9, 140.8, 152.2, 172.3 (3) IR (KBr) wavenumber [cm ^-1 ] (see FIG. 3) 3638, 2954, 1730, 1629, 1602,
1434, 1362, 1314, 1233, 1161,
1038, 978, 768, 733, 700, 521,
460 <Example 2> [3-Cyclohexylmethyl-2,2,6,6-tetramethylpiperidin-4-yl 3- (3,5-di-t-
Production of butyl-4-hydroxyphenyl) propanoate (Compound No. 2)] In Example 1, instead of 3-benzyl-2,2,6,6-tetramethyl-4-hydroxypiperidine, 3-cyclohexylmethyl-2 was used. ，
Using 7.6 g (30 mmol) of 2,6,6-tetramethyl-4-hydroxypiperidine, the same procedure as in Example 1 was carried out to obtain 15.2 g of a pale yellow viscous liquid. This was purified by silica gel chromatography (chloroform-ethyl acetate mixed solvent) to obtain the target colorless transparent viscous liquid 1
1.2 g was obtained. (Yield 73%) The physical properties are as follows. (1) ¹ H-NMR (CDCl ₃ ) δ [ppm] 0.75-0.90 (m, 1H), 1.05-1.29
(M, 19H), 1.43 (s, 18H), 1.45
1.78 (m, 9H), 2.56-2.64 (m, 2
H), 2.83-2.92 (m, 2H), 5.08
(S, 1H), 5.25-5.32 (m, 1H), 6.
99 (s, 2H) (2) ¹³ C-NMR (CDCl ₃ ) δ [ppm] 26.1, 26.3, 26.4, 30.2, 30.4,
30.9, 31.7, 32.9, 33.3, 34.3,
35.5, 36.9, 40.4, 43.2, 50.4,
54.3, 69.8, 124.7, 130.9, 13
5.9, 152.1, 172.5 (3) IR (KBr) wave number [cm ⁻¹ ] 3640, 2922, 1727, 1434, 1377,
1362, 1232, 1214, 1161, 908, 7
57, 733 <Example 3> [3-benzylidene-2,2,6,6-tetramethylpiperidin-4-yl 3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propanoate (Compound No. 3)] In Example 1, 3-benzyl-2
Example 1 using 7.4 g (30 mmol) of 3-benzyl-2,2,6,6-tetramethyl-4-hydroxypiperidine instead of 2,6,6-tetramethyl-4-hydroxypiperidine By the same operation as above, 14.5 g of a pale yellow viscous liquid was obtained. This was purified by silica gel chromatography (chloroform-ethyl acetate mixed solvent) to obtain 12.3 g of a target colorless transparent viscous liquid. (Yield 81%) The physical properties are as follows. (1) ¹ H-NMR (CDCl ₃ ) δ [ppm] 1.13 (s, 3H), 1.16 (s, 3H), 1.1
6-1.20 (m, 1H), 1.42 (s, 18H),
1.46 (s, 3H), 1.49 (s, 3H), 1.6
8 (dd, 1H), 1.99 (dd, 1H), 2.54
(T, 1H), 2.86 (t, 1H), 5.06 (s,
1H), 5.84 (t, 1H), 6.67 (s, 1
H), 7.00 to 7.25 (m, 7H) (2) ¹³ C-NMR (CDCl ₃ ) δ [ppm] 30.2, 30.7, 32.4, 32.9, 33.4,
34.3, 36.7, 41.1, 48.4, 54.2,
69.2, 124.7, 126.9, 127.6, 12
8.1, 128.4, 130.8, 135.8, 13
6.7, 142.9, 152.1, 172.4 (3) IR (KBr) Wavenumber [cm ⁻¹ ] 3638, 2958, 1729, 1631, 1598,
1434, 1363, 1233, 1159, 1023,
982, 922, 873, 769, 736, 699, 6
14 <Example 4> [3-benzyl-1,2,2,6,6-pentamethylpiperidin-4-yl 3- (3,5-di-t-butyl-4]
Preparation of -Hydroxyphenyl) propanoate (Compound No. 6)] In a 30 ml reactor, 3-benzyl-2,2,6,6-tetramethylpiperidin-4-yl 3- (3, prepared in Example 1 was added. 5-di-t-butyl-4-hydroxyphenyl) propanoate (Compound No. 1)
5.1 g (10 mmol), 37% aqueous formaldehyde solution 4.1 g (20 mmol) and formic acid 0.5 g (1
(0 mmol) was added, and the mixture was reacted at 80 ° C for 8 hours.

After the reaction is completed, the reaction solution is cooled to room temperature,
50 ml of 10% sodium hydroxide aqueous solution was added and stirred. Add 100 ml of diethyl ether and extract,
The ether layer thus obtained was washed twice with 50 ml of water. Then, it was dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 5.3 g of a pale yellow viscous liquid. This was purified by silica gel chromatography (chloroform-ethyl acetate mixed solvent) to give 4.8 g of the target colorless transparent viscous liquid.
Got (Yield 92%) The physical properties are as follows. (1) ¹ H-NMR (CDCl ₃ ) δ [ppm] 1.05-1.54 (m, 31H), 1.64-1.7
7 (m, 1H), 2.24 (s, 3H), 2.48-
2.88 (m, 4H), 2.87-3.04 (m, 2
H), 4.91-5.05 (m, 1H), 5.08
(S, 1H), 6.97-7.30 (m, 7H), (2) ¹³ C-NMR (CDCl ₃ ) δ [ppm] 26.4, 26.9, 30.3, 30.4, 31.0,
32.8, 33.3, 34.3, 34.4, 36.8,
40.8, 49.2, 49.9, 53.1, 69.9,
124.8, 126.0, 128.4, 128.9, 1
31.0, 135.9, 140.8, 152.4, 17
2.3 (3) IR (KBr) wave number [cm ⁻¹ ] 3640, 2954, 1732, 1629, 1602,
1436, 1362, 1315, 1233, 1161,
1040, 978, 768, 733, 702, 522,
460 <Example 5> [3-benzyl-2,2,6,6-tetramethylpiperidin-4-yl 3- (3-t-butyl-4-hydroxy-5-methylphenyl) propanoate (Compound No. 16) Production of Methyl 3- (3,
Instead of 5-di-t-butyl-4-hydroxyphenyl) propanoate, methyl 3- (3-t-butyl-
Using 7.5 g (30 mmol) of 4-hydroxy-5-methylphenyl) propanoate, the same procedure as in Example 1 was carried out to obtain 13.8 g of a pale yellow viscous liquid. This was purified by silica gel chromatography (chloroform-ethyl acetate mixed solvent) to obtain the target colorless transparent viscous liquid 1
0.9 g was obtained. (Yield 78%) The physical properties are as follows. (1) ¹ H-NMR (CDCl ₃ ) δ [ppm] 0.85 (bs, 1H), 1.05-1.59 (m, 2)
2H), 1.62-1.77 (m, 1H), 1.77-
1.91 (m, 1H), 2.23 (s, 3H), 2.4
5-2.85 (m, 4H), 2.87-3.00 (m,
2H), 4.90-5.03 (m, 1H), 5.07
(S, 1H), 6.95-7.35 (m, 7H) (2) ¹³ C-NMR (CDCl ₃ ) δ [ppm] 26.9, 30.3, 30.4, 31.0, 32 .8,
33.3, 34.3, 34.4, 36.9, 40.6,
49.3, 49.9, 53.0, 70.0, 124.
8, 125.9, 128.4, 128.9, 130.
9, 136.1, 140.9, 152.2, 173.0 (3) IR (KBr) wave number [cm ⁻¹ ] 3640, 2954, 1731, 1629, 1601,
1434, 1364, 1315, 1233, 1163,
1038, 981, 768, 733, 700, 522,
464 <Example 6> [3-Cyclohexylmethyl-2,2,6,6-tetramethylpiperidin-4-yl 3- (3-t-butyl-
Preparation of 4-Hydroxy-5-methylphenyl) propanoate (Compound No. 17)] In Example 2, instead of methyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propanoate, methyl 3- (3-t
By using 7.5 g (30 mmol) of -butyl-4-hydroxy-5-methylphenyl) propanoate, the same procedure as in Example 1 was carried out to obtain 13.9 g of a pale yellow viscous liquid.
This is subjected to silica gel chromatography (chloroform-
The mixture was purified with an ethyl acetate mixed solvent) to obtain 10.1 g of a target colorless transparent viscous liquid. (Yield 72%) The physical properties are as follows. (1) ¹ H-NMR (CDCl ₃ ) δ [ppm] 0.83 (bs, 1H), 1.06-1.33 (m, 1
9H), 1.43 (s, 9H), 1.45 to 1.76.
(M, 9H), 2.23 (s, 3H), 2.56-2.
64 (m, 2H), 2.83-2.97 (m, 2H),
5.08 (s, 1H), 5.25-5.32 (m, 1
H), 7.02 (s, 2H), (2) ¹³ C-NMR (CDCl ₃ ) δ [ppm] 26.0, 26.3, 26.4, 30.2, 30.5,
30.9, 31.9, 32.9, 33.3, 34.4,
35.5, 36.9, 40.6, 43.2, 50.4,
54.3, 70.2, 124.7, 130.9, 13
5.9, 152.1, 171.8 (3) IR (KBr) wavenumber [cm ⁻¹ ] 3636, 2922, 1730, 1434, 1377,
1360, 1232, 1216, 1161, 911, 7
57, 735 <Example 7> [Evaluation of light stabilization effect] The intrinsic viscosity measured in 135 ° C. tetralin is 1.9 and the isotactic is 98.
% Polypropylene powder 100 parts by weight, tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane 0.1 parts by weight, calcium stearate 0.05 parts by weight Then
0.2 parts by weight of each of the compounds prepared in Examples 1 to 6 was added as an added compound to the mixture, thoroughly mixed with a mixer, and melt-kneaded with a 20 mm diameter extruder at a cylinder temperature of 260 ° C. to granulate. 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. In addition, as a test piece for comparison, a test piece without a light stabilizer (Experiment No. 1) and the compounding composition of the above test piece were used instead of the compounds produced in Examples 1 to 6 in Japanese Examined Patent Publication No. 58-38471. Except that 2,2,6,6-tetramethylpiperidin-4-yl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propanoate prepared by the method described in Japanese Patent Publication No. A sheet (Experiment No. 2) was made into a sheet by the same method 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 the time until deterioration of each test piece was compared. The obtained results are as shown in Table 2.

Table 2 _{Experiments Deterioration time} number Addition compound [hr] 1 _None 100 _{2 2,2,6,6-Tetramethylpiperidin-4-yl 3-} (3,5-di-t-butyl- 4-Hydroxyphenyl) pro 460 ^panoate _{3 3-benzyl-2,2,6,6-tetramethylpiperidin-} 4-yl 3- (3,5-di-t-butyl-4-hydroxy ^{720phenyl ) propanoate (compound No. 1)} _{4 3-Cyclohexylmethyl-2,2,6,6-tetramethylpiperidin-} 4-yl 3- (3,5-di-t-butyl-4 780 ^{-hydroxyphenyl) propanoate (Compound No. 2)} _{5 3-benzylidene-2,2,6,6-tetramethyl piperidinyloxy} down-yl 3- (3,5-di -t- butyl-4-hydro 580 ^{Kishifeniru) propanoate Compound No.} _{3) 6 3-benzyl-1,2,2,6,6-pentamethyl piperidinium} down-yl 3- (3,5-di -t- butyl-4-hydro 740 ^{Kishifeniru) propanoate (Compound No. 6)} _{7 3-benzyl-2,2,6,6-tetramethylpiperidin-} 4-yl 3- (3-t-butyl-4-hydroxy-5 760 ^{-methylphenyl) propanoate (Compound No. 16)} _{8 3 -Cyclohexylmethyl-2,2,6,6-tetramethylpiperidin-} 4-yl 3- (3-t-butyl-4-hydro ^{800oxy-5-methylphenyl) propanoate (Compound No. 17)}

[0027]

As described above in the section "Means for Solving Problems", the novel compound according to the present invention has a photostabilizing ability for organic compounds and is easy to produce.

[Brief description of drawings]

FIG. 1 is 3-benzyl-2,2 produced in Example 1.
6,6-Tetramethylpiperidin-4-yl 3-
(3,5-di-t-butyl-4-hydroxyphenyl)
1 is a ¹ H-NMR spectrum of propanoate (Compound No. 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.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akira Onishi 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Petrochemical Co., Ltd. Yokkaichi Research Institute

Claims (1)

Claims: 1. A phenolic compound represented by the following general formula [I]. [Chemical 1] [In the formula, R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be the same or different. R ³ and R ⁴ together are ═CH—R ⁷ , or R ³ is a hydrogen atom and R ⁴ is —CH ₂ —.
R ⁷ or either of them (provided that R ⁷ represents a substituted or unsubstituted phenyl group or cyclohexyl group (provided that the substituent is an alkyl group having 1 to 4 carbon atoms)). R ⁵ represents a hydrogen atom or a methyl group. R ^{6 represents a} hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is 0
Represents an integer of 3; ]