JPH04308592A - Polycyclic amine derivative - Google Patents

Abstract

PURPOSE:To obtain a new polycyclic amine derivative useful as a light stabilizer for various kinds of organic materials or intermediate thereof because of excellent light stabilizing effect and further also as intermediate for medicine, agricultural chemical, etc. CONSTITUTION:A compound expressed by formula I(R<1> and R<2> are H or 1-4C alkyl; R<3> and R<4> form=CH2 together or R<3> is H and R<4> is methyl; R<5> is H or 1-8C alkyl; R<6> is H, 6-18C aryl, etc.), e.g. 3',4',5',6',7',8'- hexahydro-2,2,5',5',6,6,7',7'-octamethyl-8'-methylene-5-(2,2,6,6-tetra methylpiperidin-4- ylaminomethyl)-spiro(piperidine-3,2'-(2H)pyrano[3,2-C]pyridine)-4-one. The compound is obtained by subjecting a polycyclic amino compound expressed by formula II to Mickael type addition reaction with a diamine compound expressed by formula III. The above-mentioned reaction is preferably carried out at 0-100 deg.C.

Description

[Detailed description of the invention]

[Background of the invention]

FIELD OF THE INVENTION The present invention relates to a polycyclic amine derivative having a novel structure having a piperidine group. Specifically, the present invention relates to a 2,2,6,6-tetraalkylpiperidine skeleton that 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. The present invention relates to a polycyclic amine derivative containing.

0002

[Prior Art] Conventionally, 2,2,6,6-tetraalkylpiperidine skeleton (so-called hindered amine skeleton)
Compounds having an excellent radical scavenging ability are particularly used as light stabilizers for various organic materials including resins.

As one of them, the polycyclic amine compound shown in the following formula (a) is known to be effective as a light stabilizer (German Published Patent No. 273138 (1978)).
Year)). In particular, this compound has two hindered amine skeletons in its molecule and has a high hindered amine skeleton content per molecular weight, so it has a high photostabilizing effect and is particularly effective as a photostabilizer for resins.

0004

[C4]

[0005]

[Problems to be Solved by the Invention] The present inventors have conducted studies aimed at finding a compound with even higher photostabilizing effect by chemically derivatizing the above-mentioned polycyclic amine compound (a). , a polycyclic amine derivative having a novel structure shown in the following general formula [I], which can be produced industrially, has less bleed-out from the resin, and greatly exceeds compound (a) in terms of photostabilizing effect. They discovered this and completed the present invention.

[Summary of the invention]

[Means for Solving the Problems] <Summary> The polycyclic amine derivative according to the present invention is represented by the following general formula [I].

[0007]

embedded image In the formula, R1 and R2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R3 and R4 together represent either =CH2, or R3 is a hydrogen atom and R4 is a methyl group. R5
represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R6 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms (however, it may contain an oxygen atom or a nitrogen atom), or the following: represents the general formula [II] (however, R7
represents an alkylene group having 1 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, or an aralkylene group having 7 to 18 carbon atoms (which may contain an oxygen atom or a nitrogen atom).

[0008]

[Image Omitted] Alternatively, R5 and R6 together have 4 to 4 carbon atoms.
7 cyclic alkyl group (however, it may contain an oxygen atom or a nitrogen atom, and may have a substituent selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group) or the following general formula Represents [III].

[0009]

[C7]

<Effect> The compound of the present invention can be easily produced by, for example, a Michael-type addition reaction of amines to the polycyclic amine compound (a), and moreover, the compound has a hindered amine skeleton having photostabilizing ability in the molecule. Since it is a compound that can be contained in a large amount, it is possible to efficiently prevent organic materials from deteriorating due to light.

For example, if an amine compound having a hindered amine skeleton in the molecule is used as the amine to be added, a compound having many hindered amine skeletons in one molecule can be produced, and a light stabilizer with a high photostabilizing effect can be produced. can be obtained.

Furthermore, if an amine compound having an aliphatic alkyl group or an alicyclic alkyl group is used as the amine to be added, compatibility with various organic materials including resins, especially polyolefins such as polyethylene, polypropylene, and polystyrene, can be improved. It is possible to obtain a highly effective light stabilizer with excellent properties.

[Detailed Description of the Invention] <Polycyclic amine derivative> R1 and R2 in the general formula [I] of the compound of the present invention are a hydrogen atom and a carbon atom having 1 to 1 carbon atoms, respectively.
Any of the alkyl groups listed in No. 4 can be arbitrarily selected, and each case exhibits a similar photostabilizing effect, but from the viewpoint of production, a hydrogen atom or a methyl group is preferred, and a hydrogen atom is particularly preferred.

R3 and R4 together represent =CH2
or R3 is a hydrogen atom and R4 is a methyl group, but the photostabilizing effect is the same in either case, and in production, R3 and R4 are combined together. Therefore, it is preferable that =CH2.

R5 can be arbitrarily selected from either a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, but from the viewpoint of production, a hydrogen atom or a methyl group is preferred, with a hydrogen atom being particularly preferred.

R6 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a aryl group having 7 to 18 carbon atoms.
An aralkyl group (which may contain an oxygen atom or a nitrogen atom) or a group represented by the general formula [II] can be arbitrarily selected, but it has 1 to 10 carbon atoms.
Preferred are alkyl groups (which may contain an oxygen atom or a nitrogen atom), such as ethyl group, n-butyl group, n-hexyl group, cyclohexyl group, hydroxyethyl group, 2,2,6,6 -Tetramethyl-4-piperidyl group and the like are preferred.

Alternatively, R5 and R6 may be taken together to form a cyclic alkyl group having 4 to 7 carbon atoms (which may contain an oxygen atom or a nitrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group) (which may have a substituent selected from or may have a substituent selected from an alkyl group having 1 to 2 carbon atoms and a hydroxyalkyl group) is preferable.

When R6 is a group represented by the general formula [II], R7 is an alkylene group having 1 to 18 carbon atoms, or an alkylene group having 6 to 18 carbon atoms.
18 arylene group, aralkylene group having 7 to 18 carbon atoms (however, it may contain an oxygen atom or a nitrogen atom)
Any one of these can be arbitrarily selected, but the number of carbon atoms is 2 to 6.
Alkylene groups having 6 to 8 carbon atoms, arylene groups having 6 to 8 carbon atoms, and aralkylene groups having 7 to 10 carbon atoms (however, they may contain an oxygen atom or a nitrogen atom) are preferable, such as ethylene groups, n-butylene groups, n-butylene groups, -hexylene group, cyclohexylene group, phenylene group, m-xylylene group, etc. are preferred.

Representative examples of the polycyclic amine derivatives represented by the general formula [I] of the present invention include those in which substituents R1 to R7 are as shown in Tables 1 and 2.

[0020] These compounds will be referred to by the corresponding numbers below.

[0021]

[Table 1]

[0022]

[Table 2]

<Production of compound> The polycyclic amine derivative of the present invention can be produced by any method suitable for forming bonds and introducing or forming substituents. One suitable production method is, for example, as shown in the following formula, by subjecting a polycyclic amine compound [IV] to a monoamine compound [V] or a diamine compound [VI] in a Michael type addition reaction.

[0024]

[Chemical formula 8]

[0025]

embedded image In particular, a cyclic compound in which R5 and R6 are combined can also be produced as shown in Chemical Formula 10 and Chemical Formula 11, respectively, by a Michael type addition reaction.

[0026]

[Chemical formula 10]

[0027]

[Image Omitted] This Michael-type addition reaction can be carried out without a solvent, or
A solvent can also be used, and in the latter case, water, an organic solvent that uniformly dissolves the reaction system, or a mixed solvent of both can be selected. The reaction temperature can be selected within the range of -50 to 150°C as long as the reaction system or solvent does not coagulate, but the preferred reaction temperature is 0 to 10°C.
It is 0°C.

<Utility of compounds> Compounds according to the present invention [
I] 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, etc.

[0029]

EXAMPLES The following examples are intended to specifically illustrate the compounds according to the present invention.

Example 1 [3',4',5',6',7',8'-hexahydro-2,2,5',5',6,6,7',7'-octamethyl-8 '-Methylene-5-(2,2,6,6-tetramethylpiperidin-4-ylaminomethyl)-spiro(
Piperidine-3,2'-(2H)pyrano[3,2-C]
Production of pyridin)-4-one (compound number 5)]

00
31] 3', 4', 5', 6' in a 200 ml reactor
,7',8'-hexahydro-2,2,5',5',6
, 6,7',7'-octamethyl-5,8'-bis(methylene)-spiro(piperidin-3,2'-(2H)pyrano[3,2-C]pyridin)-4-one 10.8 g (
30 mmol), 6.3 g (40 mmol) of 4-amino-2,2,6,6-tetramethylpiperidine, and 80 ml of ethanol were added, and the mixture was reacted at room temperature for 20 hours.

After the reaction, add 300% diethyl ether to the reaction solution.
ml was added, and this was washed with 100 ml of water. The obtained organic layer was dried with anhydrous magnesium sulfate, and after filtration,
The white solid obtained by concentration was washed with acetonitrile to obtain 8.0 g of the target white solid (yield 52%).
.

The physical property values are as follows. (1) Melting point 170.1°C (2) 1H-NMR (CDCl3) δ [ppm]
(See Figure 1) 0.60-1.63 (m, 40H), 1.74-2.2
1 (m, 7H), 2.34-2.57 (m, 2H), 2
．． 80-3.12 (m, 3H), 4.92 (s, 1H)
, 5.32 (s, 1H) (3) 13C-NMR (CDCl3) δ[ppm
] (See Figure 2) 19.5, 25.5, 26.1, 26.6, 28.9,
30.1, 30.7, 32.7, 35.1, 42.2,
46.2, 50.2, 50.8, 52.3, 52.9,
58.1, 60.5, 86.2, 103.2, 113.
5, 142.0, 145.6, 208.7 (4) IR (
KBr) Wave number [cm-1] (see Figure 3) 3326, 2962, 2920, 2864, 1743,
1706, 1648, 1603, 1478, 1460,
1364, 1239, 1197, 1181, 1089,
1071, 972, 889, 736, 710 (5) Mass spectrum m/e (relative intensity) (see Figure 4) 514 (17, M+), 499 (35), 343 (67
), 331 (36), 286 (30), 274 (26)
, 178(31), 164(69), 141(33),
124 (32), 98 (64), 58 (53), 40 (
100)

Example 2 [3',4',5',6',7',8'-hexahydro-2,2,5',5',6,6,7',7'-octamethyl-8 '-Methylene-5-cyclohexylaminomethyl-spiro(piperidine-3,2'-(2H)pyrano[
Production of 3,2-C]pyridin)-4-one (compound number 3)]

4-Amino-2,2,6,6- of Example 1
A white solid obtained in the same manner as in Example 1 using 4.0 g (40 mmol) of cyclohexylamine instead of tetramethylpiperidine was recrystallized from acetonitrile to obtain 7.6 g of white crystals of the target product. (yield 55
%).

The physical property values are as follows. (1) Melting point 148.9℃ (2) 1H-NMR (CDCl3) δ [ppm]
1.55-2.20 (m, 5H), 2.33-2.55
(m, 1H), 2.88-3.07 (m, 2H), 4.
91 (s, 1H), 5.32 (s, 1H) (3) 13C
-NMR (CDCl3) δ [ppm] 19.6,
24.9, 25.4, 26.1, 26.6, 28.9,
30.1, 30.7, 32.7, 33.5, 42.5,
52.4, 53.0, 57.1, 58.1, 60.6,
86.3, 103.2, 113.6, 142.0, 14
5.7, 208.7 (4) IR (KBr) wave number [cm-1] 3326,
2970, 2924, 2850, 1704, 1648,
1604, 1459, 1449, 1365, 1236,
1197, 1179, 1127, 1089, 1070,
974, 888, 725 (5) Mass spectrum (FD method) m/e457 (M
+)

Example 3 [3',4',5',6',7',8'-hexahydro-2,2,5',5',6,6,7',7'-octamethyl-8 '-Methylene-5-(2-hydroxyethylaminomethyl)-spiro(piperidine-3,2'-(2H
) Production of pyrano[3,2-C]pyridin)-4-one (compound number 4)]

[0038] In a 200 ml reactor, 3', 4', 5'
,6',7',8'-hexahydro-2,2,,5',
5',6,6,7',7'-octamethyl-5,8'-
Bis(methylene)-spiro(piperidine-3,2'-(
2H) Pyrano[3,2-C]pyridin)-4-one 10
．． 8 g (30 mmol), 2-hydroxyethylamine 2.4 g (40 mmol), tetrahydrofuran 60 m
1 and 30 ml of water were added thereto, and the mixture was allowed to react at room temperature for 2 hours.

After the reaction, 350 ml of water was added to the reaction solution, and the precipitated white solid was filtered and dried to obtain 10.7 g of the target white solid (yield: 85%).

The physical property values are as follows. (1) Melting point 174.3℃ (2) 1H-NMR (CD3OD) δ [ppm]
0.95-1.45 (m, 24H), 1.75-2.8
0 (m, 7H), 2.67 (t, 2H), 3.50-3
．． 70 (m, 2H), 4.91 (s, 1H), 5.27
(s, 1H) (3) 13C-NMR (CD3OD) δ[ppm
]20.1, 25.1, 25.7, 26.2, 26.8
, 28.7, 30.1, 30.5, 30.8, 31.8
, 46.0, 52.4, 53.6, 54.2, 58.3
, 59.1, 61.3, 61.7, 87.7, 104.
3, 114.6, 142.9, 146.4, 209.9
(4) IR (KBr) wave number [cm-1] 3332,
2964, 1702, 1648, 1604, 1459,
1443, 1365, 1236, 1179, 1121,
1070, 1050, 976, 895, 696 (5) Mass spectrum (FD method) m/e419 (M
+)

Example 4 [N,N'-bis[3', 4', 5', 6', 7', 8
'-hexahydro-2,2,5',5',6,6,7'
, 7'-octamethyl-8'-methylene-spiro(piperidine-3,2'-(2H)pyrano[3,2-C]pyridine)-4-one-5-ylmethyl]-1,6-diaminohexane( Production of compound number 23)]

1
00ml reactor, 3', 4', 5', 6', 7',
8'-hexahydro-2,2,5',5',6,6,7
',7'-octamethyl-5,8'-bis(methylene)
-spiro(piperidine-3,2'-(2H)pyrano[3
, 2-C]pyridin)-4-one, 1.2 g (10 mmol) of 1,6-diaminohexane, and 60 ml of ethanol, and the mixture was reacted at room temperature for 30 hours.

After the reaction, the white solid produced was filtered and dried to obtain 3.6 g of the target white solid (yield 43%).
.

The physical property values are as follows. (1) Melting point 208.6℃ (2) 1H-NMR (CDCl3) δ [ppm]
0.90-1.65 (m, 54H), 1.74-2.6
4 (m, 22H), 2.95 (t, 4H), 4.90 (
s, 2H), 5.31 (s, 2H) (3) 13C-NMR (CDCl3) δ [ppm
]19.4, 25.4, 25.5, 26.2, 26.6
, 27.3, 29.0, 30.1, 30.2, 30.5
, 30.6, 32.7, 45.8, 50.6, 52.4
, 52.9, 57.9, 60.5, 86.2, 103.
2, 113.5, 142.0, 145.6, 208.7
(4) Mass spectrum (FD method) m/e833 (M
+)

Example 5 [3',4',5',6',7',8'-hexahydro-1,2,2,5',5',6,6,6',7',7 ′
-decamethyl-8'-methylene-5-(2,2,6,6
-Tetramethylpiperidin-4-ylaminomethyl)-
spiro(piperidine-3,2'-(2H)pyrano[3,
Production of 2-C]pyridin)-4-one (compound number 10)]

[0046] In a 100 ml reactor, 3', 4', 5'
,6',7',8'-hexahydro-1,2,2,5'
,5',6,6,6',7',7'-decamethyl-5,
8'-bis(methylene)-spiro(piperidine-3,2
'-(2H)pyrano[3,2-C]pyridin)-4-one 11.6 g (30 mmol), 4-amino-2,2,
6.3 g (40 mmol) of 6,6-tetramethylpiperidine and 30 ml of ethanol were added and reacted at room temperature for 6 hours.

After the reaction, the white solid produced was filtered and recrystallized from acetonitrile to obtain white crystals of the target product.
g (yield 82%).

The physical property values are as follows. (1) Melting point 167.3℃ (2) 1H-NMR (CDCl3) δ [ppm]
0.62-1.43 (m, 38H), 1.73-3.1
8 (m, 18H), 4.96 (s, 1H), 5.33 (
s, 1H) (3) 13C-NMR (CDCl3) δ[ppm
]17.0, 19.6, 23.0, 24.1, 25.5
, 26.0, 26.6, 28.8, 29.9, 31.4
, 35.2, 42.2, 46.2, 50.2, 50.9
, 56.1, 56.8, 57.5, 62.8, 65.3
, 86.0, 103.4, 113.0, 141.6, 1
46.0, 208.0 (4) IR (KBr) wave number [cm-1] 2964,
2910, 2810, 1718, 1661, 1610,
1471, 1377, 1363, 1264, 1243,
1227, 1191, 1090, 978, 903, 73
0 (5) Mass spectrum (FD method) m/e542 (M
+)

Example 6 [3',4',5',6',7',8'-hexahydro-1,2,2,5',5',6,6,6',7',7 ′
-decamethyl-8'-methylene-5-cyclohexylaminomethyl-spiro(piperidine-3,2'-(2H)
Production of pyrano[3,2-C]pyridin)-4-one (compound number 8)]

4-Amino-2,2,6,6- of Example 5
Using 4.0 g (40 mmol) of cyclohexylamine instead of tetramethylpiperidine, 10.9 g of white crystals of the target product were obtained in the same manner as in Example 5 (yield: 75%).

The physical property values are as follows. (1) Melting point 128.6°C (2) 1H-NMR (CDCl3) δ [ppm]
0.63-1.42 (m, 35H), 1.60-3.0
5 (m, 14H), 4.95 (s, 1H), 5.32 (
s, 1H) (3) 13C-NMR (CDCl3) δ [ppm
]17.0, 19.6, 23.2, 24.2, 24.8
, 24.9, 25.3, 25.9, 26.1, 26.6
, 28.4, 29.9, 31.3, 33.4, 42.4
, 56.0, 57.0, 62.7, 65.1, 103.
3, 112.9, 141.5, 146.0, 208.0
(4) IR (KBr) wave number [cm-1] 2978,
2926, 2848, 2802, 1719, 1664,
1611, 1461, 1376, 1266, 1227,
1190, 1139, 1118, 1088, 980, 9
63, 891 (5) Mass spectrum (FD method) m/e485 (M
+)

Example 7 [3',4',5',6',7',8'-hexahydro-1,2,2,5',5',6,6,6',7',7 ′
-decamethyl-8'-methylene-5-(2-hydroxyethylaminomethyl)-spiro(piperidine-3,2'
-Production of (2H)pyrano[3,2-C]pyridin)-4-one (compound number 9)]

[0053] In a 100 ml reactor, 3', 4', 5'
,6',7',8'-hexahydro-1,2,2,5'
,5',6,6,6',7',7'-decamethyl-5,
8'-bis(methylene)-spiro(piperidine-3,2
'-(2H)pyrano[3,2-C]pyridin)-4-one 11.6 g (30 mmol), 2-hydroxyethylamine 2.4 g (40 mmol) and ethanol 40
ml and reacted at room temperature for 30 hours.

After the reaction, add 300% diethyl ether to the reaction solution.
ml was added, and this was washed with 100 ml of water. The obtained organic layer was dried with anhydrous magnesium sulfate, and after filtration,
The white solid obtained by concentration was washed with hexane,
9.7 g of a white solid, the desired product, was obtained (yield 72%).

The physical property values are as follows. (1) Melting point 98.1°C (2) 1H-NMR (CDCl3) δ [ppm]
0.76-1.39 (m, 25H), 1.74-3.6
2 (m, 18H), 4.95 (s, 1H), 5.32 (
s, 1H) (3) 13C-NMR (CDCl3) δ [ppm
]17.5, 19.8, 24.0, 24.7, 25.6
, 25.9, 26.0, 26.3, 27.1, 28.8
, 31.6, 31.8, 45.1, 51.6, 56.5
, 57.2, 57.8, 61.0, 62.8, 65.6
, 87.2, 103.8, 113.5, 142.5, 1
46.0, 209.2 (4) Mass spectrum (FD method) m/e447 (M
+)

Example 8 [N,N'-bis[3', 4', 5', 6', 7', 8
'-hexahydro-1,2,2,5',5',6,6,
6',7',7'-decamethyl-8'-methylene-spiro(piperidine-3,2'-(2H)pyrano[3,2-
C]pyridin)-4-one-5-ylmethyl]-1,4
-Production of Diaminocyclohexane (Compound No. 27)]

[0057] In a 100 ml reactor, 3', 4', 5'
,6',7',8'-hexahydro-1,2,2,5'
,5',6,6,6'7',7'-decamethyl-5,8
'-bis(methylene)-spiro(piperidine-3,2'
-(2H)pyrano[3,2-C]pyridin)-4-one 7.7 g (20 mmol), 1,4-diaminocyclohexane 1.1 g (10 mmol) and ethanol 40
Millimoles were added and allowed to react at room temperature for 30 hours.

After the reaction, the white solid produced was filtered and washed with acetonitrile to obtain 5.7 g of the desired white solid (yield: 64%).

The physical property values are as follows. (1) Melting point 178.5℃ (2) 1H-NMR (CDCl3) δ [ppm]
0.74-1.48 (m, 58H), 1.78-3.1
0 (m, 28H), 4.95 (s, 2H), 5.32 (
s, 2H) (3) 13C-NMR (CDCl3) δ [ppm
]16.9, 19.6, 23.0, 23.4, 24.2
, 25.4, 26.0, 26.3, 27.9, 28.5
, 28.7, 29.9, 31.4, 31.8, 32.0
, 42.4, 42.8, 54.5, 55.9, 56.2
, 57.0, 57.5, 62.7, 65.2, 86.0
, 103.2, 103.4, 113.0, 113.2,
141.4, 141.5, 146.0, 146.1,
207.9 (4) Mass spectrum (FD method) m/e886 (M
+)

Example 9 [N,N'-bis[3', 4', 5', 6', 7', 8
'-hexahydro-1,2,2,5',5',6,6,
6',7',7'-decamethyl-8'-methylene-spiro(piperidine-3,2'-(2H)pyrano[3,2-
C]pyridin)-4-one-5-ylmethyl]-1,6
-Production of diaminohexane (compound number 26)]

00
61] 3', 4', 5', 6' in a 100 ml reactor
,7',8'-hexahydro-1,2,2,5',5'
,6,6,6',7',7'-decamethyl-5,8'-
Bis(methylene)-spiro(piperidine-3,2'-(
2H) Pyrano[3,2-C]pyridin)-4-one7.
7 g (20 mmol), 1,6-diaminohexane 1.
2 g (10 mmol) and 30 ml of ethanol were added, and the mixture was reacted at room temperature for 12 hours.

After the reaction, the white solid produced was filtered and dried to obtain 5.5 g of the target white solid (yield 62%).
.

The physical property values are as follows. (1) Melting point 150.8℃ (2) 1H-NMR (CDCl3) δ [ppm]
0.77-1.42 (m, 50H), 1.73-3.0
5 (m, 38H), 4.95 (s, 2H), 5.31 (
s, 2H) (3) 13C-NMR (CDCl3) δ [ppm
]16.9, 17.1, 19.6, 23.6, 24.4
, 25.3, 25.8, 26.0, 26.7, 27.4
, 28.5, 29.9, 30.2, 31.3, 45.9
, 50.7, 55.9, 56.8, 57.5, 62.6
, 65.2, 86.0, 103.3, 113.0, 14
1.5, 146.1, 208.1 (4) Mass spectrum (FD method) m/e888 (M
+)

Example 10 [3',4',5',6',7',8'-hexahydro-2,2,5',5',6,6,7',7'-octamethyl-8 '-Methyl-5-(2,2,6,6-tetramethylpiperidin-4-ylaminomethyl)-spiro(piperidine-3,2'-(2H)pyrano[3,2-C]pyridine)-4 -Production of one (compound number 14)]

00
65] In a 200 ml reactor, 3 prepared in Example 1 was added.
',4',5',6',7',8'-hexahydro-2
,2,5',5',6,6,7',7'-octamethyl-8'-methylene-5-(2,2,6,6-tetramethylpiperidin-4-ylaminomethyl)-spiro( 10.3 g (20 mmol) of piperidine-3,2'-(2H)pyrano[3,2-C]pyridin)-4-one (compound no. 5), 100 ml of 1,4-dioxane and 10%
0.2 g of palladium-carbon was added and reacted for 5 hours at room temperature under a hydrogen atmosphere at atmospheric pressure.

After the reaction, the catalyst was removed by filtration, and the resulting white solid was recrystallized from acetonitrile to obtain 7.8 g of white crystals (yield: 75%).

The physical property values are as follows. (1) Melting point 173.7°C (2) 1H-NMR (CDCl3) δ [ppm]
0.69-1.42 (m, 43H), 1.52-2.0
8 (m, 7H), 2.37-2.54 (m, 3H), 2
．． 81-3.10 (m, 3H) (3) 13C-NMR (CDCl3) δ [ppm
]14.1, 18.6, 25.2, 26.5, 26.8
, 27.4, 28.8, 29.4, 29.8, 31.0
, 32.7, 35.1, 41.8, 42.2, 46.2
, 50.1, 50.9, 51.9, 52.5, 58.0
, 60.4, 86.2, 106.8, 147.9, 20
8.8 (4) Mass spectrum (FD method) m/e516 (M
+)

Example 11 [3',4',5',6',7',8'-hexahydro-1,2,2,5',5',6,6,6',7',7 ′
-decamethyl-8'-methyl-5-(2,2,6,6-
Tetramethylpiperidin-4-ylaminomethyl)-spiro(piperidine-3,2'-(2H)pyrano[3,2
-C] Production of pyridin)-4-one (compound number 16)]

3', 4', 5', 6', 7 of Example 10
',8'-hexahydro-2,2,5',5',6,6
,7',7'-octamethyl-8'-methylene-5-(
2,2,6,6-tetramethylpiperidin-4-ylaminomethyl)-spiro(piperidine-3,2'-(2H
) 3',4' produced in Example 5 instead of pyrano[3,2-C]pyridin)-4-one (compound number 5)
,5',6',7',8'-hexahydro-1,2,2
,5',5',6,6,6',7',7'-decamethyl-8'-methylene-5-(2,2,6,6-tetramethylpiperidin-4-ylaminomethyl)-spiro (Piperidin-3,2'-(2H)pyrano[3,2-C]pyridin)-4-one (Compound No. 10) 10.9 g (20
In the same manner as in Example 10, 8.7 g of white crystals of the target product were obtained (yield: 80%).

The physical property values are as follows. (1) Melting point 170.0°C (2) 1H-NMR (CDCl3) δ [ppm]
0.70-1.48 (m, 41H), 1.60-3.1
8(m, 19H) (3) 13C-NMR (CDCl3) δ [ppm
]14.3, 16.7, 16.8, 18.9, 21.0
, 21.7, 25.9, 26.6, 27.2, 28.2
, 28.5, 28.7, 29.6, 31.4, 35.1
, 42.2, 44.3, 46.1, 50.0, 50.9
, 55.5, 55.9, 57.1, 62.9, 65.1
, 86.0, 106.9, 147.5, 208.5 (4
) Mass spectrum (FD method) m/e544 (M+)

Example 12 [Evaluation of photostabilizing effect] The intrinsic viscosity measured in tetralin at 135°C was 1.9, and the isotactic one was 98.
% polypropylene powder, Examples 1-1
0.2 parts by weight of each of the compounds produced in step 1, 0.1 parts by weight of tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxymethyl]methane, and 0 parts by weight of calcium stearate. After blending .05 parts by weight and thoroughly mixing with a mixer, the cylinder temperature was 260℃.
The mixture was melt-kneaded and granulated using a 20 mm diameter extruder. The obtained pellets were compression molded at 230° C. into a sheet with a thickness of 0.5 mm to prepare a test piece. Among the compound compositions of the above test pieces, 3',4',5',6',7',8'-hexahydro-2,2,5',5 ',6,6,7',7'-octamethyl-5,8'-bis(methylene)-spiro(piperidin-3,2'-(2H)pyrano[3,2-C]pyridin)-4-one A comparative test piece was made into a sheet in the same manner as the above test piece except that 0.2 parts by weight of (compound (a)) was used.

[0072] These test pieces were prepared using Atlas Co., Ltd. 65/XW.
- Using a WR type xenon weatherometer, light was irradiated at a black panel temperature of 80° C., and the time required for each test piece to deteriorate was compared. The results obtained were as shown in the table below.

[0073]

[Table 3]

[0074]

As described above, the novel compound according to the present invention has an ability to photostabilize organic compounds and is easy to produce.

[Brief explanation of the drawing]

[Figure 1] 3', 4', 5', 6' produced in Example 1
,7',8'-hexahydro-2,2,5',5',6
,6,7',7'-octamethyl-8'-methylene-5
-(2,2,6,6-tetramethylpiperidin-4-ylaminomethyl)-spiro(piperidine-3,2'-(
2H) 1H-NMR spectrum of pyrano[3,2-C]pyridin)-4-one (compound number 5).

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

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

FIG. 4 is a mass spectrum of the same compound.

Claims (1)

[Claims] [Claim 1] A polycyclic amine derivative represented by the following general formula [I]. embedded image In the formula, R1 and R2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R3 and R4 together represent either =CH2, or R3 is a hydrogen atom and R4 is a methyl group. R5
represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R6 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms (however, it may contain an oxygen atom or a nitrogen atom), or the following: represents the general formula [II] (however, R7
represents an alkylene group having 1 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, and an aralkylene group having 7 to 18 carbon atoms (which may contain an oxygen atom or a nitrogen atom). [Image Omitted] Alternatively, R5 and R6 together have 4 to 4 carbon atoms.
7 cyclic alkyl group (however, it may contain an oxygen atom or a nitrogen atom, and may have a substituent selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group) or the following general formula Represents [III]. [Chemical formula 3]