ROTAXANE COMPOUND

Abstract

A rotaxane compound comprising one or more cyclic molecules and an axial molecule penetrating through inner holes of the cyclic molecules and having cap structures disposed lest the cyclic molecules should be detached, where one of the cyclic molecule and the axial molecule has one of a functional group being capable of reacting with silica and a functional group being capable of reacting with a carbon-carbon unsaturated bond, and the other of the cyclic molecule and the axial molecule has the other of the functional group being capable of reacting with silica and the functional group being capable of reacting with a carbon-carbon unsaturated bond.

Claims

1-10. (canceled)

11. A rotaxane compound comprising one or more cyclic molecules and an axial molecule penetrating through inner holes of the cyclic molecules and having cap structures disposed lest the cyclic molecules should be detached, wherein one of the cyclic molecule or the axial molecule has one of a functional group being capable of reacting with silica or a functional group being capable of reacting with a carbon-carbon unsaturated bond, and the other one of the cyclic molecule or the axial molecule has the other one of the functional group being capable of reacting with silica or the functional group being capable of reacting with a carbon-carbon unsaturated bond, wherein the cyclic molecule is at least one selected from the group consisting of crown ether, cyclodextrin, cyclophane, calixarene, cucurbituril, and pillararene, and wherein the functional group being capable of reacting with silica is at least one selected from the group consisting of alkoxysilyl, acetoxysilyl and chlorosilyl.

12. The rotaxane compound of claim 11, wherein the cyclic molecule is a crown ether cyclic molecule represented by the following formula (1a), (1b) or (1c): ##STR00011## wherein W.sup.4 is a single bond, or a spacer being composed of 1 to 100 atoms and having one or more constituent unit selected from the group consisting of linear or branched alkylene chain, —CO—O—, —O—CO—, —O—, —CO—, —S—, —CS—, —NH—, —NR.sup.1— (where R.sup.1 is an alkyl group having 1 to 6 carbon atoms), a benzene ring, a heteroaromatic ring, a saturated or partially unsaturated hydrocarbon ring and a saturated or partially unsaturated hetero ring; R.sup.3 is a functional group being capable of reacting with silica or a functional group being capable of reacting with a carbon-carbon unsaturated bond; here, the cyclic molecule may be substituted with the same or different 1 to 4 groups independently selected from the group consisting of halogen, alkyl and alkoxy; and 1 to 3 of oxygen atoms constituting the ring may be replaced by NH or S, and if there are plural cyclic molecules in the rotaxane compound, the cyclic molecules may be the same or different.

13. The rotaxane compound of claim 11, wherein the axial molecule is an axial molecule represented by the following formula (3): ##STR00012## wherein B.sup.1 and B.sup.2 are independently cap structure; W.sup.1 and W.sup.2 are independently a single bond, or a spacer being composed of 1 to 100 atoms and having one or more constituent unit selected from the group consisting of linear or branched alkylene chain, —CO—O—, —O—CO—, —O—, —CO—, —S—, —CS—, —NH—, —NR.sup.1— (where R.sup.1 is an alkyl group having 1 to 6 carbon atoms), a benzene ring, a heteroaromatic ring, a saturated or partially unsaturated hydrocarbon ring and a saturated or partially unsaturated hetero ring; here, at least either one of B.sup.1 or B.sup.2 is substituted with —W.sup.3—R.sup.2 (where W.sup.3 is a single bond, or a spacer being composed of 1 to 100 atoms and having one or more constituent unit selected from the group consisting of linear or branched alkylene chain, —CO—O—, —O—CO—, —O—, —CO—, —S—, —CS—, —NH—, —NR.sup.1— (where R.sup.1 is an alkyl group having 1 to 6 carbon atoms), a benzene ring, a heteroaromatic ring, a saturated or partially unsaturated hydrocarbon ring and a saturated or partially unsaturated hetero ring; R.sup.2 is a functional group being capable of reacting with silica or a functional group being capable of reacting with a carbon-carbon unsaturated bond); B.sup.1 and B.sup.2 may be substituted with the same or different 1 to 4 groups independently selected from the group consisting of halogen, alkyl and alkoxy; hydrogen atoms in a secondary ammonium (—N.sup.+H.sub.2—) moiety may be substituted with alkyl, alkylcarbonyl, alkylaminocarbonyl, alkoxycarbonyl, optionally-substituted phenylcarbonyl, optionally-substituted phenylaminocabonyl, or optionally-substituted phenoxycarbonyl; when a plurality of R.sup.1, R.sup.2 and W.sup.3 exists, those may be the same or different.

14. The rotaxane compound of claim 11, wherein one of the axial molecules penetrates one of the cyclic molecules.

15. The rotaxane compound of claim 11, wherein the functional group being capable of reacting with a carbon-carbon unsaturated bond is at least one selected from the group consisting of nitrile oxide, azide, nitron, nitrileimine, sydnone, methylolphenol, mercapto, sulfide, vinyl, vinylene, ethynyl, ethynylene, cyano, isocyanate, isocyanurate, epoxy, glycidyloxy, acryloyl, methacryloyl and ureido.

16. A polymer composition comprising a polymer having a carbon-carbon unsaturated bond and the rotaxane compound of claim 11.

17. The polymer composition of claim 16, wherein the polymer is a diene rubber.

18. A rubber composition comprising a diene rubber, silica and the rotaxane compound of claim 11.

19. The rotaxane compound of claim 11, wherein the alkoxysilyl is trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethylmethoxysilyl or dimethylethoxysilyl.

20. The rotaxane compound of claim 11, wherein the cap structure is at least one selected from the group consisting of an optionally-substituted monocyclic or polycyclic aromatic group, an optionally-substituted hetero aromatic ring, an optionally-substituted saturated or partially unsaturated hydrocarbon ring, an optionally-substituted saturated or partially unsaturated hetero ring, and a non-cyclic group having such a group or a ring.

21. The rotaxane compound of claim 11, wherein the cap structure is at least one selected from the group consisting of phenyl which may be substituted with one or more alkyl groups having 1 to 6 carbon atoms, tert-butyl, diphenylmethyl, trityl, naphthyl and anthracenyl.

Description

EXAMPLE

[0108] The present invention is then explained by means of Examples, but is not limited to the Examples.

[0109] Meanings of symbols and abbreviations in Examples are shown below. [0110] DIC: Diisopropylcarbodiimide [0111] BuP: Tri(tert-butyl)phosphine [0112] THF: Tetrahydrofuran [0113] Ph: Phenyl [0114] Et: Ethyl

Example 1

[0115] A rotaxane compound (1-4) was synthesized by a method and conditions shown by means of the following formulation.

##STR00008## ##STR00009##

Example 1-1: Synthesis of Alkoxysilane Compound (1-1)

[0116] ##STR00010##

[0117] A nitroalkane compound (1-0) was obtained in accordance with a known method using commercially available 3-mercaptopropyltriethoxysilane and diphenylnitroethene. Phenyl isocyanate (6.3 g) and triethylamine (7.8 g) were added to a THF (150 ml) solution of the compound (1-0) (12 g), followed by 5-hour stirring at room temperature. After filtration of a reaction solution, a solvent of a filtrate was distilled off, followed by refining using silica gel column chromatography (eluent: ethyl acetate/hexane=1/10). Thus, an alkoxysilane compound (1-1) (10 g) was obtained.

[0118] .sup.1H-NMR (500 Hz, CDCl.sub.3, 298K): δ (ppm) 7.60-7.47 (m, 4H), 7.42-7.30 (m, 6H), 3.78 (q, J=7.0 Hz, 6H), 2.61 (t, J=7.3 Hz, 2H), 1.72-1.65 (m, 2H), 1.20 (t, J=7.0 Hz, 9H), 0.70-0.67 (m, 2H);

[0119] .sup.13C-NMR (125 Hz, CDCl.sub.3, 298K): δ (ppm) 139.2, 128.8, 128.6, 127.4, 58.4, 57.2, 35.7, 22.0, 18.3, 10.3;

[0120] IR (NaCl): υ 2287 (CNO) cm.sup.−1;

[0121] MALDI-TOF MS (Matrix: dithranol, Cationizing agent: CF.sub.3COONa): m/z calcd for C.sub.23H.sub.31NO.sub.4SSiNa [M+Na].sup.+: 468.17, found: 468.34.

Example 1-2: Synthesis of Nitroalkane Compound (1-3)

[0122] An axial molecule component (1-a) (470 mg) was added to a dichloromethane (1.4 mL) solution of a cyclic molecule component (1-r) (710 mg), followed by 2-hour stirring. Subsequently thereto were added a compound (1-2) (660 mg), DIC (0.47 mL) and (tert-butyl)phosphine (50 μL), followed by 24-hour stirring at room temperature. A reaction solution was subjected to re-precipitation in hexane and refining using GPC for isolation (eluent: chloroform) to obtain a nitroalkane compound (1-3) (620 mg).

[0123] .sup.1H-NMR (500 Hz, CDCl.sub.3, 298K): δ (ppm) 7.35-7.21 (m, 20H), 7.19-7.05 (m, 2H), 6.97-6.82 (m, 10H), 5.85-5.77 (m, 1H), 5.34 (s, 2H), 5.04-4.94 (m, 2H), 4.51 (q, J=7.0 Hz, 2H), 4.40 (s, 2H), 4.25-4.21 (m, 4H), 4.12-4.09 (m 4H), 4.05 (t, J=6.9 Hz, 2H), 3.86-3.81 (m 8H), 3.64-3.61 (m, 4H), 3.46 (m, t, J=6.9 Hz, 2H), 3.43-3.38 (m, 4H), 3.09-3.03 (m, 2H), 2.49 (t, J=7.5 Hz, 2H), 2.13 (q, J=7.2 Hz, 2H), 1.98-1.93 (m, 2H), 1.73-1.67 (m, 2H), 1.64-1.58 (m, 2H), 1.44-0.96 (m, 20H);

[0124] .sup.13C-NMR (125 Hz, CDCl.sub.3, 298K): δ (ppm) 173.6, 147.5, 147.4, 146.9, 141.4, 138.3, 138.2, 132.3, 132.3, 130.7, 128.4, 128.1, 127.3, 126.6, 121.8, 121.0, 114.8, 112.7, 112.6, 112.4, 112.1, 81.3, 79.7, 72.4, 70.7, 70.2, 69.7, 68.4, 68.3, 68.2, 64.5, 62.0, 52.2, 49.0, 31.1, 30.4, 29.5, 29.4, 29.3, 29.2, 28.9, 28.6, 26.6, 26.4, 25.9, 25.0, 21.2;

[0125] MALDI-TOF MS (Matrix: dithranol, Cationizing agent: CF.sub.3COONa): m/z calcd for C.sub.69H.sub.97N.sub.2O.sub.14Na [M+Na].sup.+: 1177.74, found: 1177.26.

Example 1-3: Synthesis of Rotaxane Compound (1-4)

[0126] The compound (1-1) (290 mg) was added to a chloroform (5.0 mL) solution of the compound (1-3) (560 mg), followed by 12-hour stirring at 50° C. The solvent was distilled off, the compound was dissolved in THF (8.6 mL), and thereto were added phenyl isocyanate (290 mg) and triethylamine (350 mg), followed by 4-hour stirring at room temperature. After filtration of a reaction solution, a solvent of a filtrate was distilled off, followed by refining using GPC for isolation (eluent: chloroform) to obtain a rotaxane compound (1-4) (200 mg).

[0127] .sup.1H-NMR (500 Hz, CDCl.sub.3, 298K): δ (ppm) 7.52-7.14 (m, 23H), 6.92-6.67 (m, 12H), 4.58-4.52 (m, 1H), 4.48 (s, 2H), 4.36 (s, 2H), 4.20-4.04 (m, 8H), 4.00 (t, J=6.9 Hz, 2H), 3.74 (q, J=6.7 Hz, 6H), 3.73-3.68 (m, 8H), 3.61-3.36 (m, 14H), 2.96-2.91 (m, 1H), 2.53-2.48 (m, 3H), 2.33-2.24 (m, 2H), 2.20 (s, 6H), 2.15-2.09 (m, 2H), 2.00-1.95 (m, 2H), 1.74-1.65 (m, 1H), 1.59-1.50 (m, 8H), 1.18 (t, J=6.7 Hz, 9H), 1.30-0.91 (m, 18H), 0.62-0.59 (m 2H);

[0128] .sup.13C-NMR (125 Hz, CDCl.sub.3, 298K): δ (ppm) 173.7, 161.0, 155.8, 148.2, 147.7, 141.3, 141.2, 140.7, 140.6, 139.2, 137.4, 130.5, 128.9, 128.6, 128.5, 128.4, 128.3, 128.1, 127.3, 126.6, 126.3, 124.9, 121.7, 120.5, 119.9, 119.8, 111.9, 111.5, 83.9, 80.9, 72.7, 70.8, 69.7, 69.5, 68.4, 68.3, 68.2, 65.9, 64.8, 61.0, 58.3, 49.2, 47.5, 41.6, 33.8, 31.8, 30.8, 30.1, 29.8, 29.7, 29.6, 29.3, 28.6, 27.6, 26.6, 25.9, 25.8, 24.7, 22.1, 21.4, 18.3, 10.4;

[0129] IR (NaCl): υ 2275 (CNO) cm.sup.−1;

[0130] MALDI-TOF MS (Matrix: dithranol, Cationizing agent: CF.sub.3COONa): m/z calcd for C.sub.99H.sub.130N.sub.4O.sub.18SSiNa [M+Na].sup.+: 1745.93, found: 1745.89.

INDUSTRIAL APPLICABILITY

[0131] The rotaxane compound of the present invention can be used as a silane coupling agent imparting specific dynamic characteristic and physical properties to a composition obtained by compounding the rotaxane compound thereto.