JP4873570B2 - POLY [2] CATENAN COMPOUND AND MONOMER THEREOF AND METHOD FOR PRODUCING THEM - Google Patents

Description

  The present invention relates to a novel polymer compound, a monomer thereof, and a production method thereof.

  In recent years, research on polymer materials as polymer elastomers has been actively conducted.

  The formation of a polymer elastomer or the like requires that the polymer main chain has high mobility.

  For the purpose of imparting mobility to a polymer main chain, synthesis of a polymer having a structure in which catenane compounds are linked has been attempted. The catenane compound has two or more cyclic molecules linked together in a chain form (interlock structure). Polymers obtained by linking catenane compounds are considered to have a much greater degree of freedom of movement than conventional polymers in which the atoms constituting the polymer chain are chemically bonded to each other and their movement is restricted. Therefore, it is expected as a polymer having new and useful properties.

  In order to obtain such a polymer, synthesis of a polymer called polycatenan has been attempted by repeatedly constructing an interlock structure by a cyclization reaction. However, in this method, since a significant decrease in yield due to the cyclization reaction cannot be avoided, it has not been reported that a high molecular weight catenane polymer was obtained.

On the other hand, synthesis examples of poly [2] catenan having a structure in which catenane compounds are linked by chemical bonds (for example, Patent Document 1) have been reported, but there are still few reports on such compounds.
JP 9-48849 A

  The problem to be solved by the present invention is to provide a novel poly [2] catenan and a catenane compound which is a monomer thereof, and a method for producing them.

  In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, a high molecular weight poly [2] catenan can be synthesized by copolymerizing two types of bifunctional [2] catenanes. The present invention has been completed by finding out what can be done.

  That is, the present invention is a copolymer obtained by copolymerizing two types of bifunctional [2] catenane, wherein [2] catenane is formed by a chemical bond such as an ester bond, an amide bond, or a triazole bond. The present invention relates to poly [2] catenan having a structure linked to each other.

In particular, the present invention provides the following general formula (1)
(Wherein n is an integer of 5 to 10, m is an integer of 5 to 10, and k is an integer of 1 to 100).

Furthermore, the present invention provides the following general formula (2)
(In the formula, n is an integer of 5 to 10.)
Diazide [2] catenan represented by the following general formula (3)
(In the formula, m is an integer of 5 to 10.)
It is related with the manufacturing method of said poly [2] catenane characterized by polymerizing by the 1, 3- dipole cycloaddition reaction with diethynyl [2] catenane represented by these.

Further, the present invention provides the following general formula (2)
(In the formula, n is an integer of 5 to 10.)
It is related with diazide [2] catenane represented by these.

Furthermore, the present invention provides the formula (4)
And an integer of ClOC (CH ₂ ) _n COCl (where n is 5 to 10). And a method for producing the diazide [2] catenan, which comprises carrying out a cyclization reaction with the above.

Further, the present invention provides the following general formula (3)
(In the formula, m is an integer of 5 to 10.)
It is related with diethynyl [2] catenan represented by these.

Furthermore, the present invention provides the following formula (5)
And an integer of ClOC (CH ₂ ) _m COCl (where m is 5 to 10). And a method for producing the above-mentioned diethynyl [2] catenan.

  The poly [2] catenan represented by the general formula (1) according to the present invention has an unprecedented structure in which [2] catenan is linked via a triazole bond, and is a functional material such as a polymer elastomer. Usefulness is expected as a raw material.

Poly [2] catenan Poly [2] catenan represented by the general formula (1) according to the present invention has an unprecedented structure in which [2] catenanes are linked via a triazole group.

  In the poly [2] catenan of the present invention, the number of repeating units k is not particularly limited and can be changed according to the production conditions described later, but is usually about 1 to 100. Moreover, n and m depend on the reagent used in the production described later, and both are integers of 5 to 10. Note that n and m may be different or the same.

  Since the poly [2] catenan of the present invention has an interlock structure between repeating units, the degree of freedom of movement of the molecule is much higher than that of a conventional polymer compound in which a plurality of atoms are connected only by chemical bonds. Therefore, application as an elastomer having a novel viscoelastic property is expected.

Production method of poly [2] catenan Poly [2] catenan represented by the general formula (1) of the present invention has the novel chemical structure described above, that is, [2] catenanes are linked via a triazole group. Has a structure. Therefore, there is no particular limitation as long as it is a method capable of producing a polymer having such a structure.

  In the present invention, poly [2] catenan is particularly preferably copolymerized with diazide [2] catenan represented by general formula (2) and diethynyl [2] catenan represented by general formula (3). The reaction is a generally known 1,3-dipolar cycloaddition reaction (click reaction). References can be made to Journal of Medicinal Chemistry 2006, 49, 467-470 and Chemical Communication 2005, 4333-4335.

  Although there are no particular restrictions on the method for obtaining the raw materials diazide [2] catenan and diethynyl [2] catenan, they can be synthesized in a short process and in high yield by the synthesis route described below.

  In the 1,3-dipolar cycloaddition reaction (click reaction) using diazide [2] catenan and diethynyl [2] catenan, it is preferable to perform the reaction using a monovalent copper catalyst. Further, a divalent copper catalyst may be used together with a reducing agent such as ascorbic acid to produce a monovalent copper catalyst in the reaction system. As the monovalent copper catalyst, copper bromide, copper iodide or the like can be used, and as the divalent copper catalyst, copper sulfate or the like can be used.

  The chemical structure of poly [2] catenan according to the present invention can be confirmed by molecular weight measurement and various spectroscopic measurements.

  In particular, it is possible to measure the molecular weight and molecular weight distribution of poly [2] catenan by a generally known gel permeation chromatograph (hereinafter referred to as “GPC”) (the value of k is determined).

  Furthermore, if necessary, a specific fraction can be used as a sample for detailed analysis such as an infrared absorption spectrum (hereinafter “IR”) or a nuclear magnetic resonance spectrum (hereinafter “NMR”).

In IR, the formation of the poly [2] catenan of the present invention can be qualitatively confirmed by the disappearance / reduction of absorption based on the azide group and ethynyl group. In ¹ H-NMR, the generation of the poly [2] catenan of the present invention can be qualitatively confirmed by the disappearance / reduction of the absorption based on the protons of the terminal acetylene.

Diazide [2] catenane diazide [2] catenane (Compound 1) can be synthesized through the following synthetic steps.

  5-Azidoisophthalic acid (Compound 4) can be synthesized by converting 5-aminoisophthalic acid (Compound 3) as a starting material and converting the amino group to an azide group via diazotization. Specifically, compound 3 can be synthesized by reacting nitrite with acid under diacidification and then reacting with sodium azide. The conditions at this time are not particularly limited, and generally known conditions can be adopted. However, in order to stabilize the resulting diazonium salt, the diazotization reaction is usually performed at about 0 to 5 ° C. preferable.

  Subsequently, azidodiamine (compound 5) can be synthesized by performing an amide bond forming reaction between 5-azidoisophthalic acid (compound 4) and 4-aminobenzylamine. Specifically, 4-aminobenzylamine is added to compound 4 in the presence of a compound containing a carbodiimide group as a dehydrating condensing agent. The dehydrating condensing agent having a carbodiimide group is not particularly limited, and examples thereof include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and the like. At this time, it is preferable to use 1-hydroxybenzotriazole (HOBt), N-hydroxysuccinimide (HOSu), or the like as an additive for promoting dehydration condensation and suppressing side reactions.

Furthermore, by carrying out a cyclization reaction between azidodiamine (compound 5) and ClOC (CH ₂ ) _n COCl (where n is an integer of 5 to 10), the desired diazide [2] catenane (compound 1) can be synthesized. As the ClOC (CH ₂ ) _n COCl, a commercially available product can be used as it is, or an α, ω-alkanediol or α, ω-alkanedicarboxylic acid which can be easily obtained can be synthesized and used as a starting material. is there. The reaction is a known amide formation reaction with an acid chloride and a primary amine, and the conditions are not particularly limited. At this time, it is preferable to use a base having low nucleophilicity (such as triethylamine) for the purpose of neutralizing the hydrochloric acid produced.

  The product of the reaction includes, in addition to diazide [2] catenan, a cyclic compound having no interlock structure. Separation and purification of diazide [2] catenan can be performed from the product by using silica gel chromatography.

  The chemical structure of diazide [2] catenane can be confirmed by molecular weight measurement and various structural analysis means.

  In particular, it can be determined by NMR, IR, mass spectrometry (hereinafter, “MS”) or the like.

For example, a peak derived from each proton can be confirmed by a ¹ H-NMR spectrum. Moreover, absorption based on an azide group etc. can be confirmed by IR. Furthermore, when MS, particularly MALDI TOF-MS, is used, a peak can be observed in the vicinity of the molecular weight (1163) of diazide [2] catenan.

Further, when ¹ H-NMR of diazide [2] catenan is compared with a compound that does not have an interlock structure obtained by the above reaction, in diazide [2] catenan, the signal derived from each proton is shifted to the high magnetic field side. (See David, AL et al. Angew. Chem. Int. Ed. Engl. 1996, 35, 306-309.). Thereby, a catenane compound (construction of an interlock structure) can be confirmed.

The diethynyl [2] catenandiethynyl [2] catenan (compound 2) can be synthesized through the following synthesis steps.

  5-Iodoisophthalic acid (Compound 6) can be synthesized by substituting 5-aminoisophthalic acid (Compound 3) with iodine for the amino group via diazotization. Specifically, compound 3 can be synthesized by reacting nitrite with acid under diacidification and then reacting with alkali metal iodide such as potassium iodide. The conditions at this time are not particularly limited, and generally known conditions can be adopted. However, in order to stabilize the resulting diazonium salt, the diazotization reaction is usually performed at about 0 to 5 ° C. preferable.

  Subsequently, the dicarboxylic acid of compound 6 is converted to an alkyl ester. For the reaction, generally known ester forming reaction can be preferably employed. More specifically, dimethyl iodoisophthalate (compound 7) can be synthesized by dissolving compound 6 in an alcohol such as methanol and heating to reflux under acidic conditions.

  Compound 7 is subjected to Sonogashira acetylene coupling reaction using trimethylsilylacetylene (see Sonogashira, K. et al. Tetrahedron lett. 1975, 50, 4467, etc.) to convert iodine to a trimethylsilylethynyl group. , Dimethyl 5-trimethylsilylethynylisophthalate (Compound 8) can be obtained. Specifically, Pd (0) catalyst, copper iodide and amine are added to compound 7, and then trimethylsilylacetylene is reacted. After the reaction, dimethyl 5-trimethylsilylethynylisophthalate (Compound 8) can be separated and purified from the reaction product by using silica gel chromatography.

  Subsequently, 5-ethynylisophthalic acid (Compound 9) can be obtained by hydrolyzing the alkyl ester of Compound 8 under basic conditions and then removing the trimethylsilyl group.

  Next, ethynyldiamine (compound 10) can be synthesized by performing an amide bond forming reaction between 5-ethynylisophthalic acid (compound 9) and 4-aminobenzylamine. The reaction can be carried out in the same manner as in the synthesis of the above azidodiamine (Compound 5).

Furthermore, by carrying out a cyclization reaction between ethynyldiamine (compound 10) and ClOC (CH ₂ ) _m COCl (where m is an integer of 5 to 10), the desired diethynyl [2] catenan (compound) 2) can be synthesized. The reaction and purification can be carried out in the same manner as in diazide [2] catenane (compound 1).

  Confirmation of the chemical structure of diethynyl [2] catenan can also be carried out in the same manner as diazide [2] catenan.

  Hereinafter, the present invention will be specifically described by way of examples. These examples are for explaining the present invention, and do not limit the scope of the present invention.

In this example, 5-aminoisophthalic acid: manufactured by Tokyo Chemical Industry Co., Ltd. (> 98.0%), 1-hydroxybenzotriazole monohydrate: manufactured by Tokyo Chemical Industry Co., Ltd. (> 97.0) %), Dicyclohexylcarbodiimide: manufactured by Tokyo Chemical Industry Co., Ltd. (> 98.0%), 4-aminobenzylamine: manufactured by Tokyo Chemical Industry Co., Ltd. (> 98.0%), sebacoyl dichloride (ClOC (CH _{2 8} COCl): Kanto Chemical Co., Ltd. (> 97.0%, deer grade) Palladium acetate: Aldrich (98%), Copper iodide: Kanto Chemical Co., Ltd. (> 99.0%) Triphenyl Phosphine: Wako Pure Chemical Industries, Ltd. (> 97%), Trimethylsilylacetylene: Tokyo Chemical Industry Co., Ltd. (> 98.0%), Ascorbic acid sodium: Kanto Chemical Co., Ltd. (> 98.0%) , Deer special grade).

  Moreover, as a measuring apparatus of a present Example, GPC: HLC-8121GPC / HT (made by Tosoh Corporation), FT-IR (KBr method): 1600-FT-IR (made by Perkin Elmer Co., Ltd.), FT-NMR : JNM-GX400 (manufactured by JEOL Ltd.), MALDI TOF-MS: Voyager RP-PRO (manufactured by Applied Biosystems).

(Example 1) Synthesis of diazide [2] catenane In the above general formula (2), n = 8 diazide [2] catenane was synthesized according to the above synthesis route.

  To a solution obtained by dissolving 0.90 g of 5-aminoisophthalic acid (compound 3) in 15 ml of 1.5N hydrochloric acid, 1 ml of a 0.42 g aqueous solution of sodium nitrite was added dropwise in an ice bath, and the mixture was stirred for 30 minutes. .1 ml of 40 g aqueous solution was added dropwise and stirred for 24 hours. After completion of the reaction, the produced precipitate was filtered and washed with pure water to obtain white solid 5-azidoisophthalic acid (Compound 4) in a yield of 85%.

  Dissolve 0.83 g of 5-azidoisophthalic acid and 1.29 g of 1-hydroxybenzotriazole monohydrate in 10 ml of THF, add dropwise thereto a 20 ml solution of THF containing 1.73 g of dicyclohexylcarbodiimide, and bath in an ice bath for 6 hours under nitrogen. Stir in. After the reaction, the produced precipitate was filtered, and the obtained filtrate was slowly added dropwise to 20 ml of THF solution containing 0.95 ml of 4-aminobenzylamine, and stirred at room temperature for 24 hours under nitrogen. After completion of the reaction, the solvent was removed under reduced pressure until it was halved, chloroform was added thereto, washed with a saturated aqueous sodium hydrogen carbonate solution, and then the organic layer solvent was removed under reduced pressure to give a pale yellow color. Solid azidodiamine (compound 5) was obtained with a yield of 51%.

  Dissolve 0.42 g of azidodiamine in 12 ml of acetonitrile, add 250 ml of chloroform, and add 50 ml of chloroform solution containing 0.21 ml of sebacoyl dichloride and 0.31 ml of triethylamine over 5 hours. Stir for hours. After completion of the reaction, the produced precipitate was filtered, and the filtrate was washed with 1N hydrochloric acid and saturated sodium bicarbonate in this order. The solvent of the organic layer was removed under reduced pressure, and the resulting residue was purified by preparative thin layer chromatography (chloroform: methanol = 93: 7 (v: v)) to obtain a white solid diazide [2 Catenane was obtained with a yield of 6%.

FIG. 1 (a) shows a ¹ H-NMR spectrum (400 MHz, DMSO-d ₆ ) of diazide [2] catenan. 1 (b) and 1 (c) are ¹ H-NMR charts of compounds that are products of the reaction and do not have an interlock structure.

  Comparing FIG. 1 (a) with (b) or (c), it can be seen that the signal of each proton (especially the signal derived from the methylene proton of the sebacoil chain) is shifted to the high magnetic field side. It can be seen that these compounds have an interlock structure.

Further, as a result of mass spectrometry (MALDI TOF-MS), a peak was confirmed in the vicinity of 1163 (m / z). When analyzed by GPC using DMF as a developing solvent, the number average molecular weight (Mn) in terms of polystyrene was 3.5 × 10 ³ .

(Example 2) Synthesis of diethynyl [2] catenane m = 8 diethynyl [2] catenane in the above general formula (3) was synthesized according to the above synthesis route.

  Dissolve 10.87 g of 5-aminoisophthalic acid (compound 3) in 15 ml of 1.5N hydrochloric acid, add 60 ml of a 4.57 g aqueous solution of sodium nitrite and stir for 30 minutes, and then add 60 ml of a 19.92 g aqueous solution of potassium iodide. The mixture was further stirred for 24 hours. The reaction mixture was subjected to suction filtration, and the precipitate was washed with pure water and dried under reduced pressure to obtain ocherous solid 5-iodoisophthalic acid (Compound 6) in a yield of 83%.

  2.92 g of 5-iodoisophthalic acid was dissolved in 80 ml of methanol, 2 ml of concentrated sulfuric acid was added thereto, and the mixture was refluxed with heating under nitrogen for 24 hours. After completion of the reaction, the solvent is removed under reduced pressure, ethyl acetate is added to the resulting residue, and the mixture is washed with pure water until neutral. The organic layer is dehydrated with magnesium sulfate, and then the solvent is removed under reduced pressure. Gave dimethyl 5-iodoisophthalate (compound 7) as a yellow solid in a yield of 90%.

  0.64 g of dimethyl 5-iodoisophthalate, 0.023 g of palladium acetate, 0.081 g of triphenylphosphine, and 0.058 g of copper iodide were dissolved in 4 ml of THF, to which 2 ml of triethylamine and 0.33 ml of trimethylsilylacetylene were added, and nitrogen was added. And stirred for 24 hours at room temperature. After completion of the reaction, ethyl acetate was added and the resulting precipitate was filtered, and the filtrate removed the solvent under reduced pressure. Pure water was added to the resulting residue, the formed precipitate was filtered, and this precipitate was isolated and purified by silica gel chromatography (ethyl acetate: hexane = 2: 1), and then a brown solid dimethyl 5-trimethylsilylethynylisophthalate ( Compound 8) was obtained with a yield of 93%.

  0.44 g of dimethyl 5-trimethylsilylethynylisophthalate was dissolved in 30 ml of ethanol, 7.5 ml of 1N aqueous potassium hydroxide solution was added thereto, and the mixture was stirred for 1 hour in an ice bath. After the reaction, the solvent was removed under reduced pressure, the residue was dissolved in pure water, acidified with 1N hydrochloric acid, and the resulting precipitate was filtered to obtain brown solid 5-ethynylisophthalic acid (compound 9). Obtained in 77% yield.

  To a solution of 0.76 g of 5-ethynylisophthalic acid and 1.26 g of 1-hydroxybenzotriazole monohydrate in 10 ml of THF, 20 ml of a THF solution containing 1.69 g of dicyclohexylcarbodiimide was added dropwise, and 6 ml in an ice bath under nitrogen. Stir for hours. After the reaction, the produced precipitate was filtered, and the obtained filtrate was slowly added dropwise to 20 ml of THF solution containing 0.95 ml of 4-aminobenzylamine, and stirred at room temperature for 24 hours under nitrogen. After the reaction, the solvent was removed in half under reduced pressure, chloroform was added thereto, washed with a saturated aqueous sodium hydrogen carbonate solution, and the organic layer solvent was removed under reduced pressure to remove ethynyl as a brown solid. Diamine (Compound 10) was obtained in a yield of 87%.

  Ethynyldiamine (0.40 g) is dissolved in acetonitrile (12 ml), and chloroform (250 ml) is added. To this, 50 ml of a chloroform solution containing 0.21 ml of sebacoyl dichloride and 0.31 ml of triethylamine is added dropwise over 5 hours. Stir for hours. After the reaction, the produced precipitate was filtered, and the filtrate was washed with 1N hydrochloric acid and saturated sodium bicarbonate in this order. The solvent of the organic layer was removed under reduced pressure, and the resulting residue was purified using preparative thin layer chromatography (chloroform: methanol = 93: 7) to yield a white solid, diethynyl [2] catenan. Obtained at 5%.

FIG. 2A shows a ¹ H-NMR spectrum (400 MHz, DMSO-d ₆ ) of diethynyl [2] catenan. 2B and 2C are ¹ H-NMR charts of compounds that are products of the reaction and do not have an interlock structure. Comparing FIG. 2 (a) with (b) or (c), it can be seen that the signal of each proton (especially the signal derived from the methylene proton of the seba coil chain) is shifted to the high magnetic field side. It can be seen that these compounds have an interlock structure.

Further, as a result of mass spectrometry (MALDI TOF-MS), a peak was confirmed in the vicinity of 1129 (m / z). When DMF was analyzed by GPC using DMF as a developing solvent, the number average molecular weight (Mn) in terms of polystyrene was 3.8 × 10 ³ .

Example 3 Synthesis of Poly [2] Catenan (1)
Using a capped test tube, 0.0104 g of diazide [2] catenan and 0.0102 g of diethynyl [2] catenan were dissolved in 100 μl of DMF. To this, 1.1 mg of copper sulfate pentahydrate, 3.6 mg of sodium ascorbate and 10 μl of water were added and stirred at room temperature for 2 days under nitrogen. After the reaction, pure water was added, and the generated precipitate was filtered to obtain poly [2] catenan of n = m = 8 in the general formula (1) as a yellow solid. When DMF was analyzed by GPC using DMF as a developing solvent, the number average molecular weight (Mn), weight average molecular weight (Mw), and dispersity (Mw / Mn) were 37 × 10 ³ , 44 × 10 ³ , and 1. It was 19.

Example 4 Synthesis of Poly [2] Catenan (2)
Using a capped test tube, 0.0104 g of diazide [2] catenan and 0.0102 g of diethynyl [2] catenan were dissolved in 100 μl of DMF. To this, 1.1 mg of copper sulfate pentahydrate, 3.6 mg of sodium ascorbate and 10 μl of water were added and stirred at room temperature for 2 days under nitrogen. On the second day, 1.1 mg of copper sulfate pentahydrate and 3.6 mg of sodium ascorbate were added, and the mixture was further stirred for 2 days. After the reaction, pure water was added, and the generated precipitate was filtered to obtain poly [2] catenan of n = m = 8 in the general formula (1) as a yellow solid. When DMF was analyzed by GPC using DMF as a developing solvent, the number average molecular weight (Mn), the weight average molecular weight (Mw), and the dispersity (Mw / Mn) were 31 × 10 ³ , 49 × 10 ³ , and 1. 58.

Example 5 Synthesis of poly [2] catenan (3)
Using a capped test tube, 0.0104 g of diazide [2] catenan and 0.0102 g of diethynyl [2] catenan were dissolved in 100 μl of DMF. To this, 1.1 mg of copper sulfate pentahydrate, 3.6 mg of sodium ascorbate and 10 μl of water were added and stirred at room temperature for 2 days under nitrogen. On the second day, 1.1 mg of copper sulfate pentahydrate and 3.6 mg of sodium ascorbate were added, and the mixture was further stirred for 2 days. On day 4, 1.1 mg of copper sulfate pentahydrate and 3.6 mg of sodium ascorbate were added, and the mixture was further stirred for 3 days. After the reaction, pure water was added, and the generated precipitate was filtered to obtain poly [2] catenan of n = m = 8 in the general formula (1) as a yellow solid. When GMF was analyzed using DMF as a developing solvent, the number average molecular weight (Mn), the weight average molecular weight (Mw), and the dispersity (Mw / Mn) were 46 × 10 ³ , 60 × 10 ³ , and 1. 31.

IR spectra of the catenane compound (raw material) and poly [2] catenan obtained in each of the above examples are shown in FIG. From FIG. 3, it can be seen that in poly [2] catenan ((c)), the peak derived from the azide group disappears. Further, in ¹ H-NMR of poly [2] catenan, a peak derived from the proton of terminal acetylene was not confirmed.

  All publications cited in this specification are incorporated herein by reference in their entirety.

  The poly [2] catenan of the present invention forms a polymer in which a catenane molecule having an interlock structure is firmly linked via a triazole group, and has a polymer having excellent mechanical properties and rheological properties, or a unique function. Applications as super plastics such as polymers are expected. For example, it is expected to be applied to a selectively permeable membrane by an elastomer having a novel elastic property or a catenane interlock structure.

FIG. 1 is a ¹ H-NMR spectrum (400 MHz, DMSO-d ₆ ) of the product of the cyclization reaction. FIG. 1 (a) is a ¹ H-NMR spectrum of diazide [2] catenan, and FIGS. 1 (b) and (c) are ¹ H-NMR charts of compounds that do not have an interlock structure. FIG. 2 is a ¹ H-NMR spectrum (400 MHz, DMSO-d ₆ ) of the product of the cyclization reaction. FIG. 2 (a) is a ¹ H-NMR spectrum of diethynyl [2] catenan, and FIGS. 2 (b) and 2 (c) are ¹ H-NMR charts of compounds that do not have an interlock structure. FIG. 3 is an IR spectrum of (a) diazide [2] catenane, (b) diethynyl [2] catenane, and (c) poly [2] catenane.

Claims (4)

The following general formula (1)
Wherein n is an integer of 5 to 10, m is an integer of 5 to 10, and k is an integer of 1 to 100. The following general formula (2)
(In the formula, n is an integer of 5 to 10.)
Diazide [2] catenan represented by the following general formula (3)
(In the formula, m is an integer of 5 to 10.)
2. The method for producing poly [2] catenan according to claim 1, wherein the diethynyl [2] catenan represented by the formula is polymerized by 1,3-dipolar cycloaddition reaction. The following general formula (2)
(In the formula, n is an integer of 5 to 10.)
The diazide [2] catenane represented by these. The following general formula (3)
(In the formula, m is an integer of 5 to 10.)
Diethynyl [2] catenan represented by