JPH0681768B2 - Method for producing optically active organic polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to the polymerizability of an optically active ester containing a pyridyl group having excellent solubility in an organic solvent using an optically active catalyst having axial asymmetry. It is a thing.

[Problems to be Solved by Prior Art and Invention]

Japanese Patent Application No. 58-177814 is already known as to a method for polymerizing an optically active polyester containing a pyridyl group. That is,
Using diphenyl-2-pyridylmethylmethacrylate as a monomer, n-butyllithium-spartine or N, N'-diphenylethylenediaminelithiumamide-optically active 1,4-dimethylamino-2,3 as an optically active polymerization catalyst. -A method for obtaining optically active polydiphenyl-2-pyridylmethylmethacrylate in combination with -dimethoxybutane.

In the process of searching for an optically active polymerization catalyst, the present inventors have found that an optically active ligand having axial asymmetry has a higher optical rotation as a polymerization catalyst for diphenyl-2-pyridylmethylmethacrylate and has high solubility in an organic solvent. It has been found to give excellent polyesters.

[Means for solving problems]

That is, the present invention has the general formula (A) (In the formula, Ar represents an aromatic hydrocarbon having 6 to 14 carbon atoms and is, for example, a phenyl, naphthyl or anthryl group. R ₁ and R ₂ are hydrogen atoms or a straight chain having 1 to 20 carbon atoms. Alternatively, it is a hydrocarbon group having a branched chain, and the structure may include an aromatic hydrocarbon.

Preferably -CH ₃ group, or C ₂ H ₅ group. Further m,
n represents the number of methylene chains, m is 0 to 4, and preferably 0 or 1. n represents 1 to 5, preferably 2 or 3, and most preferably 2. The following general formula (B) is used, using an optically active polymerization catalyst comprising an optically active ligand having axial chirality represented by) and an anionic polymerization initiator. (However, at least one of R ₃ , R ₄ and R _{5 in} the formula is a pyridyl group, for example, a 2-pyridyl group, a 3-pyridyl group, or a 4-pyridyl group. The same or different, each of which is a phenyl group or a pyridyl group) is represented by the following general formula (C): (However, n is an integer of 3 or more) The present invention relates to a method for synthesizing a chloroform-soluble optically active organic polymer having an absolute value of optical rotation [α ▲] ²⁵ ₃₆₅ of 800 or more.

The optically active polymer obtained in the present invention is capable of discriminating asymmetry of molecules, and is expected as a high performance separating agent.

Examples of the ligand having the axial asymmetry represented by the general formula (A) used in the present invention are as follows.

_{R 1 = CH 3, R 2} = CH 3, m = 1, n = 2 R ₁ = H, R ₂ = CH ₃ , m = 1, n = 2 Among these asymmetric ligands, for example, optically active N- (2
-Dimethylaminoethyl) -4 ', 1 "-dimethyl-2,7-
Dihydro-3,4,5,6-dibenzazepine (1) can be synthesized by the following method. That is, after obtaining optically active 6,6'-dimethyldiphenic acid using brucine,
After undergoing methyl esterification, reduction, and bromination to give 2,2'-bis (bromomethyl) -6,6'-dimethylbiphenyl,
Then, it was treated with 2-dimethylaminoethylamine to synthesize optically active N- (2-dimethylaminoethyl) -4 ', 1 "-dimethyl-2,7-dihydro-3,4,5,6-dibenzazepine. .

The anionic polymerization initiator for constituting the optically active polymerization catalyst of the present invention is used as an anionic polymerization initiator, and is any one as long as it can form a complex with the asymmetric ligand. But good. Specifically, an anionic polymerization initiator comprising an alkali metal, an alkaline earth metal, aluminum or a similar metal as a counter ion and anions such as carbon, nitrogen, oxygen and sulfur as anions is used. Preferred are anionic polymerization initiators composed of carbon anions, and the following are exemplified.

_{R'MgX, R 2 'Mg, R'CaX} , Al (C 2 H 5) 3, LiR', LiAlH 4, Na
R ', KR' (wherein R'is an alkyl group having 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms such as butyl, benzyl and phenyl groups;
An alkyl group or an aromatic group, and X is a halogen).

Further, an anion polymerization initiator obtained from a nitrogen anion, that is, a secondary amine is also preferably used. Examples of such an anionic polymerization initiator are as follows.

(However, R ″ and R are alkyl groups having 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms, aralkyl groups or aromatic groups, and M is a counterion).

A preferred method for preparing the optically active polymerization catalyst of the present invention is to use an anionic polymerization initiator and a dehydrated and dried asymmetric ligand represented by the general formula (A) in a solvent, for example, in a hydrocarbon solvent. It is a method of mixing and forming a complex. The amount of the asymmetric ligand used here is 0.2 to 2, and preferably 0.5 to 2, in molar ratio with respect to the anionic polymerization initiator.
In order to polymerize the polymerizable monomer using the polymerization catalyst of the present invention, the polymerizable monomer may be polymerized as it is or may be dissolved in a solvent and polymerized. However, the solvent used must not inhibit anionic polymerization.

Examples of the methacrylic acid ester containing a pyridyl group represented by the general formula (B) include the following.

Incidentally, these pyridyl group and phenyl group may have a substituent.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to synthesis examples and examples, but the present invention is not limited thereto.

Synthesis Example 1. (Synthesis of 2-amino-m-toluic acid ( 3 )) 2-Nitro-m-toluic acid (120 g, 0.66 mol), tin powder (220
g, 1.85 mol) in 0.5 ethanol suspension system, and 9N-HCl in 1.2
Was dripped. The dropping rate was controlled so that the reaction temperature was 50 to 60 ° C. After allowing to cool, concentrated ammonia water was added to make it basic, and the precipitate was separated. After concentrating the mother liquor, add acetic acid to adjust the pH.
5, and the precipitated crystal was separated. Crystallization was performed from ethanol to obtain colorless crystals of 2-amino-m-toluic acid ( 3 ) (87 g, yield 87%).

mp 171-173 ℃ IR spectrum (KBr) 3500,3300-2500,1670cm- ¹ Synthesis example 2. (Synthesis of 2-iodo-m-toluic acid ( 4 )) 33% dilute sulfuric acid 0.9 to 2-amino-m- 75 g of toluylic acid ( 3 )
(0.5 mol) was added, and the mixture was stirred at room temperature for 1 hour to give a sulfate. An aqueous solution of 45 g (0.65 mol) of sodium nitrite is added to this.
It was added so that the temperature did not exceed 10 ° C. to obtain a uniform aqueous solution of diazonium salt. After decomposing excess nitrous acid with urea, a saturated aqueous solution of 420 g (2.5 mol) of potassium iodide and 3 g of Guttaman copper.
Was added all at once and left overnight. After separating the precipitate, it was dissolved in ethyl acetate and washed with an aqueous sodium sulfite solution.

After drying, the solvent was removed, and the residue was recrystallized from hydrous ethanol to give 2-iodo-m-toluic acid ( 4 ).

Yield 106g Yield 81% mp 144-146 ° C Synthesis Example 3. (Synthesis of methyl 2-iodo-m-toluate ( 5 )) 2-iodo-m-toluic acid ( 4 ) (129g, 0.49mol) in methanol It was dissolved in 600 ml and absorbed hydrogen chloride. After completion of the initial exothermic reaction, hydrogen chloride was blown in at the reflux temperature for another hour. After removing the solvent under reduced pressure,
The residue was extracted with ether and washed with aqueous sodium hydrogen carbonate solution and saturated brine. The solvent was removed, and the residue was distilled under reduced pressure to give methyl 2-iodo-m-toluate ( 5 ).

Yield 128g Yield 94% bp 115 ℃ / 0.05mmHg IR spectrum (liquid film) 1730,1295,1145cm- ¹ Synthetic example 4. (Dimethyl 6,6'-dimethyldiphenate ( 6 ))
Synthesis of methyl 2-iodo-m-toluate ( 5 ) (209g, 0.76mol) and copper powder (104g, treated with iodine and hydrochloric acid in acetone) were added to N, N-dimethylformamide. The mixture was heated under reflux for 6 hours with stirring.

After removing the copper powder separately, the product was extracted with benzene and washed with dilute hydrochloric acid. After removing the solvent, the residue was distilled under reduced pressure to obtain dimethyl 6,6'-dimethyldiphenate ( 6 ).

Yield 107g Yield 95% bp 140 ℃ / 0.04mmHg IR spectrum (liquid film) 1735,1280,1150cm- ¹ Synthetic example 5. (Synthesis of 6,6'-dimethyldiphenic acid ( 7 )) 6,6'- Dimethyl dimethyl diphenate ( 6 ) (37g, 0.12
(mol) was refluxed in 340 g of 16% aqueous sodium hydroxide solution for 5 hours. After allowing to cool, it was poured into dilute hydrochloric acid to obtain a white precipitate.
After separating the precipitate, it was recrystallized from acetonitrile to give 6,6 '
-Dimethyldiphenic acid ( 7 ) was obtained.

Yield 30 g Yield 95% mp 240 to 241 ° C IR spectrum (KBr) 3300 to 2400,1700 cm- ¹ Synthesis example 6. (Optically active dimethyl 6,6'-dimethyldiphenate (R)-( 6 ), ( Synthesis of (S)-( 6 )) 72 g (0.18 mol) of brucine was suspended in 300 ml of hot acetone. To this, 47 g (0.17) of 6,6'-dimethyldiphenic acid ( 7 )
An acetone (200 ml) solution of (mol) was added all at once, and the mixture was allowed to cool.

After standing overnight, the crystals were separated and recrystallized from a mixed solution of methanol and acetone to obtain an optically active brucine salt of (R) -6,6'-dimethyldiphenic acid {(R)-( 7 )}; [Α
▲] ²⁵ _D ▼ + 38.1 ° (C1.0, methanol).

Then, the mother liquor was concentrated and recrystallized from a mixture of acetone and petroleum ether to obtain an optically active brucine salt of (S) -6,6'-dimethyldiphenic acid {(S)-( 7 )}; [α ▲] ²⁵ _D
▼ -39.3 ° (C1.0, methanol).

Each salt was decomposed in a mixture of ethyl acetate and 1N hydrochloric acid, and the organic layer was concentrated to give optically active 6,6'-dimethyldiphenic acid {(R)-( 7 ) and (S)-( 7 ). Obtained. The optical rotation of the recrystallized product is (R)-( 7 ); [α ▲] ²⁵
_D ▼ -21.3 ° ((C1.0, methanol), (S)-
( 7 ); [α ▲] ²⁵ _D ▼ + 22.1 ° (C1.0, methanol)
Met.

These optically active 6,6'-dimethyldiphenic acids were esterified with hydrogen chloride in methanol without isolation and distilled under reduced pressure to obtain optically active dimethyl 6,6'-dimethyldiphenate (R). Isolated as-( 6 ) and (S)-( 6 ). The following yields were calculated based on the used 6,6'-dimethyldiphenic acid ( 7 ).

(R)-( 6 ) Yield 21.7g Yield 42% [α ▲] ²⁵ _D ▼ -56.4 ° (C2.0, benzene) (S)-( 6 ) Yield 21.7g Yield 42% [α ▲] ²⁵ _D ▼ -55.6 ° (C2.0, benzene) Synthesis example 7. (Optically active 2,2'-bis (hydroxymethyl))
-6,6'-Dimethylbiphenyl (R)-( 8 ), (S)
-Synthesis of ( 8 )) 3.1 g (82 mmol) of lithium aluminum hydride was suspended in 50 ml of dry ether. Dimethyl (S) -6,6'-dimethyldiphenate {(S)-( 6 )} 12.2g (41m
A solution of (mol) in dry ether (70 ml) was added dropwise at a gentle reflux rate. Ethyl acetate, hydrated ether, and 2N hydrochloric acid were added to the reaction mixture in this order, and the organic layer was separated.
After removing the solvent, the oil was recrystallized from benzene to obtain (S) -2,2'-bis (hydroxymethyl) -6,6'-dimethylbiphenyl {(S)-( 8 )}.

Also for (R) -2,2'-bis (hydroxymethyl) -6,6'-dimethylbiphenyl {(S)-( 8 )},
Dimethyl (R) -6,6'-dimethyldiphenate {(R)
It was possible to obtain in the same manner from-( 6 )}.

Yield 9.6 g Yield 97% Melting point 120-122 ° C (S-form) Optical rotation (R)-( 8 ) [α ▲] ²⁵ _D ▼ + 110.1 ° (C1.0, benzene) (S)-( 8 ) [Α ▲] ²⁵ _D ▼ -111.6 ° (C1.0, benzene) ・ IR spectrum (KBr) 3400-3000, 1010cm- ¹ Synthesis Example 8. (Optically active 2,2'-bis (bromomethyl) -6,
6'-Dimethylbiphenyl (S)-( 9 ), (R)-
(Synthesis of 9 ) 240 g of benzene was added with (g) (S) -2,2'-bis (hydroxymethyl) -6,6'-dimethylbiphenyl {(S)-( 8 )
(66 mmol) was dissolved. Add phosphorus tribromide to this solution under reflux.
A 7.7 ml (81 mmol) benzene (20 ml) solution was added dropwise.
After heating under reflux for a further 1 hour, the reaction mixture was poured into water and the organic layer was separated. The organic layer was washed with an aqueous sodium hydrogen carbonate solution, dried and concentrated. The residue was distilled under reduced pressure to obtain (S) -2,2'-bis (bromomethyl) -6,6'-dimethylbiphenyl {(S)-( 9 )}.

For (R) -2,2'-bis (bromomethyl) -6,6'-dimethylbiphenyl {(R)-( 9 )} also, (R)-
It could be similarly obtained from 2,2'-bis (hydroxymethyl) -6,6'-dimethylbiphenyl {(R)-( 8 )}.

Yield 23g Yield 93% bp 160 ° C / 0.05mmHg ・¹ H-NMR spectrum (in CDCl ₃ , δppm) 1.99 (s, 6H, ArCH ₃ ), 415 (s, 4H, ArCH _2- ), 7.3-7.5
(M, 6H, ArH) ・ Opticality (R)-( 9 ) [α ▲] ²⁵ _D ▼ + 51.8 ° (C0.75, benzene) (S)-( 9 ) [α ▲] ²⁵ _D ▼- 55.1 ° (C0.33, benzene) Synthesis example 9. (Optically active N- (2-dimethylaminoethyl))
Synthesis of -4 ', 4 "-dimethyl-2,7-dihydro-3,4,5,6-dibenzazepine (R)-( 1 ), (S)-( 1 )) 250 ml of anhydrous tetrahydrofuran under nitrogen atmosphere ( S)-
2,2'-bis (bromomethyl) -6,6'-dimethylbiphenyl {(S)-( 9 )} 10.3 g (28 mmol) and 2-dimethylaminoethylamine 9.2 ml (84 mmol) were dissolved with stirring. The mixture was heated under reflux for 25 hours. After removing the solvent, the diluted hydrochloric acid-soluble portion was separated from the residue. This aqueous solution was made basic with ammonia and the liberated oil was extracted with ether. The ether layer is dried and then concentrated, and the oil is distilled under reduced pressure (S) -N-
(2-Dimethylaminoethyl) 4 ', 1 "-dimethyl-
2,7-Dihydro-3,4,5,6-dibenzazepine {(S)-
( 1 )} was obtained.

Similarly, from (R) -2,2'-bis (bromomethyl) -6,6'-dimethylbiphenyl {(R)-( 9 )},
(R) -N- (2-Dimethylaminoethyl) -4 ', 1 "
-Dimethyl-2,7-dihydro-3,4,5,6-dibenzazepine {(R)-( 1 )} was obtained.

Yield 7.4g Yield 90% bp 145 ℃ / 0.04mmHg ・ IR spectrum (liquid film) 2810, 2770cm- ¹ ・¹³ C { ¹ H} NMR spectrum (in CDCl ₃ , δppm): δ = 19.8 (q), 46.0 (q), 52.8 (t), 55.4 (t), 5
8.0 (t), 126.5 (d), 127.1 (d), 129.4 (d), 134.
4 (s), 135.6 (s), 138.3 (s) ・ MS (20ev): m / e294 (M ⁺ ) ・ Elemental analysis C ₂₀ H ₂₆ N ₂ (294.4) Calculated value C; 81.56, H; 8.90, N ; 9.51% Measured value C; 81.29, H; 8.92, N; 9.26% ・ Optical rotation (R)-( 1 ) [α ▲] ²⁵ _D ▼ + 24.2 ° (C1.
0, ethanol) (S)-( 1 ) [α ▲] ²⁵ _D ▼ -24.5 (C1.0, ethanol) Synthesis Example 10. Synthesis of 1-bromo-2-methylnaphthalene ( 10 ) Known method (J Amer, Chem, Soc., 63 , 277 <1941>), and 1-bromo-2-methylnaphthalene was synthesized from 2-methylnaphthalene.

Synthesis example 11. (2,2'-dimethyl-1,1'-binaphthyl ( 1
1 ) Synthesis) Magnesium metal (0.28g, 12mmol), compound ( 10 )
(5.12g, 23m mol), bis (triphenylphosphino)
After adding nickel chloride, (Ph ₃ P) ₂ NiCl ₂ (70 mg) in 30 ml of dry ether, the mixture was stirred and refluxed for 24 hours. Then metal magnesium (0.14g, 6mmol) and (Ph ₃
P) ₂ NiCl ₂ (35 mg) was added, and the mixture was stirred and refluxed for 12 hours. After cooling, water and 2N sulfuric acid were added to dissolve the precipitate, and then the organic layer was decomposed. After removing the solvent, distillation under reduced pressure was performed to obtain a compound ( 2 ).

Yield 2.1 g (64%) bp 145 to 150 ° C / 4 mmHg Mass spectrum m / Z: 282 (M ⁺ ) ¹ H-NMR spectrum (in CDCl ₃ , δppm) 2.03 (S, 6H, ArCH ₃ ) 7.1 to 7.9 (M, 12H, ArH) References 1. Chem, Ber., 107 , 2926 (1974) 2. J. Chem, Soc., 1958 , 719 Synthesis Example 12. (2,2-bis (bromomethyl) -1, Synthesis of 1'-binaphthyl ( 12 )) N-bromosuccinimide (2.7g, 15.3mmol) and compound ( 11 ) (1.8g, 6.4mmol) and benzoyl peroxide (16m)
g) was stirred and suspended in 30 ml of carbon tetrachloride and refluxed for 2.5 hours.

The precipitate was separated by heat and washed repeatedly with hot carbon tetrachloride.
After removing the solvent from the liquid, the residue was recrystallized from methyl ethyl ketone to obtain a compound ( 12 ).

Yield 2.4 g (85%) Melting point 146-149 ° C Mass spectrum m / e (I%): 4.42 (81Br ₂ -M ⁺ , 8.8) 440 (81Br 79Br-M ⁺ , 16.2) 438 (79Br ₂ , -M ⁺ , 8.5) ¹ H-NMR spectrum (CDCl ₃ ) δppm: 4.25 (S, ArCH ₂ , 4H) 8.9 to 7.0 (m, ArH, 12H) Synthesis example 13. (S) -N- (2-dimethylaminoethyl)
-2,7-Dihydrodinaphtho [2 ', 1': 3.4] [1 ', 2':
5.6] Azepine ( 2 ) synthesis Compound ( 12 ) (16.5g, 37.5m mo in 100ml of dry benzene)
l) and 2-dimethylaminoethylamine (7.0 g, 80 mmol)
Was dissolved and refluxed with stirring for 2.5 hours. After removing the solvent under reduced pressure, the residue was dissolved in a small amount of methanol and separated using dilute aqueous ammonia and ether. The ether layer was washed several times with water and dried over Na ₂ SO ₄ to remove the solvent. After drying under reduced pressure, yellow oily (RS)-( 2 ) was obtained.

Crude ( 2 ) and (-)-dibenzoyl tartaric acid (14.8 g) were dissolved in 500 ml of ethanol while hot, water was added to 95% ethanol, and the mixture was allowed to cool to obtain (S)-( 2 ) tartrate salt. It was This was repeatedly recrystallized from 95% ethanol several times, and the obtained salt was decomposed in a 10% NH ₃ -ether mixture. After the ether layer was separated and dried, the solvent was removed and the residue was dried under reduced pressure to obtain (S)-( 2 ) which was semi-solid at room temperature.

Yield 3.36 g (24.5%) [α ▲] ²⁵ ₅₄₆ ▼ -407 ° (C1.0, ethanol) Literature value (413 ° to 410 °) Mass spectrum m / e (I%): 366 (M ⁺ , 15.0) , 308 (M ⁺ -58,100.0), 58 (CH ₂ N (CH ₃ ) ₂ ⁺ , 44.6) Elemental analysis As C ₂₆ H ₂₆ N ₂ (366.5): Calculated value C85.21, H7.15, N7.64% Measured value C85.42, H7.14, N7.75% References J.Amer, Chem, Soc ., 103 , 4585 (1981) Synthesis Example 14. (Synthesis of diphenyl-2-pyridylmethylmethacrylate ( 13 )) Japanese Patent Application for diphenyl-2-pyridylmethylmethacrylate
Synthesized from 2-benzoylpyridine according to 58-176474.

Example 1. (R) -N- (2-Dimethylaminoethyl) -4 ', 1 "
-Dimethyl-2,7-dihydro-3,4,5,6-dibenzazepine {(R)-( 1 )}-BuLi complex in toluene, -78
Asymmetric polymerization of diphenyl-2pyridylmethylmethacrylate (hereinafter abbreviated as D2pyMA) at ℃ was carried out as follows.

D2pyMA (1 g, 3.0 mmol) was placed in the sealed tube, and degassing nitrogen substitution was repeated. To this, 18 ml of anhydrous toluene was added and dissolved, and then cooled to -78 ° C.

Then advance (R) - were prepared at room temperature by mixing equimolar BuLi in anhydrous toluene solution (1) (R) - ( 1) -BuLi
A 2 ml (0.20 mmol) solution of the complex was added to the toluene solution of the monomer to initiate the polymerization. Polymerization was stopped with a small amount of methanol, the polymer was precipitated in 200 ml of methanol, centrifuged, dried under reduced pressure and weighed. Chloroform was added to the polymer, and the mixture was stirred for 3 to 4 hours, and separated into a chloroform insoluble portion and a soluble portion. After measuring the optical rotation, the chloroform-soluble portion was dissolved in chloroform and precipitated in hexane. After centrifuging and drying under reduced pressure, the specific optical rotation ([α
▲] ²⁵ _D ▼) was measured. The results are shown in Table 1.

The optical rotation was measured using JASCO DIP-181.

Example 2. D2pyMA (3 g, 9.1 mmol) was polymerized in the same manner as in Example 1 using (R)-( 1 ) -BuLi complex (0.455 mmol). The results are shown in Table 1.

Example 3. D2pyMA (1g 3.0mmol) of (S)-( 1 ) -BuLi complex
Polymerization was carried out in the same manner as in Example 1 using 2 ml (0.15 mmol). The results are shown in Table 1.

Example 4. D2pyMA (1g 3.0mmol) of (R)-( 2 ) -BuLi complex
Polymerization was carried out in the same manner as in Example 1 using 2 ml (0.15 mmol). The results are shown in Table 1.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-60-69111 (JP, A) JP-A-56-142216 (JP, A) J. Am. Chem. Soc. 103 (15). 4585-4586

Claims (1)

[Claims] 1. A general formula (A) (In the formula, Ar represents an aromatic hydrocarbon having 6 to 14 carbon atoms, R ₁ and R ₂ are a hydrogen atom or a linear or branched hydrocarbon group having 1 to 20 carbon atoms, It may contain aromatic hydrocarbons in its structure.
n, represents the number of methylene chains, m is 0 to 4, and n is 1 to 5. ), An optically active ligand having an axial chirality and an anionic polymerization initiator is used to prepare a compound represented by the general formula (B): (However, in the formula, at least one of R ₃ , R ₄ , and R ₅ is a pyridyl group, and the remaining two substituents may be the same or different from each other, and each is a phenyl group or a pyridyl group.) By polymerizing the polymerizable monomer represented by (Where n is an integer of 3 or more), and an optically active organic polymer soluble in chloroform having an optical rotation [α ▲] ²⁵ ₃₆₅ ▼ absolute value of 800 or more is obtained. Method for producing organic polymer.