JPH11124355A - New optically active acrylic acid ester, optically active polyacrylic acid ester and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound containing an optically active ether group at a position and useful as a raw material for optically active polyacrylic acid ester useful as a functional material for liquid crystals, nonlinear optical materials or the like and a reagent for optical resolution. SOLUTION: This compound having an optically active ether group at α-position is represented by formula I [(m) is 0-10; R<1> is a 1-30C optically active atomic group having one or more asymmetric elements selected from asymmetric carbon, axial asymmetry and face asymmetry; R<2> is a 1-30C atomic group], e.g. α-[(R)-1-phenylethoxymethyl]-acrylic acid benzyl ester. The compound of formula I can be produced by cooling an optically active alcohol of the formula R<1> -OH to about 0 deg.C, adding triethylamine thereto and then slowly adding α- haloalkylacrylic acid ester of formula II (X is a halogen) thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel optically active acrylic acid ester, an optically active polyacrylic acid ester obtained by polymerizing the same, and a method for producing the same. The optically active acrylic ester obtained by the present invention can be expected to be used as an optical resolving agent. In addition, optically active polyacrylates obtained by subjecting this acrylate to radical polymerization or anion polymerization can also be expected to be used as an optical resolving agent and used as functional materials such as liquid crystals and nonlinear optical materials. There is expected.

[0002]

2. Description of the Related Art Optically active polymer substances have been known. For example, JP-A-56-106907 discloses an optically active polymer of triphenylmethyl methacrylate, which has a helical structure, exhibits high optical rotation, and is useful as an optical resolving agent. It is stated that there is. Also, JP-A-56-16
No. 7708 discloses an optically active polymer of acrylic acid amide, and describes that this substance exhibits a large optical rotation based on its molecular asymmetry and is useful as an optical resolving agent. Further, JP-A-63-1446 discloses an optically active poly (meth) acrylamide compound. This substance has an optically active group in a side chain, and a racemic mixture is prepared by mixing the optically enantiomers thereof. It is described as being useful as an adsorbent for separation into water. JP-A-1-79230 discloses a liquid crystal composition using an optically active polymer compound.

[0003] As described above, the optically active polymer substance has a unique function and is applied to various uses. At present, social needs are increasing and research is being actively pursued. Accordingly, an object of the present invention is to provide a novel optically active polymer having a specific function and a method for producing the same under such a background.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, the present invention provides an optically active acrylate represented by the following general formula (I), which has an optically active ether group at the α-position.

[0005]

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(Wherein, m represents an integer of 0 to 10, R ¹ has 1 to 30 carbon atoms, and at least one asymmetric element selected from asymmetric carbon, axial asymmetry and plane asymmetry) And R ² represents an atomic group having 1 to 30 carbon atoms.) Further, the present invention mainly comprises a structural unit represented by the following general formula (II), and has a degree of polymerization of It is intended to provide an optically active polyacrylic ester having 5 or more and a method for producing the same.

[0007]

Embedded image

(Wherein, m, R ¹ and R ² have the same meanings as described above)

[0009]

Embodiments of the present invention will be described below in detail.

In the optically active acrylate represented by the general formula (I) according to the present invention, m represents an integer of 0 to 10, preferably 1 to 5 and particularly preferably 1. R ¹ represents an optically active atomic group having 1 to 30 carbon atoms and having at least one asymmetric element, specifically, an optically active 1-phenylethyl group, an optically active 1, And a 1'-binaphthyl group. R ² represents an atomic group having 1 to 30 carbon atoms, and specific examples include a lower alkyl group such as a methyl group, a phenyl group, and a benzyl group.

The method for producing the optically active acrylate represented by the general formula (I) of the present invention includes the general formula (III) R ¹ —OH (III) (wherein R ¹ has the same meaning as described above) The optically active alcohol represented by the formula (1) is cooled to 0 ° C., and triethylamine is added thereto.

[0012]

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(Wherein, R ² and m have the same meaning as described above, and X represents a halogen atom.) A method of slowly adding an α-haloalkyl acrylate represented by the formula:

The optically active polyacrylic ester of the present invention is mainly composed of the structural unit represented by the general formula (II), and has a degree of polymerization of 5 or more, preferably 20 to 1000.

The optically active polyacrylate of the present invention can be obtained by converting the optically active acrylate represented by the above general formula (I) into an initiator such as perloyl ((i-PrOCO ₂ ) ₂ ). It can be obtained by radical polymerization or by anionic polymerization using n-butyllithium as an initiator. NMR for stereoregularity of polymer produced
As a result, radical polymerization yielded atactic polymers, and anion polymerization yielded highly isotactic polymers.

When the circular dichroism spectra of the polymer thus obtained and the monomer were compared, in the phenyl group absorption region around 250 nm, the monomer and the polymer showed the same negative absorption pattern. In the region of, the polymer exhibits positive absorption opposite to that of the monomer, and the absorption intensity of the polymer obtained by anionic polymerization reaches more than three times that of the polymer obtained by radical polymerization, and the optical rotation of the formed polymer becomes It was suggested that this was not due to the asymmetric carbon possessed by the monomer, but to be derived from an asymmetric element different from the monomer, for example, an asymmetric element induced in the main chain.

The optically active acrylic acid ester of the present invention is useful as a raw material for an optically active polyacrylic acid ester, but is itself also useful as an optical resolving agent.
The optically active polyacrylate of the present invention is useful not only as an optical resolving agent but also as a functional material such as a liquid crystal or a nonlinear optical material.

[0018]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but it goes without saying that the present invention is not limited to these Examples.

Example 1 α-((R) -1-phenylethoxy)
Shimechiru) Synthesis dry benzyl acrylate ((R) -BPEMA), the reaction vessel was purged with nitrogen, (R)-1-phenylethanol (5.5 ml, 45 mmol) and the mixture was cooled to 0 ° C.,
Triethylamine (4.5 ml, 32 mmol) was added and stirred for 30 minutes. Under stirring, benzyl α-bromomethylacrylate (3.4 g, 13 mmol) was slowly added dropwise. After stirring at 0 ° C. for 4 hours and at room temperature for 24 hours, 1N hydrochloric acid (50 ml) was added. The aqueous layer was extracted with dichloromethane (50 ml × 2), and the obtained organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate (100 ml), dried over magnesium sulfate. After filtration, the solvent was concentrated to obtain a crude product. The crude product was purified by column chromatography (ether / hexane = 1/10) to obtain the target compound as a colorless viscous liquid. Yield 1.65 g (yield 69%), [α] ₃₆₅ ²⁵ = + 157 ° (c = 1.
0, CHCl ₃ ).

An infrared absorption spectrum of the compound obtained,
^{The 1} H-NMR spectrum and the elemental analysis values are shown below.

IR (neat): 1725, 1330, 1307, 1222,
1176, 1116, 698 cm ^{-1 1} H-NMR (500 MHz, CDCl ₃ ): δ 1.45 (d, 3H, J = 6.5 Hz, CH ₃ ), 4.09 (m, 2H, OCH ₂ ), 4.48 (q, 1
(H, J = 6.5Hz, CH) 5.18 (m, 2H, CH ₂ Ph), 5.94 (q, 1H, J = 1.5Hz, vinyl), 6.34
(q, 1H, J = 1.5Hz, vinyl) 7.2-7.4 (m, 10H, aromatic) Elemental analysis value (C ₁₉ H ₂₀ O ₃ ); Calculated value (%): C 77.00, H 6.80, Actual measured value (% ): C 77.00, H 6.80, Example 2: Synthesis of benzyl α-((S) -1-phenylethoxymethyl) acrylate ((S) -BPEMA) Instead of (R) -1-phenylethanol, (S Except for using) -1-phenylethanol, the target compound was obtained as a colorless viscous liquid in the same manner as in Example 1. Yield 3.41 g (78% yield), [α] ₃₆₅ ²⁵ = -149 ° (c = 1.
0, CHCl ₃ ).

An infrared absorption spectrum of the obtained compound,
^{The 1} H-NMR spectrum and the elemental analysis value were consistent with the compound of Example 1.

Examples 3 and 4: Anionic polymerization The monomers (3.0 g, 10 mmol) shown in Table 1 were converted to toluene (7.0 m).
l) The solution was added, CaH ₂ (10 mg) was added, and the mixture was stirred for 30 minutes to dry the monomer and filtered under a nitrogen atmosphere. A toluene solution of the above monomer (1.2 ml) was added to the dried glass ampoule, and the ampoule was cooled to -78 ° C. While thoroughly shaking the ampoule, n-butyllithium was added in an amount of 1/20 of the monomer to initiate polymerization. 24 hours later, a small amount of methanol was added to stop the polymerization,
The polymerization mixture was precipitated in a large amount of methanol (about 100 ml), and the insoluble portion was recovered by centrifugation. Further, the obtained insoluble portion was vacuum-dried (60 ° C., 7 hours) to obtain a polymer. Table 1 shows the yield, degree of polymerization, molecular weight distribution, and optical rotation of the obtained polymer.

Examples 5 and 6: Radical polymerization The monomers shown in Table 1 (0.36
g, 1.2 mmol), and the initiator parloyl ((i-PrOC
0.08 ml (0.49 M) of a toluene solution of O ₂ ) ₂ ) was added, and the ampoule was immersed in a thermostat at 30 ° C. to initiate polymerization. After 48 hours, the polymerization was stopped by cooling the polymerization ampoule to -78 ° C, and the polymerization mixture was poured into a large amount of hexane (about 10
0 ml), and the insoluble portion was recovered by centrifugation. The polymer was obtained by vacuum drying (60 ° C., 7 hours) the insoluble portion. Table 1 shows the yield, degree of polymerization, molecular weight distribution, and optical rotation of the obtained polymer.

[0025]

[Table 1]

Note) * 1: GPC result using standard polystyrene sample * 2: Ratio of (weight average molecular weight / number average molecular weight) * 3: Measured in chloroform (c = 1.0) Application Example Obtained in Example 1 R) -BPEMA, (R) -BP of Example 3
FIG. 1 shows a circular dichroism spectrum of the (R) polymer obtained by anionic polymerization of EMA and the (R) polymer obtained by radical polymerization of (R) -BPEMA obtained in Example 5.

In FIG. 1, (A) was obtained in Example 1.
(R) -BPEMA spectrum, (B) is the (R) -BPEMA of Example 3.
FIG. 5C is a spectrum of the (R) polymer obtained by anionic polymerization of EMA, and FIG. 5C is a spectrum of the (R) polymer obtained by radical polymerization of (R) -BPEMA obtained in Example 5.

As apparent from FIG. 1, in the absorption region of the phenyl group near 250 nm, the monomer (A) and the polymer (B)
, (C) showed a similar negative absorption pattern, but in the shorter wavelength region, polymers (B) and (C)
In addition, the absorption intensity of the polymer (B) of the anionic polymerization reaches more than three times that of the polymer (C) of the radical polymerization, and the optical rotation of the formed polymer is changed by the asymmetric carbon possessed by the monomer. It was suggested that this was not due to the chiral element alone, but was derived from an asymmetric element different from the monomer, for example, an asymmetric element induced in the main chain.

[Brief description of the drawings]

FIG. 1 is a circular dichroism spectrum showing a result of an application example.

Claims (7)

[Claims] 1. An optically active acrylate represented by the following general formula (I), which has an optically active ether group at the α-position. Embedded image (In the formula, m represents an integer of 0 to 10, and R ¹ has ^{1 to 1} carbon atoms.
30 represents an optically active atomic group having an asymmetric element selected from at least one asymmetric carbon, axial asymmetry or plane asymmetry, and R ² represents an atomic group having 1 to 30 carbon atoms. ) 2. R ¹ is an optically active 1-phenylethyl group or an optically active 1,1′-binaphthyl group; R ² is a lower alkyl group, a phenyl group or a benzyl group;
The optically active acrylate according to claim 1, which is: 3. An optically active polyacrylic ester mainly comprising a structural unit represented by the following general formula (II) and having a degree of polymerization of 5 or more. Embedded image (In the formula, m, R ¹ and R ² have the same meanings as described above.) 4. R ¹ is an optically active 1-phenylethyl group or an optically active 1,1′-binaphthyl group; R ² is a lower alkyl group, a phenyl group or a benzyl group;
The optically active polyacrylate according to claim 3, which is: 5. The method according to claim 3, wherein the optically active acrylate represented by the general formula (I) is polymerized.
Or a process for producing an optically active polyacrylate according to item 4. 6. The method according to claim 1, wherein the optically active acrylic acid ester represented by the general formula (I) is anionically polymerized to produce an optically active polyacrylic acid ester rich in isotacticity. 5. The production method according to 5. 7. The atactic optically active polyacrylic acid ester is produced by radically polymerizing the optically active acrylic acid ester represented by the general formula (I). Manufacturing method.