JP2005330202A - Deuterated haloacryl compound, its production method, polymerizable composition, polymer and optical member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an α-haloacrylic acid derivative, especially an α-chloroacrylate deuteration product, useful for optical materials such as optical members, especially plastic optical fibers. <P>SOLUTION: This compound represented by the general formula (R<SP>1</SP>is an alkoxy, an aryloxy, hydroxy, amino, an alkylamino or an arylamino; X<SP>1</SP>is Cl or Br; U groups are each independently<SP>1</SP>H or<SP>2</SP>H, provided that ≥40% of U connected to the ethylene unsaturated group is<SP>2</SP>H). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a deuterated product of an α-haloacrylate ester useful as a raw material for a transparent resin material, particularly a transparent resin for optical materials such as optical fibers and optical waveguides, and further using the compound as a raw material. The present invention relates to applications to polymers and optical members.

Technical background

While inexpensive and easily processed as polymethylmethacrylate (PMMA) is known as a plastic optical fiber materials, can be used only in limited applications because the transmission loss derived from the ^C-1 H coupling. As a means for solving this problem, a method using deuterated methacrylic acid methyl ester (Patent Document 1) and the like has been proposed, but durability problems such as heat resistance and moisture resistance still remain.
On the other hand, as a material capable of improving hygroscopicity and heat resistance, for example, methyl α-chloroacrylate has been proposed (Patent Document 2). However, these are fibers made of a polymer obtained by polymerizing this because it has a lot of ^C-1 H coupling there was a problem that a high transmission loss. If the ¹ H atom of the compound can be converted to ² H, it can be a material capable of achieving both optical properties and durability, but no means for synthesizing such a deuterium compound has been known. Development of an effective synthesis method of deuterated α-haloacrylic acid derivatives, particularly deuterated α-chloroacrylic acid esters, capable of forming a transparent resin having both optical properties and durability is desired. It was.

  α-Haloacrylic acid esters can be synthesized by dihalogenating (dihalogenating) 2,3-unsaturated carboxylic acid esters into 2,3-dihalocarboxylic acid esters and then dehydrohalogenating them. (Patent Documents 1 and 2). That is, if a deuteride of 2,3-unsaturated carboxylic acid ester can be synthesized, α-haloacrylic acid esters can be derived into a deuteride. As a method for synthesizing a deuterated 2,3-unsaturated carboxylic acid ester, an example in which deuterium exchange of methyl acrylate in the presence of a catalyst such as heavy water / platinum is known (Patent Document 3). However, the deuteration rate was not satisfactory, and the reaction conditions were very strong at 85 to 100 ° C. for 16 to 65 hours, which was not an effective method.

JP 58-154803 A Japanese Patent Publication No. 6-44085 JP 61-148141 A J. Am. Chem. Soc .; 62; 1940; 3495-3498 J. Chem. Soc. Perkin Trans. 2; 1987; 1473-1476.

  An object of the present invention is to provide a deuterated product of an α-haloacrylic acid derivative, particularly an α-chloroacrylic acid ester, which is useful as an optical member, particularly an optical material such as a plastic optical fiber material. Another object of the present invention is to provide a novel optical material using an α-haloacrylic acid analog, a polymer thereof, and a polymerizable composition, and an optical member using the same.

  As a result of various studies, the present inventors have succeeded in synthesizing a compound represented by the following general formula (1), and further studied application to a polymer material and an optical material using the compound. It came to solve.

（一般式（１）中、Ｒ¹はアルコキシ基、アリールオキシ基、ヒドロキシ基、アミノ基、アルキルアミノ基、またはアリールアミノ基を表し、Ｘ¹は塩素原子または臭素原子を表し、Ｕはそれぞれ独立に¹Ｈまたは²Ｈを表し、エチレン性不飽和基に連結するＵの４０％以上が²Ｈである。） Means for solving the above-mentioned problems are as follows.
(1) A compound represented by the following general formula (1).
General formula (1)

(In the general formula (1), R ¹ represents an alkoxy group, an aryloxy group, a hydroxy group, an amino group, an alkylamino group, or an arylamino group, X ¹ represents a chlorine atom or a bromine atom, and U represents each independently. Represents ¹ H or ² H, and 40% or more of U linked to the ethylenically unsaturated group is ² H.)

(2) The compound according to (1), wherein R ¹ is an alkoxy group or an aryloxy group.
(3) The compound according to (1) or (2), wherein 80% or more of U is ² H.

（一般式（２）および一般式（３）中、Ｒ¹はアルコキシ基、アリールオキシ基、ヒドロキシ基、アミノ基、アルキルアミノ基、またはアリールアミノ基を表す。） (4) including the step of converting a compound represented by the following general formula (2) from ¹ H to ² H in heavy water to obtain a compound represented by the general formula (3): The manufacturing method of the compound in any one.

(In General Formula (2) and General Formula (3), R ¹ represents an alkoxy group, an aryloxy group, a hydroxy group, an amino group, an alkylamino group, or an arylamino group.)

（一般式（４）および（５）中、Ｕは¹Ｈまたは²Ｈ表し、Ｒ¹はアルコキシ基、アリールオキシ基、ヒドロキシ基、アミノ基、アルキルアミノ基、またはアリールアミノ基を表す。） (5) In any one of (1) to (3), including a step of adding ² H ₂ to a compound represented by the following general formula (4) to form a compound represented by the general formula (5) A method for producing the described compound.

(In the general formulas (4) and (5), U represents ¹ H or ² H, and R ¹ represents an alkoxy group, an aryloxy group, a hydroxy group, an amino group, an alkylamino group, or an arylamino group.)

反応式（２）

反応式（３）

反応式（４）

（一般式（１）、（６）、（７）、（８）および（９）中、Ｒ¹は、アルコキシ基、アリールオキシ基、ヒドロキシ基、アミノ基、アルキルアミノ基、またはアリールアミノ基を表し、それぞれの式中のＲ¹は同一でも、異なっていても良い。Ｕはそれぞれ独立に¹Ｈまたは²Ｈを表し、Ｘ¹は塩素原子または臭素原子を表す。） (6) In order, the step of exchanging from ¹ H to ² H in heavy water represented by the following reaction formula (1), the step of adding ² H ₂ represented by the following reaction formula (2), the following reaction formula ( (1) to (3), including a step of adding a chlorine molecule or a bromine molecule represented by 3) and a step of removing hydrogen chloride or hydrogen bromide represented by the following reaction formula (4) The manufacturing method of the compound in any one of.
Reaction formula (1)

Reaction formula (2)

Reaction formula (3)

Reaction formula (4)

(In the general formulas (1), (6), (7), (8) and (9), R ¹ represents an alkoxy group, an aryloxy group, a hydroxy group, an amino group, an alkylamino group, or an arylamino group. R ¹ in each formula may be the same or different, U represents each independently ¹ H or ² H, and X ¹ represents a chlorine atom or a bromine atom.)

（一般式（１０）中、Ｕはそれぞれ独立に¹Ｈまたは²Ｈを表し、Ｒ¹はアルコキシ基、アリールオキシ基、ヒドロキシ基、アミノ基、アルキルアミノ基、またはアリールアミノ基を表し、Ｘ¹は塩素原子または臭素原子を表す。ただし、Ｕの４０％以上が²Ｈである。） (7) A polymer containing a repeating unit represented by the following general formula (10).
General formula (10)

(In General Formula (10), each U independently represents ¹ H or ² H, R ¹ represents an alkoxy group, an aryloxy group, a hydroxy group, an amino group, an alkylamino group, or an arylamino group, and X ¹ Represents a chlorine atom or a bromine atom, provided that 40% or more of U is ² H.)

(8) A polymerizable composition comprising at least one compound according to any one of (1) to (3).
(9) A polymer obtained by polymerizing at least the polymerizable composition according to (8).
(10) An optical member comprising the polymer according to (7) or (9).

  The α-haloacrylic acid derivative of the present invention, in particular, a deuterated product of α-chloroacrylic acid ester, is useful as a raw material for a transparent resin, particularly a transparent resin for optical fibers. Moreover, according to the production method of the present invention, it is possible to provide a method for easily producing an α-haloacrylic acid derivative having a high deuteration rate using an inexpensive deuterium source. Moreover, the optical member of the present invention can be processed into a desired shape and used as various optical components.

The present invention is described in detail below. In the present specification, “to” means a range including numerical values described before and after the minimum and maximum values. Moreover, in this invention, when either a deuterium atom and a light hydrogen atom may be sufficient, this may be represented by U.
In the present specification, ¹ H represents normal hydrogen, and ² H represents deuterium. Further with respect to the ratio of ² H atoms, but to define the average value of {(the number of ² H atoms) / ⁽¹ Number of Number + ² H atoms H atoms)} as "deuteration ratio", in this, The whole compound containing a hydrogen atom directly connected to the main chain of the polymer, that is, a hydrogen atom connected to the ethylenically unsaturated group in R ¹ in general formulas (1) to (10) Is called the “total deuteration rate”.
In addition, in the present invention, the “polymer” includes not only a polymer obtained by polymerizing a single monomer but also a copolymer obtained by polymerizing two or more types of monomers.

First, the compound represented by the general formula (1) of the present invention will be described in detail.
General formula (1)

R ¹ may be an alkoxy group (straight, branched, or cyclic, such as a cycloalkyl group having a plurality of rings such as a methoxy group, an ethoxy group, an isopropyloxy group, a cyclohexyloxy group, a bicycloalkoxy group, or a tricycloalkoxy group. Alkoxy group, fluorine-containing alkoxy group, etc.), aryloxy group, hydroxy group, amino group, alkylamino group (eg, methylamino group, dimethylamino group, etc.), or arylamino group (eg, anilino group, pentafluoroanilino group, etc.) Represents an alkoxy group, an aryloxy group, a hydroxy group, an amino group or an alkylamino group, more preferably an alkoxy group or an aryloxy group, still more preferably a fluorine-containing alkoxy group or a fluorine-containing aryloxy group, linear or Branch footage Alkoxy group is most preferred.
R ¹ may further have a substituent that can be substituted without radical polymerization. Examples of substituents at that time include halogen atoms (preferably fluorine atoms), alkyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups, silyloxy groups. , Heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group , Sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or Reelsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group Examples include halogen atoms (for example, fluorine atoms), alkyl groups, aryl groups, hydroxyl groups, carboxyl groups, alkoxy groups, aryloxy groups, and amino groups, and halogen atoms (preferably fluorine atoms) are more preferable. .

Examples of the fluorine-containing alkoxy group for R ¹ include 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 2 2,3,3,4,4,4-heptafluorobutoxy group, 2,2,3,3,4,4,5,5-octafluoropentoxy group and the like. Examples of the fluorine-containing aryloxy group include a pentafluorophenoxy group.

When R ¹ in the general formula (1) is a fluorine-containing alkoxy group, deuterated fluorine-containing alcohol can be used as a raw material, which is preferable. Specific examples of the method for synthesizing the deuterated fluorinated alkyl alcohol include a deuterated fluorinated alkyl alcohol described in US Pat. No. 4,072,726 by reducing perfluoroalkylcarboxylic acid with deuterium. And a method obtained by batch telomerization reaction of tetrafluoroethylene and deuterated methanol (C ² H ₃ O ² H) described in JP-A No. 54-154707.
X ¹ represents a chlorine atom or a bromine atom, preferably a chlorine atom.

Each U independently represents ¹ H or ² H, and 40% or more of U in the general formula (1) is ² H. Here, 40% or more of U means, for example, a case where 40% or more of the compound group represented by the general formula (1) obtained by the method described later is ² H. A hydrogen atom not represented in the general formula (1) is either ¹ H or ² H.
When R ¹ contains a hydrogen atom, part or all of it may be a deuterium atom, which is preferable. The deuteration ratio (total deuteration ratio) of the entire compound including the group represented by R ¹ is preferably 30% or more, more preferably 50% or more, and 80% or more. Particularly preferred.

Although the exemplary compound of a compound represented with general formula (I) below is shown, this invention is not limited by these. U in the exemplary compounds independently represents ¹ H or ² H, and 40% or more of the main chain of U linked to the ethylenically unsaturated group is ² H.

Next, the manufacturing method of this invention is demonstrated.
The production method of the present invention is a method for producing a deuterated α-haloacrylic acid derivative represented by the general formula (1), and is at least one of the following reaction formula (A) and reaction formula (B): It is a manufacturing method containing. In the reaction formula (A), ² H represents a deuterium atom, but indicates that at least a part of the hydrogen atom has been deuterated by the reaction, and 100% of the hydrogen atoms are deuterium atoms. It does not mean that there is (the same applies to reaction formula (B) and the following).

（一般式（２）および一般式（３）中、Ｒ¹はアルコキシ基、アリールオキシ基、ヒドロキシ基、アミノ基、アルキルアミノ基、またはアリールアミノ基を表す。） Reaction formula (A)

(In General Formula (2) and General Formula (3), R ¹ represents an alkoxy group, an aryloxy group, a hydroxy group, an amino group, an alkylamino group, or an arylamino group.)

（一般式（４）および（５）中、Ｕは¹Ｈまたは²Ｈ表し、Ｒ¹はアルコキシ基、アリールオキシ基、ヒドロキシ基、アミノ基、アルキルアミノ基、またはアリールアミノ基を表す。） Reaction formula (B)

(In the general formulas (4) and (5), U represents ¹ H or ² H, and R ¹ represents an alkoxy group, an aryloxy group, a hydroxy group, an amino group, an alkylamino group, or an arylamino group.)

反応式（２）

反応式（３）

（一般式（１）、（６）、（７）、（８）および（９）中、Ｒ¹は、アルコキシ基、アリールオキシ基、ヒドロキシ基、アミノ基、アルキルアミノ基、またはアリールアミノ基を表し、それぞれの式中のＲ¹は同一でも、異なっていても良い。Ｕはそれぞれ独立に¹Ｈまたは²Ｈを表し、Ｘ¹は塩素原子または臭素原子を表す。） A method of performing the reaction represented by the reaction formula (B) using the compound represented by the general formula (4) and U being ¹ H without passing through the step of the above reaction formula (A), or After performing the step of reaction formula (A), reduction (for example, addition of ¹ H ₂ ) is performed without passing through the step of reaction formula (B) to obtain the compound represented by general formula (5). Even with the method, partially deuterated acrylic acid or acrylic acid derivatives can be obtained, but when the reactions are performed in the order represented by the following reaction formulas (1) to (4), a higher deuteration rate is obtained. It is more preferable (hereinafter, this series of reaction formulas will be referred to as reaction formula (C)). The method represented by the following reaction formula (C) is, in order, the step of exchanging from ¹ H to ² H in heavy water represented by the following reaction formula (1), ² H represented by the following general formula (2). ₂ through the step of adding ₂ , the step of adding a chlorine or bromine molecule represented by the following general formula (3), and the step of removing hydrogen chloride or hydrogen bromide represented by the following general formula (4) This is a method for obtaining the compound represented by (1).
Reaction formula (1)

Reaction formula (2)

Reaction formula (3)

(In the general formulas (1), (6), (7), (8) and (9), R ¹ represents an alkoxy group, an aryloxy group, a hydroxy group, an amino group, an alkylamino group, or an arylamino group. R ¹ in each formula may be the same or different, U represents each independently ¹ H or ² H, and X ¹ represents a chlorine atom or a bromine atom.)

Hereinafter, reaction formulas (A) to (C) will be described in detail.
The step represented by the reaction formula (A) is performed in heavy water. The reaction solvent is preferably stirred during the reaction. Although the usage-amount of heavy water is not limited, It is preferable to add about 0.5 to 10 times by mass ratio with respect to the compound represented by General formula (2).

A base may be added to promote the reaction. The type of base is not limited as long as it does not depart from the spirit of the present invention. Specific examples of preferred bases include NaO ² U, KO ² U, metallic sodium, sodium methoxide (NaOCU ₃ ), sodium t-butoxide (NaOt-Bu), potassium methoxide (KOCU ₃ ), potassium t-butoxide ( KOt-Bu), potassium carbonate (K ₂ CO _3), sodium carbonate (Na ₂ CO _3), triethylamine, and the like, in terms of cost and _{safety, NaOCU 3, KOt-Bu,} K 2 CO 3, Na More preferably, any of ₂ CO ₃ is used. On the other hand, those having an O—H bond or an N—H bond (eg, NaHCO ₃ , NH _3, etc.) are not preferable because they cause a decrease in the deuteration rate.
Although the usage-amount of the said base is not limited, It is preferable to use 0.01%-10% by molar ratio with respect to heavy water, More preferably, it is 0.03-1.0%.
Although reaction temperature is not specifically limited, It is preferable to carry out at -10-30 degreeC. The reaction time is not particularly limited, but it is preferably 10 minutes to 6 hours.

Although the compound represented by the general formula (2) depends on the type of R ¹ , it is generally insoluble in water, so the reaction solution is separated into two phases. Although it is possible to exchange ¹ H- ² H even if the two phases remain separated, a compatible liquid or a phase transfer catalyst may be added. Specific examples of the additive include dimethyl sulfoxide (DMSO), deuterated methanol, tetrahydrofuran, 1,4-dioxane, quaternary ammonium salts, and quaternary phosphonium salts.

The deuteration rate of the product can be measured by an integral value of ¹ H-NMR.
When R ¹ contains ¹ H, the deuteration rate can be easily calculated by comparing the integrated value of the remaining ¹ H of acetylene hydrogen with the integrated value of ¹ H in R ¹ that is not exchanged. When R ¹ does not contain ¹ H, the deuteration rate can be measured by weighing the standard substance and adding the integrated value of ¹ H-NMR.

Next, the process represented by the above reaction formula (B) will be described.
The step represented by the reaction formula (B) is a deuterium addition step to acetylene carboxylic acids, but using conditions known as a method for converting acetylenes to olefin acids by adding ¹ H ₂ is used. it can. Specifically, as also shown in this example, a method such as atmospheric pressure catalytic hydrogen reduction in the presence of a Lindlar catalyst (palladium on calcium carbonate, lead poisoning) can be mentioned.

Finally, in the step of adding chlorine or bromine molecules represented by the reaction formula (C), conditions known as a method for deriving acrylic acids to 2,3-dihalopropionic acids can be used as they are. As a specific example, a method of chlorinating an acrylic ester described in JP-A-7-17578 can be employed. Although the final dehydrohalogenation step can be performed by heat treatment, the triethylamine of 2,3-dihalopropionic acid esters described in J. Chem. Soc. Perkin Trans. 2; 1987; As in the example of dehydrohalogenation using, it is preferable to perform the reaction with a base. Although the kind of base to be used is not limited, it is preferable to use an organic base such as a tertiary amine or pyridine in an organic solvent or without a solvent in order to suppress hydrolysis as a side reaction. The route represented by the reaction formula (C) is not necessarily 4 continuous steps, and may include a conversion step of the substituent R ¹ between each reaction. For example, after the compound represented by the general formula (6) is exchanged from ¹ H to ² H in heavy water, R ¹ of the compound represented by the general formula (7) thus obtained is changed to another substituent R ¹ . After the conversion, deuterium addition may be performed to obtain a compound represented by the general formula (8). Another example is Example 2 described later.

  Hereinafter, an example will be described. The materials, amounts used, ratios, processing contents, processing means, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1] Synthesis of exemplary compound (1-1) (97% deuteration of hydrogen linked to an ethylenically unsaturated group) Exemplary compound (1-1) was synthesized by the method shown in the following reaction formula (D). Manufactured. According to this example, exemplary compound (1-1) in which the deuteration rate of hydrogen linked to the ethylenically unsaturated group is 97% can be obtained. It is possible to synthesize a compound having a high deuteration rate using ² H ₂ O and ² H ₂ which are inexpensive deuterium sources, which shows the usefulness of the production method of the present invention.

Reaction formula (D)

Synthesis of deuterated methyl propiolate (acetylene carboxylic acid methyl ester) -d ₁ (1-1B):
Sodium methoxide (13.0 g, 0.24 mol) and methylpropiolate (1-1A, manufactured by Tokyo Chemical Industry Co., Ltd.) (101 g, 1.20 mol) were added at room temperature to 1.2 ml (66 mol) of heavy water. Stir for hours. The reaction solution was transferred to a separatory funnel, 400 ml of methylene chloride was added to carry out a liquid separation operation, and the organic layer was dried over anhydrous sodium sulfate. The methylene chloride was distilled off under reduced pressure, followed by distillation (200 mmHg, 68 ° C.) to obtain 74.5 g (yield 73%) of a colorless transparent liquid (1-1B). ^From the integral value of ¹ H-NMR, the hydrogen deuteration rate of the acetylene moiety was determined to be 94%.
The ¹ H-NMR (300 MHz, C ² HCl ₃ ) data is shown below.
δ2.90 (s, 0.06H), 3.82 (s, 3H)

Synthesis of methyl acrylate-d ₃ (1-1C):
To 60 g (0.71 mol) of methylpropiolate-d ₁ (1-1B), add 3.5 g of palladium-calcium carbonate-lindler catalyst (lead poisoned) (Pd 5%) manufactured by Wako Pure Chemical Industries, Ltd. Balloons filled with deuterium ² H ₂ (deuteration rate 99.8%) were connected and stirred at room temperature under normal pressure deuterium for 10 hours. After the reaction solution was filtered through Celite, the assembled product was purified by silica gel column chromatography (developing solution: ethyl acetate: hexane = 1: 10), and 60 mg of Irganox was added as a polymerization inhibitor, followed by atmospheric distillation ( 81 ° C.) and 36 g (yield 57%) of a colorless and transparent liquid (1-1C) were obtained.

Synthesis of methyl dichloropropionate-d ₃ (1-1D):
To 30 g (0.34 mol) of methyl acrylate-d ₃ (1-1C), 0.73 ml (0.02 eq) of pyridine and 30 mg of Irganox as a polymerization inhibitor were added, and chlorine gas was added to the inside temperature at 30 to 40 ° C. while stirring. I kept blowing for 2 hours while keeping it. After the reaction solution was cooled to room temperature, nitrogen gas was blown to remove residual chlorine gas, vacuum distillation was performed (8 mmHg, 78 ° C), and 48 g of colorless transparent liquid (1-1D) (yield 88%) )Obtained.

Synthesis of methyl α-chloroacrylate-d ₂ (1-1):
Methyl dichloropropionate-d ₃ (1-1D) 40 g (0.25 mol) in 120 ml of methylene chloride was added to a solution of triethylamine 38 ml (1.1 eq) in 120 ml of methylene chloride over 20 minutes while maintaining the internal temperature at 0-10 ° C. And dripped. After filtering the reaction solution, transfer to a separatory funnel, add 200 ml of water to remove the liquid separation and aqueous layer (upper layer), and wash the organic layer once with 150 ml of 2% hydrochloric acid and then twice with 200 ml of saturated saline. And dried over anhydrous sodium sulfate. After adding 40 mg of Irganox as a polymerization inhibitor, methylene chloride was distilled off under reduced pressure, and distillation under reduced pressure (65 mmHg, 61 ° C.) gave 26 g of colorless transparent liquid (1-1) (yield 85%).
The ¹ H-NMR (300 MHz, C ² HCl 3) data is shown below. ^From the comparison of the integral value of ¹ H (methyl 3H and olefin 2H), the deuteration rate of hydrogen linked to the ethylenically unsaturated group is calculated to be 97%.
δ3.85 (s, 3H), 6.02 (s, 0.03H), 6.53 (s, 0.03H)

[Example 2] Exemplified compound (1-8) (α-chloroacrylic acid-2,2,3,3,4,4,4-heptafluorobutyl ester-d4) (of hydrogen linked to an ethylenically unsaturated group) Synthesis of 97% deuteration rate and 96% total deuteration rate:
Exemplified compound (1-8) was produced by the method shown in the following reaction formula (E). 2,2,3,3,4,4,4-heptafluorobutanol, which is a raw material alcohol having a deuterium ratio of 95%, is obtained by the method described in J. Org. Chem. 1959, 24, 1852. Instead, it was synthesized by catalytic reduction of 2,2,3,3,4,4,4-heptafluorobutanoic acid using deuterium / heavy water.

Reaction formula (E)

Synthesis of 2,3-dichloropropionic acid 2,2,3,3,4,4,4-heptafluorobutyl ester-d5 (1-8A):
2,3-dichloropropionate-d3 (1-1D) 26.0 g (0.16 mol) synthesized by the method shown in Example 1, formic acid 10.2 ml (1.6 eq), and a deuteration rate of 95% To a mixed solution of 2,3,3,4,4,4-heptafluorobutanol 52 g (1.6 eq), 10 ml of concentrated sulfuric acid was added at room temperature, and the mixture was stirred at an internal temperature of 90 to 100 ° C. for 2 hours. The reaction solution was cooled to room temperature, poured into ice water, extracted with 200 ml of methylene chloride, and the organic layer (lower layer) was washed 3 times with saturated brine and dried over anhydrous sodium sulfate. The methylene chloride was distilled off under reduced pressure and then purified by distillation (4 mmHg, 47 ° C.) to obtain 27.1 g (yield 51%) of a colorless transparent liquid (1-8A).

Synthesis of α-chloroacrylic acid 2,2,3,3,4,4,4-heptafluorobutyl ester-d4 (1-8):
2,3-dichloropropionic acid 2,2,3,3,4,4,4-heptafluorobutyl ester-d5 (1-8A) 24.0 g (0.073 mol) in 90 ml of methylene chloride was added to 11.2 ml (1.1 ml) of triethylamine. eq) in 40 ml of methylene chloride was added dropwise over 20 minutes while maintaining the internal temperature at 0-10 ° C. The reaction solution was filtered and transferred to a separatory funnel, 100 ml of water was added to separate and remove the aqueous layer (upper layer), and the organic layer was washed once with 70 ml of 2% hydrochloric acid and then twice with 100 ml of saturated saline. And dried over anhydrous sodium sulfate. After adding 40 mg of irganox as a polymerization inhibitor, methylene chloride was distilled off under reduced pressure, and 18.9 g (yield 88%) of a colorless and transparent liquid compound (1-8) was obtained by distillation under reduced pressure (47 mmHg, 79 ° C.). It was.
The deuteration rate of hydrogen linked to the ethylenically unsaturated group is 97%, similar to the compound (1-1) obtained in Example 1, and 2,2,3,3,4,4,4-heptafluorobutanol. Since the deuterium ratio of is 95%, the total deuteration ratio of the compound (1-8) is 96%.

[Comparative Example 1] Production of plastic optical fiber preform (S-1) by interfacial gel polymerization:
An example is shown in which a plastic optical fiber was prepared using the following compound (2-8) (α-chloroacrylic acid 2,2,3,3,4,4,4-heptafluorobutyl ester) as a monomer raw material.
As shown in the following reaction formula (E-2), compound (2-8) is a compound of methyl 2,3-dichloropropionate (non-deuterated product) represented by compound (1-1H) and compound (2-8A). ), 2,2,3,3,4,4,4-heptafluorobutanol (non-deuterated) was synthesized in the same manner as in Example 2.

Reaction formula (E-2)

  A hollow pipe tube (with one end sealed with the same resin) of polyvinylidene fluoride resin (refractive index: 1.38) having a thickness of 1 mm, an inner diameter of 22 mm, and a length of 30 cm, prepared in advance by melt extrusion molding, is a stainless steel pipe. And set in a rotary polymerization apparatus. Next, moisture, polymerization inhibitor and dust were sufficiently removed from the inside of the tube. Then, a polymerization initiator (dimethyl 2,2′-azobisisobutyrate, 0.24% by weight of the compound (2-8)), a chain transfer agent (n-lauryl mercaptan, 0.02 of the compound (2-8)). 3 wt.%), And after purging with nitrogen, it was sealed and rotated at 1500 rpm for 3 hours at 65 ° C., 2 hours at 70 ° C., and 12 hours at 90 ° C., and a 4 mm thick outer core. Part (corresponding to the outermost layer) was produced.

  Polymerization of the inner core portion was performed as follows. The hollow tube made up to the outer core part was heated to 80 ° C. and allowed to stand vertically in a pressure polymerization vessel (inserted into a glass tube if necessary and inserted into an autoclave). Next, compound (2-8) and a dopant (diphenyl sulfide (DPS), 5% by weight based on compound (2-8)) are added, and a polymerization initiator (di-tert-butyl peroxide, compound (2) is added. −8) 0.3 wt%), a chain transfer agent (n-lauryl mercaptan, 0.6 wt% with respect to compound (2-8)) was added, degassed sufficiently, and 80 ° C. Warmed up. Next, these were gently added to the hollow portion of the hollow tube, and then the inside of the pressure polymerization vessel was replaced with a nitrogen atmosphere, and then the pressure was increased to 0.2 MPa and the polymerization was carried out at 100 ° C. for 48 hours. Thereafter, while maintaining the pressurized state, it was subjected to heat polymerization and heat treatment at 140 ° C. for 24 hours to obtain a preform. The refractive index in the cross-sectional direction of the optical fiber preform was constant at 1.380 for the cladding part, constant at 1.401 for the outer core part, and 1.401 to 1.424 (center part) for the inner core part. The refractive index distribution of the inner core portion had a convex parabola.

Next, the preform obtained above was melt stretched. The preform was inserted vertically downward into a heating furnace adjusted to 220 to 260 ° C., and the diameter of the fiber measured through a fiber diameter measuring device so that the drawing speed became the target fiber outer diameter (300 μm). Was used to control the stretching speed. The obtained fiber diameter was 750 ± 9 μm. The fiber was primary-coated with low-density polyethylene and further coated with a coating material in which magnesium hydroxide was kneaded with nitrile butadiene rubber and polyethylene.
Table 1 shows the transmission loss of the obtained coated fiber, the transmission band, the glass transition temperature of the polymer in the center of the core, and the increase in loss before and after the coated fiber was placed at 75 ° C. and 80% RH for 240 hours.

[Example 3] Production of plastic optical fiber preform (S-2) by interfacial gel polymerization:
In Comparative Example 1, the monomer used is Example Compound (1-8) and the dopant is bromobenzene-d5 (BB-d5) (7% by weight with respect to Example Compound (1-8)). Similarly, a coated fiber was produced. The evaluation results are shown in Table 1.

[Comparative Examples 2 and 3] Production of plastic optical fiber preforms (R-1 and 2) by interfacial gel polymerization:
A coated fiber was prepared in the same manner as in Comparative Example 1 except that the monomer, dopant type, and dopant amount used were changed as described in Table 1. The evaluation results are summarized in Table 1. Here, R-2 was synthesized by synthesizing deuterated methacrylic acid by the method described in JP-A-61-20906 and condensing with commercially available heavy methanol.

 Table 1 shows that deuterated α-haloacrylates produced by the method of the present invention are useful as raw materials for optical fibers.

Claims (10)

A compound represented by the following general formula (1).
General formula (1)

(In the general formula (1), R ¹ represents an alkoxy group, an aryloxy group, a hydroxy group, an amino group, an alkylamino group, or an arylamino group, X ¹ represents a chlorine atom or a bromine atom, and U represents each independently. Represents ¹ H or ² H, and 40% or more of U linked to the ethylenically unsaturated group is ² H.) The compound according to claim 1, wherein R ¹ is an alkoxy group or an aryloxy group. A compound according to claim 1 or 2 more than 80% of said U is ² H. 4. The method according to claim 1, comprising a step of exchanging a compound represented by the following general formula (2) from ¹ H to ² H in heavy water to obtain a compound represented by the general formula (3). Compound production method.

(In General Formula (2) and General Formula (3), R ¹ represents an alkoxy group, an aryloxy group, a hydroxy group, an amino group, an alkylamino group, or an arylamino group.) The production of the compound according to any one of claims 1 to 3, comprising a step of adding ² H ₂ to the compound represented by the following general formula (4) to form a compound represented by the general formula (5). Method.

(In the general formulas (4) and (5), U represents ¹ H or ² H, and R ¹ represents an alkoxy group, an aryloxy group, a hydroxy group, an amino group, an alkylamino group, or an arylamino group.) In order, the step of exchanging from ¹ H to ² H in heavy water represented by the following reaction formula (1), the step of adding ² H ₂ represented by the following reaction formula (2), and the following reaction formula (3) 4. The method according to claim 1, further comprising a step of adding a chlorine molecule or a bromine molecule represented by the formula and a step of removing hydrogen chloride or hydrogen bromide represented by the following reaction formula (4): A method for producing the compound.
Reaction formula (1)

Reaction formula (2)

Reaction formula (3)

Reaction formula (4)

(In the general formulas (1), (6), (7), (8) and (9), R ¹ represents an alkoxy group, an aryloxy group, a hydroxy group, an amino group, an alkylamino group, or an arylamino group. R ¹ in each formula may be the same or different, U represents each independently ¹ H or ² H, and X ¹ represents a chlorine atom or a bromine atom.) The polymer containing the repeating unit represented by following General formula (10).
General formula (10)

(In General Formula (10), each U independently represents ¹ H or ² H, R ¹ represents an alkoxy group, an aryloxy group, a hydroxy group, an amino group, an alkylamino group, or an arylamino group, and X ¹ Represents a chlorine atom or a bromine atom, provided that 40% or more of U is ² H.) The polymeric composition containing at least 1 sort (s) of the compound in any one of Claims 1-3. A polymer obtained by polymerizing at least the polymerizable composition according to claim 8. An optical member comprising the polymer according to claim 7.