JP4390065B2 - Fluorine-containing polymerizable ester compound and process for producing the same - Google Patents

Description

The present invention relates to a novel fluorine-containing polymerizable ester compound and a method for producing the same. The fluorine-containing polymerizable ester compound is useful as a raw material for polymer compounds, functional materials, pharmaceuticals, agricultural chemicals and the like, and is particularly suitable for radiation having a wavelength of 500 nm or less, particularly 200 nm or less, such as ArF laser light and F ₂ laser light. In contrast, it is very useful as a monomer for producing a polymer for producing a radiation-sensitive resist composition having excellent transparency and good dry etching resistance.

In recent years, along with the high integration and high speed of LSIs, far-ultraviolet lithography is considered promising as a next-generation microfabrication technique, while miniaturization of pattern rules is required. In particular, photolithography using KrF laser light, ArF laser light, or F ₂ laser light as a light source is highly desired to be realized as an indispensable technique for ultrafine processing of 0.3 μm or less. As the base resin of these resist compositions, various alkali-soluble resins are used.

  As a base resin of a resist composition for KrF, a polyhydroxystyrene resin having a phenolic hydroxyl group as an alkali-soluble functional group has become a de facto standard. As the base resin of the resist composition for ArF, a resin using a poly (meth) acrylate resin using a carboxyl group as an alkali-soluble group or an aliphatic cyclic olefin such as norbornene as a polymerization unit has been studied. Of these, poly (meth) acrylate is considered promising for practical use because of its ease of polymerization. However, in the case of a resist resin that uses a carboxyl group having a higher acidity than the phenolic hydroxyl group as an alkali-soluble functional group, control of dissolution is a problem, and pattern collapse due to swelling or the like is likely to occur.

As a functional group having a phenolic hydroxyl group-like acidity, alcohols substituted with a plurality of fluorine atoms at the α-position and α′-position (for example, those having a partial structure —C (CF ₃ ) ₂ OH) are alkali-soluble functional groups Resins used as are also proposed. 2nd International Symposium on 157 nm Lithography (Non-patent Document 1). An example can be found in Wallluff et al., Active Fluororists for 157 nm Lithography. They have proposed a compound in which fluoroalcohol —C (CF ₃ ) ₂ OH is introduced into styrene or norbornene as a monomer used in the production of the base resin. Similarly, examples of fluoroalcohol-substituted norbornene can also be found in Japanese Patent Application Laid-Open No. 2003-192729 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2002-72484 (Patent Document 2). Radical polymerization is difficult, and special polymerization methods such as coordination polymerization using a special transition metal catalyst and ring-opening metathesis polymerization are required. Although alternating polymerization of norbornene monomer and a comonomer such as maleic anhydride or maleimide can be carried out by radical polymerization, the presence of the comonomer greatly limits the degree of freedom in resin design.

  JP-A-2003-040840 (Patent Document 3) describes a fluoroalcohol-substituted acrylate monomer. The production method is not necessarily clear, but hexafluoroacetone (boiling point -27 ° C.) is used as a starting material. This is a gas at room temperature and is difficult to handle, and the process for synthesizing polymerizable compounds is long. However, it has problems such as difficult industrial production.

  Therefore, the emergence of a polymerizable compound having both a (meth) acrylate structure that is industrially easy to produce and easy to produce (polymerize) as a resist resin and a functional group having a phenolic hydroxyl group-like acidity is strong. It was desired.

JP 2003-192729 A JP 2002-72484 A JP 2003-040840 A Active Fluororesist for 157nm Lithography (2nd International Symposium on 157nm Lithography)

  The present invention has been made in view of the above circumstances, and is intended to produce a resist base resin having excellent transparency and dry etching resistance to laser light having a wavelength of 500 nm or less, particularly 200 nm or less, and good development characteristics. It is an object of the present invention to provide a novel fluorine-containing polymerizable ester compound that is useful as a monomer and that can be produced from readily available and easy-to-handle materials and a method for producing the same.

  As a result of intensive studies in order to achieve the above-mentioned problems, the inventor of the present invention has made it possible to obtain a fluorine-containing polymerizable ester compound represented by the following general formulas (1) and (2) from easily available raw materials by the method described below. This compound can be easily obtained in a yield and can be polymerized by an industrially easy polymerization method such as radical polymerization. If a resin obtained by polymerization is used, transparency at a wavelength of 200 nm or less, etching resistance It was found that a radiation-sensitive resist composition having excellent resistance and development characteristics can be obtained.

（式中、Ｒ¹は水素原子、メチル基又はトリフルオロメチル基を表す。Ｒ²、Ｒ³はそれぞれ独立に水素原子又は炭素数１〜１５のヘテロ原子を含んでもよい一価の炭化水素基を表し、Ｒ²とＲ³は互いに結合してこれらが結合する炭素原子と共に環を形成してもよく、その場合には炭素数１〜１５のヘテロ原子を含んでもよい二価の炭化水素基を表す。Ｒ⁴は水酸基、又は炭素数１〜１５のヘテロ原子を含んでもよい一価の炭化水素基を表す。Ｒ⁵は下記一般式（Ｌ１）〜（Ｌ４）で示される基、炭素数４〜２０の三級アルキル基、各アルキル基がそれぞれ炭素数１〜６のトリアルキルシリル基、炭素数４〜２０のオキソアルキル基から選ばれる酸不安定基を示す。

（式中、破線は結合手を示す。Ｒ^L01、Ｒ^L02は水素原子又は炭素数１〜１８の直鎖状、分岐状又は環状のアルキル基を示し、Ｒ^L03は炭素数１〜１８のヘテロ原子を有してもよい１価の炭化水素基を示す。Ｒ^L01とＲ^L02、Ｒ^L01とＲ^L03、Ｒ^L02とＲ^L03とは互いに結合してこれらが結合する炭素原子と共に環を形成してもよく、環を形成する場合にはＲ^L01、Ｒ^L02、Ｒ^L03はそれぞれ炭素数１〜１８の直鎖状又は分岐状のアルキレン基を示す。
Ｒ^L04は炭素数４〜２０の三級アルキル基、各アルキル基がそれぞれ炭素数１〜６のトリアルキルシリル基、炭素数４〜２０のオキソアルキル基又は上記一般式（Ｌ１）で示される基を示す。
Ｒ^L05は炭素数１〜８のヘテロ原子を含んでもよい１価の炭化水素基又は炭素数６〜２０の置換されていてもよいアリール基を示す。ｍは０又は１、ｎは０、１、２、３のいずれかであり、２ｍ＋ｎ＝２又は３を満足する数である。
Ｒ^L06は炭素数１〜８のヘテロ原子を含んでもよい１価の炭化水素基又は炭素数６〜２０の置換されていてもよいアリール基を示す。Ｒ^L07〜Ｒ^L16はそれぞれ独立に水素原子又は炭素数１〜１５のヘテロ原子を含んでもよい１価の炭化水素基を示す。Ｒ^L07〜Ｒ^L16から選ばれる２個はこれらが結合する炭素原子と共に環を形成していてもよく、その場合にはこの環を形成する各基は炭素数１〜１５のヘテロ原子を含んでもよい２価の炭化水素基を示す。また、Ｒ^L07〜Ｒ^L16は隣接する炭素に結合するもの同士で何も介さずに結合し、二重結合を形成してもよい。））
［２］下記式で示される含フッ素重合性エステル化合物の中から選択される含フッ素重合性エステル化合物。

［３］下記一般式（３）で表されるケトアルコール化合物に一般式Ｒ⁴−Ｚで表される化合物を反応させて下記一般式（４）で表されるジオール化合物を得、このジオール化合物をアシル化して下記一般式（１）で表される含フッ素重合性エステル化合物を得ることを特徴とする下記一般式（１）で表される含フッ素重合性エステル化合物の製造方法。

（式中、Ｒ¹は水素原子、メチル基又はトリフルオロメチル基を表す。Ｒ²、Ｒ³はそれぞれ独立に水素原子又は炭素数１〜１５のヘテロ原子を含んでもよい一価の炭化水素基を表し、Ｒ²とＲ³は互いに結合してこれらが結合する炭素原子と共に環を形成してもよく、その場合には炭素数１〜１５のヘテロ原子を含んでもよい二価の炭化水素基を表す。Ｒ⁴は水素原子、水酸基、又は炭素数１〜１５のヘテロ原子を含んでもよい一価の炭化水素基を表す。ＺはＲ⁴−ＺがＲ⁴アニオン等価体を与える１価の基を表す。）
［４］下記一般式（３）で表されるケトアルコール化合物に一般式Ｒ⁴−Ｚで表される化合物を反応させて下記一般式（４）で表されるジオール化合物を得、このジオール化合物を保護して下記一般式（５）で表されるアルコール化合物を得、このアルコール化合物をアシル化して下記一般式（６）で表される保護化含フッ素重合性エステル化合物を得、この保護化含フッ素重合性エステル化合物を脱保護して下記一般式（１）で表される含フッ素重合性エステル化合物を得ることを特徴とする下記一般式（１）で表される含フッ素重合性エステル化合物の製造方法。

（式中、Ｒ¹は水素原子、メチル基又はトリフルオロメチル基を表す。Ｒ²、Ｒ³はそれぞれ独立に水素原子又は炭素数１〜１５のヘテロ原子を含んでもよい一価の炭化水素基を表し、Ｒ²とＲ³は互いに結合してこれらが結合する炭素原子と共に環を形成してもよく、その場合には炭素数１〜１５のヘテロ原子を含んでもよい二価の炭化水素基を表す。Ｒ⁴は水素原子、水酸基、又は炭素数１〜１５のヘテロ原子を含んでもよい一価の炭化水素基を表す。Ｒ⁶は保護基を表す。ＺはＲ⁴−ＺがＲ⁴アニオン等価体を与える１価の基を表す。）
［５］下記一般式（３）で表されるケトアルコール化合物に一般式Ｒ⁴−Ｚで表される化合物を反応させて下記一般式（４）で表されるジオール化合物を得、このジオール化合物を酸不安定基で保護して下記一般式（７）で表されるアルコール化合物を得、このアルコール化合物をアシル化して下記一般式（２）で表される含フッ素重合性エステル化合物を得ることを特徴とする下記一般式（２）で表される含フッ素重合性エステル化合物の製造方法。

（式中、Ｒ¹は水素原子、メチル基又はトリフルオロメチル基を表す。Ｒ²、Ｒ³はそれぞれ独立に水素原子又は炭素数１〜１５のヘテロ原子を含んでもよい一価の炭化水素基を表し、Ｒ²とＲ³は互いに結合してこれらが結合する炭素原子と共に環を形成してもよく、その場合には炭素数１〜１５のヘテロ原子を含んでもよい二価の炭化水素基を表す。Ｒ⁴は水素原子、水酸基、又は炭素数１〜１５のヘテロ原子を含んでもよい一価の炭化水素基を表す。ＺはＲ⁴−ＺがＲ⁴アニオン等価体を与える１価の基を表す。Ｒ⁵は下記一般式（Ｌ１）〜（Ｌ４）で示される基、炭素数４〜２０の三級アルキル基、各アルキル基がそれぞれ炭素数１〜６のトリアルキルシリル基、炭素数４〜２０のオキソアルキル基から選ばれる酸不安定基を示す。

（式中、破線は結合手を示す。Ｒ^L01、Ｒ^L02は水素原子又は炭素数１〜１８の直鎖状、分岐状又は環状のアルキル基を示し、Ｒ^L03は炭素数１〜１８のヘテロ原子を有してもよい１価の炭化水素基を示す。Ｒ^L01とＲ^L02、Ｒ^L01とＲ^L03、Ｒ^L02とＲ^L03とは互いに結合してこれらが結合する炭素原子と共に環を形成してもよく、環を形成する場合にはＲ^L01、Ｒ^L02、Ｒ^L03はそれぞれ炭素数１〜１８の直鎖状又は分岐状のアルキレン基を示す。
Ｒ^L04は炭素数４〜２０の三級アルキル基、各アルキル基がそれぞれ炭素数１〜６のトリアルキルシリル基、炭素数４〜２０のオキソアルキル基又は上記一般式（Ｌ１）で示される基を示す。
Ｒ^L05は炭素数１〜８のヘテロ原子を含んでもよい１価の炭化水素基又は炭素数６〜２０の置換されていてもよいアリール基を示す。ｍは０又は１、ｎは０、１、２、３のいずれかであり、２ｍ＋ｎ＝２又は３を満足する数である。
Ｒ^L06は炭素数１〜８のヘテロ原子を含んでもよい１価の炭化水素基又は炭素数６〜２０の置換されていてもよいアリール基を示す。Ｒ^L07〜Ｒ^L16はそれぞれ独立に水素原子又は炭素数１〜１５のヘテロ原子を含んでもよい１価の炭化水素基を示す。Ｒ^L07〜Ｒ^L16から選ばれる２個はこれらが結合する炭素原子と共に環を形成していてもよく、その場合にはこの環を形成する各基は炭素数１〜１５のヘテロ原子を含んでもよい２価の炭化水素基を示す。また、Ｒ^L07〜Ｒ^L16は隣接する炭素に結合するもの同士で何も介さずに結合し、二重結合を形成してもよい。））
［６］下記一般式（１）で表される含フッ素重合性エステル化合物を酸不安定基で保護し下記一般式（２）で表される含フッ素重合性エステル化合物を得ることを特徴とする下記一般式（２）で表される含フッ素重合性エステル化合物の製造方法。

（式中、Ｒ¹は水素原子、メチル基又はトリフルオロメチル基を表す。Ｒ²、Ｒ³はそれぞれ独立に水素原子又は炭素数１〜１５のヘテロ原子を含んでもよい一価の炭化水素基を表し、Ｒ²とＲ³は互いに結合してこれらが結合する炭素原子と共に環を形成してもよく、その場合には炭素数１〜１５のヘテロ原子を含んでもよい二価の炭化水素基を表す。Ｒ⁴は水素原子、水酸基、又は炭素数１〜１５のヘテロ原子を含んでもよい一価の炭化水素基を表す。Ｒ⁵は下記一般式（Ｌ１）〜（Ｌ４）で示される基、炭素数４〜２０の三級アルキル基、各アルキル基がそれぞれ炭素数１〜６のトリアルキルシリル基、炭素数４〜２０のオキソアルキル基から選ばれる酸不安定基を示す。

（式中、破線は結合手を示す。Ｒ^L01、Ｒ^L02は水素原子又は炭素数１〜１８の直鎖状、分岐状又は環状のアルキル基を示し、Ｒ^L03は炭素数１〜１８のヘテロ原子を有してもよい１価の炭化水素基を示す。Ｒ^L01とＲ^L02、Ｒ^L01とＲ^L03、Ｒ^L02とＲ^L03とは互いに結合してこれらが結合する炭素原子と共に環を形成してもよく、環を形成する場合にはＲ^L01、Ｒ^L02、Ｒ^L03はそれぞれ炭素数１〜１８の直鎖状又は分岐状のアルキレン基を示す。
Ｒ^L04は炭素数４〜２０の三級アルキル基、各アルキル基がそれぞれ炭素数１〜６のトリアルキルシリル基、炭素数４〜２０のオキソアルキル基又は上記一般式（Ｌ１）で示される基を示す。
Ｒ^L05は炭素数１〜８のヘテロ原子を含んでもよい１価の炭化水素基又は炭素数６〜２０の置換されていてもよいアリール基を示す。ｍは０又は１、ｎは０、１、２、３のいずれかであり、２ｍ＋ｎ＝２又は３を満足する数である。
Ｒ^L06は炭素数１〜８のヘテロ原子を含んでもよい１価の炭化水素基又は炭素数６〜２０の置換されていてもよいアリール基を示す。Ｒ^L07〜Ｒ^L16はそれぞれ独立に水素原子又は炭素数１〜１５のヘテロ原子を含んでもよい１価の炭化水素基を示す。Ｒ^L07〜Ｒ^L16から選ばれる２個はこれらが結合する炭素原子と共に環を形成していてもよく、その場合にはこの環を形成する各基は炭素数１〜１５のヘテロ原子を含んでもよい２価の炭化水素基を示す。また、Ｒ^L07〜Ｒ^L16は隣接する炭素に結合するもの同士で何も介さずに結合し、二重結合を形成してもよい。））
That is, the present invention provides the following fluorine-containing polymerizable ester compound and a method for producing the same.
[1] A fluorine-containing polymerizable ester compound represented by the following general formula (1a) or (2a).

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ² and R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may contain a C 1-15 hetero atom. R ² and R ³ may be bonded to each other to form a ring together with the carbon atom to which they are bonded, in which case a divalent hydrocarbon group that may contain a heteroatom having 1 to 15 carbon atoms R ⁴ represents a hydroxyl group or a monovalent hydrocarbon group which may contain a hetero atom having 1 to 15 carbon atoms, R ⁵ represents a group represented by the following general formulas (L1) to (L4), or a carbon number 4 to 20 tertiary alkyl groups, each alkyl group is an acid labile group selected from a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

(In the formula, a broken line represents a bond. R ^L01 and R ^L02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and R ^L03 represents a heterogeneous group having 1 to 18 carbon atoms. A monovalent hydrocarbon group which may have an atom, R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R ^L03 are bonded to each other to form a ring with the carbon atom to which they are bonded. In the case of forming a ring, R ^L01 , R ^L02 and R ^L03 each represent a linear or branched alkylene group having 1 to 18 carbon atoms.
R ^L04 is a tertiary alkyl group having 4 to 20 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or a group represented by the above general formula (L1) Indicates.
R ^L05 represents a monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. m is 0 or 1, n is 0, 1, 2, or 3, and 2m + n = 2 or 3.
R ^L06 represents a monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. R ^{L07 to} R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group that may contain a C 1-15 hetero atom. Two ^members selected from R ^{L07 to} R ^L16 may form a ring together with the carbon atom to which they are bonded, and in this case, each group forming this ring may contain a hetero atom having 1 to 15 carbon atoms. A good divalent hydrocarbon group is shown. R ^{L07 to} R ^L16 may be bonded to adjacent carbons without any intervening bonds to form a double bond. ))
[2] A fluorine-containing polymerizable ester compound selected from fluorine-containing polymerizable ester compounds represented by the following formula.

[3] A diol compound represented by the following general formula (4) is obtained by reacting a keto alcohol compound represented by the following general formula (3) with a compound represented by the general formula R ⁴ -Z. A method for producing a fluorine-containing polymerizable ester compound represented by the following general formula (1), wherein the fluorine-containing polymerizable ester compound represented by the following general formula (1) is obtained.

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ² and R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may contain a C 1-15 hetero atom. R ² and R ³ may be bonded to each other to form a ring together with the carbon atom to which they are bonded, in which case a divalent hydrocarbon group that may contain a heteroatom having 1 to 15 carbon atoms R ⁴ represents a hydrogen atom, a hydroxyl group, or a monovalent hydrocarbon group that may contain a hetero atom having 1 to 15 carbon atoms, Z represents a monovalent group in which R ⁴ —Z provides an R ⁴ anion equivalent. Represents a group.)
[4] A diol compound represented by the following general formula (4) is obtained by reacting a keto alcohol compound represented by the following general formula (3) with a compound represented by the general formula R ⁴ -Z. Is protected to obtain an alcohol compound represented by the following general formula (5), and this alcohol compound is acylated to obtain a protected fluorine-containing polymerizable ester compound represented by the following general formula (6). A fluorine-containing polymerizable ester compound represented by the following general formula (1), wherein the fluorine-containing polymerizable ester compound represented by the following general formula (1) is obtained by deprotecting the fluorine-containing polymerizable ester compound Manufacturing method.

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ² and R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may contain a C 1-15 hetero atom. R ² and R ³ may be bonded to each other to form a ring together with the carbon atom to which they are bonded, in which case a divalent hydrocarbon group that may contain a heteroatom having 1 to 15 carbon atoms R ⁴ represents a hydrogen atom, a hydroxyl group, or a monovalent hydrocarbon group that may contain a hetero atom having 1 to 15 carbon atoms, R ⁶ represents a protecting group, and Z represents R ⁴ -Z is R ^4. Represents a monovalent group giving an anion equivalent)
[5] A diol compound represented by the following general formula (4) is obtained by reacting a keto alcohol compound represented by the following general formula (3) with a compound represented by the general formula R ⁴ -Z. Is protected with an acid labile group to obtain an alcohol compound represented by the following general formula (7), and the alcohol compound is acylated to obtain a fluorinated polymerizable ester compound represented by the following general formula (2). A process for producing a fluorine-containing polymerizable ester compound represented by the following general formula (2):

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ² and R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may contain a C 1-15 hetero atom. R ² and R ³ may be bonded to each other to form a ring together with the carbon atom to which they are bonded, in which case a divalent hydrocarbon group that may contain a heteroatom having 1 to 15 carbon atoms R ⁴ represents a hydrogen atom, a hydroxyl group, or a monovalent hydrocarbon group that may contain a hetero atom having 1 to 15 carbon atoms, Z represents a monovalent group in which R ⁴ —Z provides an R ⁴ anion equivalent. R ⁵ represents a group represented by the following general formulas (L1) to (L4), a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group in which each alkyl group has 1 to 6 carbon atoms, carbon An acid labile group selected from oxoalkyl groups of 4 to 20 is shown.

(In the formula, a broken line represents a bond. R ^L01 and R ^L02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and R ^L03 represents a heterogeneous group having 1 to 18 carbon atoms. A monovalent hydrocarbon group which may have an atom, R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R ^L03 are bonded to each other to form a ring with the carbon atom to which they are bonded. In the case of forming a ring, R ^L01 , R ^L02 and R ^L03 each represent a linear or branched alkylene group having 1 to 18 carbon atoms.
R ^L04 is a tertiary alkyl group having 4 to 20 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or a group represented by the above general formula (L1) Indicates.
R ^L05 represents a monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. m is 0 or 1, n is 0, 1, 2, or 3, and 2m + n = 2 or 3.
R ^L06 represents a monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. R ^{L07 to} R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group that may contain a C 1-15 hetero atom. Two ^members selected from R ^{L07 to} R ^L16 may form a ring together with the carbon atom to which they are bonded, and in this case, each group forming this ring may contain a hetero atom having 1 to 15 carbon atoms. A good divalent hydrocarbon group is shown. R ^{L07 to} R ^L16 may be bonded to adjacent carbons without any intervening bonds to form a double bond. ))
[6] A fluorine-containing polymerizable ester compound represented by the following general formula (1) is protected with an acid labile group to obtain a fluorine-containing polymerizable ester compound represented by the following general formula (2). The manufacturing method of the fluorine-containing polymeric ester compound represented by following General formula (2).

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ² and R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may contain a C 1-15 hetero atom. R ² and R ³ may be bonded to each other to form a ring together with the carbon atom to which they are bonded, in which case a divalent hydrocarbon group that may contain a heteroatom having 1 to 15 carbon atoms R ⁴ represents a hydrogen atom, a hydroxyl group, or a monovalent hydrocarbon group which may contain a hetero atom having 1 to 15 carbon atoms, and R ⁵ represents a group represented by the following general formulas (L1) to (L4). And a tertiary alkyl group having 4 to 20 carbon atoms, and each alkyl group is an acid labile group selected from a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

(In the formula, a broken line represents a bond. R ^L01 and R ^L02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and R ^L03 represents a heterogeneous group having 1 to 18 carbon atoms. A monovalent hydrocarbon group which may have an atom, R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R ^L03 are bonded to each other to form a ring with the carbon atom to which they are bonded. In the case of forming a ring, R ^L01 , R ^L02 and R ^L03 each represent a linear or branched alkylene group having 1 to 18 carbon atoms.
R ^L04 is a tertiary alkyl group having 4 to 20 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or a group represented by the above general formula (L1) Indicates.
R ^L05 represents a monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. m is 0 or 1, n is 0, 1, 2, or 3, and 2m + n = 2 or 3.
R ^L06 represents a monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. R ^{L07 to} R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group that may contain a C 1-15 hetero atom. Two ^members selected from R ^{L07 to} R ^L16 may form a ring together with the carbon atom to which they are bonded, and in this case, each group forming this ring may contain a hetero atom having 1 to 15 carbon atoms. A good divalent hydrocarbon group is shown. R ^{L07 to} R ^L16 may be bonded to adjacent carbons without any intervening bonds to form a double bond. ))

  The present invention provides a novel fluorine-containing polymerizable ester compound, and the fluorine-containing polymerizable ester compound is useful as a raw material for polymer compounds, functional materials, pharmaceuticals and agricultural chemicals, and in particular, has a wavelength of 500 nm or less, Very useful as a monomer for polymer production for producing a radiation-sensitive resist composition having excellent development characteristics because it has excellent transparency to radiation of a wavelength of 200 nm or less and has a phenolic acidic hydroxyl group. It is.

  The fluorine-containing polymerizable ester compound of the present invention is represented by the following general formula (1) or (2).

Here, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group.
R ² and R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group that may contain a heteroatom having 1 to 15 carbon atoms, and a monovalent hydrocarbon that may contain a heteroatom having 1 to 15 carbon atoms As the group, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, n-octyl group N-nonyl group, n-decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group, etc. Chain, branched or cyclic alkyl group, phenyl group, methylphenyl group, naphthyl group, anthri Groups, aryl groups such as phenanthryl groups, aralkyl groups such as benzyl groups, diphenylmethyl groups, phenethyl groups, etc., and some of the hydrogen atoms of these groups are halogen atoms, alkyl groups, aryl groups, alkoxy groups, It may be substituted with an alkoxycarbonyl group, an oxo group or the like. R ² and R ³ may be bonded to each other to form a ring together with the carbon atom to which they are bonded, in which case R ² and R ³ may be a divalent divalent atom containing 1 to 15 carbon atoms. Represents a hydrocarbon group. Here, as a ring to be formed, cyclopropane, cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] Decane, adamantane and the like can be exemplified, and some of hydrogen atoms in these rings may be substituted with a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, an oxo group or the like.

R ⁴ represents a hydrogen atom, a hydroxyl group, or a monovalent hydrocarbon group that may contain a hetero atom having 1 to 15 carbon atoms. Examples of the monovalent hydrocarbon group which may contain a hetero atom having 1 to 15 carbon atoms are the same as those exemplified for R ² and R ³ above.

R ⁵ represents an acid labile group. The acid labile group can be variously used, specifically, groups represented by the following general formulas (L1) to (L4), tertiary alkyl groups having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, Examples of each alkyl group include a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

Here, a broken line shows a bond (hereinafter the same). In the above formula, R ^L01 and R ^L02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, specifically, methyl group, ethyl group, propyl group. Group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group and the like. R ^L03 represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, a linear, branched or cyclic alkyl group, Examples include those in which a part of the hydrogen atoms are substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group, and the like.

R ^L01 and R ^L02, R ^L01 and R ^L03, R ^L02 and R ^L03 and may form a ring together with the carbon atoms to which they are attached to each other, in the case of forming the ring R ^L01, R ^L02 , R ^L03 each represents a linear or branched alkylene group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms.

R ^L04 is a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the above general formula ( L1) represents a tertiary alkyl group, specifically, a tert-butyl group, a tert-amyl group, a 1,1-diethylpropyl group, a 2-cyclopentylpropan-2-yl group, 2- Cyclohexylpropan-2-yl group, 2- (bicyclo [2.2.1] heptan-2-yl) propan-2-yl group, 2- (adamantan-1-yl) propan-2-yl group, 1- Ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexyl group Examples include xenyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group and the like. Specific examples of trialkylsilyl group include trimethylsilyl group, triethylsilyl group, dimethyl-tert-butylsilyl group and the like. Specific examples of the oxoalkyl group include 3-oxocyclohexyl group, 4-methyl-2-oxooxan-4-yl group, and 5-methyl-2-oxooxolan-5-yl group. it can. y is an integer of 0-6.

R ^L05 represents a monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms or an aryl group which may be substituted having 6 to 20 carbon atoms, and may be a monovalent hydrocarbon which may contain a hetero atom Specific examples of the group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, Linear, branched or cyclic alkyl groups such as cyclopentyl group and cyclohexyl group, and some of these hydrogen atoms are hydroxyl, alkoxy, carboxy, alkoxycarbonyl, oxo, amino, alkylamino, cyano Group, mercapto group, alkylthio group, sulfo group and the like can be exemplified. As the aryl group which may be substituted, specifically, phenyl group , Methylphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group and the like. m is 0 or 1, n is 0, 1, 2, or 3, and 2m + n = 2 or 3.

R ^L06 represents a monovalent hydrocarbon group which may contain a heteroatom having 1 to 8 carbon atoms or an aryl group which may be substituted having 6 to 20 carbon atoms, specifically the same as R ^L05 and the like Can be illustrated. R ^{L07 to} R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group that may contain a hetero atom having 1 to 15 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, n -Butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, A linear, branched or cyclic alkyl group such as a cyclopentylmethyl group, a cyclopentylethyl group, a cyclopentylbutyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylbutyl group, a part of these hydrogen atoms being a hydroxyl group, an alkoxy group, Carboxy group, alkoxycarbonyl group, oxo group, amino group, alkylamino group, cyano group, merca DOO group, an alkylthio group, such as those substituted on the sulfo group and the like. 2 selected from R ^{L07 to} R ^L16 (for example, R ^L07 and R ^L08 , R ^L07 and R ^L09 , R ^L08 and R ^L10 , R ^L09 and R ^L10 , R ^L11 and R ^L12 , R ^L13 and R ^L14, etc.) May form a ring together with the carbon atom to which they are bonded, in which case each group forming the ring represents a divalent hydrocarbon group that may contain a heteroatom having 1 to 15 carbon atoms, Specifically, what remove | excluded one hydrogen atom from what was illustrated with the said monovalent | monohydric hydrocarbon group can be illustrated. R ^{L07 to} R ^L16 may be bonded to each other adjacent to each other to form a double bond (for example, R ^L07 and R ^L09 , R ^L09 and R ^L15 , R ^L13 and R ^L15 etc.).

  Of the acid labile groups represented by the above formula (L1), specific examples of the linear or branched groups include the following groups.

  Among the acid labile groups represented by the above formula (L1), specific examples of cyclic groups include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, 2 -A methyltetrahydropyran-2-yl group etc. can be illustrated.

  Specific examples of the acid labile group of the above formula (L2) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1,1-diethyl. Propyloxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethyl-2 Examples include -cyclopentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

  Specific examples of the acid labile group of the above formula (L3) include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, 1-sec- Butylcyclopentyl, 1-cyclohexylcyclopentyl, 1- (4-methoxy-n-butyl) cyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopentene Examples include -3-yl, 3-methyl-1-cyclohexen-3-yl, and 3-ethyl-1-cyclohexen-3-yl.

  Specific examples of the acid labile group of the above formula (L4) include the following groups. Here, a chain line indicates a bonding position and a bonding direction.

Further, tertiary alkyl groups having 4 to 20 carbon atoms, trialkylsilyl groups each having 1 to 6 carbon atoms, and oxoalkyl groups having 4 to 20 carbon atoms are specifically exemplified as ^RL04 . The thing similar to a thing etc. can be illustrated.

R ² , R ³ , R ⁴ and R ⁵ can be appropriately selected in consideration of various resist performances such as transparency, etching resistance and solubility of a resist resin using the fluorine-containing polymerizable ester compound.

Depending on the type of R ² , R ³ , R ⁴ , OR ⁵ , the carbon atom of the anchor may be an asymmetric carbon, and there are enantiomers and diastereomers. General formulas (1) and (2) represent all of these stereoisomers. These stereoisomers may be used alone or as a mixture.

  Specific examples of the fluorine-containing polymerizable ester compound of the present invention include the following, but are not limited thereto. In the following examples, Me represents a methyl group, t-Bu represents a tert-butyl group, and Ph represents a phenyl group.

Next, the manufacturing method of the fluorine-containing polymerizable ester compound of the present invention will be described.
The starting ketoalcohol compound (3) comprises 1,1,1,3,3,3-hexafluoro-2-propanol (which is commercially available in large quantities and has a melting point − Enolate (1,1,3,3,3-pentafluoro-2-propenyl oxide) prepared from 4 to -2 ° C, boiling point 59 to 60 ° C and liquid at normal temperature and easy to handle (See T. Nakai et al., Tetrahedron Letters, Vol. 29, P. 4119, 1988, and T. Nakai et al., Organic Synthesis, Vol. 76, P. 151, 1998). In this nucleophilic addition reaction of fluoroenolate to a carbonyl compound, various aldehydes and ketones can be used as the carbonyl compound (8).

  The resulting ketoalcohol compound (3) is a hydrate represented by the following general formula (9) in which water is added to the carbonyl group by post-treatment using water, or the hydroxyl group in the molecule is a carbonyl group. And may be obtained as an oxetane hemiacetal compound represented by the following general formula (10) or as a mixture of these three.

Here, when these mixtures can be used in the reaction as they are, or in some cases, it is possible to easily equilibrate the keto alcohol compound by a simple dehydration operation before the reaction. It will be represented as a representative.
In addition, when R ² and R ³ are different, the carbon atoms attached to them are asymmetric carbons. Furthermore, in the oxetane hemiacetal compound (10), the carbon attached to the CF ₃ group and the hydroxyl group is also asymmetric carbons, Although enantiomers and diastereomers may exist, the general formula (3) represents all of these stereoisomers. These stereoisomers may be used alone or as a mixture.

When this keto alcohol compound (9) equivalent (equilibrium mixture) is directly acylated, a keto ester compound in which the hydroxyl group of compound (9) is acylated cannot be obtained, and the hydroxyl group of oxetane compound (10) is acylated. As described below, the acylation after the reaction with R ⁴ —Z is advantageous as described below.

As a first method of manufacturing a polymerizable fluorinated ester compound of the present invention, by reacting a compound R ⁴ -Z in the keto-alcohol compound represented by the following general formula (3), represented by the general formula (4) A diol compound is obtained, and the diol compound is acylated to obtain a fluorine-containing polymerizable ester compound represented by the general formula (1).

（上述した通り、式中、Ｒ¹は水素原子、メチル基又はトリフルオロメチル基を表す。Ｒ²、Ｒ³はそれぞれ独立に水素原子又は炭素数１〜１５のヘテロ原子を含んでもよい一価の炭化水素基を表し、Ｒ²とＲ³は互いに結合してこれらが結合する炭素原子と共に環を形成してもよく、その場合には炭素数１〜１５のヘテロ原子を含んでもよい二価の炭化水素基を表す。Ｒ⁴は水素原子、水酸基、又は炭素数１〜１５のヘテロ原子を含んでもよい一価の炭化水素基を表す。ＺはＲ⁴−ＺがＲ⁴アニオン等価体を与える１価の基を表す。）
第１段階として、出発原料ケトアルコール化合物（３）にＲ⁴−Ｚを反応させる。

(As described above, in the formula, R ¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group. R ² and R ³ each independently represents a hydrogen atom or a monovalent atom that may contain a hetero atom having 1 to 15 carbon atoms. R ² and R ³ may be bonded to each other to form a ring together with the carbon atom to which they are bonded, and in this case, a divalent which may contain a hetero atom having 1 to 15 carbon atoms R ⁴ represents a hydrogen atom, a hydroxyl group, or a monovalent hydrocarbon group that may contain a hetero atom having 1 to 15 carbon atoms, Z represents an R ⁴ anion equivalent of R ⁴ —Z. Represents a monovalent group to be given.)
As a first step, R ⁴ —Z is reacted with the starting material ketoalcohol compound (3).

This reaction is carried out by mixing compound (3) and R ⁴ —Z in a solvent or without a solvent. R ⁴ —Z represents an R ⁴ anion equivalent and can be appropriately selected depending on the type of R ⁴ of interest. Specifically, water (when R ⁴ is a hydroxyl group), alkyl metals such as methyl lithium, butyl lithium, phenyl lithium, methyl magnesium chloride, ethyl magnesium chloride, phenyl magnesium chloride (when R ⁴ is a hydrocarbon group), Metal hydrides such as sodium hydride, potassium hydride, calcium hydride, aluminum hydride, borane, diisobutylaluminum hydride (when R ⁴ is a hydrogen atom), metal hydrogen such as sodium borohydride, lithium aluminum hydride Examples thereof include complex compounds or alkyl and alkoxy derivatives thereof (when R ⁴ is a hydrogen atom). The amount of R ⁴ -Z used is from 1 mol to a large excess with respect to 1 mol of the compound (3). A large excess amount is preferred.

  When the reaction is carried out in a solvent, the solvent includes hexane, heptane, benzene, toluene, xylene, cumene and other hydrocarbons, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, ethers such as 1,4-dioxane, Nitriles such as acetonitrile, ketones such as acetone, esters such as ethyl acetate, aprotic polar solvents such as N, N-dimethylformamide, hexamethylphosphoric triamide and the like alone or in combination of two or more It can be used by mixing.

In the above reaction, an appropriate reaction temperature can be selected depending on the type of R ⁴ —Z to be used. The reaction time for the above addition reaction is preferably determined by monitoring the progress of the reaction by thin layer chromatography, gas chromatography or the like in order to improve the yield, but is usually about 0.1 to 50 hours. After completion of the reaction, the objective diol compound (4) is obtained by ordinary aqueous work-up. Compound (4) can be purified by a conventional method such as recrystallization, chromatography, distillation or the like, if necessary.

Next is a step of acylating the obtained diol compound (4).
At this stage, since there are two hydroxyl groups that can be acylated, the regioselectivity of the reaction becomes a problem. That is, the regioisomer represented by the target product (1) and the following general formula (1 ′) may be formed.

  In the case where the two hydroxyl groups of the diol compound (4) are distinguished by steric hindrance and the target acylation position is more sterically free, or even if the degree of steric hindrance is similar, Since the acidity differs, (1) may be selectively obtained by appropriately controlling the reaction conditions. In these cases, the acylation reaction described below can be applied using the diol compound (4) as a reaction substrate as it is without protecting any hydroxyl group. This method has a short industrial process and high industrial value as compared with a method through protection / deprotection described later.

For the acylation reaction, a known ester production method, for example, reaction with an acylating agent, reaction with a carboxylic acid, or transesterification can be applied.
In the reaction using an acylating agent, chlorinated solvents such as methylene chloride, chloroform and trichloroethylene, hydrocarbons such as hexane, heptane, benzene, toluene, xylene and cumene, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether , Ethers such as tetrahydrofuran and 1,4-dioxane, nitriles such as acetonitrile, ketones such as acetone and 2-butanone, esters such as ethyl acetate and n-butyl acetate, N, N-dimethylformamide, dimethylsulfate In a solvent selected from aprotic polar solvents such as foxoxide and hexamethylphosphoric triamide alone or in a mixture of two or more, the starting diol compound (4), acrylic acid chloride, methacrylate Acid halides such as acid chloride, acrylic acid bromide, methacrylic acid bromide, α-trifluoromethylacrylic acid chloride, etc., or acrylic anhydride, methacrylic acid anhydride, α-trifluoromethyl acrylic acid, trifluoroacetic acid mixed Acid anhydride, trifluoroacetic acid mixed acid anhydride, α-trifluoromethylacrylic acid trifluoroacetic acid mixed acid anhydride, acrylic acid p-nitrobenzoic acid mixed acid anhydride, methacrylic acid p-nitrobenzoic acid mixed acid Acylating agents such as anhydrides, acid anhydrides such as ethyl acrylate carbonate mixed acid anhydride, ethyl methacrylate carbonate mixed acid anhydride and the like and triethylamine, diisopropylethylamine, N, N-dimethylaniline, pyridine, 4-dimethylaminopyridine Etc. . An appropriate reaction temperature can be selected as the reaction temperature depending on the type of acylating agent used and the reaction conditions. In general, the reaction temperature is preferably from -50 ° C to the boiling point of the solvent, and more preferably from -20 ° C to room temperature. Although the usage-amount of an acylating agent is dependent on a structure, it is 1-40 mol with respect to 1 mol of diol compounds (4), Preferably it is the range of 1-5 mol.

  In the reaction using the acylating agent described here, the regioisomer (1 ′) is formed as a main product as a product at the initial stage of the reaction. However, if the reaction is continued for a long time, it is gradually isomerized to the target product (1). May happen. This phenomenon is caused by, for example, acylation of a hydroxyl group having higher acidity (easily deprotonated by a base) at the beginning of the reaction under basic conditions, and producing a positional isomer (1 ′ ′) as a kinetic product (Kinetic product). However, it can be considered that the target product (1) which is considered to be stable in the system as a thermodynamic product accumulates in a long-time reaction.

  The reaction with the carboxylic acid is a dehydration reaction from the corresponding carboxylic acid, that is, any one of acrylic acid, methacrylic acid, and α-trifluoromethylacrylic acid and the starting diol compound (4), and is carried out in the presence of an acid catalyst. Is common. Although the usage-amount of carboxylic acid is dependent on a structure, it is 1-40 mol with respect to 1 mol of diol compounds (4), Preferably it is the range of 1-5 mol. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid and nitric acid, and organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid. Are used alone or in combination. The usage-amount of an acid catalyst is 0.001-1 mol with respect to 1 mol of diol compounds (4), Preferably it is a catalyst amount of 0.01-0.05 mol. Examples of the solvent include the same solvents as mentioned in the reaction with the acylating agent. In general, the reaction temperature is preferably from −50 ° C. to the boiling point of the solvent. Using a solvent containing hydrocarbons such as hexane, heptane, benzene, toluene, xylene, cumene and the like, the reaction may be allowed to proceed while removing generated water out of the system by azeotropic distillation. In this case, water may be distilled off while refluxing at the boiling point of the solvent at normal pressure, but water may be distilled off at a temperature lower than the boiling point under reduced pressure.

  In the transesterification reaction, the corresponding carboxylic acid ester, that is, any one of acrylic acid ester, methacrylic acid ester, and α-trifluoromethyl acrylic acid ester is reacted with the starting diol compound (4) in the presence of a catalyst. This is done by removing the alcohol. As the carboxylic acid ester to be used, a primary alkyl ester is preferable, and methyl ester, ethyl ester, and n-propyl ester are particularly preferable from the viewpoints of price, easiness of progress of reaction, and the like. Although the usage-amount of carboxylic acid ester is dependent on a structure, it is 1-40 mol with respect to 1 mol of diol compounds (4), Preferably it is the range of 1-5 mol. Catalysts include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid and nitric acid, organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid, sodium methoxide, sodium ethoxy , Bases such as potassium t-butoxide, 4-dimethylaminopyridine, sodium cyanate, potassium cyanate, sodium acetate, potassium acetate, calcium acetate, tin acetate, aluminum acetate, aluminum acetoacetate, alumina, and other salts, aluminum trichloride , Aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride, Titanium tetrabromide, titanium (IV) methoxide Titanium (IV) ethoxide, titanium (IV) isopropoxide, Lewis acids such as titanium (IV) oxide can be mentioned, which may be used alone or in combination. The usage-amount of a catalyst is 0.001-20 mol with respect to 1 mol of diol compounds (4), Preferably it is the amount of a catalyst of 0.01-0.05 mol. The reaction can be carried out without a solvent (the carboxylic acid ester itself as a reaction reagent may be used as a solvent), and it is preferable because it does not require extra operations such as concentration and solvent recovery. It is also possible to use a solvent supplementarily for the purpose of preventing polymerization. In this case, hydrocarbons such as hexane, heptane, benzene, toluene, xylene, cumene, and ethers such as dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane are used alone or in combination. Is preferred. An appropriate reaction temperature can be selected as the reaction temperature depending on the type of carboxylic acid ester used and the reaction conditions, but it is usually carried out under heating, and a low-boiling point alcohol produced by the transesterification reaction, that is, methanol, ethanol, 1-propanol, etc. It is good to carry out the reaction in the vicinity of the boiling point and distill off the resulting alcohol. The alcohol may be distilled off at a temperature lower than the boiling point under reduced pressure.

  The reaction time of the above acylation reaction should be determined by monitoring the progress of the reaction (including not only the acylation reaction but also the isomerization reaction) by thin layer chromatography, gas chromatography, etc. in order to improve the yield. Is usually about 0.1 to 240 hours. After completion of the reaction, the target fluorine-containing ester compound (1) is obtained by aqueous work-up or post-treatment such as concentration.

  The desired product (1) can be purified by a conventional method such as recrystallization, chromatography, distillation, etc., if necessary. In addition, the target product and the positional isomer of the target product (1 ′) may be separated by these purification methods, but the mixture of (1) and (1 ′) remains as it is for the purpose of producing a resin. It can also be used. The isomer ratio of (1) and (1 ′) can take any value from 0 to 1, but the ratio of (1) having phenol-like acidity is 0.3 or more, more preferably It is good that it is 0.5 or more.

In addition, the reaction intermediate (4) and the target product (1) may have an asymmetric carbon as the carbon atom attached to them depending on the types of R ² , R ³ , and R ^4. Enantiomers and diastereomers may exist, but (4) and (1) represent all of these stereoisomers. These stereoisomers may be used alone or as a mixture.

As a second production method of the fluorine-containing ester compound of the present invention, a diol compound represented by the general formula (4) is prepared by reacting a keto alcohol compound represented by the following general formula (3) with a compound R ⁴ -Z. The diol compound is protected to obtain an alcohol compound (5), and the alcohol compound is acylated to obtain a protected fluorine-containing polymerizable ester compound represented by the general formula (6). The fluorine-containing polymerizable ester compound represented by the general formula (1) can be obtained by deprotecting the functional ester compound. This method can be preferably applied to the above-described first method, that is, when the regioselectivity is low in the direct acylation reaction of the diol compound (4).

（Ｒ¹〜Ｒ⁴、Ｚ（Ｒ⁴−Ｚ）は上記の通り。Ｒ⁶は保護基を示す。）

(R ^{1 to} R ⁴ and Z (R ⁴ —Z) are as described above. R ⁶ represents a protecting group.)

The above-mentioned first method can be applied to the step of reacting the keto alcohol compound (3) with the compound R ⁴ —Z to obtain the diol compound (4) represented by the general formula. In the step of acylating the protected alcohol compound (5) to obtain the protected fluorine-containing polymerizable ester compound represented by the general formula (6), the diol compound (4) of the first method is directly acylated. Thus, a method for obtaining the fluorine-containing polymerizable ester compound (1) can be applied. In this case, since the protected alcohol compound (5) has only one hydroxyl group to be acylated, the reaction can be accelerated by increasing the number of reaction reagents such as acylating agents, carboxylic acids and esters. it can.

As the protecting group R ⁶ , those similar to the acid labile group R ⁵ described above or other protecting groups can be used.
When the protecting group R ⁶ is an acid labile group R ⁵ , the protected fluorine-containing polymerizable ester compound represented by the general formula (6) is protected with the acid labile group represented by the general formula (2). The fluorine-containing polymerizable ester compound itself is a method for producing the fluorine-containing polymerizable ester compound (2) of the present invention.

  Other protective groups include formyl, benzoylformyl, acetyl, chloroacetyl, dichloroacetyl, trichloroacetyl, trifluoroacetyl, methoxyacetyl, triphenylmethoxyacetyl, phenoxyacetyl, phenylacetyl Group, nicotinyl group, 3-phenylpropionyl group, 4-pentenoyl group, 4-oxopentanoyl group, pivaloyl group, 1-adamantoyl group, crotonyl group, 4-methoxycrotonyl group, benzoyl group, 4-phenylbenzoyl group And an acyl group such as a mesitoyl group.

The reaction for protecting / deprotecting the hydroxyl group varies depending on the type of R ⁶ , but can be carried out according to a conventional method. For example, when protecting with an acyl group, a known ester production method can be used, and the reaction with the above-mentioned acylating agent, the reaction with a carboxylic acid, and the transesterification reaction can be carried out using the corresponding reaction reagent. Applicable. Examples of the deprotection of the acyl group include, but are not limited to, hydrolysis / solvolysis using an acid or base, elimination reaction under acidic conditions, and the like.

Reaction intermediates (4), (5), (6) and target products (1), (2) [when protecting group R ⁶ is acid-labile group R ⁵ in (6)] are optionally used It can be purified by conventional methods such as recrystallization, chromatography, distillation and the like. In addition, the reaction intermediates (4), (5), (6) and the target products (1), (2) are carbon atoms depending on the types of R ² , R ³ , R ⁴ , OR ^6. An atom may be an asymmetric carbon, and enantiomers and diastereoisomers may exist. However, the general formulas (1) and (2) represent all of these stereoisomers. Represented as a representative. These stereoisomers may be used alone or as a mixture.

  As a third production method of the fluorine-containing polymerizable ester compound of the present invention, the fluorine-containing polymerizable ester compound represented by the following general formula (1) is protected with an acid labile group and represented by the following general formula (2). The fluorine-containing polymerizable ester compound can be obtained.

（式中、Ｒ¹〜Ｒ⁵は上記の通り。）

(Wherein R ^{1 to} R ⁵ are as described above.)

  This method is a step of obtaining a target product (2) protected with an acid labile group by a protection reaction of the target product (1) with an acid labile group, and the kind of the acid labile group is the same as described above. Yes, the reaction can be carried out according to conventional methods. For example, when protecting with an acyl group, a known ester production method can be used, and the reaction with the above-mentioned acylating agent, the reaction with a carboxylic acid, and the transesterification reaction can be carried out using the corresponding reaction reagent. Applicable. In addition, when using an ether protecting group, reaction of halide under basic conditions, addition reaction to unsaturated compounds under acidic conditions, etc., when using silyl protecting group, reaction with chlorosilane under basic conditions However, the present invention is not limited to these.

The desired product (2) can be purified by a conventional method such as recrystallization, chromatography, distillation or the like, if necessary. In addition, the target product (2) may have an asymmetric carbon as a carbon atom depending on the types of R ² , R ³ , R ⁴ , and OR ⁵ , and it may be an enantiomer or diastereomer. Although stereoisomers can exist, general formula (2) represents all of these stereoisomers. These stereoisomers may be used alone or as a mixture.

  Using the fluorine-containing polymerizable ester compound of the present invention, a copolymer can be produced by copolymerizing a homopolymer or one or more other polymerizable monomers by a conventional method such as radical polymerization.

The polymer obtained using the fluorine-containing polymerizable ester compound of the present invention as a raw material is excellent in transparency to radiation having a wavelength of 500 nm or less, particularly 200 nm or less, and has a phenolic acidic hydroxyl group, and thus has good development characteristics. It is suitably used as a base resin for radiation resists. Examples of the radiation having a wavelength of 200 nm or less include ArF laser light (193 nm), F ₂ laser light (157 nm), Ar ₂ laser light (126 nm), extreme ultraviolet light (EUV: 13 nm), and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

[Example 1] Synthesis of 2- (2-hydroxy-2-methyl-1,1,3,3,3-pentafluoropropyl) -2-adamantyl methacrylate

[1-1] Synthesis of 2- (2-oxo-1,1,3,3,3-pentafluoropropyl) adamantan-2-ol equivalent 1,1,1,3,3,3 under nitrogen atmosphere -A mixture of 41.5 g of hexafluoro-2-propanol and 500 ml of tetrahydrofuran was cooled to -50 ° C while stirring. To this mixture, 2.46M of n-butyllithium-n-hexane solution and 200 ml were added dropwise, and the mixture was stirred at -70 ° C for 10 minutes and further at 5 ° C for 90 minutes. A solution prepared by dissolving 18.5 g of 2-adamantanone in 100 ml of tetrahydrofuran was added to the reaction mixture, and the mixture was stirred at 5 ° C. for 1 hour and further at room temperature for 18 hours. To the reaction mixture was added 400 ml of 10% hydrochloric acid, and the mixture was extracted with ethyl acetate. After the usual washing, drying and concentration post-treatment operations, 36.9 g of a mixture of about 89:11 oxetane hemiacetal compound and hydrate, which is an equivalent of the target ketoalcohol compound, was obtained as a crude product (quantitative). Yield).

Spiro [adamantane-2,2 ′-(3 ′, 3′-difluoro-4′-hydroxy-4′-trifluoromethyloxetane)] and 2- (2,2-dihydroxy-1,1,3,3, About 89:11 (molar ratio) mixture of 3-pentafluoropropyl) adamantan-2-ol

Colorless solid IR (KBr): ν = 3588, 3442, 2921, 2865, 1456, 1338, 1203, 1041, 912 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.46-2.41 (14H, m), 6.97 (0.11H, s, adamantyl-OH), 8.11 (2 × 0.11H, s, two hydroxyl groups of the hydrate), 9.44 (0.89H, s, oxetane-OH) ppm.
¹⁹ F-NMR (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = -125.6 (0.89F, dq, J = 208, 13 Hz), −122.5 (0.89F, d, J = 208Hz), -114.2 (2x0.11F, q, J = 13Hz), -81.7 (3x0.89F, d, J = 13Hz), -81.1 (3x0.11F, t, J = 13Hz) ppm.

[1-2] Synthesis of 2- (2-hydroxy-2-methyl-1,1,3,3,3-pentafluoropropyl) -adamantan-2-ol Ketoalcohol compound obtained in [1-1] above 30 g of the equivalent crude product was dissolved in 800 ml of benzene and refluxed while removing water produced by heating and stirring. This solution was added dropwise to 250 ml of 1.0M tetrahydrofuran solution of methylmagnesium chloride stirred at room temperature. The mixture was stirred at room temperature for 30 minutes and then heated to reflux for 1 hour. After cooling, 700 ml of 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. Ordinary washing, drying, and concentration post-treatment operations were performed to obtain a crude product. This was recrystallized from n-hexane to obtain 28.9 g (yield 92%) of the target diol compound.

2- (2-hydroxy-2-methyl-1,1,3,3,3-pentafluoropropyl) adamantan-2-ol colorless solid IR (KBr): ν = 3355, 3129, 2937, 2921, 2871, 1457 , 1292, 1213, 1174, 1074, 1039 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.39-1.46 (2H, t-like m), 1.55 (3H, br.s), 1.58-1.73 (5H M), 1.79 (1H, br.s), 2.12-2.20 (3H, m), 2.22-2.30 (2H, t-like m), 2.33 (1H, br.s), 5.34 (1H, s, OH), 6.77 (1H, s, OH) ppm.
¹³ C-NMR (150 MHz in CDCl ₃ ): δ = 19.73, 26.60, 27.11, 32.94, 33.21, 33.57, 34.01, 34.09, 34.25, 39 0.03, 77.51 (t-like, J = 24 Hz), 77.10-78.2 (m), 123.22 (dd-like, J = 260, 267 Hz), 125.60 (q, J = 289 Hz) ppm.
¹⁹ F-NMR (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = −110.5 (1F, d-like, J = 262 Hz), −107.8 (1F, dq, J = 262, 15 Hz), −77.0 (3F, t, J = 15 Hz) ppm.

[1-3] Synthesis of 2- (2-hydroxy-2-methyl-1,1,3,3,3-pentafluoropropyl) -2-adamantyl methacrylate 20 g of the diol compound obtained in the above [1-2] 14 ml of triethylamine was added dropwise to a mixture of 7.4 ml of methacryloyl chloride and 500 ml of methylene chloride at 5 ° C. with stirring. The reaction mixture was stirred at 0 ° C. for 30 minutes and then at room temperature for 48 hours. When the reaction was followed by gas chromatography, the ratio of regioisomers was large at the beginning of the reaction (after 4 hours, target product: regioisomer = 24: 76), but isomerization to the target product was gradually observed. After 48 hours, the target almost converged. 100 ml of water was added to the reaction mixture, and the mixture was stirred at room temperature for 2 hours and extracted with diethyl ether. Ordinary washing, drying, and concentration post-treatment operations were performed to obtain a crude product. This was recrystallized from n-hexane to obtain 20.7 g (yield 85%) of the target fluorine-containing ester compound.

2- (2-Hydroxy-2-methyl-1,1,3,3,3-pentafluoropropyl) methacrylate methacrylate colorless solid GC-MS (EI): (m / z) ⁺ = 41, 69 141, 183, 207, 296, 382 (M ⁺ ).
GC-MS (CI, ^{isobutane) :( m / z) + =} 277,297,383 [(M + H) +].
IR (KBr): ν = 3494, 2981, 2954, 2927, 2892, 2869, 1710, 1463, 1326, 1286, 1214, 1187, 1170, 1095, 1079, 1045 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.50-1.88 (11H, m), 1.91 (3H, s), 2.02-2.32 (4H, m), 2 .69 (1H, br.s), 3.41 (1H, br.s), 5.71 (1H, br.s), 6.04 (1H, br.s), 7.08 (1H, s) ) Ppm.
¹⁹ F-NMR (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = −107.6 (1F, dd, J = 277, 1790 Hz), −101.0 (1F, dd-like, J = 277, 513 Hz) ), -76.5 (3F, d, J = 275 Hz) ppm.

[Comparative Example 1] Direct esterification of ketoalcohol compound equivalent-of spiro methacrylate [adamantane-2,2 '-(3', 3'-difluoro-4'-trifluoromethyloxetane)]-4'-yl Composition

  Instead of the diol compound obtained in [1-2] of Example [1-3] above, 5.0 g of the crude product of the keto alcohol compound equivalent obtained in [1-1] above was used. 1-3] When the esterification (methacryloylation) reaction was carried out in the same manner as in 1-3], the product obtained was only 5.5 g (yield 95%) of the ester compound of the title oxetane compound. A product ester compound was not obtained. It is thought that the reaction proceeded while the equilibrium moved to the oxetane compound side.

Spiro methacrylate [adamantane-2,2 ′-(3 ′, 3′-difluoro-4′-trifluoromethyloxetane)]-4′-yl colorless liquid IR (KBr): ν = 2937, 2863, 1758, 1456 1334, 1305, 1214, 1126, 1097, 1037968 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.60-1.98 (15H, m), 2.30-2.33 (2H, m), 5.97 (1H, t, J = 1 Hz), 6.19 (br.s) ppm.
¹³ C-NMR (150 MHz in DMSO-d6): δ = 18.11, 25.54, 26.08, 31.66, 31.76, 31.87, 33.39 (d-like, J = 4 Hz), 34.78, 35.00, 35.89, 99.86 (t, J = 22 Hz), 101.5-103.5 (m), 116.65 (dd, J = 282, 296 Hz), 120.13 (Q, J = 287 Hz), 130.21, 134.64, 162.22 ppm.
¹⁹ F-NMR (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = 123.36 (1F, dq, J = 208, 13 Hz), −116.70 (1F, d, J = 208 Hz), − 76.36 (3F, d, J = 13 Hz) ppm.

[Example 2] Synthesis of 1- (2-hydroxy-1,1,3,3,3-pentafluoropropyl) 1-cyclohexyl methacrylate

[2-1] Synthesis of 1- (2-oxo-1,1,3,3,3-pentafluoropropyl) cyclohexane-1-ol equivalent In place of 2-adamantanone of Example [1-1] Using 294 g of cyclohexanone, a reaction is carried out in the same manner as in Example [1-1] to obtain a crude product, which is recrystallized from n-hexane and is an equivalent of the target keto alcohol compound. 565 g of hydrate (yield 71%) was obtained.

1- (2,2-dihydroxy-1,1,3,3,3-pentafluoropropyl) cyclohexane-1-ol colorless solid IR (KBr): ν = 3505, 3353, 2954, 2865, 1452, 1307, 1205 1103, 1076, 1062, 979 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.12-1.20 (1H, m), 1.50-1.64 (7H, m), 1.97-2.05 (2H, m), 6.39 (1H, br.s, OH), 7.93 (2H, br.s, 2OH) ppm.
¹³ C-NMR (150 MHz in DMSO-d6): δ = 21.67, 26.26, 31.29, 77.32 (t, J = 25 Hz), 95.40 (hex, J = 30 Hz), 118. 84 (t, J = 262 Hz), 123.63 (q, 292 Hz) ppm.
¹⁹ F-NMR (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = -123.8 (2F, q, J = 13 Hz), −81.1 (3F, t, J = 13 Hz) ppm.

[2-2] Synthesis of 1- (2-hydroxy-2-methyl-1,1,3,3,3-pentafluoropropyl) cyclohexane-1-ol [1-1] of Example [1-2] Using the ketoalcohol compound equivalent 272g obtained in [2-1] instead of the ketoalcohol compound equivalent obtained in the above, the reaction was carried out in the same manner as in Example [1-2] to obtain a crude product. This was recrystallized from n-hexane to obtain 217 g (yield 80%) of the target diol compound.

1- (2-hydroxy-2-methyl-1,1,3,3,3-pentafluoropropyl) cyclohexane-1-ol colorless solid IR (KBr): ν = 3448, 3195, 2968, 2954, 2945, 2873 2861, 1303, 1176, 1087, 1054, 985 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.08-1.18 (1H, m), 1.45-1.63 (10H, m), 1.81 (1H, d-like, J = 12 Hz), 2.02 (1H, d-like, J = 13 Hz), 5.16 (1H, br.s, OH), 6.69 (1H, s, OH) ppm.
¹³ C-NMR (150 MHz in DMSO-d6): δ = 20.15, 21.83, 21.95, 26.51, 31.33, 32.25, 76.42 (t, J = 25 Hz), 77 .67 (hex-like, J = 26 Hz), 122.31 (dd, J = 258, 263 Hz), 126.52 (q, J = 290 Hz) ppm.
¹⁹ F-NMR (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = -120.5 (1F, dq, J = 262, 13 Hz), -118.3 (1F, dq, J = 262, 15 Hz) -77.3 (3F, t-like, J = 14 Hz) ppm.

[2-3] Synthesis of 1- (2-hydroxy-2-methyl-1,1,3,3,3-pentafluoropropyl) -1-cyclohexyl methacrylate [1-2] of Example [1-3] Using the diol compound obtained in [2-2] instead of the diol compound obtained in [2-2], the reaction was carried out in the same manner as in Example [1-3] to obtain a crude product. In this case, the stirring time at room temperature was 18 hours, and there was almost no regioisomer, and the target product was obtained. The obtained crude product was recrystallized from n-hexane to obtain 154 g (yield 85%) of the target fluorine-containing ester compound.

Methacrylic acid 1- (2-hydroxy-2-methyl-1,1,3,3,3-pentafluoropropyl) -1-cyclohexyl colorless solid GC-MS (EI): (m / z) ⁺ = 41, 69 87, 111, 131, 224, 330 (M ⁺ ).
IR (KBr): ν = 3390, 3025, 3000, 2942, 2873, 1706, 1463, 1328, 1164, 1128, 1062 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.3-1.30 (2H, m), 1.32-1.41 (1H, m), 1.51 (3H, s), 1 .57-1.70 (5H, m), 1.92 (3H, s), 2.70-2.75 (1H, m), 2.78-2.83 (1H, m), 5.74 (1H, quint-like, J = 1 Hz), 6.08 (1H, q-like, J = 0.7 Hz), 7.09 (1H, s) ppm.
¹³ C-NMR (150 MHz in DMSO-d6): δ = 19.46, 19.67, 22.30, 22.38, 25.67, 29.79, 31.41, 77.80 (hex, J = 27 Hz), 86.79 (t, J = 27 Hz), 121.23 (t, J = 262 Hz), 126.15 (q, J = 289 Hz), 127.36, 138.16, 165.71 ppm.
¹⁹ F-NMR (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = −112.8 to −112.9 (2F, m), −77.1 (t, J = 14 Hz) ppm.

Example 3 Synthesis of 1- (1,1,3,3,3-pentafluoro-2-trimethylsilyloxypropyl) 1-cyclohexyl methacrylate

  While stirring at room temperature under a nitrogen atmosphere, 38.3 ml of trimethylsilyl chloride was dissolved in a solution of 50.0 g of the fluorinated ester compound obtained in Example [2-3] and 41.2 g of imidazole in 300 g of N, N-dimethylformamide. Was dripped. After stirring at room temperature for 16 hours, 500 ml of water was added to the reaction mixture, and the mixture was extracted with diethyl ether. Ordinary washing, drying, and concentration post-treatment operations were performed to obtain 59.0 g (yield 97%) of a fluorine-containing ester compound in which the target hydroxyl group was protected.

Methacrylic acid 1- (1,1,3,3,3-pentafluoro-2-trimethylsilyloxypropyl) 1-cyclohexyl colorless liquid IR (NaCl): ν = 2944, 2865, 1735, 1454, 1257, 1195, 1184, 1159, 1147, 1132, 1058, 981 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 0.17 (9H, s), 1.18-1.36 (3H, m), 1.50-1.64 (8H, m), 3 .23 (3H, s), 2.61 (1H, d-like, J = 12 Hz), 2.79 (1H, d-like, J = 13 Hz), 5.69 (1H, t, J = 1.4 Hz) 6.03 (1H, s) ppm.
¹³ C-NMR (150 MHz in DMSO-d6): δ = 1.58, 18.10 (2C), 20.82, 20.91, 24.08, 28.72, 29.44, 79.50 (hex , J = 29 Hz), 84.91 (t, J = 27 Hz), 119.09 (t, J = 263 Hz), 123.95 (q, J = 286 Hz) 125.93, 136.59, 164.13 ppm.
¹⁹ F-NMR (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = −111.93 (1F, dq, J = 273, 11 Hz), −11.35 (1F, dq, J = 273, 11 Hz) , −76.30 (3F, t, J = 11 Hz) ppm.

Example 4 Synthesis of 1- (2-methoxymethoxy-1,1,3,3,3-pentafluoropropyl) 1-cyclohexyl methacrylate

  To a solution of 5.0 g of the fluorinated ester compound obtained in Example [2-3] above, 0.1 g of sodium iodide and 12.6 ml of diisopropylethylamine in 30 g of acetonitrile while stirring at room temperature under a nitrogen atmosphere, 4.6 ml of methyl methyl ether was added dropwise. The reaction mixture was gradually heated and stirred at 70 ° C. for 16 hours. After cooling, 500 ml of water was added to the reaction mixture and extracted with diethyl ether. Ordinary washing, drying, and concentration post-treatment operations were performed, and the product was further purified by silica gel column chromatography to obtain 4.6 g (yield 81%) of the target fluorine-containing ester compound having a protected hydroxyl group.

Methacrylic acid 1- (2-methoxymethoxy-1,1,3,3,3-pentafluoropropyl) 1-cyclohexyl colorless liquid GC-MS (EI): (m / z) ⁺ = 45, 69, 101, 131 167, 256, 284, 313, 344.
GC-MS (CI, isobutane): (m / z) ⁺ = 101, 131, 267, 375 [(M + 1) ⁺ ].
IR (NaCl): ν = 2996, 2940, 2865, 1733, 1454, 1321, 1299, 1911, 1160, 1143, 1070 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.3-1.37 (3H, m), 1.56-1.70 (8H, m), 1.92 (3H, t, J = 1.2 Hz), 2.75 (2H, br.d, J = 13 Hz), 3.35 (3H, s), 4.80 (1H, d, J = 7 Hz), 4.97 (1H, d, J = 7 Hz), 5.75 (1H, t, J = 1.7 Hz), 6.09 (1H, q, J = 1.0 Hz) ppm.
¹³ C-NMR (150 MHz in DMSO-d6): δ = 14.34, 19.59, 22.25, 22.40, 25.59, 30.46, 57.25, 82.68 (q-like, J = 27 Hz), 86.45 (t, J = 27 Hz), 93.84, 116.58 (d, J = 167 Hz), 120.87 (t, J-263 Hz), 125.40 (q, J = 288 Hz) ), 127.51, 138.05, 165.72 ppm.
¹⁹ F-NMR (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = −110.40 (2F, q, J = 11 Hz), −75.36 (3F, t, J = 11 Hz) ppm.

Example 5 Synthesis of 1- (2-hydroxy-1,1,3,3,3-pentafluoropropyl) -1-cyclohexyl methacrylate

[5-1] Synthesis of 1- (2hydroxy-1,1,3,3,3-pentafluoropropyl) cyclohexane-1-ol Hydrate of keto alcohol compound equivalent obtained in [2-1] above 24.1 g was dissolved in 200 ml of benzene and refluxed while removing water produced by heating and stirring. This solution was added dropwise to a suspension in which 9.0 g of lithium aluminum hydride stirred at 5 ° C. in a nitrogen atmosphere was suspended in 200 ml of tetrahydrofuran. The mixture was stirred at room temperature for 30 minutes and then heated to reflux for 4 hours. After cooling, 50 ml of acetone and then 250 ml of 20% hydrochloric acid were added to the reaction mixture and extracted with diethyl ether. Ordinary washing, drying, and concentration post-treatment operations were performed to obtain a crude product. This was recrystallized from n-hexane to obtain 15.0 g (yield 66%) of the target diol compound.

1- (2hydroxy-1,1,3,3,3-pentafluoropropyl) cyclohexane-1-ol colorless solid GC-MS (EI): (m / z) ⁺ = 43, 55, 81, 99.
IR (KBr): ν = 3490, 3394, 3172, 2950, 2873, 1378, 1286, 1182, 1122, 1093 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.10-1.19 (1H, m), 1.37 (1H, dt-like, J = 3.5, 13 Hz), 1.45-1 .64 (6H, m), 1.73 (1H, d-like, J = 13 Hz), 1.82 (1H, dd-like, J = 2.0, 13 Hz), 4.63-4.72 (1H, m), 5.30 (1H, s, OH), 7.01 (1H, d, J = 8.2 Hz, OH) ppm.
¹³ C-NMR (150 MHz in DMSO-d6): δ = 21.74, 21.89, 26.45, 29.85 (d, J = 5.8 Hz), 31.69 (d, J = 2.9 Hz) ), 67.0-68.2 (m), 74.16 (t, J = 24 Hz), 121.93 (dd, J = 251, 264 Hz), 125.67 (q, J = 285 Hz) ppm.
¹⁹ F-NMR (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = 127.87 (1F, dd, J = 17, 258 Hz), −123.52 (1F, dq, J = 17, 255 Hz) -73.52 (3F, dt, J = 17, 7 Hz) ppm.

[5-2] Synthesis of 1- (2-hydroxy-1,1,3,3,3-pentafluoropropyl) -1-methacrylic acid obtained in [1-2] of Example [1-3] Using 10 g of the diol compound obtained in [5-1] instead of the diol compound, the reaction was carried out in the same manner as in Example [1-3] to obtain a crude product. A mixture of the desired product: regioisomer = 5: 95 was obtained after stirring for 120 hours at room temperature. The obtained crude product was separated by silica gel chromatography to obtain 550 mg (yield 4%) of the target fluorinated ester compound and 8.0 g (yield 63%) of its positional isomer.

Methacrylic acid 1- (2-hydroxy-1,1,3,3,3-pentafluoropropyl) -1-cyclohexyl (target product)
Colorless viscous liquid GC-MS (EI): (m / z) ⁺ = 41, 69, 87, 131, 210.
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.32-1.43 (2H, m), 1.45-1.71 (6H, m), 1.93 (3H, s), 2 .54-2.65 (2H, m), 4.66 (1H, dq, J = 29, 8 Hz), 5.73 (1H, t, J = 1.5 Hz), 6.10 (1H, q, J = 1, 1.7 Hz), 7.32 (1H, d, J = 8 Hz, OH) ppm.
¹³ C-NMR (150 MHz in DMSO-d6): δ = 19.63, 22.33, 22.68, 25.66, 29.57, 30.36, 68.40-69.40 (m), 85 .68 (t, J = 25 Hz), 120.44 (dd, J = 254, 263 Hz), 125.24 (q, J = 285 Hz), 127.45, 138.04, 166.26 ppm.
¹⁹ F-NMR (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = −122.40 (1F, ddq-like, J = 264, 22, 9 Hz), −115.72 (1F, dq-like, J = 264, 17 Hz), −73.57 (3F, dt-like, J = 17, 9 Hz) ppm.

3- (1-hydroxycyclohexyl) methacrylate-1,1,1,3,3-pentafluoro-2-propyl (positional isomer)
Colorless viscous liquid GC-MS (EI): (m / z) ^<+> = 41, 69, 81, 99, 316 (M +).
IR (NaCl): ν = 3531, 2940, 2865, 1745, 1637, 1454, 1382, 1336, 1280, 1189, 1139, 1052 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.08-1.17 (1H, m), 1.35-1.41 (2H, m), 1.41-1.64 (6H, m) 1.73-1.78 (1H, m), 1.97 (3H, dd, J = 1.0, 1.4 Hz), 5.63 (1H, s), 5.97 (1H, quint-like, J = 1.4 Hz), 6.05-6.12 (1H, m), 6.23 (1H, t-like, J = 1.0 Hz) ppm.
¹³ C-NMR (150 MHz in DMSO-d6): δ = 19.10, 21.55, 21.67, 26.14, 29.83 (d, J = 4.3 Hz), 30.68, 65.9 -67.0 (m), 74.07 (t, J = 24 Hz), 121.04 (dd, J = 251, 265 Hz), 123.77 (q, J = 283 Hz) 130.90, 135.32, 165.35 ppm.
¹⁹ F-NMR (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = −123.86 (1F, dd-like, J = 13, 264 Hz), −121.25 (1F, dq-like, J = 264, 17 Hz), −72.11 (3F, dt-like, J = 17, 6.5 Hz) ppm.

Example 6 Synthesis of 1- (2-hydroxy-1,1,3,3,3-pentafluoropropyl) -1-cyclohexyl methacrylate (an example of using a protecting group)

[6-1] Synthesis of 1- (1,1,3,3,3-pentafluoro-2-trimethylsilyloxypropyl) -1-methacrylic acid Example [5] while stirring at 5 ° C. in a nitrogen atmosphere. -1], 1.03 ml of chlorotrimethylmethylsilane was added dropwise to a mixed solution of 2.0 g of the diol compound obtained in 1), 20 ml of triethylamine, 20 ml of methylene chloride, and 5 ml of tetrahydrofuran. The reaction mixture was raised to room temperature and stirred for 1 hour. Next, 650 μl of methacryloyl chloride was added, heated and stirred at 70 ° C. for 30 hours. After cooling, 80 ml of water was added to the reaction mixture and extracted with methylene chloride. Ordinary washing, drying, and concentration post-treatment operations were performed to obtain a crude product. This was used in the next step without purification.

Methacrylic acid 1- (1,1,3,3,3-pentafluoro-2-trimethylsilyloxypropyl) -1-cyclohexyl GC-MS (EI): (m / z) ⁺ = 41, 69, 87, 131, 193, 213, 282, 388 (M ⁺ ).
[6-2] Synthesis of 1- (2-hydroxy-1,1,3,3,3-pentafluoropropyl) -1-cyclohexyl methacrylate A solution obtained by dissolving the crude product of [6-1] in 6 ml of tetrahydrofuran Was added with 10 ml of 1.0 M tetra-n-butylammonium fluoride-tetrahydrofuran solution and stirred at room temperature for 18 hours. 80 ml of 15% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. Ordinary washing, drying, and concentration post-treatment operations were performed to obtain a crude product. The crude product was a mixture of target product: regioisomer = 85: 15. These were separated by silica gel chromatography to obtain 1.7 g (yield 67%) of the target fluorine-containing ester compound and 0.2 g (yield 8%) of the positional isomer thereof. These spectroscopic properties (spectrums) were consistent with those described in [Example 5].

Example 7 Synthesis of 3-hydroxy-2,2,4,4,4-pentafluoro-1-phenylbutyl methacrylate

[7-1] Synthesis of 3-oxo-2,2,4,4,4-pentafluoro-1-phenyl-1-butanol equivalent 30 g of benzaldehyde instead of 2-adamantanone of Example [1-1] To obtain a crude product, which is recrystallized from n-hexane to give a hydrate which is an equivalent of the target keto alcohol compound. 62.3 g (yield 79%) was obtained.
3,3-dihydroxy-2,2,4,4,4-pentafluoro-1-phenyl-1-butanol colorless solid IR (KBr): ν = 3532, 1492, 1456, 1288, 1251, 1207, 1164, 1099 1074, 1066, cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 5.26 (d, J = 22 Hz), 6.98 (1H, br.d, J = 3 Hz, OH), 7.33-7.45 ( 6H, m), 8.18 (1H, d, J = 2 Hz) ppm.
¹⁹ F-NMR (283 MHz in DMSO-d6, trifluoroacetic acid standard): δ = −128.95 (1F, ddq, J = 260, 22, 10 Hz), −177.03 (1F, ddq, J = 260, 10, 3 Hz), −80.31 (3F, t, J = 10 Hz) ppm.

[7-2] Synthesis of 3-hydroxy-2,2,4,4,4-pentafluoro-1-phenyl-1-butanol Ketoalcohol compound obtained in [2-1] of Example [5-1] Using the keto alcohol compound equivalent hydrate 30g obtained in [7-1] instead of the equivalent hydrate, the reaction was carried out in the same manner as in Example [5-1] to obtain a crude product. This was distilled under reduced pressure to obtain 25 g (yield 89%) of the desired diol compound.
3-hydroxy-2,2,4,4,4-pentafluoro-1-phenyl-1-butanol (43:57 diastereomeric mixture)
Pale yellow viscous liquid Boiling point: 115 ° C / 53Pa
IR (NaCl): ν = 3372, 2940, 1456, 1373, 1276, 1224, 1174, 1137, 1112, 1060, 1031 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 4.22-4.32 (0.43H, m), 4.69 (0.57H, dq, J = 30, 7 Hz), 4.99 ( 0.43H, dt, J = 5, 13 Hz), 5.04 (0.57H, dd, J = 4, 24 Hz), 6.43 (0.43H, d, J = 5 Hz, OH), 6.49 (0.57H, d, J = 4 Hz, OH), 7.30-7.56 (6H, m) ppm.
¹³ C-NMR (150 MHz in DMSO-d6): δ = 67.5-68.5 (m, major), 68.6-69.3 (m, minor), 71.35 (dd, J = 20, 32 Hz, major), 72.94 (t, J = 25 Hz, minor), 120.92 (dd, J = 251, 256 Hz, minor), 121.48 (t, J = 254 Hz, major), 125.12 ( q, J = 285 Hz, minor), 125.66 (q, J = 283 Hz, major), 129.31 (major + minor), 129.46 (major), 129.50 (minor), 129.70 (minor), 129.80 (major), 138.48 (major), 138.86 (minor) ppm.
¹⁹ F-NMR (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = −126.51 (0.57F, dhex-like, J = 258, 14 Hz), −122.72 (0.43F, dhex-like, J = 256, 9 Hz), −122.64 (0.57 F, dhex-like, J = 256, 9 Hz), −122.02 (0.43 F, dhex-like, J = 256, 11 Hz), −73.70 ( 0.43 × 3F, dt-like, J = 7, 15 Hz), −73.28 (0.57 × 3F, dt-like, J = 7, 15 Hz) ppm.

[7-3] Synthesis of 3-hydroxy-2,2,4,4,4-pentafluoro-1-phenylbutyl methacrylate In place of the diol compound obtained in [1-2] of Example [1-3] Using 11.1 g of the diol compound obtained in [7-2], a reaction was carried out in the same manner as in Example [1-3] to obtain a crude product. When the reaction was followed by gas chromatography, the ratio of regioisomers was large at the beginning of the reaction (target product: regioisomer = 23: 77 immediately after dropping), but isomerization to the target product was gradually observed, After 24 hours, the target almost converged. The crude product was purified by silica gel chromatography to obtain 7.5 g (yield 53%) of the desired fluorine-containing ester compound.

3-hydroxy-2,2,4,4,4-pentafluoro-1-phenylbutyl methacrylate (40:60 diastereomeric mixture)
Pale yellow viscous liquid IR (NaCl): ν = 3434, 2985, 1731, 1378, 1280, 1151 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.96 (0.4 × 3H, s), 1.98 (0.6 × 3H, s), 4.23-4.33 (0.4H, m) 4.62-4.73 (0.6H, m), 5.85-5.88 (0.4H + 0.6H, m), 6.12 (0.6H, d, J = 3 Hz, OH), 6.15 (0.4H, d, J = 3 Hz, OH), 6.25 (0.4H, t, J = 1.0 Hz), 6.26-6.32 (0.4H + 0.6 × 2H, m) , 7.20-7.78 (0.4x5H + 0.6x5H, m) ppm.
¹⁹ F-NMR (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = −122.50 (0.4 F, ddq-like, J = 260, 26, 10 Hz), −121.60 (0.6 F, dhex) , J = 262, 10 Hz), −120.20 (0.6 F, dhex-like, J = 262, 10 Hz), −118.65 (0.4 F, dquint-like, J = 26, 10 Hz), −73. 82 (0.4F, q-like, J = 10 Hz), −73.56 (0.6F, quint-like, J = 7 Hz) ppm.

[Example 8] Synthesis of 1- (1,1,3,3,3-pentafluoro-2-trimethylsilyloxypropyl) -1-cyclohexyl acrylate

  The reaction was carried out in the same manner as in Example [6-1] using acryloyl chloride instead of methacryloyl chloride in Example [6-1], and 2.0 g of the diol compound obtained in Example [5-1]. From 1.5 g (yield 50%) of the fluorine-containing ester compound in which the target hydroxyl group was protected.

Acrylic acid 1- (1,1,3,3,3-pentafluoro-2-trimethylsilyloxypropyl) -1-cyclohexyl GC-MS (EI): (m / z) ⁺ = 55, 77, 131, 153, 193, 213, 267, 359.

[Example 9] Synthesis of 1- (2-hydroxy-1,1,3,3,3-pentafluoropropyl) -1-cyclohexyl acrylate

  In the same manner as in Example [6-2], the hydroxyl group-protected fluorine-containing ester compound obtained in Example 8 was used instead of the crude product of [6-1] in Example [6-2]. Reaction was carried out by the method to obtain the desired fluorine-containing ester compound.

Acrylic acid 1- (2-hydroxy-1,1,3,3,3-pentafluoropropyl) -1-cyclohexyl GC-MS (EI): (m / z) ⁺ = 55, 73, 131, 153, 192 210.
GC-MS (CI, isobutane): (m / z) ⁺ = 73, 173, 193, 211, 265, 303 [(M + H) ⁺ ].

Example 10 Synthesis of 1- (2-hydroxy-2-methyl-1,1,3,3,3-pentafluoropropyl) 1-cyclohexyl α-trifluoromethyl acrylate

  Instead of the diol compound obtained in [1-2] of Example [1-3] above, the diol compound obtained in [2-2] was replaced with α-trifluoromethylacryloyl chloride instead of methacryloyl chloride. The desired product was obtained.

α-trifluoromethylacrylic acid 1- (2-hydroxy-2-methyl-1,1,3,3,3-pentafluoropropyl) 1-cyclohexyl GC-MS (EI): (m / z) ⁺ = 81 , 123, 131, 221, 364 [(M-HF) ⁺ ].
GC-MS (CI, isobutane): (m / z) ⁺ = 141, 207, 225, 245, 385 [(M + H) ⁺ ].

Example 11 Synthesis of 1-ethyl-3-hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate

[11-1] Synthesis of 2-oxo-1,1,1,3,3-pentafluoro-4-hexanol equivalents [Example 1-1] except that propionaldehyde was used instead of 2-adamantanone. The crude product was obtained as a solid. The obtained crude product was washed with hexane, dried under reduced pressure, and hydrate, ie, 1,1,1,3,3-pentafluoro-2,2,4, which is an equivalent of the target ketoalcohol compound. -Hexanetriol was obtained as a colorless solid (yield 65%). The physical properties of this product were in good agreement with the literature (Nakai et al., Organic Synthesis, Vol. 76, pp. 151, (1998)).

[11-2] Synthesis of 1,1,1,3,3-pentafluoro-2,4-hexanediol A mixture of 100 g of the triol compound obtained in the above [11-1], 400 g of tetrahydrofuran and 200 g of water at 5 ° C. The mixture was stirred, and a mixture of 17 g of sodium borohydride and 200 g of water was added dropwise thereto over 1 hour. The temperature was gradually raised to room temperature and stirred for 16 hours. After stopping the reaction by adding 100 g of 20% hydrochloric acid, ordinary post-treatment operations such as washing, drying and concentration were performed to obtain a crude product. This was distilled under reduced pressure to obtain 86 g (yield 93%) of 1,1,1,3,3-pentafluoro-2,4-hexanediol as a colorless solid.

1,1,1,3,3-pentafluoro-2,4-hexanediol (mixture of two diastereomers)
Boiling point: 82 ° C / 600Pa
Colorless solid at room temperature IR (KBr): ν = 3403 (br.), 2985, 2954, 2890, 1465, 1446, 1382, 1371, 1280, 1232, 1176, 1153, 1110, 1058, 1024, 989, 848, 840 , 829, 690, 680 cm ⁻¹ .
¹ H-NMR of main isomer (600 MHz in DMSO-d6): δ = 0.93 (3H, t, J = 7.6 Hz), 1.42 (1H, m), 1.60 (1H, m) 3.72 (1H, m), 4.50 (1H, m), 5.57 (1H, d, J = 6.5 Hz), 7.13 (1H, d, J = 7.9 Hz) ppm.

[11-3] Synthesis of 1-ethyl-3-hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate Instead of the diol compound obtained in Example [1-2], [11- Synthesis was performed in the same manner as in Example [1-3] except that the diol compound obtained in 2] was used. The resulting crude product was purified by silica gel column chromatography to obtain the target fluorinated ester compound (yield 85%).

1-ethyl-3-hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate (mixture of two diastereomers)
Colorless liquid GC-MS (EI): (m / z) ^<+> = 41, 69, 87, 170, 276 (M ^<+> ).
GC-MS (CI, methane): (m / z) ⁺ = 87, 115, 171, 237, 257, 277 [(M + H) ⁺ ].

[Example 12] Synthesis of 1-cyclohexyl-3-hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate

[12-1] Synthesis of 1-cyclohexyl-2-oxo-2,2,4,4,4-pentafluoro-1-butanol equivalent Synthesis was performed in the same manner as in Example [1-1] to obtain a hydrate (yield: 72%) which is an equivalent of the target keto alcohol compound.

1-cyclohexyl-2,2,4,4,4-pentafluorobutane-1,3,3-triol colorless solid IR (KBr): ν = 3558, 3334 (br.), 3093, 2942, 2859, 1454, 1373, 1303, 1216, 1207, 1164, 1116, 1099, 1074, 1068, 1043, 993, 887, 871, 796, 734 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.02-1.32 (5H, m), 1.53 (1H, m), 1.58 (1H, m), 1.69 (2H) , M), 1.77 (2H, m), 3.88 (1H, m), 5.83 (1H, d, J = 6.5 Hz), 7.50 (1H, s), 7.90 ( 1H, d, J = 1.0 Hz) ppm.

[12-2] Synthesis of 1-cyclohexyl-2,2,4,4,4-pentafluorobutane-1,3-diol In place of the triol compound obtained in Example [11-1], the above example was used. Synthesis was performed in the same manner as in Example [11-2] except that the triol compound obtained in [12-1] was used to obtain the target diol compound (quantitative yield).

1-cyclohexyl-2,2,4,4,4-pentafluorobutane-1,3-diol (mixture of two diastereomers)
Colorless solid IR (KBr): ν = 3394 (br.), 3257 (br.), 2931, 2859, 1456, 1417, 1378, 1359, 1268, 1224, 1193, 1184, 1151, 1118, 1091, 1056, 1025 998, 948, 881, 869, 831, 705, 682 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6) of major isomers: δ = 1.00-1.30 (5H, m), 1.55-1.80 (6H, m), 3.54 (1H, ddt, J = 6.9, 2.4, 9.7 Hz), 4.49 (1H, m), 5.48 (1H, d, J = 6.9 Hz), 7.14 (1H, d, J = 7.9 Hz) ppm.

[12-3] Synthesis of 1-cyclohexyl-3-hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate Instead of the diol compound obtained in the above Example [1-2], [12 -2] was synthesized in the same manner as in Example [1-3] except that the diol compound obtained in [-2] was used. The obtained crude product was purified by silica gel column chromatography to obtain the target fluorinated ester compound (yield 75%).

1-cyclohexyl-3-hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate (mixture of two diastereomers)
Colorless liquid IR (NaCl): ν = 3446 (br.), 2933, 2858, 1710, 1637, 1454, 1380, 1351, 1278, 1226, 1170, 1112, 1027, 950, 827, 686 cm ⁻¹ .
¹ H-NMR of main isomer (600 MHz in DMSO-d6): δ = 0.95-1.30 (5H, m), 1.58 (2H, m), 1.67 (2H, m), 1 .79 (1H, m), 1.90-2.00 (4H, m), 4.70 (1H, m), 5.27 (1H, ddd, J = 19.9, 8.3, 2. 8 Hz), 5.77 (1 H, m), 6.11 (1 H, m), 7.55 (1 H, d, J = 7.6 Hz) ppm.
¹³ C-NMR (150 MHz in DMSO-d6): δ = 17.84, 17.93, 25.30, 25.45, 25.55, 25.67, 25.91, 25.93, 27.10, 30.14, 36.49, 36.51, 36.63, 67.23 (m), 67.89 (m), 72.58 (dd, J = 32, 22 Hz), 73.57 (t, J = 21 Hz), 119.84 (t, J = 255 Hz), 120.38 (t, J = 254 Hz), 123.53 (q, J = 284 Hz), 123.70 (q, J = 284 Hz), 126. 81, 135.18, 135.21, 165.10, 165.59 ppm.
¹⁹ F-NMR (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = −120.97 (0.35 F, dm, J = 262 Hz), −117.97 (0.35 F, dm, J = 262 Hz) , −117.35 (0.65 F, dm, J = 259 Hz), −115.28 (0.65 F, dm, J = 259 Hz), −73.70 (1.95 F, m), 73.54 (1 .05F, m) ppm.

Example 13 Synthesis of 1- (2-adamantyl) -3-hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate

[13-1] Synthesis of 1- (2-adamantyl) -3-oxo-2,2,4,4,4-pentafluoro-1-butanol equivalent 2-adamantanecarbaldehyde instead of 2-adamantanone The synthesis was carried out in the same manner as in Example [1-1] except that it was used to obtain a hydrate (yield: 73%) of the target keto alcohol compound equivalent.

1- (2-adamantyl) -2,2,4,4,4-pentafluorobutane-1,3,3-triol colorless solid IR (KBr): ν = 3563, 3450 (br.), 3384 (br. ), 2917, 2854, 1456, 1380, 1276, 1230, 1213, 1199, 1182, 1139, 1091, 1054, 1035, 997, 973, 937, 908, 877, 829, 709 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.50-1.58 (2H, m), 1.70-1.77 (4H, m), 1.77-1.94 (6H, m), 2.02 (1H, m), 2.06-2.12 (2H, m), 4.43 (1H, m), 6.53 (1H, br.d, J = 5.5 Hz) , 7.43 (1H, br.s), 8.04 (1H, br.s) ppm.

[13-2] Synthesis of 1- (2-adamantyl) -2,2,4,4,4-pentafluorobutane-1,3-diol Instead of the triol compound obtained in the above Example [11-1] The target diol compound (quantitative yield) was obtained by the same synthesis as in Example [11-2] except that the triol compound obtained in Example [13-1] was used. .

1- (2-adamantyl) -2,2,4,4,4-pentafluorobutane-1,3-diol (mixture of two diastereomers)
Colorless solid IR (KBr): ν = 3426 (br.), 3249 (br.), 2908, 2850, 1456, 1378, 1274, 1230, 1203, 1174, 1141, 1120, 1106, 1091, 1074, 1056, 1041 1034, 1002, 885, 844, 819 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.45-1.50 (2H, m), 1.60-1.90 (10H, m), 1.90-2.05 (2H, m), 2.07 (1H, m), 3.94 (0.74H, m), 4.08 (0.26H, dt, J = 24.1, 9.1 Hz), 4.50-4. 60 (1H, m), 5.49 (0.26H, br.d, J = 8.6 Hz), 5.72 (0.74H, d, J = 7.2 Hz), 7.07 (0.74H) , D, J = 7.6 Hz), 7.19 (0.26H, br.d, J = 7.2 Hz) ppm.

[13-3] Synthesis of 1- (2-adamantyl) -3-hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate instead of the diol compound obtained in Example [1-2] above The synthesis was performed in the same manner as in Example [1-3] except that the diol compound obtained in [13-2] was used. The resulting crude product was purified by silica gel column chromatography to obtain the target fluorine-containing ester compound (yield 81%).

1- (2-adamantyl) methacrylate-3-hydroxy-2,2,4,4,4-pentafluorobutyl (mixture of two diastereomers)
Colorless liquid IR (NaCl): ν = 3446 (br.), 2912, 2856, 1710, 1637, 1456, 1380, 1342, 1276, 1218, 1168, 1116, 1025, 946, 819, 811 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.46 (1H, m), 1.59 (1H, m), 1.68-1.89 (10H, m), 1.90 (3H) M), 2.07 (1H, m), 2.22 (0.24H, br.d, J = 10.3 Hz), 2.33 (0.76H, br.d, 10.0 Hz), 4 .28 (0.24H, m), 4.51 (0.76H, m), 5.60-5.70 (1H, m), 5.73 (0.24H, br.s), 5.76 (0.76H, br.s), 6.09 (0.24H, br.s), 6.11 (0.76H, br.s), 7.28 (0.24H, d, J = 7. 9 Hz), 7.38 (0.76 H, d, J = 7.9 Hz) ppm.
¹³ C-NMR (150 MHz in DMSO-d6): δ = 17.59, 17.72, 26.56, 26.66, 26.91, 27.47, 27.61, 28.27 (d-like, J = 5 Hz), 28.47 (d-like, J = 4 Hz), 31.24, 31.34, 31.45, 31.49, 37.08, 37.09, 37.77, 37.89, 38. 03, 38.07, 89.08, 39.22, 42.97 (d-like, J = 2 Hz), 42.57 (d-like, J = 3 Hz), 67.10 (ddq, J = 22, 30, 30 Hz), 67.72 (m), 69.68 (dd, J = 32, 26 Hz), 71.43 (dd, J = 27, 24 Hz), 119.46 (dd, J = 258, 251 Hz), 120 .73 (t, J = 255 Hz), 123.32 (q, J = 285H) z), 123.51 (q, J = 285 Hz), 126.50, 126.75, 134.89, 135.07, 164.68, 169.97 ppm.
¹⁹ F-NMR (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = −119.08 (0.24F, dm, J = 264 Hz), −118.98 (0.76F, dm, J = 265 Hz) -111.82 (0.24F, dm, J = 264 Hz), -112.92 (0.76F, dm, J = 265 Hz), -73.5-7-33.4 (3F, m) ppm.

Example 14 Synthesis of 1- (1-adamantyl) -3-hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate

[14-1] Synthesis of 1- (1-adamantyl) -3-oxo-2,2,4,4,4-pentafluoro-1-butanol equivalents 1-adamantanecarbaldehyde instead of 2-adamantanone The synthesis was carried out in the same manner as in Example [1-1] except that it was used to obtain a hydrate (yield: 83%) of the target keto alcohol compound equivalent.

1- (1-adamantyl) -2,2,4,4,4-pentafluorobutane-1,3,3-triol colorless solid IR (KBr): ν = 3411 (br.), 3243 (br.), 2908, 2850, 1454, 1344, 1290, 1267, 1211, 1193, 1149, 1110, 1093, 1072, 1039, 867 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.60 (3H, dm, J = 11.3 Hz), 1.65 (3H, dm, J = 11.3 Hz), 1.68 (3H, dm, J = 14.1 Hz), 1.69 (3H, dm, J = 14.1 Hz), 1.98 (3H, m), 3.71 (1H, br.d, J = 27 Hz), 6. 38 (1H, br.), 7.33 (1H, br.), 8.00 (1H, br.) Ppm.

[14-2] Synthesis of 1- (1-adamantyl) -2,2,4,4,4-pentafluorobutane-1,3-diol Instead of the triol compound obtained in the above Example [11-1] The synthesis was performed in the same manner as in Example [11-2] except that the triol compound obtained in Example [14-1] was used to obtain the desired diol compound (yield 99%). .

1- (1-adamantyl) -2,2,4,4,4-pentafluorobutane-1,3-diol (mixture of two diastereomers)
Colorless solid IR (KBr): ν = 3482 (br.), 3376 (br.), 2906, 2850, 1450, 1407, 1361, 1265, 1203, 1187, 1160, 1147, 1137, 1103, 1087, 1054, 1045 1024, 987, 971, 877, 833, 819, 761 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6) of major isomers: δ = 1.61 (3H, dm, J = 11.7 Hz), 1.64 (3H, dm, J = 11.7 Hz), 1 .67 (3H, dm, J = 12.7 Hz), 1.72 (3H, dm, J = 12.7 Hz), 1.92 (3H, m), 3.23 (1H, dm, J = 24. 4 Hz), 4.53 (1 H, m), 5.58 (1 H, br.d, J = 6.2 Hz), 7.01 (1 H, m) ppm.

[14-3] Synthesis of 1- (1-adamantyl) -3-hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate instead of the diol compound obtained in Example [1-2] above The synthesis was performed in the same manner as in Example [1-3] except that the diol compound obtained in [14-2] was used. The resulting crude product was purified by silica gel column chromatography to obtain the target fluorinated ester compound (yield 85%).

1- (1-adamantyl) methacrylate-3-hydroxy-2,2,4,4,4-pentafluorobutyl (mixture of two diastereomers)
Colorless solid IR (KBr): ν = 3386 (br.), 2915, 2854, 1718, 1639, 1452, 1407, 1384, 1365, 1351, 1344, 1315, 1299, 1274, 1218, 1164, 1114, 1025, 1016 941, 854, 827, 813, 759, 682 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6) of major isomer: δ = 1.58-1.75 (12H, m), 1.90-1.95 (6H, m), 4.14 (1H, m), 5.38 (1H, dd, J = 25.7, 3.1 Hz), 5.78 (1H, m), 6.13 (1H, m), 7.34 (1H, m) ppm.
¹³ C-NMR (150 MHz in DMSO-d6) of major isomer: δ = 19.51, 29.00, 37.68, 38.69, 39.53, 69.03 (ddq, J = 22, 30, 30 Hz), 75.73 (dd, J = 32, 22 Hz), 123.42 (t, J = 257 Hz), 125.17 (q, J = 285 Hz), 128.34, 136.74, 166.32 ppm.
¹⁹ F-NMR of major isomer (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = −117.77 (1F, ddq, J = 262, 22, 10 Hz), −116.04 (1F, ddq, J = 262, 27, 14 Hz), −73.22 (3F, ddd, J = 14, 10, 8 Hz) ppm.

Example 15 Synthesis of 3-hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate

[15-1] Synthesis of 2,2,4,4,4-pentafluoro-1,3-butanediol Under a nitrogen atmosphere, 109 g of 1,1,1,3,3,3-hexafluoro-2-propanol A mixture of 500 g of tetrahydrofuran was cooled to 5 ° C. with stirring. To this mixture, n-butyllithium-n-hexane solution (2.71M, 500 ml) was added dropwise, followed by stirring at 5 ° C. for 2 hours. 19.5 g of formaldehyde was added to the reaction mixture, followed by stirring at 5 ° C. for 1 hour and further at room temperature for 18 hours. To the reaction mixture, a mixture of 500 g of water, 37.0 g of sodium borohydride and 300 g of water was successively added dropwise and stirred at room temperature for 10 hours. After stopping the reaction by adding 330 g of 20% hydrochloric acid, ordinary post-treatment operations such as washing, drying and concentration were performed to obtain a crude product. Purification was performed by distillation under reduced pressure, and 58.3 g (boiling point: 90-100 ° C./1660 Pa, yield 50%) of the target 2,2,4,4,4-pentafluoro-1,3-butanediol was obtained as a yellow liquid. Got as.

GC-MS (EI): (m / z) ⁺ = 30, 51, 63, 80, 113, 132.
GC-MS (CI, methane): (m / z) ⁺ = 141, 161, 181 [(M + H) ⁺ ].

[15-2] Synthesis of 3-hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate 2,2,4,4,4-pentafluoro- obtained in [Example 15-1] above A mixture of 10 g of 1,3-butanediol, 9.6 g of methacrylic acid, 1.1 g of p-toluenesulfonic acid, and 30 g of toluene was heated to reflux for 3 hours while distilling off water generated by the reaction. After cooling to room temperature, ordinary post-treatment operations such as washing, drying and concentration were performed to obtain a crude product. Purification was performed by silica gel column chromatography to obtain 9.9 g (yield 72%) of the target fluorine-containing ester compound.
3-Hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate Colorless liquid GC-MS (EI): (m / z) ⁺ = 41, 69, 86, 99, 248 (M ⁺ ).
GC-MS (CI, methane): (m / z) ⁺ = 69, 181, 209, 229, 249 [(M + H) ⁺ ].

Example 16 Synthesis of 2,2-dimethyl-3-hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate

[16-1] Synthesis of 4-methyl-1,1,1,3,3-pentafluoropentane-2,4-diol Except that acetone was used instead of formaldehyde, the above Example [15-1] and By the same method, the target diol compound (yield 71%) was obtained.

4-methyl-1,1,1,3,3-pentafluoropentane-2,4-diol Boiling point: 105 ° C./1730 Pa
Colorless solid at room temperature IR (KBr): ν = 3432 (br.), 3257 (br.), 3020, 3006, 2960, 2917, 2863, 1475, 1461, 1394, 1376, 1359, 1282, 1259, 1224, 1191 1174, 1155, 1112, 1095, 1041, 970, 877, 835, 808, 694 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.22 (3H, s), 1.24 (3H, s), 4.62 (1H, m), 5.46 (1H, br.) 7.05 (1H, m) ppm.

[16-2] Synthesis of 2,2-dimethyl-3-hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate 4-methyl-1,1,1 obtained in [16-1] above , 3,3-pentafluoropentane-2,4-diol (43 g), triethylamine (52 g), and acetonitrile (250 g) were added dropwise at 0 ° C. with 24 g of chlorotrimethylsilane. After stirring for 1 hour, 26 g of methacrylic acid chloride was added dropwise, followed by stirring at 0 ° C. for 1 hour and then at room temperature for 16 hours. Next, 50 g of 20% hydrochloric acid was added, and the mixture was stirred at room temperature for 24 hours, and then subjected to usual post-treatment operations such as extraction, washing, drying and concentration to obtain a crude product. This was distilled under reduced pressure to obtain 36 g (yield 63%) of the target fluorine-containing ester compound.

2,2-dimethyl-3-hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate Boiling point: 56 ° C./40 Pa
Colorless liquid IR (NaCl): ν = 3451 (br.), 3002, 2960, 2935, 1710, 1637, 1463, 1394, 1376, 1336, 1309, 1286, 1263, 1193, 1157, 1105, 1049, 1010, 946 , 848, 825, 700, 661 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d6): δ = 1.61 (3H, s), 1.66 (3H, s), 1.85 (3H, m), 4.71 (1H, m), 5.69 (1H, m), 5.99 (1H, m), 7.32 (1H, br.d, J = 7.6 Hz) ppm.
¹³ C-NMR (150 MHz in CDCl ₃ ): δ = 19.29, 20.70 (dd, J = 6, 4 Hz), 21.67 (m), 68.56 (ddq, J = 22, 30, 30 Hz) ), 83.62 (dd, J = 30, 24 Hz), 120.09 (dd, J = 259, 255 Hz), 125.28 (q, J = 285 Hz), 127.78, 137.88, 166.14 ppm .
¹⁹ F-NMR (565 MHz in DMSO-d6, trifluoroacetic acid standard): δ = 127.78 (1F, ddq, J = 261, 21, 8 Hz), 119.57 (1F, dq, J = 261, 17), -73.70 (3F, dt, J = 17, 8 Hz) ppm.

Example 17 Synthesis of 1,3-di (trifluoromethyl) -3-hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate

[17-1] Synthesis of 2-trifluoromethyl-1,1,1,3,3,5,5,5-octafluoropentane-2,4-diol Except for using hexafluoroacetone instead of formaldehyde The target diol compound was synthesized by the same reaction as in Example [15-1] above (yield 67%).

[17-2] 1,3-di (trifluoromethyl) -3-hydroxy-2,2,4,4,4-pentafluorobutyl methacrylate instead of the diol compound obtained in Example [1-2] The reaction was carried out in the same manner as in Example [1-3] except that the diol compound obtained in [17-1] was used, and the resulting crude product was purified by silica gel column chromatography. A fluorine-containing ester compound (yield 77%) was obtained.

[Example 18] Synthesis of 3-difluoromethyl-3-hydroxy-2,2,4,4,4-pentafluoro-1-trifluoromethylbutyl methacrylate

[18-1] Synthesis of 2-difluoromethyl-1,1,1,3,3,5,5,5-octafluoropentane-2,4-diol 1,1,1,3,3 under nitrogen atmosphere A mixture of 109 g of 1,3-hexafluoro-2-propanol and 500 g of tetrahydrofuran was cooled to 5 ° C. with stirring. To this mixture, n-butyllithium-n-hexane solution (2.71M, 500 ml) was added dropwise, followed by stirring at 5 ° C. for 2 hours. To the reaction mixture, a mixture of 6.0 g of water and 50 g of tetrahydrofuran was added dropwise over 2 hours, and the mixture was stirred at 5 ° C. for 1 hour and then at room temperature for 16 hours. To the reaction mixture, a mixture of 500 g of water, 25 g of sodium borohydride and 300 g of water was sequentially added dropwise and stirred at room temperature for 24 hours. After adding 260 g of 20% hydrochloric acid to stop the reaction, ordinary post-treatment operations such as washing, drying and concentration were performed to obtain a crude product. Purification was performed by distillation under reduced pressure to obtain 53 g (yield 55%) of the objective diol compound as a colorless liquid.

2-difluoromethyl-1,1,1,3,3,5,5,5-octafluoropentane-2,4-diol (mixture of two diastereomers)
Boiling point: 115 ° C./13300 Pa,
Colorless liquid
¹ H-NMR (600 MHz in DMSO-d6): δ = 4.69 (0.7 H, dm, J = 14.0, HO—C H ), 4.78 (0.3 H , dm, J = 20. 6 Hz, HO-C H ), 6.53 (0.7 H , t, J = 51.7 Hz, −CF ₂ H ), 6.61 (0.3 H , t, J = 50.8 Hz, —CF ₂ H ), 7.64 (0.7 H , br., CH—O H ), 7.95 (0.3 H , br., CH—O H ), 8.65 (0.7 H , br.≡C—O) H ), 8.88 (0.3 H , br.≡C—O H ) ppm.

[18-2] Synthesis of 3-difluoromethyl-3-hydroxy-2,2,4,4,4-pentafluoro-1-trifluoromethylbutyl methacrylate The diol compound obtained in Example [1-2] Instead, the reaction was carried out in the same manner as in Example [1-3] except that the diol compound obtained in [18-1] was used, and the resulting crude product was purified by silica gel column chromatography. The target fluorine-containing ester compound (yield 78%) was obtained.

3-Difluoromethyl-3-hydroxy-2,2,4,4,4-pentafluoro-1-trifluoromethylbutyl methacrylate (mixture of two diastereomers)
Colorless liquid GC-MS (EI): (m / z) ^<+> = 41, 69, 86, 113, 197, 347, 366 (M ^<+> ).
GC-MS (CI, methane): (m / z) ^<+> = 69, 243, 259, 299, 347, 367 [(M + H) ^<+ >].

Claims (6)

A fluorine-containing polymerizable ester compound represented by the following general formula (1a) or (2a).

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ² and R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may contain a C 1-15 hetero atom. R ² and R ³ may be bonded to each other to form a ring together with the carbon atom to which they are bonded, in which case a divalent hydrocarbon group that may contain a heteroatom having 1 to 15 carbon atoms R ⁴ represents a hydroxyl group or a monovalent hydrocarbon group which may contain a hetero atom having 1 to 15 carbon atoms, R ⁵ represents a group represented by the following general formulas (L1) to (L4), or a carbon number 4 to 20 tertiary alkyl groups, each alkyl group is an acid labile group selected from a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

(In the formula, a broken line represents a bond. R ^L01 and R ^L02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and R ^L03 represents a heterogeneous group having 1 to 18 carbon atoms. A monovalent hydrocarbon group which may have an atom, R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R ^L03 are bonded to each other to form a ring with the carbon atom to which they are bonded. In the case of forming a ring, R ^L01 , R ^L02 and R ^L03 each represent a linear or branched alkylene group having 1 to 18 carbon atoms.
R ^L04 is a tertiary alkyl group having 4 to 20 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or a group represented by the above general formula (L1) Indicates.
R ^L05 represents a monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. m is 0 or 1, n is 0, 1, 2, or 3, and 2m + n = 2 or 3.
R ^L06 represents a monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. R ^{L07 to} R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group that may contain a C 1-15 hetero atom. Two ^members selected from R ^{L07 to} R ^L16 may form a ring together with the carbon atom to which they are bonded, and in this case, each group forming this ring may contain a hetero atom having 1 to 15 carbon atoms. A good divalent hydrocarbon group is shown. R ^{L07 to} R ^L16 may be bonded to adjacent carbons without any intervening bonds to form a double bond. )) A fluorine-containing polymerizable ester compound selected from fluorine-containing polymerizable ester compounds represented by the following formula.

A keto alcohol compound represented by the following general formula (3) is reacted with a compound represented by the general formula R ⁴ -Z to obtain a diol compound represented by the following general formula (4), and the diol compound is acylated. A method for producing a fluorine-containing polymerizable ester compound represented by the following general formula (1), wherein a fluorine-containing polymerizable ester compound represented by the following general formula (1) is obtained.

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ² and R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may contain a C 1-15 hetero atom. R ² and R ³ may be bonded to each other to form a ring together with the carbon atom to which they are bonded, in which case a divalent hydrocarbon group that may contain a heteroatom having 1 to 15 carbon atoms R ⁴ represents a hydrogen atom, a hydroxyl group, or a monovalent hydrocarbon group that may contain a hetero atom having 1 to 15 carbon atoms, Z represents a monovalent group in which R ⁴ —Z provides an R ⁴ anion equivalent. Represents a group.) A keto alcohol compound represented by the following general formula (3) is reacted with a compound represented by the general formula R ⁴ -Z to obtain a diol compound represented by the following general formula (4), and this diol compound is protected. To obtain an alcohol compound represented by the following general formula (5), acylate the alcohol compound to obtain a protected fluorine-containing polymerizable ester compound represented by the following general formula (6), and this protected fluorine-containing polymerization: A method for producing a fluorine-containing polymerizable ester compound represented by the following general formula (1), wherein the fluorine-containing polymerizable ester compound represented by the following general formula (1) is obtained by deprotecting the functional ester compound .

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ² and R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may contain a C 1-15 hetero atom. R ² and R ³ may be bonded to each other to form a ring together with the carbon atom to which they are bonded, in which case a divalent hydrocarbon group that may contain a heteroatom having 1 to 15 carbon atoms R ⁴ represents a hydrogen atom, a hydroxyl group, or a monovalent hydrocarbon group that may contain a hetero atom having 1 to 15 carbon atoms, R ⁶ represents a protecting group, and Z represents R ⁴ -Z is R ^4. Represents a monovalent group giving an anion equivalent) A keto alcohol compound represented by the following general formula (3) is reacted with a compound represented by the general formula R ⁴ -Z to obtain a diol compound represented by the following general formula (4). Protecting with a stable group to obtain an alcohol compound represented by the following general formula (7), acylating this alcohol compound to obtain a fluorinated polymerizable ester compound represented by the following general formula (2), The manufacturing method of the fluorine-containing polymerizable ester compound represented by the following general formula (2).

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ² and R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may contain a C 1-15 hetero atom. R ² and R ³ may be bonded to each other to form a ring together with the carbon atom to which they are bonded, in which case a divalent hydrocarbon group that may contain a heteroatom having 1 to 15 carbon atoms R ⁴ represents a hydrogen atom, a hydroxyl group, or a monovalent hydrocarbon group that may contain a hetero atom having 1 to 15 carbon atoms, Z represents a monovalent group in which R ⁴ —Z provides an R ⁴ anion equivalent. R ⁵ represents a group represented by the following general formulas (L1) to (L4), a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group in which each alkyl group has 1 to 6 carbon atoms, carbon An acid labile group selected from oxoalkyl groups of 4 to 20 is shown.

(In the formula, a broken line represents a bond. R ^L01 and R ^L02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and R ^L03 represents a heterogeneous group having 1 to 18 carbon atoms. A monovalent hydrocarbon group which may have an atom, R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R ^L03 are bonded to each other to form a ring with the carbon atom to which they are bonded. In the case of forming a ring, R ^L01 , R ^L02 and R ^L03 each represent a linear or branched alkylene group having 1 to 18 carbon atoms.
R ^L04 is a tertiary alkyl group having 4 to 20 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or a group represented by the above general formula (L1) Indicates.
R ^L05 represents a monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. m is 0 or 1, n is 0, 1, 2, or 3, and 2m + n = 2 or 3.
R ^L06 represents a monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. R ^{L07 to} R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group that may contain a C 1-15 hetero atom. Two ^members selected from R ^{L07 to} R ^L16 may form a ring together with the carbon atom to which they are bonded, and in this case, each group forming this ring may contain a hetero atom having 1 to 15 carbon atoms. A good divalent hydrocarbon group is shown. R ^{L07 to} R ^L16 may be bonded to adjacent carbons without any intervening bonds to form a double bond. )) A fluorine-containing polymerizable ester compound represented by the following general formula (1) is protected with an acid labile group to obtain a fluorine-containing polymerizable ester compound represented by the following general formula (2). A method for producing a fluorine-containing polymerizable ester compound represented by (2).

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ² and R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may contain a C 1-15 hetero atom. R ² and R ³ may be bonded to each other to form a ring together with the carbon atom to which they are bonded, in which case a divalent hydrocarbon group that may contain a heteroatom having 1 to 15 carbon atoms R ⁴ represents a hydrogen atom, a hydroxyl group, or a monovalent hydrocarbon group which may contain a hetero atom having 1 to 15 carbon atoms, and R ⁵ represents a group represented by the following general formulas (L1) to (L4). And a tertiary alkyl group having 4 to 20 carbon atoms, and each alkyl group is an acid labile group selected from a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

(In the formula, a broken line represents a bond. R ^L01 and R ^L02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and R ^L03 represents a heterogeneous group having 1 to 18 carbon atoms. A monovalent hydrocarbon group which may have an atom, R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R ^L03 are bonded to each other to form a ring with the carbon atom to which they are bonded. In the case of forming a ring, R ^L01 , R ^L02 and R ^L03 each represent a linear or branched alkylene group having 1 to 18 carbon atoms.
R ^L04 is a tertiary alkyl group having 4 to 20 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or a group represented by the above general formula (L1) Indicates.
R ^L05 represents a monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. m is 0 or 1, n is 0, 1, 2, or 3, and 2m + n = 2 or 3.
R ^L06 represents a monovalent hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. R ^{L07 to} R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group that may contain a C 1-15 hetero atom. Two ^members selected from R ^{L07 to} R ^L16 may form a ring together with the carbon atom to which they are bonded, and in this case, each group forming this ring may contain a hetero atom having 1 to 15 carbon atoms. A good divalent hydrocarbon group is shown. R ^{L07 to} R ^L16 may be bonded to adjacent carbons without any intervening bonds to form a double bond. ))