JP5564966B2 - Method for producing salt - Google Patents
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Description
本発明は、特定の構造を有する塩の製造方法、中でも半導体の微細加工に用いられる化学増幅型フォトレジスト組成物において好適に用いられる特定の構造を有する塩の製造方法に関する。 The present invention relates to a method for producing a salt having a specific structure, and more particularly to a method for producing a salt having a specific structure that is suitably used in a chemically amplified photoresist composition used for fine processing of semiconductors.
化学増幅型フォトレジスト組成物は、通常、樹脂及び酸発生剤を含有し、該酸発生剤としては、スルホニウム塩などの塩が用いられる。
特許文献1には、ハロゲンイオンを有するオニウム誘導体に、スルホン酸エステル誘導体を反応させることによりオニウムスルホン酸誘導体を得る化学増幅型フォトレジスト組成物に含有される塩の製造方法として、トリフェニルスルホニウム・アイオダイドに、ジメチル硫酸を反応させ、得られた反応物にトリフルオロメタンスルホン酸を反応させることによりトリフェニルスルホニウム・トリフルオロメタンスルホネートを得る製造方法が提案されている。
The chemically amplified photoresist composition usually contains a resin and an acid generator, and a salt such as a sulfonium salt is used as the acid generator.
Patent Document 1 discloses a method for producing a salt contained in a chemically amplified photoresist composition that obtains an onium sulfonic acid derivative by reacting a sulfonic acid ester derivative with an onium derivative having a halogen ion. There has been proposed a production method in which triphenylsulfonium trifluoromethanesulfonate is obtained by reacting iodide with dimethyl sulfate and reacting the obtained reaction product with trifluoromethanesulfonic acid.
従来の製造方法では、得られる塩の収率が十分には満足することができない場合があった。 In the conventional production method, the yield of the obtained salt may not be sufficiently satisfied.
そこで本発明者らは、上記課題について検討した結果、本発明に至った。
1.式(A)で表される塩と式(B)で表される塩とを、塩化銀の存在下で反応させることを特徴とする式(C)で表される塩の製造方法。
Then, as a result of examining the above problems, the present inventors have reached the present invention.
1. A method for producing a salt represented by formula (C), comprising reacting a salt represented by formula (A) with a salt represented by formula (B) in the presence of silver chloride.
Z+X− (A)
A+−O3SR (B)
Z+−O3SR (C)
Z + X − (A)
A + -O 3 SR (B)
Z + -O 3 SR (C)
[式(A)、式(B)及び式(C)中、Z+は、有機カチオンを表し、X−は、Br−又はI−を表し、A+は、アルカリ金属カチオンを表す。
Rは、直鎖状又は分岐状の炭素数1〜12の脂肪族炭化水素基、置換基を有してもよい炭素数4〜36の脂環式炭化水素基あるいは置換基を有してもよい炭素数6〜18の芳香族炭化水素基を表す。前記脂肪族炭化水素基に含まれるメチレン基は、酸素原子及び/又はカルボニル基で置換されていてもよく、前記脂肪族炭化水素基に含まれる水素原子は、フッ素原子又は炭素数1〜6のペルフルオロアルキル基で置換されていてもよい。]
[In Formula (A), Formula (B), and Formula (C), Z + represents an organic cation, X − represents Br − or I − , and A + represents an alkali metal cation.
R may have a linear or branched aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 36 carbon atoms which may have a substituent, or a substituent. It represents a good aromatic hydrocarbon group having 6 to 18 carbon atoms. The methylene group contained in the aliphatic hydrocarbon group may be substituted with an oxygen atom and / or a carbonyl group, and the hydrogen atom contained in the aliphatic hydrocarbon group is a fluorine atom or having 1 to 6 carbon atoms. It may be substituted with a perfluoroalkyl group. ]
2.塩化銀を、式(A)で表される塩1モルに対して、0.7〜1.2モル使用することを特徴とする前1項記載の製造方法。
3.式(C)で表される塩が、式(I)で表される塩である前1項記載の製造方法。
2. 2. The production method according to 1 above, wherein 0.7 to 1.2 mol of silver chloride is used per 1 mol of the salt represented by the formula (A).
3. 2. The production method according to 1 above, wherein the salt represented by the formula (C) is a salt represented by the formula (I).
[式(I)、Q1及びQ2は、互いに独立に、フッ素原子又は炭素数1〜6のペルフルオロアルキル基を表す。
X1は、単結合又は−[CH2]k−を表し、該−[CH2]k−に含まれるメチレン基は酸素原子及び/又はカルボニル基で置換されていてもよく、該−[CH2]k−に含まれる水素原子は直鎖状又は分岐状の炭素数1〜4の脂肪族炭化水素基で置換されていてもよい。kは、1〜17の整数を表す。
Y1は、置換基を有してもよい炭素数4〜36の脂環式炭化水素基を表す。
Z+は、有機カチオンを表す。]
[Formula (I), Q 1 and Q 2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
X 1 represents a single bond or — [CH 2 ] k —, and the methylene group contained in — [CH 2 ] k — may be substituted with an oxygen atom and / or a carbonyl group. 2 ] The hydrogen atom contained in k- may be substituted with a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms. k represents an integer of 1 to 17.
Y 1 represents an alicyclic hydrocarbon group having 4 to 36 carbon atoms which may have a substituent.
Z + represents an organic cation. ]
4.前記Z+が、直鎖状又は分岐状の炭素数1〜12の脂肪族炭化水素基、置換基を有してもよい脂環式炭化水素基を有する炭素数4〜36の炭化水素基あるいは置換基を有してもよい炭素数6〜18の芳香族炭化水素基を有するスルホニウムカチオンであることを特徴とする前1〜3項のいずれか記載の製造方法。
5.前記Z+が、置換基を有してもよい炭素数6〜18の芳香族炭化水素基を有するスルホニウムカチオンであることを特徴とする前1〜4項のいずれか記載の製造方法。
4). The Z + is a linear or branched aliphatic hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbon group having 4 to 36 carbon atoms having an alicyclic hydrocarbon group which may have a substituent, or 4. The production method according to any one of the preceding items 1 to 3, which is a sulfonium cation having an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent.
5. Said Z <+> is the sulfonium cation which has a C6-C18 aromatic hydrocarbon group which may have a substituent, The manufacturing method in any one of the preceding 1-4 characterized by the above-mentioned.
本発明の製造方法によれば、得られる塩の収率が高い。 According to the production method of the present invention, the yield of the obtained salt is high.
本発明の式(C)で表される塩の製造方法は、式(A)で表される塩と式(B)で表される塩とを、塩化銀の存在下で、反応させることを特徴とする。 The method for producing a salt represented by the formula (C) of the present invention comprises reacting the salt represented by the formula (A) with the salt represented by the formula (B) in the presence of silver chloride. Features.
Z+X− (A)
A+−O3SR (B)
Z+−O3SR (C)
Z + X − (A)
A + -O 3 SR (B)
Z + -O 3 SR (C)
[式(A)、式(B)及び式(C)中、Z+は、有機カチオンを表す。
X−は、Br−又はI−を表す。
A+は、アルカリ金属カチオンを表す。
Rは、直鎖状又は分岐状の炭素数1〜12の脂肪族炭化水素基、置換基を有してもよい脂環式炭化水素基を有する炭素数4〜36の炭化水素基、置換基を有してもよい炭素数6〜18の芳香族炭化水素基を表す。前記脂肪族炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基で置換されていてもよい。前記脂肪族炭化水素基に含まれる水素原子は、フッ素原子又は炭素数1〜6のペルフルオロアルキル基で置換されていてもよい。]
[In Formula (A), Formula (B), and Formula (C), Z + represents an organic cation.
X − represents Br − or I − .
A + represents an alkali metal cation.
R is a linear or branched aliphatic hydrocarbon group having 1 to 12 carbon atoms, an optionally substituted alicyclic hydrocarbon group having 4 to 36 carbon atoms, a substituent. Represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have The methylene group contained in the aliphatic hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a fluorine atom or a C 1-6 perfluoroalkyl group. ]
前記反応は、例えば、クロロホルム、アセトニトリル、メタノール、プロピレングリコールモノメチルエーテルアセテート等の溶媒中にて、塩化銀存在下で、0〜150℃程度の温度範囲、好ましくは0〜100℃程度の温度範囲で、より好ましくは10〜40℃の温度範囲で攪拌して反応させて行われる。
式(A)で表される塩の使用量は、式(B)で表される塩1モルに対して、通常、0.5〜2モル程度であり、好ましくは0.7〜1.5モル程度である。
塩化銀の使用量は、式(A)で表される塩1モルに対して、通常、1〜3モル、好ましくは、1.0〜1.2モル程度である。
The reaction is carried out, for example, in a solvent such as chloroform, acetonitrile, methanol, propylene glycol monomethyl ether acetate, in the presence of silver chloride, in a temperature range of about 0 to 150 ° C, preferably in a temperature range of about 0 to 100 ° C. More preferably, the reaction is carried out with stirring in a temperature range of 10 to 40 ° C.
The usage-amount of the salt represented by Formula (A) is about 0.5-2 mol normally with respect to 1 mol of salts represented by Formula (B), Preferably it is 0.7-1.5. It is about a mole.
The amount of silver chloride to be used is generally 1 to 3 mol, preferably about 1.0 to 1.2 mol, per 1 mol of the salt represented by the formula (A).
得られた式(C)で表される塩は、再結晶で取り出してもよいし、水洗して精製してもよい。 The obtained salt represented by the formula (C) may be taken out by recrystallization, or may be purified by washing with water.
前記の塩は、式(II)で表される塩であることが好ましい。 The salt is preferably a salt represented by the formula (II).
[式(II)中、Q1、Q2、X1、Y1及びZ+は、式(I)におけるものと同じ意味を表す。] [In formula (II), Q 1 , Q 2 , X 1 , Y 1 and Z + represent the same meaning as in formula (I). ]
式(II)で表される塩の製造方法としては、例えば、式(IIa)で表される塩と式(IIb)で表される塩とを、例えば、クロロホルム、アセトニトリル、水、メタノール等の不活性溶媒中にて、塩化銀存在下で0℃〜150℃程度の温度範囲、好ましくは0〜100℃程度の温度範囲にて攪拌して反応させて、塩を得る方法などが挙げられる。 Examples of the method for producing the salt represented by the formula (II) include a salt represented by the formula (IIa) and a salt represented by the formula (IIb), such as chloroform, acetonitrile, water, and methanol. Examples thereof include a method of obtaining a salt by stirring and reacting in an inert solvent in the presence of silver chloride in a temperature range of about 0 ° C. to 150 ° C., preferably in a temperature range of about 0 to 100 ° C.
[式(IIa)中、Q1、Q2、X1及びY1は、式(II)におけるものと同じ意味を表す。
A+は、アルカリ金属カチオンを表す。
式(IIb)中、Z+は、式(II)におけるものと同じ意味を表す。X−は、Br−又はI−を表す。]
[In formula (IIa), Q 1 , Q 2 , X 1 and Y 1 represent the same meaning as in formula (II).
A + represents an alkali metal cation.
In formula (IIb), Z + represents the same meaning as in formula (II). X − represents Br − or I − . ]
式(IIb)で表される塩の使用量は、通常、式(IIa)で表される塩1モルに対して、0.5〜2モル程度である。
塩化銀の使用量は、通常、式(IIb)で表される塩1モルに対して、1モル程度である。
該塩は再結晶で取り出してもよいし、水洗して精製してもよい。
The amount of the salt represented by the formula (IIb) is usually about 0.5 to 2 mol with respect to 1 mol of the salt represented by the formula (IIa).
The amount of silver chloride used is usually about 1 mol per 1 mol of the salt represented by the formula (IIb).
The salt may be taken out by recrystallization or may be purified by washing with water.
製造に用いられる式(IIa)で表される塩の製造方法としては、例えば、先ず、式(IIa−1)で表されるアルコールと、式(IIa−2)で表されるカルボン酸とをエステル化反応させて、式(IIa)で表される塩を得る方法などが挙げられる。 As a manufacturing method of the salt represented by the formula (IIa) used for manufacture, first, for example, an alcohol represented by the formula (IIa-1) and a carboxylic acid represented by the formula (IIa-2) Examples thereof include a method of obtaining a salt represented by the formula (IIa) by an esterification reaction.
[式(IIa−1)中、X1及びY1は、式(II)におけるものと同じ意味を表す。
式(IIa−2)中、A+は、式(IIa)におけるものと同じ意味を表す。]
[In formula (IIa-1), X 1 and Y 1 represent the same meaning as in formula (II).
In formula (IIa-2), A + represents the same meaning as in formula (IIa). ]
別法としては、式(IIa−1)で表されるアルコールと式(IIa−3)で表されるカルボン酸とをエステル化反応した後、AOHで加水分解して式(IIa)で表される塩を得る方法もある。(Aは、アルカリ金属を表す。) As another method, the alcohol represented by the formula (IIa-1) and the carboxylic acid represented by the formula (IIa-3) are esterified, and then hydrolyzed with AOH to be represented by the formula (IIa). There is also a method of obtaining a salt. (A represents an alkali metal.)
[式(IIa−1)中、X1及びY1は、式(II)におけるものと同じ意味を表す。] [In formula (IIa-1), X 1 and Y 1 represent the same meaning as in formula (II). ]
前記エステル化反応は、通常、ジクロロエタン、トルエン、エチルベンゼン、モノクロロベンゼン、アセトニトリル等の非プロトン性溶媒中にて、20〜200℃程度の温度範囲、好ましくは、50〜150℃程度の温度範囲で攪拌して行えばよい。エステル化反応においては、通常は酸触媒としてp−トルエンスルホン酸などの有機酸及び/又は硫酸等の無機酸を添加する。 The esterification reaction is usually stirred in an aprotic solvent such as dichloroethane, toluene, ethylbenzene, monochlorobenzene, acetonitrile, etc. in a temperature range of about 20 to 200 ° C., preferably in a temperature range of about 50 to 150 ° C. You can do it. In the esterification reaction, an organic acid such as p-toluenesulfonic acid and / or an inorganic acid such as sulfuric acid is usually added as an acid catalyst.
また、エステル化反応は、ディーンスターク装置を用いるなどして、脱水しながら実施すると、反応時間が短縮化される傾向があることから好ましい。 Further, the esterification reaction is preferably carried out while dehydrating using a Dean Stark apparatus or the like because the reaction time tends to be shortened.
エステル化反応における式(IIa−2)で表されるカルボン酸の使用量は、式(IIa−1)で表されるアルコール1モルに対して、0.2〜3モル程度、好ましくは0.5〜2モル程度である。
エステル化反応における酸触媒は、触媒量でも溶媒に相当する量でもよく、通常、0.001〜5モル程度である。
The amount of the carboxylic acid represented by the formula (IIa-2) used in the esterification reaction is about 0.2 to 3 mol, preferably about 0.2 mol per 1 mol of the alcohol represented by the formula (IIa-1). About 5 to 2 moles.
The acid catalyst in the esterification reaction may be a catalytic amount or an amount corresponding to a solvent, and is usually about 0.001 to 5 mol.
前記の塩は、式(II’)で表される塩であることが好ましい。 The salt is preferably a salt represented by the formula (II ′).
[式(II’)中、Q1、Q2、Y1及びZ+は、式(II)におけるものと同じ意味を表す。
X11は、直鎖状若しくは分岐状の炭素数1〜15のアルキレン基を表す。]
[In formula (II ′), Q 1 , Q 2 , Y 1 and Z + represent the same meaning as in formula (II).
X 11 represents a linear or branched alkylene group having 1 to 15 carbon atoms. ]
式(II’)で表される塩の製造方法としては、例えば、式(IIa’)で表される塩と式(IIb’)で表される塩とを、例えば、アセトニトリル、水、メタノール、クロロホルム、塩化メチレン等の不活性溶媒中にて、あるいはそれらの混合溶媒中にて、0〜150℃程度の温度範囲、好ましくは0〜100℃程度の温度範囲にて攪拌して反応させて、式(II’)で表される塩を得る方法などが挙げられる。 Examples of the method for producing the salt represented by the formula (II ′) include a salt represented by the formula (IIa ′) and a salt represented by the formula (IIb ′), for example, acetonitrile, water, methanol, In an inert solvent such as chloroform and methylene chloride, or in a mixed solvent thereof, stirring and reacting in a temperature range of about 0 to 150 ° C, preferably in a temperature range of about 0 to 100 ° C, Examples thereof include a method for obtaining a salt represented by the formula (II ′).
[式(IIa’)中、Q1、Q2、X11及びY1は、式(II’)におけるものと同じ意味を表す。
A+は、アルカリ金属カチオンを表す。
式(IIb)中、Z+は、式(II’)におけるものと同じ意味を表す。
X−は、Br−又はI−を表す。]
[In formula (IIa ′), Q 1 , Q 2 , X 11 and Y 1 represent the same meaning as in formula (II ′).
A + represents an alkali metal cation.
In formula (IIb), Z + represents the same meaning as in formula (II ′).
X − represents Br − or I − . ]
式(IIb’)で表される塩の使用量としては、通常、式(IIa’)で表される塩1モルに対して、0.5〜2モル程度である。該塩(II’)は再結晶によって取り出してもよいし、水洗して精製してもよい。
ここで、Q1及びQ2としては、それぞれ独立に、フッ素原子又はトリフルオロメチル基である場合が好ましく、フッ素原子である場合がさらに好ましい。
The amount of the salt represented by the formula (IIb ′) is usually about 0.5 to 2 mol relative to 1 mol of the salt represented by the formula (IIa ′). The salt (II ′) may be taken out by recrystallization or may be purified by washing with water.
Here, Q 1 and Q 2 are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably a fluorine atom.
式(II’)で表される塩の製造に用いられる式(IIa’)で表される塩の製造方法としては、例えば、先ず、式(IIa’−1)で表される塩と式(IIa’−2)で表される化合物とをエステル化反応させて、式(IIa)で表される塩を得る方法などが挙げられる。 As a manufacturing method of the salt represented by the formula (IIa ′) used for the production of the salt represented by the formula (II ′), for example, first, the salt represented by the formula (IIa′-1) and the formula (II And a method of obtaining a salt represented by the formula (IIa) by esterifying the compound represented by IIa′-2).
[式(IIa’−1)中、A、X11、Q1及びQ2は、式(IIa’)におけるものと同じ意味を表す。
式(IIa’−2)中、Y1は、式(IIa)におけるものと同じ意味を表す。]
[In formula (IIa′-1), A, X 11 , Q 1 and Q 2 represent the same meaning as in formula (IIa ′).
In formula (IIa′-2), Y 1 represents the same meaning as in formula (IIa). ]
別法としては、式(IIa’−3)で表されるアルコールと式(IIa’−2)で表されるカルボン酸とをエステル化反応した後、AOHで加水分解して式(IIa’)で表される塩を得る方法もある。(Aは、アルカリ金属を表す。) As an alternative method, the alcohol represented by the formula (IIa′-3) and the carboxylic acid represented by the formula (IIa′-2) are esterified and then hydrolyzed with AOH to obtain the formula (IIa ′). There is also a method for obtaining a salt represented by: (A represents an alkali metal.)
[式(IIa’−3)中、X11、Q1及びQ2は、式(IIa’)におけるものと同じ意味を表す。
式(IIa’−2)中、Y1は、式(IIa)におけるものと同じ意味を表す。]
[In formula (IIa′-3), X 11 , Q 1 and Q 2 represent the same meaning as in formula (IIa ′).
In formula (IIa′-2), Y 1 represents the same meaning as in formula (IIa). ]
ここで、Q1及びQ2としては、それぞれ独立に、フッ素原子又はトリフルオロメチル基である場合が好ましく、フッ素原子である場合がさらに好ましい。 Here, Q 1 and Q 2 are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably a fluorine atom.
式(IIa’−2)と式(IIa’−1)とのエステル化反応は、通常、ジクロロエタン、トルエン、エチルベンゼン、モノクロロベンゼン、アセトニトリル、N,N−ジメチルホルムアミド等の非プロトン性溶媒中にて、20〜200℃程度の温度範囲、好ましくは、50〜150℃程度の温度範囲で攪拌して行えばよい。エステル化反応においては、通常、酸触媒としてp−トルエンスルホン酸などの有機酸及び/又は硫酸等の無機酸を添加する。あるいは脱水剤として、例えば、ジシクロヘキシルカルボジイミド、1−アルキル−2−ハロピリジニウム塩、1,1−カルボニルジイミダゾール、ビス(2−オキソ−3−オキサゾリジニル)ホスフィン酸塩化物、1−エチル−3−(3−ジメチルアミノプロピル)カルボジイミド塩酸塩、ジ−2−ピリジル炭酸塩、ジ−2−ピリジルチオノ炭酸塩、6−メチル−2−ニトロ安息香酸無水物/4−(ジメチルアミノ)ピリジン(触媒)等を添加してもよい。
酸触媒を用いたエステル化反応は、ディーンスターク装置を用いるなどして、脱水しながら実施すると、反応時間が短縮化される傾向があることから好ましい。
The esterification reaction of formula (IIa′-2) and formula (IIa′-1) is usually carried out in an aprotic solvent such as dichloroethane, toluene, ethylbenzene, monochlorobenzene, acetonitrile, N, N-dimethylformamide and the like. What is necessary is just to stir in the temperature range of about 20-200 degreeC, Preferably, it is about 50-150 degreeC. In the esterification reaction, an organic acid such as p-toluenesulfonic acid and / or an inorganic acid such as sulfuric acid is usually added as an acid catalyst. Alternatively, as a dehydrating agent, for example, dicyclohexylcarbodiimide, 1-alkyl-2-halopyridinium salt, 1,1-carbonyldiimidazole, bis (2-oxo-3-oxazolidinyl) phosphine chloride, 1-ethyl-3- ( 3-dimethylaminopropyl) carbodiimide hydrochloride, di-2-pyridyl carbonate, di-2-pyridylthiono carbonate, 6-methyl-2-nitrobenzoic anhydride / 4- (dimethylamino) pyridine (catalyst), etc. It may be added.
The esterification reaction using an acid catalyst is preferably carried out while dehydrating using a Dean Stark apparatus or the like because the reaction time tends to be shortened.
エステル化反応における式(IIa’−1)で表される塩の使用量としては、式(IIa’−2)で表されるカルボン酸1モルに対して、0.5〜3モル程度、好ましくは1〜2モル程度である。エステル化反応における酸触媒は式(IIa’−2)で表されるカルボン酸1モルに対して、触媒量でも溶媒に相当する量でもよく、通常、0.001〜5モル程度である。エステル化反応における脱水剤は式(IIa’−2)で表されるカルボン酸1モルに対して、0.5〜5モル程度、好ましくは1〜3モル程度である。 The amount of the salt represented by the formula (IIa′-1) used in the esterification reaction is preferably about 0.5 to 3 mol with respect to 1 mol of the carboxylic acid represented by the formula (IIa′-2). Is about 1 to 2 moles. The acid catalyst in the esterification reaction may be a catalytic amount or an amount corresponding to a solvent with respect to 1 mol of the carboxylic acid represented by the formula (IIa′-2), and is usually about 0.001 to 5 mol. The dehydrating agent in the esterification reaction is about 0.5 to 5 mol, preferably about 1 to 3 mol, per 1 mol of the carboxylic acid represented by the formula (IIa′-2).
式(IIa’−2)で表されるカルボン酸と式(IIa’−1)で表される塩とのエステル化反応は、式(IIa’−2)で表されるカルボン酸を対応する酸ハライドに変換して、式(IIa’−1)で表される塩と反応させることにより行うこともでき、その反応により式(II’)で表される化合物を得ることもできる。酸ハライドに変換する試薬としては、塩化チオニル、臭化チオニル、三塩化リン、五塩化リン、三臭化リン等が挙げられる。酸ハライド化反応は、不活性溶媒、例えば、ジクロロエタン、トルエン、エチルベンゼン、モノクロロベンゼン、N,N−ジメチルホルムアミド等の非プロトン性溶媒が挙げられる。反応は、20〜200℃程度の温度範囲、好ましくは、50〜150℃程度の温度範囲で、攪拌して行えばよい。触媒として、アミン化合物を添加することも可能である。得られた酸ハライドは、式(IIa’−1)と不活性溶媒(例えば、ジクロロエタン、トルエン、エチルベンゼン、モノクロロベンゼン、N,N−ジメチルホルムアミド等の非プロトン性溶媒等が挙げられる。)中で反応させることにより、式(IIa’)で表される塩を得ることができる。反応は、20〜200℃程度の温度範囲、好ましくは、50〜150℃程度の温度範囲で行い、好ましくは脱酸剤を用いる方がよい。
脱酸剤としては、トリエチルアミン、ピリジン等の有機塩基あるいは水酸化ナトリウム、炭酸カリウム、水素化ナトリウム等の無機塩基が挙げられる。用いる塩基の量は、酸ハライド1モルに対して、溶媒に相当する量でもよく、通常、0.001〜5モル程度で、好ましくは1〜3モル程度である。
The esterification reaction between the carboxylic acid represented by the formula (IIa′-2) and the salt represented by the formula (IIa′-1) is carried out by reacting the carboxylic acid represented by the formula (IIa′-2) with the corresponding acid. It can also carry out by converting into a halide and making it react with the salt represented by Formula (IIa'-1), and the compound represented by Formula (II ') can also be obtained by the reaction. Examples of the reagent that converts to an acid halide include thionyl chloride, thionyl bromide, phosphorus trichloride, phosphorus pentachloride, and phosphorus tribromide. Examples of the acid halide reaction include inert solvents such as aprotic solvents such as dichloroethane, toluene, ethylbenzene, monochlorobenzene, and N, N-dimethylformamide. The reaction may be carried out with stirring in a temperature range of about 20 to 200 ° C., preferably in a temperature range of about 50 to 150 ° C. An amine compound can be added as a catalyst. The obtained acid halide is in the formula (IIa′-1) and an inert solvent (for example, aprotic solvents such as dichloroethane, toluene, ethylbenzene, monochlorobenzene, N, N-dimethylformamide, etc.). By reacting, a salt represented by the formula (IIa ′) can be obtained. The reaction is carried out in a temperature range of about 20 to 200 ° C., preferably in a temperature range of about 50 to 150 ° C., and preferably a deoxidizer is used.
Examples of the deoxidizer include organic bases such as triethylamine and pyridine, and inorganic bases such as sodium hydroxide, potassium carbonate, and sodium hydride. The amount of the base used may be an amount corresponding to the solvent with respect to 1 mol of the acid halide, and is usually about 0.001 to 5 mol, preferably about 1 to 3 mol.
式(I)で表される塩のアニオン部としては、例えば、以下の式(IA)〜式(ID)で表されるアニオン等が挙げられる。 Examples of the anion moiety of the salt represented by the formula (I) include anions represented by the following formulas (IA) to (ID).
[式(IA)〜(ID)中、Q1、Q2及びY1は、式(I)におけるにものと同じ意味を表す。
X10は、単結合あるいは直鎖状又は分岐状の炭素数1〜15のアルキレン基を表す。
X11及びX12は、互いに独立に、直鎖状又は分岐状の炭素数1〜15のアルキレン基を表す。]
アルキレン基としては、メチレン、エチレン、n−プロピレン基、イソプロピレン基、n−ブチレン基、sec−ブチレン基、tert−ブチレン基、n−ペンチレン基、n−ヘキシレン基などが挙げられる。
中でも、X10としては、好ましくは単結合である。
[In formulas (IA) to (ID), Q 1 , Q 2 and Y 1 represent the same meaning as in formula (I).
X 10 represents a single bond or a linear or branched alkylene group having 1 to 15 carbon atoms.
X 11 and X 12 each independently represent a linear or branched alkylene group having 1 to 15 carbon atoms. ]
Examples of the alkylene group include methylene, ethylene, n-propylene group, isopropylene group, n-butylene group, sec-butylene group, tert-butylene group, n-pentylene group, and n-hexylene group.
Among these, X 10 is preferably a single bond.
式(IA)中、環Wに含まれる水素原子が炭化水素基のみで置換された(該炭化水素基に含まれるメチレン基は酸素原子で置換されていてもよい。)アニオンの具体例としては、例えば、下記のもの等が挙げられる。 In formula (IA), the hydrogen atom contained in ring W is substituted only with a hydrocarbon group (the methylene group contained in the hydrocarbon group may be substituted with an oxygen atom). For example, the following may be mentioned.
式(IA)中、環Wに含まれる水素原子が芳香族炭化水素基で置換されたアニオンの具体例としては、例えば、下記のもの等が挙げられる。 In the formula (IA), specific examples of the anion in which the hydrogen atom contained in the ring W is substituted with an aromatic hydrocarbon group include the following.
式(IA)中、環Wに含まれる水素原子が水酸基又は水酸基を含む基で置換されたアニオン(ただし、ラクトン構造を有さない。)の具体例としては、例えば、下記のもの等が挙げられる。 In the formula (IA), specific examples of the anion in which the hydrogen atom contained in the ring W is substituted with a hydroxyl group or a group containing a hydroxyl group (but not having a lactone structure) include the following. It is done.
式(IA)中、環Wに含まれるメチレン基が酸素原子で置換されたエーテル構造を有するアニオンの具体例としては、例えば、下記のもの等が挙げられる。 In the formula (IA), specific examples of the anion having an ether structure in which the methylene group contained in the ring W is substituted with an oxygen atom include the followings.
式(IA)中、環Wに含まれる隣接する2つのメチレン基が酸素原子とカルボニル基とで置換されたラクトン構造を有するアニオンの具体例としては、例えば、下記のもの等が挙げられる。 In the formula (IA), specific examples of the anion having a lactone structure in which two adjacent methylene groups contained in the ring W are substituted with an oxygen atom and a carbonyl group include the following.
式(IA)中、環Wに含まれるメチレン基がカルボニル基で置換されたケトン構造を有するアニオンの具体例としては、例えば、下記のもの等が挙げられる。 In the formula (IA), specific examples of the anion having a ketone structure in which the methylene group contained in the ring W is substituted with a carbonyl group include the following.
式(IB)中、環Wに含まれる水素原子が置換されていないか又は炭化水素基のみで置換された(環Wに含まれるメチレン基は酸素原子で置換されていてもよい。)アニオンの具体例としては、例えば、下記のもの等が挙げられる。 In formula (IB), the hydrogen atom contained in ring W is not substituted or substituted only with a hydrocarbon group (the methylene group contained in ring W may be substituted with an oxygen atom). Specific examples include the following.
式(IB)中、環Wに含まれる水素原子が水酸基又は水酸基を含む基で置換されたアニオンの具体例としては、例えば、下記のもの等が挙げられる。 In the formula (IB), specific examples of the anion in which the hydrogen atom contained in the ring W is substituted with a hydroxyl group or a group containing a hydroxyl group include the following.
式(IB)中、環Wに含まれる隣接する2つのメチレン基が酸素原子とカルボニル基とで置換されたラクトン構造を有するアニオンの具体例としては、例えば、下記のもの等が挙げられる。 In the formula (IB), specific examples of the anion having a lactone structure in which two adjacent methylene groups contained in the ring W are substituted with an oxygen atom and a carbonyl group include the following.
式(IB)中、環Wに含まれる1つのメチレン基がカルボニル基で置換されたケトン構造を有するアニオンの具体例としては、例えば、下記のもの等が挙げられる。 In the formula (IB), specific examples of the anion having a ketone structure in which one methylene group contained in the ring W is substituted with a carbonyl group include the following.
式(IB)中、環Wに含まれる水素原子が芳香族炭化水素基で置換されたアニオンの具体例としては、例えば、下記のもの等が挙げられる。 Specific examples of the anion in which the hydrogen atom contained in the ring W in the formula (IB) is substituted with an aromatic hydrocarbon group include the following.
式(IC)中、環Wに含まれる水素原子が置換されていないか又は炭化水素基のみで置換された(環Wに含まれるメチレン基は酸素原子で置換されていてもよい。)アニオンの具体例としては、例えば、下記のもの等が挙げられる。 In formula (IC), a hydrogen atom contained in ring W is not substituted or substituted only with a hydrocarbon group (a methylene group contained in ring W may be substituted with an oxygen atom). Specific examples include the following.
式(IC)中、環Wに含まれる水素原子が水酸基又は水酸基を含む基で置換されたアニオンの具体例としては、例えば、下記のもの等が挙げられる。 In the formula (IC), specific examples of the anion in which the hydrogen atom contained in the ring W is substituted with a hydroxyl group or a group containing a hydroxyl group include the following.
式(IC)中、環Wに含まれる1つのメチレン基がカルボニル基で置換されたケトン構造を有するアニオンの具体例としては、例えば、下記のもの等が挙げられる。 Specific examples of the anion having a ketone structure in which one methylene group contained in the ring W is substituted with a carbonyl group in the formula (IC) include the following.
式(ID)中、環Wに含まれる水素原子が置換されていないか又は炭化水素基のみで置換された(環Wに含まれるメチレン基は酸素原子で置換されていてもよい。)アニオンの具体例としては、例えば、下記のもの等が挙げられる。 In formula (ID), the hydrogen atom contained in ring W is not substituted or substituted only with a hydrocarbon group (the methylene group contained in ring W may be substituted with an oxygen atom). Specific examples include the following.
式(ID)中、環Wに含まれる水素原子が水酸基又は水酸基を含む基で置換されたアニオンの具体例としては、例えば、下記のもの等が挙げられる。 In the formula (ID), specific examples of the anion in which the hydrogen atom contained in the ring W is substituted with a hydroxyl group or a group containing a hydroxyl group include the following.
式(ID)中、環Wに含まれる1つのメチレン基がカルボニル基で置換されたケトン構造を有するアニオンの具体例としては、例えば、下記のもの等が挙げられる。 In the formula (ID), specific examples of the anion having a ketone structure in which one methylene group contained in the ring W is substituted with a carbonyl group include the following.
これらのアニオンのうち、好ましくは下記のアニオンが挙げられる。 Among these anions, the following anions are preferable.
式(I)におけるZ+で表される有機カチオンとしては、例えば、式(IXz)、式(IXb)、式(IXc)又は式(IXd)などで表されるカチオン等が挙げられる。 Examples of the organic cation represented by Z + in formula (I) include cations represented by formula (IXz), formula (IXb), formula (IXc), formula (IXd), and the like.
[式(IXa)中、Pa、Pb及びPcは、互いに独立に、直鎖状又は分岐状の炭素数1〜30のアルキル基あるいは炭素数3〜30の脂環式炭化水素基を表す。Pa、Pb及びPcのいずれかがアルキル基である場合、該アルキル基は、水酸基、直鎖状又は分岐状の炭素数1〜12のアルコキシ基あるいは炭素数3〜12の脂環式炭化水素基で置換されていてもよく、Pa、Pb及びPcのいずれかが脂環式炭化水素基である場合には、水酸基、直鎖状又は分岐状の炭素数1〜12のアルキル基あるいは炭素数1〜12のアルコキシ基で置換されていてもよい。
式(IXb)中、P4及びP5は、互いに独立に、水素原子、水酸基、直鎖状又は分岐状の炭素数1〜12のアルキル基あるいは炭素数1〜12のアルコキシ基を表す。
式(IXc)中、P6及びP7は、互いに独立に、直鎖状又は分岐状炭素数1〜12のアルキル基あるいは炭素数3〜12のシクロアルキル基を表すか、P6とP7とが一緒になって、炭素数3〜12の環を形成してもよい。
P8は、水素原子を表し、P9は、直鎖状又は分岐状の炭素数1〜12のアルキル基、炭素数3〜12のシクロアルキル基、置換されていてもよい炭素数6〜20の芳香族炭化水素基を表すか、P8とP9とが一緒になって、炭素数3〜12の環を形成してもよい。
式(IXd)中、P10〜P21は、互いに独立に、水素原子、水酸基、炭素数1〜12のアルキル基又は炭素数1〜12のアルコキシ基を表す。Eは、硫黄原子又は酸素原子を表す。
mは、0又は1を表す。]
[In the formula (IXa), P a , P b and P c are each independently a linear or branched alkyl group having 1 to 30 carbon atoms or an alicyclic hydrocarbon group having 3 to 30 carbon atoms. Represent. When any of P a , P b and P c is an alkyl group, the alkyl group is a hydroxyl group, a linear or branched alkoxy group having 1 to 12 carbon atoms or an alicyclic group having 3 to 12 carbon atoms. It may be substituted with a hydrocarbon group, and when any of P a , P b and P c is an alicyclic hydrocarbon group, it is a hydroxyl group, a linear or branched C 1-12. It may be substituted with an alkyl group or an alkoxy group having 1 to 12 carbon atoms.
In formula (IXb), P 4 and P 5 each independently represent a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
In formula (IXc), P 6 and P 7 each independently represent a linear or branched alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, or P 6 and P 7. And may form a ring having 3 to 12 carbon atoms.
P 8 represents a hydrogen atom, and P 9 is a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an optionally substituted carbon atom having 6 to 20 carbon atoms. Or P 8 and P 9 may be combined to form a ring having 3 to 12 carbon atoms.
In formula (IXd), P 10 to P 21 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. E represents a sulfur atom or an oxygen atom.
m represents 0 or 1. ]
アルコキシ基としては、メチトキシ基、エトキシ基、n−プロポキシ基、イソプロポキシ基、n−ブトキシ基、sec−ブチトキシ基、tert−ブチトキシ基、n−ペントキシ基、n−ヘキトキシ基、ヘプトキシ基、オクトキシ基、2−エチルヘキシルオキシ基、ノニルオキシ基、デシルオキシ基、ウンデシルオキシ基、ドデシルオキシ基等のアルキル基が挙げられる。
シクロアルキルとしては、上述した脂環式炭化水素基と同様のものが例示される。
P6とP7とが一緒になって形成する環としては、テトラヒドロチオフェニウム基などが挙げられる。
P8における芳香族炭化水素基の置換基としては、炭素数1〜12のアルキル基等が挙げられる。
P8とP9とが一緒になって形成する環としては、上述した式(W13)〜式(W15)の基などが挙げられる。
As an alkoxy group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, an n-hexoxy group, a heptoxy group, an octoxy group Alkyl groups such as 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, and the like.
Examples of cycloalkyl are the same as those described above for the alicyclic hydrocarbon group.
Examples of the ring formed by combining P 6 and P 7 include a tetrahydrothiophenium group.
The substituent of the aromatic hydrocarbon group for P 8, include alkyl groups of 1 to 12 carbon atoms.
Examples of the ring formed by combining P 8 and P 9 include the groups of the above formulas (W13) to (W15).
前記の式(IXa)で表されるカチオンの中でも、例えば、式(IXaa)で表されるカチオン等が好ましく挙げられる。 Among the cations represented by the formula (IXa), for example, a cation represented by the formula (IXaa) and the like are preferable.
[式(IXaa)中、P1〜P3は、互いに独立に、水素原子、水酸基、直鎖状又は分岐状の炭素数1〜12のアルキル基、直鎖状又は分岐状の炭素数1〜12のアルコキシ基あるいは炭素数4〜36の脂環式炭化水素を表し、該脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、水酸基、直鎖状又は分岐状の炭素数1〜12のアルキル基、直鎖状又は分岐状の炭素数1〜12のアルコキシ基、炭素数6〜12のアリール基、炭素数7〜12のアラルキル基、グリシドキシ基あるいは炭素数2〜4のアシル基で置換されていてもよい。] [In Formula (IXaa), P 1 to P 3 are each independently a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched carbon number 1 to 1. Represents an alkoxy group having 12 carbon atoms or an alicyclic hydrocarbon having 4 to 36 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, a hydroxyl group, a linear or branched carbon atom having 1 to 12 carbon atoms. An alkyl group, a linear or branched alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidoxy group, or an acyl group having 2 to 4 carbon atoms. May be substituted. ]
特に、脂環式炭化水素基としては、アダマンチル骨格、イソボルニル骨格を含むものなどが挙げられ、好ましくは2−アルキル−2−アダマンチル基、1−(1−アダマンチル)−1−アルキル基及びイソボルニル基などが好ましい。 In particular, examples of the alicyclic hydrocarbon group include those containing an adamantyl skeleton and an isobornyl skeleton, preferably a 2-alkyl-2-adamantyl group, a 1- (1-adamantyl) -1-alkyl group and an isobornyl group. Etc. are preferable.
式(IXaa)で表されるカチオンの具体例としては、例えば、下記のもの等が挙げられる。 Specific examples of the cation represented by the formula (IXaa) include the following.
式(IXaa)で表されるカチオンの中でも、式(IXaaa)で表されるカチオンが、その製造が容易であること等の理由により、好ましく挙げられる。 Among the cations represented by the formula (IXaa), the cation represented by the formula (IXaaa) is preferably used because of its easy production.
[式(IXe)中、P22、P23及びP24は、互いに独立に、水素原子、水酸基、直鎖状又は分岐状の炭素数1〜12のアルキル基あるいは直鎖状又は分岐状の炭素数1〜12のアルコキシ基を表す。] [In formula (IXe), P 22 , P 23 and P 24 are independently of each other a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched carbon atom. The number 1-12 alkoxy group is represented. ]
前記式(IXb)で表されるカチオンの具体例としては、例えば、下記のもの等が挙げられる。 Specific examples of the cation represented by the formula (IXb) include the followings.
前記式(IXc)で表されるカチオンの具体例としては、例えば、下記のもの等が挙げられる。 Specific examples of the cation represented by the formula (IXc) include the followings.
前記式(IXd)で表されるカチオンの具体例としては、例えば、下記のもの等が挙げられる。 Specific examples of the cation represented by the formula (IXd) include the followings.
上記カチオンのうち、アリールスルホニウムカチオンが好ましい。 Of the above cations, arylsulfonium cations are preferred.
前記のアニオン及びカチオンは、任意に組合せることができる。
例えば、式(I)で表される塩として、式(Xa)〜式(Xi)で表される塩が挙げられる。これらの塩は、優れた解像性能及びパターン形状を示すレジスト組成物を与える酸を発生するため好ましい。
The above anions and cations can be arbitrarily combined.
For example, examples of the salt represented by the formula (I) include salts represented by the formula (Xa) to the formula (Xi). These salts are preferable because they generate an acid that gives a resist composition exhibiting excellent resolution performance and pattern shape.
[式(Xa)〜(Xi)中、P25、P26及びP27は、互いに独立に、水素原子、直鎖状又は分岐状の炭素数1〜4の脂肪族炭化水素基あるいは炭素数4〜36の脂環式炭化水素基を表す。
P28及びP29は、互いに独立に、直鎖状又は分岐状の炭素数1〜12の脂肪族炭化水素基あるいは炭素数4〜36の脂環式炭化水素基を表すか、あるいはP28とP29とが一緒になってS+を含んで炭素数2〜6の環を形成してもよい。
P30は、直鎖状又は分岐状の炭素数1〜12の脂肪族炭化水素基、炭素数4〜36の脂環式炭化水素基あるいは置換されていてもよい炭素数6〜20の芳香族炭化水素基を表すか、あるいはP30とP31とが一緒になって炭素数3〜12の環を形成してもよい。
ここで、該環に含まれるメチレン基は、任意に、酸素原子、硫黄原子又はカルボニル基で置換されていてもよい。
Q1及びQ2は、上記と同義である。
X13は、単結合またはメチレン基を表す。]
[In Formulas (Xa) to (Xi), P 25 , P 26 and P 27 are each independently a hydrogen atom, a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms, or 4 carbon atoms. -36 alicyclic hydrocarbon groups are represented.
P 28 and P 29 each independently represent a linear or branched aliphatic hydrocarbon group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group having 4 to 36 carbon atoms, or P 28 and may form a ring of 2 to 6 carbon atoms include S + and P 29 together.
P 30 is a linear or branched aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 36 carbon atoms, or an optionally substituted aromatic group having 6 to 20 carbon atoms. It may represent a hydrocarbon group, or P 30 and P 31 may form a ring having 3 to 12 carbon atoms together.
Here, the methylene group contained in the ring may be optionally substituted with an oxygen atom, a sulfur atom or a carbonyl group.
Q 1 and Q 2 are as defined above.
X 13 represents a single bond or a methylene group. ]
P28とP29とが一緒になって形成する環としては、テトラヒドロチオフェニウム基などが挙げられる。
P30とP31とが一緒になって形成する環としては、上述した式(W13)〜式(W15)の基などが挙げられる。
Examples of the ring and P 28 and P 29 are formed together, such as tetrahydrothiophenium group.
Examples of the ring formed by combining P 30 and P 31 include the groups of the above-described formulas (W13) to (W15).
上記の組合せのうち、以下の塩が好ましい。 Of the above combinations, the following salts are preferred.
中でも、カチオンとして式(IXe)で表されるカチオンにおいて、P22、P23及びP24がいずれも水素原子であるトリフェニルスルホニウムカチオンと、式(IB)で表されるアニオンの具体的例示に挙げられたものとを組合せた塩が好ましい。
式(I)で表される塩は、単独で又は2種以上を組合せて用いてもよい。
Among them, in the cation represented by the formula (IXe) as a cation, specific examples of the triphenylsulfonium cation in which P 22 , P 23 and P 24 are all hydrogen atoms and the anion represented by the formula (IB) Salts in combination with those listed are preferred.
You may use the salt represented by a formula (I) individually or in combination of 2 or more types.
本発明の製造方法により得られる塩は、酸発生剤の有効成分として用いることができる。該酸発生剤は、化学増幅型フォトレジスト組成物(以下、「レジスト組成物」という場合がある)の成分として用いることができる。レジスト組成物は、酸発生剤のほかに、樹脂、クエンチャー、溶媒等を含有することが好ましい。 The salt obtained by the production method of the present invention can be used as an active ingredient of an acid generator. The acid generator can be used as a component of a chemically amplified photoresist composition (hereinafter sometimes referred to as “resist composition”). The resist composition preferably contains a resin, a quencher, a solvent and the like in addition to the acid generator.
以下、本発明を実施例によって詳細に説明するが、本発明はこれらに限定されるもので
はない。
実施例及び参考例中、含有量ないし使用量を表す%及び部は、特記ないかぎり質量基準
である。
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
In Examples and Reference Examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.
化合物又は塩の構造はNMR(日本電子製GX−270型又はEX−270型)、質量分析(
LCはAgilent製1100型、MASSはAgilent製LC/MSD型又はL
C/MSD TOF型)で確認した。
純度は、NMR及びLCで確認した。
収率は、以下の計算式で求めた。
収率=100×[反応により生成した生成物の量(モル)]/[出発物質の量(モル)]
The structure of the compound or salt is NMR (JEOL GX-270 type or EX-270 type), mass spectrometry (
LC is Agilent 1100, MASS is Agilent LC / MSD or L
C / MSD TOF type).
Purity was confirmed by NMR and LC.
The yield was determined by the following calculation formula.
Yield = 100 × [Amount of product produced by reaction (mole)] / [Amount of starting material (mole)]
式(A1−a)で表される化合物100部(0.521mol)及びイオン交換水250部の混合物を氷浴し、これに30%水酸化ナトリウム水溶液230部を滴下した。得られた混合物を100℃で2時間還流し、冷却した後、これを濃塩酸88部で中和した。得られた溶液を濃縮することにより式(A1−b)で表される塩149部(無機塩含有、純度69.2%)(0.521mol)を得た。
式(A1−b)で表される塩4.5部(純度69.2%)(0.0157mol)、式(A1−c)で表される化合物2.6部(0.0156mol)及びエチルベンゼン100部を仕込み、これに濃硫酸0.8部を加え、24時間加熱還流した。得られた混合物を23℃まで冷却した後、濾過して残渣を回収し、該残渣をtert−ブチルメチルエーテルで洗浄して、式(A1)で表される塩5.7部(純度49.1%:1H−NMRによる純度分析)(0.00808mol)を得た。
A mixture of 100 parts (0.521 mol) of the compound represented by the formula (A1-a) and 250 parts of ion-exchanged water was placed in an ice bath, and 230 parts of a 30% aqueous sodium hydroxide solution was added dropwise thereto. The resulting mixture was refluxed at 100 ° C. for 2 hours, cooled, and neutralized with 88 parts of concentrated hydrochloric acid. The obtained solution was concentrated to obtain 149 parts (inorganic salt content, purity: 69.2%) (0.521 mol) of the salt represented by the formula (A1-b).
4.5 parts of salt represented by formula (A1-b) (purity 69.2%) (0.0157 mol), 2.6 parts of compound represented by formula (A1-c) (0.0156 mol) and ethylbenzene 100 parts were charged, 0.8 part of concentrated sulfuric acid was added thereto, and the mixture was refluxed for 24 hours. The obtained mixture was cooled to 23 ° C., and then filtered to collect a residue. The residue was washed with tert-butyl methyl ether to give 5.7 parts of a salt represented by the formula (A1) (purity 49.75). 1%: purity analysis by 1 H-NMR) (0.00808 mol).
実施例1
[式(C1)で表される塩の合成例]
式(B1)で表される塩2.77部(0.00710mol)及びクロロホルム13.83部を仕込んだ溶液に、塩化銀1.02部(0.00712mol)を添加し、これを23℃で12時間攪拌した。該クロロホルム溶液に、式(A1)で表される塩5.00部(純度49.1%)(0.00709mol)及びイオン交換水10.00部を仕込み、更に、クロロホルム27.67部を加え、23℃で12時間撹拌した後、濾過して濾液を回収した。
得られた濾液が2層に分離していたので、クロロホルム層を分液して取り出し、更に、該クロロホルム層にイオン交換水10.38部を添加し、水洗した。この操作を5回繰り返した。クロロホルム層を濃縮し、淡黄色オイル5.62部を得た。得られた淡黄色オイルに酢酸エチル22.48部を添加し攪拌することにより結晶が析出し、濾過することにより白色固体として式(C1)で表される塩3.61部(純度100%、収率87%)(0.00615mol)を得た。塩化銀の使用量は、式(A1)で表される塩1モルに対して、1.0モルであった。
収率=100×0.00615/0.00710=86.7
Example 1
[Synthesis Example of Salt Represented by Formula (C1)]
To a solution charged with 2.77 parts (0.00710 mol) of the salt represented by the formula (B1) and 13.83 parts of chloroform, 1.02 part (0.00712 mol) of silver chloride was added, and this was added at 23 ° C. Stir for 12 hours. Into the chloroform solution, 5.00 parts (purity 49.1%) (0.00709 mol) of salt represented by the formula (A1) and 10.00 parts of ion-exchanged water were added, and 27.67 parts of chloroform was further added. After stirring at 23 ° C. for 12 hours, the filtrate was collected by filtration.
Since the obtained filtrate was separated into two layers, the chloroform layer was separated and taken out. Further, 10.38 parts of ion-exchanged water was added to the chloroform layer and washed with water. This operation was repeated 5 times. The chloroform layer was concentrated to obtain 5.62 parts of pale yellow oil. Crystals are precipitated by adding 22.48 parts of ethyl acetate to the obtained pale yellow oil and stirring, and filtering to obtain 3.61 parts of salt represented by the formula (C1) as a white solid (purity 100%, Yield 87%) (0.00615 mol). The amount of silver chloride used was 1.0 mol with respect to 1 mol of the salt represented by the formula (A1).
Yield = 100 × 0.00615 / 0.00710 = 86.7
参考例1
[式(C1)で表される塩の合成例]
式(A1)で表される塩5.4部(純度35.6%)(0.00555mol)、アセトニトリル16部及びイオン交換水16部の混合溶媒を調製した。これに、式(B2)で表される塩1.7部(0.00569mol)、アセトニトリル5部及びイオン交換水5部の溶液を添加した。得られた混合物を23℃で15時間撹拌後、濃縮し、クロロホルム142部を加えた後、分液操作により、有機層を回収した。回収された有機層をイオン交換水で洗浄し、得られた有機層を濃縮した。得られた濃縮液をtert−ブチルメチルエーテル24部でリパルプして、白色固体として式(C1)で表される塩1.7部(純度100%、収率52%)(0.00290mol)を得た。
収率=100×0.00290/0.00555=52.3
Reference example 1
[Synthesis Example of Salt Represented by Formula (C1)]
A mixed solvent of 5.4 parts (purity 35.6%) (0.00555 mol) of the salt represented by the formula (A1), 16 parts of acetonitrile and 16 parts of ion-exchanged water was prepared. To this was added a solution of 1.7 parts (0.00569 mol) of the salt represented by the formula (B2), 5 parts of acetonitrile and 5 parts of ion-exchanged water. The resulting mixture was stirred at 23 ° C. for 15 hours, concentrated, 142 parts of chloroform was added, and the organic layer was recovered by liquid separation operation. The collected organic layer was washed with ion-exchanged water, and the obtained organic layer was concentrated. The obtained concentrated liquid was repulped with 24 parts of tert-butyl methyl ether, and 1.7 parts (purity 100%, yield 52%) (0.00290 mol) of the salt represented by the formula (C1) as a white solid was obtained. Obtained.
Yield = 100 × 0.00290 / 0.00555 = 52.3
参考例2
[式(C1)で表される塩の合成例]
式(B1)で表される塩2.77部(0.00710mol)及びクロロホルム13.83部の溶液に、式(A1)で表される塩5.00部(純度49.1%)(0.00709mol)及びイオン交換水10.00部の溶液を滴下し、23℃で12時間攪拌したが、目的物である式(C1)で表される塩は得られなかった。
Reference example 2
[Synthesis Example of Salt Represented by Formula (C1)]
In a solution of 2.77 parts (0.00710 mol) of the salt represented by the formula (B1) and 13.83 parts of chloroform, 5.00 parts (purity 49.1%) of the salt represented by the formula (A1) (0 .00709 mol) and 10.00 parts of ion-exchanged water were added dropwise and stirred for 12 hours at 23 ° C., but the salt represented by the formula (C1) as the target product was not obtained.
式(A2−a)で表される化合物100部(0.521mol)及びイオン交換水250部の混合物を氷浴し、これに30%水酸化ナトリウム水溶液230部を滴下した。得られた混合物を100℃で2時間加熱攪拌し、冷却した後、これを濃塩酸88部で中和した。得られた溶液を濃縮して、式(A2−b)で表される塩149部(無機塩含有、純度69.2%)(0.521mol)を得た。
式(A2−b)で表される塩99部(純度69.2%)(0.346mol)及びメタノール600部を仕込み、これに硫酸18.8部を加えた後、24時間加熱還流した。その後、得られた反応物を濃縮してメタノールを留去した後、n−ヘプタン477部添加し、撹拌後、濾過した。得られた残渣にアセトニトリル434部を添加撹拌した後、濾過し、さらに残渣にアセトニトリル197部を添加撹拌した後、濾過した。濾液を合わせて濃縮することにより、式(A2)で表される塩73.1部(0.345mol)を得た。
A mixture of 100 parts (0.521 mol) of the compound represented by the formula (A2-a) and 250 parts of ion-exchanged water was placed in an ice bath, and 230 parts of a 30% aqueous sodium hydroxide solution was added dropwise thereto. The resulting mixture was heated and stirred at 100 ° C. for 2 hours, cooled, and then neutralized with 88 parts of concentrated hydrochloric acid. The obtained solution was concentrated to obtain 149 parts of salt represented by formula (A2-b) (containing inorganic salt, purity: 69.2%) (0.521 mol).
99 parts (purity 69.2%) (0.346 mol) of salt represented by the formula (A2-b) and 600 parts of methanol were charged, and 18.8 parts of sulfuric acid was added thereto, followed by heating under reflux for 24 hours. Then, after concentrating the obtained reaction material and distilling methanol off, 477 parts of n-heptane was added, and after stirring, it filtered. To the obtained residue, 434 parts of acetonitrile was added and stirred, followed by filtration. Further, 197 parts of acetonitrile was added to the residue and stirred, followed by filtration. The filtrates were combined and concentrated to obtain 73.1 parts (0.345 mol) of the salt represented by the formula (A2).
実施例2
[式(C2)で表される塩の合成例]
式(B1)で表される塩2.77部(0.00710mol)及びクロロホルム13.83部の溶液に、塩化銀1.02部(0.00712mol)を添加し、23℃で12時間攪拌した。得られたクロロホルム溶液に、式(A2)で表される塩2.18部(純度69.2%)(0.00710mol)とイオン交換水6.40部との水溶液を滴下し、更に、クロロホルム13.85部を加え、23℃で12時間撹拌後、濾過して、濾液を回収した。回収された濾液が2層に分離していたので、クロロホルム層を分液し、更に、イオン交換水7.21部を添加し、クロロホルム層を水洗した。この水洗操作を5回繰り返した。得られたクロロホルム層を濃縮し、淡黄色オイル3.22部を得た。得られた淡黄色オイルに酢酸エチル9.66部を添加し攪拌すると、結晶が析出し、濾過して白色固体として式(C2)で表される塩2.85部(純度100%、収率89%)(0.00630mol)を得た。塩化銀の使用量は、式(A2)で表される塩1モルに対して、1.0モルであった。
収率=100×0.00630/0.00710=88.7
Example 2
[Synthesis Example of Salt Represented by Formula (C2)]
To a solution of 2.77 parts (0.00710 mol) of the salt represented by the formula (B1) and 13.83 parts of chloroform, 1.02 part (0.00712 mol) of silver chloride was added and stirred at 23 ° C. for 12 hours. . An aqueous solution of 2.18 parts (purity 69.2%) (0.00710 mol) of the salt represented by the formula (A2) and 6.40 parts of ion-exchanged water and 6.40 parts of ion-exchanged water was added dropwise to the resulting chloroform solution. 13.85 parts were added, and the mixture was stirred at 23 ° C. for 12 hours and then filtered to collect the filtrate. Since the collected filtrate was separated into two layers, the chloroform layer was separated, and 7.21 parts of ion-exchanged water was added, and the chloroform layer was washed with water. This washing operation was repeated 5 times. The obtained chloroform layer was concentrated to obtain 3.22 parts of pale yellow oil. When 9.66 parts of ethyl acetate was added to the obtained pale yellow oil and stirred, crystals were precipitated and filtered to obtain 2.85 parts of salt represented by the formula (C2) as a white solid (purity 100%, yield). 89%) (0.00630 mol). The amount of silver chloride used was 1.0 mol with respect to 1 mol of the salt represented by the formula (A2).
Yield = 100 × 0.00630 / 0.00710 = 88.7
比較例1
[式(C2)で表される塩の合成例]
実施例2において、塩化銀1.02部(0.00712mol)に代えて、ジエチル硫酸[(C2H5)2SO4]1.08部(0.00712mol)を用いる以外は実施例2と同様にして、反応を行い、白色固体として式(C2)で表される塩0.92部(純度96%、収率29%)(0.00203mol)を得た。
収率=100×0.00203/0.00710=28.6
Comparative Example 1
[Synthesis Example of Salt Represented by Formula (C2)]
In Example 2, Example 2 was used except that 1.08 part (0.00712 mol) of diethyl sulfate [(C 2 H 5 ) 2 SO 4 ] was used instead of 1.02 part (0.00712 mol) of silver chloride. The reaction was conducted in the same manner to obtain 0.92 parts (purity 96%, yield 29%) (0.00203 mol) of the salt represented by the formula (C2) as a white solid.
Yield = 100 × 0.00203 / 0.00710 = 28.6
実施例3
[式(C3)で表される塩の合成例]
式(B3)で表される塩9.74部(0.0194mol)及びクロロホルム48.69部の溶液に、塩化銀2.78部(0.0194mol)を添加し、23℃で12時間攪拌した。得られたクロロホルム溶液に、式(A2)で表される塩5.94部(純度69.2%)(0.0194mol)とイオン交換水11.88部との水溶液を滴下し、23℃で12時間撹拌後、濾過して、濾液を回収した。回収された濾液が2層に分離していたので、クロロホルム層を分液し、更に、イオン交換水12.17部を添加し、クロロホルム層を水洗した。この水洗操作を5回繰り返した。得られたクロロホルム層を濃縮し、淡黄色オイル16.75部を得た。得られた淡黄色オイルにメチル−t−ブチルエーテル45.85部、酢酸エチル30.56部を添加し攪拌後、2層に分離していたので、下層を取り出し濃縮することにより淡黄色オイルとして式(C3)で表される塩8.48部(純度100%、収率77%)(0.0150mol)を得た。塩化銀の使用量は、式(A2)で表される塩1モルに対して、1.0モルであった。
収率=100×0.0150/0.0194=77.3
Example 3
[Synthesis Example of Salt Represented by Formula (C3)]
To a solution of 9.74 parts (0.0194 mol) of the salt represented by the formula (B3) and 48.69 parts of chloroform, 2.78 parts (0.0194 mol) of silver chloride was added and stirred at 23 ° C. for 12 hours. . An aqueous solution of 5.94 parts (purity 69.2%) (0.0194 mol) of the salt represented by the formula (A2) and 11.88 parts of ion-exchanged water and 11.88 parts of ion-exchanged water was added dropwise to the obtained chloroform solution. After stirring for 12 hours, the filtrate was recovered by filtration. Since the collected filtrate was separated into two layers, the chloroform layer was separated, and 12.17 parts of ion-exchanged water was further added, and the chloroform layer was washed with water. This washing operation was repeated 5 times. The obtained chloroform layer was concentrated to obtain 16.75 parts of pale yellow oil. After adding 45.85 parts of methyl-t-butyl ether and 30.56 parts of ethyl acetate to the obtained pale yellow oil and stirring, it was separated into two layers. The lower layer was taken out and concentrated to obtain a pale yellow oil. 8.48 parts (purity 100%, yield 77%) (0.0150 mol) of the salt represented by (C3) were obtained. The amount of silver chloride used was 1.0 mol with respect to 1 mol of the salt represented by the formula (A2).
Yield = 100 × 0.0150 / 0.0194 = 77.3
比較例2
[式(C3)で表される塩の合成例]
実施例3において、塩化銀2.78部(0.0194mol)に代えて、ジエチル硫酸[(C2H5)2SO4]2.99部(0.0194mol)を用いる以外は実施例3と同様にして、反応を行い、淡黄色オイルとして式(C3)で表される塩4.15部(純度61%、収率23%)(0.00448mol)を得た。
収率=100×0.00448/0.0194=23.1
Comparative Example 2
[Synthesis Example of Salt Represented by Formula (C3)]
In Example 3, Example 3 was used except that 2.99 parts (0.0194 mol) of diethyl sulfate [(C 2 H 5 ) 2 SO 4 ] was used instead of 2.78 parts (0.0194 mol) of silver chloride. The reaction was conducted in the same manner to obtain 4.15 parts (purity 61%, yield 23%) (0.00448 mol) of the salt represented by the formula (C3) as a pale yellow oil.
Yield = 100 × 0.00448 / 0.0194 = 23.1
実施例4
[式(C4)で表される塩の合成例]
式(B4)で表される塩8.66部(0.0155mol)及びクロロホルム43.30部の溶液に、塩化銀2.22部(0.0155mol)を添加し、23℃で12時間攪拌した。得られたクロロホルム溶液に、式(A2)で表される塩4.75部(純度69.2%)(0.0155mol)とイオン交換水9.50部との水溶液を滴下し、23℃で12時間撹拌後、濾過して、濾液を回収した。回収された濾液が2層に分離していたので、クロロホルム層を分液し、更に、イオン交換水12.99部を添加し、クロロホルム層を水洗した。この水洗操作を5回繰り返した。得られたクロロホルム層を濃縮し、淡黄色オイル12.25部を得た。得られた淡黄色オイルにメチル−tert−ブチルエーテル61.25部を添加すると、結晶が析出し、濾過して白色固体として式(C4)で表される塩7.25部(純度100%、収率75%)(0.0117mol)を得た。塩化銀の使用量は、式(A2)で表される塩1モルに対して、1.0モルであった。
収率=100×0.00117/0.0155=75.4
Example 4
[Synthesis Example of Salt Represented by Formula (C4)]
To a solution of 8.66 parts (0.0155 mol) of the salt represented by the formula (B4) and 43.30 parts of chloroform, 2.22 parts (0.0155 mol) of silver chloride was added and stirred at 23 ° C. for 12 hours. . An aqueous solution of 4.75 parts (purity 69.2%) (0.0155 mol) of the salt represented by the formula (A2) and 9.50 parts of ion-exchanged water and 9.50 parts of ion-exchanged water was added dropwise to the obtained chloroform solution. After stirring for 12 hours, the filtrate was recovered by filtration. Since the recovered filtrate was separated into two layers, the chloroform layer was separated, and 12.99 parts of ion-exchanged water was further added, and the chloroform layer was washed with water. This washing operation was repeated 5 times. The obtained chloroform layer was concentrated to obtain 12.25 parts of pale yellow oil. When 61.25 parts of methyl-tert-butyl ether was added to the obtained pale yellow oil, crystals were precipitated and filtered to give 7.25 parts of salt represented by the formula (C4) as a white solid (purity 100%, yield). 75%) (0.0117 mol). The amount of silver chloride used was 1.0 mol with respect to 1 mol of the salt represented by the formula (A2).
Yield = 100 × 0.00117 / 0.0155 = 75.4
比較例3
[式(C4)で表される塩の合成例]
実施例4において、塩化銀2.22部(0.0155mol)に代えて、ジエチル硫酸[(C2H5)2SO4]2.47部(0.0155mol)を用いる以外は実施例4と同様にして、反応を行い、白色固体として式(C4)で表される塩2.12部(純度100%、収率22%)(0.00341mol)を得た。
収率=100×0.00341/0.0155=22
Comparative Example 3
[Synthesis Example of Salt Represented by Formula (C4)]
In Example 4, instead of 2.22 parts (0.0155 mol) of silver chloride, Example 4 was used except that 2.47 parts (0.0155 mol) of diethyl sulfate [(C 2 H 5 ) 2 SO 4 ] was used. Similarly, the reaction was performed to obtain 2.12 parts (purity 100%, yield 22%) (0.00341 mol) represented by the formula (C4) as a white solid.
Yield = 100 × 0.00341 / 0.0155 = 22
実施例5
[式(C5)で表される塩の合成例]
式(B5)で表される塩6.92部(0.0155mol)及びクロロホルム34.60部の溶液に、塩化銀2.22部(0.0155mol)を添加し、23℃で12時間攪拌した。得られたクロロホルム溶液に、式(A2)で表される塩4.75部(純度69.2%)(0.0155mol)とイオン交換水9.50部との水溶液を滴下し、23℃で12時間撹拌後、濾過して、濾液を回収した。回収された濾液が2層に分離していたので、クロロホルム層を分液し、更に、イオン交換水10.38部を添加し、クロロホルム層を水洗した。この水洗操作を5回繰り返した。得られたクロロホルム層を濃縮し、淡黄色オイル10.15部を得た。得られた淡黄色オイルにメチル−tert−ブチルエーテル50.75部を添加し攪拌後、2層に分離していたので、下層を取り出し濃縮することにより淡黄色オイルとして式(C5)で表される塩7.35部(純度100%、収率94%)(0.0145mol)を得た。塩化銀の使用量は、式(A2)で表される塩1モルに対して、1.0モルであった。
収率=100×0.0145/0.0155=93.5
Example 5
[Synthesis Example of Salt Represented by Formula (C5)]
To a solution of 6.92 parts (0.0155 mol) of the salt represented by the formula (B5) and 34.60 parts of chloroform, 2.22 parts (0.0155 mol) of silver chloride was added and stirred at 23 ° C. for 12 hours. . An aqueous solution of 4.75 parts (purity 69.2%) (0.0155 mol) of the salt represented by the formula (A2) and 9.50 parts of ion-exchanged water and 9.50 parts of ion-exchanged water was added dropwise to the obtained chloroform solution. After stirring for 12 hours, the filtrate was recovered by filtration. Since the recovered filtrate was separated into two layers, the chloroform layer was separated, and 10.38 parts of ion-exchanged water was further added, and the chloroform layer was washed with water. This washing operation was repeated 5 times. The obtained chloroform layer was concentrated to obtain 10.15 parts of pale yellow oil. After adding 50.75 parts of methyl-tert-butyl ether to the obtained pale yellow oil and stirring, it was separated into two layers. By removing the lower layer and concentrating, it was expressed by the formula (C5) as a pale yellow oil. 7.35 parts of salt (purity 100%, yield 94%) (0.0145 mol) were obtained. The amount of silver chloride used was 1.0 mol with respect to 1 mol of the salt represented by the formula (A2).
Yield = 100 × 0.0145 / 0.0155 = 93.5
比較例4
[式(C5)で表される塩の合成例]
実施例5において、塩化銀2.22部(0.0155mol)に代えて、ジエチル硫酸[(C2H5)2SO4]2.47部(0.0155mol)を用いる以外は実施例5と同様にして、反応を行い、淡黄色オイルとして式(C5)で表される塩2.29部(純度100%、収率29%)(0.00450mol)を得た。
収率=100×0.00450/0.0155=29.0
Comparative Example 4
[Synthesis Example of Salt Represented by Formula (C5)]
In Example 5, Example 2 was used except that 2.47 parts (0.0155 mol) of diethyl sulfate [(C 2 H 5 ) 2 SO 4 ] was used instead of 2.22 parts (0.0155 mol) of silver chloride. The reaction was conducted in the same manner to obtain 2.29 parts (purity 100%, yield 29%) (0.00450 mol) of the salt represented by the formula (C5) as a pale yellow oil.
Yield = 100 × 0.00450 / 0.0155 = 29.0
実施例6
[式(C1)で表される塩の合成例]
実施例1において、塩化銀の使用量を1.02部(0.00712mol)に代えて2.04部(0.0142mol)とする以外は実施例1と同様にして、反応を行い、白色固体として式(C1)で表される塩3.66部(純度100%、収率88%)(0.00624mol)を得た。塩化銀の使用量は、式(A1)で表される塩1モルに対して、2.0モルであった。
収率=100×0.00624/0.0710=87.9
Example 6
[Synthesis Example of Salt Represented by Formula (C1)]
In Example 1, the reaction was performed in the same manner as in Example 1 except that the amount of silver chloride used was changed to 2.04 parts (0.0142 mol) instead of 1.02 parts (0.00712 mol). As a result, 3.66 parts (purity 100%, yield 88%) (0.00624 mol) of the salt represented by the formula (C1) was obtained. The amount of silver chloride used was 2.0 mol with respect to 1 mol of the salt represented by the formula (A1).
Yield = 100 × 0.00624 / 0.0710 = 87.9
実施例7
[式(C1)で表される塩の合成例]
実施例1において、塩化銀の使用量を1.02部(0.00712mol)に代えて3.06部(0.0214mol)とする以外は実施例1と同様にして、反応を行い、白色固体として式(C1)で表される塩3.58部(純度100%、収率86%)(0.00610mol)を得た。塩化銀の使用量は、式(A1)で表される塩1モルに対して、3.0モルであった。
収率=100×0.00610/0.0710=85.9
Example 7
[Synthesis Example of Salt Represented by Formula (C1)]
In Example 1, the reaction was performed in the same manner as in Example 1 except that the amount of silver chloride used was changed to 3.06 parts (0.0214 mol) instead of 1.02 parts (0.00712 mol). As a result, 3.58 parts (purity 100%, yield 86%) (0.00610 mol) of the salt represented by the formula (C1) was obtained. The amount of silver chloride used was 3.0 mol with respect to 1 mol of the salt represented by the formula (A1).
Yield = 100 × 0.00610 / 0.0710 = 85.9
実施例8
[式(C1)で表される塩の合成例]
実施例1において、塩化銀の使用量を1.02部(0.00712mol)に代えて1.12部(0.00781mol)とする以外は実施例1と同様にして、反応を行い、白色固体として式(C1)で表される塩3.61部(純度100%、収率87%)(0.00615mol)を得た。塩化銀の使用量は、式(A1)で表される塩1モルに対して、1.1モルであった。
収率=100×0.00615/0.0710=86.6
Example 8
[Synthesis Example of Salt Represented by Formula (C1)]
In Example 1, the reaction was performed in the same manner as in Example 1 except that the amount of silver chloride used was changed to 1.12 parts (0.00781 mol) instead of 1.02 parts (0.00712 mol). As a result, 3.61 parts (purity 100%, yield 87%) (0.00615 mol) of the salt represented by the formula (C1) was obtained. The amount of silver chloride used was 1.1 mol with respect to 1 mol of the salt represented by the formula (A1).
Yield = 100 × 0.00615 / 0.0710 = 86.6
実施例9
[式(C1)で表される塩の合成例]
実施例1において、塩化銀の使用量を1.02部(0.00712mol)に代えて1.22部(0.00851mol)とする以外は実施例1と同様にして、反応を行い、白色固体として式(C1)で表される塩3.63部(純度100%、収率87%)(0.00619mol)を得た。塩化銀の使用量は、式(A1)で表される塩1モルに対して、1.2モルであった。
収率=100×0.00619/0.0710=87.2
Example 9
[Synthesis Example of Salt Represented by Formula (C1)]
In Example 1, the reaction was performed in the same manner as in Example 1 except that the amount of silver chloride used was changed to 1.22 parts (0.00851 mol) instead of 1.02 parts (0.00712 mol), and a white solid was obtained. As a result, 3.63 parts (purity 100%, yield 87%) (0.00619 mol) of the salt represented by the formula (C1) was obtained. The amount of silver chloride used was 1.2 mol with respect to 1 mol of the salt represented by the formula (A1).
Yield = 100 × 0.00619 / 0.0710 = 87.2
[式(A3)で表される塩の合成]
リチウムアルミニウムハイドライド10.4部(0.275mol)、無水テトラヒドロフラン120部を仕込み23℃で30分間攪拌した。式(A3−a)で表される塩62.2部(0.275mol)を無水THF900部に溶かした溶液を氷冷下で滴下し、23℃で5時間攪拌した。反応マスに酢酸エチル50.0部、6N塩酸50.00部を添加、攪拌後、分液を行った。有機層を濃縮後、カラム(メルク シリカゲル60−200メッシュ 展開溶媒:クロロホルム/メタノール=5/1)分取することにより、式(A3−b)で表される塩84.7g(純度60%)(0.275mol)を得た。
式(A3−c)で表される化合物4.5部(0.0232mol)及び無水THF90部を添加し室温で30分間攪拌し溶解した。この溶液にカルボニルジイミダゾール3.77部(0.0233mol)、無水THF45部の混合溶液を室温で滴下し、23℃で4時間攪拌した。得られた反応溶液を、式(A3−b)で表される塩7.87部(純度60%)(0.0256mol)及び無水THF50部の混合中に、54℃〜60℃で30分間で滴下した。反応溶液を65℃で18時間加熱し、冷却後、ろ過した。得られたろ液を濃縮し、濃縮物をカラム(メルク シリカゲル60−200メッシュ 展開溶媒:クロロホルム/メタノール=5/1)分取することにより、式(A3)で表される塩4.97部(0.0138mol)を得た。
[Synthesis of Salt Represented by Formula (A3)]
10.4 parts (0.275 mol) of lithium aluminum hydride and 120 parts of anhydrous tetrahydrofuran were charged and stirred at 23 ° C. for 30 minutes. A solution prepared by dissolving 62.2 parts (0.275 mol) of the salt represented by the formula (A3-a) in 900 parts of anhydrous THF was added dropwise under ice cooling, and the mixture was stirred at 23 ° C. for 5 hours. To the reaction mass, 50.0 parts of ethyl acetate and 50.00 parts of 6N hydrochloric acid were added, followed by liquid separation. After concentrating the organic layer, by separating the column (Merck silica gel 60-200 mesh developing solvent: chloroform / methanol = 5/1), 84.7 g of salt represented by the formula (A3-b) (purity 60%) (0.275 mol) was obtained.
4.5 parts (0.0232 mol) of the compound represented by the formula (A3-c) and 90 parts of anhydrous THF were added and dissolved by stirring for 30 minutes at room temperature. To this solution, a mixed solution of 3.77 parts (0.0233 mol) of carbonyldiimidazole and 45 parts of anhydrous THF was added dropwise at room temperature, followed by stirring at 23 ° C. for 4 hours. The obtained reaction solution was mixed with 7.87 parts (purity 60%) (0.0256 mol) of the salt represented by the formula (A3-b) and 50 parts of anhydrous THF at 54 ° C to 60 ° C for 30 minutes. It was dripped. The reaction solution was heated at 65 ° C. for 18 hours, cooled and then filtered. The obtained filtrate was concentrated, and the concentrate was fractionated in a column (Merck silica gel 60-200 mesh developing solvent: chloroform / methanol = 5/1), whereby 4.97 parts of the salt represented by the formula (A3) ( 0.0138 mol) was obtained.
実施例10
[式(C6)で表される塩の合成例]
式(B1)で表される塩2.77部(0.00710mol)及びクロロホルム15部を仕込んだ溶液に、塩化銀1.02部(0.00712mol)を添加し、これを23℃で12時間攪拌した。該クロロホルム溶液に、式(A3)で表される塩2.56部(0.00710mol)及びイオン交換水10.00部を仕込み、更に、クロロホルム30部を加え、23℃で12時間撹拌した後、濾過して濾液を回収した。得られた濾液が2層に分離していたので、クロロホルム層を分液して取り出し、更に、該クロロホルム層にイオン交換水10部を添加し、水洗した。この操作を5回繰り返した。その後、硫酸マグネシウム1部を添加、23℃で30分間攪拌後、ろ過し、ろ液を濃縮して、式(C6)で表される塩3.92部(純度100%、収率92%)(0.00653mol)を得た。
収率=100×0.00653/0.0710=92.0
Example 10
[Synthesis Example of Salt Represented by Formula (C6)]
To a solution charged with 2.77 parts (0.00710 mol) of the salt represented by the formula (B1) and 15 parts of chloroform, 1.02 part (0.00712 mol) of silver chloride was added, and this was added at 23 ° C. for 12 hours. Stir. To the chloroform solution, 2.56 parts (0.00710 mol) of the salt represented by the formula (A3) and 10.00 parts of ion-exchanged water were added, and 30 parts of chloroform was further added, followed by stirring at 23 ° C. for 12 hours. The filtrate was recovered by filtration. Since the obtained filtrate was separated into two layers, the chloroform layer was separated and taken out. Further, 10 parts of ion exchange water was added to the chloroform layer and washed with water. This operation was repeated 5 times. Thereafter, 1 part of magnesium sulfate was added, stirred at 23 ° C. for 30 minutes, filtered, and the filtrate was concentrated to give 3.92 parts of the salt represented by the formula (C6) (purity 100%, yield 92%). (0.00653 mol) was obtained.
Yield = 100 × 0.00653 / 0.0710 = 92.0
参考例
[式(C6)で表される塩の合成例]
式(A3)で表される塩1.0部(0.00277mol)、クロロホルム20部を仕込み、23℃で30分間攪拌後、更に式(B2)で表される塩(13.1%水溶液)6.3部(0.00277mol)を23℃で加えた。
12時間室温で攪拌した後、分液を行った。有機層にイオン交換水10部を添加、分液水洗を行った。この操作を5回行った。その後、硫酸マグネシウム1部を添加、23℃で30分間攪拌後、ろ過し、ろ液を濃縮して、式(C6)で表される塩1.36部(純度100%、収率82%)(0.00226mol)を得た。
収率=100×0.00226/0.0277=81.5
Reference Example [Synthesis Example of Salt Represented by Formula (C6)]
1.0 part (0.00277 mol) of a salt represented by the formula (A3) and 20 parts of chloroform were added, stirred at 23 ° C. for 30 minutes, and further a salt represented by the formula (B2) (13.1% aqueous solution). 6.3 parts (0.00277 mol) was added at 23 ° C.
After stirring at room temperature for 12 hours, liquid separation was performed. 10 parts of ion-exchanged water was added to the organic layer, followed by liquid separation washing. This operation was performed 5 times. Thereafter, 1 part of magnesium sulfate was added, stirred at 23 ° C. for 30 minutes, filtered, and the filtrate was concentrated to obtain 1.36 parts of a salt represented by the formula (C6) (purity 100%, yield 82%). (0.00226 mol) was obtained.
Yield = 100 × 0.00226 / 0.0277 = 81.5
合成例1
〔樹脂(1)の合成〕
モノマーA、モノマーB、モノマーDをモル比50:25:25の比率で仕込み、全モノマーの合計質量に対して1.5質量倍のジオキサンを加えて溶液とした。そこに開始剤としてアゾビスイソブチロニトリルとアゾビス(2,4−ジメチルバレロニトリル)とを全モノマーの合計モル数に対して、それぞれ、1mol%と3mol%との比率で添加し、77℃で約5時間加熱した。その後、反応液を、大量のメタノールと水の混合溶媒に注いで沈殿させる操作を3回行って精製し、重量平均分子量が約8000である共重合体(1)を収率60%で得た。
Synthesis example 1
[Synthesis of Resin (1)]
Monomer A, monomer B, and monomer D were charged at a molar ratio of 50:25:25, and 1.5 mass times dioxane was added to the total mass of all monomers to obtain a solution. Thereto, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators at a ratio of 1 mol% and 3 mol%, respectively, with respect to the total number of moles of all monomers, and 77 ° C. For about 5 hours. Thereafter, the reaction solution was purified by pouring it into a large amount of methanol / water mixed solvent for precipitation three times to obtain a copolymer (1) having a weight average molecular weight of about 8000 in a yield of 60%. .
参考例1
以下の各成分を混合して溶解し、さらに孔径0.2μmのフッ素樹脂製フィルターで濾過して、レジスト組成物を調製した。
Reference example 1
The following components were mixed and dissolved, and further filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.
<酸発生剤>
式(C1)で表される塩
式(C6)で表される塩
<樹脂>
樹脂(1)
<クエンチャー>
Q1:2,6−ジイソプロピルアニリン
<溶剤>
プロピレングリコールモノメチルエーテルアセテート 265部
2−ヘプタノン 20.0部
プロピレングリコールモノメチルエーテル 20.0部
γ−ブチロラクトン 3.5部
<Acid generator>
Salt represented by formula (C1) Salt represented by formula (C6) <Resin>
Resin (1)
<Quencher>
Q1: 2,6-diisopropylaniline <solvent>
Propylene glycol monomethyl ether acetate 265 parts 2-heptanone 20.0 parts Propylene glycol monomethyl ether 20.0 parts γ-butyrolactone 3.5 parts
シリコンウェハーに、有機反射防止膜用組成物(ARC−29;日産化学(株)製)を塗布して、205℃、60秒の条件でベークすることによって、厚さ780Åの有機反射防止膜を形成させた。次いで、前記の有機反射防止膜の上に、上記のレジスト組成物を乾燥後の膜厚が0.15μmとなるようにスピンコートした。レジスト組成物塗布後は、ダイレクトホットプレート上にて、95℃で60秒間プリベーク(以下、PBと略す。)した。こうしてレジスト膜を形成したそれぞれのシリコンウェハーに、ArFエキシマステッパー(FPA5000−AS3;(株)キャノン製、NA=0.75、2/3Annular)を用いて、露光量を段階的に変化させてラインアンドスペースパターンを露光した。
露光後は、ホットプレート上にて95℃で60秒間ポストエキスポジャーベーク(以下、PEBと略す。)を行い、さらに2.38重量%テトラメチルアンモニウムヒドロキシド水溶液で60秒間のパドル現像を行った。
有機反射防止膜基板上のもので現像後のダークフィールドパターンを走査型電子顕微鏡で観察し、その結果を表2に示した。なお、ここでいうダークフィールドパターンとは、外側にクロム層(遮光層)をベースとしてライン状にガラス面(透光部)が形成されたレチクルを介した露光及び現像によって得られ、したがって露光現像後は、ラインアンドスペースパターンの周囲のレジスト層が残されるパターンである。
実効感度:100nmのラインアンドスペースパターンが1:1となる露光量で示した。
An organic antireflective coating composition (ARC-29; manufactured by Nissan Chemical Co., Ltd.) is applied to a silicon wafer and baked at 205 ° C. for 60 seconds to form an organic antireflective coating having a thickness of 780 mm. Formed. Subsequently, the resist composition was spin-coated on the organic antireflection film so that the film thickness after drying was 0.15 μm. After application of the resist composition, it was pre-baked (hereinafter abbreviated as PB) at 95 ° C. for 60 seconds on a direct hot plate. Each of the silicon wafers thus formed with the resist film is lined by changing the exposure amount in stages using an ArF excimer stepper (FPA5000-AS3; manufactured by Canon Inc., NA = 0.75, 2/3 Annular). The andspace pattern was exposed.
After exposure, post-exposure baking (hereinafter abbreviated as PEB) was performed at 95 ° C. for 60 seconds on a hot plate, and paddle development was further performed for 60 seconds with a 2.38 wt% tetramethylammonium hydroxide aqueous solution. .
The dark field pattern after development on the organic antireflection film substrate was observed with a scanning electron microscope. The results are shown in Table 2. The dark field pattern referred to here is obtained by exposure and development through a reticle having a glass surface (translucent portion) formed in a line form on the outside with a chromium layer (light-shielding layer) as a base, and thus exposure development. The rest is a pattern in which the resist layer around the line and space pattern is left.
Effective sensitivity: The exposure amount at which a 100 nm line and space pattern is 1: 1 is shown.
本発明の製造方法により得られた塩は、化学増幅型フォトレジスト組成物に用いられる
酸発生剤として有用であることが確認された。
It was confirmed that the salt obtained by the production method of the present invention is useful as an acid generator used in a chemically amplified photoresist composition.
本発明の製造方法によれば、得られる塩の収率が高い。 According to the production method of the present invention, the yield of the obtained salt is high.
Claims (4)
Z+X− (A)
A+−O3SR (B)
[ 式(A)、式(B)及び式(I)中、Z+は、有機カチオンを表し、X−は、Br−又はI−を表し、A+は、アルカリ金属カチオンを表す。
Rは、*−CQ1Q2−X1−Y1を表す。*はSO3 −との結合手を表す。
Q1及びQ2は、互いに独立に、フッ素原子又は炭素数1〜6のペルフルオロアルキル基を表す。
X1は、単結合又は−[CH2]k−を表し、該−[CH2]k−に含まれるメチレン基は酸素原子及び/又はカルボニル基で置換されていてもよく、該−[CH2]k−に含まれる水素原子は直鎖状又は分岐状の炭素数1〜4の脂肪族炭化水素基で置換されていてもよい。kは、1〜17の整数を表す。
Y1は、炭素数4〜36の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる水素原子は、炭化水素基(該炭化水素基に含まれるメチレン基は酸素原子又はオキシカルボニル基で置換されていてもよい)、芳香族炭化水素基、水酸基又は水酸基を含む基で置換されていてもよく、該脂環式炭化水素基に含まれるメチレン基は酸素原子で置換されてエーテル構造を有していてもよく、該脂環式炭化水素基に含まれるメチレン基は、カルボニル基で置換されてケトン構造を有していてもよく、該脂環式炭化水素基に含まれる隣接する2つのメチレン基が、それぞれカルボニル基又は酸素原子で置換されてラクトン構造を有してもよい。ただし、水酸基又は水酸基を含む基で置換された炭素数4〜36の脂環式炭化水素基はラクトン構造を有さない。] A method for producing a salt represented by formula (I), comprising reacting a salt represented by formula (A) and a salt represented by formula (B) in the presence of silver chloride.
Z + X − (A)
A + -O 3 SR (B)
[In Formula (A), Formula (B), and Formula (I), Z + represents an organic cation, X − represents Br − or I − , and A + represents an alkali metal cation.
R is, * - representing the CQ 1 Q 2 -X 1 -Y 1 . * Is SO 3 - represents a bond to.
Q 1 and Q 2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
X 1 represents a single bond or — [CH 2 ] k —, and the methylene group contained in — [CH 2 ] k — may be substituted with an oxygen atom and / or a carbonyl group. 2 ] The hydrogen atom contained in k- may be substituted with a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms. k represents an integer of 1 to 17.
Y 1 represents an alicyclic hydrocarbon group having 4 to 36 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group is a hydrocarbon group (the methylene group contained in the hydrocarbon group is an oxygen atom or May be substituted with an oxycarbonyl group), may be substituted with an aromatic hydrocarbon group, a hydroxyl group or a group containing a hydroxyl group, and the methylene group contained in the alicyclic hydrocarbon group is substituted with an oxygen atom. May have an ether structure, and the methylene group contained in the alicyclic hydrocarbon group may be substituted with a carbonyl group to have a ketone structure, and is contained in the alicyclic hydrocarbon group. Two adjacent methylene groups may each be substituted with a carbonyl group or an oxygen atom to have a lactone structure. However, the C4-C36 alicyclic hydrocarbon group substituted with a hydroxyl group or a group containing a hydroxyl group does not have a lactone structure. ]
[式(IXa)中、P a 、P b 及びP c は、互いに独立に、直鎖状又は分岐状の炭素数1〜30のアルキル基あるいは炭素数3〜30の脂環式炭化水素基を表す。P a 、P b 及びP c のいずれかがアルキル基である場合、該アルキル基は、水酸基、直鎖状又は分岐状の炭素数1〜12のアルコキシ基あるいは炭素数3〜12の脂環式炭化水素基で置換されていてもよく、P a 、P b 及びP c のいずれかが脂環式炭化水素基である場合には、水酸基、直鎖状又は分岐状の炭素数1〜12のアルキル基あるいは炭素数1〜12のアルコキシ基で置換されていてもよい。] The method according to claim 1 or 2, wherein Z + is a cation represented by the formula (IXa) .
[In the formula (IXa), P a , P b and P c are each independently a linear or branched alkyl group having 1 to 30 carbon atoms or an alicyclic hydrocarbon group having 3 to 30 carbon atoms. Represent. When any of P a , P b and P c is an alkyl group, the alkyl group is a hydroxyl group, a linear or branched alkoxy group having 1 to 12 carbon atoms or an alicyclic group having 3 to 12 carbon atoms. It may be substituted with a hydrocarbon group, and when any of P a , P b and P c is an alicyclic hydrocarbon group, it is a hydroxyl group, a linear or branched C 1-12. It may be substituted with an alkyl group or an alkoxy group having 1 to 12 carbon atoms. ]
[式(IXaa)中、P 1 〜P 3 は、互いに独立に、水素原子、水酸基、直鎖状又は分岐状の炭素数1〜12のアルキル基、直鎖状又は分岐状の炭素数1〜12のアルコキシ基あるいは炭素数4〜36の脂環式炭化水素を表し、該脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、水酸基、直鎖状又は分岐状の炭素数1〜12のアルキル基、直鎖状又は分岐状の炭素数1〜12のアルコキシ基、炭素数6〜12のアリール基、炭素数7〜12のアラルキル基、グリシドキシ基あるいは炭素数2〜4のアシル基で置換されていてもよい。] The production method according to claim 1 or 2, wherein the Z + is a cation represented by the formula (IXaa) .
[In Formula (IXaa), P 1 to P 3 are each independently a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched carbon number 1 to 1. Represents an alkoxy group having 12 carbon atoms or an alicyclic hydrocarbon having 4 to 36 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, a hydroxyl group, a linear or branched carbon atom having 1 to 12 carbon atoms. An alkyl group, a linear or branched alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidoxy group, or an acyl group having 2 to 4 carbon atoms. May be substituted. ]
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