KR102141103B1 - Compound and process for producing the same - Google Patents
Compound and process for producing the same Download PDFInfo
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- KR102141103B1 KR102141103B1 KR1020190025989A KR20190025989A KR102141103B1 KR 102141103 B1 KR102141103 B1 KR 102141103B1 KR 1020190025989 A KR1020190025989 A KR 1020190025989A KR 20190025989 A KR20190025989 A KR 20190025989A KR 102141103 B1 KR102141103 B1 KR 102141103B1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
- C07D311/84—Xanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D311/88—Nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/14—Benzoxanthene dyes; Benzothioxanthene dyes
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Abstract
식 (Ｉ)로 나타내는 화합물을 제공한다.
[식 (Ｉ)에서, R1은 탄소수 1 내지 8개의 지방족 탄화수소기 또는 탄소수 5 내지 8개의 지환식 탄화수소기를 나타내고, 상기 지방족 탄화수소기에 포함되는 수소 원자는 탄소수 6 내지 10개의 방향족 탄화수소기(상기 방향족 탄화수소기에 포함되는 수소 원자는 탄소수 1 내지 3개의 알킬기 또는 탄소수 1 내지 3개의 알콕시기로 치환되어 있어도 됨)로 치환되어 있어도 된다. Ar은 식 (ｉ)로 나타내는 기를 나타낸다.
(식 (ｉ)에서, R2는 탄소수 1 내지 3개의 알킬기를 나타내고, 상기 알킬기에 포함되는 수소 원자는 할로겐 원자로 치환되어 있어도 된다. m은 1 내지 5의 정수를 나타낸다. m이 2 이상일 경우, 복수의 R2는 각각 동일하거나 상이하여도 된다. *는 질소 원자와의 결합팔을 나타냄)] The compound represented by Formula (I) is provided.
[In the formula (I), R 1 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 5 to 8 carbon atoms, and the hydrogen atom contained in the aliphatic hydrocarbon group is an aromatic hydrocarbon group having 6 to 10 carbon atoms (the aromatic The hydrogen atom contained in the hydrocarbon group may be substituted with an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms). Ar represents a group represented by formula (i).
(In the formula (i), R 2 represents an alkyl group having 1 to 3 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom. m represents an integer of 1 to 5. When m is 2 or more, The plurality of R 2 may be the same or different, respectively. * represents a bonding arm with a nitrogen atom)]
Description
본 발명은 염료로서 유용한 화합물 및 이의 제조 방법에 관한 것이다. The present invention relates to compounds useful as dyes and methods for their preparation.
염료는, 예를 들어 섬유 재료, 액정 표시 장치, 잉크젯 등의 분야에서 반사광 또는 투과광을 이용하여 색을 표시하기 위하여 사용되고 있다. 이와 같은 염료로서는, 예를 들어 크산텐 골격을 가지는 하기식(ａ)로 나타내는 로다민B가 널리 알려져 있다[호소다 유타카 저「신염료화학」1 판 274 페이지, 1973년 5월, (주) 지보당]. Dyes are used, for example, in the fields of fiber materials, liquid crystal displays, inkjets, etc., to display colors using reflected light or transmitted light. As such a dye, for example, rhodamine B represented by the following formula (a) having a xanthene skeleton is widely known. [Yosaka Hosoda, 274 pages of "New Dye Chemistry", May 1973, Ltd. Jibodang].
종래부터 알려진 상기의 화합물은 유기 용매에 대한 용해성이 반드시 충분하게 만족할 수 있는 것이 아니었다.The above-mentioned compound, which has been conventionally known, was not necessarily capable of sufficiently satisfying solubility in an organic solvent.
본 발명은 이하의 [１] 내지 [６]에 기재된 발명을 포함한다. The present invention includes the inventions described in [1] to [6] below.
[１] 식 (Ｉ)로 나타내는 화합물. [1] A compound represented by formula (I).
[식 (Ｉ)에서, [In equation (I),
R1은 탄소수 1 내지 8개의 지방족 탄화수소기 또는 탄소수 5 내지 8개의 지환식 탄화수소기를 나타내고, 상기 지방족 탄화수소기에 포함되는 수소 원자는 탄소수 6 내지 10개의 방향족 탄화수소기(상기 방향족 탄화수소기에 포함되는 수소 원자는 탄소수 1 내지 3개의 알킬기 또는 탄소수 1 내지 3개의 알콕시기로 치환되어 있어도 됨)로 치환되어 있어도 된다. R 1 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 5 to 8 carbon atoms, and the hydrogen atom contained in the aliphatic hydrocarbon group is an aromatic hydrocarbon group having 6 to 10 carbon atoms (the hydrogen atom contained in the aromatic hydrocarbon group is May be substituted with an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms).
Ar은 식 (ｉ)로 나타내는 기를 나타낸다. Ar represents a group represented by formula (i).
(식 (ｉ)에서, R2는 탄소수 1 내지 3개의 알킬기를 나타내고, 상기 알킬기에 포함되는 수소 원자는 할로겐 원자로 치환되어 있어도 된다. m은 1 내지 5의 정수를 나타낸다. m이 2 이상일 경우, 복수의 R2는 각각 동일하거나 상이하여도 된다. *는 질소 원자와의 결합팔(結合手)을 나타냄)] (In the formula (i), R 2 represents an alkyl group having 1 to 3 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom. m represents an integer of 1 to 5. When m is 2 or more, The plurality of R 2 may be the same or different, respectively, * represents a bonding arm with a nitrogen atom)]
[２] R1이 에틸기, n-프로필기, 이소프로필기, n-부틸기 또는 2-에틸헥실기인 [１]에 기재된 화합물. [2] The compound according to [1], wherein R 1 is an ethyl group, n-propyl group, isopropyl group, n-butyl group or 2-ethylhexyl group.
[３] R2가 메틸기인 [１] 또는 [２]에 기재된 화합물. [3] The compound according to [1] or [2], wherein R 2 is a methyl group.
[４] m이 1 또는 2인 [１] 내지 [３] 중 어느 하나에 기재된 화합물. [4] The compound according to any one of [1] to [3], wherein m is 1 or 2.
[５] Ar이 식 (Ｃ―１)로 나타내는 기 또는 식 (Ｃ―２)로 나타내는 기인 [１] 또는 [２]에 기재된 화합물. [5] The compound according to [1] or [2], wherein Ar is a group represented by formula (C-1) or a group represented by formula (C-2).
(식 (Ｃ―１) 및 식 (Ｃ―２)에서, *는 질소 원자와의 결합팔을 나타냄) (In formulas (C-1) and (C-2), * represents a bonding arm with a nitrogen atom)
[６] 식 (ＩＩ)[6] Expression (II)
로 나타내는 화합물과, 식 (ＩＩＩ)Compound represented by and formula (III)
[식 (ＩＩＩ)에서, R1, R2 및 m은 각각 상기와 동일한 의미를 나타냄] [In the formula (II), R 1 , R 2 and m each have the same meaning as above]
으로 나타내는 화합물을 실질적으로 용매 부존재 하에서 반응시키는 공정을 포함하는 식 (Ｉ) Formula (I) comprising the step of reacting the compound represented by substantially in the absence of a solvent
[식 (Ｉ)에서, R1 및 Ar은 각각 상기와 동일한 의미를 나타냄] [In formula (I), R 1 and Ar each have the same meaning as above]
로 나타내는 화합물의 제조 방법. Method for producing a compound represented by.
본 발명의 화합물은 유기 용매에 대한 용해성이 우수하다. The compounds of the present invention are excellent in solubility in organic solvents.
본 발명의 화합물은 식 (Ｉ)로 나타내는 화합물(이하,「화합물(Ｉ)」이라고 기재함)이다. 본 발명의 화합물에는 이의 호변이성체도 포함된다. The compound of the present invention is a compound represented by formula (I) (hereinafter referred to as "compound (I)"). The compounds of the present invention also include tautomers thereof.
[식 (Ｉ)에서, [In equation (I),
R1은 탄소수 1 내지 8개의 지방족 탄화수소기 또는 탄소수 5 내지 8개의 지환식 탄화수소기를 나타내고, 상기 지방족 탄화수소기에 포함되는 수소 원자는 탄소수 6 내지 10개의 방향족 탄화수소기(상기 방향족 탄화수소기에 포함되는 수소 원자는 탄소수 1 내지 3개의 알킬기 또는 탄소수 1 내지 3개의 알콕시기로 치환되어 있어도 됨)로 치환되어 있어도 된다. R 1 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 5 to 8 carbon atoms, and the hydrogen atom contained in the aliphatic hydrocarbon group is an aromatic hydrocarbon group having 6 to 10 carbon atoms (the hydrogen atom contained in the aromatic hydrocarbon group is May be substituted with an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms).
Ar은 식 (ｉ)로 나타내는 기를 나타낸다. Ar represents a group represented by formula (i).
(식 (ｉ)에서, R2는 탄소수 1 내지 3개의 알킬기를 나타내고, 상기 알킬기에 포함되는 수소 원자는 할로겐 원자로 치환되어 있어도 된다. m은 1 내지 5의 정수를 나타낸다. m이 2 이상일 경우, 복수의 R2는 각각 동일하거나 상이하여도 된다. *는 질소 원자와의 결합팔을 나타냄)] (In the formula (i), R 2 represents an alkyl group having 1 to 3 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom. m represents an integer of 1 to 5. When m is 2 or more, The plurality of R 2 may be the same or different, respectively. * represents a bonding arm with a nitrogen atom)]
R1로 나타내는 탄소수 1 내지 8개의 지방족 탄화수소기로서는, 예를 들어 메틸기, 에틸기, n-프로필기, n-부틸기, n-펜틸기, n-헥실기, n-헵틸기, n-옥틸기 등의 직쇄형 지방족 탄화수소기; Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R 1 include, for example, a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group. Linear aliphatic hydrocarbon groups such as;
이소프로필기, 이소부틸기, sec-부틸기, 이소펜틸기, 1-메틸펜틸기, 2-메틸펜틸기, 3-메틸펜틸기, 4-메틸펜틸기, 1-에틸부틸기, 2-에틸부틸기, 1-메틸헥실기, 2-메틸헥실기, 3-메틸헥실기, 4-메틸헥실기, 5-메틸헥실기, 1-에틸펜틸기, 2-에틸펜틸기, 3-에틸펜틸기, 1-프로필부틸기, 1-(1-메틸에틸)부틸기, 1-(1-메틸에틸)-2-메틸프로필기, 1-메틸헵틸기, 2-메틸헵틸기, 3-메틸헵틸기, 4-메틸헵틸기, 5-메틸헵틸기, 6-메틸헵틸기, 1-에틸헥실기, 2-에틸헥실기, 3-에틸헥실기, 4-에틸헥실기, 1-n-프로필펜틸기, 2-프로필펜틸기, 1-(1-메틸에틸)펜틸기, 1-부틸부틸기, tert-부틸기, 1,1-디메틸프로필기, 1,1-디메틸부틸기, 1,2-디메틸부틸기, 1,3-디메틸부틸기, 2,3-디메틸부틸기, 1-에틸-2-메틸프로필기, 1,1-디메틸펜틸기, 1,2-디메틸펜틸기, 1,3-디메틸펜틸기, 1,4-디메틸펜틸기, 2,2-디메틸펜틸기, 2,3-디메틸펜틸기, 2,4-디메틸펜틸기, 3,3-디메틸펜틸기, 3,4-디메틸펜틸기, 1-에틸-1-메틸부틸기, 1-에틸-2-메틸부틸기, 1-에틸-3-메틸부틸기, 2-에틸-1-메틸부틸기, 2-에틸-3-메틸부틸기, 1,1-디메틸헥실기, 1,2-디메틸헥실기, 1,3-디메틸헥실기, 1,4-디메틸헥실기, 1,5-디메틸헥실기, 2,2-디메틸헥실기, 2,3-디메틸헥실기, 2,4-디메틸헥실기, 2,5-디메틸헥실기, 3,3-디메틸헥실기, 3,4-디메틸헥실기, 3,5-디메틸헥실기, 4,4-디메틸헥실기, 4,5-디메틸헥실기, 1-에틸-2-메틸펜틸기, 1-에틸-3-메틸펜틸기, 1-에틸-4-메틸펜틸기, 2-에틸-1-메틸펜틸기, 2-에틸-2-메틸펜틸기, 2-에틸-3-메틸펜틸기, 2-에틸-4-메틸펜틸기, 3-에틸-1-메틸펜틸기, 3-에틸-2-메틸펜틸기, 3-에틸-3-메틸펜틸기, 3-에틸-4-메틸펜틸기, 1-프로필-1-메틸부틸기, 1-프로필-2-메틸부틸기, 1-프로필-3-메틸부틸기, 1-(1-메틸에틸)-1-메틸부틸기, 1-(1-메틸에틸)-2-메틸부틸기, 1-(1-메틸에틸)-3-메틸부틸기, 1,1-디에틸부틸기, 1,2-디에틸부틸기 등의 분지쇄형 지방족 탄화수소기; 등을 들 수 있다. Isopropyl group, isobutyl group, sec-butyl group, isopentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethyl Butyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group , 1-propylbutyl group, 1-(1-methylethyl)butyl group, 1-(1-methylethyl)-2-methylpropyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group , 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1-n-propylpentyl group , 2-propylpentyl group, 1-(1-methylethyl)pentyl group, 1-butylbutyl group, tert-butyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, 1,2-dimethyl Butyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethyl Pentyl group, 1,4-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3,4-dimethylpentyl group , 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-3-methylbutyl group , 1,1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,2-dimethylhexyl group, 2 ,3-dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,3-dimethylhexyl group, 3,4-dimethylhexyl group, 3,5-dimethylhexyl group, 4,4 -Dimethylhexyl group, 4,5-dimethylhexyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, 1-ethyl-4-methylpentyl group, 2-ethyl-1-methyl Pentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-ethyl-4-methylpentyl group, 3-ethyl-1-methylpentyl group, 3-ethyl-2-methyl Pentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, 1-propyl-1-methylbutyl group, 1-propyl-2-methylbutyl group, 1-propyl-3-methyl Butyl group, 1-(1-methylethyl)-1-methylbutyl group, 1-(1-methylethyl) Branched chain aliphatic hydrocarbon groups such as -2-methylbutyl group, 1-(1-methylethyl)-3-methylbutyl group, 1,1-diethylbutyl group and 1,2-diethylbutyl group; And the like.
이러한 탄소수 1 내지 8개의 지방족 탄화수소기에 포함되는 수소 원자가 치환되어 있어도 되는 탄소수 6 내지 10개의 방향족 탄화수소기로서는 페닐기, 나프틸기, 바이페닐기 등을 들 수 있다. 이러한 탄소수 6 내지 10개의 방향족 탄화수소기에 포함되는 수소 원자가 치환되어 있어도 되는 기 중에서, 탄소수 1 내지 3개의 알킬기로서는 메틸기, 에틸기, n-프로필기 및 이소프로필기를 들 수 있고, 탄소수 1 내지 3개의 알콕시기로서는 메톡시기, 에톡시기, n-프로폭시기 및 이소프로폭시기를 들 수 있다. Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms in which the hydrogen atom contained in the aliphatic hydrocarbon group having 1 to 8 carbon atoms may be substituted include a phenyl group, a naphthyl group, and a biphenyl group. Among the groups in which the hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted, examples of the alkyl group having 1 to 3 carbon atoms include methyl group, ethyl group, n-propyl group and isopropyl group, and alkoxy group having 1 to 3 carbon atoms. Examples of the methoxy group, ethoxy group, n-propoxy group and isopropoxy group.
이와 같은 탄소수 6 내지 10개의 방향족 탄화수소기로 치환된 지방족 탄화수소기로서는, 예를 들어 하기의 기를 들 수 있다. Examples of the aliphatic hydrocarbon group substituted with such an aromatic hydrocarbon group having 6 to 10 carbon atoms include the following groups.
(식에서, *는 질소 원자와의 결합팔을 나타냄) (In the formula, * represents a bonding arm with a nitrogen atom.)
R1로 나타내는 탄소수 5 내지 8개의 지환식 탄화수소기로서는, 예를 들어 하기의 기를 들 수 있다. Examples of the alicyclic hydrocarbon group having 5 to 8 carbon atoms represented by R 1 include the following groups.
(식에서, *는 질소 원자와의 결합팔을 나타냄) (In the formula, * represents a bonding arm with a nitrogen atom.)
R1이 지방족 탄화수소기이면, 유기 용매에 대한 용해성에 특히 우수하다는 점에서 바람직하다. R1이 에틸기, n-프로필기, 이소프로필기, n-부틸기 또는 2-에틸헥실기인 것이 더욱 바람직하다. When R 1 is an aliphatic hydrocarbon group, it is preferable in that it is particularly excellent in solubility in an organic solvent. It is more preferable that R 1 is an ethyl group, n-propyl group, isopropyl group, n-butyl group or 2-ethylhexyl group.
R2로 나타내는 탄소수 1 내지 3개의 알킬기로서는 메틸기, 에틸기, n-프로필기 및 이소프로필기를 들 수 있다. 또한, 이러한 탄소수 1 내지 3개의 알킬기에 포함되는 수소 원자가 할로겐 원자로 치환된 기로서는, 예를 들어 하기의 기를 들 수 있다. Examples of the alkyl group having 1 to 3 carbon atoms represented by R 2 include methyl group, ethyl group, n-propyl group and isopropyl group. Moreover, the following group is mentioned as a group in which the hydrogen atom contained in such a C1-C3 alkyl group was substituted with the halogen atom.
R2는 원료 입수의 관점에서 메틸기인 것이 바람직하다. m은 1 내지 5의 정수를 나타내고, 1 또는 2인 것이 바람직하다. R 2 is preferably a methyl group from the viewpoint of obtaining raw materials. m represents the integer of 1-5, and it is preferable that it is 1 or 2.
Ar로 나타내는 기로서는, 예를 들어 하기의 기를 들 수 있다. 이 중에서도, 식 (Ｃ―１)로 나타내는 기 또는 식 (Ｃ―２)로 나타내는 기가 바람직하다. Examples of the group represented by Ar include the following groups. Among these, groups represented by formula (C-1) or groups represented by formula (C-2) are preferable.
(식에서, *는 질소 원자와의 결합팔을 나타냄) (In the formula, * represents a bonding arm with a nitrogen atom.)
화합물(Ｉ)로서는, 예를 들어 표 1 및 표 2에 기재한 화합물(Ｉ―１) 내지 화합물(Ｉ―５4)를 들 수 있다. 표 1 및 표 2의 R1란의 기재 중에서 A 또는 B로 시작하는 번호는 R1로 나타내는 기로서 예시한 상기의 식의 번호를 나타낸다. Ar란은 Ar로 나타내는 기로서 예시한 상기의 식의 번호를 나타낸다. 이 중에서도, 유기 용매에 대한 용해성에 특히 우수하다는 점에서, 화합물(Ｉ―１), 화합물(Ｉ―２), 화합물(Ｉ―１3), 화합물(Ｉ―１4), 화합물(Ｉ―１9), 화합물(Ｉ―２0), 화합물(Ｉ―４4), 화합물(Ｉ―５0) 또는 화합물(Ｉ―５6)이 바람직하고, 화합물(Ｉ―１)이 더욱 바람직하다. Examples of the compound (I) include the compounds (I-1) to (I-54) shown in Table 1 and Table 2. The numbers starting with A or B in the description of the column of R 1 in Table 1 and Table 2 represent the numbers of the above formulas exemplified as groups represented by R 1 . Ar column represents the number of the above formula illustrated as a group represented by Ar. Among these, compounds (I-1), compounds (I-2), compounds (I-13), compounds (I-14), and compounds (I-19), in that they are particularly excellent in solubility in organic solvents, Compound (I-20), compound (I-44), compound (I-50) or compound (I-56) is preferable, and compound (I-1) is more preferable.
이어서, 화합물(Ｉ)의 제조 방법에 대하여 설명한다. Next, a method for producing compound (I) will be described.
화합물(Ｉ)의 제조 방법으로서는 식 (ＩＩ)As a method for preparing compound (I), formula (II)
로 나타내는 화합물(이하,「화합물(ＩＩ)」라고 기재함)과 식 (ＩＩＩ) Compound represented by (hereinafter referred to as "compound (II)") and formula (III)
[식 (ＩＩＩ)에서, R1, R2 및 m은 각각 상기와 동일한 의미를 나타냄][In the formula (II), R 1 , R 2 and m each have the same meaning as above]
으로 나타내는 화합물(이하,「화합물(ＩＩＩ)」이라고 기재함)을 반응시키는 공정을 포함하는 제조 방법을 들 수 있다. 이와 같은 반응은 용매의 존재 하에서 실시할 수 있으나, 수율의 관점에서 실질적으로 용매를 사용하지 않고, 즉 실질적으로 용매 부존재 하에서 실시하는 것이 바람직하다. 반응은 통상적으로 화합물(ＩＩ)와 화합물(ＩＩＩ)을 혼합하여, 얻어진 혼합물을 교반 하에서 숙성함으로써 실행된다. 여기서,「실질적으로 용매를 사용하지 않고」란 화합물(ＩＩ)와 화합물(ＩＩＩ)을 함께 용해시켜 반응장(反應場)을 제공할 수 있도록 충분한 양의 용매를 사용하지 않는 것,「실질적으로 용매 부존재 하에서」란 화합물(ＩＩ)와 화합물(ＩＩＩ)을 함께 용해시켜 반응장을 제공할 수 있도록 충분한 양의 용매가 존재하지 않는 것을 각각 의미하고, 통상적으로 화합물(ＩＩ)와 화합물(ＩＩＩ)의 사용량의 합계에 대하여 1 질량% 미만, 바람직하게는 0.1 질량% 미만의 양이다. And a method of reacting a compound represented by (hereinafter referred to as “compound (II)”). Such a reaction can be carried out in the presence of a solvent, but from the viewpoint of yield, it is preferable to use substantially no solvent, that is, substantially in the absence of a solvent. The reaction is usually carried out by mixing compound (II) and compound (III) and aging the resulting mixture under stirring. Here, "substantially without using a solvent" means that a sufficient amount of solvent is not used to dissolve the compound (II) and the compound (III) together to provide a reaction field, and "substantially a solvent" In the absence of" means that a sufficient amount of a solvent is not present to dissolve the compound (II) and the compound (III) together to provide a reaction field, and the amount of compound (II) and compound (III) is usually used. It is an amount of less than 1 mass%, preferably less than 0.1 mass% with respect to the total of.
상기 용매로서는 톨루엔, 크실렌 등의 탄화수소 용매; 클로로벤젠, 디클로로벤젠, 클로로포름 등의 할로겐화 탄화수소 용매; 메탄올, 에탄올, 부탄올 등의 알코올 용매; 니트로벤젠 등의 니트로 탄화수소 용매; 메틸이소부틸케톤 등의 케톤 용매; 1-메틸-2-피롤리돈 등의 아미드 용매; 등을 들 수 있다. Examples of the solvent include hydrocarbon solvents such as toluene and xylene; Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; Alcohol solvents such as methanol, ethanol, and butanol; Nitro hydrocarbon solvents such as nitrobenzene; Ketone solvents such as methyl isobutyl ketone; Amide solvents such as 1-methyl-2-pyrrolidone; And the like.
반응 온도는 30 ℃ 내지 180 ℃가 바람직하고, 80 ℃ 내지 130 ℃가 더욱 바람직하다. 반응 시간은 1 시간 내지 12 시간이 바람직하고, 3 시간 내지 8 시간이 더욱 바람직하다. The reaction temperature is preferably 30°C to 180°C, and more preferably 80°C to 130°C. The reaction time is preferably 1 hour to 12 hours, and more preferably 3 hours to 8 hours.
화합물(ＩＩＩ)의 사용량은 화합물(ＩＩ) 1 몰에 대하여, 바람직하게는 2 몰 이상 30 몰 이하이고, 더욱 바람직하게는 2 몰 이상 20 몰 이하이다. The amount of the compound (II) used is preferably 2 mol or more and 30 mol or less, more preferably 2 mol or more and 20 mol or less, per 1 mol of the compound (II).
화합물(Ｉ)의 제조 방법은 더욱더 반응 혼합물로부터 화합물(Ｉ)을 취득하는 공정을 포함하여도 된다. The method for producing compound (I) may further include a step of obtaining compound (I) from the reaction mixture.
반응 혼합물로부터 목적 화합물인 화합물(Ｉ)을 취득하는 방법은 특별히 한정되지 않고, 공지된 여러 가지의 수법을 채용할 수 있다. 예를 들어, 반응 혼합물을 산(예를 들어, 아세트산 등)과 함께 혼합하고, 석출한 결정을 여과하여 얻을 수 있다. 상기 산은 미리 산의 수용액을 조제한 후에, 반응 혼합물을 상기 수용액에 첨가하는 것이 바람직하다. 반응 혼합물을 첨가할 때의 온도는 바람직하게 10 ℃ 이상 50 ℃ 이하, 더욱 바람직하게는 20 ℃ 이상 50 ℃ 이하, 더욱더 바람직하게는 20 ℃ 이상 30 ℃ 이하이다. 또한, 반응 혼합물을 산의 수용액에 첨가한 후에는 동일한 온도에서 0.5 내지 2 시간 정도 교반하는 것이 바람직하다. 여과하여 얻은 결정은 물 등으로 세정하고, 이어서 건조하는 것이 바람직하다. 또한, 필요에 따라서 재결정 등의 공지된 수법에 의해서 더욱더 정제하여도 된다. The method for obtaining the target compound (I) from the reaction mixture is not particularly limited, and various known techniques can be employed. For example, the reaction mixture can be obtained by mixing with an acid (for example, acetic acid, etc.) and filtering the precipitated crystals. It is preferable that the acid is prepared in advance with an aqueous solution of the acid, and then the reaction mixture is added to the aqueous solution. The temperature when the reaction mixture is added is preferably 10°C or more and 50°C or less, more preferably 20°C or more and 50°C or less, even more preferably 20°C or more and 30°C or less. Further, after adding the reaction mixture to the aqueous solution of the acid, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals obtained by filtration are preferably washed with water or the like, and then dried. Moreover, if necessary, you may further refine|purify by well-known methods, such as recrystallization.
본 발명의 화합물은 염료로서 유용하다. 몰 흡광계수가 높고, 또한 유기 용매에 대한 높은 용해성을 보이므로, 특히 액정 표시 장치 등의 표시 장치의 컬러 필터에 사용되는 염료로서 유용하다.The compounds of the present invention are useful as dyes. Since the molar extinction coefficient is high and shows high solubility in an organic solvent, it is particularly useful as a dye used in color filters of display devices such as liquid crystal displays.
이어서, 실시예를 들면서, 본 발명을 더욱더 구체적으로 설명한다. 예시 중, 함유량 내지 사용량을 나타내는 % 및 부는 특별히 기재하지 않는 한, 질량 기준이다. Subsequently, the present invention will be described more specifically with reference to examples. In the example,% and parts indicating the content to the amount of use are based on mass unless otherwise specified.
이하의 실시예에 있어서, 화합물의 구조는 질량분석(LC; Agilent제 1200형, MASS; Agilent제 LC/MSD형)으로 확인하였다. In the following examples, the structure of the compound was confirmed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC/MSD type).
실시예 1 Example 1
화합물(ＩＩ) 20 부와, 화합물(ＩＩＩ)으로서 N-에틸-오쏘-톨루이딘[와코준야쿠공업(주) 제] 200 부를 차광 조건 하에서 혼합하여, 얻어진 용액을 110 ℃에서 6시간 교반하였다. 얻어진 반응액을 실온까지 냉각한 후, 물 800 부, 35 % 염산 50 부의 혼합액 중에 첨가하여 실온에서 1 시간 교반한 후, 결정이 석출된다. 석출한 결정을 흡인 여과의 잔여물로서 취득한 후에 건조하여, 식 (Ｉ―１)로 나타내는 화합물 24 부를 얻었다. 수율은 80 %이었다. 20 parts of compound (II) and 200 parts of N-ethyl-ortho-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) as compound (II) were mixed under light-shielding conditions, and the resulting solution was stirred at 110°C for 6 hours. After the obtained reaction solution was cooled to room temperature, it was added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid, stirred at room temperature for 1 hour, and crystals precipitated. The precipitated crystal was obtained as a residue for suction filtration and then dried to obtain 24 parts of the compound represented by formula (I-1). The yield was 80%.
식 (Ｉ―１)로 나타내는 화합물의 동정 Identification of the compound represented by formula (I-1)
실시예 2 내지 9 Examples 2 to 9
화합물(ＩＩＩ)으로서, 얻어진 화합물(Ｉ)에 대응하는 화합물을 사용한 것 이외에는 실시예 1과 동일하게 하여, 식 (Ｉ―２)로 나타내는 화합물(실시예 2), 식 (Ｉ―１3)으로 나타내는 화합물(실시예 3), 식 (Ｉ―１4)로 나타내는 화합물(실시예 4), 식 (Ｉ―１9)로 나타내는 화합물(실시예 5), 식 (Ｉ―２0)으로 나타내는 화합물(실시예 6), 식 (Ｉ―４4)로 나타내는 화합물(실시예 7), 식 (Ｉ―５0)으로 나타내는 화합물(실시예 8) 및 식 (Ｉ―５6)으로 나타내는 화합물(실시예 9)를 각각 얻었다. As a compound (II), a compound represented by formula (I-2) (Example 2) and a formula (I-13) were obtained in the same manner as in Example 1, except that the compound corresponding to the obtained compound (I) was used. Compound (Example 3), compound represented by formula (I-14) (Example 4), compound represented by formula (I-19) (Example 5), compound represented by formula (I-20) (Example 6) ), a compound represented by formula (I-44) (Example 7), a compound represented by formula (I-50) (Example 8), and a compound represented by formula (I-56) (Example 9) were obtained, respectively.
식 (Ｉ―２)로 나타내는 화합물의 동정 Identification of the compound represented by formula (I-2)
식 (Ｉ―１3)으로 나타내는 화합물의 동정 Identification of the compound represented by formula (I-13)
식 (Ｉ―１4)로 나타내는 화합물의 동정 Identification of the compound represented by formula (I-14)
식 (Ｉ―１9)로 나타내는 화합물의 동정 Identification of compound represented by formula (I-19)
식 (Ｉ―２0)으로 나타내는 화합물의 동정 Identification of the compound represented by formula (I-20)
식 (Ｉ―４4)로 나타내는 화합물의 동정 Identification of the compound represented by formula (I-44)
식 (Ｉ―５0)으로 나타내는 화합물의 동정 Identification of compound represented by formula (I-50)
식 (Ｉ―５6)으로 나타내는 화합물의 동정 Identification of the compound represented by formula (I-56)
<용해도의 측정> <Measurement of solubility>
실시예 1 내지 9에서 각각 얻어진 화합물과 로다민B[도쿄카세이공업(주) 제]의 프로필렌글리콜 모노메틸에테르(이하, PGME로 약칭), 에틸락테이트(이하, EL로 약칭), 프로필렌글리콜 모노메틸에테르아세테이트(이하, PGMEA로 약칭)에 대한 용해도를 이하와 같이 하여 구하였다. Compounds obtained in Examples 1 to 9 and rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.) propylene glycol monomethyl ether (hereinafter abbreviated as PGME), ethyl lactate (hereinafter abbreviated as EL), and propylene glycol mono Solubility in methyl ether acetate (hereinafter abbreviated as PGMEA) was determined as follows.
50 mL 샘플관 중에서, 하기의 비율로 화합물과 상기 용매를 혼합하고, 그 후에 샘플관을 밀봉(密栓)하여, 30 ℃에서 3 분간 초음파 진동기로 진동시켰다. 뒤이어, 실온에서 30 분간 방치한 후, 흡인 여과하여, 이의 잔여물을 눈으로 관찰하였다. 불용물을 확인할 수 없었던 경우에는 용해성이 양호하다고 판단하여 표 3에 ○로 기록하고, 불용물을 확인할 수 있었던 경우에는 용해성이 불량하다고 판단하여 표 3에 ×로 기록하였다. In a 50 mL sample tube, the compound and the solvent were mixed in the following ratio, and then the sample tube was sealed and vibrated with an ultrasonic vibrator for 3 minutes at 30°C. Subsequently, the mixture was left at room temperature for 30 minutes, and then filtered by suction to observe its residue. When insoluble matters could not be identified, the solubility was judged to be good and recorded in Table 3 as ○. When insoluble matters could be confirmed, the solubility was judged to be poor and recorded in Table 3 as ×.
10 % 화합물 0.1 g, 용매 1 g 10% compound 0.1 g, solvent 1 g
15 % 화합물 0.15 g, 용매 1 g 15% compound 0.15 g, solvent 1 g
1 % 화합물 0.01 g, 용매 1 g 0.01 g of 1% compound, 1 g of solvent
화합물(Ｒ―１)은 로다민B[도쿄카세이공업(주) 제]이다. The compound (R-1) is rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.).
본 발명의 화합물은 유기 용매에 대한 용해성이 우수하다. The compounds of the present invention are excellent in solubility in organic solvents.
Claims (2)
[식 (Ｉ)에서,
R1은 탄소수 2 내지 8개의 지방족 탄화수소기 또는 탄소수 5 내지 8개의 지환식 탄화수소기를 나타내고, 당해 지방족 탄화수소기에 포함되는 수소 원자는 탄소수 6 내지 10개의 방향족 탄화수소기(당해 방향족 탄화수소기에 포함되는 수소 원자는 탄소수 1 내지 3개의 알킬기 또는 탄소수 1 내지 3개의 알콕시기로 치환되어 있어도 됨)로 치환되어 있어도 된다.
Ar은 식 (Ｃ―１)로 나타내는 기 또는 식 (Ｃ―２)로 나타내는 기를 나타낸다.
(식 (Ｃ―１) 및 식 (Ｃ―２)에서, *는 질소 원자와의 결합팔을 나타냄)] Compound represented by formula (I).
[In equation (I),
R 1 represents an aliphatic hydrocarbon group having 2 to 8 carbon atoms or an alicyclic hydrocarbon group having 5 to 8 carbon atoms, and the hydrogen atom contained in the aliphatic hydrocarbon group is an aromatic hydrocarbon group having 6 to 10 carbon atoms (the hydrogen atom contained in the aromatic hydrocarbon group is May be substituted with an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms).
Ar represents a group represented by formula (C-1) or a group represented by formula (C-2).
(In formulas (C-1) and (C-2), * represents a bonding arm with a nitrogen atom)]
R1이 에틸기, n-프로필기, 이소프로필기, n-부틸기 또는 2-에틸헥실기인 화합물. According to claim 1,
A compound wherein R 1 is an ethyl group, n-propyl group, isopropyl group, n-butyl group or 2-ethylhexyl group.
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