TW200916441A - Azo compound or salts thereof - Google Patents
Azo compound or salts thereof Download PDFInfo
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- TW200916441A TW200916441A TW097121690A TW97121690A TW200916441A TW 200916441 A TW200916441 A TW 200916441A TW 097121690 A TW097121690 A TW 097121690A TW 97121690 A TW97121690 A TW 97121690A TW 200916441 A TW200916441 A TW 200916441A
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- azo compound
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- aliphatic hydrocarbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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 to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/69—Two or more oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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 to ring carbon atoms
- C07D213/72—Nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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 to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/86—Hydrazides; Thio or imino analogues thereof
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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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
- C09B29/3617—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
- C09B29/3621—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring
- C09B29/3626—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more hydroxyl groups (or = O)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
200916441 . 九、發明說明： 【發明所屬之技術領域】 本發明係關於有用於作為色素之偶氮化合物及其鹽 【先前技術】 先別偶氮化合物等的色素，在於各式各樣的領域（例 、戴維材料’液晶顯示裝置等）使用於利用反射光或穿透 光顯示顏色，例如，p L 士 g 士 ，& 已知有具有吡啶酮環之偶氮化合物（專 利文獻卜4等）。具體而言，專利文獻i及2揭示^個聯苯 骨架(聯二亞苯基)與2個吡啶酮環以2個偶氮基連結之色 素’專利文獻3揭示！其、K ^•甘& 句丁本暴亞本基與吡啶酮環以2個偶氮 基連結之色素，專利文獻4揭示苯基與心_環以偶氮某 連結之色素。於該等專利讀卜3,並無任何記載關於該 等色素之色濃度。另-方面’揭示於專利文獻4之色素之 構造，與以下詳細記載之本發明之偶氮化合物及其鹽完全 不同。 [專利文獻1 ]德國專利出願公開第3 4丨6 3 2 7號 [專利文獻2]美國專利第3979378號 [專利文獻3 ]日本特開昭5卜6 4 5 3 6號 [專利文獻4]日本特公平7 —88633號 【發明内容】 [發明所欲解決的課題] 近年，關於染色物的色濃度及色相，由需 w南衣各戶的要 2226-9735-PF;Ahddub 5 200916441 求、文厭，特別是要求色濃度高 因此本發明之㈣^ 彳穎偶虱化合物及其鹽。 月之目的係在於提供顯示高 合物及其鹽。 巴礙度之新穎偶亂化 [用以解決課題的手段] 本發明者們，為改良偶f 艮偶虱化合物及其鹽之色濃度銳意 結果，發現於聯苯骨架的兩端經由偶氮基連結吼唆 酮環之化合物或其鹽，顯示高的色濃度。由如此之見識’ 達成上述目地之本發明之偶氮化合物及其鹽，係、以式⑴ 表示者。再者有將式⑴所示偶氮化合物及其鹽，於以下簡 稱為「偶氮化合物⑴」之情形。以其他的化學式表示之化 合物或其鹽，亦有同樣地簡稱之情形。200916441. IX. EMBODIMENT OF THE INVENTION The present invention relates to an azo compound and a salt thereof for use as a pigment. [Prior Art] A dye which is an azo compound or the like is used in various fields ( For example, a David material 'liquid crystal display device, etc.' is used for displaying a color by using reflected light or penetrating light, for example, p L 士士士, & an azo compound having a pyridone ring is known (Patent Document 4, etc.) ). Specifically, Patent Documents i and 2 disclose a colorant in which a biphenyl skeleton (biphenylene group) and two pyridone rings are linked by two azo groups. Further, K ^ · Gan & 句 本 暴 暴 暴 与 与 与 与 与 与 与 与 与 与 与 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 In these patents, there is no record of the color density of such pigments. The structure of the dye disclosed in Patent Document 4 is completely different from the azo compound of the present invention and its salt described in detail below. [Patent Document 1] German Patent Laid-Open Publication No. 3 4 丨 6 3 2 7 [Patent Document 2] US Pat. No. 3,979,378 [Patent Document 3] Japanese Patent Laid-Open No. Hei No. 5 4 5 3 6 [Patent Document 4] Japanese Special Fair No. 7-88633 [Summary of the Invention] [Problems to be Solved by the Invention] In recent years, regarding the color density and hue of dyed products, it is necessary to use 2226-9735-PF for each household of Nanzhao; Ahddub 5 200916441 In particular, it is required to have a high color density, and therefore the (four)^ 彳 虱 虱 compound and its salt of the present invention. The purpose of the month is to provide a display of the high compound and its salt. Inventors have found that the ends of the biphenyl skeleton are azo-based at the two ends of the biphenyl skeleton. A compound which binds an anthrone ring or a salt thereof exhibits a high color density. The azo compound and the salt thereof of the present invention which achieve the above object by the above-mentioned object are represented by the formula (1). Further, the azo compound represented by the formula (1) and a salt thereof are hereinafter referred to as "azo compound (1)". The compounds represented by other chemical formulas or salts thereof are also referred to in the same manner.
2226-9735-PF;Ahddub 6 200916441 、）中，較佳的是R5〜R12之至少1個係N-取代磺醯 基。R5〜R8之5小1 Λ» 至J 1個、以及R9〜R12之至少1個以Ν-取代磺 醯基更佳，p8 + s , 及R之至V 1個、以及R9及R12之至少1個 進一步以N-取代磺酸基為佳。上述n_取代磺醯基，以 - SChNHR15 基在主—、 、 尔表不u C1-1。飽和脂肪烴基、Cl-8烷氧基取 代之G卞飽和脂肪烴基、碳數6〜2Q之芳基、碳數7〜20之 方=、或碳數2~10之醯基）為佳。N_取代磧龜基，較佳 、1由、有S〇2NHR5基，可使本發明之偶氮化合物及A 具水溶性及油溶性。式⑴中，較佳的是R13及R1、4 越1個係氰基。具有氰基之本發明之偶氮化合物及i 鹽，可顯示特別高的色濃度。又，R13及〜 传 一 C0W6)R”基（式中 R之至夕1個係 及R係分別獨立地表示，氳原 丁 Li-丨ϋ飽和脂肪烴基、 肪炉芙、以c】-«烷氧基取代之Ci_ie飽和脂 肪/工暴、奴數6〜2〇之芳 2〜10之醯A。）者 厌~20之芳烷基、或碳數 再者:於二:亦為本發明較佳的偶氮化合物及其鹽。 者，亦勺 ’明之偶氮化合物及其鹽，除了式⑴所干 者亦包含其互變異構物。 Ί」所不 [發明效果] 本發明之偶氮化合物及其鹽， 上 用於作為例如用於纖維 ' 的色遭度，有 夜日日顯不裝置等之色素。 【實施方式】 本發明之偶氮化合物及其鹽，复 所示’於聯苯骨架的兩端經由偶：美：、徵在於：如式⑴ 2226~9735-PF;Ahddub 土 ”有吡啶_環。再者， 7 200916441 酮 於°比錢環之部分，以式⑴表示之烯醇型之外，亦勺人 型。藉由如此之構造’本發明之偶氮化合物及其鹽二 高的色濃度。又，本發明之偶氮化合物及其鹽，於其；不 的態樣’對溶劑的溶解性（特別是油溶性）優良，極為=佳 利用穿透光之顯色。再者，於上述溶劑，可選擇例如，和 基叛酸醋類（乳酸乙醋等），經基酮類（二丙_醇等），„ (丙一醇早甲鱗’丙：醇單甲_酸§旨等）等揮發性低 溶性溶劑。 -幻八 以下，詳細說明式（1)。式（1)中’R1〜R4係表示氫原子、 Ch。徵和脂㈣基錢基。R1〜R4之㈣絲烴基，可為直 鍵狀、分枝狀或環狀之任何。於飽和脂肪煙基之碳數，不 包含取代基之碳數。該碳數之下限，通常為i’較佳的是2, 該碳數之上限’通常為10,較佳的是8，更佳的是6，進 -步較佳的是3。於飽和脂肪烴基，包含例如，甲基、乙 基、正丙基、異丙基、I ^ 円丞正丁基、異丁基、第二丁基、第三 丁基等。 式⑴令分別獨立地表示，氨原子、齒素原 子(較佳的是氟原子’氣原子或溴原子）、Cw。飽和脂肪烴 土ΰ素原子鍵結於該飽和腊肪煙基者）、Ch燒氧 基羧基&基、命酿基、或取代續酿基。 Π2之飽和脂肪烴基，與形同樣地，以直 賴、分枝狀或環狀均可，其碳數，通常為卜1()，較佳的 是l84，更佳的是3〜6。R5~R12之飽和脂肪烴基之具體例， 與R K之情形相同。r5〜rI2之飽和脂肪烴基，亦可以齒素 2226-9735-PF;Ahddub 8 200916441 原子，較佳的是氟原子取代者。鹵化飽和脂肪烴基之具體 例，可舉三氟甲基等。 R 之烷氧基之碳數，通常為1〜8，較佳的是1〜4。 該烷氧基，可舉例如，f氧基、乙氧基、異丙氧基、正丙 氧基、正丁氧基、異丁氧基、第二丁氧基、及第三丁氧基 等。 R〜R之N-取代項醯基，係例如，N —單取代續醯基， 可以式-SChNHR15表示。該R”係Cl_lfl飽和脂肪烴基（包含8 烧氧基鍵結於該Ciμ。飽和脂肪烴基者）、碳數6〜2 〇之芳基、 石厌數7〜20之芳炫基、或碳數2〜1〇之醯基。 R15之飽和脂肪烴基，以直鏈狀、分枝狀或環狀均可。 於飽和脂肪烴基之碳數不包含取代基之碳數。該碳數之下 限，通常為1，較佳的是3 ,更佳的是6 ,其上限，通常為 1 〇，較佳的是8。於R15之飽和脂肪烴基，包含例如甲基、 乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第 三丁基、甲基丁基（1，1，3, 3-四甲基丁基等）、甲基己基 (1，5-二甲基己基等）、乙基己基（2—乙基己基等）、環戊基、 %己基、甲基環己基（2-曱基環己基等）、環己基烷基等。 R之飽和脂肪烴基，如上所述，亦可以Ci_8(較佳的是Ci 〇 烷氧基等之取代基取代。該取代飽和脂肪烴基，可例示丙 氧基丙基（3-(異丙氧基）丙基等）等。 R15之芳基，可為無取代，亦可具有飽和脂肪烴基或羥 基等的取代基。上述芳基之碳數，以包含取代基之碳數數 之’通常為6〜20，較佳的是6〜10。該等芳基，可舉例如苯 2226-9735-PF；Ahddub 9 200916441 基、羥基苯基（4-羥基苯基等）、三氟甲基苯基（4_三氟甲美 苯基等）等之無取代或取代苯基等。 R15之芳烷基之烷基部分，以直鏈狀或分枝狀均可。芳 烷基之碳數，通常為7~20,較佳的是7〜1(N代表性的芳烷 基，有节基、苯基丁基（3 —胺基—丨―苯基丁基等）等之苯基^ 基。 70 之醯基，可為無取代，亦可鍵結飽和脂肪烴基、烷 氧基的取代基。醯基之碳數，以包含取代基之碳數數之， 其數通常為2〜10’較佳的是6~1G。上述醯基，可舉例如乙 醯基、苯甲基、曱氧基苯甲基(對曱氧基苯甲基等）等。 R及R14係表是氫原子、氰基、甲醯基、或N—取代甲 醯基。上述甲醯基，可以一c〇N(R]6)Ri7之構造式（式中，^ 及R 7係分別獨立地表示，氫原子、Ci i。飽和脂肪烴基、以 Ci-8烷氧基取代之Cl〜飽和脂肪烴基、碳數6〜2〇之芳基、 石反數7〜20之芳烷基、或碳數2〜1〇之醯基。）表示。及 R之飽和脂肪烴基、芳基、芳烷基及醯基之說明及具體例， :於上述P所述者相同。惟，醯基之具體例，可舉進—步 a有鹵素原子之苯甲基、例如溴笨曱基（對溴苯甲基等）等。 *上述R1〜Rn由提高色漠度、水溶性、油溶性、耐光性 等的觀點，亦可進-步限^。例&，為提高色濃度，建議 於R〜R4之至少1個（較佳的是全部），選擇碳數5以下（較 佳的是3以下）之飽和脂肪烴基（例如，曱基、乙基等）、或 氫原子。 又，為提高色濃度，建議於以及γ之至少丄個（較佳 2226-9735-PF;Ahddub 10 200916441 的疋又方），選擇碳數3以下之飽和脂肪烴基（例如甲基、 乙基等1別是甲基），或氫原子。又，為提高溶解性，於 R及Rl?之至少1個，選擇乙醯基為佳。 再者，由提高色濃度與水溶性之觀點，建議於R5〜R〗2 之中的1個或2個以上(例如由r5~r8i個以上(特別是1 個）’5及由R0〜R121個以上（特別是1個））採用磺基，於剩下 的R5咄12採用氫原子或磺基。藉由提高水溶性，可廣泛地 使用作為衣料領域的色素。衣料領域之色素，可將偶氮化 合物（I)之1種單獨使用，亦可併用2種以上。 由提高色濃度與油溶性之觀點’建議R5〜R12之令的ι 個或2個以上（例如由以81個以上（特別是！個），及由 個以上（特別是^固）），採用 ?木用—貺甲基、N-取代磺醯 :二特別是R5〜R12之中的1個為_输基之偶氮化合 )，即使…12之剩下的1個為親水性的續基之情 瓜’仍顯示尚的油溶性。藉由坦古4 A U 曰翻一壯 精由“油溶性’可提高作為液 日日顯不裝置領域之色素之有 1 农日日顯不裝置領域之色 素，可將偶氮化合物（1)之丨種單 干调使用，亦可併用2種以 上0 用#併用2種以上偶氮化合物⑴，則可較將其！種單獨使 用時，對有機溶劑之溶解量（ ^ ψ, 士 ό ，合庄J权大。因此由油溶性 化合物⑴使用亦為較佳的能丄5 2種以上的偶氣 ㈣目士 恶樣°提升油溶性之組合之例， 了舉具有2個取代磺醯基之 且古！ Μ Α 馬11化5物（二磺醯胺），與 具有1個N-琅代磺醯基及i個 只基之偶氮化合物（單磺醯 2226-9735-PF;Ahddub 200916441 胺）之組合。士 μ 之、、.5之中，R5〜r8之中的1個及r9〜r12 之中的1個為N _取我石&航甘 戈s酿基’剩下的為氫原子之二磺醯 胺，盘r5h t 、 中的1個為N一取代磺醯基，R9〜Rl2之中的丄 個為橫基，剩下& & $ β π 〇 的為虱原子之單磺醯胺脂組合為佳。再者， 早㉖酿胺’在由由：隹^； — λι_ 色又之硯點，較二磺醯胺更佳。因為分 子量較低。 由提间dj·生之觀點，亦建議於r5 ji2之中的1個或2 個以上（例如由m個以上（特別是工個），及由π] 個以^ (特別I i個））由上述例選擇相對較大的基，或將 广R12之中的1個或2個以上（例如由r5〜r8u固以上（特別是 斤個）及由Ri個以上（特別是】個））之取代位置對偶 氮基呈間位或鄰位。藉由選擇較大的基，或使取代位置對 偶氮基呈間位’可減低聯笨部位之堆疊，可提高油溶性。 又’藉由選擇較大的基，或使取代位置對偶氮基呈鄰位， :保護偶氮基’可提高m上述較r5〜r12可例示 第三丁基等之分枝狀飽和脂肪烴基（特別是3級飽和脂肪 烴基）、三氟曱基等鹵素原子鍵結2個以上(特別是3個以 上）的飽和脂肪烴基、N-取代磺醯基等。 再者，N-取代確醯基之Ru，由更加提高色漠度、油溶 性等之觀點，亦可進一步限定。於如此之Rls，可舉例如， 甲基丁基（1，1，3,3-四甲基丁基等）、曱基己基（丨，5_二甲美 己基等）、乙基己基（2-乙基己基等）、甲基環己基（2〜甲^ 環己基等）、苯基丁基（3-胺基-1-苯基丁基等）等之分枝狀 飽和脂肪烴基、或芳競基。 2226-9735-PF;Ahddub 12 200916441 於特別佳的偶氮化合物（I)，R5~R12之中1個以上，較 佳的是2個以上（例如由R5~R81個以上（特別是1個）’及由 R9〜R12l個以上（特別是1個））為N-取代磺醯基。 於式（I)之較佳的例，可舉式（I_1)~(I-11)。 〇 〇In 2226-9735-PF; Ahddub 6 200916441, it is preferred that at least one of R5 to R12 is an N-substituted sulfonyl group. R5 to R8 of 5 small 1 Λ» to J 1 and at least 1 of R9 to R12 are preferably Ν-substituted sulfonyl groups, p8 + s , and R to V 1 , and at least R 9 and R 12 One is further preferably an N-substituted sulfonic acid group. The above n-substituted sulfonyl group, with the -SChNHR15 group in the main-, argon, is not u C1-1. A saturated aliphatic hydrocarbon group, a C8 saturated aliphatic hydrocarbon group substituted with a C8 alkoxy group, an aryl group having a carbon number of 6 to 2 Q, a carbon number of 7 to 20, or a fluorenyl group having 2 to 10 carbon atoms is preferred. The N-substituted anthraquinone group, preferably, has a S〇2NHR5 group, and the azo compound and A of the present invention are water-soluble and oil-soluble. In the formula (1), it is preferred that one of R13 and R1 and 4 is a cyano group. The azo compound and the i salt of the present invention having a cyano group can exhibit a particularly high color density. Further, R13 and ~ are transmitted to a C0W6)R" group (in the formula, the R system and the R system are independently represented, and the Lithium sulphate saturated aliphatic hydrocarbon group, the fat furnace, and the c]-« Alkoxy-substituted Ci_ie saturated fat/work storm, slave number 6~2〇 芳 2~10 醯A.) 厌 ~ ~ 20 aralkyl, or carbon number again: Yu 2: also the invention A preferred azo compound and a salt thereof, and a azo compound and a salt thereof are also included in the formula (1), and the tautomer thereof is also contained in the formula (1). The compound and its salt are used for, for example, coloring of the fiber, and there are pigments such as a device which is not visible at night. [Embodiment] The azo compound of the present invention and a salt thereof are shown in the two ends of the biphenyl skeleton via an anomeric group: the merging is: as in the formula (1) 2226 to 9735-PF; the Ahddub soil has a pyridine ring. Furthermore, 7 200916441 The ketone is in the form of the enol type represented by the formula (1), and is also in the human form. The azo compound of the present invention and its salt are high in color. Further, the azo compound of the present invention and a salt thereof are excellent in the solubility in a solvent (especially oil-soluble), and are excellent in color development using penetrating light. The above solvent may, for example, be selected from the group consisting of ketones (acetic acid vinegar, etc.), ketones (dipropanol, etc.), „ (propanol early formazan 'c: alcohol monomethyl _ acid § Etc.) Other volatile low solubility solvents. - Magic Eight Below, the formula (1) will be described in detail. In the formula (1), 'R1 to R4' represent a hydrogen atom and Ch. Requiring and fat (4) Ji Qianji. The (tetra)silyl hydrocarbon group of R1 to R4 may be any of a straight bond, a branched form or a cyclic form. The carbon number of the saturated fatty acid group does not include the carbon number of the substituent. The lower limit of the carbon number is usually i' is preferably 2, and the upper limit ' of the carbon number is usually 10, preferably 8, more preferably 6, and further preferably 3. The saturated aliphatic hydrocarbon group includes, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an I?-n-butyl group, an isobutyl group, a second butyl group, a tert-butyl group and the like. The formula (1) independently represents an ammonia atom, a dentate atom (preferably a fluorine atom 'gas atom or a bromine atom), and Cw. The saturated aliphatic hydrocarbon is bonded to the saturated waxy base, the Ch-Oxy-carboxyl group, the base, or the substituted extender. The saturated aliphatic hydrocarbon group of Π2 may be in the form of a straight, branched or cyclic shape, and its carbon number is usually 1 (), preferably 18, more preferably 3 to 6. Specific examples of the saturated aliphatic hydrocarbon group of R5 to R12 are the same as those of R K . The saturated aliphatic hydrocarbon group of r5 to rI2 may also be a dentin 2226-9735-PF; Ahddub 8 200916441 atom, preferably a fluorine atom. Specific examples of the halogenated saturated aliphatic hydrocarbon group include a trifluoromethyl group and the like. The carbon number of the alkoxy group of R is usually from 1 to 8, preferably from 1 to 4. The alkoxy group may, for example, be an oxy group, an ethoxy group, an isopropoxy group, a n-propoxy group, a n-butoxy group, an isobutoxy group, a second butoxy group, a third butoxy group or the like. . The N-substituted fluorenyl group of R to R, for example, N-monosubstituted fluorenyl group, may be represented by the formula -SChNHR15. The R" is a Cl_lfl saturated aliphatic hydrocarbon group (containing 8 alkoxy groups bonded to the Ciμ. saturated aliphatic hydrocarbon group), an aryl group having a carbon number of 6 to 2, an aromatic group of 7 to 20, or a carbon number. a sulfhydryl group of 2 to 1 。. A saturated aliphatic hydrocarbon group of R15 may be linear, branched or cyclic. The carbon number of the saturated aliphatic hydrocarbon group does not include the carbon number of the substituent. The lower limit of the carbon number is usually 1 is preferably 3, more preferably 6 and the upper limit thereof is usually 1 Torr, preferably 8. The saturated aliphatic hydrocarbon group at R15 contains, for example, methyl, ethyl, n-propyl or isopropyl. Base, n-butyl, isobutyl, t-butyl, tert-butyl, methylbutyl (1,1,3,3-tetramethylbutyl, etc.), methylhexyl (1,5-di Methylhexyl or the like), ethylhexyl (2-ethylhexyl or the like), cyclopentyl, % hexyl, methylcyclohexyl (2-nonylcyclohexyl, etc.), cyclohexylalkyl, etc. R saturated aliphatic hydrocarbon group As described above, Ci_8 (preferably a substituent such as a Ci decyloxy group may be substituted. The substituted saturated aliphatic hydrocarbon group may, for example, be a propoxypropyl group (3-(isopropoxy)propyl group or the like). Etc. R15 The aryl group may be unsubstituted or may have a substituent such as a saturated aliphatic hydrocarbon group or a hydroxyl group, etc. The carbon number of the above aryl group is usually from 6 to 20, preferably 6 to the number of carbon atoms including a substituent. 10. The aryl group may, for example, be benzene 2226-9735-PF; Ahddub 9 200916441, hydroxyphenyl (4-hydroxyphenyl, etc.), trifluoromethylphenyl (4-trifluoromethylphenyl), etc. Or an unsubstituted or substituted phenyl group, etc. The alkyl moiety of the aralkyl group of R15 may be linear or branched. The carbon number of the aralkyl group is usually 7 to 20, preferably 7 ～1 (N representative aralkyl group, a phenyl group such as a benzyl group or a phenylbutyl group (3-amino-anthracene-phenyl butyl group). The thiol group of 70 may be unsubstituted. Further, a substituent of a saturated aliphatic hydrocarbon group or an alkoxy group may be bonded. The carbon number of the fluorenyl group is usually a number of carbon atoms including a substituent, and the number thereof is usually 2 to 10', preferably 6 to 1 G. Examples thereof include an ethyl hydrazino group, a benzyl group, a decyloxybenzyl group (p-methoxybenzyl group, etc.), etc. The R and R14 groups are a hydrogen atom, a cyano group, a decyl group, or an N-substituted group. A sulfhydryl group. Taking a structural formula of c〇N(R)6)Ri7 (wherein, ^ and R 7 are each independently represented, a hydrogen atom, a Ci i. a saturated aliphatic hydrocarbon group, and a Cl~saturation substituted with a Ci-8 alkoxy group) An aliphatic hydrocarbon group, an aryl group having 6 to 2 carbon atoms, an aralkyl group having an inverse number of 7 to 20, or a fluorenyl group having a carbon number of 2 to 1 Å.) and a saturated aliphatic hydrocarbon group, an aryl group, and an aralkyl group having R The description and specific examples of the thiol group and the sulfhydryl group are the same as those described in the above P. However, specific examples of the fluorenyl group include a benzyl group having a halogen atom, for example, a bromide group (p-bromobenzene). Methyl group, etc. * The above R1 to Rn are further limited by the viewpoint of improving color insolation, water solubility, oil solubility, light resistance and the like. For example, in order to increase the color density, it is recommended to select at least one (preferably all) of R to R4, and to select a saturated aliphatic hydrocarbon group having a carbon number of 5 or less (preferably 3 or less) (for example, thiol and B). Base, etc.), or a hydrogen atom. Further, in order to increase the color density, it is recommended to select at least one of γ (preferably 2226-9735-PF; Ahddub 10 200916441), and select a saturated aliphatic hydrocarbon group having a carbon number of 3 or less (for example, methyl, ethyl, etc.) 1 is a methyl group, or a hydrogen atom. Further, in order to improve the solubility, it is preferred to select an acetamidine group in at least one of R and R1. Further, from the viewpoint of improving the color density and water solubility, one or two or more of R5 to R 2 are recommended (for example, r5 to r8i or more (especially one) '5 and R0 to R121. More than one (particularly one) is a sulfo group, and the remaining R5咄12 is a hydrogen atom or a sulfo group. By increasing the water solubility, it is widely used as a pigment in the field of clothing. One type of the azo compound (I) may be used alone or two or more types may be used in combination. From the viewpoint of improving the color density and the oil solubility, it is recommended to use ι or more of the orders of R5 to R12 (for example, by 81 or more (especially!), and by more than one (especially ^ solid)) Wood - 贶 methyl, N-substituted sulfonium: two, especially one of R5 to R12 is the azo group of _transport, even if the remaining one of ... 12 is a hydrophilic contig The love melon still shows the oil solubility. By using Tangu 4 AU 曰 一 壮 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 偶 偶 偶 偶 偶 偶 偶 偶 偶 偶 偶 偶 偶 偶 偶 偶 偶 偶 偶 偶 偶 偶 偶 偶丨 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单 单 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Therefore, the use of the oil-soluble compound (1) is also preferred as an example of a combination of more than 52 kinds of odors (4), a miscellaneous sample, and an improved oil solubility, and has two substituted sulfonyl groups.古! Μ Α Horse 11 5 5 (disulfonamide), with an azo compound having 1 N-deuterosulfonyl group and i radicals (monosulfonate 2226-9735-PF; Ahddub 200916441 amine) In the combination of s μ, , .5, one of R5 to r8 and one of r9 to r12 is N _ take my stone & Hangango s brewing base 'the rest is hydrogen One of the disulfonamides of the atom, one of the disks r5h t , is an N-substituted sulfonyl group, and one of R9 to Rl2 is a transverse group, and the remaining &&&&<< The monosulfonamide combination is preferred. Furthermore, the early 26-branched amine is better than the disulfonamide in the color of: 隹^; - λι_. Because the molecular weight is lower. From the point of view of life, it is also suggested that one or more of r5 ji2 (for example, by m or more (especially for work), and for π] for ^ (special I i)) a larger group, or one or more of the broad R12 (for example, r5~r8u solid (especially jin) and Ri or more (especially)) substituted position azo group Being in the meta or ortho position. By selecting a larger base, or by making the substitution position to the azo group meta-' can reduce the stacking of the stupid part, the oil solubility can be improved. And by selecting a larger base, or The substitution position is ortho to the azo group, and the protection of the azo group can be increased by m. The above-mentioned r5 to r12 can be exemplified by a branched saturated aliphatic hydrocarbon group such as a tertiary butyl group (particularly a tertiary saturated aliphatic hydrocarbon group), and a trifluoro group. A halogen atom such as a fluorenyl group is bonded to two or more (particularly three or more) saturated aliphatic hydrocarbon groups, N-substituted sulfonyl groups, etc. Further, N-take It is also possible to further define Ru from the viewpoint of further improving the color indifference, oil solubility, etc. In such Rls, for example, methylbutyl (1,1,3,3-tetramethyl) Butyl group, etc., mercaptohexyl (fluorene, 5-dimethyl hexyl, etc.), ethylhexyl (2-ethylhexyl, etc.), methylcyclohexyl (2 to methylcyclohexyl, etc.), phenylbutyl Branched saturated aliphatic hydrocarbon group such as (3-amino-1-phenylbutyl group), or aryl group. 2226-9735-PF; Ahddub 12 200916441 Especially excellent azo compound (I), R5~ One or more of R12, preferably two or more (for example, R5 to R81 or more (particularly one)' and R9 to R12l or more (particularly one) are N-substituted sulfonyl groups. . In the preferred examples of the formula (I), the formulae (I_1) to (I-11) can be given. 〇 〇
(KI) (1-2) (1-3)(KI) (1-2) (1-3)
2226-9735-PF;Ahddub 13 2009164412226-9735-PF; Ahddub 13 200916441
(MO) (1-11) Ίΐ^ 虱化合物（I ) 、—/〜丫，Μ式U i)所示，R5〜r8 至少1個（特別mR8之任何1幻，以及之至 ^個（特別是R9及γ之任何i個）為_s〇細15基，剩下的 氫原子之化合物為佳。#h 更佳的偶氮化合物（丨），可 中的ir〜R4係分別獨立地表 9 巧衣不烷基，尺5及Rs為—s〇 w 基，R15為Cho烷基（特別是 技 W疋C6·10烷基），R6〜R7及R1。〜Rl2 虱原子，β13及β14係分別掘 _权 '(MO) (1-11) Ίΐ^ 虱 compound (I), —/~丫, ΜU i), R5~r8 at least 1 (extra mR8 any 1 illusion, and to ^ (special Any one of R9 and γ) is _s 〇 fine 15 group, and the remaining hydrogen atom compound is preferred. #h Better azo compound (丨), which can be independently ir~R4 It is not alkyl, the 5 and Rs are -s〇w groups, R15 is Cho alkyl (especially W疋C6·10 alkyl), R6~R7 and R1. ~Rl2 虱 atom, β13 and β14 Dig _ right '
d16 也表示氰基或-COND16 also means cyano or -CON
R及β17係分別獨立地表 )R 虱原子或Cho烷基（特別是氫 2226-9735-PF;Ahddub 14 (II) 200916441 子）之化合物。R and β17 are each independently a compound of an R 虱 atom or a Cho alkyl group (particularly hydrogen 2226-9735-PF; Ahddub 14 (II) 200916441).
式（11)之較佳的例係式（II -1) ~ (II- 8)。 222 6-97 35-PF,· Ahddub 15 200916441A preferred example of the formula (11) is a formula (II-1) ~ (II-8). 222 6-97 35-PF,· Ahddub 15 200916441
(Π-1) (ΙΙ-3) (11-4) 2226-9735-PF;Ahddub 16 200916441(Π-1) (ΙΙ-3) (11-4) 2226-9735-PF; Ahddub 16 200916441
(11-7) (Π-8) 本發明，並非限定於式（i)所示之化^ 鹽。鹽，可舉R5〜R12為磺基時之磺酸鹽、R5 羧酸鹽。又形成該等鹽之陽離子並無特別f 物，亦包含其 R12為羧基時之 定，考慮對溶 2226-9735-PF;Ahddub 17 200916441 劑之溶解性，則以鐘 „ 7 ^ 鈉鹽，鉀鹽等鹼金屬越 及乙醇胺鹽、烷基 屬鹽，·銨鹽； 也丞胺鹽寺之有機胺鹽等 屬盤（軚伕的是鈉，右 土。特別是鹼金 有機胺鹽，有用於人/ 、土材之情形。又 有用於3在树脂硬化性化合物 於是非金屬赜，亦古田3形，再者由 ^ 才有用於重視絕緣性之領域。 本發明之偶氮化合物，可如色音領衿& 重，鹽與-唆酮類偶合而製造。例如將式\)=藉：由使 :胺化合物(重氮成分)以亞硝酸、亞硝酸鹽或亞硝酸 si 4匕而得之或α、今儿人.，， 及（b)中， R5- R12 與' «L逃表示相同 R6 V R5 J T,R11 h2n \ \ Λ_/--ΝΗ2 (a) R7 R8 R9 R10 R6 ® \ R5 Ν=Ν- Νξμ (b) R9 R10 d後可藉由使重氮鹽（b)、與式（c)所示吡啶酮類（偶合 成分），通常在水性溶劑中以20〜60t反應，而製造偶氮化 合物（I)U(C)中，Rl8係表示與上述R1或R3相同者，R】£ 你表U述κ或R4相同者，r2s係表示與上述R;3或^ 相同者）。 2226-9735-PF；Ahddub 18 200916441(11-7) (Π-8) The present invention is not limited to the compound represented by the formula (i). The salt may, for example, be a sulfonate or a R5 carboxylate when R5 to R12 are a sulfo group. Further, the cation forming the salt has no specific substance, and the R12 is a carboxyl group. Considering the solubility of the solution 2226-9735-PF; Ahddub 17 200916441, it is s 7 ^ sodium salt, potassium. The alkali metal such as salt and the ethanolamine salt, the alkyl salt, the ammonium salt; the organic amine salt of the guanamine salt temple is a disk (the sodium is the sodium, the right soil, especially the alkali gold organic amine salt, which is used for In the case of humans and soil materials, there are also 3 kinds of resin-hardening compounds, such as non-metal bismuth, and also Gutian 3 shape, and further, it is used in the field of importance for insulation. The azo compound of the present invention can be used in color.衿 衿 衿 & heavy, salt and - ketone ketone coupling. For example, the formula \) = borrow: by: amine compound (diazonium component) with nitrous acid, nitrite or nitrous acid si 4 匕Or α, 今人.,, and (b), R5- R12 and '«L escape means the same R6 V R5 JT, R11 h2n \ \ Λ_/--ΝΗ2 (a) R7 R8 R9 R10 R6 ® \ R5 Ν=Ν- Νξμ (b) R9 R10 d can be obtained by using a diazonium salt (b) and a pyridone (a couple) represented by the formula (c), usually in an aqueous solvent. 0~60t reaction, and in the manufacture of the azo compound (I) U (C), Rl8 represents the same as the above R1 or R3, R] £ you are the same as κ or R4, r2s is expressed as the above R; 3 or ^ the same). 2226-9735-PF; Ahddub 18 200916441
(c) 在於式（I) ’ R5〜R12之至少1個係磺醯基或N —取代磺醯 基之目的化合物，亦可由具有磺醯基或N-取代磺醯基之化 5物（a )製造，惟使用具有確基之化合物（a )進行偶合反應 後，磺醯胺化而製造較確實。例如在於式（丨），先合成R5〜RU 之至少1個係磺基之化合物（以下，稱為「偶氮磺酸（I )」）， 藉由亞硫醯鹵化合物將磺基（―SO』）變成磺醯鹵（_s⑴X ; X 為鹵素原子），接著使之與胺反應，可將磺基磺醯胺化。 於偶氮磺酸（I )之較佳的例，包含式（〗_丨）〜（丨—7)、（卜9) 及（1-10)，特別是可舉式（1_1)〜（1_3)、（I —9)及（1_1〇)。 亞硫醯i化合物，可例示亞硫醯氟、亞硫醯氯、亞硫醯溴、 亞瓜埃等，較佳的是亞硫醯氯、亞硫醯溴等，特別是亞 硫醯氯。亞硫醯鹵之使用量’對偶氮磺酸（ί)1莫耳，例如 為莫耳程度。再者，於反應系中帶有水時，過剩使用 亞硫醯鹵化合物為佳。 κ西胜南化，通常’係於溶劑中進行。溶劑，可用例如， 1’4-二㈣等的酸類（特別是環狀㈣）；氣仿、二氣甲貌、 四氯化奴1,2 一氯乙烷、二氣乙烯、三氣乙烯、全氯乙 烯、二氯丙烷、正戊基氯、！，2_二漠乙烷等㈣化烴類等。 溶劑的使用量，對偶氮化合物⑴1質量部’例如為3質旦 部以地佳的是5質量部以上），1〇質量部以下(較佳： 是8質量部以下）程度。 2226-9735-PF;Ahddub 19 200916441 又，建議於石黃酿鹵化，併用N，N -二烧基曱醯胺（例如 N，N-二甲基曱醯胺，N, N-二乙基曱醯胺等）。使用N, N-二 烷基曱醯胺時，其使用量，對亞硫醯鹵1莫耳，例如為 0.05〜1莫耳程度。將偶氮磺酸（I)與N，N-二烷基甲醯胺於 溶劑中預先混合後，添加亞硫醯鹵，則可抑制發熱。 反應溫度，例如為〇乞以上（較佳的是3(TC以上），70 °C以下（較佳的是60。(：以下）。反應時間，例如為〇. 5小時(c) a compound of the formula (I) 'R5 to R12, at least one of a sulfonyl group or an N-substituted sulfonyl group, or a compound having a sulfonyl group or an N-substituted sulfonyl group (a) Manufactured, but after the coupling reaction using the compound (a) having a certain group, the sulfonium is aminated to be more reliable. For example, in the formula (丨), a compound of at least one sulfo group of R5 to RU (hereinafter referred to as "azo sulfonic acid (I)") is synthesized, and a sulfo group (SO) is used by a sulfinium halide compound. 』) A sulfonium halide (_s(1)X; X is a halogen atom), which is then reacted with an amine to amination of the sulfosulfonium. Preferred examples of the azosulfonic acid (I) include the formulae (〗 〖丨)~(丨-7), (Bu 9) and (1-10), in particular, the formula (1_1)~(1_3) ), (I-9) and (1_1〇). The sulfinium i compound may, for example, be sulfinium fluoride, sulfinium chloride, sulfinium bromide or guaiac, and the like, preferably sulfinium chloride, sulfinium bromide or the like, particularly sulfoxide. The amount of sulfoxide used is 'toluene sulfonic acid (1 molar), for example, to the extent of mole. Further, when water is contained in the reaction system, it is preferred to use a sulfoxide halogen compound in excess. κ Xisheng Nanhua is usually carried out in a solvent. As the solvent, for example, an acid such as 1'4-di(tetra) or the like (especially a cyclic (iv)); a gas-like, a two-gas form, a tetrachloride, a 1,2-chloroethane, a diethylene, a triethylene, Perchloroethylene, dichloropropane, n-pentyl chloride,! , 2_Second Molybdenum, etc. (4) Hydrocarbons, etc. The amount of the solvent to be used is, for example, a mass portion of the azo compound (1), which is preferably 5 parts by mass or more, and a mass of 1 part or less (preferably 8 parts or less). 2226-9735-PF; Ahddub 19 200916441 Also, it is recommended to halogenate in Shihuang, and use N,N-dialkyl decylamine (such as N, N-dimethyl decylamine, N, N-diethyl hydrazine) Amidoxime, etc.). When N, N-dialkyl decylamine is used, the amount thereof is 1 mol to the sulfinium halide, for example, 0.05 to 1 mol. When azobenzenesulfonic acid (I) and N,N-dialkylformamide are preliminarily mixed in a solvent, and sulfite halide is added, heat generation can be suppressed. The reaction temperature is, for example, 〇乞 or more (preferably 3 (TC or more), 70 ° C or less (preferably 60 ((:)). The reaction time is, for example, 〇. 5 hours.
I: 以上（較佳的是3小時以上），8小時以下（較佳的是5小時 以下）程度。 如上述调製之罐醯鹵化合物’可單離後再與胺反應， 亦可不單離而直接以反應混合物與胺反應。再者，單離時， 例如，只要將反應混合物與水混合，濾取析出之結晶即可。 取得之磺醯鹵化合物之結晶，亦可按照需要於與胺反應 前，水洗及乾燥。 上返胺，可舉例如 ' ^ 吓从工、η 2 in - κ 表示（R15與上述相同）。之具體例，包含正丙基胺， 胺正己基胺、二曱基己基胺（1,5 -二甲基己基胺 ^)、四甲基丁基胺四甲基丁基胺等）、乙基己基 胺(2-乙基己基胺等）、胺基苯基丁烷(3,基]—苯基丁烷 等）、異丙氧基丙基胺等。胺之使用量，對磺酿齒化合物】 莫耳通*為3莫耳以上，1G莫耳以下（較佳的是7莫耳 :):度。再者，於本說明書，為將該胺，與後述之鹼性 觸媒區別，D *17 π h 下有稱為反應性胺之情形。 _鹵化σ物與胺之添加順序並無特別限[對續酿 20 2226-9735-PF；Ahddub 200916441 又，磺醯自化合物與 ’可使用與調製磺醯 鹵化合物添加（滴入）胺之情形為多。 胺之反應，通常於溶劑中進行。溶劑 鹵化合物時同樣的溶劑。 入 «函興反應性胺之反應，較佳的是在驗 的存在下進行。鹼性觸媒，可舉例如3級胺（特別是—、 胺、：乙醇胺等的脂肪族3級胺)"比。定、甲基n比二：： 。定驗專。料之中，以3級胺，特別是以三乙胺等的 族3級胺為佳。㈣觸媒之使用量，對反應性胺（與^ 反應之上述胺），通常$ U莫耳以上，6莫耳以下( 的是5莫耳以下）程度。 對確醯_化合物添加反應性胺與驗性觸媒時，驗性觸 媒之添加時機並無特別限^，反應性胺之添加前及添加後 均可，亦可與反應性胺以相同時機添加。又，可預先與反 應性胺混合再添加，亦可另於反應性胺添加。 ，例如為 反應時間 〇°c以上，5〇 ’通常為1〜5 磺醯齒與反應性胺之反應溫度 C以下（較佳的是3 〇它以下）。又， 小時程度。 由反應此e物取得目的化合物續醯胺體之方法並無特 別限疋▼才木用習知之各種手法，例如，將反應混合物與 酸(醋酸)及水一起混合’濾取析出之結晶。上述酸與水， 以預先調製酸的水溶液再使用為多，將反應混合物添加於 該酸水溶液為多。反應混合物之添加溫度，通常為HTC以 上（杈佳的是2(TC以上），5(rc以下（較佳的是3(rc以下）。 又添加後，-般以同溫度攪拌G.5小時~2小時程度。遽取 2226-9735-PP；Ahddub 21 200916441 之結晶’通常以水等清洗’接著乾燥。又，亦可按照需要， 藉由再結晶等的習知手法，進一步純化。 [實施例] 以下，舉實施例更具體說明本發明，惟本發明並非受 限於以下實施例者，當然可以在符合上述.下述之趣旨之 範圍加以適當的變更實施’料均包含於本發明之技術的 fe圍。再者，實施例及比較例中的「％」及「部」，若無特 別提及係質量％及質量部。 實施例1 對式（a-〇所示之2,2，_聯苯胺二磺酸（含水3〇%)1〇 :加入水m部後，於冰浴τ，卩3Q%氫氧化鈉水溶液調 即成pH7〜8。以下的操作係於冰浴下進行。加入亞硝酸鈉 5· 6部授掉30分鐘。少量少量地加入35%鹽酸14. 8部成褐 色溶液之後’攪拌2小時。將硫酸醯胺3. 8部溶解於水38 3 部之水溶液加人反應溶液攪拌，得到含重氮鹽之懸濁液。I: The above (preferably 3 hours or more), 8 hours or less (preferably 5 hours or less). The canister halo compound as prepared above may be reacted with an amine after isolation, or may be directly reacted with an amine by a reaction mixture. Further, in the case of isolation, for example, the reaction mixture may be mixed with water, and the precipitated crystals may be collected by filtration. The obtained sulfonium halide compound crystals may be washed with water and dried before being reacted with an amine as needed. The upper amine may be represented by, for example, ' ^ scare work, η 2 in - κ (R15 is the same as above). Specific examples include n-propylamine, amine n-hexylamine, dinonylhexylamine (1,5-dimethylhexylamine), tetramethylbutylamine tetramethylbutylamine, etc., and ethyl Hexylamine (such as 2-ethylhexylamine), aminophenylbutane (3,yl)-phenylbutane, etc., isopropoxypropylamine, and the like. The amount of amine used, the sulfonated tooth compound] Molot* is more than 3 moles, less than 1G molar (preferably 7 moles:): degrees. Further, in the present specification, the amine is distinguished from the alkaline catalyst described later, and a compound called a reactive amine is present at D * 17 π h . The order of addition of _halogenated σ and amine is not particularly limited [for continuous brewing 20 2226-9735-PF; Ahddub 200916441, sulfonate from compound and 'addition (instillation) of amine can be used and prepared with sulfonium halide compound More. The reaction of the amine is usually carried out in a solvent. Solvent The same solvent as the halogen compound. Into the reaction of the letter-reactive amine, it is preferred to carry out the test in the presence of the test. The basic catalyst may, for example, be a tertiary amine (particularly, an aliphatic amine such as an amine or an amine amine). Ding, methyl n ratio two::. Verification. Among the materials, a tertiary amine, particularly a trisamine such as triethylamine, is preferred. (4) The amount of catalyst used, for reactive amines (reacting with the above amines), usually above $U molar, below 6 m (below 5 m). When the reactive amine and the test catalyst are added to the compound, the timing of the addition of the test catalyst is not particularly limited. The reactive amine may be added before and after the addition, and may also be the same timing as the reactive amine. Add to. Further, it may be added in advance by mixing with a reactive amine or may be added to a reactive amine. For example, the reaction time is 〇°c or more, and 5 〇 ' is usually 1 to 5, and the reaction temperature of the sulfonate and the reactive amine is C or less (preferably 3 Å or less). Again, the hour. The method for obtaining the target compound hydrazine by reacting the e-object is not particularly limited to various conventional methods, for example, mixing the reaction mixture with an acid (acetic acid) and water, and filtering out the precipitated crystal. The above acid and water are reused in an aqueous solution in which an acid is previously prepared, and the reaction mixture is added to the aqueous acid solution. The addition temperature of the reaction mixture is usually HTC or higher (preferably 2 (TC or more), 5 (rc or less (preferably 3 (rc or less). After the addition, the mixture is stirred at the same temperature for G. 5 hours. ~2 hours to the extent. 2226-9735-PP; Ahddub 21 200916441 crystal 'usually washed with water, etc.' followed by drying. Further, if necessary, further purification by conventional techniques such as recrystallization. The present invention will be more specifically described by the following examples, but the present invention is not limited to the following examples, and may be appropriately modified and implemented in the scope of the present invention. In addition, in the examples and comparative examples, "%" and "part", unless otherwise mentioned, are the mass% and mass parts. Example 1 The formula (a-〇2, 2) , _benzidine disulfonic acid (3 % by water) 1 〇: After adding m part of water, it is adjusted to pH 7~8 in an ice bath τ, 卩3Q% sodium hydroxide solution. The following operation is carried out in an ice bath. Adding 5 parts of sodium nitrite to give 5 minutes, adding a small amount of 35% hydrochloric acid to 14. 8 parts of brown After was' stirred for 2 hours. The acyl 3.8 ammonium sulfate was dissolved in water addition of aqueous portion 383 of the reaction solution was stirred to obtain a suspension containing the diazonium salt.
對式（C-1)所示卜乙基—3-甲醯基-4-甲基-6-羥基吡啶 -2-嗣9.6部加入水47.9部後，於冰浴下，以3〇%氫氧化 鈉水溶液調節成ρ Η 8〜9。 2226~9735-PF/Ahddub 22 200916441Adding 47.9 parts of water to the 9.6 part of the ethyl group of the formula (C-1), and then adding 3 % of sodium hydroxide to the ice bath. The aqueous solution is adjusted to ρ Η 8 to 9. 2226~9735-PF/Ahddub 22 200916441
以下的操作係於冰浴下進行。將上n定酮類之驗性 水溶液攪拌成無色溶液彳L 3峨氧化料溶液調節 成pH8〜9,將含重氮鹽之懸濁液以幫浦滴入。滴入終了後， 進一步授拌3小時攪拌得到黃色懸濁液。過遽得到黃色固 體’於減壓下卩6(TC乾燥，得到式(Ι_υ所示偶氮化合物 15. 7 部。 〇The following operations were carried out under an ice bath. The aqueous test solution of the above n-butanone was stirred into a colorless solution, and the oxidized solution of 彳L 3 调节 was adjusted to pH 8 to 9, and the suspension containing the diazonium salt was dropped as a pump. After the completion of the dropwise addition, the mixture was further stirred for 3 hours to obtain a yellow suspension. After hydrazine, a yellow solid was obtained, and 卩6 was reduced under reduced pressure (TC was dried to give the formula: azo υ υ azo compound 15. 7 parts. 〇
(H) 偶氮化合物（1-1)之構造，係以lH_NMR及— 分析 鑑定。分析機器使用ECA-500(曰本電子（株）製）。 H-NMR(500MHz，3 值（ppm , TMS 基準），DMS0); 1. 15(6H’t’ J = 6. 9Hz)，2· 25(6H，s)，3· 91(4H，q，J = 6. 9Hz)， 7·37(2H ’ d ，5Hz) ， 7.46(2H ， dd ， J=8·5 ， 2.3Hz)， 7.51(2H，br.d，J = 1.9Hz)，7.71(2H，br.d，J = 1.9Hz)， 8.03(2H ’ d ’ J=2.3Hz) ， 14.44(2H ， s) 13C-NMR( 125MHz ’ 6 值（ppm，TMS 基準），DMSO) ; 12. 9， 14. 1，33. 8，114_ 9，115. 1, 123. 1，125. 4，133· 9，135· 〇， 139.6，143.8，146_2，160.6，160.7，166.4 將所得偶氮化合物（1-1)0.35g溶解於N,N -二甲基曱 2226-9735-PF;Ahddub 23 200916441 醯胺使體積為250cm3 ’將其中的2cm3以水稀釋使體積為 100cm (濃度.〇.〇28g/L) ’使用分光光度計〔石英比色管， 比色管長lcm〕測定吸收光譜。將所得吸收光譜示於圖1。 該化合物，於；I max = 450nm顯示吸光度2. 86(任意單位）。 實施例2 對式（a-2)所示2，2 —雙（三氟甲基）聯苯胺1 〇· 4部加 入乙醇156部及水52部之後，於冰浴下，以3〇%氫氧化鈉 水溶液調節成PH7~8。以下的操作係於冰浴下進行。加 亞硝酸鈉6.7部攪拌30分鐘。少量少量地加入35%^ = 30. 4部成褐色懸濁液後，攪拌2小時。將硫酸醯胺3= 溶解於水31部之水溶液加入反應溶液攪拌， 人 ' Ί 3垔氮鹽(H) The structure of the azo compound (1-1) was identified by lH_NMR and - analysis. The analysis machine used ECA-500 (manufactured by Sakamoto Electronics Co., Ltd.). H-NMR (500 MHz, 3 (ppm, TMS basis), DMS0); 1. 15 (6H't' J = 6. 9 Hz), 2 · 25 (6H, s), 3 · 91 (4H, q, J = 6. 9Hz), 7·37(2H 'd , 5Hz), 7.46(2H , dd , J=8·5 , 2.3Hz), 7.51(2H,br.d,J = 1.9Hz), 7.71( 2H, br.d, J = 1.9 Hz), 8.03 (2H 'd ' J = 2.3 Hz), 14.44 (2H, s) 13C-NMR (125 MHz '6 value (ppm, TMS basis), DMSO); 9, 14. 1,33. 8,114_ 9,115. 1, 123. 1,125. 4,133· 9,135· 〇, 139.6,143.8,146_2,160.6,160.7,166.4 The obtained azo compound ( 1-1) 0.35 g dissolved in N,N-dimethylhydrazine 2226-9735-PF; Ahddub 23 200916441 guanamine to a volume of 250 cm 3 '2 cm 3 of which was diluted with water to make a volume of 100 cm (concentration. 〇.〇28g /L) 'The absorption spectrum was measured using a spectrophotometer [quartz colorimetric tube, colorimetric tube length lcm]. The obtained absorption spectrum is shown in Fig. 1. The compound exhibits an absorbance of 2.86 (arbitrary units) at; I max = 450 nm. Example 2 After adding 2,2-bis(trifluoromethyl)benzidine 1 〇·4 parts represented by formula (a-2) to 156 parts of ethanol and 52 parts of water, 3 〇% hydrogen was added in an ice bath. The aqueous sodium oxide solution is adjusted to pH 7-8. The following operations were carried out under an ice bath. Add 6.7 parts of sodium nitrite and stir for 30 minutes. Add a small amount of 35%^ = 30. 4 parts to a brown suspension and stir for 2 hours. Add hydrazine sulfate 3 = an aqueous solution dissolved in water 31 to the reaction solution to stir, human ' Ί 3 垔 nitrogen salt
對式π-ι)所 签暴-6 —羥基。比 _2-酮14.7部加入乙醇15部與水221部後，於冰浴 30%氳氧化鈉水溶液調節成ρΗ8~9。 ’ λ 以下的操作係於冰浴下進彳干。胳μ、+ 進仃將上述吡啶_類之For the formula π-ι), the -6-hydroxy group is violent. After adding 15 parts of ethanol and 221 parts of water to 14.7 parts of _2-ketone, it was adjusted to ρΗ8~9 in an ice bath 30% aqueous sodium oxide solution. The operation below λ is carried out in an ice bath. Μμ,+进仃 The above pyridine
水溶液攪拌成褐色溶液之後’邊以3〇%氫氧化鈉水…: 節成ΡΗ8〜9以幫浦滴入含重氮鹽之懸濁液。滴入：:夜自 藉由進-步攪拌3小時得到黃色懸濁液。將過濾：：後: 色固體於減壓下以60t：乾燥，得到式（卜8) 之J 物19· 2部。 不馬敦化< 2226-9735-PF;Ahddub 24 200916441After the aqueous solution was stirred into a brown solution, the suspension was poured into a diazonium salt with a concentration of 3% by weight of sodium hydroxide water. Instillation:: Night self-stirring was carried out by stirring for 3 hours to obtain a yellow suspension. Filtration:: After: The color solid was dried at 60 t under reduced pressure to give a material of the formula (b). Not Ma Dunhua <2226-9735-PF; Ahddub 24 200916441
將所得偶氮化合物（I -8)0. 35g溶解於乳酸乙酿使體積 成25〇cm3，將其中的2cm3以乳酸乙酯稀釋使體積成 l〇〇cm3(濃度：〇. 〇28g/L) ’使用分光光度計〔石英比色管， 比色管長lcm〕測定吸收光譜。將所得吸收光譜示於圖2。 該化合物，於又max = 43〇nm顯示吸光度2. 42(任意單位）。 實施例3 對式（a-1)所示2, 2’ -聯苯胺二磺酸（水30%含有）ι〇〇 部加入水1 〇〇〇部之後，於冰浴下，以3〇%氩氧化鈉水溶液 調節成pH7〜8。以下的操作係於冰浴下進行。將亞硝酸鈉 加入5 6 · 1部授拌3 0分鐘。少量地少量地加入3 5 %鹽酸14 8 部成褐色溶液後’攪拌2小時。將硫酸醯胺3 8. 3部溶解於 水3 8 3部之水溶液加入反應溶液攪掉，得到含重氮鹽之懸 濁液。 對式（C-2)所示1-乙基-3 -氰基—4-甲基—經基n比。定 -2 -酮7 6 · 1部加入水7 61部後，於冰浴下，以3 0 %氫氧化 鈉水溶液調節成PH8〜9。The obtained azo compound (I -8) was dissolved in lactic acid to a volume of 25 〇 cm 3 , and 2 cm 3 of the azo compound (I -8 ) was diluted with ethyl lactate to a volume of 10 〇〇 cm 3 (concentration: 〇. 〇 28 g / L ) 'The absorption spectrum was measured using a spectrophotometer [quartz colorimetric tube, colorimetric tube length lcm]. The obtained absorption spectrum is shown in Fig. 2 . The compound exhibits an absorbance of 2.42 (arbitrary units) at a maximum of max = 43 〇 nm. Example 3 After adding 2,2'-benzidine disulfonic acid (30% of water) to the oxime portion of the formula (a-1), water was added to the crotch portion, and then, in an ice bath, 3% by weight. The aqueous sodium argonoxide solution was adjusted to pH 7-8. The following operations were carried out under an ice bath. Sodium nitrite was added to 5 6 · 1 part for 30 minutes. A small amount of 14 8 hydrochloric acid was added in a small amount to a brown solution, and the mixture was stirred for 2 hours. An aqueous solution in which 3,3 parts of decylamine sulfate was dissolved in 3 3 of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt. The 1-ethyl-3-cyano-4-methyl-perylene group represented by the formula (C-2). After the addition of 7 parts of water to 6 -1 -ketone 7 6 · 1 part, the mixture was adjusted to pH 8 to 9 with a 30% aqueous sodium hydroxide solution in an ice bath.
以下的操作係於冰浴下進行。將上述吡啶酮類之鹼性 2226-9735-PF；Ahddub 25 200916441 水溶液攪拌成無色溶液之後，邊以30%氮氧化鈉水溶液調 節成pH8〜9以幫浦滴入含重氮鹽之懸濁液。滴入终了後， 藉由進一步攪拌3小時得到黃色懸濁液。將過濾所得之黃 色固體於減壓下以6(TC乾燥，得到式（1-9)所示偶氮化合 物15 7部。The following operations were carried out under an ice bath. After the above-mentioned pyridone-based basic 2226-9735-PF; Ahddub 25 200916441 aqueous solution was stirred into a colorless solution, the solution was adjusted to pH 8 to 9 with a 30% aqueous sodium hydride solution to drip the suspension into the suspension containing the diazonium salt. . After the completion of the dropwise addition, a yellow suspension was obtained by further stirring for 3 hours. The yellow solid obtained by filtration was dried under reduced pressure at 6 (TC) to afford 15 portions of the azo compound of the formula (1-9).
(1-9) 偶氮化合物（1-9)之構造，係1H-NMR及13C-NMR分析以 鑑定。分析機器使用ECA-500C日本電子（株）製）。 NMR(500MHz，5 值（ppm ’ TMS 基準），DMS0); 1.14(6H ’ t ’ J=7.1Hz) ， 2.53(6H ， s) ， 3.89(4H ， br.q , J二7· 1Hz) ’ 7· 37(2H ’ d，J = 8. 5IIz)，7. 59(2H，dd，J = 8. 5 , 2. 3Hz)，8. 15(2H，br. d，J:2.3Hz)，14.73(2H，br.s) V·/ - N M R ( 1 2 5 Μ H z ’ 5 值（ρ ρ in ’ T M S 基準）5 D M S 0) ; 1 2. §， 16. 4 ’ 34. 5 ’ 100· 〇，115. 3，116. 3，116. 5，123· 1，133. 9， 136.5’ 139.3，146.1，158.9，159.9，160.2 將所得偶氮化合物（I -9) 0 · 35g，以與實施例1同樣的 條件測定。將所得吸收光譜示於圖3。該化合物，以 λ max = 463nui顯示吸光度3. 31(任意單位）。 實施例4 於具備冷卻管及攪拌裝置之反應瓶，投入偶氮化合物 (1-1)5部、氣仿50部及n，N-二甲基曱醯胺2.1部，於搜 26 2226-9735-PF；Ahddub 200916441 .拌下’邊維持20V以下，滴人亞硫醯氣6部。滴人終了後 升溫成5〇t，以同溫度維持5小時使之反應，之後冷卻成 2(TC。將冷卻後之反應溶液於㈣下邊維㈣紙以下， 滴入1，5-二甲基己基胺4部及三乙胺14部之混合液。之 後，以同溫度攪拌整晚使之反應。接著將所得反應混合物 以減壓濃縮機餾除溶劑後，加入少量甲醇劇烈攪拌。將該 混合物，邊攪拌加入醋酸29部及去離子水3⑽部之混合液 中’使結晶析出。將析出之結晶濾別，以去離子水清洗， 以60 C減壓乾燥，得到式⑴所示偶氣化合物& 6部（產 率 5 60/〇)。(1-9) The structure of the azo compound (1-9) was identified by 1H-NMR and 13C-NMR analysis. The analysis machine uses ECA-500C, manufactured by JEOL Ltd.). NMR (500 MHz, 5 values (ppm 'TMS basis), DMS0); 1.14 (6H 't 'J=7.1 Hz), 2.53 (6H, s), 3.89 (4H, br.q, J 2:1 Hz) 7· 37(2H ' d, J = 8. 5IIz), 7. 59 (2H, dd, J = 8. 5 , 2. 3Hz), 8. 15 (2H, br. d, J: 2.3Hz), 14.73(2H,br.s) V·/ - NMR ( 1 2 5 Μ H z ' 5 value (ρ ρ in ' TMS basis) 5 DMS 0) ; 1 2. §, 16. 4 ' 34. 5 ' 100 · 〇, 115. 3,116. 3,116. 5,123· 1,133. 9, 136.5' 139.3,146.1,158.9,159.9,160.2 The obtained azo compound (I -9) 0 · 35g The measurement was carried out under the same conditions as in Example 1. The obtained absorption spectrum is shown in Fig. 3. The compound exhibits an absorbance of 3.31 (arbitrary unit) at λ max = 463 nui. Example 4 In a reaction bottle equipped with a cooling tube and a stirring device, 5 parts of azo compound (1-1), 50 parts of gas, and 2.1 parts of n,N-dimethyl decylamine were introduced, and the search was made on 26 2226-9735. -PF;Ahddub 200916441 . Mix under the 'maintaining 20V, and drop 6 people of sulfite. After the end of the drip, the temperature is raised to 5 〇t, and the reaction is maintained at the same temperature for 5 hours, and then cooled to 2 (TC. The cooled reaction solution is placed below the (4) lower dimension (4) paper, and 1,5-dimethyl is added dropwise. A mixture of 4 parts of hexylamine and 14 parts of triethylamine. Thereafter, the mixture was stirred at the same temperature overnight to cause a reaction. Then, the obtained reaction mixture was subjected to distillation under reduced pressure, and then stirred, and then stirred with stirring. While adding a mixture of 29 parts of acetic acid and 3 parts of deionized water, the crystals were precipitated. The precipitated crystals were filtered, washed with deionized water, and dried under reduced pressure at 60 C to obtain an azo compound represented by the formula (1). & 6 parts (yield 5 60/〇).
將偶氮化合物（I I — D之吸收光譜，以與實施例2同樣 的條件測定。將所得吸收光譜示於圖4。該化合物，於 λ inax = 451nm顯示吸光度2. 64(任意單位）。 實施例5 於具備冷卻管及攪拌裝置之反應瓶，投入偶氮化合物 (I-9)5部、氯仿50部及N，N_二曱基甲醯胺2· 部，於攪 2226-9735-PF;Ahddub 27 200916441 邊維持20°c以下’滴入亞硫醯氯3部。滴入終了後 5〇'，以同溫度維持5小時使之反應，之後冷卻成 將冷郃後之反應溶液於攪拌下邊維持於別。c以下， 5 —-甲基己基胺4部及三乙胺} 4部之混合液。之 同μ度攪拌整晚使之反應。接著將所得反應混合物 拌下， 升溫成 20°C。 滴入1， 後，以 :減壓濃縮機餾除溶劑後，加入少量f醇劇烈攪拌。將該 此合物’邊攪拌加人醋酸29部及去離子水则部之混合液 中，使結晶析出。將析出之結晶慮別，以去離子水清洗， 以6〇°C減壓乾燥’得到偶氮化合物5. 6部。 對所得偶氮化合物，進行以LC_MS分析之構造解析。 二析機益使用 Agilent ll〇〇(Agilent Technology 公司 製），管柱使用Sumipax 0DS(住化分析中心（株）製）。沖提 洛劑使用於水—乙腈混合溶劑添加三氟甲基醋酸〇. 1%之溶 劑系。結果，所得偶氮化合物，係以式⑴、6)所示之偶氮 化合物（二磺醯胺，精密質量944)於全固形分中存在58 3 質量％，以式（I —11)所示之偶氮化合物（單磺醯胺，精密質 置833)於全固形分中存在30. 1質量％之混合物。 2226-9735-PF;Ahddub 28 200916441The absorption spectrum of the azo compound (II-D) was measured under the same conditions as in Example 2. The obtained absorption spectrum is shown in Fig. 4. The compound showed an absorbance of 2.64 (arbitrary unit) at λ inax = 451 nm. Example 5 In a reaction bottle equipped with a cooling tube and a stirring device, 5 parts of azo compound (I-9), 50 parts of chloroform, and N,N-dimercaptocarbamide 2 parts were placed, and 2226-9735-PF was stirred. ; Ahddub 27 200916441 While maintaining the temperature below 20 ° C 'drip thiocyanate 3 parts. After the end of the dropwise addition 5 〇 ', the reaction was maintained at the same temperature for 5 hours, and then cooled to a stirred reaction solution after stirring. The mixture is maintained below, c is a mixture of 5 - methylhexylamine 4 and triethylamine 4, which is stirred overnight with the same degree of stirring. The resulting reaction mixture is then mixed and heated to 20 After dropping into 1, the solvent was distilled off under a reduced pressure concentrator, and a small amount of f alcohol was stirred vigorously. The mixture was stirred while adding 29 parts of acetic acid and deionized water. To precipitate crystals. Separate the precipitated crystals, wash them with deionized water, and dry them under reduced pressure at 6 ° C. To the azo compound, 5.6. The structure of the obtained azo compound was analyzed by LC-MS analysis. Agilent ll (available from Agilent Technology) was used, and the column was Sumipax 0DS (Daily Analysis Center ( The azo compound represented by the formula (1), 6) is added to a water-acetonitrile mixed solvent in which a solvent of trifluoromethyl acetate is added in a solvent of 1%. As a result, the obtained azo compound is an azo compound represented by the formula (1), 6). (disulfonamide, precision mass 944) is 58.3% by mass in the total solids, and the azo compound (monosulfonamide, precision 833) represented by formula (I-11) is in the total solids. There is a mixture of 30. 1% by mass. 2226-9735-PF; Ahddub 28 200916441
將偶氮化合物（II-6)之吸收光譜，以與實施例2同樣 的條件測定。將所得吸收光譜示於圖5。該化合物，於 λ max = 45 2nni顯示吸光度3. 47(任意單位）。 比較例1 將式（II卜1)所示偶氮化合物（BASF社製：「Ne的⑽ Yellow 075」）之吸收光譜，以與實施例2同樣的條件測定。 將所得吸收光譜示於圖6。該化合物，於λιη3χ=428ηη]顯 示吸光度2.46(任意單位）。The absorption spectrum of the azo compound (II-6) was measured under the same conditions as in Example 2. The obtained absorption spectrum is shown in Fig. 5. The compound exhibits an absorbance of 3.47 (arbitrary unit) at λ max = 45 2nni. Comparative Example 1 The absorption spectrum of an azo compound ("(10) Yellow 075" manufactured by BASF Corporation) of the formula (II) was measured under the same conditions as in Example 2. The obtained absorption spectrum is shown in Fig. 6. This compound showed an absorbance of 2.46 (arbitrary unit) at λιη3χ = 428ηη].
實施例4及5之偶氮化合物（丨丨_丨）及（〗丨_ 6 )，與比較 例1之偶氮化合物（111 -1 )，係公克當量的偶氮基、苯基、 2226-9735-PF/Ahddub 29 200916441 及。比啶i同環$ 數（莫耳數）大致相同。 (11-1)^^ ^ ^ W而，偶氮化合物 及先度（浪度：0.028g/L)，較间一.曲电々加斤 合物（11丨1、·ν 同一 /辰度之偶氮化 物UU〜1)之吸光度大〇18。再 an)，@ _ f # ，於偶氮化合物 1.01。該望奴偶氧化合物（ΙΙΙ-1)大 本笋明之^ ㈣本月木的兩蠕具有吼啶酮環之 本 之偶氮化合物及其鹽，顯示高的色濃产。 實施例6 具有續基之偶氮化合物（Η)與I取代㈣基之偶氮 (ί I 1)之油浴性（對丙二醇單曱醚之溶解度）， 下求得： 一壹將偶氮化合物1£及丙二醇單甲醚仏放入微量瓶攪拌 Υ晝夜後，將溶殘之固形分以過濾去除（若偶氮化合物完全 冷解％，濾液濃度為1 〇質量。將如此所得濾液之吸收光 譜，使用濾液3. 5g以外以與實施例}同樣地測定，求得各 偶虱化合物於λ max之吸光度（Int(a))。又，使用各偶氮 化合物0. 35g，以與實施例】同樣地，求在於各偶氮化合 物之λ max之吸光度（I n t (r))。然後由下式： 溶解度（質量％) = (Int(a)xlO)/Int(r) 計算各偶氮化合物之溶解度。將結果示於表1。 [表1] 「偶氮化合物 「 （11) (ΪΜ) ] 溶解度 _ -— 0.05質量％ 9.54質量％ 由表1之結果，可知藉由導入N -取代續酿基，可提升 本發明之偶氮化合物之油溶性。 2226-9735-PF;Ahddub 30 200916441 [產業上的可利性] 因此=明之偶氮化合物及其鹽，顯示非常高的色漠戶。 因此即使以报少的使用量， -的色濃度 其鹽，得到I# n 本毛明之偶虱化合物及 # μ有與先前同樣的 利。又，在於製造液晶顯示零件之:=，在成本面有 用本發明之偶氮化合物及性⑽旨組成物中使 此可得耐溶劑性及耐熱性等於可減少使用量，因 明之偶氮化合物及其 ;b '良的零件。再者本發 亦可作為調色用色专' 早獨使用作為優良的色素， 高的本於Γ 其他的色素併用。如此地色漠度 件之製造以外，亦可用染色物或液晶顯示零 刀丁用於各式各樣的用途。 【圖式簡單說明】 圖1係表示式π-i)所示 光譜之圖。 圖2係表示式（丨_8)所示 光譜之圖。 圖3係表示式（I _ 9)所示 光譜之圖。 圖4係表示式（丨卜丨）所 收光譜之圖。 圖5係表示式（II-6)所 收光譜之圖。 偶氮化合物（實施例1)之吸收 偶氮化合物（實施例2)之吸收 偶氮化合物（實施例3 )之吸收 示偶氮化合物（實施例4 )之吸 示偶氮化合物（實施例5 )之吸 圖6係表示式（III~ 1)所示偶氮化合物（比較例1)之吸 2226-9735-PF；Ahddub 31 200916441 , 收光譜之圖。 【主要元件符號說明】 益 〇 / 2226-9735-PF;Ahddub 32The azo compounds (丨丨_丨) and (〖丨_6) of Examples 4 and 5, and the azo compound (111-1) of Comparative Example 1, are gram equivalents of azo, phenyl, 2226- 9735-PF/Ahddub 29 200916441 and. It is roughly the same as the number of oxime i (the number of moles). (11-1)^^ ^ ^ W, the azo compound and the first degree (wavelength: 0.028g / L), compared with the first one. Qudian gong plus jin (11 丨 1, · ν same / Chen The absorbance of the azo nitride UU~1) is greater than 18. Again an), @ _ f # , in the azo compound 1.01. The sulphate oxy-compound (ΙΙΙ-1) 大大本本明^ (4) The two worms of this month have an acridine ketone ring and an azo compound and a salt thereof, showing a high color yield. Example 6 Oil-bathability (solubility to propylene glycol monoterpene ether) of an azo compound (Η) having a recurring group and an azo (I) having a substituted (tetra) group, which is determined by the following: 1£ and propylene glycol monomethyl ether oxime are placed in a micro-bottle and stirred overnight, and the dissolved solid fraction is removed by filtration (if the azo compound is completely cold-dissolved, the filtrate concentration is 1 〇 mass. The absorption spectrum of the filtrate thus obtained And the absorbance (Int (a)) of each of the oxime compounds at λ max was measured in the same manner as in Example 5. The azo compound was used in an amount of 0.35 g, and the examples were as follows. Similarly, the absorbance (I nt (r)) of λ max of each azo compound is determined. Then, each azo compound is calculated by the following formula: Solubility (% by mass) = (Int(a)xlO)/Int(r) The solubility is shown in Table 1. [Table 1] "Azo compound" (11) (ΪΜ) ] Solubility _ - - 0.05% by mass 9.54% by mass From the results of Table 1, it can be seen that by introducing N - substitution Brewing base can improve the oil solubility of the azo compound of the present invention. 2226-9735-PF; Ahddub 30 200916441 [Industry The arbitrage of the azo compound and its salt, which shows a very high color desert. Therefore, even if the salt is used in a small amount, the salt of the color is obtained, and the I# n And #μ has the same benefits as before. In addition, it is in the manufacture of liquid crystal display parts: =, in the cost aspect, the solvent and heat resistance of the azo compound and the (10) composition of the present invention are used to make the solvent resistance and heat resistance equal. Reduce the amount of use, because of the azo compounds and their 'b' good parts. In addition, this hair can also be used as a coloring agent for the coloring of the early use as a good pigment, high in the use of other pigments. In addition to the manufacture of ground color inferior parts, it is also possible to use a dye or liquid crystal display for various purposes. [Simplified Schematic] Fig. 1 is a diagram showing the spectrum of the formula π-i). 2 shows the spectrum of the spectrum shown by the formula (丨_8). Fig. 3 is a diagram showing the spectrum of the formula (I -9). Fig. 4 is a diagram showing the spectrum of the equation (丨卜丨). A graph showing the spectrum of the formula (II-6). The azo compound of the azo compound (Example 1) The absorption of the azo compound (Example 2) (Example 3) shows the absorption of the azo compound (Example 4). The absorption of the azo compound (Example 5) is shown in Figure 6 (III-1). The azo compound (Comparative Example 1) is shown as 2226-9735-PF; Ahddub 31 200916441, and the spectrum is shown. [Key element symbol description] YI〇 / 2226-9735-PF; Ahddub 32
Claims (1)
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| JP2007176765A JP2009013290A (en) | 2007-07-04 | 2007-07-04 | Azo compound or its salt |
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| EP2868708A1 (en) * | 2013-10-29 | 2015-05-06 | DyStar Colours Distribution GmbH | Metal-free acid dyes, process for the production thereof and their use |
| TWI608056B (en) * | 2013-10-29 | 2017-12-11 | 德司達染料分銷有限公司 | Acid dyes, process for the production thereof and their use |
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| JP5581566B2 (en) * | 2007-08-24 | 2014-09-03 | 住友化学株式会社 | Colored curable composition |
| JP5609229B2 (en) * | 2009-04-27 | 2014-10-22 | 住友化学株式会社 | Compound and colored photosensitive resin composition containing the compound |
| WO2015062929A1 (en) | 2013-10-29 | 2015-05-07 | Dystar Colours Distribution Gmbh | Acid dyes, process for the production thereof and their use |
| EP2868709A1 (en) | 2013-10-29 | 2015-05-06 | DyStar Colours Distribution GmbH | Metal free acid dyes, process for the production thereof and their use |
| EP2868715A1 (en) | 2013-10-29 | 2015-05-06 | DyStar Colours Distribution GmbH | Metal free acid dyes, process for the production thereof and their use |
| EP2868712A1 (en) | 2013-10-29 | 2015-05-06 | DyStar Colours Distribution GmbH | Metal free acid dyes, process for the production thereof and their use |
| EP2868705A1 (en) | 2013-10-29 | 2015-05-06 | DyStar Colours Distribution GmbH | Metal free acid dyes, process for their production and their use |
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| GB1285339A (en) * | 1968-12-09 | 1972-08-16 | Ici Ltd | New water-insoluble disazo dyestuffs containing 2-hydroxy-3-azo-6-pyridone residues |
| DE3309718A1 (en) * | 1983-03-18 | 1984-09-20 | Basf Ag, 6700 Ludwigshafen | DISAZO DYES |
| JPS63131146A (en) * | 1986-11-21 | 1988-06-03 | Nippon Kayaku Co Ltd | Electrophotographic sensitive body |
| JPH01120563A (en) * | 1987-11-05 | 1989-05-12 | Fuji Electric Co Ltd | Electrophotographic sensitive body |
| US4988594A (en) * | 1989-07-26 | 1991-01-29 | Fuji Electric, Co. Ltd. | Diazo photoconductor for electrophotography |
| GB9809823D0 (en) * | 1998-05-09 | 1998-07-08 | Zeneca Ltd | Compounds |
| JP2005126529A (en) * | 2003-10-22 | 2005-05-19 | Fuji Photo Film Co Ltd | Ink, inkjet recording method, and bisazo compound |
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- 2008-06-11 TW TW097121690A patent/TW200916441A/en unknown
- 2008-07-03 CN CN2008101379132A patent/CN101337925B/en not_active Expired - Fee Related
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2868708A1 (en) * | 2013-10-29 | 2015-05-06 | DyStar Colours Distribution GmbH | Metal-free acid dyes, process for the production thereof and their use |
| TWI608056B (en) * | 2013-10-29 | 2017-12-11 | 德司達染料分銷有限公司 | Acid dyes, process for the production thereof and their use |
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| KR20090004758A (en) | 2009-01-12 |
| JP2009013290A (en) | 2009-01-22 |
| CN101337925A (en) | 2009-01-07 |
| CN101337925B (en) | 2013-09-11 |
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