JPH0240350A - 1-hydroxy-2,3-dicyanonaphthalene and production thereof - Google Patents
1-hydroxy-2,3-dicyanonaphthalene and production thereofInfo
- Publication number
- JPH0240350A JPH0240350A JP63189660A JP18966088A JPH0240350A JP H0240350 A JPH0240350 A JP H0240350A JP 63189660 A JP63189660 A JP 63189660A JP 18966088 A JP18966088 A JP 18966088A JP H0240350 A JPH0240350 A JP H0240350A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxy
- dicyanonaphthalene
- formula
- compound
- fumaronitrile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、色材の中間体として有用な新規な！−ヒドロ
キシー２．３−ジシアノナフタレンおよびその製造方法
に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a novel product useful as an intermediate for colorants! -Hydroxy-2,3-dicyanonaphthalene and its manufacturing method.
［従来の技術］
一般に２．３−ジシアノナフタレン類は、Ｊｏｕｒｎａ
ｌｏｆ 八ｍｅｒｉｃａｎ （：ｈｅｍｉｃａｌ
５ｏｃｉｅｔｙ ６．７４０５．１９８４、あるい
はＺｈｕｒｎａｌ Ｏｒｇａｎｉｃｈｅｓｈｏｉ Ｋｎ
ｉｍｉｉ ７，３６９゜１９７１に記載されているよう
に、キシリレンテトラブロマイドから合成されることが
多かった。しかし、この方法によると、１位に置換基を
有する２、３−ジシアノナフタレンの合成は非常に困難
であり、本発明に記載の１−ヒドロキシ−２，３−ジシ
アノナフタレン及びその製造方法は現在まで知られてい
ない。[Prior Art] Generally, 2,3-dicyanonaphthalenes are prepared by Journa
lof 8merican (:chemical
5ocity 6.7405.1984, or Zhurnal Organicheshoi Kn.
It was often synthesized from xylylene tetrabromide, as described in IMII 7, 369° 1971. However, according to this method, it is very difficult to synthesize 2,3-dicyanonaphthalene having a substituent at the 1-position, and the 1-hydroxy-2,3-dicyanonaphthalene and its production method described in the present invention are currently unknown until now.
［発明が解決しようとする課題］
本発明は、ナフタロシアニン系又は縮合多環系の色材の
中間体として有用な新規なＩ−ヒドロキシ−２，３−ジ
シアノナフタレン及びその製造方法を提供するものであ
る。[Problems to be Solved by the Invention] The present invention provides a novel I-hydroxy-2,3-dicyanonaphthalene useful as an intermediate for naphthalocyanine-based or fused polycyclic coloring materials, and a method for producing the same. It is.
［課題を解決するための手段］
本発明は、式（１）
で表わされる１−ヒドロキシ−２，３−ジシアノナフタ
レンであり、他の発明は一般式（ＩＩ）［式中、Ｒはア
ルキル基を表し、Ｒｏはアリール基を表わすコ
で表わされる化合物とフマロニトリルとを、塩基の存在
下に反応させることを特徴とする式（Ｉ）ｎｌ＋
で表わされる１−ヒドロキシ−２，３−ジシアノナフタ
レンの製造方法である。[Means for Solving the Problem] The present invention relates to 1-hydroxy-2,3-dicyanonaphthalene represented by formula (1); another invention relates to 1-hydroxy-2,3-dicyanonaphthalene represented by formula (1); of 1-hydroxy-2,3-dicyanonaphthalene represented by formula (I)nl+, which is characterized by reacting a compound represented by , where Ro represents an aryl group, and fumaronitrile in the presence of a base. This is the manufacturing method.
式（ＩＩ）中、Ｒはアルキル基を表わし、好ましくは炭
素数１〜８のアルキル基を表わす。その例としては、メ
チル基、エチル基、プロピル基、ブチル基、ペンチル基
、ヘキシル基、ヘプチル基、オクチル基などが挙げられ
る。Ｒｏはアリール基を表わし、好ましくは、フェニル
基、メチルフェニル基、クロロフェニル基などが挙げら
れる。化合物（ｎ）は、例えばＴｅｔｒａｈｅｄｒｏｎ
Ｌｅｔｔｅｒｓ ２２１３−２２１６頁、１９７８に
記載の方法により合成することができる。In formula (II), R represents an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms. Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like. Ro represents an aryl group, preferably phenyl group, methylphenyl group, chlorophenyl group, etc. Compound (n) is, for example, Tetrahedron
It can be synthesized by the method described in Letters, pages 2213-2216, 1978.
塩基としては、水素化ナトリウム、水素化カリウム、ナ
トリウムアルコキサイド、アルキルリチウム、リチウム
ジイソプロピルアミン等力τ挙（ずられる。また、化合
物（ＩＩ）とフマロニトリルとの反応温度は一７８〜１
５０℃であり、好ましくは０〜１００℃である。Examples of the base include sodium hydride, potassium hydride, sodium alkoxide, alkyl lithium, and lithium diisopropylamine. Also, the reaction temperature between compound (II) and fumaronitrile is 178 to 1
The temperature is 50°C, preferably 0 to 100°C.
またこの反応に好ましい溶媒は、エチレングリコールジ
メチルエーテル、ジエチレングリコールジメチルエーテ
ル、ジブチルエーテル、ジブロヒ。Preferred solvents for this reaction are ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, and dibrohyde.
ルエーテル、ジエチルエーテルなどのエーテル系溶媒、
及びジメチルホルムアミド、ジメチルスルホキシド、ジ
メチルイミダゾリジノン、Ｎ−メチルピロリドンなどの
非プロトン性極性溶媒である。ether solvents such as diethyl ether and diethyl ether,
and aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, dimethylimidazolidinone, and N-methylpyrrolidone.
この反応で使用するフマロニトリルの量は、化合物（■
）に対して０．５〜３．０モル当量、好ましくは０．９
〜１．２当量であり、塩基のイ吏用量は、０．５〜５．
０モル当量、好ましくは １，０〜３．０モル当量であ
る。反応時間は１〜１５時間であり、好ましくは１〜Ｉ
Ｏ時間である。The amount of fumaronitrile used in this reaction is determined by the amount of fumaronitrile used in the compound (■
), preferably 0.5 to 3.0 molar equivalents, preferably 0.9
~1.2 equivalents, and the amount of base is 0.5-5.
0 molar equivalent, preferably 1.0 to 3.0 molar equivalent. The reaction time is 1 to 15 hours, preferably 1 to I
It's O time.
［実施例］ 以下、本発明を実施例により、さらに詳細に説明する。[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
窒素気流下、６０％水素化ナトリウム６０ｇとエチレン
グリコールジメチルエーテルｌ（１００ｍｌを混合し、
０℃に冷却後、下に示す化合物
１９１ｇを０℃で徐々に加えた。添加後、０℃で１時間
、室温で１．５時間攪拌後、再び反応系を０℃まで冷却
した。これに、フマロニトリル５１．４ｇをエチレング
リコールジメチルエーテル４００ｍ１に溶解させた溶液
を０℃で滴下した。その後Ｏ℃で２時間、室温で５時間
攪拌した。その後、メタノール２００１を滴下し、さら
に１時間還流させた。その後、濃縮し、濃縮物を水ｉＩ
Ｌに排出し、これを吸引濾過し、濾液をｉ酸水溶液を用
いて弱酸性とした。Example 1 Under a nitrogen stream, 60 g of 60% sodium hydride and 100 ml of ethylene glycol dimethyl ether were mixed,
After cooling to 0°C, 191 g of the compound shown below was gradually added at 0°C. After the addition, the reaction system was stirred at 0°C for 1 hour and at room temperature for 1.5 hours, and then cooled to 0°C again. A solution of 51.4 g of fumaronitrile dissolved in 400 ml of ethylene glycol dimethyl ether was added dropwise to this at 0°C. Thereafter, the mixture was stirred at 0° C. for 2 hours and at room temperature for 5 hours. Thereafter, methanol 2001 was added dropwise, and the mixture was further refluxed for 1 hour. After that, it was concentrated and the concentrate was dissolved in water iI.
This was filtered under suction, and the filtrate was made weakly acidic using an aqueous solution of acid I.
その後これを吸引濾過し、得られた結晶を再沈（アセト
ン：クロロホルムの１：２混合液）した。この遍、液部
分を濃縮し、得られた結晶をクロロホルムで洗浄し、４
０ｇ（収率３４％）の結晶を得た。Thereafter, this was suction-filtered, and the obtained crystals were reprecipitated (1:2 mixture of acetone and chloroform). At this time, the liquid portion was concentrated, the obtained crystals were washed with chloroform, and
0 g (yield 34%) of crystals was obtained.
この結晶のＩＲ及びＮＭＲスペクトルチャートを第１図
及び第２図に示す。IR and NMR spectrum charts of this crystal are shown in FIGS. 1 and 2.
実施例２
窒素気流下、ナトリウムメトキサイド４０．５ｇとジメ
チルホルムアミド１００ｎｌを混合し、０℃に冷却後、
下に示す化合物
元素分析値
１９１ｇを０℃で徐々に加えた。添加後、０℃で１時間
、室温で１．５時間攪拌後、再び反応系を０℃まで冷却
した。これに、フマロニトリル５１．４ｇをジメチルホ
ルムアミド４００１に溶解させた溶液を０℃で滴下した
。その後０℃で２時間、室温で５時間攪拌した。その後
、これを水３２に排出し、これを吸引濾過し、濾液を硫
酸水溶液を用いて弱酸性とした。その後これを吸引濾過
し、得られた結晶を再沈（アセトン：クロロホルムの１
：２混合液）した。この濾液部分を濃縮し、得られた結
晶をクロロホルムで洗浄し、３５ｇ（収率３０％）の結
晶を得た。Example 2 40.5 g of sodium methoxide and 100 nl of dimethylformamide were mixed under a nitrogen stream, and after cooling to 0°C,
191 g of the compound elemental analysis value shown below was gradually added at 0°C. After the addition, the reaction system was stirred at 0°C for 1 hour and at room temperature for 1.5 hours, and then cooled to 0°C again. A solution of 51.4 g of fumaronitrile dissolved in dimethylformamide 4001 was added dropwise to this at 0°C. Thereafter, the mixture was stirred at 0° C. for 2 hours and at room temperature for 5 hours. Thereafter, this was discharged into water 32, filtered under suction, and the filtrate was made weakly acidic using an aqueous sulfuric acid solution. After that, this was suction-filtered, and the obtained crystals were reprecipitated (acetone:chloroform 1
:2 mixed solution). This filtrate portion was concentrated, and the obtained crystals were washed with chloroform to obtain 35 g (yield: 30%) of crystals.
この結晶の元素分析値は次に示す通りであった。The elemental analysis values of this crystal were as shown below.
［発明の効果］
以上説明したように、本発明によれば式（Ｉ）で表され
る新規な化合物及びその有利な製造方法を提供すること
ができた。本発明の１−ヒドロキシ−２，３−ジシアノ
ナフタレンは、従来、多くの２．３−ジシアノナフタレ
ン類が１位に置換基を有していなかったのに対し、１位
にヒドロキシ基を有するものであり、これはまたナフタ
ロシアニン系又は縮合多環系等の色材の中間体としての
価値も大きい。[Effects of the Invention] As explained above, according to the present invention, a novel compound represented by formula (I) and an advantageous manufacturing method thereof could be provided. The 1-hydroxy-2,3-dicyanonaphthalene of the present invention has a hydroxy group at the 1-position, whereas many conventional 2,3-dicyanonaphthalenes did not have a substituent at the 1-position. It also has great value as an intermediate for naphthalocyanine-based or condensed polycyclic-based coloring materials.
第１図は、実施例１で得られた本発明による１−ヒドロ
キシ−２，３−ジシアノナフタレンのＩＲスペクトルチ
ャート、第２図はそのＮＭＲチャートである。FIG. 1 is an IR spectrum chart of 1-hydroxy-2,3-dicyanonaphthalene according to the present invention obtained in Example 1, and FIG. 2 is an NMR chart thereof.
Claims (2)
レン。(1) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼1-Hydroxy-2,3-dicyanonaphthalene represented by (I).
わす］ で表わされる化合物とフマロニトリルとを、塩基の存在
下に反応させることを特徴とする式（ I ）▲数式、化
学式、表等があります▼（ I ） で表わされる１−ヒドロキシ−２、３−ジシアノナフタ
レンの製造方法。(2) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, R represents an alkyl group and R' represents an aryl group] A compound represented by the following and fumaronitrile are combined with a base A method for producing 1-hydroxy-2,3-dicyanonaphthalene represented by formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) characterized by reacting in the presence of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63189660A JPH0791257B2 (en) | 1988-07-30 | 1988-07-30 | 1-hydroxy-2,3-dicyanonaphthalene and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63189660A JPH0791257B2 (en) | 1988-07-30 | 1988-07-30 | 1-hydroxy-2,3-dicyanonaphthalene and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0240350A true JPH0240350A (en) | 1990-02-09 |
| JPH0791257B2 JPH0791257B2 (en) | 1995-10-04 |
Family
ID=16245040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63189660A Expired - Lifetime JPH0791257B2 (en) | 1988-07-30 | 1988-07-30 | 1-hydroxy-2,3-dicyanonaphthalene and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0791257B2 (en) |
-
1988
- 1988-07-30 JP JP63189660A patent/JPH0791257B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0791257B2 (en) | 1995-10-04 |
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