JPH045067B2 - - Google Patents
Info
- Publication number
- JPH045067B2 JPH045067B2 JP59195471A JP19547184A JPH045067B2 JP H045067 B2 JPH045067 B2 JP H045067B2 JP 59195471 A JP59195471 A JP 59195471A JP 19547184 A JP19547184 A JP 19547184A JP H045067 B2 JPH045067 B2 JP H045067B2
- Authority
- JP
- Japan
- Prior art keywords
- calculated value
- nmr
- ethanol
- synthesis example
- crystals
- 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.)
- Expired - Lifetime
Links
- 150000002790 naphthalenes Chemical class 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 42
- 239000000243 solution Substances 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 239000000835 fiber Substances 0.000 description 13
- RQNVIKXOOKXAJQ-UHFFFAOYSA-N naphthazarin Chemical compound O=C1C=CC(=O)C2=C1C(O)=CC=C2O RQNVIKXOOKXAJQ-UHFFFAOYSA-N 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000012300 argon atmosphere Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 8
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 6
- 210000004209 hair Anatomy 0.000 description 6
- 239000000984 vat dye Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 5
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 229940097275 indigo Drugs 0.000 description 4
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 description 4
- 229940075931 sodium dithionate Drugs 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HQFIIOPDBQMRIE-UHFFFAOYSA-N 5,8-dihydroxy-2,3-dihydronaphthalene-1,4-dione Chemical compound O=C1CCC(=O)C2=C1C(O)=CC=C2O HQFIIOPDBQMRIE-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000118 hair dye Substances 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- QTWZICCBKBYHDM-UHFFFAOYSA-N leucomethylene blue Chemical compound C1=C(N(C)C)C=C2SC3=CC(N(C)C)=CC=C3NC2=C1 QTWZICCBKBYHDM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- BRKFSNHJZDVDKY-UHFFFAOYSA-N 2-(heptylamino)-5,8-dihydroxynaphthalene-1,4-dione Chemical compound C1=CC(O)=C2C(=O)C(NCCCCCCC)=CC(=O)C2=C1O BRKFSNHJZDVDKY-UHFFFAOYSA-N 0.000 description 1
- UIVVUNVPTGYZQL-UHFFFAOYSA-N 2-(hexylamino)-5,8-dihydroxynaphthalene-1,4-dione Chemical compound C1=CC(O)=C2C(=O)C(NCCCCCC)=CC(=O)C2=C1O UIVVUNVPTGYZQL-UHFFFAOYSA-N 0.000 description 1
- MNXGOYMKQHECLJ-UHFFFAOYSA-N 5,8-dihydroxy-2-(octylamino)naphthalene-1,4-dione Chemical compound C1=CC(O)=C2C(=O)C(NCCCCCCCC)=CC(=O)C2=C1O MNXGOYMKQHECLJ-UHFFFAOYSA-N 0.000 description 1
- FTITXWKPKMETDH-UHFFFAOYSA-N 5,8-dihydroxy-2-(pentylamino)naphthalene-1,4-dione Chemical compound C1=CC(O)=C2C(=O)C(NCCCCC)=CC(=O)C2=C1O FTITXWKPKMETDH-UHFFFAOYSA-N 0.000 description 1
- ZTAVRZYAHWNEFT-UHFFFAOYSA-N 6-(heptylamino)-5,8-dihydroxy-2,3-dihydronaphthalene-1,4-dione Chemical compound O=C1CCC(=O)C2=C(O)C(NCCCCCCC)=CC(O)=C21 ZTAVRZYAHWNEFT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002791 naphthoquinones Chemical group 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- -1 sulfate ester Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/10—Preparations for permanently dyeing the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/35—Ketones, e.g. benzophenone
- A61K8/355—Quinones
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Emergency Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Coloring (AREA)
- Cosmetics (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は染料および顔料もしくはその中間体と
して価値ある新規なナフタレン誘導体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to novel naphthalene derivatives that are valuable as dyes and pigments or intermediates thereof.
［従来の技術］
従来の繊維用建染染料は、浴中で還元剤を用い
て染料をロイコ体となし、該浴中に繊維を浸しな
がら上記ロイコ体を空気酸化して発色させ繊維に
吸着させるタイプのものである。[Prior art] Conventional vat dyes for textiles are made by converting the dye into leuco bodies using a reducing agent in a bath, and while the fibers are immersed in the bath, the leuco bodies are oxidized in the air to develop color and are adsorbed onto the fibers. It is the type of thing that makes you
たとえば、建染染料として代表的なインジゴは
下記式（）の構造を有しており、染色にあたつ
てはインジゴとアルカリおよび還元剤とを含有す
る溶液中に繊維を浸漬させる。インジゴは上記条
件下で下記式（）のロイコ体になつており、こ
のものが空気酸化を受けて発色し同時に繊維に染
め付くと考えられている。 For example, indigo, which is a typical vat dye, has the structure of the following formula (), and for dyeing, fibers are immersed in a solution containing indigo, an alkali, and a reducing agent. Under the above conditions, indigo becomes a leuco substance of the following formula (), and it is thought that this substance undergoes air oxidation, develops color, and at the same time dyes fibers.
また、この他に建染染料にはインダスレン系染
料、アントラキノン系染料などがあるが、これら
もまた同様の機構で染色されると考えられてい
る。 In addition, there are other vat dyes such as indasthrene dyes and anthraquinone dyes, which are also thought to be dyed by a similar mechanism.
［発明が解決しようとする問題点］
しかしながら、これらのロイコ体は非常に不安
定で空気に触れるとたちどころに酸化されてしま
うので、浴中には多量の還元剤を共存させる必要
があり、繊維にとつては苛酷な条件となる。さら
に、還元はアルカリ条件下で行われるのでなおさ
ら繊維が傷む原因になつていた。 [Problems to be solved by the invention] However, these leuco bodies are extremely unstable and are immediately oxidized when exposed to air, so it is necessary to coexist a large amount of reducing agent in the bath. This is a harsh condition for fibers. Furthermore, since the reduction was carried out under alkaline conditions, this caused further damage to the fibers.
Cassella社により開発されたHelindon
YellowRは縮合Carbazole環を有するナフトキノ
ン系染料で、羊毛用黄色建染染料であるが、還元
に強アルカリ浴を必要とするので市販されなかつ
たことは良く知られていることである。 Helindon developed by Cassella
YellowR is a naphthoquinone dye with fused carbazole rings, and is a yellow vat dye for wool, but it is well known that it was not commercially available because it required a strong alkaline bath for reduction.
また、インジゴのロイコ体の硫酸エステルでは
逆に安定性がよすぎて、強い酸化剤、たとえば過
マンガン酸カリウムを用いなければ発色させるこ
とができず、これもまた繊維に対してはよい条件
ではない。 On the other hand, the sulfate ester of the leuco form of indigo is too stable and cannot be colored without using a strong oxidizing agent, such as potassium permanganate, which is also not a good condition for fibers. do not have.
本発明者らは、上記事情にかんがみ、適度な安
定性を有する、つまりロイコ体として単離できか
つ緩和な条件下で酸化されて強く発色するロイコ
体が得られないかと鋭意研究した結果、本発明を
完成するに至つた。 In view of the above-mentioned circumstances, the present inventors have conducted intensive research to find out whether it is possible to obtain a leuco compound that has appropriate stability, that is, can be isolated as a leuco compound, and which develops a strong color when oxidized under mild conditions. The invention was completed.
［問題点を解決するための手段］
すなわち、本発明は、下記一般式（）で表さ
れるナフタレン誘導体である。[Means for Solving the Problems] That is, the present invention is a naphthalene derivative represented by the following general formula ().
［式（）中、ＲはCnH2o+1、ただしｎは５，
６，７，８のいずれかの数字を表す。］
上記ナフタレン誘導体としては、ｎ＝５の場合
の６−ペンチルアミノ−２，３−ジヒドロ−５，
８−ジヒドロキシナフタレン−１，４−ジオン、
ｎ＝６の場合の６−ヘキシルアミノ−２，３−ジ
ヒドロ−５，８−ジヒドロキシナフタレン−１，
４−ジオン、ｎ＝７の場合の６−ヘプチルアミノ
−２，３−ジヒドロ−５，８−ジヒドロキシナフ
タレン−１，４−ジオン、ｎ＝８の場合の６−オ
クチルアミノ−２，３−ジヒドロ−５，８−ジヒ
ドロキシナフタレン−１，４−ジオンが挙げられ
る。 [In formula (), R is CnH 2o+1 , where n is 5,
Represents any number 6, 7, or 8. ] The above naphthalene derivatives include 6-pentylamino-2,3-dihydro-5, when n=5,
8-dihydroxynaphthalene-1,4-dione,
6-hexylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1 when n=6,
4-dione, 6-heptylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione when n=7, 6-octylamino-2,3-dihydro when n=8 -5,8-dihydroxynaphthalene-1,4-dione is mentioned.
上記ナフタレン誘導体は２−（アルキル）アミ
ノ−５，８−ジヒドロキシナフトキノンを水酸化
カリウム、水酸化ナトリウムまたは炭酸ナトリウ
ムなどのアルカリ存在下、ジチオン酸ナトリウム
などの還元剤を用いて水、アルコール、水−アル
コール混合溶液、もしくは亜鉛存在下塩酸水溶液
中で環元することによつて得られる。適当な反応
条件は嫌気下、室温〜還流温度で１〜５時間の反
応である。 The above naphthalene derivatives are produced by converting 2-(alkyl)amino-5,8-dihydroxynaphthoquinone into water, alcohol, water- It can be obtained by ring formation in an alcohol mixed solution or an aqueous hydrochloric acid solution in the presence of zinc. Suitable reaction conditions are anaerobic reaction at room temperature to reflux temperature for 1 to 5 hours.
本発明のナフタレン誘導体を用いて染色を行う
に際しては、浴中に0.7〜2.0重量％のアンモニア
を共存させると、さらに繊維は良好に染色され
る。 When dyeing using the naphthalene derivative of the present invention, the fibers can be dyed even better if 0.7 to 2.0% by weight of ammonia is present in the bath.
［発明の効果］
本発明のナフタレン誘導体は、上述のごとく、
嫌気下、反応系中からロイコ体として単離するこ
とができ、安定保存することができ、しかも特別
な酸化剤を用いずとも浴中で酸化して良好に発色
して繊維を染色することができる。[Effect of the invention] As mentioned above, the naphthalene derivative of the present invention has the following properties:
It can be isolated as a leuco form from the reaction system under anaerobic conditions, and can be stored stably.Furthermore, it can be oxidized in a bath without using a special oxidizing agent to develop good color and dye fibers. can.
従来の建染染料は通常５％濃度以上でないと充
分な染色は望めなかつたが、本発明のナフタレン
誘導体は0.1％程度の濃度から実用に耐える染色
力を発揮する。 With conventional vat dyes, sufficient dyeing cannot normally be expected unless the concentration is 5% or higher, but the naphthalene derivative of the present invention exhibits a dyeing power sufficient for practical use at a concentration of about 0.1%.
本発明のナフタレン誘導体、繊維用の建染染料
としてだけではなく、人毛用の染毛剤としても使
用可能であり、染毛剤として用いる場合には緩和
な条件で用いうることがとくに好ましい性質とし
て認識される。 The naphthalene derivative of the present invention can be used not only as a vat dye for textiles but also as a hair dye for human hair, and when used as a hair dye, it has a particularly desirable property that it can be used under mild conditions. recognized as.
［合成例］
以下、本発明のナフタレン誘導体の合成例をあ
げて本発明をさらに詳細に説明する。[Synthesis Example] Hereinafter, the present invention will be explained in more detail by giving examples of the synthesis of the naphthalene derivative of the present invention.
合成例 １
ｎ−ペンチルアミン20mmol中にナフタザリン
10mmolを含むエタノール溶液80mlをゆつくり添
加し温度０〜２℃で3.5時間撹拌した。反応終了
後、希塩酸水溶液中に反応物をあけ沈澱物を濾過
し、減圧乾燥した。この乾燥物を充填剤としてシ
リカゲル、溶媒としてベンゼンを用いたカラムク
ロマトグラフイーにかけて分画精製して目的物で
ある結晶1.230ｇ（収率44.5％）を得、さらにエ
タノールで再結晶した。このものは下記の分析値
によつて２−ペンチルアミノ−５，８−ジヒドロ
キシナフトキノンであることを確認した。Synthesis example 1 Naphthazarin in 20 mmol of n-pentylamine
80 ml of an ethanol solution containing 10 mmol was slowly added and stirred at a temperature of 0 to 2°C for 3.5 hours. After the reaction was completed, the reactant was poured into a dilute aqueous hydrochloric acid solution, and the precipitate was filtered and dried under reduced pressure. This dried product was fractionated and purified by column chromatography using silica gel as a filler and benzene as a solvent to obtain 1.230 g (yield: 44.5%) of the desired crystals, which were further recrystallized from ethanol. This product was confirmed to be 2-pentylamino-5,8-dihydroxynaphthoquinone based on the following analytical values.
マススペクトル M+＝275
元素分析値 Ｃ＝65.41（計算値65.44）
Ｈ＝ 6.25（計算値 6.22）
Ｎ＝ 5.08（計算値 5.09）
核磁気共鳴スペクトル（CDCl3、δ、ppm）
1H−NMR 13.37（1H，OH，Ｓ），11.81（1H，
OH），Ｓ），7.01−7.30（2H，arom.，ｑ），
6.07（1H，NH，broad），5.66（1H，
quinone，ｓ），0.90〜3.29（11H，pentyl
group）
13C−NMR carbonyl group，187.0，183.8
合成例 ２
ｎ−ヘキシルアミン20mmol中にナフタザリン
10mmolを含むエタノール溶液80mlをゆつくり添
加し温度２〜４℃で2.5時間撹拌した。反応終了
後、希塩酸水溶液中に反応物をあけ沈澱物を濾過
し、減圧乾燥した。この乾燥物を充填剤としてシ
リカゲル、溶媒としてベンゼンを用いたカラムク
ロマトグラフイーにかけて分画精製して目的物で
ある結晶1.381ｇ（収率47.5％）を得、エタノー
ルで再結晶した。このものは下記の分析値によつ
て２−ヘキシルアミノ−５，８−ジヒドロキシナ
フトキノンであることを確認した。 Mass spectrum M + = 275 Elemental analysis values C = 65.41 (calculated value 65.44) H = 6.25 (calculated value 6.22) N = 5.08 (calculated value 5.09) Nuclear magnetic resonance spectrum (CDCl 3 , δ, ppm) 1 H-NMR 13.37 (1H, OH, S), 11.81 (1H,
OH), S), 7.01-7.30 (2H, arom., q),
6.07 (1H, NH, broad), 5.66 (1H,
quinone, s), 0.90-3.29 (11H, pentyl
group) 13 C-NMR carbonyl group, 187.0, 183.8 Synthesis example 2 Naphthazarin in 20 mmol of n-hexylamine
80 ml of an ethanol solution containing 10 mmol was slowly added and stirred at a temperature of 2 to 4°C for 2.5 hours. After the reaction was completed, the reaction product was poured into a dilute aqueous hydrochloric acid solution, and the precipitate was filtered and dried under reduced pressure. The dried product was fractionated and purified by column chromatography using silica gel as a filler and benzene as a solvent to obtain 1.381 g (yield: 47.5%) of the desired crystals, which were recrystallized from ethanol. This product was confirmed to be 2-hexylamino-5,8-dihydroxynaphthoquinone based on the following analytical values.
マススペクトル M+＝289
元素分析値 Ｃ＝66.42（計算値66.42）
Ｈ＝ 6.62（計算値 6.62）
Ｎ＝ 4.88（計算値 4.84）
核磁気共鳴スペクトル（CDCl3，δ，ppm）
1H−NMR 13.37（1H，OH，Ｓ），11.81（1H，
OH，Ｓ），7.00−7.30（2H，arom.，ｑ），
6.07（1H，NH，broad），5.65（1H，
quinone，ｓ），0.90〜3.29（13H，hexyl
droup）
13C−NMR carbonyl group，187.0，183.7
合成例 ３
ｎ−ヘプチルアミン20mmol中にナフタザリン
10mmolを含むエタノール溶液80mlをゆつくり添
加し温度０〜２℃で3.5時間撹拌した。反応終了
後、希塩酸水溶液中に反応物をあけ沈澱物を濾過
し、減圧乾燥した。この乾燥物を充填剤としてシ
リカゲル、溶媒としてベンゼンを用いたカラムク
ロマトグラフイーにかけて分画精製して目的物で
ある結晶1.438ｇ（収率43.2％）を得、エタノー
で再結晶した。このものは下記の分析値によつて
２−ヘプチルアミノ−５，８−ジヒドロキシナフ
トキノンであることを確認した。 Mass spectrum M + = 289 Elemental analysis values C = 66.42 (calculated value 66.42) H = 6.62 (calculated value 6.62) N = 4.88 (calculated value 4.84) Nuclear magnetic resonance spectrum (CDCl 3 , δ, ppm) 1 H-NMR 13.37 (1H, OH, S), 11.81 (1H,
OH, S), 7.00-7.30 (2H, arom., q),
6.07 (1H, NH, broad), 5.65 (1H,
quinone, s), 0.90-3.29 (13H, hexyl
13 C-NMR carbonyl group, 187.0, 183.7 Synthesis example 3 Naphthazarin in 20 mmol of n-heptylamine
80 ml of an ethanol solution containing 10 mmol was slowly added and stirred at a temperature of 0 to 2°C for 3.5 hours. After the reaction was completed, the reactant was poured into a dilute aqueous hydrochloric acid solution, and the precipitate was filtered and dried under reduced pressure. This dried product was fractionated and purified by column chromatography using silica gel as a filler and benzene as a solvent to obtain 1.438 g (yield: 43.2%) of the desired crystals, which were recrystallized from ethanol. This product was confirmed to be 2-heptylamino-5,8-dihydroxynaphthoquinone based on the following analytical values.
マススペクトル M+＝303
元素分析値 Ｃ＝67.13（計算値67.31）
Ｈ＝ 6.98（計算値 6.98）
Ｎ＝ 4.59（計算値 4.62）
核磁気共鳴スペクトル（CDCl3，δ，ppm）
1H−NMR 13.37（1H，OH，Ｓ），11.82（1H，
OH，Ｓ），7.02−7.31（1H，arom.，ｑ），
6.05（1H，NH，broad），5.67（1H，
quinone，ｓ），0.90〜3.30（15H，heptyl
group）
13C−NMR carbonyl grouq、187.1，183.8
合成例 ４
ｎ−オクチルアミン20mmol中にナフタザリン
10mmolを含むエタノール溶液80mlをゆつくり添
加し温度０〜２℃で3.5時間撹拌した。反応終了
後、希塩酸水溶液中に反応物をあけ沈澱物を濾過
し、減圧乾燥した。この乾燥物を充填剤としてシ
リカゲル、溶媒としてベンゼンを用いたカラムク
ロマトグラフイーにかけて分画精製して目的物で
ある結晶1.591ｇ（収率50.0％）を得、エタノー
ルで再結晶した。このものは下記の分析値によつ
て２−オクチルアミノ−５，８−ジヒドロキシナ
フトキノンであることを確認した。 Mass spectrum M + = 303 Elemental analysis value C = 67.13 (calculated value 67.31) H = 6.98 (calculated value 6.98) N = 4.59 (calculated value 4.62) Nuclear magnetic resonance spectrum (CDCl 3 , δ, ppm) 1 H-NMR 13.37 (1H, OH, S), 11.82 (1H,
OH, S), 7.02-7.31 (1H, arom., q),
6.05 (1H, NH, broad), 5.67 (1H,
quinone, s), 0.90-3.30 (15H, heptyl
group) 13 C-NMR carbonyl grouq, 187.1, 183.8 Synthesis example 4 Naphthazarin in 20 mmol of n-octylamine
80 ml of an ethanol solution containing 10 mmol was slowly added and stirred at a temperature of 0 to 2°C for 3.5 hours. After the reaction was completed, the reactant was poured into a dilute aqueous hydrochloric acid solution, and the precipitate was filtered and dried under reduced pressure. This dried product was fractionated and purified by column chromatography using silica gel as a filler and benzene as a solvent to obtain 1.591 g (yield: 50.0%) of the desired crystals, which were recrystallized from ethanol. This product was confirmed to be 2-octylamino-5,8-dihydroxynaphthoquinone based on the following analytical values.
マススペクトル M+＝317
元素分析値 Ｃ＝68.10（計算値68.12）
Ｈ＝ 7.29（計算値 7.30）
Ｎ＝ 4.38（計算値 4.41）
核磁気共鳴スペクトル（CDCl3，δ，ppm）
1H−NMR 13.38（1H，OH，Ｓ），11.83
（（1H，OH，Ｓ），7.02−7.31（2H，
arom.，ｑ），6.07（1H，NH，broad），
5.67（1H，quinone，ｓ），0.89〜3.30
（17H，octyl group）
13C−NMR carbonyl group、187.0，183.8
合成例 ５
合成例１で得た２−ペンチルアミノ−５，８−
ジヒドロキシナフトキノン600mgを炭酸ナトリウ
ム600mg、ジチオン酸ナトリウム1600mgとともに
エタノール水溶液（エタノール15、水20）35ml中
に溶解し、アルゴン雰囲気下、還流温度で３時間
撹拌した。溶液が黄褐色に変わつて、充分に還元
が進行したことを確認し、室温まで冷却した後、
濾過し、結晶を脱気した水で充分洗浄した。これ
らの操作はすべてアルゴン雰囲気下で行つた。結
晶を減圧乾燥して目的物461mg（収率76.8％）を
得、さらにアルゴン雰囲気下エタノールで再結晶
した。 Mass spectrum M + = 317 Elemental analysis values C = 68.10 (calculated value 68.12) H = 7.29 (calculated value 7.30) N = 4.38 (calculated value 4.41) Nuclear magnetic resonance spectrum (CDCl 3 , δ, ppm) 1 H-NMR 13.38 (1H, OH, S), 11.83
((1H, OH, S), 7.02−7.31(2H,
arom., q), 6.07 (1H, NH, broad),
5.67 (1H, quinone, s), 0.89~3.30
(17H, octyl group) 13 C-NMR carbonyl group, 187.0, 183.8 Synthesis example 5 2-pentylamino-5,8- obtained in synthesis example 1
600 mg of dihydroxynaphthoquinone, along with 600 mg of sodium carbonate and 1,600 mg of sodium dithionate, was dissolved in 35 ml of an aqueous ethanol solution (15 ethanol, 20 water) and stirred at reflux temperature for 3 hours under an argon atmosphere. The solution turns yellowish brown to confirm that reduction has proceeded sufficiently, and after cooling to room temperature,
It was filtered and the crystals were thoroughly washed with degassed water. All these operations were performed under an argon atmosphere. The crystals were dried under reduced pressure to obtain 461 mg (yield 76.8%) of the desired product, which was further recrystallized from ethanol under an argon atmosphere.
このものには数種の互変異性体が考えられる
が、下記の分析値にみられるごとく、13C−NMR
におけるカルボニル基の化学シフトがキノン類の
それより著しく低磁場側に認められることから、
カルボニル基の隣接にメチル基あるいはメチレン
基が存在すると考えられ、６−ペンチルアミノ−
２，３−ジヒドロ−５，８−ジヒドロキシナフタ
レン−１，４−ジオンであると確認した。 There are several possible tautomers of this substance, but as seen in the analysis values below, 13 C-NMR
Since the chemical shift of the carbonyl group in is observed to be significantly lower than that of quinones,
It is thought that a methyl group or methylene group exists adjacent to the carbonyl group, and 6-pentylamino-
It was confirmed to be 2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione.
マススペクトル M+＝277
元素分析値 Ｃ＝64.97（計算値64.97）
Ｈ＝ 6.92（計算値 6.91）
Ｎ＝ 5.01（計算値 5.05）
核磁気共鳴スペクトル（CDCl3，δ，ppm）
1H−NMR 12.94（1H，OH，Ｓ），12.49（1H，
OH，Ｓ），6.21（1H，arom.，Ｓ），5.33
（1H，NH，broad），2.95（4H，−（CH2）2
−，Ｓ），0.90〜3.30（11H，pentyl group）
13C−NMR carbonyl group；203.0，196.9
合成例 ６
合成例２で得た２−ヘキシルアミノ−５，８−
ジヒドロキシナフトキノン300mgを炭酸ナトリウ
ム300mg、ジチオン酸ナトリウム900mgとともにエ
タノール水溶液（エタノール10、水10）20ml中に
溶解し、アルゴン雰囲気下、還流温度で１時間撹
拌した。溶液が黄褐色に変わつて、充分に還元が
進行したことを確認し、室温まで冷却した後、濾
過し、結晶を脱気した水で充分洗浄した。これら
の操作はすべてアルゴン雰囲気下で行つた。結晶
を減圧乾燥して目的物220mg（収率72.8％）を得、
さらにアルゴン雰囲気下エタノールで再結晶し
た。 Mass spectrum M + = 277 Elemental analysis value C = 64.97 (calculated value 64.97) H = 6.92 (calculated value 6.91) N = 5.01 (calculated value 5.05) Nuclear magnetic resonance spectrum (CDCl 3 , δ, ppm) 1 H-NMR 12.94 (1H, OH, S), 12.49 (1H,
OH, S), 6.21 (1H, aroma., S), 5.33
(1H, NH, broad), 2.95 (4H, −(CH 2 ) 2
-, S), 0.90-3.30 (11H, pentyl group) 13 C-NMR carbonyl group; 203.0, 196.9 Synthesis Example 6 2-hexylamino-5,8- obtained in Synthesis Example 2
300 mg of dihydroxynaphthoquinone was dissolved together with 300 mg of sodium carbonate and 900 mg of sodium dithionate in 20 ml of an aqueous ethanol solution (10 ethanol, 10 water) and stirred at reflux temperature for 1 hour under an argon atmosphere. The solution turned yellowish brown, confirming that the reduction had progressed sufficiently, and after cooling to room temperature, it was filtered, and the crystals were thoroughly washed with degassed water. All these operations were performed under an argon atmosphere. The crystals were dried under reduced pressure to obtain 220 mg (yield 72.8%) of the target product.
Further, it was recrystallized from ethanol under an argon atmosphere.
このものには数種の互変異性体が考えられる
が、下記の分析値から６−ヘキシルアミノ−２，
３−ジヒドロ−５，８−ジヒドロキシナフタレン
−１，４−ジオンであると確認した。 There are several possible tautomers of this substance, but from the analytical values below, 6-hexylamino-2,
It was confirmed to be 3-dihydro-5,8-dihydroxynaphthalene-1,4-dione.
マススペクトル M+＝291
元素分析値 Ｃ＝65.82（計算値65.96）
Ｈ＝ 7.25（計算値 7.26）
Ｎ＝ 4.57（計算値 4.81）
核磁気共鳴スペクトル（CDCl3，δ，ppm）
1H−NMR 12.94（1H，OH，Ｓ），12.49（1H，
OH，Ｓ），6.21（1H，arom.，Ｓ），5.33
（1H，NH，broad），2.94（4H，−（CH2）2
−，Ｓ），0.91〜3.35（13H，hexyl group）
13C−NMR carbonyl group；203.0，196.9
合成例 ７
合成例３で得た２−ヘプチルアミノ−５，８−
ジヒドロキシナフナキノン200mgを炭酸ナトリウ
ム200mg、ジチオン酸ナトリウム700ftとともにエ
タノール水溶液（エタノール10、水20）30ml中に
溶解し、アルゴン雰囲気下、還流温度で１時間撹
拌した。溶液が黄褐色に変わつて、充分に還元が
進行したことを確認し、室温まで冷却した後、濾
過し、結晶を脱気した水で充分洗浄した。これら
の操作はすべてアルゴン雰囲気下で行つた。結晶
を減圧乾燥して目的物98mg（収率48.7％）を得、
さらにアルゴン雰囲気下エタノールで再結晶し
た。 Mass spectrum M + = 291 Elemental analysis value C = 65.82 (calculated value 65.96) H = 7.25 (calculated value 7.26) N = 4.57 (calculated value 4.81) Nuclear magnetic resonance spectrum (CDCl 3 , δ, ppm) 1 H-NMR 12.94 (1H, OH, S), 12.49 (1H,
OH, S), 6.21 (1H, aroma., S), 5.33
(1H, NH, broad), 2.94 (4H, −(CH 2 ) 2
-, S), 0.91-3.35 (13H, hexyl group) 13 C-NMR carbonyl group; 203.0, 196.9 Synthesis Example 7 2-heptylamino-5,8- obtained in Synthesis Example 3
200 mg of dihydroxynaphnaquinone was dissolved together with 200 mg of sodium carbonate and 700 ft of sodium dithionate in 30 ml of an aqueous ethanol solution (10 ethanol, 20 ml of water), and the mixture was stirred at reflux temperature for 1 hour under an argon atmosphere. The solution turned yellowish brown, confirming that the reduction had progressed sufficiently, and after cooling to room temperature, it was filtered, and the crystals were thoroughly washed with degassed water. All these operations were performed under an argon atmosphere. The crystals were dried under reduced pressure to obtain 98 mg (yield 48.7%) of the target product.
Further, it was recrystallized from ethanol under an argon atmosphere.
このものには数種の互変異性体が考えられる
が、下記の分析値から６−ヘプチルアミノ−２，
３−ジヒドロ−５，８−ジヒドロキシナフタレン
−１，４−ジオンであると確認した。 There are several possible tautomers of this substance, but from the analytical values below, 6-heptylamino-2,
It was confirmed to be 3-dihydro-5,8-dihydroxynaphthalene-1,4-dione.
マススペクトル M+＝305
元素分析値 Ｃ＝67.07（計算値66.86）
Ｈ＝ 7.81（計算値 7.59）
Ｎ＝ 4.20（計算値 4.59）
核磁気共鳴スペクトル（CDCl3，δ，ppm）
1H−NMR 12.94（1H，OH，Ｓ），12.49（1H，
OH，Ｓ），6.21（1H，arom.，Ｓ），5.32（1H，
NH，broad），2.94（4H，−（CH2）2−，Ｓ），0.89
〜3.31（15H，heptyl group）
13C−NMR carbonyl group；203.0，196.9
合成例 ８
合成例４で得た２−オクチルアミノ−５，８−
ジヒドロキシナフトキノン600mgを炭酸ナトリウ
ム600mg、ジチオン酸ナトリウム1600mgとともに
エタノール水溶液（エタノール15、水15）30ml中
に溶解し、アルゴン雰囲気下、還流温度で４時間
撹拌した。溶液が黄褐色に変わつて、充分に還元
が進行したことを確認し、室温まで冷却した後、
濾過し、結晶を脱気した水で充分洗浄した。これ
らの操作はすべてアルゴン雰囲気下で行つた。結
晶を減圧乾燥して目的物（118mg（収率69.2％）
を得、さらにアルゴン雰囲気下エタノールで再結
晶した。 Mass spectrum M + = 305 Elemental analysis value C = 67.07 (calculated value 66.86) H = 7.81 (calculated value 7.59) N = 4.20 (calculated value 4.59) Nuclear magnetic resonance spectrum (CDCl 3 , δ, ppm) 1 H-NMR 12.94 (1H, OH, S), 12.49 (1H,
OH, S), 6.21 (1H, arom., S), 5.32 (1H,
NH, broad), 2.94 (4H, −(CH 2 ) 2 −, S), 0.89
~3.31 (15H, heptyl group) 13 C-NMR carbonyl group; 203.0, 196.9 Synthesis example 8 2-octylamino-5,8- obtained in synthesis example 4
600 mg of dihydroxynaphthoquinone was dissolved in 30 ml of an aqueous ethanol solution (15 ethanol, 15 water) along with 600 mg of sodium carbonate and 1,600 mg of sodium dithionate, and the mixture was stirred at reflux temperature for 4 hours under an argon atmosphere. The solution turns yellowish brown to confirm that reduction has proceeded sufficiently, and after cooling to room temperature,
It was filtered and the crystals were thoroughly washed with degassed water. All these operations were performed under an argon atmosphere. Dry the crystals under reduced pressure to obtain the desired product (118 mg (yield 69.2%)
was obtained and further recrystallized from ethanol under an argon atmosphere.
このものには数種の互変異性体が考えられる
が、下記の分析値から６−オクチルアミノ−２，
３−ジヒドロ−５，８−ジヒドロキシナフタレン
−１，４−ジオンであると確認した。 There are several possible tautomers of this substance, but from the analytical values below, 6-octylamino-2,
It was confirmed to be 3-dihydro-5,8-dihydroxynaphthalene-1,4-dione.
マススペクトル M+＝319
元素分析値 Ｃ＝67.48（計算値67.69）
Ｈ＝ 7.94（計算値 7.89）
Ｎ＝ 4.26（計算値 4.39）
核磁気共鳴スペクトル（CDCl3，δ，ppm）
1H−NMR 12.95（1H，OH，Ｓ），12.50（1H，
OH，Ｓ），6.21（1H，arom.S），5.32（1H，
NH，broad），2.95（4H，−（CH2）2−，
Ｓ），0.90〜3.36（15H，heptyl group）
13C−NMR carbonyl group；203.0，196.9
次ぎに本発明のナフタレン誘導体を用いた染色
の実施例を示す。 Mass spectrum M + = 319 Elemental analysis values C = 67.48 (calculated value 67.69) H = 7.94 (calculated value 7.89) N = 4.26 (calculated value 4.39) Nuclear magnetic resonance spectrum (CDCl 3 , δ, ppm) 1 H-NMR 12.95 (1H, OH, S), 12.50 (1H,
OH, S), 6.21 (1H, aroma.S), 5.32 (1H,
NH, broad), 2.95 (4H, −(CH 2 ) 2 −,
S), 0.90 to 3.36 (15H, heptyl group) 13 C-NMR carbonyl group; 203.0, 196.9 Next, examples of staining using the naphthalene derivative of the present invention will be shown.
実施例 １
合成例５〜８で得られた６−アルキルアミノ−
２，３−ジヒドロ−５，８−ジヒドロキシナフタ
レン−１，４−ジオン各々200mgを水20ｇ中に溶
解し、該溶液中に株式会社色染社製の羊毛モスリ
ン試験用繊維を浴比１／40で浸漬して30℃または
40℃の温度で45分間震盪染色し、いずれの場合も
鮮やかな赤褐色の羊毛モスリンを得た。Example 1 6-alkylamino- obtained in Synthesis Examples 5 to 8
Dissolve 200 mg of each of 2,3-dihydro-5,8-dihydroxynaphthalene-1,4-diones in 20 g of water, and add wool muslin test fiber manufactured by Shikisensha Co., Ltd. to the solution at a bath ratio of 1/40. Soak at 30℃ or
Shaking dyeing at a temperature of 40° C. for 45 minutes gave in each case a bright reddish-brown wool muslin.
なお、この際、0.7〜2.0重量％のアンモニアを
共存させると染色がさらに良好に行われる。 In addition, at this time, if 0.7 to 2.0% by weight of ammonia is co-present, the dyeing will be performed even better.
実施例 ２
合成例５〜８で得られた６−アルキルアミノ−
２，３−ジヒドロ−５，８−ジヒドロキシナフタ
レン−１，４−ジオン各々20mgを水20ｇ中に溶解
し、該溶液中に株式会社アベイユから購入した白
髪混じりの毛髪1.0ｇを浸漬して30℃で45分間震
盪染色した。その後、染色毛髪を水200mlより30
℃５分間洗浄して白髪が全く感じられない毛髪を
得た。Example 2 6-alkylamino- obtained in Synthesis Examples 5 to 8
20 mg each of 2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione was dissolved in 20 g of water, and 1.0 g of gray hair purchased from Abeille Co., Ltd. was immersed in the solution at 30°C. Shake and stain for 45 minutes. After that, add 30ml of dyed hair to 200ml of water.
After washing for 5 minutes at ℃, hair with no gray hair was obtained.
得られた染色毛髪を市販のシヤンプーを用いて
洗浄し、さらにリンスを用いてトリートメントし
たが、色調の変化はなかつた。 The obtained dyed hair was washed using a commercially available shampoo and further treated using a rinse, but there was no change in color tone.
実施例 ３
実施例１に準じて株式会社色染社製の試験用マ
ルチフアイバー（17種の繊維からなる。アセテー
トがベージユ、他は白色）を染色し、アンモニア
の有無およびその量に準じた鮮やかな赤褐色の染
色繊維を得た。Example 3 Test multi-fiber manufactured by Shirozome Co., Ltd. (consisting of 17 types of fibers. Acetate is beige, others are white) was dyed according to Example 1, and brightness was determined according to the presence or absence of ammonia and its amount. A reddish-brown dyed fiber was obtained.
Claims (1)
体 ［式（）中、ＲはCnH2o+1、ただしｎは５，
６，７，８のいずれかの数字を表す。］[Claims] 1. A naphthalene derivative represented by the following general formula () [In formula (), R is CnH 2o+1 , where n is 5,
Represents any number 6, 7, or 8. ]
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59195471A JPS6172063A (en) | 1984-09-18 | 1984-09-18 | Naphthalene derivative |
| DE19853514092 DE3514092A1 (en) | 1984-04-20 | 1985-04-18 | NAPHTHALINE DERIVATIVES AND USE THEREOF FOR DYING HAIR |
| GB08509909A GB2159828B (en) | 1984-04-20 | 1985-04-18 | Naphthalene derivatives and hair dye compositions containing them |
| US06/725,069 US4605419A (en) | 1984-04-20 | 1985-04-19 | 5,8-dihydroxy naphthalene-1,4-dione derivative and a hair dye composition containing the same |
| FR8505964A FR2563215B1 (en) | 1984-04-20 | 1985-04-19 | NAPHTHALENE DERIVATIVES AND DYE COMPOSITION FOR HAIR CONTAINING THE SAME |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59195471A JPS6172063A (en) | 1984-09-18 | 1984-09-18 | Naphthalene derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6172063A JPS6172063A (en) | 1986-04-14 |
| JPH045067B2 true JPH045067B2 (en) | 1992-01-30 |
Family
ID=16341630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59195471A Granted JPS6172063A (en) | 1984-04-20 | 1984-09-18 | Naphthalene derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6172063A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3300200B2 (en) * | 1995-06-20 | 2002-07-08 | 株式会社日立製作所 | Rotating electric machines and electric vehicles |
| DE102015216055B4 (en) | 2015-08-21 | 2019-07-18 | Continental Automotive Gmbh | Cooling system for an electric machine |
-
1984
- 1984-09-18 JP JP59195471A patent/JPS6172063A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6172063A (en) | 1986-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5536865A (en) | Process for the preparation of 5,6-dihydroxyindole and intermediate compounds | |
| DE60125958T2 (en) | REAGENTS FOR THE DETERMINATION OF ATOMIC OXYGEN | |
| US4036859A (en) | Method for the preparation of 2-hydroxybenzanthrone compounds | |
| DE2518587C2 (en) | Process for the preparation of basic oxazine dyes | |
| JPH046224B2 (en) | ||
| JPH0514743B2 (en) | ||
| JPS6172063A (en) | Naphthalene derivative | |
| DE2849471A1 (en) | AZO DYES WITH HETEROCYCLIC DIAZO COMPONENTS | |
| DE3425219A1 (en) | USE OF ANILINE DERIVATIVES AS A CLUTCH COMPONENT IN OXIDATIVE COLOR FORMING REACTIONS | |
| JPH0528747B2 (en) | ||
| EP1458724B1 (en) | Total synthesis of galanthamine, analogues and derivatives thereof | |
| JPS6215063B2 (en) | ||
| US4605419A (en) | 5,8-dihydroxy naphthalene-1,4-dione derivative and a hair dye composition containing the same | |
| JPH0521944B2 (en) | ||
| DE2536051C3 (en) | Process for the preparation of anthraquinone dyes | |
| DE2238330C3 (en) | Benzoxanthene and benzothioxanthene dyes and processes for their preparation | |
| EP0036555A1 (en) | Zinc chloride complex derivatives, preparation and use thereof, and process for the preparation of phenoxazine derivatives | |
| US5185447A (en) | Polycyclic ketones and preparative methods therefor | |
| JPH0549670B2 (en) | ||
| JPS61250060A (en) | 2-benzylaminonaphthazarin and its preparation | |
| JPS6259668A (en) | Naphthalene derivative | |
| JPS62249954A (en) | Naphthalene derivative | |
| DE824819C (en) | Process for the production of cyanine dyes | |
| Kidani | Studies on Phenazines. XIX. Synthesis of Phenazine-carboxylic Acids. | |
| JPS6172710A (en) | Hair dye |