JP3020433B2 - Manufacturing method of yellow vat dye - Google Patents
Manufacturing method of yellow vat dyeInfo
- Publication number
- JP3020433B2 JP3020433B2 JP7154241A JP15424195A JP3020433B2 JP 3020433 B2 JP3020433 B2 JP 3020433B2 JP 7154241 A JP7154241 A JP 7154241A JP 15424195 A JP15424195 A JP 15424195A JP 3020433 B2 JP3020433 B2 JP 3020433B2
- Authority
- JP
- Japan
- Prior art keywords
- sulfuric acid
- gcn
- temperature
- water
- hours
- 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
Classifications
-
- 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
- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/24—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic rings being only condensed with an anthraquinone nucleus in 1-2 or 2-3 position
- C09B5/2409—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic rings being only condensed with an anthraquinone nucleus in 1-2 or 2-3 position not provided for in one of the sub groups C09B5/26 - C09B5/62
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、2,6−ジアミノアン
トラキノンから黄色建染染料であるアントラキノンチア
ゾール化合物を製造する方法に関する。The present invention relates to a process for producing an anthraquinone thiazole compound as a yellow vat dye from 2,6-diaminoanthraquinone.
【0002】[0002]
【従来の技術】本発明の目的化合物である式(1)(化
2)2. Description of the Related Art The compound of formula (1) (formula 2) which is the object compound of the present invention
【0003】[0003]
【化2】 のアントラキノンチアゾール化合物(2,8−ジフェニ
ル−アントラ[2,1−d:6,5−d’]ビスチアゾ
ール−6,12−ジオン;C.I.Vat Yello
w 2;Mikethren Yellow GCN)
(以下、GCNと略す。)は、古くから黄色の建染染料
としてよく知られる化合物である。Embedded image Anthraquinone thiazole compound (2,8-diphenyl-anthra [2,1-d: 6,5-d '] bisthiazole-6,12-dione; CI Vat Yellow
w2; Mikethren Yellow GCN)
(Hereinafter abbreviated as GCN) is a compound well known as a yellow vat dye for a long time.
【0004】このGCNを製造する方法としては、2,
6−ジアミノアントラキノンをベンゾイルクロリド及び
水硫化ソーダと反応させ、得られた反応物を硫酸によっ
てチアゾール化する方法が古くから知られており、現在
も一般的な製造方法である。[0004] As a method of manufacturing this GCN,
A method of reacting 6-diaminoanthraquinone with benzoyl chloride and sodium bisulfide and converting the resulting reaction product to thiazole with sulfuric acid has been known for a long time, and is still a general production method.
【0005】その具体的な方法は、例えば細田豊著「理
論製造染料化学」(技報堂,1968年)に記載されて
いるように、96%或いは100%硫酸中でチアゾール
化後、反応液を水に排出し、硫酸濃度を急激に下げるこ
とでGCNを析出させてろ取する方法である。As a specific method, as described in, for example, “Theoretical Production Dye Chemistry” by Yutaka Hosoda (Gihodo, 1968), after the thiazolation in 96% or 100% sulfuric acid, the reaction solution is water And GCN is precipitated by rapidly lowering the concentration of sulfuric acid and then filtered.
【0006】しかし、この従来技術で得られたGCN
は、赤色暗色或いは青色暗色となる原因の構造不明の不
純物が含まれることが多く、またこれを精製する方法も
知られていないため、赤色暗色或いは青色暗色となった
場合には黄色染料として使用することができなかった。However, the GCN obtained by this prior art
Often contains impurities of unknown structure that cause dark red or dark blue, and there is no known purification method. I couldn't.
【0007】[0007]
【発明が解決しようとする課題】本発明は、これら従来
技術を更に改良し、収率を損なうことなく、高品質のG
CNを得る方法を提供するものである。SUMMARY OF THE INVENTION The present invention is a further improvement of the prior art, which provides a high-quality G without impairing the yield.
It provides a method for obtaining CN.
【0008】[0008]
【課題を解決するための手段】本発明者らは、上記問題
を解決するために鋭意検討した結果、工業的に極めて価
値のある方法を見出し、本発明を完成した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found an industrially extremely valuable method, and have completed the present invention.
【0009】即ち、本発明は、2,6−ジアミノアント
ラキノンをベンゾイルクロリド及び水硫化ソーダと反応
させ、式(1)(化3)That is, according to the present invention, 2,6-diaminoanthraquinone is reacted with benzoyl chloride and sodium hydrosulfide to obtain a compound of the formula (1)
【0010】[0010]
【化3】 の黄色建染染料を製造する方法において、反応後生成し
た該化合物を、硫酸水溶液に加熱溶解させ、その後冷却
して結晶を析出させることを特徴とする黄色建染染料の
製造方法に関するものである。Embedded image A method for producing a yellow vat dye, the method comprising the step of heating and dissolving the compound produced after the reaction in an aqueous sulfuric acid solution, followed by cooling to precipitate crystals. .
【0011】以下、本発明を詳細に説明する。本発明の
方法の具体的な実施態様は、例えば反応後、生成したG
CNを硫酸に溶解させ、水を加えて硫酸と水の比を、6
0:40〜90:10に調製する。更に加熱して完全に
GCNを溶解させた後、ゆっくりと40℃以下に冷却
し、結晶部をろ取する方法等が挙げられる。更に結晶部
をきれいにするために次亜塩素酸ソーダ水溶液で撹拌し
てもよいが、硫酸濃度調製後、溶解、冷却すれば、この
方法に限定されるものではない。Hereinafter, the present invention will be described in detail. A specific embodiment of the method of the invention is that the G
Dissolve CN in sulfuric acid and add water to adjust the ratio of sulfuric acid to water to 6
Prepare from 0:40 to 90:10. After further heating, the GCN is completely dissolved, and then slowly cooled to 40 ° C. or lower, and a crystal part is collected by filtration. Further, the crystal part may be stirred with an aqueous solution of sodium hypochlorite in order to clean the crystal part.
【0012】本発明方法において、用いるGCNは、反
応後の硫酸溶液中のGCNをそのまま用いても、或いは
結晶として取り出したものを用いてもいずれでも問題な
い。即ち、本発明方法は、赤色暗色、青色暗色となって
単離されたGCNについても使用することができる。In the method of the present invention, there is no problem in using GCN in the sulfuric acid solution after the reaction as it is or using GCN extracted as a crystal. That is, the method of the present invention can also be used for GCNs isolated as dark red and dark blue.
【0013】本発明方法において、用いる硫酸の濃度
は、GCNを完全に溶解し得る濃度であれば問題ない。
通常はその使用量にもよるが、60%以上の濃度であれ
ばよい。In the method of the present invention, there is no problem with the concentration of sulfuric acid used as long as it can completely dissolve GCN.
Normally, the concentration may be 60% or more, though it depends on the amount used.
【0014】本発明方法において、GCNを溶解させた
後の硫酸と水の比は、60:40〜90:10、更に好
ましくは80:20〜90:10の範囲に調製すること
が好ましい。In the method of the present invention, the ratio of sulfuric acid to water after dissolving GCN is preferably adjusted in the range of 60:40 to 90:10, more preferably 80:20 to 90:10.
【0015】本発明方法においてGCNを硫酸中で加熱
溶解する際の温度は、通常60℃以上、好ましくは70
℃以上である。更には、その温度において目的のGCN
が析出しないことが好ましいが、析出しても温度を更に
上げることによって再び溶解すればよい。In the method of the present invention, the temperature for heating and dissolving GCN in sulfuric acid is usually 60 ° C. or higher, preferably 70 ° C. or higher.
° C or higher. Furthermore, at that temperature, the desired GCN
Is preferably not precipitated, but even if precipitated, it may be dissolved again by further raising the temperature.
【0016】冷却温度は、硫酸濃度と冷却開始温度によ
って異なり、GCNが析出し得る温度であれば何ら問題
ないが、通常60℃以下、好ましくは40℃以下まで冷
却する。The cooling temperature depends on the sulfuric acid concentration and the cooling start temperature, and there is no problem as long as GCN can be precipitated.
【0017】冷却時間は、冷却開始温度によって異な
り、一義的に決まるものではないが、通常、1〜24時
間の範囲で行う。The cooling time varies depending on the cooling start temperature and is not uniquely determined, but is usually in the range of 1 to 24 hours.
【0018】[0018]
【実施例】以下、実施例により本発明を更に説明する
が、本発明はその要旨を越えない限り、以下の実施例に
限定されるものではない。EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.
【0019】実施例1 o−クロロベンゼン3600gに、2,6−ジアミノア
ントラキノン600gを懸濁させ、40℃に昇温する。
ベンゾイルクロリド920gを滴下した後、150℃ま
で昇温し、5時間反応させた。その後30℃まで冷却
し、三塩化リン900gを裝入、次いで塩素514gを
12時間かけて吹き込む。120℃に昇温、2時間撹拌
した後、40℃まで冷却する。結晶部をろ取し、アルコ
ール洗浄する。この結晶にアルコール2685g、水硫
化ソーダ640gを加え、80℃で7時間撹拌する。水
2000gを加え、結晶部をろ取し、水洗浄を行い、乾
燥させる。このチアゾール前駆体の結晶973.8gを
98%硫酸4300gに溶解させ、105℃で6時間撹
拌する。以上の操作により、目的化合物が合成できる。Example 1 600 g of 2,6-diaminoanthraquinone was suspended in 3600 g of o-chlorobenzene, and the temperature was raised to 40 ° C.
After dropping 920 g of benzoyl chloride, the temperature was raised to 150 ° C., and the reaction was carried out for 5 hours. Thereafter, the mixture is cooled to 30 ° C., 900 g of phosphorus trichloride is charged, and then 514 g of chlorine is blown in for 12 hours. After heating to 120 ° C and stirring for 2 hours, the mixture is cooled to 40 ° C. The crystal part is collected by filtration and washed with alcohol. To the crystals are added 2885 g of alcohol and 640 g of sodium hydrogen sulfide, and the mixture is stirred at 80 ° C. for 7 hours. 2000 g of water is added, and the crystal part is collected by filtration, washed with water, and dried. 973.8 g of the crystals of the thiazole precursor are dissolved in 4300 g of 98% sulfuric acid, and the mixture is stirred at 105 ° C. for 6 hours. By the above operation, the target compound can be synthesized.
【0020】温度を80℃以上に保ちながら水658g
を滴下して硫酸濃度を調整し、温度を130℃まで昇温
して、目的化合物を溶解させ、30分間撹拌する。その
後40℃まで冷却する。析出した結晶をろ取し、中性に
なるまで水洗浄し、ろ塊を乾燥させる。これにより、鮮
明黄色のGCNが550g得られる。658 g of water while maintaining the temperature at 80 ° C. or higher.
Is added dropwise to adjust the sulfuric acid concentration, and the temperature is raised to 130 ° C. to dissolve the target compound, followed by stirring for 30 minutes. Thereafter, it is cooled to 40 ° C. The precipitated crystals are collected by filtration, washed with water until neutral, and the filter cake is dried. This gives 550 g of a bright yellow GCN.
【0021】実施例2 98%硫酸270g中に赤味暗色のGCN30gを加
え、105℃に昇温し、溶解させる。内温を90〜11
0℃に保ちながら、水78gを滴下して硫酸濃度を調整
する。130℃に昇温後、40℃まで冷却し、析出した
結晶をろ取する。中性になるまで水洗浄を行い、乾燥さ
せると、鮮明黄色のGCN25.5gが得られる。Example 2 30 g of red and dark GCN was added to 270 g of 98% sulfuric acid, and the mixture was heated to 105 ° C. and dissolved. Internal temperature 90 ~ 11
While maintaining the temperature at 0 ° C., 78 g of water is added dropwise to adjust the sulfuric acid concentration. After the temperature was raised to 130 ° C, the temperature was cooled to 40 ° C, and the precipitated crystals were collected by filtration. Washing with water until neutral and drying yields 25.5 g of bright yellow GCN.
【0022】実施例3 98%硫酸270g中に、赤味暗色のGCN30gを加
え、105℃に昇温し、2時間攪拌して溶解させる。9
0℃に冷却後、内温を90〜110℃に保つように水4
1gを滴下する。その後、130℃に昇温し、30分間
攪拌しながら溶解させ、40℃までゆっくりと冷却させ
た後、結晶部を濾取し、中性になるまで水で洗浄する。
これを水600gに懸濁させ、温度を70℃に保ちなが
らNaOH水溶液でpHを11〜12に調整する。ヨウ
化カリ澱粉紙が紫色を呈するまで次亜塩素酸ソーダ水溶
液を加える。95℃に昇温し、3時間攪拌後、40℃に
冷却する。結晶部を濾取し、中性になるまで水で洗浄す
る。これを乾燥させると、鮮明黄色のGCNが26g得
られる。Example 3 To 270 g of 98% sulfuric acid was added 30 g of dark red GCN, the temperature was raised to 105 ° C., and the mixture was stirred for 2 hours to dissolve. 9
After cooling to 0 ° C, water 4 was added to maintain the internal temperature at 90-110 ° C.
1 g is added dropwise. Thereafter, the temperature is raised to 130 ° C., and the mixture is dissolved with stirring for 30 minutes. After slowly cooling to 40 ° C., the crystal part is collected by filtration and washed with water until neutral.
This is suspended in 600 g of water, and the pH is adjusted to 11 to 12 with an aqueous NaOH solution while maintaining the temperature at 70 ° C. An aqueous solution of sodium hypochlorite is added until the potassium iodide starch paper turns purple. The temperature is raised to 95 ° C., stirred for 3 hours, and then cooled to 40 ° C. The crystal part is collected by filtration and washed with water until neutral. Drying gives 26 g of a bright yellow GCN.
【0023】実施例4 98%硫酸270g中に、青味暗色のGCN30gを加
え、105℃に昇温し、2時間攪拌して溶解させる。9
0℃に冷却後、内温を90〜110℃に保つように水7
8gを滴下する。他は実施例3と同様に行うと、鮮明黄
色のGCNが22.5g得られる。Example 4 To 270 g of 98% sulfuric acid was added 30 g of bluish dark GCN, and the mixture was heated to 105 ° C. and stirred for 2 hours to dissolve. 9
After cooling to 0 ° C, water 7 was added to maintain the internal temperature at 90 to 110 ° C.
8 g are added dropwise. Otherwise, the same procedure as in Example 3 is carried out to obtain 22.5 g of bright yellow GCN.
【0024】比較例 o−クロロベンゼン3600gに、2,6−ジアミノア
ントラキノン600gを懸濁させ、40℃に昇温する。
ベンゾイルクロリド920gを滴下した後、150℃ま
で昇温し、5時間反応させた。その後30℃まで冷却
し、三塩化リン900gを裝入、次いで塩素514gを
12時間かけて吹き込む。120℃に昇温、2時間撹拌
した後、40℃まで冷却する。結晶部をろ取し、アルコ
ール洗浄する。この結晶にアルコール2685g水硫化
ソーダ640gを加え、80℃で7時間撹拌する。水2
000gを加え、結晶部をろ取し、水洗浄を行い、乾燥
させる。このチアゾール前駆体の結晶973.8gを9
8%硫酸4300gに溶解させ、105℃で6時間撹拌
する。以上の操作により、目的化合物が合成できる。Comparative Example 600 g of 2,6-diaminoanthraquinone was suspended in 3600 g of o-chlorobenzene, and the temperature was raised to 40.degree.
After dropping 920 g of benzoyl chloride, the temperature was raised to 150 ° C., and the reaction was carried out for 5 hours. Thereafter, the mixture is cooled to 30 ° C., 900 g of phosphorus trichloride is charged, and then 514 g of chlorine is blown in for 12 hours. After heating to 120 ° C and stirring for 2 hours, the mixture is cooled to 40 ° C. The crystal part is collected by filtration and washed with alcohol. To the crystals are added 2885 g of alcohol and 640 g of sodium hydrogen sulfide, and the mixture is stirred at 80 ° C. for 7 hours. Water 2
000 g is added, the crystal part is collected by filtration, washed with water, and dried. 973.8 g of the crystals of this thiazole precursor were added to 9
Dissolve in 4300 g of 8% sulfuric acid and stir at 105 ° C. for 6 hours. By the above operation, the target compound can be synthesized.
【0025】20℃まで冷却後、40℃以下に保ちなが
ら水2700gで洗浄した後、析出した結晶をろ取す
る。49%硫酸2700gで洗浄した後、水1000g
に懸濁させる。pHを11〜12に保ちながら、次亜塩
素酸ソーダ水溶液をヨウ化カリデンプン紙が紫色を呈す
るまで加える。95℃で3時間撹拌後、40℃まで冷却
する。結晶部をろ取し、中性まで水洗浄する。これを乾
燥させると、赤味暗色GCN558gが得られる。After cooling to 20 ° C. and washing with 2700 g of water while maintaining the temperature at 40 ° C. or lower, the precipitated crystals are collected by filtration. After washing with 2700 g of 49% sulfuric acid, 1000 g of water
Suspended in While maintaining the pH at 11 to 12, an aqueous sodium hypochlorite solution is added until the potassium iodide paper turns purple. After stirring at 95 ° C for 3 hours, it is cooled to 40 ° C. The crystal part is collected by filtration and washed with water until neutral. Drying gives 558 g of reddish dark GCN.
【0026】[0026]
【発明の効果】本発明の方法によれば、黄色建染染料と
して工業上極めて有用な化合物であるアントラキノンチ
アゾール化合物を高品質で得ることができる。即ち本発
明は、アントラキノンチアゾール化合物を高品質で得る
ことができる工業的に効率のよい、極めて価値のある方
法である。According to the method of the present invention, anthraquinone thiazole compounds which are industrially extremely useful as yellow vat dyes can be obtained with high quality. That is, the present invention is an industrially efficient and extremely valuable method by which anthraquinone thiazole compounds can be obtained with high quality.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) C09B 67/28 C09B 5/60 ──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. 7 , DB name) C09B 67/28 C09B 5/60
Claims (3)
ゾイルクロリド及び水硫化ソーダと反応させ、式(1)
(化1) 【化1】 の黄色建染染料を製造する方法において、反応後生成し
た該化合物を、硫酸水溶液に加熱溶解させ、その後冷却
して結晶を析出させることを特徴とする黄色建染染料の
製造方法。1. A method of reacting 2,6-diaminoanthraquinone with benzoyl chloride and sodium hydrosulfide to obtain a compound of the formula (1)
(Formula 1) A method for producing a yellow vat dye, comprising the steps of: dissolving the compound produced after the reaction in an aqueous sulfuric acid solution, followed by cooling to precipitate crystals.
0〜90:10である請求項1記載の方法。2. The ratio of sulfuric acid to water after heat dissolution is 60: 4.
The method according to claim 1, wherein the ratio is 0 to 90:10.
項1記載の方法。3. The method according to claim 1, wherein the heat dissolution temperature is 60 ° C. or higher.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7154241A JP3020433B2 (en) | 1995-06-21 | 1995-06-21 | Manufacturing method of yellow vat dye |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7154241A JP3020433B2 (en) | 1995-06-21 | 1995-06-21 | Manufacturing method of yellow vat dye |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH093351A JPH093351A (en) | 1997-01-07 |
JP3020433B2 true JP3020433B2 (en) | 2000-03-15 |
Family
ID=15579929
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7154241A Expired - Lifetime JP3020433B2 (en) | 1995-06-21 | 1995-06-21 | Manufacturing method of yellow vat dye |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3020433B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103707314A (en) * | 2014-01-15 | 2014-04-09 | 北京理工大学 | Paw force sensor of ground robot |
CN106497135B (en) * | 2016-09-07 | 2020-10-23 | 孙雪良 | Production method of vat yellow GCN |
-
1995
- 1995-06-21 JP JP7154241A patent/JP3020433B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH093351A (en) | 1997-01-07 |
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