CAS号 [129-56-6] 生产工艺  吡唑蒽酮

CAS名: Anthra[1,9-cd]pyrazol-6(2H)-one, 参考文献: Beil. 24, E¹, 276; E², 108; E^3/4, 713.

用途: C.I.还原红13, 34。 C.I.还原蓝25。C.I.还原黑8。C.I.颜料红195。（中间产品用途见国外文献。）

中间产品:  CAS号[54345-83-4]. 名:  1,2-Hydrazinedisulfonic acid, 1-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-, disodium salt.

生产工艺文献:

BIOS 987, 128. (=胶卷PB 75860)  Pyrazole anthrone   英国人译自德文。抄录如下。

反应式:  这是Mainkur厂生产工艺，译者未说明译自哪个德文原件？本人有加注。

Production 2000 kg. per year (100%)

To 760 l. 94% H₂SO₄, is added 282 kg. nitrosyl sulphuric acid recognized at 100%. Actually 40% solution prepared at Hoechst is used.

466 kg. 1-aminoanthraquinone is stirred in cold and the mixture run at 15-17⁰ for 4 hours, finally heating to 35⁰C. The diazo is poured on to ice, so that the temperature does not rise above 10⁰, requiring about 3200 kg. ice. Filtered by vacuum and washed with brine.

The diazo paste is then added to a solution prepared from 580 kg. sodium bisulphite 100% powder, 680 kg. NaOH 33⁰Be’, 700 l. water, 600 kg. ice. It is stirred for a time at 17-20⁰, heated to 70⁰, salted out with 800 kg. salt, cooled, filtered and pressed.

The pressed hydrazine paste is stirred into 2400 kg. monohydrate at 40-50⁰, heated to 90-95⁰, until the reaction is complete, cooled to 75⁰, and diluted below 75⁰ with 2400 kg. water. The product is filtered on a tile filter, washed and dried.

FIAT 1313,II, 160-161. (=胶卷PB 85172)  Pyrazol anthrone.  (Mainkur)  美国人译自德文。未说明资料来源。抄录如下。

Into a 1000 liter, homogeneously, lead-lined, jacketed, agitated kettle are placed 735 kilograms of 66⁰Be’ sulfuric acid (93%), 800 kilograms of nitrosyl sulfuric acid (25%).

The two acids are mixed and with the temperature adjusted to 15⁰- 17⁰ are added 240 kilograms 1-aminoanthraquinone. This addition is made by hand through a 60-mesh screen to remove lumps. After all 1-aminoanthraquinone has been added (about 2 hours), the mixture is warmed slowly (1 hour) to 30⁰- 35⁰, and allowed to mix for 3-4 hours longer. The mixture is then tested for completion of diazotization; a sample is diluted in cold water, and a clear solution should result and excess of nitrous acid should be shown on starch-KI-paper. When diazotization has been shown to be complete, the charge is blown over into 4000 liters of water plus 2000 kilograms of ice in an acid-proof, brick-lined, 10,000 liter tank.

This diazo slurry if filtered off on a porous stone nutsch, 40 square meters, and washed with 23⁰ Be’ sodium chloride solution at room temperature; three 200 liter portions being used.

To the combined filtrate and first wash,, about 4000 liters, are added 100 kilograms of salt and 20 kilograms of zinc chloride. This precipitates the zinc salt of diazo compound and this zinc salt is filtered off upon another nutsch and the nutsch cake washed with 23⁰Be’ brine, and this additional diazo cake added to the principal portion. It was stated that this additional diazo compound recovery amounted to about 20 kilograms of zinc salt per batch and that this was perfectly satisfactory for use. （抄注：请见C.I.冰染重氮盐36.）

The diazo paste obtained as above described is converted as follows: A solution of sodium sulfite is prepared by adding 440 kilograms of sodium hydroxide solution 33⁰Be’ (27%) and 700 kilograms sodium bisulfate solution 39⁰Be’ (44%), to a 10,000 liter, iron, agitated, jacketed tank, containing 4500 liters of water to which has been added 500 kilograms of ice. To this solution the diazo paste id added at 17⁰- 20⁰ gradually in about 1 hour.

This slurry is agitated at 17⁰- 20⁰ for 15 hours, and this slurry must always remain alkaline. No control test is run except test paper. The resultant slurry is then heated to 75⁰ through the jacket in about 1 hour, and the entire mass must be in solution at this point.

Then add activated charcoal, 8 kilograms, and filter through a clarifying filter (either wood or iron press can be used), and wash the press with hot water. The filtrate and washings, about 4000 liters, are then salted out with 400 kilograms of dry potassium chloride, and the slurry cooled to 20⁰ and the hydrazine filtered off. The press cakes from this press are then pressed in a hydraulic press to remove as much mother liquor as possible. The cakes are wrapped in jute cloths in portions of about 3 cakes per cloth, and pressed under 150 atmospheres (2250 lbs.) per square inch. The solids are thereby increased from 25% to 50% and the cakes weigh about 600 kilograms after pressing. （抄注：这里是1-蒽醌肼二磺酸二钾盐，二钠盐CAS号[54345-83-4]）

These cakes are then dissolved in 2400 kilograms of sulfuric acid 66⁰Be’ at 40⁰- 50⁰, the cakes being added in 5-6 hours in a homogeneously lead-lined kettle (3000 liters). The temperature is then held at 40⁰- 50⁰ for 6-7 hours until complete solution is obtained (Observe in test tube). The temperature is then raised to 90⁰- 95⁰ and held for 1 hour, then cooled back to 75⁰ and an equal quantity of water is added (2400 liters) while the temperature is held at 60⁰ with jacket cooling. The sulfuric acid should have a strength 40⁰ Be’ at this point (from a filtered sample). If satisfactory, cool the charge to 25⁰ and filter on a porous stone nutsch and wash with cold water until acid-free. Dry in vacuum at 100⁰ – 110^0.

Yield = 204 kilograms, 85% of theory from 1-aminoanthraquinone.  Melting point = 280⁰ – 282⁰.

日文译文。细田豊。 《理论制造染料化学》1957年。P.  568-9. ヒラソ-ル アンスロン 译自FIAT 1313；BIOS 987.  抄录如下。

(1)  1-Diao-anthraquinone.

1 m³ ホモケ^”ン铅张シ^”ヤケツト釜に66⁰Be’硫酸735 kgと,ニトロシル硫酸25% 800 kgを混合し，15-17⁰て^”1-アミノアントラキノン240 kgを60メツサユ金网を通して约2 hて^”加え, 1 hて^”30-35⁰に温め3-4 h搅拌し，水4 t, 冰2 tに排出しシ^”アソ^”の沉淀をstone filterし,23⁰Be’ NaCl水200 l.す^”つて^”3回洗う。滤洗液约4 tにNaCl 100 kg, ZnCl₂ 20 kgを加えてシ^”アソ^”のZn盐を沉淀させ滤過しNaCl水て^”洗い约20 kgを回收し一绪に利用する。

(2)  1-Anthraquinonylhydrazine sulfonate.

NaOH 27%液440 kgに44% NaHSO₃ 700 kgを加えて造つたNa₂SO₃液と水4.5 t, 冰500 kgの混合液に前记シ^”アソ^”ヘ⁰-ストを17-20⁰て^”约1 hに加え15 h搅拌する。つき^”に约1 hて^”75⁰に加热し，活性炭8 kgを加えて滤過し，滤洗液约4 m³にKCl 400 kgを加えて盐析し20⁰て^”滤過し，水压机にかけて50%固形约600 kgとする.

(3)  Pyrazolanthrone.

66⁰Be’硫酸2.4 t の中に前记cakeを40-50⁰て^”5-6 hに加えて完全に溶解するまて^”6-7 h保温する。90-95⁰に上け^”1 h保温，60⁰に冷して水2.4 tを加えて硫酸浓度を40⁰Be’とし,25⁰て^”stone filterし,水洗，亁燥する。204 kg,收率85% /アミノ.

熔点280-282⁰.

PB 25625, 326-331.  Echtrotsalz AL  1934年3月8日。 1美元。有1-氨基蒽醌重氮化生产工艺。 请见C.I,冰染重氮组分36.

PB 25628, 3860-3867.  Vojda and Max (General Aniline Works, Inc., (West Works), GRASSELLI, N.J.  Pyrazole anthrone.  I.G. 

Farbenindustries A.G. TEA Buro-Report)  Feb 1936- Apr 1939.  8 p. 售价 1美元。美国人介绍如下。  

The method of preparation, preliminarly described, consists of diazotization of 1-aminoanthraquinone, reduction to anthraquinonyl hydrazine disulfonic acid, salting out with potassium chloride, splitting off the sulfonic group and simultaneous ring closure in sulfuric acid. Legibility is not very good in parts. In English and German. 今将部分原件抄录如下。

General Aniline Works, Inc. (West Works) Grasslli N. J.   Research Laboratory December 23, 1938.

Dr. A. M., Va jde Report No. 54. Pyrazole anthrone. 以下为实验室研究报告。

1. Introduction:

Pyrazole anthrone is a necessary intermediate for the production of Indanthrene Rubine RD. Since a prescription for the latter was desired, it was necessary first to study the preparation of pyrazole anthrone. There are possible two ways.

I.  From 1-chloroanthraquinone. II.  From 1-aminoanthraquione. 反应式：略！

The first method is sues in Germany as far as we known. However, because Hydrazine hydrate is very expensive, and the supply of Pyridine is restricted, we have studied the second way,

2. Discution of Experimentt:

The first step we investigated was the dehydration of anthraquinonyl-1-hydrazine. The latter was made by diazotizing 1-aminoanthraquinone reduction of the diazo sulfate with sodium sulfite to the hydrazine disulfonic acid, scission of the sulfonic groups with concentrated HCl to anthraquinonyl-1-hydrazine hydrochloride, followed by decomposition with sodium acetate or soda ash (DRP. 163447. Bayer, F., 8. 301).

Dehydration of the anthraquinone hydrazine by heating in aniline and aniline hydrochloride, (DRP. 171293. Bayer. F.,8. 304) gave an impure pyrazole anthrone, requiring recrystallization from nitrobenzene. Heating with diluted HCl was without effect. The ring closure was easily effected by heating in 96% sulfuric acid at 65⁰C for 2 hrs. with yields of 95% or better. However, further were in this direction was discontinued. Since a sufficiently pure anthraquinonyl-hydrazine could be obtained only in yield of about 70% by this way.

Attempts were made to eliminate the necessity of making the free anthraquionyl hydrazine. It was thought that anthraqinonyl hydrazine sulfate could be used for the ring closure. However, this could not be obtained with constant composition, and ring closures on the press cakes gave pyrazole anthrone for poor quality and only about 70% yield.

Since it was known that the sulfonic acid group of the anthraquinonyl hydrazine disulfonic acid were easily split off by strong acid, it was thought that a ring closure to pyrazole anthrone could be effected at the same time, if concentrated sulfuric acid is used. This was found to be the case. When the product obtained by salting out with KCl after the sulfite reduction of the diazo sulfate is dried and heated in 10 parts 96% sulfuric acid at 85⁰C for 1 hour, pyrazole anthrone of good quality is obtained in a yield of about 75%.

The yield was thought to be too low. Ring closure was known to give better yields: increasing the amount of KCl in salting out did not increase the yield. It was also determined that diazotization proceeded to the extent of at least 96% by converting the diazo sulfate to 1-hydroxyanthraquinone, consequently,the losses seemed to occur during the sulfite reduction. It has been found that when a 20% excess of caustic soda beyond one equivalent, was added to the sodium bisulfate solution used in the reduction, yields of pyrazole anthrone averaging around 90% were obtained.

There follows a preliminary prescription:

3. Preliminary prescriptin for pyrazole anthrone: 实验室合成方法:

(a)  Diazotizitation of 1-aminoanthraquinone.  Dissolve 134 g of 1-aminoanthraquinone (tech.) in 1072 g (584 cc) of 96% sulfuric acid add at 10⁰C 45 g sodium nitrite in small portions during approximately 15 minutes. Then charge 2155 g water at 15⁰C. After about 800 g water has been added during approximately 2 hours, a yellow precipitate begins to form. At this point the remaining water may be added as rapidly as the temperature of the mix can be maintained at 15-20⁰C. Then stir for 1 hour, or until the product is crystalline. The time up to this point is about 4 hours. Filter with suction and press out thoroughly.

(b)  Anthraquinonyl-hydrazine disulfonic acid.  Prepare first a sulfite solution by adding 1190 g bisulfate solution to a mixture of 415 g of 50% caustic soda solution and 625 g water. Cool to 30⁰C. The product from step (1) is sludged in 600 cc. water, then add rapidly with good agitation, the above sulfite solution. Temperature goes to about 35⁰C, stir ¹/₂ hour, then raise temperature to 50⁰C in about ¹/₂ hour, hold for 15 min., add 375 g KCl, allow to stir while cooling to 25⁰C. Filter. Press out and dry. Yield about 309 g (approx. 4% KCl)

(c)  Pyrazole anthrone.  Dissolve the 309 g from step (b) in 3090 g of 96% sulfuric acid as rapidly as the heat to 85⁰C for 1 hour, pour into 10 liter water, filter, wash free of acid and dry. Yield: 119 g  (90% theory calc. on the aminoanthraquinone used).

m. p. 281-283⁰C (Lit. 277-278⁰C). % N= 11.66 found.  12.72 calc. (11.88 for product).

Report No. 54-a.  Pyrazole anthrone 1939年4月26日 实验室合成方法。抄录如下。

    Addendum to Report No. 54. Dec. 23. 1938.  In the report No. 54 of Dec. 23. 1938, the diazotization of 1-aminoanthraquinone was completed by charging water very slowly into the sulfuric acid solution of the 1-aminoanthraquione and NaNO₂. In order to economize on the time necessary for the diazotization. It was suggested to proceed in the reverse order, namely, to charge the sulfuric acid mix into ice and water. This was done and it was found to give equality as good results.

Diazotization of 1-aminoanthraquionone.  67 g of a-aminoanthraquinone (tech.) was dissolved in 536 g of sulfuric acid 96% and cooled to 10⁰C, then 27.5 g NaNO₂, finally powdered was added during 15 minutes. After stirring for ¹/₂ hr. at 10-15⁰C, the mixture was charged during ¹/₂ hr. into 540 g ice and 540 g water, while keeping the temperature below 15⁰C. After stirring for 1 hr., the product was filtered, pressed well, and worked up to pyrazole anthrone as described in Report No. 54, using ¹/₂ the quantitative throughout.

Yield: 57 g (86.5% of theory).   m.p. 279-282⁰C.

PB 73719, 2104-2110.  Pyrazole anthrone. 1936年7月8日。未抄录。

产品分析方法:  德文。

10 g Pyrazolanthron werden mit 50 ccm Sprit + 300 ccm Wasser 15 Stunden verkugelt, mit 1200 ccm Wasser quantitativ in einen 3 L kolben gespuelt und nach Zugatz von wiederen 200 ccm Sprit und 100 ccm Natronlauge 40⁰Be‘ 20‘ unter Rueckfluss zum Sieder erhitzt. Dann wird heiss abgesaugt und mit heissem Wasser, das zunaechst noch etwas alkalisch gehalten wird, bis zum voellig farblosen Ablauf gewaschen. Der Filterrueckstand wird bei 100⁰ getrocknet und gewogen = alkaliumloesliche Verunreinigung. Filtrat und Waschwasser wird noch heiss mit verduennter Salzsaeure schwach kongosauer gemacht, und nach voelligem Erkalten das abgeschliedene Pyrazianthron abgesaugt und eben kongoneutral gewaschen. Trocken bei 100⁰ = reines Pyrazolanthron.

Es soll 95%ig sein.   Trockengehalt: 99-100%.   Aschegehalt: nicht ueber 1%. 

产品分析方法:   英文译文。抄自FIAT 1313,I, 526. (=胶卷PB 85172)。但译者未说明资料来源？

    Ball mill a 10.0 g. Sample with 50 cc., Ethanol and 300 cc. Water for 15 hours. Rinse out the mill into a 3 l. flask with 1200 cc. Water. Add 200 cc. Ethanol and 100 cc. Sodium Hydroxide solution, 40⁰Be’. Heat to reflux temperature and hold 20 minutes. Filter hot and wash with hot water containing a trace of Sodium Hydroxide until the washings are colorless. The filtrate and washings are precipitated with Hydrochloric acid to a weak Congo acidity, cooled and filtered. The precipitate is washed with water until acid-free and dried at 100⁰C. The weight is reported as the assay figure. It should be 95% or over for acceptable material. The ash is also determined: it should not becover 1%.

国内生产工艺:

天津染料生产工艺汇编。 吡唑蒽酮。1980年。P. 223. 抄录如下。

    A. 亚硝酰硫酸制备:  将硫酸850公斤放入重氮罐内夹套降温10⁰C以下，加入亚硝酸钠63公斤，控制温度20-40⁰C, 加完升温至70⁰C, 搅拌30分钟，控制温度70-75⁰C.

B. 重氮化:  将重氮罐内物料降温至15⁰C以下，加入1-氨基蒽醌温度控制40⁰C以下，加完料搅拌3小时，温度控制40-50⁰C.

在稀释罐中加入碎冰1300公斤，将重氮液慢慢加入，控制温度15⁰C以下，过滤，滤饼为重氮盐。

C. 还原:  在还原罐内加入水2000升，亚硫酸氢钠214公斤和苛性钠160公斤，搅拌30分钟，夹套冷却至10⁰C以下，加入重氮液滤饼，温度控制在15⁰C以下，pH = 9-10,搅拌30分钟，升温至17-20⁰C,保温10小时，升温至65⁰C，在65-70⁰C保温10分钟并加入工业盐600公斤，搅拌1小时，静置2小时，降温至30⁰C压滤，滤饼为肼盐折干品320公斤。

D. 闭环:  将硫酸1800升，放入闭环罐内放入肼盐滤饼，温度控制在40-45⁰C,保温3小时，酸度为81-84%，升温90⁰C,在90-95⁰C保温1小时，降温60⁰C以下，将水细流注入罐内温度不超过60⁰C,酸度控制为45-49%，降温至30⁰C,压淋干燥得步骤蒽酮106.2公斤。

国外研究动态:

捷克专利。 CS. 201997. 1980年12月31日。 主要是合成1-蒽醌肼二磺酸钠盐。

美国专利。 US. 5385842. 1995年1月31日。主要是1-蒽醌肼二磺酸钠盐的应用。

加注:

译文和引用文都应该写上资料来源，这是技术人员应该遵守的，最基本的职业道德。美，英的上述译文不说了。然而，当今仍有一些出版物有这类问题出现？难道你的翻译没有错？编写中也没有抄错？

陈忠源  2017年2月28日     于 无锡   明辉国际。



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