【CAS名】8,16-Pyranthrene dione, CA [128-70-1, (日)化审5–2202.

【用途】织物染色，树脂，涂料等着色。也可用于生产C.I.还原橙2。

【生产工艺】(按国内外出版物报道年份抄录如下，其中所有CAS号均为本人所加), 1952年, K. Venkataraman, The Chemistry of Synthetic Dyes, 共2卷, P.951-952, (反应式：略) 摘录：

P.952, In the IG process (摘译自FIAT 1313) for Indanthrene Golden Orange G, 1-chloro-2-methylanthraquinone [129-35-1] (416kg), o-dichlorobenzene (40kg), copper bronze (225kg) and pyridine (135kg) are heated at 150-160°C for 3 hours; more o-dichlorobenzen (1150kg) and sodium carbonate (200kg) are added, and boiling continued for 3 hours. The product [81-26-5] is filtered off (316kg; 88% theory), and freed from copper by heating with dilute hydrochloric acid and sodium chlorate. Cyclization to pyranthrone [128-70-1] is effected by refluxing (150kg), caustic potash (81kg) and isobutyl alcohol (576kg) for 3 hours. The dye, recovered by adding water and distilling off the solvent, may be purified by a hydrochlorite treatment (yield 152kg, corresponding to 138kg of pure dye [128-70-1]).

Besides being an anthrone derivative, pyranthrone contains the benzanthrone and pyrene [129-00-0] ring systems. Scholl demonstrated the relationship to pyrene, as well as the constitution of pyranthrone, by baking 1,6-dibenzopyrene [54811-16-4] with aluminium chloride when pyranthrone was formed. The yield is improved by using air or manganese dioxide to facilitate dehydrogenation.

【抄注】全书引用的生产工艺，主要是BIOS 和FIAT的资料，未见有“特种文献–PB报告”资料的报道。

1956年, Colour Index Second Edition, Vol.3, P.3484, C.I. 59700, C.I. Vat Orange 9 (Yellowish orange) (结构式：略)

a) Eliminate 2mol water from 2,2’-dimethyl-1,1’-bianthraquinone by heating alone at 350-380°C or with dehydrating agents at lower temperatures.

b) Heat an aqueous paste of 2,2’-dimethyl-1,1’-bianthraquinone, with or without the addition of ammonia or salts, at 230-250°C under pressure for 10-12 hrs.

c) Heat 2,2’-dimethyl-1,1’-bianthraquinone with alcoholic caustic potash.

d) Fuse 1,6-dibenzoylpyrene with aluminium chloride and sodium chloride and pass in oxygen.

【Discoverer】R. H. Scholl, 1905

【生产工艺参考文献】BIOS 987, 60; FIAT 1313, 2, 113, 114; FIAT 764–Indanthrengoldorange G.

1957年，细田豊《理论制造染料化学》，技报當出版，P.701-703，インダンスレン ゴ-ルド オレンジG(ビランスロ)。

1. Methylanthraquinone [84-54-8]よりの制法。

1) 2,2’-Dimethyl-1,1’-dianthraquinonyl [81-26-5]の制法。

i. 1-Chloro-2-methylanthraquinone[129-35-1]よりの制法. 【抄注】[129-35-1]生产工艺，已在2020年2月20日上传。

ii. 1-氯-2-甲基蒽醌 [129-35-1] / 1-氨基-2-甲基蒽醌 [82-28-0] / 3,8-二苯甲酰吡 [54811-16-4](路线合成方法反应式：略)。

1-Amino-2-methylanthraquione [82-28-0] よりの制法，译自德国专利DRP 215006。

iii. アミノメチルアントラキノン[82-28-0]30gを浓硫酸150gに溶し，计算量のNaNO₂を加えてジアゾ化し，盐化第一铜24gを水100gにまぜて煮沸した中徐徐に注加し暂时煮沸する。【抄注】1-氨基-2-甲基蒽醌，经重氮化，脱重氮基合成2,2’-二甲基联二蒽醌 [81-26-5]德文生产工艺，已在2016年5月上传

2) Indanthrene Gold Orange G. 摘译自FIAT 1313, 2, 114.

3m³の铸铁釜でイソブタノ-ル576kgをKOH 90kgを还流下1h煮沸してとかし，70°Cに冷してジメチルジアンスラキノニル[81-26-5] 150kgを30mで加え，30mで煮沸(105°C)3h保つ。つぎにNa₂HPO₄ 12kgを含む前回分离水1,500Lを加え20–30°Cに冷して空气を43/hの割で9h位通して酸化させた後，イソブタノ-ルを水とともに蒸馏し，上层のイソブタノ-ル(83%)と下层の分离水(イソブタノ-ル5%)に分离して後者は釜に返す。内温が101 - 102°Cに达したら分离水を返さずに30mイソブタノ-ルが出なくなるまでつづけ，22 m3 の钢制稀释槽の温水11t，Na₂HPO₄ 6kgの中排出し80-900 に2h保ち，冷水を充して滤過水洗する，138 kg [128-70-1]。

2. pyrene [129-00-0]よりの制法。译自Vollmann et. Ann, 531, 116 (1937).【抄注】德国生产工艺，未提及。

ピレン[129-00-0](mp 151 - 152°C)20gとAlCl₃ 40gをよく粉碎混和してCS₂ 200g中に悬浊し，室温で盐化ベンゾイル[98-88-4]，30gを30mに滴下し沸点47°Cで4h煮沸する。盐酸で分解しCS₂を追出した生成物はDibenzoylpyrane [54811-16-4]约40gよりなるが,3,8-の异性体がほぼ1:2の比に含まれる故アセトン(溶解比沸腾时1:34)で3,10异性体を溶出することにより3,8の收率13g, 31.7%で得られる。

1985年，(日)《有机化合物辞典》，有机合成化学协会编，P.719，ピグメントオレンジ40.

C.I.Pigment Orange 30; 8,16-Pyranthrene dione; Pyranthrone: C.I. Vat Orange 9.

CA [128-70-1]，化审5 – 2202. C20H14O2 = 406.44。(结构式：略, 未提及“制法”)

C.I. 59700，树脂，涂料などの着色用赤橙色颜料。

1993年，赵维绳，陈彬，汪维凤编著《还原染料》，P.232-309，第五章，蒽酮类还原染料，第三节，芘蒽酮系。

P.244–245，只有反应式：略，无具体生产工艺说明，其参考文献是BIOS 987,60; FIAT 1313, 2, 113, 114。

1995年，丁忠传主编《染料品种指南》，中国化工信息中心出版，P.678，C.I.还原橙9(C.I.59700)。

【化学结构】略

【制法】

a) 2,2’-二甲基-1,1’-联二蒽醌在350 – 380°C下单独加热，或在低温下用脱水剂处理，脱去两摩尔水

b) 2,2’-二甲基-1,1’-联二蒽醌的含水膏状物(加或不加氨或盐均可)，在230 – 250°C和压力下加热10 – 12小时

c) 2,2’-二甲基-1,1’-联二蒽醌与乙醇/苛性钾加热

d) 1,6-二苯甲酰芘用氯化铝和氯化钠熔融，并通入氧气。

【主要文献】BIOS 987, 60; FIAT 1313,2,113,114; FIAT 764–Indanthrengoldorange G.

2000年，杨新玮，肖刚主编《世界染料品种–2000年》，沈阳院出版，P.1598-1599，C.I.还原橙9(C.I. 59700)。

【制法】/【参考文献】译自原版Colour Index，同上，不再抄录。

2005年，肖刚，杨新玮主编《世界染料品种–2005年》，全国染料信息中心出版，P.850，C.I.还原橙9(C.I. 59700)。

【制法】/【参考文献】译自原版Colour Index，同上，不再抄录。

2018年，何岩彬主编《染料品种大全》，沈阳出版社出版，2018年，P.1464，C.I.还原橙9(C.I. 59700)。

【参考文献】增补了本人免费提供的部分“特种文献”资料目录。

【特种文献】抄录。

BIOS 987(=胶卷PB 75860), German Dyestuffs and Intermeiates industry Vat dyestuffs and Intermediate.

BIOS 987, 60, Indanthrene Golden Orange G. [128-70-1]。

1) 1-Chloro-2-methylanthraquinone [129-35-1], 已在2020年2月20日上传。

2) “Dichinyl C”= 2,2’-Dimethyl-1,1’-dianthraquinonyl [81-26-5]。

416kg 1-chloro-2-methylanthraquinone (100%); 40kg o-dichlorobenzene; 225kg powdered copper (copper bronze); 135kg Pyridine Ib or II.

The above mixture is heated at 150 - 160°C for 3 hours. 1150kg o-chlorobenzene and 200kg of sodium carnonate are added. And boiled 3 hours. Filtered, washed (with o-dichlorobenzene) and the filter cake distilled in a Venuleth (排式真空干燥器) to remove o-dichlorobenzene and pyridine and finally to dryness.

【Removal of the copper】

The dried powder from the Venuleth is boiled for 3 hours with water, 30% HCl and sodium chlorate in a similar manner to that used for the removal of copper from the“Dichinyl phthalide [32495-71-9]”in the Indanthrene Yellow G process. Yield = 316 kg, “Dichinyl C”= 88% of theory.  The test of this compound is the making of Gold Orange G.

3) Ring closure to the colour. [128-70-1]。

150 kg “Dichinyl C”; 576 kg Isobutylalcohol; 90 kg KOH 90%.

The above mixture is boiled (1050) for 3 hours. Then 1,500 litres of water are added and the alcohol is steam distilled off. During this distilled the boiling point rises from 900 to 102°C. When this is reached all the alcohol is off. The melt is cooled down and oxidized by air blowing (another version says“Boiled with water and blown with air.”). The mixture is put into 11,000 litres of water in which are dissolved 6kg of disodium phosphate. Heated to 80-90°C and stirred for 2 hours at this temperature (another version says“If necessary, it is purified with sodium hypochlorite.”). Yield = 152kg 100% Indanthrene Golden Orange G (kept as a paste).

FIAT 1313(=胶卷PB 85172), German Dyestuffs and Dyestuff Intermediates, 1 February 1948. 本资料共有三卷。

FIAT 1313,2, 114-116, Indanthrene Golden G Paste / Powder [128-70-1].

These products are manufactured at Ludwigshafen Plant from dimethyl dianthraquinone C [81-26-5] by fusion with potassium hydroxide in isobutyl alcohol, the product precipitated in the desired physical form, and standardized as either paste or powder. 150 kilograms Dichinyl C [81-26-5] (ground); 90 kilograms caustic potash (ground); 576 kilograms (720 liters) isobutanol (pure). The isobutanol is first charged into three cubic meter, cast iron, agitated jacketed fusion kettle, equipped with condenser and receivers and caustic potash (ground) is added under agitation.  The mixture is then heated under reflux and the melt held at the boil (inner temperature about 105°C) for one hour. The melt is then cooled to about 70°C (which requires about one-half hour) and the Dichinyl C is added by hand, which takes about one-half hour longer. The temperature drops during the addition of the intermediate to about 50°C and the melt is then reheated to the boil in about one-half hour and held under reflux for 3 hours, with the inner temperature about 105°C. During the course of the reaction, the normal current consumption, shown by the ammeter, is about 4.5–5.0 amperes. The finished melt is then sampled, and 1500 liters of “separator water”, from the receivers, containing 12 kilograms of disodium phosphate are added to the agitated melt. (In case “separator water”; i. e., saturated with isobutanol, is not available, cold tap water is used). The temperature upon the addition of the water and sodium phosphate falls to about 60°C, and it is then further cooled, through the jacket, to about 25–30°C, which requires about two hours. At this point, air is bubbled through the melt for approximately 9 hours, at a rate of about 4 cubic meters of air per hour. Oxidation samples are taken at the end of 6, 8, and 9 hours’ time for comparison with standard for completion of the oxidation. When oxidation of the melt has been completed, the condenser connections are changed from reflux to distilling off and the solvent (isobutanol) is recovered in the form of azeotropic mixture of isobutanol and water. Upon condensation of the vapors, the isobutanol and water separate into layers; the upper layer, consisting of isobutanol, containing about 83% isobutanol and 17% water, while the lower layer consists of about 15% solution of isobutanol in water, called “separator water”,which is continuously run back into the fusion melt.  The upper layer is run into a wet isobutanol storage recovery. The distillation is run until the inner temperature reaches 101 – 1020 and then this temperature is held for one-half hour, without any return of “separator water”, until no more oily drops appear in the sight glass. The melt, which is now free of isobutanol, is at this point a bright orange mass and is blown from the fusion kettle into 11 cubic meters of water in a 22 cubic meter steel dilution tank which contains 6 kilograms of disodium phosphate dissolved in the water.  The kettle is thoroughly rinsed and the contents added to the dilution tank which is then heated to 80 - 900 which temperature is held for 2 hours and then the tank is diluted to capacity with cold water, which reduces the temperature to about 600 at which temperature the charge is filtered off in iron filter press where it is washed neutral with warm water and the cakes discharged. These cakes are sampled for dyetest and physical comparison with standard. The yield amounts to 138 kilograms (dry equivalent)[128-70-1] = 100% from Dichinyl C. The dyetest strength, however, is said to average 110% of standard on an equivalent solids basis.

下面是关于染色粉(For the production of ordinary dyeing powders)，不再抄录。

PB 25624，有关染料和染料生产工艺，共686页，这是本人手工抄录的目录。

PB 25624, 1278-1286. Chloromethylquinone [129-35-1]德文生产工艺，已上传。

PB 25627, Methods for production of dyestuffs, 1929-1940年, 1138页, Price: Microfilm $6.00, Enlargement print $114.00.

PB 25627, 2284-2292, “Indanthrengold Orange G”, Feb 1934 - Jan 1936, 9页, Price: Microfilm $1.00. Photostat $1.00.

This substance, Pyranthrone [128-70-1], is obtained by condensation of 2,2’-dimethyldianthraquinonyl [81-26-5] in alcoholic caustic potash melt. The method is described in detail. An additional document describes a laboratory method using isobutyl alcohol instead of ethyl alcohol. In German.

PB 25627,2293-2315, “Dichinyl C” from chloromethylanthraquinone, Feb 1934-Jan 1936, 24页, Price: $1.00, Photostat $2.00.

“Dichinyl C [81-26-5]” is 2,2’-dimethyl-1,1’-bianthraquinone. It is obtained by the effect of metallic copper on 1-chloro-2-methyl anthraquinone. The method is described. Experiments are reported by which it was to be determined whether the reaction is best carried out in pyridine alone or under addition of another solvent. Results are tabulated. Part of this material is illegible. In German.

PB 25627, 2316-2319, “Indanthrengoldorange G” from pyrene, Jun 1932, 4页, Price: Microfilm / Photostat $1.00.

This is a laboratory report, Pyrene [129-00-0] and benzoyl chloride [98-88-4] are added to a melt of sodium and aluminium chlorides. (The optimal proportions were yet to be established). Oxygen is conducted over the mixture. The process is described. In German.

PB 25628, Methods for production of dyestuffs, 1928-1937年, 1090页, Price: Microfilm $6.00, Enlargement print $109.00.

PB 25628, 3648-3749, “Dichinyl C” pure, Dec 1937, 2页, Price: Microfilm $1.00, Photostat $1.00.

Directions for a temporary process for “Dichinyl C [81-26-5]” pure are given. The process is essentially one of condensation, the starting products being dichlorobenzene, chloromethyl anthraquinone [129-35-1], copper powder and pyridine. In German.

PB 25628, 4222-4231, Process for crude “Dichinyl C” [81-26-5], Jan 1934年, 10页, Price: Microfilm $1.00. Photostat $1.00.

1-Amino-2-methyl anthraquinone [82-28-0] is diazotized in concentrated sulfuric acid, by means of nitrosyl sulfuric acid. The diazoniumsulfate thus obtained is condensed to 2,2’-dimethyl-1,1’-dianthraquinonyl [81-26-5], in a boiling solution of cuprous chloride. This is described in detail. Two pages (4225 and 4226) are illegible. In German.

【抄注】这是脱重氮基缩合法合成 [81-26-5]。本人的参考译文已在2016年5月18日上传。

PB 25628, 4232-4233, Process for pure “Dichinyl C” [81-26-5], Jan 1933年, 2页, Price: Microfilm $1.00, Photostat $1.00.

“T-acis [85-55-2]”is treated in monohydrate with chlorosulfonic acid at 110–115°C, to close its ring to 2-methyl anthraquinone [84-54-8]; the latter is chlorinated in 5% oleum in the presence of iodine. The chloromethylquinone [129-35-1] is dehydrated in o-dichlorobenzene, then converted to the diquinyl compound by adding copper powder and pyridine, at 150°C. By addition of soda the copper-pyridine-compound is dissociated. In German.

【抄注】这是脱氯缩合法，日文细田豊《理论制造染料化学》未提及。

PB 70057, Chemical Report, 1912-1946年, 986页, 这是手工抄录的目录，未抄录文件标价。

PB 70057, 8336-8345, Chloromethylquinone [129-35-1], By Hilvert, 1935年11月29日, 已在2020年2月上传。

PB 70057, 8433-8440, “Dichinyl C [81-26-5]”, 1938年1月3日, By Emmer, 德文生产工艺。

由1-氨基-2-甲基蒽醌经重氮化，脱重氮基，缩合制得2,2’-二甲基-1,1’-联二蒽醌 [81-26-5].

PB 73726, Technical reports on dyestuffs, dye intermediates, 1924-1945年, 868页, Price: Microfilm $6.00, Enlargement print $87.00.

PB 73726, 74-77, Indanthrengoldorange G pulver, roh and Teig, 1934年2月1日德文生产工艺, Price: $1.50.

【寄语】祝读者节日快乐！

陈忠源 2021年9月21日星期二。