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CAS号 [119-90-4] 生产工艺。 3,3’-二甲氧基联苯胺

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CAS号 [119-90-4] 生产工艺。   3,3’-二甲氧基联苯胺
 

	CAS名：[1,1’-Biphenyl]-4,4’-diamine, 3,3’-dimethoxy-    历史参考文献：Beil. 13, 807; E1, 331; E2, 502; E3, 2310; E4,
2834.
 

	用途：酸性红128。冰染偶合组分3。冰染重氮组分48。 直接红7。 直接紫13, 32, 37。 直接蓝1, 4, 8, 9, 10, 12, 15, 22, 23, 30。
 

	直接蓝35, 37, 45, 50, 65, 76, 80, 84, 90, 94, 95,
98, 136, 150, 152, 160, 168, 183, 200, 201, 202, 203, 212, 214, 215, 218, 236,
237。
 

	直接蓝256, 270, 306。 直接绿57。 直接黑20, 86, 87, 91。 分散黑6。 溶剂黄147。 颜料橙14, 16, 44, 63。
 

	颜料红37, 41, 42, 180。 颜料蓝25, 26。 颜料棕22。LookChem网登录生产与经营单位39家。盐酸盐68家。
 

	BIOS 986, 144-146.（=胶卷PB 77764）。 Dianisdine. (I.G.
Griesheim).  英国人译自德文（无资料来源）。
 

	反应式：本人有加注。其中英文称为（azo anisole）偶氮苯甲醚，CAS号 [787-77-9]，结构式中忘打字了！ 
<img src="http://www.陈忠源化学文库.cn//chenzhongyuan/Upload/ArticlePicture/QQ图片20190527095255.png" alt="" /> 
 

	Prepared by alkaline zinc reduction of o-nitroanisole. 
 

	125 kg. alcohol 95%, 50 kg. solvent naphtha and 280 kg. zinc dust are
charged to the reduction pan and heated to 40℃.  The mixture is then heated to
80℃. and reduction started by the addition of 80
kg. o-nitroanisole.  5 kg. NaOH 50% liquor.  Reduction is maintained at 80℃. under reflux by the alternate addition of small quantities of
o-nitroanisole and 50% caustic liquor, with a total addition of 20 kg. NaOH 50%
liquor and 170 kg. o-nitroanisole.  When
reduction slackens at this stage, as shown by reduction of reflux rate the
alcohol is distilled off and replaced by 300 kg. naphtha as solvent.  This stage is the reduction to azo anisole
and a sample at completion should be dark red and crystallize rapidly.
 

	Reduction to hydrazonisole is effected at 93℃. by addition of 250 kg. solvent naphtha, 45 kg. zinc dust and 20 l.
water.  At completion of the hydrazo
reduction a sample should be completely solid when cooled, and the runout on
paper should be colourless.  300 kg.
solvent naphtha is now added to assist complete solution of the hydrazo abisole
and the zinc oxide is fixed as the heavy coarse hydroxide by addition of 100
kg. water.
 

	The naphtha solution of hydrazo anisole is run off through the zinc
oxide via the bottom outlet and zinc oxide is re-extracted at 45℃. screening-filter to a receiver. 
The zinc oxide is re-extracted at 45℃. with 300
kg. solvent naphtha and the naphtha solution again run-off and combined with
the strong naphtha solution for subsequent conversion.  A third extraction of the zinc oxide is
carried out with 150 kg. naphtha and the weak extract is used for extraction of
a subsequent batch.  1050 kg. sulphuric
acid 210Be’. (23.5% H2SO4) and 30 kg. NaHSO3 40% solution are charged to the
conversion vat and cooled to 20℃.  The
naphtha solution of hydrazo anisole is then run in at 20℃. and the mixture agitated for a further 2 hr. (Completion of
conversion is tested by shaking a sample of the naphtha solution with dilute
hydrochloric acid.
 

	Nitrate solution is then added to the acid layer till there is a
definite smell of nitrous acid: 1% R salt solution is made strongly alkaline
with caustic soda and added to the nitrous solution.  No blue colour should develop – only a red
coloration.  After completion of
conversion the batch is diluted with 800 l. water and concentrated sodium
carbonate solution added whilst the temperature is raised from 40-45℃. to 90℃. addition of alkali should continue till the
batch is weakly alkaline to litmus.  The
hot aqueous sodium sulphate layer is then drawn off, the naphtha layer washed
hot with 600 l. water and the aqueous layer again drawn off.  For the preparation of dianisidine base
(ordinary quality) the interfacial layer between the hot sodium sulphate and
naphtha layers id drawn off with the naphtha layer.  For dianisidine (special quality) the
interfacial layer is run to drian.
 

	The naphtha solution of dianisidine base is then cooled with agitation
and the precipitated base filtered off on an open vacuum filter and washed
first with cold naphtha and then with water. 
The dianisidine base paste is dug off the vacuum filter and the last
trace of naphtha removed by steam distillation in a small C.I. still: the free
base is then filtered off on a vacuum filter and centrifuged for further removal
of water.
 

	The moist base is dried under vacuum and ground.  For dianisidine (pure quality) for use as
Fast Blue Base dianisidine (ordinary quality) is dissolved in 20% hydrochloric
acid at 60℃. treated with active carbon and sodium
bisulphite and the filtered through a wooden press at 60℃.  The filtrate is neutralized
with a solutionof sodium carbonate (introduced via a spray) cooled to 35-40℃. by self-cooling and the precipitated diaisidine base filtered off on
a vacuum filter and well-washed with water. 
The base is then dried in vacuum.
 

	Production of the various grades of dianisidine (in tone ). 历年产量：略。
 

	Materials consumptions / tone dianisidine (ordinary quality). 每吨产品单耗：略。Yield: 76%. 
For dianisidine special Yield – 74.5% theory.  收率：74.5%。
 

	Services consumptions / tone dianisdine (ordinary quality).  公用工程单耗：略。
 

	Analytical data: -Nitroanisole 
C.Pt  9.8℃.  Dianisidine (ordinary)  96-97% 
purplish.  (pure)  99% white with slight red tinge.
 

	细田豊 《理论制造染料化学》1957年。 P. 483.  ジアニシジン.  译自PB 77764.
 

	    溶媒法：アゾ还原法。 エタノ-ル125 kg，ソルベトナフタ50 kg，亚铅末280 kgを800に热し，o-ニトロアニゾ-ル80 kgとNaOH 50% 5 kgを加え，NaOH 50% 20 kgとo-ニトロアニゾ-ル170 kgを少しずつ交互に加え，アゾ还原が终る前にアルロ-ルを蒸馏しナフタ300 kgを加える。
 

	    ヒドラゾ还原。 ナフタ250 kg，亚铅末45 kg，水20 lを加え，93でヒドラゾイニゾ-ルに还原する。
 

	    抽出。ナフタ300 kgを加えヒドラゾを溶解し，水100 lを加えて静止し酸化亚铅を粗粒として凝集せしめ，ナフタを底からスクリ-ンを通して拨き取り，ナフタ300 kgを用いて酸化亚铅から450で抽出，最後にナフタ150 kgで抽出したものは次回の抽出に用いる。
 

	    转化。 硫酸23.5% 1030 kg とNaHSO3 40% 30 kgを转化槽で200に冷し，ヒドラゾのナフタ溶液を200で加え2 h 搅拌する。
 

	    ベ-ス。 水800 lでうすめ900まで上げながらNa2CO3浓溶液を加え弱アヨカラ性とし，搅拌後，下层のNa2SO4液を拨き，湯600 lで洗つて拨き, ナフタ部は冷してジアニシジンベ-スを滤過し，ナフタで洗い，水で洗い，水蒸汽蒸馏後滤過し，真空亁燥，粉碎する。收率76%。
 

	Fast Blue Baseとして用いる纯品を造るには盐酸と600で溶かし，脱色炭とNaHSO3を加え滤過し，滤液にNa2CO3 液をスプレ-として加え，35-400で滤過し，真空亁燥する。 收率74.5%。
 

	 
 

	张澍声 《精细化工中间体及产品生产工艺》。2006年。 P. 455.  3,3’-二甲氧基联苯胺。  译自BIOS 986, 144-146。
 

	在铸铁还原锅中，加入125 kg 95% 乙醇，50 kg溶剂石脑油和280 kg锌粉，加热到40℃。然后混合物加热到80℃，加入80 kg邻硝基苯甲醚和5 kg 50%氢氧化钠溶液，还原开始。还原温度保持在80℃，在回流下进行。交替加入小量的邻硝基苯甲醚和50% 氢氧化钠溶液。总的加入量为20 kg 50%氢氧化钠溶液和170 kg 邻硝基苯甲醚。当还原放慢时（这可以从回流速度减慢看出），蒸馏出乙醇，用300 kg 石脑油代替作为溶剂。这一阶段是还原为偶氮苯甲醚，当反应完成时，取样应为暗红色，并迅速结晶。还原为氢化偶氮苯甲醚是在93℃进行，加入250 kg 石脑油，45 kg锌粉和20 L水。当氢化偶氮苯甲醚还原完成时，取样冷却后应完全固化，并且在滤纸上的渗圈应为无色。现在加入300 kg石脑油，帮助氢化偶氮苯甲醚完全溶解。加入100 kg 水使氧化锌以粗重的氧化锌被固定。
 

	氢化偶氮苯甲醚的石脑油溶液经过氧化锌来到底部出口和300 kg石脑油再萃取，石脑油溶液流出，和前面的石脑油浓溶液合并，用于随后的重排。氧化锌的第三次萃取用150 kg石脑油实施，稀的萃取物用于下一批的萃取。
 

	在重排槽中加入1050 kg 23.5% 硫酸和30 kg 40%亚硫酸氢钠溶液，然后在20℃流入氢化偶氮苯甲醚的石脑油溶液，混合物再搅拌2小时。
 

	检验：取石脑油溶液样品与稀盐酸一起震荡，加入亚硝酸钠溶液到酸层中，直至有肯定的亚硝酸气味。将1% R盐溶液和氢氧化钠至强碱性，加到亚硝化溶液中，不显蓝色仅现红色。
 

	重排完成后，反应物用800 L水稀释，加入浓碳酸钠溶液，同时温度由40-45℃升至90℃，应继续加碱，直至反应物对石蕊试纸为弱碱性。然后抽出热的硫酸钠溶液层，石脑油层用600 L水洗涤，再抽出水层。为了制备普通质量的3,3’-二甲氧基联苯胺，热硫酸钠层和石脑油层之间的界面层与石脑油层一起抽出。特殊质量的3,3’-二甲氧基联苯胺则将界面层排放。
 

	3,3’-二甲氧基联苯胺的石脑油溶液搅拌冷却，沉淀的胺在开口的真空过滤器上滤出来。先用冷石脑油洗，再用水洗。从过滤器中挖出3,3’-二甲氧基联苯胺滤饼，最后微量的石脑油在一小铸铁锅水蒸汽蒸馏除去，游离胺在真空过滤器上过滤出来，再离心脱水。湿胺真空干燥并研磨。
 

	优质的3,3’-二甲氧基联苯胺用作色基，商品名Fast Blue B Base。普通的3,3’-二甲氧基联苯胺在60℃溶解于20% 盐酸中，用活性炭和亚硫酸氢钠处理，然后于60℃在木制压滤机上过滤。滤液用碳酸钠溶液中和，自身冷却到35-40℃，在真空过滤器上过滤出沉淀的3,3’-二甲氧基联苯胺，并用水很好洗涤，真空干燥。 收率76%（普通）；优质74.5%
 

	普通3,3’-二甲氧基联苯胺为紫色，含量96-97%；优质为白至微红色，含量99%。
 

	 
 

	BIOS 1153, 270-272.（胶卷PB 85687）。 Dianisidine
salt.  (Leverkusen).  英国人译自德文（无资料来源）。
 

	    1. Reduction:  A completely dry stirred and jacketed vessel
of 1 m3 capacity is charged with 250 kg. of o-nitroanisole and 1 l. of 50%
caustic liquor.  It is heated to 75℃. and, over 24 hours, 235 kg. of zinc dust added.  The dust should not contain more than 90%
zinc otherwise the reduction is too fierce. 
The zinc is added in 2.5 kg. lots from a small shovel.  Simultaneously with the addition of the zinc
14 l. of caustic liquor are added also over the 24 hours.
 

	The temperature during the first 8 hours must be 75℃., during the second 8 hours 78℃. and finally
80℃. 
Stirring at this temperature is continued for about 12 hours.  During this stage of the reaction,
azoxyanisole is formed which explodes spontaneously at 150℃.  Consequently, if the batch temperature  rises above 90℃., the whole batch is drowned with water.  An electrical alarm system gives the
warning.  This only happened when an
agitator fails.
 

	For reduction of the azoxy to the hydrazo-compound 200 l. water are
added as quickly as possible.  The
temperature rises to 85℃. and at this temperature 80-85 kg. of zinc
dust are added in small portions over 5-6 hours.  At the same time, sufficient water id run in
to keep the contents as a thick paste. 
Stirring is continued until a sample of the paste when shaken with
benzene does not colour the benzene red.
 

	2. Removal of zinc:  The batch
is diluted as much as possible with water, cooled to 20℃. and the contents of three reduction pans transferred to a de-zincing
vat of 11,000 l. capacity.  About 3,300
l. of sulphuric acid (300Be’) are run in at 2-10℃. until Congo paper is coloured strongly violet and remains so for at
least 20 min.
 

	The contents of two vats are filtered on a nutsche and washed with
water until the addition of sodium acetate to a sample of the wash water
precipitates no zinc hydroxide.
 

	3. Inversion of the hydrazoanisole to dianisidine:  The hydrazoanisole from one nutsche (i.e. the
combined charge from 6 reduction pans) is added at 0.5℃. over 4-5 hours to an inversion vat containing 3,300 l. of water and
2,200 l. of sulphuric acid(300Be’), and stirred at this temperature until the
inversion is complete.  Test by filtering
off a sample, shake well with benzene, filter, add concentrated hydrochloric
acid when no precipitate should be obtained.
 

	4.  Purification:  The finished charge is drawn to a lead and
tile-lined vessel, diluted with about 5000 l. of H2SO4 (600Be’) at 20℃., nutsched and twice washed with 50% sulphuric acid.  The crude dianisdine is made into a slurry
with water and transferred to a rubber and tile-lined vessel (15 m3), diluted
to 11,000 l., 500 l. of commercial conc. Hydrochloric acid added and heated to
95℃. 
About 1000 l. of 2% sodium sulphide solution are added, followed by 25
kg. of active charcoal, and allowed to settle. 
The hot clear solution is drawn to a similar lined vessel and 900 kg. of
rock salt added, cooled to 20℃. (the filtrate must precipitate no more
hydrochloride on the addition of more salt), filtered and washed twice on the
nutsche with concentrated rock-salt solution.
 

	The liquid containing the added charcoal from four bayches is united,
diluted with water, boiled and settled, the clear solution being run to a
second vessel for diluting subsequent batches. 
If the residue contains no more than the equivalent of 6 kg. of nitrite,
it is run to drain.  Otherwise the
procedure must be repeated.
 

	Dianisidine salt can be air-dried on trays or under vacuum at 60℃. and then ground.  Yield: 75%
theory.  本文译自PB 25623.
 

	 
 

	FIAT 1313, I, 134-135.（胶卷PB 85172）。 O-Dianisidine. (Leverkusen).
美国人译自德文（无资料来源）。
 

	    Charge the 1000 l. reduction
kettle with 250 kg o-nitroanisole and 1 l. sodium hydroxide solution, 50%. Heat
to 75℃. and add in 2.5 k. portions during 24 hours.
235 kg zinc dust, 90%.  At the same time
add evenly throughout the reduction, 50 l. sodium hydroxide solution, 50%.  The first third of the reduction is done at
75℃., the second at 78℃., and the third at 80℃.  If a
sudden temperature rise occurs, the charge is drowned with water from a direct
line attached attached to the kettle. 
Add 200 l. water, heat to 85℃. and
continue the reduction at this temperature by sprinkling in small portions
about 85 kg. zinc dust, 90%, during 5-6 hours, along with enough water to
maintain a thick but stirrable paste.  Test:
A sample is extracted with benzene, there should be no orange coloration in the
benzene, there layer.  When the test is satisfied
fill the kettle with water and blow to the dezincing vat.  Three reductions are combined in this vat and
with cooling at not over 10℃. run in about 3300 l. sulfuric acid 300Be’
until a weak Congo acidity is obtained that remains for 20 minutes.  Filter and wash free of zinc sulphate.  The hydrazo paste is charged at 0-5℃. into3300 l. water and 2200 l. sulfuric acid, 300Be’, during 4-5
hours.  Stir at 0-5℃. until the rearrangement is complete. 
The time varies from charge to charge but is usually 1-1.5 days.  Suck the charge into 5000 l. sulfuric acid,
600Be’, at 20℃. 
Filter and wash the cake with 50% sulfuric acid.  The above cake is charged into water and then
diluted to 11,000 l.  Add 500 l.
hydrochloric acid, 33%, and heat to 95℃.  Add about 1000 l. sodium sulphide solution,
2%, to completely precipitate the zinc, and 25 kg. “Terrana”.  Let stand to settle, suck off the supernatant
liquor into the precipitation kettle, add 900 kg. salt, and cool to 20℃.  Filter and wash twice with
saturated salt solution.  After 4 charges
the settled precipitate of zinc sulphide, “Terrana” etc. is diluted with water,
settled again, and the decanted solution used for dissolving the next
charge.  The residues remaining contain
about 6 k. nitrite and are discarded. 
The product is dried on enamel pans at 60℃. in air or vacuum.  Yield: =
75% of theory.  本文也应该是译自PB 25623.
 

	PB 25623, 567-568. O-Dianisdine. 
本人未抄录。
 

	 
 

	细田豊 《理论制造染料化学》1957年。 P. 483.  1ジアニシジン.  溶媒を用ない方法。 译自PB 25623.
 

	    0-ニトロアニゾ-ル250 kgとNaOH 50% 1 l. を750に上げ，亚铅末235 kgとNaOH 50% 14 l. を少量ずつ18-20 hで加える。最初の6-7 hを750, つぎに6-7 hを780に，残りの6-7 hを800にし，アゾ还原が终るまで续ける。つぎにヒドラゾアニゾ- ルに还原するために800で约10 hかかつて水150-200 l. を加え，亚铅末80-85 kgを10-12 hで加え，この间反应物をペ- スト状に保つため适量の水を追加し最初の5-6 hを80-750，つぎの5-6 hを75-700に保つようにする。
 

	    反应物を水でうすめ200に冷してジスインテグレ- タ- を经て脱亚铅槽に入り，100で硫酸300Be” 1-1.1 m3を徐加し後の2/3を加える时は5-60に下げる。
 

	    ヒドラゾアニゾ- ルを亚铅液から滤過，水洗し，转位槽の水550 l. + 硫酸30 0Be’ 575 l. を0-50に冷した液に加え同温で15-20 h搅拌する。ジアニシジン硫酸盐の沉淀を滤過し，溶解槽に入れ，约60 l. の盐酸を加え，生蒸汽と水で800，1.6-1.7 m3にして溶解し热滤過し，滤液に水150 kgと岩盐100 kgを加えて精制ジアニシジン盐を滤過する。粗制および精制母液は合せてさらに盐を加えて盐析，滤過し，5倍量の95%エタノ- ルと700に1-2 h热した後150にしジアニシジン盐を滤過してこれはつぎの转位液に溶し达む。收率75-80%。
 

	 
 

	PB 74239.  Reports on the
production of various organic chemicals. 
1932-1943年。未抄录。
 

	PB 74239, 129-132.  O-Dianisdine.
1940年德文生产工艺。未抄录。
 

	 
 

	天津染料生产工艺汇编。1980年。 P. 23-25.  联大茴香胺盐酸盐。
 

	    1. 还原：在还原罐中，投入邻硝基苯甲醚362.5公斤，于85℃以上，在搅拌下6-6.5小时内连续投入锌粉285公斤和50%氢氧化钠37.2公斤，到达终点时，加入200升水稀释后，进行第二阶段反应，即在85-90℃ 3-3.5小时内投入锌粉180公斤和350升水，生成的氢化偶氮苯甲醚呈结晶颗粒析出，还原物料通过缓慢转动着的圆形分离筛，在水流的冲洗下，进行分离，氧化锌随水从分离筛下流出，进行回收，氢化偶氮苯甲醚结晶从分离筛上流入转位缸中进行转位。
 

	2. 转位：一批氢化偶氮苯甲醚结晶连续投入1# 转位缸中，同时连续加入硫酸430升和水1800升保持温度为6-10℃，酸度17-18%，物料经溢流管流入2#，3#转位缸，温度同时自然上升至20-25℃。
 

	3. 盐析：转位后物料加热到85-90℃，在盐析缸内调整体积为3500-4000升，然后加入食盐1400-1500公斤，搅拌1小时，比重应控制在1.23-1.26 母液含胺量在0.5%以下。
 

	4. 成品过滤，用真空转鼓吸滤，温度60-65℃吸滤，洗涤后进行包装。总收率为75%。
 

	 
 

	侯乐山 主编 《中国精细化工产品集 – 原料及中间体10396种》。 2006年。P. 400-401.  3,3’-二甲氧基联苯胺。
 

	中国化工信息中心  全国精细化工原料及中间体行业协作组 出版 《版权所有  未经允许  报导翻印》。
 

	生产方法：是简单的摘要，无具体生产工艺。不再抄录。
 

	国内染料专业出版物。
 

	何岩彬 主编 《染料品种大全》沈阳出版社 出版。 2018年。 P. 1994.   3,3’-二甲氧基联苯胺。
 

	以上资料作为产品历史生产工艺的补充。
 

	老有所为，老有所乐。那么多抄录文，仅供读者参考。
 

	 
 

	陈忠源 2019年5月24日星期五。加注：在文件打字中出现间距大了，但本人不会更正。请读者谅解！
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