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| CAS号 [119-68-6] 生产工艺。 N-甲基邻氨基苯甲酸 |
CAS号 [119-68-6] 生产工艺。 N-甲基邻氨基苯甲酸
CAS名：Benzoic acid, 2-(methylamino)-
历史参考文献：Beil. 14, 223.
用途：冰染重氮组分5，配制稳定重氮盐用。有机合成。 LookChem网登录生产与经营单位39家。 反应类别：氯甲胺化。
BIOS 1149, 121-122.（=胶卷PB 80376）。 N-methylanthranilic
acid. (Leverkusen). 英国人译自德文，无资料来源。
反应式：本人有加注，德文原件未抄录。
Method: o-Chlorobenzoic acid is
reacted with aqueous methylamine solution.
Plant: 6000 l. autoclave with
heating and cooling coils, agitator。 Pump
for charging methylamine。
Condenser etc. for recovery of excess methylamine vat。
Nutsche。 Measure vessel。
Process:
1360 kg. o-chlorobenzoic acid 100% (M.W. =156.5) ≈600 kg.
Nitrite. 600 kg. Methylamine 100%. 1400 kg. caustic soda 50% solution. 16 kg. Copper oxychloride [3 Cu(OH)2.CuCl2]. 1000 l. hydrochloric acid (Sp. Gr. 1.16)
The o-chlorobenzoic acid is charged into the agitated 6000 l.
autoclave followed by the catalyst and the caustic solution. The acid mixture is titrated for acidity and
further NaOH run in to neutralize this excess acidity. Aqueous methylamine recovered from the steam
distillation of a previous batch is pumped into the closed autoclave, followed
by the 100% methylamine. The total
methylamine solution content not be below 30% amine strength and, if above 30%,
further water are added to adjust to 30%.
The closed autoclave is agitated and careful heated to 110℃., when the heat of reaction causes the temperature to rise to 115℃. This temperature is
controlled by means of the cooling coils.
Higher temperature result in the splitting off the carboxyl group. It is kept at 115℃ for 24 hours, the pressure falling 6 atm. at the start to 3.8 / 4
atm. as the methylamine is consumed.
Test: 500 g of the melt are sucked free from copper sludge, put into 2
l. flash and nitrosated with 10% sodium nitrite solution in the presence of
hydrochloric acid. The reaction should
be at least 90% complete.
After completion of reaction, the pressure is released with
distillation of some of the excess methylamine; 1000 l. of water are added and
the remainder of the methylamine steam distilled.
The contents of the vessel are then made up to 6000 l., 10 kg. of
sodium hydrosulphite added, and filtered through a press to remove copper
sludge, and the residue washed with 1000 l. hot water. The alkaline filtrate is made up to a total
bulk of 8000 l., cooled to normal temperature (25℃) and acidified with 1000 l. of hydrochloric acid Sp. Gr. 1.16 so that
the reaction mixture is slightly acid to litmus.
Test: 10 g. paste are diluted with 100 cc. diluted chlorine free
nitric acid and determined for Cl content.
Equivalent of 1.5 g. NaNO2 should not take more then 4-5 cc. N/10 AgNO3 solution
otherwise the batch requires further washing.
The acid dried in vacuum stove at 90℃ on Heveg trays and milled.
100 g. of dry material should require 41-43 g. NaNO2 ≈91 / 92% (M.W.
151) . Yield = 1095 kg. 100% ≈500 kg.
NaNO2 =83.2% theory.
细田豊 《理论制造染料化学》。 1957年。 P. 665. N-メチルアントラニル酸。 译自BIOS 1149.
6 m3 オ- トクレ- ブにo-クロル安息香酸1360 kg，オキシ盐化铜（3Cu(OH)2CuCl）16 kg，NaOH 50% 1.4 tを入れて中性とし，メチルアミン600 kgを回收品共30% 水溶液として加え，注意して1100に上げれば反应热で1150に上り24 h保温する。压は6气压から最后は3.8-4气压に下る。 CH3NH2を蒸馏し，水1 m3を加えCH3NH2を水蒸汽蒸馏後6 m3とし，Na2S2O4 10 kgを加え，铜盐を滤過し湯1 m3で洗い，滤液を250で盐酸1 m3でリトマス弱酸性とし滤過亁燥する。N-メチルアントラニル酸1095 kg 100%，收率83.2%。
张澍声 《精细化工中间体工业生产技术》。 1996年。 P. 30. N-甲基邻氨基苯甲酸。 译自BIOS 1149, 120.
在6000 L高压釜中加入1360 kg 100% 邻氯苯甲酸，随后加16 kg 铜氯氧化物（3Cu(OH)2.CuCl2）和若干50% 氢氧化钠溶液，酸性混合物滴定酸度，再加氢氧化钠以中和过量的酸度，总计加入1400 kg 50% 氢氧化钠溶液。然后向高压釜内加入上次反应水蒸汽蒸馏回收的甲胺水溶液，再加入100% 甲胺，总甲胺水溶液中含量要低于30%，如果高于30%，加水调节到30%，甲胺加入量为600 kg (100%)。
关闭高压釜，搅拌并仔细加热到110℃，再用冷却控制温度，高温会造成羧基的裂解，在115℃保持24小时，随着甲胺的消耗，压力由最初的6巴降至3.8-4巴。
检验：取50 g 熔融物抽滤除去铜渣，放入2 L烧瓶内，在盐酸存在下用10% 亚硝酸钠溶液亚硝化，反应至少完成90%。
反应完成后，释去压力，蒸馏出一些过量的甲胺，加入1000 L水，水汽蒸馏出其余甲胺。锅内物加水达6000 L，加入10 kg 亚硫酸氢钠，过滤除去铜渣，残留物用1000 L比重1.16的盐酸酸化，使反应混合物对石蕊试纸为微酸性。
得到的酸在90℃真空干燥并研磨，得到1095 kg 100% N-甲基邻氨基苯甲酸，收率83.2%。
PB 25602, 1146-1150. N-methylanthranilsäure. 德文生产工艺原件，未抄录。
PB 32533, II. C.
N-methylanthranilsäure. 德文生产工艺原件，未抄录。
国内出版物：本人未见有报导。
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。
按分子式，应该列入p. 1901.
陈忠源 2019年7月2日星期二。
文章作者：陈忠源 |
