Page 222 - 《精细化工》2021年第7期

·1504· 精细化工 FINE CHEMICALS 第 38 卷

反应时间 8 h，溶剂为冰醋酸，进行了硝化反应的初 [5] ZHU H Q (朱惠琴). A new method of synthesizing 5-nitroacenaphthene[J].
步放大，实验结果见图 4。 Chemical Reagents (化学试剂), 2002, 24(1): 45-46.
[6] IRANPOOR N, FIROUZABADI H, SHEKARIZE M. Micellar
从图 4 可知，随着反应原料的增加，硝化反应 media for the efficient ring opening of epoxides with CN , N 3 , NO 3,
–
–
–
– – – –
的产率在 87%~89% 之间，产品 HPLC 纯度 为 NO 2, SCN , Cl and Br catalyzed with Ce(OTf) 4[J]. Organic &
Biomolecular Chemistry, 2003, 1: 724-727.
97%~98%。
[7] LIU T (刘涛), LI Q T (李秋婷), PAN Z H (潘滋涵), et al.
3.3 合成 4-溴-5-硝基-1,8-萘酐的初步放大实验 Spectroscopic properties of fluorescent dye composed of coumarine and
4-溴-5-硝基苊的投料分别改为 0.5 mol (135 g)、 naphthalimide[J]. Chemical Reagents (化学试剂), 2019, 41(8): 794-797.
[8] ZHOU W (周五), WU A B (吴爱斌). Synthesis and properties of
1.0 mol (270 g)、1.5 mol (405 g)和 2.0 mol (540 g)， +
pyrimidine naphthalimide-based Ag fluorescent probes[J]. Chemical
n(醋酸钴)∶n(醋酸锰)∶n(NHPI)∶n(4-溴-5-硝基 Reagents (化学试剂), 2020, 42(6): 694-698.
苊)=1.2∶0.5∶1.2∶10，反应温度 110 ℃，反应时 [9] JU J (居洁), GAO J R (高建荣), LI Y J (李郁锦). Recent progress in
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间 5 h，溶剂为冰醋酸，进行了氧化反应的初步放大， Applied Chemistry (应用化学), 2010, 27(6): 621-625.
如图 4 所示。 [10] WANG H Y (王海洋), ZANG N (臧娜), ZHAO S J (赵素娟), et al.
从图 4 可知，随着反应原料的增加，氧化反应 Oxidative bromination synthesis of brominated fused ring aromatic
hydrocarbons[J]. Chinese Journal Applied Chemistry (应用化学),
的产率在 71%~73% 之间，产品 HPLC 纯度 为 2012, 29(11): 1340-1342.
95%~96%。 [11] ZHANG G F (张国富), WANG Y (王涌), DING C R (丁成荣), et al.
由初步放大实验结果可知，小试反应的实验条 Recent advances in oxybromination of aromatic compounds[J]. Chinese
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件运用到初步放大实验中，其溴化、硝化、氧化的 [12] XU Z C , QIAN X H , CUI J N , et al. Exploiting the deprotonation
产率与小试各步产率相差不大，均取得了较好的效果。 mechanism for the design of ratiometric and colorimetric Zn 2+
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合成 5-溴苊的最佳工艺条件为：反应温度 (化学世界), 2012, 3: 160-162.
25 ℃，反应时间 3 h，n(苊)∶n(CeCl 3 •7H 2 O)∶ [14] FIROUZABADI H, IRANPOOR N, KAZEMI S, et al. Highly
n(NaBr)= 2∶1∶2.4，产品收率 86.4%。合成 4-溴-5- efficient halogenation of organic compounds with halids catalyzed by
cerium(Ⅲ) chloride heptahydrate using hydrogen peroxide as the
硝基苊的最佳工艺条件为：反应温度 45 ℃，反应时 terminal oxidant in water[J]. Advanced Synthesis & Catalysis, 2009,
间 8 h，n(5-溴苊)∶n〔Al(NO 3 ) 3 •9H 2 O〕= 1∶1.2， 351: 1925-1932.
产品收率 88.4%。合成 4-溴-5-硝基-1,8-萘酐的最佳 [15] WANG S (王胜), JIANG X L (蒋旭亮). Synthesis of 3-nitro-1,8-
naphthalic acid anhydride[J]. Fine Chemical Intermediates (精细化
工艺条件为：反应温度 110 ℃，反应时间 5 h，n(醋 工中间体), 2013, 43(2): 49-50.
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原料廉价易得，大大降低了生产成本，整个制备过 of alkylbenzenes with molecular oxygen under normal pressure and
程操作简单、条件温和，原子经济性好，后处理绿 temperature by N-hydroxyphthalimide combined with Co(OAc) 2[J].
Journal of Organic Chemistry, 1997,62: 6810-6813.
色无污染，易于工业化，但在产率上还存在一定的 [18] BUKHARKINA T V, GRECHISHKINA O S, DIGUROV N G, et al.
提升空间。本工艺为 4-溴-5-硝基-1,8-萘酐的合成工 Catalytic oxidation of acenaphthene and its derivatives in acetic
艺改进积累了一定的经验和重要的基础实验数据。 acid[J]. Organic Process Research & Development, 2002, 6: 394-400.
[19] WU A B (吴爱斌), HU Y X (胡艳雄), ZHOU W (周五), et al. A kind
of preparation method of 4-bromo-5-nitro-1,8-naphthalene anhydride:
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