9, 9-二(3-氨基-4-羟基苯基)呫吨的合成

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方程, 姜建文, 刘晓玲, 盛寿日. 9, 9-二(3-氨基-4-羟基苯基)呫吨的合成. 应用化学, 32(1): 60-63
FANG Cheng, JIANG Jianwen, LIU Xiaoling, SHENG Shouri. Preparation of 9, 9-Bis(3-amino-4-hydroxyphenyl) xanthene. Chinese Journal of Applied Chemistry, 32(1): 60-63 复制到剪切板

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9, 9-二(3-氨基-4-羟基苯基)呫吨的合成

方程, 姜建文^*, 刘晓玲, 盛寿日

江西师范大学化学化工学院南昌 330022

通讯联系人:姜建文,教授; Tel/Fax:0791-88506404; E-mail:jiangjianwen@jxnu.edu.cn; 研究方向:有机合成

收稿日期:2014-08-14

基金:国家自然科学基金(20664001,51163008,21464007),江西省自然科学基金(20132BAB206031)资助项目

摘要

以醋酸酐为溶剂, 将9, 9-二(4-羟基苯基)呫吨与浓硝酸在15 ℃左右发生硝化反应1.5 h, 形成中间体—9, 9-二(3-硝基-4-羟基苯基)呫吨, 产率为88.5%;继而以Pd/C 为催化剂, 80%的水合肼为还原剂, 在乙醇和1, 4-二氧六环混合溶剂中, 于70 ℃将中间体进行还原反应10 h, 得到目标产物9, 9-二(3-氨基-4-羟基苯基)呫吨, 产率为90.8%, 两步反应总收率为80.4%。中间体与目标化合物经NMR、FTIR和元素分析等确定了它们的结构。

关键词: 二(硝基羟基苯基)呫吨; 二(氨基羟基苯基)呫吨; 硝化反应; 还原反应; 水合肼

中图分类号:O625.6 文献标志码:A 文章编号:1000-0518(2015)01-0060-04

Preparation of 9, 9-Bis(3-amino-4-hydroxyphenyl) xanthene

FANG Cheng, JIANG Jianwen^*, LIU Xiaoling, SHENG Shouri

Institutes of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, China

Corresponding author:JIANG Jianwen, professor; Tel/Fax:0791-88506404; E-mail:jiangjianwen@jxnu.edu.cn; Research interests:organic synthesis

Fund:Supported by the National Natural Science Foundation of China(No.21064003, No.51163008, No.21464007) and the Natural Science Foundation of Jiangxi Province of China(No.20132BAB206031)

Abstract

Treatment of 9, 9-bis(4-hydroxyphenyl)xanthene(1) with nitric acid(69% mass fraction) in acetic anhydride at 15 ℃ for 1.5 h afforded the intermediate, 9, 9-bis(3-nitro-4-hydroxyphenyl)xanthene(2) in 88.5% yield. Compound 2 was then reduced to the target, 9, 9-bis(3-amino-4-hydroxyphenyl)xanthene(3) in 90.8% yield by hydrazine hydrate in the presence of catalytic amount of Pd/C at 70 ℃ for 10 h in ethanol/dioxane mixed solvents. The two-step overall yield of compound 3 is about 80.4%(based on compound 1). The structures of intermediate 2 and target compound 3 were characterized by NMR, IR and elemental analysis.

Keyword: bis(nitro-hydroxyphenyl)xanthene; bis(amino-hydroxyphenyl)xanthene; nitration reaction; reduction reaction; hydrazine hydrate

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芳香族聚苯并噁唑(PBO)是一类具有优良热稳定性的芳杂环聚合物, 在薄膜、纤维业、宇航业、改性复合材料以及碳纤维母体等方面有着广泛的应用。 PBO树脂通常由芳香族双(邻氨基苯酚)与芳香族二元羧酸或其衍生物的缩聚反应而制得^{[1, 2]}。但是, 传统芳香族PBO的难溶性(只能溶解于少数强酸, 如浓硫酸等)和难加工性, 使其应用受到了很大的限制。为此, 研究者通过在聚合物分子主链中引入柔性基团^{[3, 4]}、取代基^{[5, 6]}等对其进行了结构改性, 使PBO的溶解性能得到不同程度地改善, 但往往使其耐热性下降。研究表明, 将1, 1-二苯基环己烷、9, 9-二苯基芴等环形结构引入大分子链中^{[7, 8]}, 不仅赋予了此类Cardo型PBO更好的溶解性, 且能保持其优良的热学和力学性能等。其中, 含Cardo结构的双邻氨基酚单体是制备相应聚合物的关键。在前期工作中, 我们探索了9, 9-二(4-羟基苯基)呫吨等含呫吨结构双酚化合物的制备方法^{[9, 10]}, 从结构上分析, 如果在PBO分子骨架上引入呫吨结构单元, 有望获得综合性能优异的PBO新品种。因为9, 9-二苯基呫吨结构单元中的多苯杂环结构有利于聚合物保持较高的热稳定性, 聚合物大分子链中侧挂的氧杂蒽结构具有更大的键旋转位垒, 可使聚合物具有较高的玻璃化转变温度。同时, 这种Cardo型结构降低了大分子链的堆叠密度, 破坏了分子链的规整性, 因而能使聚合物具有很好的溶解性。为了制备该类新型的PBO, 先从9, 9-二(4-羟基苯基)呫吨(1)出发, 经过硝化、还原两步反应, 合成了一种新型含Cardo结构的双邻氨基酚单体— 9, 9-二(3-氨基-4-羟基苯基)呫吨(3)(如Scheme 1所示)。

Scheme 1 The synthetic route to 9, 9-bis(3-amino-4-hydroxyphenyl)xanthene(3)

1 实验部分

1.1 仪器和试剂

9, 9-二(4-羟基苯基)呫吨按文献[9]方法制备; 浓硝酸(69%)、乙酸酐、水合肼(80%)、Pd/C(10%)、1, 4-二氧六环等为市售分析纯试剂(上海达瑞精细化学品有限公司), 直接使用。

XT4A型显微熔点测定仪(北京科仪电光仪器公司), 温度未经校正; Perkin Elmer SP One FTIR光谱仪(美国Perkin Elmer公司); Avance-400MHz型核磁共振仪(德国Bruker公司), CDCl₃为溶剂, TMS为内标; Vario EL III型元素分析仪(德国Elementar公司); EI-MS MS-7070型质谱仪(英国VG公司)。

1.2 9, 9-二(3-硝基-4-羟基苯基)呫吨(2)的制备

将9, 9-二(4-羟基苯基)呫吨(1)(3.67 g, 10 mmol)和乙酸酐(15 mL)加入250 mL的三口烧瓶中, 室温搅拌至完全溶解, 后用冰水浴冷却, 向反应体系中缓慢滴加69%的浓硝酸(1.5 mL), 在15 min内滴加完毕, 控制温度在15 ℃左右, 并搅拌1.5 h。反应结束后, 缓慢加入碳酸钠溶液(1 mol/L)至溶液显弱酸性, 继续搅拌2 h, 析出黄色固体。过滤, 水洗至中性, 粗产品用无水乙醇和DMF混合溶剂(体积比4∶ 1)重结晶, 得到黄色晶体2(4.04 g), 产率88.5%, 熔点232234 ℃; ¹H NMR(CDCl₃, 400MHz), δ :10.61(s, 2H), 7.60(s, 1H), 7.59(s, 1H), 7.377.31(m, 4H), 7.23(d, J=8.0 Hz, 2H), 7.147.09(m, 4H), 6.87(d, J=7.6 Hz, 2H); ¹³C NMR(CDCl₃, 100 MHz), δ :154.21, 152.34, 138.78, 137.32, 132.91, 129.13, 127.80, 125.48, 123.72, 120.29, 117.21, 52.83; FTIR(KBr), σ /cm^-1: 3439(N— O), 3272(O— H), 3080(Ar— H), 1579, 1474( ), 1537, 1325(NO₂), 1243(Ar— O— Ar); 元素分析(C₂₅H₁₆N₂O₇)实测值(计算值)/%: C 65.68(65.79), H 3.67(3.53), N 6.23(6.14)。

1.3 9, 9-二(3-氨基-4-羟基苯基)呫吨(3) 的制备

在N₂气保护下, 将化合物2(4.56 g, 10 mmol) 溶于无水乙醇和1, 4-二氧六环的混合溶剂(25 mL, 体积比1∶ 1)中, 加入10%的Pd/C(0.20 g), 缓慢升温至70 ℃后, 滴加80%的水合肼(5 mL)(30 min内滴加完毕), 维持此温度搅拌反应10 h。稍微冷却后, 趁热过滤, 除Pd/C, 在不断搅拌下, 将滤液缓缓注入冷水中, 析出白色固体, 再用乙醇和水混合溶剂(体积比2∶ 1)重结晶, 得到白色晶体3(3.60 g), 产率90.8%, 熔点205207 ℃。 ¹H NMR(DMSO-d₆, 400 MHz), δ : 8.95(s, 2H), 7.26(t, J=7.2 Hz, 2H), 7.137.04(m, 4H), 6.94(d, J=7.6 Hz, 2H), 6.50(d, J=8.0 Hz, 2H), 6.23(s, 2H), 5.87(d, J=8.0 Hz, 2H), 4.40(s, 4H); ¹³C NMR(CDCl₃, 100 MHz), δ :151.99, 142.95, 137.68, 136.14, 131.63, 130.82, 127.87, 123.71, 118.50, 116.60, 116.15, 113.52, 53.13; FTIR(KBr), σ /cm^-1: 3455(O— H), 3368, 3317(NH₂), 3072(Ar— H), 1597, 1475( ), 1236(Ar— O— Ar), 1279(C— N); MS-EI(m/z):419.1[M+Na]⁺; 元素分析C₂₅H₂₀N₂O₃实测值(计算值)/%:C 75.62(75.74), H 5.24(5.09), N 7.16(7.07)。

2 结果与讨论

2.1 硝化反应

在硝化反应中, 考察了反应温度、反应时间和溶剂(1, 2-二氯乙烷、乙酸和乙酸酐)对反应的影响(表1)。从表1可知, 以乙酸酐为溶剂, 在15 ℃左右搅拌反应约1.5 h, 可高产率(88.5%)获得9, 9-二(3-硝基-4-羟基苯基)呫吨(2)。实验表明, 反应温度过低会导致反应不完全; 温度过高, 反应速度会加快, 但产品易被氧化, 产生大量焦油状物, 发生副反应, 目标产品收率下降; 此外, 反应时间延长, 产率也会有所下降, 还会增加多硝基苯酚的生成。

表1 硝化反应条件的优化 Table 1 Optimization of nitration reaction conditions^a

2.2 还原反应

芳香族硝基化合物还原制备芳胺的方法较多。其中, 水合肼还原方法具有设备简单、反应条件温和、产品收率高、不产生废气废渣等优点^[11]。以Pd/C为催化剂, 80%的水合肼为还原剂, 研究了9, 9-二(3-硝基-4-羟基苯基)呫吨(2)的还原过程。由于化合物2在水中的溶解度太小, 而采用水合肼还原, 其反应介质含有水, 因而需要加入合适的有机溶剂。显然, 采用氯仿、乙酸乙酯等与水互溶性差的有机溶剂难以获得理想的还原效果。在综合文献[11]和初步实验的基础上, 选择了乙醇和1, 4-二氧六环混合溶剂。此外, 反应温度、催化剂用量也是影响还原反应的主要因素。温度高, 反应快, 但副反应多; 催化剂用量少, 产品收率低, 催化剂用量大, 成本提高。通过对水合肼和Pd/C的用量、反应温度、反应时间等几个方面进行反复实验和条件优化, 以高产率(90.8%)获得了9, 9-二(3-氨基-4-羟基苯基)呫吨(3)(表2, Entry 6)。

表2 9, 9-二(3-硝基-4-羟基苯基)呫吨(2)还原反应的实验结果 Table 2 Reduction of 9, 9-bis(3-nitro-4-hydroxyphenyl)xanthene(2)^a

3 结论

将9, 9-二(4-羟基苯基)呫吨与浓硝酸在醋酸酐中于15 ℃左右进行硝化反应; 继而以Pd/C 为催化剂, 80%的水合肼为还原剂, 在乙醇和1, 4-二氧六环混合溶剂中, 于70 ℃实施还原反应, 以80.4%的总收率合成了一种新的双邻氨基酚单体— 9, 9-二(3-氨基-4-羟基苯基)呫吨。该法具有操作简单, 反应条件温和, 收率高等优点。

参考文献

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1989

0.0

... PBO树脂通常由芳香族双(邻氨基苯酚)与芳香族二元羧酸或其衍生物的缩聚反应而制得^[1,2] ...

2008

0.0

0.7946

FEI

Fei

, YU

Xinhai.

Preparation and Application of Polybenzoxazole Resins[J]. Insulating Mater, 2008, 41(6): 8-13(in Chinese).

费斐, 虞鑫海. 聚苯并噁唑树脂的合成及其应用[J]. 绝缘材料, 2008, 41(6): 8-13.

介绍了聚苯并噁唑树脂的发展概况以及合成聚苯并噁唑树脂的主要单体和聚合工艺;阐述了聚苯并噁唑的性能和推广应用的前景.

... PBO树脂通常由芳香族双(邻氨基苯酚)与芳香族二元羧酸或其衍生物的缩聚反应而制得^[1,2] ...

1990

5.521

0.0

Hilborn J

, Labadie J

, Hedrick J

Poly(aryl ether-benzoxazoles)[J]. Macromolecules, 1990, 23(11): 2854-2861.

... 为此, 研究者通过在聚合物分子主链中引入柔性基团^[3,4]、取代基^[5,6]等对其进行了结构改性, 使PBO的溶解性能得到不同程度地改善, 但往往使其耐热性下降 ...

2002

3.543

0.0

Imai

, Maeda

, Takeuchi

, et al. Synthesis and Properties of New Aromatic Poly(ether benzoxazole)s from 2, 2'-Bis(4-amino-3-hydroxyphenoxy)biphenyl and Aromatic Dicarboxylic Acid Chlorides[J]. J Polym Sci Part A: Polym Chem, 2002, 40(15): 2656-2662.

1 Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Meguro-ku, Tokyo 152, Japan 2 Department of Industrial Chemistry, Tokyo Institute of Polytechniques, Iiyama, Atsugi-shi, Kanagawa 243-02, Japan † 1-9-2-303, Nakamagome, Ohta-ku, Tokyo 143, Japan * Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Meguro-ku, Tokyo 152, Japan

> A new bis( o -aminophenol) with a crank and twisted noncoplanar structure and ether linkages, 2,2′-bis(4-amino-3-hydroxyphenoxy)biphenyl, was synthesized by the reaction of 2-benzyloxy-4-fluoronitrobenzene with biphenyl-2,2′-diol, followed by reduction. Biphenyl-2,2′-diyl-containing aromatic poly(ether benzoxazole)s with inherent viscosities of 0.52–1.01 dL/g were obtained by a conventional two-step procedure involving the polycondensation of the bis( o -aminophenol) monomer with various aromatic dicarboxylic acid chlorides, yielding precursor poly(ether o -hydroxyamide)s, and subsequent thermal cyclodehydration. These new aromatic poly(ether benzoxazole)s were soluble in methanesulfonic acid, and some of them dissolved in m -cresol. The aromatic poly(ether benzoxazole)s had glass-transition temperatures of 190–251 °C and were stable up to 380 °C in nitrogen, with 10% weight losses being recorded above 520 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2656–2662, 2002

1998

3.543

0.0

1999

3.543

0.0

Hsiao S

, Dai L

Synthesis and Properties of Novel Aromatic Poly(o-hydroxy amide)s and Polybenzoxazoles Based on the Bis(ether benzoyl chloride)s from Hydroquinone and Its Methyl-, tert-Butyl-, and Phenyl-substituted Derivatives[J]. J Polym Sci Part A: Polym Chem, 1999, 37(13): 2129-2136.

Department of Chemical Engineering, Tatung Institute of Technology, 40 Chungshan North Rd., Sec. 3, Taipei, Taiwan, Republic of China * Department of Chemical Engineering, Tatung Institute of Technology, 40 Chungshan North Rd., Sec. 3, Taipei, Taiwan, Republic of China

> Four series of poly( o -hydroxy amide)s were prepared by the low-temperature solution polycondensation of the bis(ether benzoyl chloride)s extended from hydroquinone and its methyl-, tert -butyl-, or phenyl-substituted derivatives with three bis( o -aminophenol)s. Most of the poly( o -hydroxy amide)s displayed an amorphous nature, were readily soluble in various polar solvents such as N , N -dimethylacetamide (DMAc), and could be solution-cast into flexible and tough films. These poly( o -hydroxy amide)s had glass transition temperatures ( T g ) in the range of 152–185°C and could be thermally cyclodehydrated into the corresponding polybenzoxazoles approximately in the region of 200–400°C, as evidenced by the DSC thermograms. The thermally converted benzoxazole polymers exhibited T g s in the range of 215–247°C and did not show significant weight loss before 500°C either in nitrogen or in air. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2129–2136, 1999

2001

3.543

0.0

Hsiao S

, He M

Synthesis and Properties of Novel Cardo Aromatic Poly(ether-benzoxazole)s[J]. J Polym Sci Part A: Polym Chem, 2001, 39(22): 4014-4021.

Department of Chemical Engineering, Tatung University, 40 Chungshan North Road, Sec. 3, Taipei 104, Taiwan (Republic of China) * Department of Chemical Engineering, Tatung University, 40 Chungshan North Road, Sec. 3, Taipei 104, Taiwan (Republic of China)

> Three new bis(ether-acyl chloride) monomers, 1,1-bis[4-(4-chloroformylphenoxy)phenyl]cyclohexane ( 1a ), 5,5-bis[4-(4-chloroformylphenoxy)phenyl]-4,7-methanohexahydroindan ( 1b ), and 9,9-bis[4-(4-chloroformylphenoxy)phenyl]fluorene ( 1c ), were synthesized from readily available compounds. Aromatic polybenzoxazoles bearing ether and cardo groups were obtained by the low-temperature solution polycondensation of the bis(ether-acyl chloride)s with three bis(aminophenol)s and the subsequent thermal cyclodehydration of the resultant poly( o -hydroxy amide)s. The intermediate poly( o -hydroxy amide)s exhibited inherent viscosities in the range of 0.35–0.71 dL/g. All of the poly( o -hydroxy amide)s were amorphous and soluble in many organic polar solvents, and most of them could afford flexible and tough films by solvent casting. The poly( o -hydroxy amide)s exhibited glass-transition temperatures ( T g 's) in the range of 141–169 °C and could be thermally converted into the corresponding polybenzoxazoles approximately in the region of 240–350 °C, as indicated by the DSC thermograms. Flexible and tough films of polybenzoxazoles could be obtained by thermal cyclodehydration of the poly( o -hydroxy amide) films. All the polybenzoxazoles were amorphous and showed an enhanced T g but a dramatically decreased solubility as compared with their poly( o -hydroxy amide) precursors. They exhibited T g 's of 215–272 °C by DSC and showed insignificant weight loss before 500 °C in nitrogen or air. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4014–4021, 2001

... 研究表明, 将1, 1-二苯基环己烷、9, 9-二苯基芴等环形结构引入大分子链中^[7,8], 不仅赋予了此类Cardo型PBO更好的溶解性, 且能保持其优良的热学和力学性能等 ...

2009

2.562

0.0

Huang

, Li S

, Du C

, et al. Synthesis and Characterization of New Cardo Poly(bisbenzoxazole)s Containing Fluorenylidene Unit[J]. Eur Polym J, 2009, 45(11): 3187-3195.

A series of poly(bisbenzoxazole)s ( PBOs V ) containing fluorenylidene unit are prepared from 9,9-bis(3-amino-4-hydroxyphenyl)fluorene ( BAHPF ) and various aromatic or alkene diacids by direct polycondensation. These polymers exhibit improved solubility and good thermal stability. The decomposition temperatures at 10% weight loss of them are above 500 °C. X-ray diffractograms of PBOs V 1 – 5 show that all of them are amorphous. The maximum absorption wavelengths of PBOs V 1 – 5 are blue or red shifted relative to poly( p -phenylene-2,6-benzobisoxazole) ( PBO ). The bandgaps of PBOs V 1 – 5 are in the range of 2.48–2.98 eV, which widen the tunable range of the optical bandgap. The results of photoluminescence (PL) emission spectra indicate the energy transportation has happened between the fluorenylidene and benzoxazole ring. The emission wavelengths of PBOs V 1 – 5 are blue shifted in contrast to PBO and the emission wavelengths of them are in the region of blue or green light, respectively. The PL quantum yields of them are improved due to the introduction of fluorenylidene group. The results of EPR studies show the intrinsic paramagnetic defects in this class of polymers.

a Department of Chemistry, East China Normal University, 3663 Zhongshan North Road, Shanghai 200062, People’s Republic of China b Research Institute of Polymer Materials, School of Chemistry & Chemical Engineering, State Key Laboratory for Composite Materials, Shanghai Jiao Tong University, Shanghai 200240, People’s Republic of China

2009

1.395

0.0

Sheng S

, Ge W

, Huang Z

, et al. Synthesis and Characteriaion of Novel Soluble Cardo Poly(arylene ether ketone)s Containing Xanthene Structures[J]. J Appl Polym Sci, 2009, 114(1): 570-576.

College of Chemistry and Chemical Engineering, Jiangxi Normal University (YaoHu Campus), Nanchang 330022, People's Republic of China * College of Chemistry and Chemical Engineering, Jiangxi Normal University (YaoHu Campus), Nanchang 330022, People's Republic of China

> 9,9-Bis(4-hydroxyphenyl)xanthene (BHPX), a bisphenol monomer, was synthesized in 82% yield from xanthenone in a one-pot, two-step synthetic procedure. Four novel aromatic poly(ether ketone)s (PEKs) based on BHPX were prepared via a nucleophilic aromatic substitution polycondensation with four difluorinated aromatic ketones. The polycondensation proceeded in tetramethylene sulfone in the presence of anhydrous potassium carbonate and afforded the new cardo PEKs in nearly quantitative yields with inherent viscosities of 0.77–0.85 dL/g. High molecular weight PEKs having number-average molecular weights ( M n 's) in the range of 38,900–40,600 g/mol with the polydispersity index ranged from 1.97 to 2.06 are all amorphous and show high glass transition temperatures ranging from 210°C to 254°C, excellent thermal stability, and the temperatures at the 5% weight loss are over 538°C with char yields above 60% at 700°C in nitrogen. These new PEKs are all soluble in polar aprotic solvents such as N -methyl-2-pyrrolidone and N, N′ -dimethylacetamide and could also be dissolved in chloroform and tetrahydrofuran. All the polymers formed transparent, strong, and flexible films with tensile strengths of 78–84 MPa, Young's moduli of 2.54–3.10 GPa, and elongations at break of 14–18 %. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

... 在前期工作中, 我们探索了9, 9-二(4-羟基苯基)呫吨等含呫吨结构双酚化合物的制备方法^[9,10], 从结构上分析, 如果在PBO分子骨架上引入呫吨结构单元, 有望获得综合性能优异的PBO新品种 ...

2011

0.0

0.741

Guiyun

, YI

Fei

, SHENG

Shouri

, et al. Synthesis of Two Xthanene-Containing Bisphenols[J]. Chinese J Appl Chem, 2011, 28(8): 974-976(in Chinese).

付桂云, 易飞, 盛寿日, 等. 2个含呫吨结构双酚化合物的合成[J]. 应用化学, 2011, 28(8): 974-976.

Chlorination of xanthenone by thionyl chloride gave an intermediate 9,9-dichloroxanthene. The obtained chlorinated[JP] product is free of further isolation and purification and can react with o-cresol or 2,6-dimethylphenol for the preparation of two xthanenebiphenols including 9,9-bis(4-hydroxy-3-methylphenyl) xanthene and 9,9-bis(4-hydroxy-3,5-dimethylphenyl) xanthene with corresponding yields of 81% and 80.5%. Their structures were characterized by elemental analysis, FTIR, 1H NMR and 13C NMR spectra. The present method has advantages such as mild reaction conditions, convenient manipulation and good yield.

(Institute of Chemistry and Chemical Engineering,Jiangxi Normal University,Nanchang 330022)

以呫吨酮为原料，经二氯亚砜氯化得到9,9-二氯呫吨中间体，无需分离纯化，将其分别与邻甲酚和2,6-二甲基苯酚进行取代反应，制得2个含呫吨结构的双酚化合物9,9-二(4-羟基-3-甲基苯基)呫吨和9,9-二(4-羟基-3,5-二甲基苯基) 呫吨，产率分别为81.0%和80.5%。用FTIR、1H NMR、13C NMR和元素分析对其组成和结构进行了表征。该法具有操作简单、反应条件温和及收率高等优点。

2001

0.0

0.773

ZHANG

Zhuxia

, LYU

Rongwen

, ZHANG

Keke

, et al. Reduction of Aromatic Nitro Compounds with Hydrazine Hydrate[J]. Fine Chem, 2001, 18(4): 239-242(in Chinese).

张竹霞, 吕荣文, 张珂珂, 等. 水合肼还原芳硝基物的研究[J]. 精细化工, 2001, 18(4): 239-242.

以Pd/C为催化剂，水合肼为还原剂研究了P-硝基乙酰苯胺、P-硝基氯苯以及3-硝基-4-甲氧基乙酰苯胺的还原反应，反应在液相色谱跟踪下进行。80℃下P-硝基乙酰苯胺及P-硝基氯苯还原转化率达100％所需的条件分别为：n(P-NO2 C6H4HNCOCH3)：n(N2H4H2O)=1.0：1.6、催化剂用量11.33g/(mol p-硝基乙酰苯胺)、反应时间3 h；n(p-NO2C6H4Cl)：n(N2H2O)=1.0：1.8、催化剂用量10g/(molP-硝基氯苯)、反应时间20min；还原最终产物组成单一，均为相应的氨基物。 Abstract： p-Nitroacetanilied,p-nitrochlorobenzene and 3-nitro-4-methoxyacetanilied were reduced by hydrazine hydrate in the presence of Pd/C catalyst. The reduction of three aromatic nitro compounds was tracked by monitoring with HPLC. The conversion of p- nitroacetanilide and p-nitrochlorbenzene was 100％ when n(p-NO2C6H4NHCOCH3): n(N2H4H2O) = 1.0: 1.6,Pt/C = 11.33 g/mol p-nitroacetanilide,reaction time = 3 h and reaction temperature = 80 ℃, and n(NO2 NO2C6H4Cl):n(N2H4H2O) = 1.0:1.8,Pt/C = 10 g/mol p- nitrochlorbenzene, reaction time = 20 rmin and reaction temperature = 80 ℃.The final products were the corresponding amino compounds.