CN1785964B - Synthesis method of non symmetrical hydroazobenzene - Google Patents
Synthesis method of non symmetrical hydroazobenzene Download PDFInfo
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- CN1785964B CN1785964B CN 200410100847 CN200410100847A CN1785964B CN 1785964 B CN1785964 B CN 1785964B CN 200410100847 CN200410100847 CN 200410100847 CN 200410100847 A CN200410100847 A CN 200410100847A CN 1785964 B CN1785964 B CN 1785964B
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- dinitrofluorobenzene
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- 238000001308 synthesis method Methods 0.000 title abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 150000004031 phenylhydrazines Chemical class 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 7
- 229940067157 phenylhydrazine Drugs 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000012434 nucleophilic reagent Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 8
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 claims 4
- 229910052757 nitrogen Inorganic materials 0.000 claims 4
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- LOTKRQAVGJMPNV-UHFFFAOYSA-N 1-fluoro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C([N+]([O-])=O)=C1 LOTKRQAVGJMPNV-UHFFFAOYSA-N 0.000 abstract description 6
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical class C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000012038 nucleophile Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000007405 data analysis Methods 0.000 description 4
- 238000010183 spectrum analysis Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical class NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- -1 aromatic diazonium salts Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明本发明属于一种不对称氢化偶氮苯的合成方法。该类化合物是重要的精细有机化工原料及重要的有机合成中间体，可用于染料工业、医药工业及用于制备相应的偶氮化合物，联苯胺类化合物等。本发明以2，4-二硝基氟苯为亲核底物，以苯肼类化合物为亲核试剂，以DMSO为溶剂，通过亲核取代反应合成了一系列不对称的氢化偶氮苯类化合物。本发明反应温度低(r.t-60℃)，反应时间短(0.5h)，化学收率高(93-98％)且产物结构具有多样性。The present invention The invention belongs to a synthesis method of unsymmetrical hydroazobenzene. Such compounds are important fine organic chemical raw materials and important organic synthesis intermediates, and can be used in the dye industry, pharmaceutical industry and for the preparation of corresponding azo compounds, benzidine compounds, etc. The present invention uses 2,4-dinitrofluorobenzene as a nucleophilic substrate, phenylhydrazine compounds as nucleophiles, and DMSO as a solvent to synthesize a series of asymmetric hydroazobenzenes through nucleophilic substitution reactions. compound. The invention has low reaction temperature (r.t-60° C.), short reaction time (0.5 h), high chemical yield (93-98%) and diverse product structures.
Description
本发明属于一种不对称氢化偶氮苯的合成方法。The invention belongs to a synthesis method of unsymmetrical hydroazobenzene.
本发明所属的不对称氢化偶氮苯类化合物为具有下列结构的黄色或桔黄色针状晶体：The asymmetric hydroazobenzene compounds of the present invention are yellow or orange needle-like crystals with the following structure:
式中R1、R2、R3、R4的结构见表一。已知这类化合物是重要的精细有机化工原料及重要的有机合成中间体，可用于染料工业、医药工业及用于制备相应的偶氮化合物，联苯胺类化合物等。用于该系列化合物合成的常规方法是通过取代偶氮苯还原或通过相应的亲核取代反应制备。前一种方法中对能与芳香族重氮盐进行偶联的底物有严格限制，产物中的R基只能是羟基、氨(胺)基或其它强的给电子基，产物结构缺乏多样性；后一种方法报道的甚少，且反应在室温条件下需要三～四天方能完成，收率仅为56～58％。The structures of R 1 , R 2 , R 3 , and R 4 in the formula are shown in Table 1. It is known that such compounds are important fine organic chemical raw materials and important organic synthesis intermediates, and can be used in the dye industry, pharmaceutical industry and for the preparation of corresponding azo compounds, benzidine compounds, etc. Conventional methods for the synthesis of this series of compounds are prepared by reduction of substituted azobenzenes or by corresponding nucleophilic substitution reactions. In the former method, there are strict restrictions on the substrates that can be coupled with aromatic diazonium salts. The R group in the product can only be hydroxyl, ammonia (amine) group or other strong electron-donating groups, and the product structure lacks diversity. property; the latter method is rarely reported, and the reaction takes three to four days to complete at room temperature, and the yield is only 56 to 58%.
本发明的目的，在于提出一种新的合成方法。该方法反应温度低，反应时间短，化学收率高且产物结构具有多样性。The purpose of the present invention is to propose a new synthetic method. The method has low reaction temperature, short reaction time, high chemical yield and diverse product structures.
本发明的特征在于以2，4-二硝基氟苯为亲核底物，以取代苯肼为亲核试剂，以二甲亚砜为溶剂，通过亲核取代反应合成了一系列不对称的氢化偶氮苯类化合物。化学反应方程式如下：The present invention is characterized in that 2,4-dinitrofluorobenzene is used as nucleophilic substrate, substituted phenylhydrazine is used as nucleophilic reagent, and dimethyl sulfoxide is used as solvent to synthesize a series of asymmetric Hydrazobenzene compounds. The chemical reaction equation is as follows:
表一R1----R4的位置与结构Table 1 The position and structure of R 1 ----R 4
反应体系中物料的摩尔比为：2，4-二硝基氟苯∶取代苯肼＝1∶1.1The molar ratio of materials in the reaction system is: 2,4-dinitrofluorobenzene: substituted phenylhydrazine=1:1.1
反应过程中，反应温度为室温-60℃。其中3a-3j的合成在室温条件下进行，3k-3l的合成在分别在40℃和60℃条件下进行。During the reaction, the reaction temperature is room temperature-60°C. The synthesis of 3a-3j was carried out at room temperature, and the synthesis of 3k-3l was carried out at 40°C and 60°C, respectively.
本发明选用二甲亚砜为溶剂，反应过程中是将2，4-二硝基氟苯首先用适量的二甲亚砜稀释，然后滴加到取代的苯肼中进行反应。二甲亚砜既对底物中F-离子的离去有很好的促进作用，又有利于产物的后处理。In the present invention, dimethyl sulfoxide is selected as the solvent. During the reaction, 2,4-dinitrofluorobenzene is firstly diluted with an appropriate amount of dimethyl sulfoxide, and then dropped into substituted phenylhydrazine for reaction. Dimethyl sulfoxide can not only promote the departure of F- ions in the substrate, but also facilitate the post-treatment of the product.
其中3a-3j的重结晶用氯仿作溶剂，3k-3l的重结晶用氯仿和二甲亚砜的混合溶剂进行。The recrystallization of 3a-3j uses chloroform as a solvent, and the recrystallization of 3k-3l uses a mixed solvent of chloroform and dimethyl sulfoxide.
本发明反应时间为0.5h，化学收率93-98％。产物结构经元素分析和IR、1H NMR确证。产物的收率、物理性质见表二；产物的光谱分析数据及元素分析结果见表三。The reaction time of the present invention is 0.5h, and the chemical yield is 93-98%. The structure of the product was confirmed by elemental analysis and IR, 1 H NMR. The yield and physical properties of the product are shown in Table 2; the spectral analysis data and elemental analysis results of the product are shown in Table 3.
下面通过实施例对本发明作进一步的叙述。The present invention is described further below by embodiment.
实施例1：2，4-二硝基氢化偶氮苯的合成Embodiment 1: the synthesis of 2,4-dinitrohydroazobenzene
在带有回流冷凝管和滴液漏斗的三颈瓶中加入1.1ml(0.011mol)苯肼和15ml二甲亚砜，室温和电磁搅拌下滴加用5ml二甲亚砜稀释的1.26ml(0.01mol)的2，4-二硝基氟苯，15min滴加完毕，继续搅拌15min终止反应(反应过程经薄层色谱跟踪并确定终点)。加入2倍体积的蒸馏水，有黄色固体析出，抽滤，滤饼经乙醇、乙醚洗涤后干燥，再用氯仿进行重结晶，得到黄色针状晶体2.67g，收率97％，m.p：119～120℃。光谱分析数据及元素分析结果表明该化合物为2，4-二硝基氢化偶氮苯(3a)。Add 1.1ml (0.011mol) phenylhydrazine and 15ml dimethyl sulfoxide to a three-necked flask with a reflux condenser and a dropping funnel, and add 1.26ml (0.01 mol) diluted with 5ml dimethyl sulfoxide dropwise at room temperature and under electromagnetic stirring. mol) of 2,4-dinitrofluorobenzene, the dropwise addition was completed in 15 minutes, and the reaction was continued to be stirred for 15 minutes to terminate the reaction (the reaction process was tracked by thin-layer chromatography and the end point was determined). Add 2 times the volume of distilled water, a yellow solid precipitated, suction filtered, the filter cake was washed with ethanol and ether, dried, and then recrystallized with chloroform to obtain 2.67 g of yellow needle-shaped crystals, with a yield of 97%, m.p: 119-120 ℃. Spectral analysis data and elemental analysis results showed that the compound was 2,4-dinitrohydroazobenzene (3a).
实施例2：2，4-二硝基--2′，4′--二硝基氢化偶氮苯的合成Example 2: Synthesis of 2,4-dinitro--2', 4'--dinitrohydroazobenzene
在带有回流冷凝管和滴液漏斗的三颈瓶中加入2.18g(0.011mol)2，4-二硝基苯肼和15ml二甲亚砜，60℃和电磁搅拌下滴加用5ml二甲亚砜稀释的1.26ml(0.01mol)的2，4-二硝基氟苯，15min滴加完毕，继续搅拌15min终止反应(反应过程经薄层色谱跟踪并确定终点)。反应液冷至室温后加入2倍体积的蒸馏水，有黄色固体析出，抽滤，滤饼经乙醇、乙醚洗涤后干燥，用氯仿和二甲亚砜的混合溶剂进行重结晶，得到黄色针状晶体3.57g，收率98％，m.p：250～251℃。光谱分析数据及元素分析结果表明该化合物为2，4-二硝基-2′，4′-二硝基氢化偶氮苯(3l)。Add 2.18g (0.011mol) 2,4-dinitrophenylhydrazine and 15ml dimethyl sulfoxide to a three-necked flask with a reflux condenser and a dropping funnel, add 5ml dimethyl sulfoxide dropwise at 60°C and electromagnetic stirring 1.26ml (0.01mol) of 2,4-dinitrofluorobenzene diluted with sulfoxide was added dropwise within 15 minutes, and the reaction was continued to be stirred for 15 minutes to terminate the reaction (the reaction process was tracked by thin-layer chromatography and the end point was determined). After the reaction solution was cooled to room temperature, 2 times the volume of distilled water was added, a yellow solid was precipitated, filtered with suction, the filter cake was washed with ethanol and ether, dried, and recrystallized with a mixed solvent of chloroform and dimethyl sulfoxide to obtain yellow needle-like crystals 3.57g, yield 98%, m.p: 250-251°C. Spectral analysis data and elemental analysis results showed that the compound was 2,4-dinitro-2',4'-dinitrohydroazobenzene (3l).
表二产物的收率、熔点及外观Yield, melting point and appearance of table two products
表三产物的光谱分析数据及元素分析结果Spectral analysis data and elemental analysis results of the products in Table 3
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032657A (en) * | 1987-10-23 | 1989-05-03 | 河南省科学院化学研究所 | The method for preparing diphenyl hydrozine |
| SU1616904A1 (en) * | 1988-05-04 | 1990-12-30 | Институт Органической Химии Ан Усср | Method of producing n-nitrophenylhydrazine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032657A (en) * | 1987-10-23 | 1989-05-03 | 河南省科学院化学研究所 | The method for preparing diphenyl hydrozine |
| SU1616904A1 (en) * | 1988-05-04 | 1990-12-30 | Институт Органической Химии Ан Усср | Method of producing n-nitrophenylhydrazine |
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