CN1785964A - Synthesis method of non symmetrical hydroazobenzene - Google Patents
Synthesis method of non symmetrical hydroazobenzene Download PDFInfo
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- CN1785964A CN1785964A CN 200410100847 CN200410100847A CN1785964A CN 1785964 A CN1785964 A CN 1785964A CN 200410100847 CN200410100847 CN 200410100847 CN 200410100847 A CN200410100847 A CN 200410100847A CN 1785964 A CN1785964 A CN 1785964A
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Abstract
The present invention uses 2,4-dinitrofluorobenzene as nucleophilic substrate, uses phenyl hydrazine compound as nucleophilic reagent, uses DMSO as solvent and adopts nucleophilic substitution reaction to synthesize a series of asymmetrical hydrogenated azobenzenes compounds. Its reaction temperature is 60deg.C, reaction time is 0.5h and its chemical yield is 93-98%.
Description
The invention belongs to a kind of synthetic method of asymmetric hydrogenation nitrogen benzide.
Asymmetric hydrogenation azobenzene compound under the present invention is yellow or the orange needle-like crystal with following array structure:
R in the formula
1, R
2, R
3, R
4Structure see Table one.Known this compounds is important meticulous Organic Chemicals and important organic synthesis intermediate, can be used for dyestuffs industries, medicine industry and is used to prepare corresponding azo-compound, diphenyl amine compound etc.Being used for this series compound synthetic ordinary method is by replacing the nitrogen benzide reduction or preparing by corresponding nucleophilic substitution reaction.To carrying out the link coupled substrate with the aromatic series diazonium salt strict restriction is arranged in preceding a kind of method, the R base in the product can only be hydroxyl, ammonia (amine) base or other strong donor residues, the product structure lack of diversity; Back a kind of method report very few, and reaction needed to finish at ambient temperature in three～four days, and yield only is 56～58%.
Purpose of the present invention is to propose a kind of new synthetic method.This method temperature of reaction is low, and the reaction times is short, and chemical yield height and product structure have diversity.
The invention is characterized in that with 2 the 4-dinitrofluorobenzene is the nucleophilic substrate, is nucleophilic reagent with the phenylhydrazine compounds, is solvent with DMSO, synthesized a series of asymmetric hydrodiazo benzene-like compounds by nucleophilic substitution reaction.Chemical equation is as follows:
The position of the various R of table one and structure
| Entry | R1 | R2 | R3 | R4 | Entry | R1 | R2 | R3 | R4 |
| 3a 3b 3c 3d 3e 3f | H CH3 H H CH3 H | H H CH3 H H H | H H H CH3 H F | H H H H CH3 H | 3g 3h 3i 3j 3k 3l | H H Cl Br H NO2 | H H H H H H | Cl Br H H NO2 NO2 | H H H H H H |
The mol ratio of material is in the reaction system: 2, and 4-dinitrofluorobenzene: substituted phenylhydrazines=1: 1.1
In the reaction process, temperature of reaction is r.t-60 ℃.Wherein the synthetic of 3a-3j carries out at ambient temperature, and synthesizing of 3k-31 carried out under 40 ℃ and 60 ℃ of conditions respectively.
It is solvent that the present invention selects DMSO for use, and DMSO is both to F in the substrate
-The ionic good promoter action of having left away helps the aftertreatment of product again.
Reaction times of the present invention is 0.5h, chemical yield 93-98%.Product structure through ultimate analysis and IR,
1H NMR conclusive evidence.Yield, the physical properties of product see Table two; The spectral analysis data and the results of elemental analyses of product see Table three.
Below by embodiment the present invention is further described below.
Embodiment 1:2,4-dinitrobenzene hydrazobenzene synthetic
In the three-necked bottle that has reflux condensing tube and dropping funnel, add 1.1ml (0.011mol) phenylhydrazine and 15mlDMSO, 2 of the 1.26ml (0.01mol) that dropping usefulness 5ml DMSO dilutes under room temperature and the induction stirring, the 4-dinitrofluorobenzene, 15min dropwises, and continues to stir 15min termination reaction (reaction process is through the TLC tracking and determine terminal point).Add the distilled water of 2 times of volumes, have yellow solid to separate out, suction filtration, filter cake carries out recrystallization through ethanol, ether washing after drying with chloroform, obtains yellow needle-like crystal 2.67g, yield 97%, m.p:119～120 ℃.Spectral analysis data and results of elemental analyses show that this compound is 2,4-dinitrobenzene hydrazobenzene (3a).
Embodiment 2:2,4-dinitrobenzene-2 ', 4 '-dinitrobenzene hydrazobenzene synthetic
In the three-necked bottle that has reflux condensing tube and dropping funnel, add 2.18g (0.011mol) 2,4-dinitrophenylhydrazine and 15ml DMSO, drip under 60 ℃ and the induction stirring with 2 of the 1.26ml (0.01mol) of 5ml DMSO dilution, the 4-dinitrofluorobenzene, 15min dropwises, and continues to stir 15min termination reaction (reaction process is through the TLC tracking and determine terminal point).Reaction solution is chilled to the distilled water that adds 2 times of volumes after the room temperature, has yellow solid to separate out, suction filtration, filter cake is through ethanol, ether washing after drying, carries out recrystallization with the mixed solvent of chloroform and DMSO, obtains yellow needle-like crystal 3.57g, yield 98%, m.p:250～251 ℃.Spectral analysis data and results of elemental analyses show that this compound is 2,4-dinitrobenzene-2 ', 4 '-dinitrobenzene hydrazobenzene (31).
The yield of table two product, fusing point and outward appearance
| Product | Yield (%) | Fusing point (℃) | Outward appearance |
| 3a 3b 3c 3d 3e 3f 3g 3h 3i 3j 3k 3l | 97 96 97 95 96 97 95 96 96 95 80 65 | 119-120 101-102 100-101 101-102 193-194 125-126 128-129 138-139 124-125 152-153 199-200 250-251 | The yellow acicular crystal of the yellow acicular crystal orange colour of the yellow acicular crystal acicular crystal yellow acicular crystal of the yellow acicular crystal of the yellow acicular crystal of the yellow acicular crystal of the yellow acicular crystal of the yellow acicular crystal of the yellow acicular crystal of orange colour acicular crystal |
The spectral analysis data of table three product and results of elemental analyses
| Compound | IR(KBr) ν(cm -1) | H NMR，δ(ppm) | Elementary analysis (%) measured value (theoretical value) | ||
| C | H | N | |||
| 3a | 3337， 3110， 1625 | 9.60(s，1H)，9.16(d，1H，)，8.30(dd， 1H)7.65(d，1H)，7.33(m，2H)，7.02(m ，1H)6.86(d，2H)，5.99(s，1H) | 52.26 (52.56) | 3.30 (3.68) | 20.08 (20.43) |
| 3b | 3338，3112， 2928，2857， 1626 | 9.53(s，1H)，9.17(d，1H，)，8.29(dd， 1H)7.63(d，1H)，7.18(m，2H)，6.94(d ，1H)，6.77(d，1H)，5.91(s，1H)2.34( s，3H) | 54.49 (54.16) | 4.00 (4.20) | 19.58 (19.44) |
| 3c | 3331，3106， 2922，2870， 1622 | 9.53(s，1H)，9.16(d，1H，)，8.29(dd， 1H)7.65(d，1H)，7.19(m，1H)，6.83(d ，1H)，6.65(d，2H)，5.93(s，1H)2.33( s，3H) | 53.54 (54.16) | 4.08 (4.20) | 9.61 (19.44) |
| 3d | 3331，3105， 2928，2874， 1621 | 9.59(s，1H)，9.17(d，1H，)，8.29(dd， 1H)7.67(d，1H)，7.12(d，2H)，6.76(d ，2H)，，5.87(s，1H)2.32(s，3H) | 54.51 (54.16) | 4.02 (4.20) | 19.66 (19.44) |
| 3e | 3337，3110， 2928，2863， 1625 | 9.56(s，1H)，9.19(d，1H，)，8.30(dd， 1H)7.64(d，1H)，7.08(d，1H)， 6.76(d，1H)，，6.58(s，1H)，5.82(s， 1H)，2.27(d，6H) | 55.19 (55.63) | 4.37 (4.67) | 18.06 (18.54) |
| 3f | 3327， 3099， 1623 | 9.60(s，1H)，9.17(d，1H，)，8.32(dd， 1H)7.66(d，1H)，7.02(m，2H)， 6.82(m，2H)，5.92(s，1H)， | 49.14 (49.32) | 2.92 (3.10) | 19.45 (19.17) |
| 3g | 3326， 3112， 1622 | 9.59(s，1H)，9.17(d，1H，)，8.31(dd， 1H)7.60(d，1H)，7.26(d，2H)， 6.80(m，2H)，5.99(s，1H)， | 46.39 (46.69) | 2.66 (2.94) | 7.86 (18.15) |
| 3h | 3325， 3109， 1622 | 9.58(s，1H)，9.17(d，1H，)，8.35(dd， 1H)7.60(d，1H)，7.40(d，2H)， 6.75(d，2H)，5.98(s，1H)， | 40.53 (40.81) | 2.38 (2.57) | 15.57 (15.87) |
| 3i | 3348， 3110， 1620 | 9.57(s，1H)，9.19(d，1H，)，8.33(dd， 1H)7.60(d，1H)，7.40(d，1H)，7.21(m ，1H)，6.95(m，1H)，6.84(d，1H)， 6.50(s，1H)， | 46.35 (46.69) | 2.61 (2.94) | 17.81 (18.15) |
| 3j | 3377， 3113， 1621 | 9.59(s，1H)，9.19(d，1H，)，8.33(dd， 1H)，7.57(d，2H)，7.21(m，2H)，7.26( m，1H)，6.87(m，2H)，6.51(s，1H)， | 40.51 (40.81) | 2.30 (2.57) | 15.49 (15.87) |
| 3k | 3310， 3116， 1621 | 10.38(s，1H)，9.48(s，1H，)，8.90(dd ，1H，)，8.33(dd，1H)，8.10(m，2H)， 7.31(d，1H)6.87(m，2H)，6.92(d，2H) | 44.78 (45.15) | 2.662 (2.84) | 21.60 (21.94) |
| 3l | 3321，3105， 1615 | 10.52(s，2H)，8.92(d，2H，)， 8.30(dd，2H，)，7.40(d，2H) | 39.50 (39.57) | 2.00 (2.21) | 23.01 (23.07) |
Claims (4)
1. the synthetic method of an asymmetric hydrogenation nitrogen benzide.The structural formula of this series compound is:
Formula kind R base is respectively hydrogen, methyl, halogen (fluorine, chlorine, bromine) and nitro.It is characterized in that with 2 the 4-dinitrofluorobenzene is the nucleophilic substrate, is nucleophilic reagent with the phenylhydrazine compounds, is solvent with DMSO, synthesized a series of asymmetric hydrodiazo benzene-like compounds by nucleophilic substitution reaction.
2. according to the synthetic method of the described asymmetric hydrogenation nitrogen benzide of claim 1, reaction process 2, the mol ratio of 4-dinitrofluorobenzene and substituted phenylhydrazines are 1: 1.1; Temperature of reaction is r.t-60 ℃; 0.5h during reaction; Chemical equation is as follows.
The synthetic of 3a-3j carries out at ambient temperature, and the synthetic of 3k-3l carries out under 40 ℃ and 60 ℃ of conditions respectively.
3. according to the synthetic method of claim 1 or 2 described asymmetric hydrogenation nitrogen benzides, selecting DMSO for use is solvent, is with 2 in the reaction process, and the 4-dinitrofluorobenzene is at first with an amount of DMSO dilution, is added drop-wise to then in the phenylhydrazine of replacement to react.
4. according to the synthetic method of claim 1 or 2 or 3 described asymmetric hydrogenation nitrogen benzides, the recrystallization of 3a-3j chloroform give solvent, the recrystallization of 3k-3l carries out with the mixed solvent of chloroform and DMSO.
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| 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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Inventor after: Jin Chunxue Inventor after: Chen Qiang Inventor after: Shen Jiuming Inventor before: Jin Chunxue Inventor before: Chen Qiang Inventor before: Cao Shuqin |
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