CN104016869B - 2,4, 6-trinitro-1, 3-di (2 ', 4', 6 '-trinitro-3' -hydroxystyryl) benzene, synthetic method and application - Google Patents
2,4, 6-trinitro-1, 3-di (2 ', 4', 6 '-trinitro-3' -hydroxystyryl) benzene, synthetic method and application Download PDFInfo
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- RHVPXDSHELBTLG-UHFFFAOYSA-N 3-[2-[3-[2-(3-hydroxy-2,4,6-trinitrophenyl)ethenyl]-2,4,6-trinitrophenyl]ethenyl]-2,4,6-trinitrophenol Chemical compound [N+](=O)([O-])C1=C(C(=CC(=C1C=CC1=C(C(=C(C=C1[N+](=O)[O-])[N+](=O)[O-])O)[N+](=O)[O-])[N+](=O)[O-])[N+](=O)[O-])C=CC1=C(C(=C(C=C1[N+](=O)[O-])[N+](=O)[O-])O)[N+](=O)[O-] RHVPXDSHELBTLG-UHFFFAOYSA-N 0.000 title abstract 2
- 238000010189 synthetic method Methods 0.000 title description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000006277 sulfonation reaction Methods 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 13
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical group C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 11
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 abstract description 6
- 235000021286 stilbenes Nutrition 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 5
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 238000005474 detonation Methods 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- BJZZCHRYTNIBCS-YXLFCKQPSA-N 1,3-bis[(e)-2-phenylethenyl]benzene Chemical compound C=1C=CC=CC=1/C=C/C(C=1)=CC=CC=1\C=C\C1=CC=CC=C1 BJZZCHRYTNIBCS-YXLFCKQPSA-N 0.000 abstract 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 102
- 239000000047 product Substances 0.000 description 14
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- GGGVOOMKPJYWDF-UHFFFAOYSA-N 2,4,6-trinitroxylene Chemical group CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C)=C1[N+]([O-])=O GGGVOOMKPJYWDF-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- -1 nitros stilbene compound Chemical class 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 101100391174 Dictyostelium discoideum forC gene Proteins 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- XHJPTLWIOZRBQB-UHFFFAOYSA-N 1,3,5-trinitro-2-(2,4,6-trinitrophenyl)sulfanylbenzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1SC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O XHJPTLWIOZRBQB-UHFFFAOYSA-N 0.000 description 1
- WUUKBGNBCAPHPJ-UHFFFAOYSA-N 1,3-dimethyl-2,4,5-trinitrobenzene Chemical class CC1=CC([N+]([O-])=O)=C([N+]([O-])=O)C(C)=C1[N+]([O-])=O WUUKBGNBCAPHPJ-UHFFFAOYSA-N 0.000 description 1
- 244000178924 Brassica napobrassica Species 0.000 description 1
- 235000011297 Brassica napobrassica Nutrition 0.000 description 1
- 0 CCC(CCC(C*)C(*)*([N+])=C)*=C Chemical compound CCC(CCC(C*)C(*)*([N+])=C)*=C 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an unknown compound 2,4, 6-trinitro-1, 3-di (2 ', 4', 6 '-trinitro-3' -hydroxystyryl) benzene and a synthesis method thereof. The chemical structure of the compound is characterized in that: three nitro groups are arranged at the 2,4 and 6 positions on the middle benzene ring of the 1, 3-distyrylbenzene, the 2,4 and 6 positions on the two sides of the benzene ring are respectively connected with one nitro group, and simultaneously, a hydroxyl group is connected at the meta position. From the nuclear magnetic spectrum, the coupling constant of the stilbene double bond was about 16.75Hz, and it was confirmed that the double bond was in a trans-form. The compound is synthesized by adopting three steps of reactions, and the method has the advantages of simple operation, mild reaction conditions and higher yield. The compound has good heat resistance and detonation performance, and belongs to the field of energetic materials.
Description
Technical field
The present invention relates to a kind of compound, preparation method and application thereof, be specifically related to a kind of compound 2,4,6-trinitro--1,3-bis-(2 ', 4 ', 6 '-trinitro--3 '-hydroxystyrene based) benzene and synthetic method thereof, this compound is applied to energetic material field.
Background technology
Many nitros stilbene compound (Polynitrostilbenes) is the very important chemical intermediate of one, can be widely used in the field of nonlinear optics and the heat-resisting energetic material of high energy.Such as it can be used for synthesizing new part for nonlinear optical material and the high temperature powder being used as military and civilian.Wherein, performance significant picryl sulfide base ethene (HNS) belongs to the one in many nitros stilbene compound, it is yellow crystals, and fusing point, up to 317 DEG C, is a kind of high temperature powder, there is good physics, chemical stability, mechanical sensitivity is low, insensitive to static sparking, and radiation resistance is strong, by being first made up of Swede K.G.Shipp the sixties in last century, being widely used in the field such as oilfield exploitation and aerospace.
Document (G.X.Wang, C.H.Shi, X.D.Gong, H.M.Xiao, J.Phys.Chem.A2009,113,1318) performance such as structure, density, detonation parameter of many nitro toluylenes derivative by theoretical research, such material exhibits goes out very strong applicability.Document (Z.FengandB.Chen, Prop., Explos., Pyrotech., 1991,16,12; Z.FengandB.Chen, Prop., Explos., Pyrotech.1992,17,237; L.Wang, Y.Liu, J.Zhang, T.Zhang, L.Yang, X.Qiao, X.HuandJ.Guo, Chin.J.Chem.2007,25,1044, J.Xu, F.Li, J.Wei, X.Peng, J.Chem.Res.2014,38,240-244.) also report and synthesized the compound of a series of many nitro toluylenes, such compound structure is special, superior performance, simultaneously owing to having C=C double bond, makes whole molecular system have stronger conjugative effect, thus the fusing point of this compounds can be promoted, i.e. resistance toheat.So there is extremely important status and meaning in the synthesis of the compound building many nitros diphenylethlene class novel under other conjugated system.And along with the introducing of more nitro functions, its density (energy) and corresponding heat resisting temperature can be significantly improved, thus meet the needs of development.
Summary of the invention
The object of the present invention is to provide a kind of many nitros stilbene compound 2,4,6-trinitro--1,3-bis-(2 ', 4 ', 6 '-trinitro--3 '-hydroxystyrene based) benzene, and provide the synthetic method of this material, and this compound be can be applicable to energetic material field.
Realizing the object of the invention technical scheme is:
Compound 2,4,6-trinitro--1,3-bis-(3 '-hydroxystyrene based) benzene, has chemical structural formula shown in formula (I):
The preparation method of compound shown in formula (I): by 2,4,6-trinitro-m-xylene mixes with m-hydroxybenzaldehyde and drops in reactor, then benzene and dioxane mixed solvent is added as reaction medium, add alkali again as catalyzer, be warming up to back flow reaction, reaction terminates rear underpressure distillation removing excess of solvent, is then separated by the oily liquids of gained and obtains bright yellow solid product.
Further, 2,4,6-described trinitro-m-xylenes and the mol ratio of m-hydroxybenzaldehyde are 1: 2.1, and in mixed solvent, the volume ratio of benzene and dioxane is 1: 1, and the reaction times is greater than 10h.
Further, described alkali is selected from one or more in N methyl piperazine, morpholine, triethylamine, pyridine or piperidines.
Compound 2,4,6-trinitro--1,3-bis-(2 ', 4 ', 6 '-trinitro--3 '-hydroxystyrene based) benzene, there is chemical structural formula shown in formula (II):
The preparation method of compound shown in formula (II), comprises the following steps:
The first step, first the compound of formula (I) structure at room temperature to be dissolved in concentrated sulfuric acid, oleum is dripped as sulfonated reagent to reaction solution, be warming up to 90-100 DEG C of reaction after stirred at ambient temperature, be cooled to room temperature after reaction terminates, obtain sulfonation reaction liquid for subsequent use;
Second step, the sulfonation reaction liquid that the first step is obtained, slowly drop in concentrated nitric acid/vitriol oil mixed solution under low temperature, stirred at ambient temperature reacts, then 50-60 DEG C of reaction is warming up to, after reaction terminates, reaction solution is poured in frozen water mixed solution, separate out yellow solid, dry, recrystallization obtains the target product of formula (II) structure.
Further, the oleum mass concentration in the first step is 30%, and the reaction times is greater than 2h.
Further, in the nitric acid in second step/vitriol oil mixed solution, concentrated nitric acid and vitriol oil volume ratio are 1: 1, and the reaction times is greater than 1h.
Compound shown in formula (II) structure is applied in the heat-resisting energetic material of synthesis.
The present invention compared with prior art, its remarkable advantage is: (1) synthesizes a kind of many nitros stilbene compound 2,4,6-trinitro--1,3-bis-(2 ', 4 ', 6 '-trinitro--3 '-hydroxystyrene based) benzene, this melting point compound, higher than 210 DEG C, can be applicable to heat-resisting energetic material; (2) structure, this compound has the compound that nine nitros also have two double bonds simultaneously, the existence of multiple nitro, ensure that the energy of this compound, the existence of two double bonds, can promote the conjugation performance of whole molecule, promotes the resistance toheat of material; (3) provide the synthetic method of this material, and described method is simple to operate, reaction conditions is gentle, and productive rate is higher simultaneously.Below in conjunction with accompanying drawing, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance collection of illustrative plates of product 2,4,6-trinitro--1,3-bis-(3 '-hydroxystyrene based) benzene, and X-coordinate is chemical shift.
Fig. 2 is the nuclear magnetic resonance of carbon collection of illustrative plates of product 2,4,6-trinitro--1,3-bis-(3 '-hydroxystyrene based) benzene, and X-coordinate is chemical shift.
Fig. 3 is the high resolution mass spectrum collection of illustrative plates of product 2,4,6-trinitro--1,3-bis-(3 '-hydroxystyrene based) benzene.
Fig. 4 is the hydrogen nuclear magnetic resonance collection of illustrative plates of target product 2,4,6-trinitro--1,3-bis-(2 ', 4 ', 6 '-trinitro--3 '-hydroxystyrene based) benzene, and X-coordinate is chemical shift.
Fig. 5 is the nuclear magnetic resonance of carbon collection of illustrative plates of target product 2,4,6-trinitro--1,3-bis-(2 ', 4 ', 6 '-trinitro--3 '-hydroxystyrene based) benzene, and X-coordinate is chemical shift.
Fig. 6 is the high resolution mass spectrum collection of illustrative plates of target product 2,4,6-trinitro--1,3-bis-(2 ', 4 ', 6 '-trinitro--3 '-hydroxystyrene based) benzene.
Embodiment
The following examples can make the present invention of those skilled in the art comprehend.
The method of a kind of synthesis 2,4,6-trinitro--1,3-bis-(2 ', 4 ', 6 '-trinitro--3 '-hydroxystyrene based) benzene, comprises the following steps:
The synthesis of (1) 2,4,6-trinitro--1,3-bis-(3 '-hydroxystyrene based) benzene
Reaction equation is:
Concrete steps are as follows:
By 2,4,6-trinitro-m-xylene and m-hydroxybenzaldehyde with mol ratio 1: 2.1 ratio mixed dissolution (volume ratio is for 1: 1) in benzene and dioxane, add triethylamine as catalyzer, water trap is installed simultaneously.Slow raised temperature, to backflow, controls return velocity and is about 100/min.Reaction process is monitored, when reaction almost complete (11h) stopped reaction by TLC.Underpressure distillation remove portion solvent, by concentrated solution by pillar layer separation, (n-hexane/ethyl acetate=5: 1), it is for subsequent use that separation obtains bright yellow solid to developping agent ratio.
The sulfonation of (2) 2,4,6-trinitro--1,3-bis-(3 '-hydroxystyrene based) benzene
Concrete steps are as follows:
First by 2,4,6-trinitro--1, dissolve in concentrated sulfuric acid under 3-bis-(3 '-hydroxystyrene based) benzene room temperature, drip 30wt% oleum as sulfonated reagent to reaction solution, stirred at ambient temperature 15min forms dark brown solution, is then warming up to 90-100 DEG C, be cooled to room temperature after being incubated 2h at such a temperature, obtain sulfonation reaction liquid for subsequent use;
The synthesis of (3) 2,4,6-trinitro-s-1,3-bis-(2 ', 4 ', 6 '-trinitro--3 '-hydroxystyrene based) benzene
Reaction equation is:
Concrete steps are as follows:
Second step is obtained 2,4,6-trinitro--1, the sulfonation reaction liquid of 3-bis-(3 '-hydroxystyrene based) benzene, slowly drop in the concentrated nitric acid (65-68wt%) and the vitriol oil (98wt%) mixed solution prepared under low temperature, volume ratio is 1: 1, stirred at ambient temperature reacts, then be warming up to 50-60 DEG C, react 1.5h at such a temperature, solution colour becomes red by dark brown, reaction terminates this red reaction solution to pour in frozen water mixed solution, separate out yellow solid, dry, recrystallization obtains target product.
Wherein, catalyzer described in the first step is that one or more in N methyl piperazine, morpholine, triethylamine, pyridine, piperidines selected by alkaline catalysts.
Embodiment 1
By 2,4,6-trinitro-m-xylene (1.21g, 5.0mmol) with m-hydroxybenzaldehyde (1.28g, 10.5mmol) mixed dissolution is in 25mL benzene and 25mL dioxane, adds pyridine (0.08g) as catalyzer, installs water trap simultaneously.Slow raised temperature, to backflow, controls return velocity and is about 100/min.Reaction process is monitored, when reaction almost complete (10h) stopped reaction by TLC.Remove portion solvent (about 40mL), by concentrated solution by pillar layer separation, (n-hexane/ethyl acetate=5: 1), are separated and obtain bright yellow solid 2.00g for subsequent use, productive rate 90% developping agent ratio, for subsequent use.
Bright yellow solid, fusing point 194-196 DEG C, IR (ν, cm
-1): 3400,3095,1635,1609,1586,1514,1395,1323,972;
1hNMR (500MHz, DMSO-d
6), δ 9.60 (s, 2H), 9.00 (s, 1H), 7.29 (d, J=16.60Hz, 2H), 7.23 (t, J=7.85Hz, 2H), 6.98 (d, J=7.70Hz, 2H), 6.94 (s, 2H), 6.81-6.78 (dd, J
1=8.10Hz, J
2=1.75Hz, 2H), 6.78 (d, J=16.60Hz, 2H).
13cNMR (126MHz, DMSO-d
6), δ 157.26,149.90,145.98,136.58,135.74,129.96,129.49,122.13,117.87,116.63,116.31,112.99.HRMScalc.forC
22h
15n
3o
8(M+H)
+: 450.0968, found450.0975,511.0722 (M+Na+K).
First by 2,4, be dissolved under 6-trinitro--1,3-bis-(3 '-hydroxystyrene based) benzene (2.25g, 5.0mmol) room temperature in the 10mL vitriol oil, 30% oleum is dripped as sulfonated reagent to reaction solution, control temperature is lower than 30 DEG C, and stirred at ambient temperature 15min forms dark brown solution, is then warming up to 90 DEG C, be cooled to room temperature after being incubated 2h at such a temperature, obtain sulfonation reaction liquid product for subsequent use;
Second step is obtained 2,4,6-trinitro--1, the sulfonation reaction liquid of 3-bis-(3 '-hydroxystyrene based) benzene, slowly drop in the nitric acid (8mL) and sulfuric acid (8mL) mixed solution prepared under low temperature, stirred at ambient temperature reacts, then 50 DEG C are warming up to, react 1h at such a temperature, solution colour becomes red by dark brown, and reaction terminates this red reaction solution to pour in frozen water mixed solution, separate out yellow solid, drying, recrystallization obtains target product (1.51g, 42%).
The fusing point of this compound measures on microscopic digital melting point apparatus, and temperature rise rate is 8 DEG C/min.
Yellow solid, fusing point 209-210 DEG C, IR (ν, cm
-1): 3422,3212,3107,2908,1630,1595,1553,1451,1343,1167,966,923,825,778,754,701.
1hNMR (500MHz, DMSO-d
6), δ 8.96 (s, 1H), 8.74 (s, 2H), 8.27 (br, 2H), 7.06 (d, J=16.75Hz, 2H), 6.74 (d, J=16.75Hz, 2H).
13cNMR (126MHz, DMSO-d
6), δ 159.35,149.07,147.10,146.95,135.99,130.42,127.74,127.69,125.50,123.81,121.88,120.43.HRMScalc.forC
22h
9n
9o
20(M): 718.9174, found718.9176, elementalanalysis, calcd (%) forC
22h
9n
9o
20: C:36.73; H:1.26; N:17.52; Found, C:36.61; H:1.14; N:17.44.
The chemical structure characteristic of this compound is: on the middle phenyl ring of 1,3-diphenylethyllene benzene 2,4, and 6 have three nitros, and on the phenyl ring of both sides 2,4,6 are respectively connected with a nitro, is also connected with a hydroxyl in a position simultaneously.From nuclear magnetic spectrogram, the coupling constant of toluylene double bond is approximately 16.75Hz, confirms as transconfiguration.One has nine nitros and two double bonds and deposits.
Embodiment 2
By 2,4,6-trinitro-m-xylene (1.21g, 5.0mmol) with m-hydroxybenzaldehyde (1.28g, 10.5mmol) mixed dissolution is in 25mL benzene and 25mL dioxane, adds morpholine (0.08g) as catalyzer, installs water trap simultaneously.Slow raised temperature, to backflow, controls return velocity and is about 100/min.Reaction process is monitored, when reaction almost complete (10h) stopped reaction by TLC.Remove portion solvent (about 40mL), by concentrated solution by pillar layer separation, (n-hexane/ethyl acetate=5: 1), are separated and obtain bright yellow solid 1.84g for subsequent use, productive rate 84% developping agent ratio, for subsequent use.
Following synthetic method is according to reference example 1 step.
Embodiment 3
By 2,4,6-trinitro-m-xylene (1.21g, 5.0mmol) with m-hydroxybenzaldehyde (1.28g, 10.5mmol) mixed dissolution is in 25mL benzene and 25mL dioxane, adds morpholine (0.08g) as catalyzer, installs water trap simultaneously.Slow raised temperature, to backflow, controls return velocity and is about 100/min.Reaction process is monitored, when reaction almost complete (10h) stopped reaction by TLC.Remove portion solvent (about 40mL), by concentrated solution by pillar layer separation, (n-hexane/ethyl acetate=5: 1), are separated and obtain bright yellow solid 1.77g for subsequent use, productive rate 81% developping agent ratio, for subsequent use.
Following synthetic method is according to reference example 1 step.
Embodiment 4
Equally, 2,4,6-trinitro--1,3-bis-(3 '-hydroxystyrene based) benzene is prepared according to the method for example 1 before for subsequent use.
First by 2,4, be dissolved under 6-trinitro--1,3-bis-(3 '-hydroxystyrene based) benzene (1.2g, 2.5mmol) room temperature in the 8mL vitriol oil, 30% oleum is dripped as sulfonated reagent to reaction solution, control temperature is lower than 30 DEG C, and stirred at ambient temperature 15min forms dark brown solution, is then warming up to 90 DEG C, be cooled to room temperature after being incubated 2h at such a temperature, obtain sulfonation reaction liquid product for subsequent use; Second step is obtained 2,4,6-trinitro--1, the sulfonation reaction liquid of 3-bis-(3 '-hydroxystyrene based) benzene, slowly drop in the nitric acid (6mL) and sulfuric acid (6mL) mixed solution prepared under low temperature, stirred at ambient temperature reacts, then 50 DEG C are warming up to, react 1h at such a temperature, solution colour becomes red by dark brown, and reaction terminates this red reaction solution to pour in frozen water mixed solution, separate out yellow solid, drying, recrystallization obtains target product (0.81g, 51%).
Embodiment 5
Equally, 2,4,6-trinitro--1,3-bis-(3 '-hydroxystyrene based) benzene is prepared according to the method for example 1 before for subsequent use.
First by 2,4, be dissolved under 6-trinitro--1,3-bis-(3 '-hydroxystyrene based) benzene (1.2g, 2.5mmol) room temperature in the 8mL vitriol oil, 50% oleum is dripped as sulfonated reagent to reaction solution, control temperature is lower than 30 DEG C, and stirred at ambient temperature 15min forms dark brown solution, is then warming up to 90 DEG C, be cooled to room temperature after being incubated 2h at such a temperature, obtain sulfonation reaction liquid product for subsequent use; Second step is obtained 2,4,6-trinitro--1, the sulfonation reaction liquid of 3-bis-(3 '-hydroxystyrene based) benzene, slowly drop in the nitric acid (8mL) and sulfuric acid (8mL) mixed solution prepared under low temperature, stirred at ambient temperature reacts, then 60 DEG C are warming up to, react 1h at such a temperature, solution colour becomes red by dark brown, and reaction terminates this red reaction solution to pour in frozen water mixed solution, separate out yellow solid, drying, recrystallization obtains target product (0.86g, 56%).
2,4,6-trinitro-s-1,3-bis-(2 ' proposed by the invention, 4 ', 6 '-trinitro--3 '-hydroxystyrene based) benzene is one in many nitros stilbene compound, from structure, whole molecule has three phenyl ring, two double bonds, so have very strong conjugative effect; Have nine nitros containing energy group, two hydroxy functional groups, have and are similar to picric structure simultaneously, by Gaussian Computation, its performance, higher than conventional explosives TNT, measures gained melting point substance higher than 210 DEG C, so this material can as one heat-resisting energetic material effectively, performance is remarkable.
Claims (3)
1. a preparation method for formula II compound, comprises the following steps:
The first step, first the compound of formula I structure at room temperature to be dissolved in concentrated sulfuric acid, oleum is dripped as sulfonated reagent to reaction solution, 90-100 DEG C of reaction is warming up to after stirred at ambient temperature, room temperature is cooled to after reaction terminates, obtain sulfonation reaction liquid for subsequent use, wherein, the compound of formula I structure is as follows:
Second step, the sulfonation reaction liquid that the first step is obtained, slowly drop under low temperature in the mixed solution of 65-68wt% concentrated nitric acid and the 98wt% vitriol oil, stirred at ambient temperature reacts, then be warming up to 50-60 DEG C of reaction, after reaction terminates, reaction solution poured in frozen water mixed solution, separate out yellow solid, dry, recrystallization obtains the target product of formula II structure, and wherein, the compound of formula II structure is as follows:
2. the preparation method of compound as claimed in claim 1, it is characterized in that, the oleum mass concentration in the first step is 30%, and the reaction times is greater than 2h.
3. the preparation method of compound as claimed in claim 1, it is characterized in that, in the concentrated nitric acid in second step/vitriol oil mixed solution, concentrated nitric acid and vitriol oil volume ratio are 1:1, and the reaction times is greater than 1h.
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