CN102229574A - 3-benzotriazole-substituted-1-(1,3-diaryl) propylene compound, synthesis method and use thereof - Google Patents
3-benzotriazole-substituted-1-(1,3-diaryl) propylene compound, synthesis method and use thereof Download PDFInfo
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- 0 C[C@](C(C)(C)C(C)=*)N=C(*)c(cccc1)c1P(c1ccccc1)c1ccccc1 Chemical compound C[C@](C(C)(C)C(C)=*)N=C(*)c(cccc1)c1P(c1ccccc1)c1ccccc1 0.000 description 3
- KSYNERBUJUEZJQ-COBSHVIPSA-N CC(C)[C@@H]1NC(C)OC1 Chemical compound CC(C)[C@@H]1NC(C)OC1 KSYNERBUJUEZJQ-COBSHVIPSA-N 0.000 description 1
- XSWSOVRKAZQVPT-WJISXQBPSA-N CC(C1)C=Cc2c1nn[n]2C(/C=C/C(/C)=C/C(C)=C)C(C=C(C)C)=C Chemical compound CC(C1)C=Cc2c1nn[n]2C(/C=C/C(/C)=C/C(C)=C)C(C=C(C)C)=C XSWSOVRKAZQVPT-WJISXQBPSA-N 0.000 description 1
- VUBYVTXCBRBLKU-UHFFFAOYSA-N CCCC(C)[n]1nnc2ccccc12 Chemical compound CCCC(C)[n]1nnc2ccccc12 VUBYVTXCBRBLKU-UHFFFAOYSA-N 0.000 description 1
- PWORFEDVDWBHSJ-UHFFFAOYSA-N C[n]1nc(cccc2)c2n1 Chemical compound C[n]1nc(cccc2)c2n1 PWORFEDVDWBHSJ-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention belongs to the technical field of organic synthesis preparation, and discloses a 3-benzotriazole-substituted-1-(1,3-diaryl) propylene compound, a synthesis method and use thereof. The structure of the compound disclosed by the invention is represented by a general formula (I) or (II) as follows: FORMULAE, wherein * is a chiral carbon atom; R1 is selected from an aryl or an alkyl; and R2 is selected from hydrogen, chloride, methyl or nitro substituent. The invention further provides a method for preparing 3-benzotriazole-substituted-1-(1,3-diaryl/alkyl/alkyl) propylene compound. A catalyst used in the method is easy to obtain, high in catalytic activity and moderate in condition. The prepared chiral benzotriazole derivate can be used as research and development of a novel medicine.
Description
Technical field
The invention belongs to the organic synthesis preparing technical field, be specifically related to a kind of 3-benzotriazole replacement-1-(1, the 3-diaryl) propene compound, synthetic method and application thereof.
Background technology
Benzotriazole is the synthetic fragment of existing many medicines, is playing the part of important role [(a) Katritzky, A.L. in life chemistry; Rees, C.W.; Potts, K.T.In Comprehensive Heterocyclic Chemistry; Pergamon:Oxford, 1984. (b) Katritzky, A.R.; Todadze, E.Arkivoc 2009,248-268.], it is as biological enzyme inhibitor [Sarno, S.; Ruzzene, M.; Frascella, P.et al.Mol.Cell.Biochem.2005,274,69.], have antitumor [Zhan, T.R.; Lou, H.X.Carbohydr Res.2007,342,865.], effect [Sparatore, the A. of anti-inflammatory; Godio, C.; Perrino, E.et al.Chemistry ﹠amp; Biodiversity 2006,3, and 385.].Also have anti-Parasita medicine [Chan, C. in addition; Yin, H.; McKie, J.H.et al.Amino Acids 2002,22,297.], antipsychotic class [El-Sabbagh, O.I.; El-Nabtity, S.M.Bulletin OfThe Korean Chemical Society 2009,30,1445.], antimycotic [Ghannoum M.A., Rice L.B.ClinicalMicrobiology Reviews, 1999,12,501.], antiulcer agent [Habib, N.S.; Fahmy, S.; El-Khawass, S.M.et al.Pharmazie 2000,55,900.], hypertension [Boido, A.; Boido, C.C.; Sparatore, F.Farmaco 2001,56,263.], alleviate spasm [Dawood, K.M.; Abdel-Gawad, H.; Rageb, E. A.et al.Bioorganic ﹠amp; MedicinalChemistry 2006,14,3672.], tuberculosis [Dixit, P.P.; Patil, V.J.; Nair, P.S.; Jain, S.; Sinha, N.; Arora, S.K.European Journal Of Medicinal Chemistry 2006,41,423.] etc. the report of many pharmacological propertieses.The optically active chirality nitrogenous compound of tool synthesizes significant in organic synthesis and medicine.Since the reaction of the nineties allylation in last century chiral induction is developed to now, many methods that contain nitrogen nucleophile attack allyl group thing have been developed.[(a)Fischer，D.E.；Xin，Z.Q.；Peters，R.Angew.Chem.Int.Ed.2007，46，7704-7707.(b)Castillo，A.B.；Favier，I.；Teuma，E.；Castillon，S.；Godard，C.；Aghmiz，A.；Claver，C.；Gomez，M.Chem.Commun.2008，6197-6199.(c)Roland，S.；Cotet，W.；Mangeney，P.Eur.J.Inorg.Chem.2009，1796-1805.(d)Togni，A.；Burckhardt，U.；Gramlich，V.；Pregosin，P.S.；Salzmann，R.J.Am.Chem.Soc.1996，118，1031-1037.(e)Trost，B.M.；Madsen，R.；Guile，S.D.；Brown，B.J.Am.Chem.Soc.2000，122，5947-5956.(f)You，S.L.；Zhu，X.Z.；Luo，Y.M.；Hou，X.L.；D?ai，L.X.J.Am.Chem.Soc.2001，123，7471-7472.(g)Nemoto，T.；Fukuyama，T.；Yamamoto，E.；Tamura，S.；Fukuda，T.；Matsumoto，T.；Akimoto，Y.；Hamada，Y.Org.Lett.2007，9，927-930.(h)Zheng，W.H.；Sun，N.；Hou，X.L.Org.Lett.2005，7，5151-5154.]。It is few in number that existing formation contains the method for chirality benzotriazole compound, uses organic micromolecule catalyst to carry out the Micheal addition reaction of benzotriazole and unsaturated ketenes mostly.[(a) Wang, J.; Li, H.; Zu, L.S.; Wang, W.Org.Lett.2006,8,1391-1394. (b) Diner, P.; Nielsen, M.; Marigo, M.; Jorgensen, K.A.Angew.Chem.Int.Ed.2007,46,1983-1987. (c) Wang, J.; Zu, L.S.; Li, H.; Xie, H.X.; Wang, W.Synthesis-stuttgart.2007,2576-2580. (d) Fang, L.; Lin, A.J.; Jia, X.F.; Meng, J.; Wang, Y.N.; Zhu, C.J.Lett Org Chem 2009,6,397-399. (e) Luo, G.S.; Zhang, S.L.; Duan, W.H.; Wang, W.Synthesis-stuttgart.2009,1564-1572.] have only an example to use metallic aluminium to carry out the reaction of chiral induction as catalyzer so far.This may be because thereby benzotriazole meeting and metal carry out the carrying out of coordination influence reaction.[Gandelman，M.；Jacobsen，E.N.Angew.Chem.Int.Ed.2005，44，2393-2397.]
Summary of the invention
The purpose of this invention is to provide a kind of 3-benzotriazole replacement-1-(1, the 3-diaryl) propene compound.
Another object of the present invention provides the preparation method of a kind of 3-benzotriazole replacement-1-(1, the 3-diaryl) propene compound.
The 3rd purpose of the present invention provides the purposes of 3-benzotriazole replacement-1-(1, the 3-diaryl) propene compound as the novel drugs research and development.
Technical scheme of the present invention is as follows:
The invention provides a kind of 3-benzotriazole replacement-1-(1, the 3-diaryl) propene compound, the structure of this compounds is as general formula (I) or (II):
Wherein:
* be chiral carbon atom;
R
1Be selected from aryl or alkyl;
R
2Be selected from substituting groups such as hydrogen, chlorine, methyl or nitro.
Described aryl is selected from phenyl, naphthyl, tolyl, methoxyphenyl or bromophenyl etc.
Described alkyl is selected from methyl or ethyl.
The present invention also provides a kind of 3-benzotriazole replacement-1-(1, the 3-diaryl) preparation method of propene compound, and this method reaction formula is as follows, may further comprise the steps:
In the reaction tubes of an exsiccant argon shield, add catalyzer, part and organic solvent successively, stirred 30 minutes under the room temperature, in reaction tubes, add compound (IV), compound (III) and alkali more successively, stirring at room reaction 12-48h, after reaction finishes, prepare compound (I) or (II);
Wherein, described compound (IV): compound (III): alkali: catalyzer: the mol ratio of part is 2～1.5: 1: 1: 0.05: 0.1; Preferred mol ratio is 2: 1: 1: 0.05: 0.1.
LG is a leavings group in the described compound (III), is selected from methyl carbonate, ethyl-carbonate or acetic ester.
Described catalyzer is a non-valent palladium metal complex compound, is selected from three (dibenzalacetones), two palladiums, (dibenzalacetone) palladium or allyl palladium chloride etc.
Described part is selected from the optically pure part with following structural formula:
Described alkali is selected from a kind of in Quilonum Retard, yellow soda ash, salt of wormwood, potassiumphosphate, cesium carbonate, DBU, BSA, n-Butyl Lithium, sodium hydride, lithium hydride or the potassium hydride KH.
Described organic solvent is selected from benzene, tetracol phenixin, trichloromethane, methylene dichloride, tetrahydrofuran (THF), N, a kind of in dinethylformamide, ether, dioxane or the acetonitrile.
The method that adopts the inventive method products therefrom 3-benzotriazole replacement-1-(1, the 3-diaryl) propene compound can pass through recrystallization, thin-layer chromatography, column chromatography or underpressure distillation is separated.As use recrystallization method, the recommendation solvent is a Virahol, recommends solvent to can be methylene dichloride-normal hexane mixed solvent.With the method for thin-layer chromatography, column chromatography, used developping agent is the mixed solvent of non-polar solvent and polar solvent.Recommend solvent to can be sherwood oil-methylene dichloride, petroleum ether-ethyl acetate, mixed solvents such as sherwood oil-ether, its volume ratio can be respectively: non-polar solvent: polar solvent=50-20: 1; For example: petrol ether/ethyl acetate=50-20/1, sherwood oil/methylene dichloride=50-20/1.
The present invention also provides the purposes of 3-benzotriazole replacement-1-(1, the 3-diaryl) propene compound as the novel drugs research and development.
The present invention compares with prior art, has following advantage and beneficial effect:
The invention provides a kind of effectively with the chirality palladium complex as catalyzer, method by benzotriazole sodium salt compounds and the high enantioselectivity synthetic of allyl carbonate ester cpds 3-benzotriazole replacement-1-(1, the 3-diaryl) propene compound; The method of the basic sulphur replacement-1-of preparation multiple 3-virtue (alkane) propylene class is provided.This method is applicable to dissimilar benzotriazole sodium compounds and allyl carbonate ester compound, and the reaction conditions gentleness is easy and simple to handle.Fan Ying productive rate also better (being generally 50%-89%) in addition, enantioselectivity height (being generally 40%-95%).
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
The research of the alkali of the allylation of the catalytic benzotriazole of palladium complex, solvent and proportioning
1a assignment body wherein, 1eq Base refers to one times of equivalent alkali, and Solvent refers to solvent, and rt refers to room temperature.
Compound (III)-a (prepares Hayashi according to reference, T.; Yamamoto, A.; Ito, Y.; Nishioka, E.; Miura, H.; Yanagi, K.J.Am.Chem.Soc.1989,111,6301.)
In the reaction tubes of an exsiccant argon shield; add catalyzer (0.01mmol), part (0.02mmol) and 2mL organic solvent successively; stirred 30 minutes under the room temperature; in reaction tubes, add compound (III)-a (0.2mmol), (IV)-a (0.4mmol) and alkali (0.4mmol) more successively; stirring at room reaction 12-48h; after reaction finishes, prepare chemical combination (I)-a and (II)-a.The results are shown in Table 1.
Table 1
The result of table 1 shows, as solvent, (IV)/(III)-a proportioning 1: 2nd, the optimal conditions of this reaction had yield and ee value preferably to NaH as alkali, THF.
Embodiment 2
In order to simplify the operation of reaction, under the room temperature with 6g benzotriazole and 1.2g NaH stirring reaction 24～48 hours in tetrahydrofuran (THF).Revolve after reaction finishes and desolvate, be prepared into the benzotriazole sodium salt.
The allylation research of the catalytic benzotriazole sodium of different palladium complexs
In the reaction tubes of an exsiccant argon shield, add catalyzer (0.01mmol), part (0.02mmol) and 2mL organic solvent successively, stir half an hour under the room temperature, in reaction tubes, add compound (III)-a (0.2mmol) and compound (IV)-b (0.4mmol) more successively, stirring at room reaction 12-48h, after reaction finishes, prepare compound (I)-a and (II)-a; The results are shown in Table 2.
Table 2
| Sequence number | Part | Yield % (I)-a, (II)-a | ee％(I)-a，(II)-a |
| 1 | 1a | 40，32 | 91，77 |
| 2 | 1b | 34，31 | 11，4 |
| 3 | 1c | 35，32 | 80，67 |
| 4 | 1d | 31，37 | 75，34 |
| 5 | 1e | 21，32 | 35，9 |
| 6 | 1f | 20，18 | 14，0 |
The result shows that ligand 1 a has best effect.
Embodiment 3
The reaction of the catalytic benzotriazole sodium allyl of palladium complex
In the reaction tubes of an exsiccant argon shield, add Pd successively
2(dba)
3CHCl
3(0.01mmol), chiral ligand 1a (0.02mmol) and THF (2mL), stirred 30 minutes under the room temperature, in reaction tubes, add benzotriazole sodium (IV)-b (0.4mmol), allyl carbonate (III)-a-i (0.2mmol), stirring at room reaction more successively.After reaction finishes, after the removal of solvent under reduced pressure residue thin-layer chromatography obtain target product (sherwood oil/methylene dichloride=20/1, or petrol ether/ethyl acetate=20: 1, v/v).The results are shown in Table 3.
Table 3
Compound (I)-a:3-(2-benzotriazole base)-1-(1, the 3-phenylbenzene) propylene
Proterties: white solid, fusing point 128.6-129.0 ℃.
Molecular weight: 311
Enantiomeric excess test condition [chiral column AD-H (0.46cmx25cm); Normal hexane/Virahol=80/20; Flow velocity=1mL/min; Detect wavelength=detection wavelength 254nm; t
R=9.82min (minor), 10.56min (major)]. enantiomeric excess value 90%
1H?NMR(400MHz，CDCl
3)δ＝7.97-7.90(dd，J＝6.6Hz，3.1，2H)，7.52-7.46(m，2H)，7.46-7.39(m，5H)，7.39-7.27(m，5H)，7.09(dd，J＝15.9Hz，7.9Hz，1H)，6.79(d，J＝8.0Hz，1H)，6.71(d，J＝15.8Hz，1H).
13C?NMR(100MHz，CDCl
3)δ＝144.35，138.41，135.88，134.54，128.90，128.64，128.55，128.39，127.37，126.95，126.42，126.15，118.31，72.59.
Mass spectrum MS (EI, m/z, rel.intensity) 193 (100), 311 (M
+)
High resolution mass spectrum HRMS (EI) calcd for C
21H
17N
3(M
+): 311.1422, Found:311.1420.
Infrared spectra IR (KBr): v
Max(cm
-1)=3852,3820,3734,3710,3627,3502,3061,3082,1564,1459,1450,1384,1316,1266,965,888,745,695,541
Optical value [α]
D 20=-55.0 ° (c 1.0, CHCl
3).
Compound (II)-a:3-(1-benzotriazole base)-1-(1, the 3-phenylbenzene) propylene
Proterties: white solid, fusing point 169.4-170.4 ℃.
Molecular weight: 311
1H?NMR(400MHz，CDCl
3)δ＝8.15-8.08(m，1H)，7.46-7.40(m，3H)，7.39-7.36(m，5H)，7.36-7.27(m，5H)，7.02(dd，J＝15.9Hz，7.2Hz，1H)，6.80(d，J＝7.2Hz，1H)，6.63(d，J＝15.7Hz，1H).
13C?NMR(100MHz，CDCl
3)δ＝146.47，137.86，135.77，134.56，132.47，129.03，128.70，128.56，128.44，127.34，127.32，126.87，125.58，123.97，120.20，110.40，65.55.
Mass spectrum MS (EI, m/z, rel.intensity) 193 (100), 311 (M
+)
High resolution mass spectrum HRMS (EI) calcd for C
21H
17N
3(M
+): 311.1422, Found:311.1423.
Infrared spectra IR (KBr): v
Max(cm
-1)=3853,3825,3745,3735,3675,3629,1700,1684,1558,1490,1473,1448,1384,969,743,694.
Enantiomeric excess test condition [chiral column AD-H (0.46cmx25cm); Normal hexane/Virahol=80/20; Flow velocity=1mL/min; Detect wavelength=detection wavelength 254nm; t
R=14.65min (minor), 19.29min (major)]. enantiomeric excess value 77%ee.
Optical value [α]
D 20=-21.0 ° (c 1.0, CHCl
3).
Compound (I)-b:3-(2-benzotriazole base)-1-(1,3-two (adjacent phenmethyl)) propylene
Proterties: white solid. fusing point: 71-72 ℃.
1HNMR(400MHz，CDCl
3)δ＝7.89(dd，J＝6.5，3.1Hz，2H)，7.54(dd，J＝5.2，3.8Hz，1H)，7.40-7.33(m，3H)，7.22(dd，J＝7.2，5.1Hz，3H)，7.18-7.10(m，3H)，6.98(d，J＝6.9Hz，1H)，6.85(dd，J＝15.6，6.9Hz，1H)，6.77(d，J＝15.7Hz，1H)，2.43(s，3H)，2.26(s，3H).
13C?NMR(100MHz，CDCl
3)δ＝144.3，136.6，135.9，135.9，135.1，131.9，130.9，130.4，128.6，128.2，127.3，127.2，126.7，126.4，126.2，126.2，118.3，69.4，19.7，19.4.
Molecular weight MS (EI, m/z, rel.intensity) 221 (100), 339 (M+).
High resolution mass spectrum HRMS (EI) calcd for C
23H
21N
3(M+): 339.1735, Found:339.1738.
Infrared spectra IR (KBr): v
Max(cm
-1)=3322,2926,2853,1732,1457,1254,1004,884,745,435.
Enantiomeric excess test condition (detecting wavelength 254nm, 25 ℃) t
R=5.42min (major); 12.51min (minor) [Diacel CHIRALPAK AD-H (0.46cmx25cm), normal hexane/Virahol, 90/10,1.0mL/min] enantiomeric excess value-72%.
Optical value [α]
D 20=20.8 ° (c 1.0, CHCl
3).
Compound (II)-b:3-(1-benzotriazole base)-1-(1,3-two (adjacent phenmethyl)) propylene
Proterties: white solid. fusing point: 146-147 ℃.
1H?NMR(400MHz，CDCl
3)δ＝8.13(dd，J＝5.7，3.0Hz，1H)，7.60-7.54(m，1H)，7.38(t，J＝3.8Hz，3H)，7.34-7.25(m，(I)-h)，7.24-7.13(m，3H)，7.02(d，J＝6.2Hz，1H)，6.84(dd，J＝15.7，6.2Hz，1H)，6.66(d，J＝15.8Hz，1H)，2.38(s，3H)，2.23(s，3H).
13C?NMR(100MHz，CDCl
3)δ＝146.4，136.5，135.8，135.8，135.1，132.8，131.8，131.2，130.4，128.8，128.3，127.6，127.3，126.9，126.7，126.3，126.1，124，120.2，110.5，62.9，19.7，19.3.
Molecular weight MS (EI, m/z, rel.intensity) 221 (100), 339 (M
+).
High resolution mass spectrum HRMS (EI) calcd for C
23H
21N
3(M
+): 339.1735, Found:339.1737.
Infrared spectra IR (KBr): v
Max(cm
-1)=3031,2910,2857,1736,1612,1486,1448,1321,1267,960,795,687,441.
Enantiomeric excess test condition (detecting wavelength 254nm, 25 ℃) t
R=6.20min (major); 6.63min (minor) [Diacel CHIRALPAK AD-H (0.46cmx25cm), normal hexane/Virahol, 90/10,1.0mL/min] enantiomeric excess value-46%.
Optical value [α]
D 20=34.4 ° (c 1.0, CHCl
3).
Compound (I)-c:3-(2-benzotriazole base)-1-(1,3-two (phenmethyl)) propylene
Proterties: white solid. fusing point: 65-66 ℃.
1H?NMR(400MHz，CDCl
3)δ＝7.89(dd，J＝6.6，3.0Hz，2H)，7.37(dd，J＝6.6，3.0Hz，2H)，7.29-7.16(m，6H)，7.13-7.07(m，2H)，7.03(dd，J＝15.8，7.9Hz，1H)，6.70(d，J＝8.0Hz，1H)，6.64(d，J＝15.8Hz，1H)，2.32(s，3H)，2.31(s，3H).
13C?NMR(100MHz，CDCl
3)δ＝144.4，138.7，138.4，138.2，135.9，134.5，129.4，129.2，128.8，128.6，128.0，127.6，126.4，126.0，124.5，124.2，118.4，72.7，21.5，21.4.
Molecular weight MS (EI, m/z, rel.intensity) 221 (100), 339 (M
+).
High resolution mass spectrum HRMS (EI) calcd for C
23H
21N
3(M
+): 339.1735, Found:339.1737.
Infrared spectra IR (KBr): v
Max(cm
-1)=3060,2917,2850,1711,1612,1492,1451,1369,1277,1229,1153,1068,960,754,447.
Enantiomeric excess test condition (detecting wavelength 254nm, 25 ℃) t
R=9.46min (minor); 11.81min (major) [Diacel CHIRALPAK AD-H (0.46cmx25cm), normal hexane/Virahol, 90/10,1.0mL/min] enantiomeric excess value 95%.
Optical value [α]
D 20=-10.9 ° (c 1.0, CHCl
3).
Compound (II)-c:3-(1-benzotriazole base)-1-(1,3-two (phenmethyl)) propylene
Proterties: white solid. fusing point: 100-101 ℃.
1H?NMR(400MHz，CDCl
3)δ＝8.13(d，J＝7.8Hz，1H)，7.42-7.35(m，3H)，7.30-7.22(m，(I)-h)，7.19-7.10(m，(I)-h)，7.01(dd，J＝15.8，7.2Hz，1H)，6.75(d，J＝7.2Hz，1H)，6.60(d，J＝15.8Hz，1H)，2.36(s，3H)，2.34(s，3H).
13C?NMR(100MHz，CDCl
3)δ＝146.5，138.9，138.3，137.9，135.8，134.5，132.5，129.3，129.2，128.9，128.6，128.0，127.5，127.3，125.5，124.4，124.1，124.0，120.2，110.5，65.6，21.5，21.4.
Molecular weight MS (EI, m/z, rel.intensity) 221 (100), 339 (M
+).
High resolution mass spectrum HRMS (EI) calcd for C
23H
21N
3(M
+): 339.1735, Found:339.1737.
Infrared spectra IR (KBr): v
Max(cm
-1)=3019,2933,2847,1609,1486,1451,1267,1372,1156,1061,967,786,741,688,434.
Enantiomeric excess test condition (detecting wavelength 254nm, 25 ℃) t
R=11.16min (minor); 14.91min (major) [Diacel CHIRALPAK AD-H (0.46cmx25cm), normal hexane/Virahol, 80/20,1.0mL/min] enantiomeric excess value 95%.
Optical value [α]
D 20=-22.2 ° (c 1.0, CHCl
3).
Compound (I)-d:3-(2-benzotriazole base)-1-(1,3-two (to phenmethyl)) propylene
Proterties: white solid. fusing point: 101-102 ℃.
1H?NMR(400MHz，CDCl
3)δ＝7.88(dd，J＝6.5，2.9Hz，2H)，7.36(dd，J＝6.6，2.8Hz，2H)，7.34-7.28(m，(I)-h)，7.16(d，J＝7.8Hz，2H)，7.12(d，J＝7.7Hz，2H)，6.97(dd，J＝15.8，7.9Hz，1H)，6.70(d，J＝7.9Hz，1H)，6.62(d，J＝15.8Hz，1H)，2.32(s，6H).
13C?NMR(100MHz，CDCl
3)δ＝144.3，138.4，138.3，135.6，134.3，133.2，129.5，129.3，127.4，126.9，126.3，125.3，118.3，72.5，21.3，21.2.
Molecular weight MS (EI, m/z, rel.intensity) 221 (100), 339 (M
+).
High resolution mass spectrum HRMS (EI) calcd for C
23H
21N
3(M
+): 339.1735, Found:339.1736.
Infrared spectra IR (KBr): v
Max(cm
-1)=3021,2920,1654,1518,1451,1372,1318,1258,1182,970,887,798,745,504.
Enantiomeric excess test condition (detecting wavelength 214nm, 25 ℃) t
R=7.52min (minor); 8.26min (major) [Diacel CHIRALPAK OD-H (0.46cmx25cm), normal hexane/Virahol, 90/10,1.0mL/min] enantiomeric excess value 80%.
Optical value [α]
D 20=-19.0 ° (c 1.0, CHCl
3).
Compound (II)-d:3-(1-benzotriazole base)-1-(1,3-two (adjacent phenmethyl)) propylene
Proterties: white solid. fusing point: 136-137 ℃.
1H?NMR(400MHz，CDCl
3)δ＝8.07(d，J＝7.8Hz，1H)，7.37-7.26(m，5H)，7.20(d，J＝7.7Hz，2H)，7.17-7.08(m，(I)-h)，6.91(dd，J＝15.8，7.1Hz，1H)，6.72(d，J＝7.1Hz，1H)，6.54(d，J＝15.8Hz，1H)，2.32(s，6H).
13C?NMR(100MHz，CDCl
3)δ＝146.5，138.4，135.0，134.3，133.1，132.5，129.7，129.4，127.3，127.2，126.8，124.7，123.9，120.2，110.6，65.5，21.3，21.2.
Molecular weight MS (EI, m/z, rel.intensity) 221 (100), 339 (M
+).
High resolution mass spectrum HRMS (EI) calcd for C
23H
21N
3(M
+): 339.1735, Found:339.1736.
Infrared spectra IR (KBr): v
Max(cm
-1)=3028,2923,2860,1742,1615,1511,1451,1384,1273,1156,969,808,748,498.
Enantiomeric excess test condition (detecting wavelength 254nm, 25 ℃) t
R=23.29min (minor); 35.12min (major) [Diacel CHIRALPAK AD-H (0.46cmx25cm), normal hexane/Virahol, 80/20,1.0mL/min] enantiomeric excess value 65%.
Optical value [α]
D 20=-29.6 ° (c 1.0, CHCl
3).
Compound (I)-e:3-(2-benzotriazole base)-1-(1,3-two (to the benzene bromo)) propylene
Proterties: white solid.
1HNMR(400MHz，CDCl
3)δ＝7.91(dd，J＝6.6，3.1Hz，2H)，7.51(d，J＝8.5Hz，2H)，7.47(d，J＝8.4Hz，2H)，7.42(dd，J＝6.6，3.1Hz，2H)，7.32(d，J＝8.2Hz，2H)，7.30(d，J＝8.5Hz，2H)，7.00(dd，J＝15.9，7.7Hz，1H)，6.71(d，J＝7.7Hz，1H)，6.60(d，J＝15.8Hz，1H).
13C?NMR(100MHz，CDCl
3)δ＝144.4，137.1，134.6，133.7，132.1，131.9，129.2，128.5，126.7，126.4，122.9，122.5，118.3，71.7.
Molecular weight MS (EI, m/z, rel.intensity) 349 (100), 467 (M
+).
High resolution mass spectrum HRMS (EI) calcd for C
23H
15Br
2N
3(M
+): 466.9633, Found:466.9636.
Infrared spectra IR (KBr): v
Max(cm
-1)=3066,2920,2841,1732,1598,1486,1410,1308,1258,1261,1188,1071,1004,969,890,821,738,540,494.
Enantiomeric excess test condition (detecting wavelength 276nm, 25 ℃) tR=6.85min (minor); 7.69min (major) [Diacel CHIRALPAK OD-H (0.46cmx25cm), normal hexane/Virahol, 90/10,1.0mL/min] enantiomeric excess value 68%.
Optical value [α]
D 20=-26.2 ° (c 1.0, CHCl
3).
Compound (II)-e:3-(1-benzotriazole base)-1-(1,3-two (to the benzene bromo)) propylene
Proterties: white solid.
1H?NMR(400MHz，CDCl
3)δ＝8.12(d，J＝8.0Hz，1H)，7.51(d，J＝8.3Hz，2H)，7.46(d，J＝8.3Hz，2H)，7.44-7.33(m，3H)，7.28(d，J＝8.2Hz，2H)，7.20(d，J＝8.3Hz，2H)，6.95(dd，J＝15.9，7.0Hz，1H)，6.69(d，J＝7.0Hz，1H)，6.54(d，J＝15.8Hz，1H).
13C?NMR(100MHz，CDCl
3)δ＝146.5，136.7，134.5，133.7，132.3，132.3，131.9，129.0，128.4，127.6，125.9，124.2，122.8，122.6，120.4，110.0，64.7.
Molecular weight MS (EI, m/z, rel.intensity) 349 (100), 467 (M
+).
High resolution mass spectrum HRMS (EI) calcd for C
23H
15Br
2N
3(M
+): 466.9633, Found:466.9639.
Infrared spectra IR (KBr): v
Max(cm
-1)=3056,2923,2847,1660,1584,1486,1448,1406,1264,1156,1064,1001,963,811,748,700,545,491.
Enantiomeric excess test condition (detecting wavelength 254nm, 25 ℃) t
R=17.94min (minor); 30.25min (major) [Diacel CHIRALPAK AD-H (0.46cmx25cm), normal hexane/Virahol, 70/30,1.0mL/min] enantiomeric excess value 41%.
Optical value [α]
D 20=-55.6 ° (c 1.0, CHCl
3).
Compound (I)-f:3-(2-benzotriazole base)-1-(1,3-two (2-naphthyl)) propylene
Proterties: white solid. fusing point: 122-123 ℃.
1H?NMR(400MHz，CDCl
3)δ＝7.95-7.89(m，3H)，7.86-7.74(m，7H)，7.68(d，J＝8.6Hz，1H)，7.54(d，J＝8.5Hz，1H)，7.49-7.41(m，(I)-h)，7.38(dd，J＝6.6，3.0Hz，2H)，7.25(dd，J＝15.4，7.2Hz，1H)，6.97(d，J＝7.6Hz，1H)，6.85(d，J＝15.8Hz，1H).
13C?NMR(100MHz，CDCl
3)δ＝144.5，135.8，134.8，133.5，133.4，133.3，133.3，128.9，128.4，128.3，128.2，127.7，127.4，126.8，126.6，126.5，126.4，126.3，125.0，123.8，118.4，72.8.
Molecular weight MS (EI, m/z, rel.intensity) 293 (100), 411 (M
+).
High resolution mass spectrum HRMS (EI) calcd for C
29H
21N
3(M
+): 411.1735, Found:411.1736.
Infrared spectra IR (KBr): v
Max(cm
-1)=3053,3027,2930,1739,1650,1619,1569,1508,1441,1368,1334,1226,1033,960,852,808,741,691,475.
Enantiomeric excess test condition (detecting wavelength 254nm, 25 ℃) t
R=19.61min (minor); 23.00min (major) [Diacel CHIRALPAK AD-H (0.46cmx25cm), normal hexane/Virahol, 50/50,1.0mL/min] enantiomeric excess value 78%.
Optical value [α]
D 20=-28.5 ° (c 1.0, CHCl
3).
Compound (II)-f:3-(1-benzotriazole base)-1-(1,3-two (2-naphthyl)) propylene
Proterties: white solid. fusing point: 160-161 ℃.
1H?NMR(400MHz，CDCl
3)δ＝8.11(dd，J＝5.3，2.6Hz，1H)，7.84(d，J＝3.4Hz，2H)，7.82-7.72(m，6H)，7.65(d，J＝8.5Hz，1H)，7.49(dd，J＝5.4，2.7Hz，2H)，7.46-7.31(m，6H)，7.19(dd，J＝15.8，6.9Hz，1H)，6.97(d，J＝6.9Hz，1H)，6.78(d，J＝15.8Hz，1H).
13C?NMR(100MHz，CDCl
3)δ＝146.6，135.3，134.8，133.5，133.4，133.2，132.6，129.2，128.5，128.2，128.1，127.8，127.8，127.5，127.3，126.7，126.5，126.4，125.8，125.0，124.1，123.6，120.3，110.5，65.8
Molecular weight MS (EI, m/z, rel.intensity) 293 (100), 411 (M
+).
High resolution mass spectrum HRMS (EI) calcd for C
29H
21N
3(M
+): 411.1735, Found:411.1737.
Infrared spectra IR (KBr): v
Max(cm
-1)=3053,2932,2853,1723,1593,1505,1480,1394,1267,1251,1077,960,862,814,786,741,707,662,475.
Enantiomeric excess test condition (detecting wavelength 254nm, 25 ℃) t
R=16.83min (minor); 30.83min (major) [Diacel CHIRALPAK AD-H (0.46cmx25cm), normal hexane/Virahol, 50/50,1.0mL/min] enantiomeric excess value 44%.
Optical value [α]
D 20=-8.4 ° (c 1.0, CHCl
3).
Compound (I)-g:4-(2-benzotriazole base)-2-amylene
Proterties: colourless liquid.
1H?NMR(400MHz，CDCl
3)δ＝7.88(dd，J＝6.5，3.1Hz，2H)，7.37(dd，J＝6.5，3.1Hz，2H)，5.90(dd，J＝15.8，7.2Hz，1H)，5.85-5.75(m，1H)，5.51(p，J＝6.9Hz，1H)，1.82(d，J＝6.9Hz，3H)，1.73(d，J＝6.1Hz，3H).
13C?NMR(100MHz，CDCl
3)δ＝144.1，130.2，129.2，126.1，118.1，64.7，21.1，17.7
Molecular weight MS (EI, m/z, rel.intensity) 187 (100), 187 (M
+).
High resolution mass spectrum HRMS (EI) calcd for C
11H
13N
3(M
+): 187.1109, Found:187.1110.
Infrared spectra IR (KBr): v
Max(cm
-1)=2964,2929,2863,1726,1441,1378,1251,1080,1023,792,666.
Enantiomeric excess test condition (detecting wavelength 254nm, 25 ℃) t
R=9.50min (major); 10.26min (minor) [Diacel CHIRALPAK AD-H (0.46cmx25cm), normal hexane/Virahol, 98/2,1.0mL/min] enantiomeric excess value 71%.
Optical value [α]
D 20=48.8 ° (c 1.0, CHCl
3).
Compound (II)-g:4-(1-benzotriazole base)-2-amylene
Proterties: colourless liquid.
1H?NMR(400MHz，CDCl
3)δ＝8.06(d，J＝8.3Hz，1H)，7.55(d，J＝8.3Hz，1H)，7.45(t，J＝7.5Hz，1H)，7.35(t，J＝7.6Hz，1H)，5.84(dd，J＝15.4，6.3?Hz，1H)，5.74(dq，J＝18.2，5.9Hz，1H)，5.49(p，J＝6.4Hz，1H)，1.84(d，J＝7.0Hz，3H)，1.73(d，J＝6.0Hz，3H).
13C?NMR(100MHz，CDCl
3)δ＝146.5，132.2，130.0，128.6，126.9，123.7，120.1，110.3，57.4，20.1，17.6.
Molecular weight MS (EI, m/z, rel.intensity) 144 (100), 187 (M
+).
High resolution mass spectrum HRMS (EI) calcd for C
11H
13N
3(M
+): 187.1109, Found:187.1108.
Infrared spectra IR (KBr): v
Max(cm
-1)=2980,2923,2850,1606,1451,1384,1267,1159,1074,960,776,745.
Enantiomeric excess test condition (detecting wavelength 214nm, 25 ℃) t
R=6.86min (major); 7.56min (minor) [Diacel CHIRALPAK AD-H (0.46cmx25cm), normal hexane/Virahol, 90/10,1.0mL/min] enantiomeric excess value-61%.
Optical value [α]
D 20=8.3 ° (c 1.0, CHCl
3).
Compound (I)-h:5-(2-benzotriazole base)-3-heptene
Proterties: colourless liquid.
1H?NMR(400MHz，CDCl
3)δ＝7.88(dd，J＝6.5，3.1Hz，2H)，7.37(dd，J＝6.5，3.1Hz，2H)，5.91-5.78(m，2H)，5.23(dd，J＝14.7，6.9Hz，1H)，2.38-2.24(m，1H)，2.24-2.10(m，1H)，2.07(dt，J＝12.3，6.2Hz，2H)，0.99(t，J＝7.4Hz，3H)，0.86(t，J＝7.4Hz，3H).
13C?NMR(100MHz，CDCl
3)δ＝144.0，136.9，126.9，126，118.1，71.3，28.9，25.2，13.1，10.6.
Enantiomeric excess test condition (detecting wavelength 254nm, 25 ℃) t
R=7.92min (minor); 9.47min (major) [Diacel CHIRALPAK IC (0.46cmx25cm), normal hexane/Virahol, 99/1,1.0mL/min] enantiomeric excess value 78%
Compound (II)-h:5-(1-benzotriazole base)-3-heptene
Proterties: colourless liquid.
1H?NMR(400MHz，CDCl
3)δ＝8.07(d，J＝8.3Hz，1H)，7.55(d，J＝8.3Hz，1H)，7.45(t，J＝7.6Hz，1H)，7.35(t，J＝7.6Hz，1H)，5.87-5.71(m，2H)，5.20(dd，J＝14.7，6.7Hz，1H)，2.39-2.22(m，1H)，2.13-2.00(m，2H)，0.97(t，J＝7.4Hz，3H)，0.88(t，J＝7.4Hz，3H).
13C?NMR(100MHz，CDCl
3)δ＝146.3，136.3，132.4，126.8，126.6，123.7，120.1，110.2，63.9，27.6，25.2，13.2，10.8
Enantiomeric excess test condition (detecting wavelength 214nm, 25 ℃) t
R=6.79min (major); 7.84min (minor) [Diacel CHIRALPAK AD-H (0.46cmx25cm), normal hexane/Virahol, 90/10,1.0mL/min] enantiomeric excess value-72%.
Compound (III)-c:(1,3-two (phenmethyl)) propylene-3-ethyl-carbonate
Proterties: colourless liquid.
1H?NMR(400MHz，CDCl
3)δ＝7.26-7.21(m，3H)，7.20-7.16(m，3H)，7.12(d，J＝6.7Hz，1H)，7.07-7.02(m，1H)，6.65(d，J＝15.8Hz，1H)，6.34(dd，J＝15.3，6.5Hz，1H)，6.21(d，J＝6.8Hz，1H)，4.19(qd，J＝6.3，4.3Hz，2H)，2.35(s，3H)，2.31(s，3H)，1.29(t，J＝7.1Hz，3H).
13C?NMR(100MHz，CDCl
3)δ＝154.5，138.8，138.4，138.2，136.1，133.0，129.2，129.0，128.6，128.5，127.7，127.5，126.9，124.1，124.0，80.2，64.1，21.5，21.4，14.3.
Molecular weight MS (EI, m/z, rel.intensity) 220 (100), 310 (M
+).
High resolution mass spectrum HRMS (EI) calcd for C
20H
22O
3(M
+): 310.1569, Found:310.1570.
Infrared spectra IR (KBr): v
Max(cm
-1)=3037,2917,2847,1650,1606,1508,1457,1378,1270,1235,1156,1140,1083,973,916,811,792,740,498.
Compound (III)-e:(1,3-two (to the benzene bromo)) propylene-3-ethyl-carbonate
Proterties: yellow liquid.
1H?NMR(400MHz，CDCl
3)δ＝7.50(d，J＝8.4Hz，2H)，7.42(d，J＝8.3Hz，2H)，7.29(d，J＝8.3Hz，2H)，7.22(d，J＝8.4Hz，2H)，6.59(d，J＝15.8Hz，1H)，6.30(dd，J＝15.8，6.7Hz，1H)，6.18(d，J＝6.7Hz，1H)，4.20(qd，J＝7.1，3.1Hz，2H)，1.30(t，J＝7.1Hz，3H).
13C?NMR(100MHz，CDCl
3)δ＝154.3，137.6，134.8，132.1，131.9，131.8，128.8，128.3，127.2，122.6，122.2，79.0，64.4，14.3.
Molecular weight MS (EI, m/z, rel.intensity) 269 (100), 438 (M
+).
High resolution mass spectrum HRMS (EI) calcd for C
18H
16Br
2O
3(M
+): 437.9466, Found:437.9469.
Infrared spectra IR (KBr): v
Max(cm
-1)=2986,2917,1742,1486,1406,1368,1302,1242,1074,1004,960,807,849,846,830,564,510.
Above-mentioned description to embodiment is can understand and apply the invention for the ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. a 3-benzotriazole replacement-1-(1, the 3-diaryl) propene compound, it is characterized in that: the structure of this compounds is as general formula (I) or (II):
Wherein:
* be chiral carbon atom;
R
1Be selected from aryl or alkyl;
R
2Be selected from hydrogen, chlorine, methyl or nitro substituent.
2. 3-benzotriazole replacement-1-according to claim 1 (1, the 3-diaryl) propene compound, it is characterized in that: described aryl is selected from phenyl, naphthyl, tolyl, methoxyphenyl or bromophenyl.
3. 3-benzotriazole replacement-1-according to claim 1 (1, the 3-diaryl) propene compound, it is characterized in that: described alkyl is selected from methyl or ethyl.
4. the preparation method of the arbitrary described 3-benzotriazole replacement-1-of claim 1 to 3 (1, the 3-diaryl) propene compound, it is characterized in that: this method reaction formula is as follows, may further comprise the steps:
In the reaction tubes of an exsiccant argon shield, add catalyzer, part and organic solvent successively, stirred 30 minutes under the room temperature, in reaction tubes, add compound (IV), compound (III) and alkali more successively, stirring at room reaction 12-48h, after reaction finishes, prepare compound (I) or (II);
Wherein, described compound (IV): compound (III): alkali: catalyzer: the mol ratio of part is 2～1.5: 1: 1: 0.05: 0.1.
5. 3-benzotriazole replacement-1-(1 according to claim 4, the 3-diaryl) preparation method of propene compound is characterized in that: described compound (IV): compound (III): alkali: catalyzer: the mol ratio of part is 2: 1: 1: 0.05: 0.1.
6. the preparation method of 3-benzotriazole replacement-1-according to claim 4 (1, the 3-diaryl) propene compound is characterized in that: LG is a leavings group in the described compound (III), is selected from methyl carbonate, ethyl-carbonate or acetic ester.
7. 3-benzotriazole replacement-1-(1 according to claim 4, the 3-diaryl) preparation method of propene compound, it is characterized in that: described catalyzer is a non-valent palladium metal complex compound, is selected from three (dibenzalacetones), two palladiums, (dibenzalacetone) palladium or allyl palladium chloride.
8. the preparation method of 3-benzotriazole replacement-1-according to claim 4 (1, the 3-diaryl) propene compound, it is characterized in that: described part is selected from the optically pure part with following structural formula:
9. 3-benzotriazole replacement-1-(1 according to claim 4, the 3-diaryl) preparation method of propene compound is characterized in that: described alkali is selected from a kind of in Quilonum Retard, yellow soda ash, salt of wormwood, potassiumphosphate, cesium carbonate, DBU, BSA, n-Butyl Lithium, sodium hydride, lithium hydride or the potassium hydride KH; Described organic solvent is selected from benzene, tetracol phenixin, trichloromethane, methylene dichloride, tetrahydrofuran (THF), N, a kind of in dinethylformamide, ether, dioxane or the acetonitrile.
10. the arbitrary described 3-benzotriazole replacement-1-of claim 1 to 3 (1, the 3-diaryl) propene compound is as the purposes of novel drugs research and development.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936685A (en) * | 2014-03-25 | 2014-07-23 | 同济大学 | 3-(tri(benzotriazol-1-yl)methyl)-1-(1,3-dialkyl)propylene compounds and synthetic method thereof |
| CN107382887A (en) * | 2017-07-06 | 2017-11-24 | 浙江工业大学 | A kind of method of synthesis N alkenyloxy group benzotriazole compounds |
| CN110204499A (en) * | 2019-05-07 | 2019-09-06 | 西南民族大学 | A kind of method of regio-selective synthesis N-2- allyl -1,2,3- triazole derivative |
| CN115814849A (en) * | 2022-11-25 | 2023-03-21 | 中国科学院大学 | Synthetic catalyst and catalytic method for various tri-substituted olefin compounds and heterocyclic compounds |
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2011
- 2011-04-26 CN CN2011101059136A patent/CN102229574A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936685A (en) * | 2014-03-25 | 2014-07-23 | 同济大学 | 3-(tri(benzotriazol-1-yl)methyl)-1-(1,3-dialkyl)propylene compounds and synthetic method thereof |
| CN107382887A (en) * | 2017-07-06 | 2017-11-24 | 浙江工业大学 | A kind of method of synthesis N alkenyloxy group benzotriazole compounds |
| CN110204499A (en) * | 2019-05-07 | 2019-09-06 | 西南民族大学 | A kind of method of regio-selective synthesis N-2- allyl -1,2,3- triazole derivative |
| CN115814849A (en) * | 2022-11-25 | 2023-03-21 | 中国科学院大学 | Synthetic catalyst and catalytic method for various tri-substituted olefin compounds and heterocyclic compounds |
| CN115814849B (en) * | 2022-11-25 | 2024-03-08 | 中国科学院大学 | Catalyst and method for synthesizing various trisubstituted olefin compounds and heterocyclic compounds |
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