CN102146015A - 1,3 conjugated diyne compound and preparation method thereof - Google Patents
1,3 conjugated diyne compound and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a 1,3 conjugated diyne compound and a preparation method thereof. The compound has the structural general formula shown as the description, wherein R1 or R2 is selected from methyl-containing aryl, fluorine-containing aryl, bromine-containing aryl, methoxyl-containing aryl, alcoholic methyl, benzyloxy methyl and acetoxy methyl. Compared with the prior art, the invention can more effectively catalyze the reaction and provides a new method for more smooth reaction; meanwhile, another new property of lanthanide is discovered, so that the application of the lanthanide is wider; and the reaction condition is mild and the operation is simple and convenient, wherein the self-coupling recovery is 94-99 percent and the cross-coupling product selectivity is 58-84 percent.
Description
Technical field
The invention belongs to technical field of organic chemistry, relate to a kind of 1,3 conjugation dialkyne and preparation method thereof.
Background technology
1,3 conjugation dialkyne is the important intermediate of organic synthesis still not, and is many natural products and basic framework with physiologically active compound.Its unique physico-chemical property plays irreplaceable effect in various kinds of drug and material.In recent years, how to make this reaction more more and more receive publicity.[(a) J.M.Tour, Chem.Rev.1996,96,537. (b) R.E.Martin, F.Diederich, Angew.Chem, Int.Ed.1999,38,1350. (c) M.P.Lopez-Alberca, M.J.Mancheno, I.Fernandez, M.Gomez-Gallego, M.A.Sierra, Org.Lett.2008,10,365. (d) L.Wenjun, Z.Yan, Z.Qifeng, M.Yuguo, P.Jian, Org.Lett, 2008,10,2123. (e) Jamie Kendall, Robert McDonald, Michael J.Ferguson, Rik R.Tykwinski, Org.Lett, 2008,10,2163-2166. (f) M.D.Weller, B.M.Kariuki, L.R.Cox, J.Org.Chem.2009,74,7898. (g) Z.Ningzhang, Z.Yuming, J.Org.Chem.2010,75,1498.], very more [(a) C.Glaser of method of synthetic this compound of bibliographical information, Ber.Dtsch.Chem.Ges.1869,2,422. (b) A.S.Hay, J.Org.Chem.1962,27,3320. (c) R.Rossi, A.Carpita, C.Bigelli, Tetrahedron Lett.1985,26,523. (d) G.T.Crisp, B.L.Flynn, J.Org.Chem.1993,58,6614. (e) Q.Liu, D.J.Burton, Tetrahedron Lett.1997,38,4371. (f) A.Lei, M.Srivastava, X.Zhang, J.Org.Chem.2002,67,1969. (g) I.J.S.Fairlamb, P.S.Baeuerlein, L.R.Marrison, J.M.Dickinson, Chem.Commun.2003,632. (h) D.A.Alonso, C.Najera, M.C.Pacheco, Adv.Synth.Catal.2003,345,1146. (i) A.S.Batsanov, J.C.Collings, I.J.S.Fairlamb, J.P.Holland, J.A.K.Howard, Z.Lin, T.B.Marder, A.C.Parsons, R.M.Ward, J.Zhu, J.Org.Chem.2005,70,703. (j) J.H.Li, Y.Liang, Y.X.Xie, J.Org.Chem.2005,70,4393. (k) W.Yin, C.He, M.Chen, H.Zhang, A.Lei, Org.Lett.2009,11,709.] yet, such reaction exists temperature generally higher, defectives such as general length of reaction times.This catalyst system can strengthen reaction efficiency, also promotes the development in this field simultaneously, and a part of replenishing the rare earth metal Application Areas is blank.
Summary of the invention
Purpose of the present invention is exactly in order to overcome the defective that above-mentioned prior art exists, and provides a kind of applicable to dissimilar terminal alkyne compounds, reaction conditions gentleness, 1,3 conjugation dialkyne easy and simple to handle and preparation method thereof.
To achieve these goals, the present invention is by the following technical solutions:
A kind of 1,3 conjugation dialkyne, its general structure is as follows:
Wherein, R
1Or R
2Be selected from methylic aryl, fluorine-containing aryl, bromated aryl, the aryl that contains methoxyl group, pure methyl, benzyloxymethyl or the acetyl-o-methyl any.
The method of above-mentioned 1, the 3 conjugation dialkyne of a kind of preparation comprises step:
(1) in organic solvent, under-20 ℃ to 50 ℃, add promotor or additive earlier, add catalyzer again, after 3-7 minute, add terminal alkyne
Reacted 1-24 hour, and made 1,3 conjugation dialkyne;
(2) separate, purify, get purified 1,3 conjugation dialkyne.
Described promotor is LaCl
3
Described catalyzer is cuprous iodide (CuI) and N, N, N, N-Tetramethyl Ethylene Diamine (TMEDA).
Described terminal alkyne, LaCl
3, CuI, TMEDA mol ratio be 1: 0.03-0.15: 0.03-0.11: 0.05-0.2.
Described terminal alkyne compounds
In the structure of R be methylic aryl, fluorine-containing aryl, bromated aryl, contain the aryl of methoxyl group, any one or a few in pure methyl, benzyloxymethyl or the acetyl oxygen.
Described additive is selected from ferrous sulfate, iron(ic) chloride, Silver monobromide, Sulfuric acid disilver salt, three fluosulfonic acid copper (Cu (OTf)
2) or thiophenic acid cuprous (CuTc) in any.
Described organic solvent is a triethylamine, tetrahydrofuran (THF), in toluene, methylene dichloride or the acetonitrile any.
Described 1,3 conjugation dialkyne separates through thin-layer chromatography, column chromatography, recrystallization or underpressure distillation.
Described recrystallization method, solvent are Virahol or methylene dichloride-normal hexane mixed solvent.
Described thin-layer chromatography, column chromatography, used developping agent are the mixed solvent of non-polar solvent and polar solvent.
The mixed solvent of described non-polar solvent and polar solvent is sherwood oil-methylene dichloride, mixed solvents such as petroleum ether-ethyl acetate or sherwood oil-ether, and its volume ratio can be respectively: non-polar solvent: polar solvent=100-20: 1.For example: petrol ether/ethyl acetate=100-20: 1, sherwood oil/methylene dichloride=100-20: 1.
The invention has the beneficial effects as follows:
The present invention relates to a kind of LaCl
3Help the linked reaction of catalytic terminal alkyne, it is in organic solvent that the linked reaction of described terminal alkyne generates 1,3 conjugation diine, under the room temperature, with LaCl
3, CuI, TMEDA are the common catalyst system, are raw material with different terminal alkynes, react to make the terminal alkyne coupled product in 1-24 hour.Compared with prior art, the present invention's catalysis more effectively should react, and for this reaction provides new method more smoothly, simultaneously, had also found another new character of lanthanon, made its application more extensive, and this reaction conditions gentleness is easy and simple to handle.Be 94%-99% from the coupling yield wherein, the cross-coupling selectivity of product also can reach 58%-84%.
Embodiment
To help to understand the present invention by following embodiment, but not limit content of the present invention.
Embodiment 1:
Lanthanum helps in the catalytic terminal alkyne coupling reaction process, and additive, temperature, solvent are studied the influence of reaction.
(1) according to each amounts of components and the reaction conditions that provide in the table 1, in organic solvent, under-20 ℃ to 50 ℃, add promotor or additive earlier, add catalyzer again, after 3-7 minute, add terminal alkyne
Reacted 1-12 hour, and made 1,3 conjugation dialkyne;
(2) separate, purify, get purified 1,3 conjugation dialkyne.
Table 1 Lanthanum trichloride helps the conditional filtering of catalytic terminal alkyne linked reaction
A: do not add Lewis acid; B:Et
3N/THF=2/1; C:NR=does not react .d: do not add LaCl
3E: post separates.
Wherein DCM is a methylene dichloride, and Toluene is a toluene, and THF is a tetrahydrofuran (THF), Et
3N is a triethylamine, CH
3CN is an acetonitrile.Rt refers to room temperature.
Embodiment 2:
Lanthanon helps the research of catalysis terminal alkyne linked reaction:
(1) according to each amounts of components and the reaction conditions that provide in the table 2, in organic solvent, under the room temperature, add promotor or additive earlier, add catalyzer again, after 3-7 minute, add terminal alkyne
Reacted 1-24 hour, and made 1,3 conjugation dialkyne;
(2) separate, purify, get purified 1,3 conjugation dialkyne.
The screening of table 2 lanthanide series compound
Under uncovered condition, once add Et
3N, THF, TMEDA, Ln, CuI stirred after 5 minutes, added terminal alkyne.Stirring at room.The thin-layer chromatography detection reaction.After reaction finished, the residue thin-layer chromatography obtained target product (sherwood oil) after the removal of solvent under reduced pressure.
Embodiment 3:
Lanthanum trichloride help catalytic terminal alkyne from linked reaction research.
(1) according to each amounts of components and the reaction conditions that provide in the table 3, in organic solvent, under the room temperature, add the promotor Lanthanum trichloride earlier, add the catalyzer cuprous iodide again, N, N, N, the N-Tetramethyl Ethylene Diamine after 3-7 minute, adds terminal alkyne
Reacted 1-12 hour, and made 1,3 conjugation dialkyne;
(2) separate, purify, get purified 1,3 conjugation dialkyne.
Table 3 Lanthanum trichloride help catalytic terminal alkyne from linked reaction
Embodiment 4:
Lanthanum trichloride helps the research of the cross-coupling reaction of catalytic terminal alkyne.
(1) according to each amounts of components and the reaction conditions that provide in the table 4, in organic solvent, under the room temperature, the promotor Lanthanum trichloride adds the catalyzer cuprous iodide again, N, and N, N, the N-Tetramethyl Ethylene Diamine after 3-7 minute, adds terminal alkyne
Reacted 12 hours, and made 1,3 conjugation dialkyne;
(2) separate, purify, get purified 1,3 conjugation dialkyne.
Table 4 Lanthanum trichloride helps the cross-coupling reaction of catalytic terminal alkyne
[1] than substrate that value representation adds
With
Between the amount of substance ratio.[2] time of cross-coupling reaction is 12 hours in the present embodiment.
P1:1,4-phenylbenzene-1,3-diacetylene (2a)
White crystal, fusing point 88.0-88.7 ℃,
1H NMR (400MHz) δ 7.53 (d, J=7.2Hz, 4H), 7.34 (d, J=7.6Hz, 6H).
P2:1,4-two p-methylphenyls-1,3-diacetylene (2b)
White solid, fusing point 136.6-137.8 ℃,
1H NMR (400MHz) δ 7.45-7.38 (dt, J=8.0Hz J=1.6Hz, 4H), 7.14 (dd, J=8.4, J=0.4Hz, 4H), 2.36 (s, 6H).
P3:1,4-Dimethoxyphenyl-1,3-diacetylene (2c)
White-yellowish solid, fusing point 137.5-138.9 ℃,
1H NMR (400MHz) δ 7.45 (d, J=7.2Hz, 4H), 6.84 (d, J=7.2Hz, 4H), 3.81 (d, J=0.8Hz, 6H).
P4:1, two pairs of bromo phenyl-1 of 4-, 3-diacetylene (2d)
Yellow solid, fusing point 141.2-142.5 ℃,
1H NMR (400MHz) δ 7.48 (d, J=7.6Hz, 4H), 7.38 (d, J=8.0Hz, 4H).
P5:1, two pairs of fluorine-based phenyl-1 of 4-, 3-diacetylene (2e)
Yellow solid, fusing point 180.3-181.9 ℃,
1H NMR (400MHz) δ 7.51 (s, 4H), 7.04 (t, J=7.6Hz, 4H) .FHMR (400MHz) δ-108.4804 (d, J=11Hz)
P6:1, aminomethyl phenyl between 4--1,3-diacetylene (2f)
White crystal, fusing point 67.5-68.7 ℃,
1H NMR (400MHz) δ 7.34 (s, 1H), 7.26-7.13 (m, 1H), 2.33 (s, 6H).
P7:1,6-benzyloxy-2,4-hexadiyne (2g)
Yellow oily liquid,
1H NMR (400MHz) δ 7.44-7.35 (m, 10H), 4.66 (s, 1H), 4.30 (s, 1H).
P8:1,6-diacetate base-2,4-hexadiyne (2h)
Yellow solid, fusing point 29.7-31.0 ℃,
1H NMR (400MHz) δ 4.73 (d, J=2.0Hz, 1H), 2.10 (d, J=2.4Hz, 1H).
P9:1-acetate groups-5-phenyl-2,4-pentadiine (3a)
White yellow solid, fusing point 120.3-121.7 ℃,
1H NMR (400MHz) δ 7.49 (d, J=7.2Hz, 2H), 7.40-7.31 (m, 3H), 4.82 (s, 2H), 2.12 (s, 3H).
P10:1-acetate groups-5-(to bromo) phenyl-2,4-pentadiine (3d)
White-yellowish solid, fusing point 82.1-82.8 ℃,
1H NMR (400MHz) δ 7.48 (d, J=6.4Hz, 2H), 7.36 (d, J=6.8Hz, 2H), 4.83 (d, J=2.0Hz, 2H), 2.14 (d, J=2.0Hz, 3H).
13C NMR (100MHz) δ 170.05,134.01,131.83,124.07,120.19,77.63,74.18,71.82,70.95,52.52,20.66.MS (EI) 276.IR (KBr): v
Max(cm
-1)=2960,2913,2421,2360,1739,1643,1382,1213,817,739,521.
P11:1-acetate groups-5-(to fluorine-based) phenyl-2,4-pentadiine (3c)
White solid, fusing point 79.7-81.2 ℃,
1H NMR (400MHz) δ 7.48 (d, J=2.8Hz, 2H), 7.02 (t, J=8.0Hz, J=8.4Hz, 2H), 4.81 (s, 2H), 2.12 (s, 3H).
13C NMR (100MHz) δ 170.08,163.21 (d, J=250.9Hz), 134.75 (d, J=8.7Hz), 117.34 (d, J=3.6Hz), 115.94 (d, J=11.9Hz), 77.71,76.19,72.85,71.03,52.54,20.66.
19F NMR (400MHz) δ-108.09.MS (EI) 216.IR (KBr): v
Max(cm
-1)=3104,3056,2926,2247,1730,1595,1504,1434,1365,1247,1217,1160,1110,917,839,786,595,534.
P12:1-phenyl-5-benzyloxy-2,4-pentadiine (3d)
Yellow solid, fusing point 98.1-98.7 ℃,
1H NMR (400MHz) δ 7.52-7.49 (m, 2H), 7.39-7.30 (m, 8H), 4.64 (s, 1H), 4.32 (s, 1H)
P13:1-(to bromo) phenyl-5-benzyloxy-2,4-pentadiine (3e)
White-yellowish solid, fusing point 59.4-60.8 ℃,
1H NMR (400MHz) δ 7.47 (d, J=8.4Hz, 2H), 7.37-7.31 (m, 7H), 4.64 (s, 2H), 4.32 (s, 2H).
13C NMR (100MHz) δ 137.10,134.00,131.82,128.55,128.21,128.08,123.88,120.44,79.45,74.41,71.85,70.97,57.77,53.47.MS (EI) 325.IR (KBr): v
Max(cm
-1)=2921,2856,2234,1943,1895,1639,1582,1487,1452,1391,1347,1065,1004,900,813,739,691,513.
P13:1-hydroxyl-5-phenyl-2,4-pentadiine (3f)
White solid, fusing point 41.0-42.1 ℃,
1H NMR (400MHz) δ 7.49 (d, J=7.2Hz, 2H), 7.37-7.30 (m, 3H), 4.42 (s, 2H), 1.96 (s, 1H).
P14:1-hydroxyl-5-(to methyl) phenyl-2,4-pentadiine (3g)
White solid, fusing point 81.5-82.7 ℃,
1H NMR (400MHz) δ 7.39 (s, 2H), 7.13 (s, 2H), 4.42 (s, 2H), 2.36 (s, 3H), 1.77 (s, 1H).
P15:1-hydroxyl-5-(to bromo) phenyl-2,4-pentadiine (3h)
White-yellowish solid, fusing point 129.0-130.7 ℃,
1H NMR (400MHz) δ 7.46 (d, J=8.0Hz, 2H), 7.34 (d, J=7.6Hz, 2H), 4.42 (s, 2H), 2.36 (s, 3H), 1.80 (s, 1H).
The above-mentioned description to embodiment is can understand and apply the invention for 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. conjugation dialkyne, it is characterized in that: it is as follows that it has general structure:
Wherein, R
1Or R
2Be selected from methylic aryl, fluorine-containing aryl, bromated aryl, the aryl that contains methoxyl group, pure methyl, benzyloxymethyl or the acetyl-o-methyl any.
2. method for preparing 1,3 conjugation dialkyne described in the claim 1 is characterized in that: comprise following steps:
(1) in organic solvent, under-20 ℃ to 50 ℃, add promotor or additive earlier, add catalyzer again, after 3-7 minute, add terminal alkyne
Reacted 1-24 hour, and made 1,3 conjugation dialkyne;
(2) separate, purify, get purified 1,3 conjugation dialkyne.
3. method according to claim 2 is characterized in that: described promotor is LaCl
3Or described catalyzer is cuprous iodide and N, N, N, N-Tetramethyl Ethylene Diamine.
4. method according to claim 2 is characterized in that: described terminal alkyne, LaCl
3, cuprous iodide, N, N, N, the mol ratio of N-Tetramethyl Ethylene Diamine is 1: 0.03-0.15: 0.03-0.11: 0.05-0.2.
5. method according to claim 2 is characterized in that: described terminal alkyne compounds
In the structure of R be selected from methylic aryl, fluorine-containing aryl, bromated aryl, contain the aryl of methoxyl group, any one or a few in pure methyl, benzyloxymethyl or the acetyl oxygen.
6. method according to claim 2 is characterized in that: described additive be selected from ferrous sulfate, iron(ic) chloride, Silver monobromide, Sulfuric acid disilver salt, three fluosulfonic acid copper or thiophenic acid cuprous in any; Or described organic solvent is triethylamine, tetrahydrofuran (THF), in toluene, methylene dichloride or the acetonitrile any.
7. method according to claim 2 is characterized in that: described 1,3 conjugation dialkyne separates through thin-layer chromatography, column chromatography, recrystallization or underpressure distillation.
8. method according to claim 7 is characterized in that: described recrystallization method, solvent are Virahol or methylene dichloride-normal hexane mixed solvent.
9. method according to claim 7 is characterized in that: described thin-layer chromatography, column chromatography, used developping agent are the mixed solvent of non-polar solvent and polar solvent.
10. method according to claim 9, it is characterized in that: the mixed solvent of described non-polar solvent and polar solvent is sherwood oil-methylene dichloride, the mixed solvent of petroleum ether-ethyl acetate or sherwood oil-ether, its volume ratio is: non-polar solvent: polar solvent=100-20: 1.
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| CN104710254A (en) * | 2015-01-23 | 2015-06-17 | 绍兴文理学院 | Preparation method of symmetric 1,4-disubstituted-1,3-diacetylene |
| CN104974008A (en) * | 2015-06-02 | 2015-10-14 | 湖南大学 | Novel method for catalytically synthesizing 1,3-diyne compound with simple, highly efficient and reusable copper catalytic system |
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| CN101948463A (en) * | 2010-01-19 | 2011-01-19 | 清华大学 | Method for synthesizing substituted pyrrole by cycloaddition reaction of 1, 3-diyne and primary amine |
| CN102120735A (en) * | 2011-01-20 | 2011-07-13 | 清华大学 | Method for preparing substituted furan containing 2,5-di-substituent |
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| CN102964370B (en) * | 2012-12-10 | 2016-01-20 | 同济大学 | 2,3,5-trisubstituted thiophenes and its production and use |
| CN104710254A (en) * | 2015-01-23 | 2015-06-17 | 绍兴文理学院 | Preparation method of symmetric 1,4-disubstituted-1,3-diacetylene |
| CN105859529A (en) * | 2015-02-06 | 2016-08-17 | 信越化学工业株式会社 | Method for producing asymmetric conjugated diyne compound and method for producing Z,Z-conjugated diene compound using the same |
| CN105859529B (en) * | 2015-02-06 | 2020-10-16 | 信越化学工业株式会社 | Method for producing asymmetric conjugated diyne compound and method for producing Z, Z-conjugated diene compound using the same |
| CN105013535A (en) * | 2015-05-29 | 2015-11-04 | 湖南大学 | Catalyst for preparing asymmetric conjugated dialkyne compound and synthesis method therefor |
| CN105013535B (en) * | 2015-05-29 | 2018-02-02 | 湖南大学 | A kind of catalyst and its synthetic method for preparing asymmetric conjugation diine hydrocarbon compound |
| CN104974008B (en) * | 2015-06-02 | 2019-05-28 | 湖南大学 | A kind of method that easy, efficient, reusable copper catalyst system catalyzes and synthesizes 1,3-, bis- acetylene compound |
| CN104974008A (en) * | 2015-06-02 | 2015-10-14 | 湖南大学 | Novel method for catalytically synthesizing 1,3-diyne compound with simple, highly efficient and reusable copper catalytic system |
| CN106631718A (en) * | 2016-12-12 | 2017-05-10 | 安徽师范大学 | Synthesis method of asymmetric conjugated diyne |
| CN113636904A (en) * | 2021-08-12 | 2021-11-12 | 浙江工业大学 | Green preparation method of conjugated diyne compound with participation of water-soluble vitamin E |
| CN115073259A (en) * | 2022-06-20 | 2022-09-20 | 常州大学 | Preparation method for synthesizing 1, 4-diphenyl-1, 3-diacetylene or derivatives thereof |
| CN115073259B (en) * | 2022-06-20 | 2023-09-29 | 常州大学 | Preparation method for synthesizing 1, 4-diphenyl-1, 3-diacetylene or derivatives thereof |
| CN115385842A (en) * | 2022-08-23 | 2022-11-25 | 清华大学 | Pyrrole derivative containing triarylamine substituent and preparation method and application thereof |
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Application publication date: 20110810 |