CN104119255A - Method for preparing polyfluoro-alkyl-containing cyclobutene derivatives - Google Patents
Method for preparing polyfluoro-alkyl-containing cyclobutene derivatives Download PDFInfo
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Abstract
The invention relates to a method for preparing polyfluoro-alkyl-containing cyclobutene derivatives from 3-aza-1-ene-5-yne derivatives, and concretely relates to a method for efficiently generating cyclobutene derivatives by heating 3-aza-1-ene-5-yne derivatives. The employed method does not use transition-metal catalysts, and polysubstituted cyclobutene derivatives, which are difficult to obtain by employing other methods, are obtained through simple steps.
Description
Technical field
The present invention relates to a kind ofly by 3-azepine-1,5-eneyne derivative is prepared the method for the Cycloene derivate of polyfluorinated alkyl.
Background technology
Cycloene derivate is the important carbocyclic ring of a class, as important structural unit be extensively present in natural product and have in the molecule of physiologically active (document 1:Dembitsky, V.M.J.Nat.Med.2008,62,1.).Owing to there being very large ring strain, cyclobutene is also that important synthesis module is used for synthesizing a series of complex compound (document 2:Namyslo, J.C.; Kaufmann, D.E.Chem.Rev.2003,103,1485.).Synthetic Cycloene derivate mainly contains following four class methods: method one: [2+2] cycloaddition alkynes and alkene (document 3:(a) Nishimura, A.; Ohashi, M.; Ogoshi, S.J.Am.Chem.Soc.2012,134,15692; (b) L ó pez-Carrillo, V.; Echavarren, A.M.J.Am.Chem.Soc.2010,132,9292; (c) Ishihara, K.; Fushimi, M.J.Am.Chem.Soc.2008,130,7532; (d) Inanaga, K.; Takasu, K.; Ihara, M.J.Am.Chem.Soc.2005,127,3668; (e) Liu, Y.; Liu, M.; Song, Z.J.Am.Chem.Soc.2005,127,3662; (f) Sweis, R.F.; Schramm, M.P.; Kozmin, S.A.J.Am.Chem.Soc.2004,126,7442. (g) Treutwein, J.; Hilt, G.Angew.Chem., Int.Ed.2008,47,6811; (h) Lu, B.L.; Shi, M.Angew.Chem., Int.Ed.2011,50,12027; (i) Schotes, C.; Mezzetti, A.Angew.Chem., Int.Ed.2011,50,3072; (j) Treutwein, J.; Hilt, G.Angew.Chem., Int.Ed.2008,47,6811.).Method two: obtain (document 4:(a) F ü rstner, A. by ring expansion by cyclopropane derivative; A ü ssa, C.J.Am.Chem.Soc.2006,128,6306; (b) Shi, M.; Liu, L.-P.; Tang, J.J.Am.Chem.Soc.2006,128,7430; (c) Li, C.W.; Pati, K.; Lin, G.Y.; Abu Sohel, S.M.; Hung, H.H.; Liu, R.S.Angew.Chem., Int.Ed.2010,49,9891; (d) Xu, H.D.; Zhang, W.; Shu, D.X.Werness, J.B.; Tang, W.P.Angew.Chem., Int.Ed.2008,47,8933; (e) Liu, L.; Zhang, J.L.Angew.Chem., Int.Ed.2009,48,6093; (f) Liu, R.; Zhang, M.; Wyche, T.P.; Winston-McPherson, G.N.; Bugni, T.S.; Tang, W.P.Angew.Chem., Int.Ed.2012,51,7503; (g) Trost, B.M.; Keeley, D.E.; Arndt, H.C.; Bogdanowicz, M.J.J.Am.Chem.Soc.1977,99,3088; (h) Tian, G. – Q.; Yuan, Z. – L.; Zhu Z. – B.; Shi, M.Chem.Commun.2008,2668; (i) Masarwa, A.; F ü rstner, A.; Marek, I.Chem.Commun.2009,5760.).Method three: obtain (document 5:(a) F ü rstner, A. by eneyne cyclization isomerization reaction; Davies, P.W.; Gress, T.J.Am.Chem.Soc.2005,127,8244; (b) Escribano-Cuesta, A.; P é rez-Gal á n, P.; Herrero-G ó mez, E.; Sekine, M.; Braga, A.A.C.; Maseras, F.; Echavarren, A.M.Org.Biomol.Chem.2012,10,6105; (c) Matsuda, T.; Kadowaki, S.; Goya, T.; Murakami, M.Synlett, 2006,575.).Method four: obtain (document 6:(a) Marvell, E.N.Thermal Electrocyclic Reactions through electrocyclic reaction by connection alkene-ene derivative; Academic Press:New York, 1980; Pp145-146; (b) Schuster, H.F.; Coppola, G.M.Allenes in Organic Synthesis; Wiley:New York, 1984; Pp89-104; (c) Pasto, D.J.; Kong, W.J.Org.Chem.1989,54,4028. (a) Delas, C.; Urabe, H.; Sato, F.J.Am.Chem.Soc.2001,123,7937; (d) Gil-Av, E.; Herling, J.Tetrahedron Lett.1967,1.Schneider, R.; Siegel, H.; Hopf, H.Liebigs Ann.Chem.1981,1812; (e) Rey, J.G.; Rodr1 ' rguez, J.; De Lera, A.R.Tetrahedron Lett.1993,34,6293; (f) Murakami, M.; Amii, H.; Itami, K.; Ito, Y.Angew.Chem., Int.Ed.Engl.1995,34,1476.).We have developed azepine-1 by 3-, and 5-eneyne derivative is prepared the novel method of polyfluorinated alkyl Cycloene derivate.Organic fluorocompound has unique physics and chemistry character, thereby is widely used in key areas (document 7:For recent reviews, the see:(a) Tomaschenko such as medicine, material, agricultural chemicals, O.A.; Grushin, V.V.Chem.Rev.2011,111,4475; (b) Purser, S.; Moore, P.R.; Swallow, S.; Gouverneur, V.Chem.Soc.Rev.2008,37,320; (c) Mu ller, K.; Faeh, C.; Diederich, F.Science2007,317,1881; (d) Kirsch, P.Modern Fluoroorganic Chemistry:Synthesis, Reactivity, Applications; Wiley-VCH:Weinhiem, Germany, 2004; (e) Hiyama, T.Organofluorine Chemistry, Principles, and Commercial Applications; Banks, R.E., Smart, B.E., Tatlow, C.J., Eds.; Springer:New York, 1994; Pp237-262.).The cyclobutene product of present method synthesized contains the functional groups such as Polyfluoroalkyl, has potential physiologically active.Substituting group new style, is difficult to synthetic this compound by other method.The method is not used transition-metal catalyst, the functionalized cyclobutene biologic that obtains through simple operation step with regard to the high yield of energy.
Summary of the invention
The object of the present invention is to provide a kind of novel method of synthetic polyfluorinated alkyl Cycloene derivate.
Reaction equation 1. is by 3-azepine-1, and 5-eneyne synthesizes Cycloene derivate
Concrete operation step following (reaction equation 1):
In reactor, react, reactor vacuumizes rear logical argon replaces, adds 3-azepine-1, and then 5-eneyne 1 adds solvent, reacts 12 to 96 hours at 20 ℃-140 ℃; After reaction finishes, with Rotary Evaporators, take out solvent, solid is dissolved in methylene dichloride loading and carries out silica gel column chromatography, obtains Cycloene derivate 2.
R wherein
1, R
2, R
3, R
4the phenyl that is respectively C1-C8 alkyl, pyridyl, phenyl or replaces, the substituting group on phenyl is C1-C8 alkyl, C1-C8 alkoxyl group, F, Cl, Br, I, NO
2in a kind of or two kinds or three kinds; R
ffor Polyfluoroalkyl: CF
3, CF
2cl, C
2f
5, C
3f
7or C
4f
9.
Solvent is DMF, N,N-dimethylacetamide, methyl-phenoxide, toluene, Isosorbide-5-Nitrae-dioxane, 1, one or both in 2-ethylene dichloride, acetonitrile, tetrahydrofuran (THF), methyl alcohol, acetone, methylene dichloride; The consumption of solvent is every mmole reactant 3-azepine-1,20 milliliters of solvent 5 – for 5-eneyne (1);
Building-up reactions thing 3-azepine-1, reaction formula and the step of 5-eneyne 1 are as follows:
R wherein
1, R
2, R
3, R
4for the phenyl of C1-C8 alkyl, pyridyl, phenyl or replacement, the substituting group on phenyl is C1-C8 alkyl, C1-C8 alkoxyl group, F, Cl, Br, I, NO
2in a kind of or two kinds or three kinds; R
ffor Polyfluoroalkyl: CF
3, CF
2cl, C
2f
5, C
3f
7or C
4f
9;
Concrete operation step is as follows:
In reactor, react, reactor vacuumizes after logical argon replaces, adds the new CH steaming of 40ml
2cl
2; Then add the N-alkylsulfonyl-allylamine of 5mmol formula 3 and the alkynes of 5.0-7.5mmol formula 4; The Cs that finally adds 5-20mol%
2cO
3, 0 ℃-stirring at room 1-24 hour; After reaction finishes, revolve and evaporate partial solvent to the 1/4-1/5 of liquor capacity for liquor capacity before not evaporating, loading is carried out 3-azepine-1 that silica gel column chromatography obtains formula 1,5-eneyne.
N-alkylsulfonyl-allylamine 3 is 1:1-1.5 with the mol ratio of alkynes 4; The CH that N-alkylsulfonyl-allylamine 3 of every 1mmol adopts
2cl
2for 6-15ml.
The present invention has following advantage:
1. reactant 3-azepine-1,5-eneyne 1 is obtained through simple reaction step by raw material aldehyde cheap and easy to get, sulphonamide and Terminal Acetylenes warp and interior alkynes, and raw material is cheap and easy to get.
2. operation is simple; Do not use transition-metal catalyst, environmental friendliness.
3. cyclobutene product functional group is abundant, contains the functional groups such as Polyfluoroalkyl, sulfoamido and exocyclic double bond, by other method, is difficult to the synthetic Cycloene derivate with this substituting group pattern.
Embodiment
In order to understand better the present invention, by following instance, describe.
Embodiment 1
In reactor, react, reactor vacuumizes rear logical argon replaces three times, adds 0.2mmol(102.7mg) 3-azepine-1,5-eneyne 1a and 1mL1,4-dioxane, stirring reaction is 24 hours at 100 ℃.After reaction finishes, under vacuum, take out solvent, then sample is dissolved in to methylene dichloride loading and carries out silica gel column chromatography, eluent is the mixed solvent of sherwood oil: ethyl acetate=20:1, obtains the cyclobutene 2a of 93.2mg.Separation yield is 91%.
The characterization data of compound 1a is as follows:
1H?NMR(500MHz,CDCl
3)δ7.85(d,J=8.3Hz,2H),7.59–7.49(m,2H),7.39–7.32(m,4H),7.32–7.26(m,4H),7.24–7.14(m,2H),6.40(s,2H),3.74(s,3H),2.37(s,3H);
13C?NMR(125MHz,CDCl3)δ162.57,144.87,135.29,134.87(d,J=39.2Hz),134.37,133.17,131.61,129.82,129.32,129.23,129.17,128.75,128.74,128.49,121.62,119.54(d,J=277.4Hz),89.53,83.72,56.82,52.73,21.66;
19F?NMR(471MHz,CDCl
3)δ-62.80;HRMS?calcd?for?C
27H
22NO
4F
3NaS[M+Na]
+536.1119,found536.1139.
The sign number of compound 2a is as follows:
1H?NMR(500MHz,CDCl
3)δ7.75–7.70(m,2H),7.31(m,1H),7.18–7.08(m,7H),7.00(dd,J=10.7,4.8Hz,2H),6.74(d,J=7.3Hz,2H),6.57(s,1H),6.03(s,1H),3.75(s,3H),2.26(s,3H);
13C?NMR(125MHz,CDCl
3)δ161.26,161.22,143.93,137.94,133.48,130.89,130.74,130.56,129.91,129.59,129.54,129.41,128.54,128.14,127.80,127.73,127.64,123.91(q,J=283.2Hz),67.00(q,J=32.1Hz),51.98,21.48;
19F?NMR(471MHz,CDCl
3)δ-74.65;HRMS?calcd?for?C
27H
22NO
4F
3NaS[M+Na]
+536.1119,found536.1141.
Embodiment 2
In reactor, react, reactor vacuumizes rear logical argon replaces three times, adds 0.2mmol(106.0mg) 3-azepine-1,5-eneyne 1b and 1mL1,4-dioxane, stirring reaction is 24 hours at 100 ℃.After reaction finishes, under vacuum, take out solvent, then sample is dissolved in to methylene dichloride loading and carries out silica gel column chromatography, eluent is the mixed solvent of sherwood oil: ethyl acetate=20:1, obtains the cyclobutene 2b of 77.3mg.Separation yield is 73%.
The characterization data of compound 1b is as follows:
1H?NMR(500MHz,CDCl
3)δ7.86(d,J=8.3Hz,2H),7.56(dd,J=7.5,1.8Hz,2H),7.38–7.32(m,4H),7.32–7.27(m,4H),7.20(d,J=7.1Hz,2H),6.40(s,1H),6.34(s,1H),3.75(s,3H),2.36(s,3H);
13C?NMR(125MHz,CDCl
3)δ162.73,144.88,139.17,135.14,134.61,131.59,129.78,129.50,129.29,129.14,128.84,128.69,128.46,121.65(t,J=294.0Hz),89.60,83.73,56.99,52.62,21.63;
19F?NMR(471MHz,CDCl
3)δ-48.40;HRMS?calcd?for?C
27H
22NO
4F
2NaSCl[M+Na]
+552.0824,found552.0834.
The sign number of compound 2b is as follows:
1H?NMR(500MHz,CDCl
3)δ7.72(d,J=8.3Hz,2H),7.29(t,J=7.4Hz,1H),7.18–7.06(m,7H),6.99(t,J=7.7Hz,2H),6.74(d,J=7.6Hz,2H),6.64(s,1H),6.03(s,1H);3.75(s,3H),2.27(s,3H);
19F?NMR(471MHz,CDCl
3)δ-59.05(dd,J=610.6,165.4Hz);HRMS?calcd?for?C
27H
22NO
4F
2NaSCl[M+Na]
+552.0824,found552.0808.
Embodiment 3
In reactor, react, reactor vacuumizes rear logical argon replaces three times, adds 0.2mmol(95.9mg) 3-azepine-1,5-eneyne 1c and 1mL1,4-dioxane, stirring reaction is 24 hours at 100 ℃.After reaction finishes, under vacuum, take out solvent, then sample is dissolved in to methylene dichloride loading and carries out silica gel column chromatography, eluent is the mixed solvent of sherwood oil: ethyl acetate=20:1, obtains the cyclobutene 2c of 88.6mg.Separation yield is 92%.
The characterization data of compound 1c is as follows:
1H?NMR(500MHz,CDCl
3)δ7.81(d,J=8.3Hz,2H),7.46(dd,J=7.3,2.0Hz,2H),7.37–7.29(m,5H),6.32(s,1H),6.16(t,J=2.1Hz,1H),3.74(s,3H),2.45(s,3H),2.12–1.99(m,2H),1.38(h,J=7.3Hz,2H),0.90–0.84(m,3H);
13C?NMR(125MHz,CDCl
3)δ162.58,144.66,135.39,134.95,134.87(d,J=39.2Hz,1H),133.10,129.63,129.11,129.03,128.73,128.52,119.49(q,J=277.5Hz),90.64,77.41,77.16,76.91,74.92,56.58,52.63,21.68,20.66,13.53;
19F?NMR(471MHz,CDCl
3)δ-62.83;HRMS?calcd?for?C
24H
24NO
4F
3NaS[M+Na]
+502.1276,found502.1278.
The sign number of compound 2c is as follows:
1H?NMR(500MHz,CDCl
3)δ7.70(d,J=8.3Hz,2H),7.30(dd,J=5.8,4.7Hz,3H),7.17(d,J=8.0Hz,2H),7.08–6.98(m,2H),6.43(s,1H),5.89(s,1H),3.75(s,3H),2.51(m,1H),2.34(s,3H),2.32–2.25(m,1H),1.16(m,1H),1.12–0.97(m,1H),0.69(t,J=7.4Hz,3H);
13C?NMR(125MHz,CDCl
3)δ167.13,161.60,143.84,138.08,134.65,133.83,132.57,129.49,128.61,128.56,128.30,127.78,127.27,123.88(d,J=283.0Hz),66.97(q,J=32.3Hz),51.72,29.95,21.52,20.39,13.70;
19F?NMR(471MHz,CDCl
3)δ-74.92;HRMS?calcd?for?C
24H
24NO
4F
3NaS[M+Na]
+502.1276,found502.1274.
Claims (5)
1. a method of preparing the Cycloene derivate of polyfluorinated alkyl, is characterized in that:
With 3-azepine-1 shown in following formula, 5-eneyne derivative (1) is raw material generation Cycloene derivate (2), and reaction formula is as follows:
R wherein
1, R
2, R
3, R
4the phenyl that is respectively C1-C8 alkyl, pyridyl, phenyl or replaces, the substituting group on phenyl is C1-C8 alkyl, C1-C8 alkoxyl group, F, Cl, Br, I, NO
2in a kind of or two kinds or three kinds; R
ffor Polyfluoroalkyl: CF
3, CF
2cl, C
2f
5, C
3f
7or C
4f
9.
2. it is characterized in that in accordance with the method for claim 1:
Solvent is DMF, N,N-dimethylacetamide, methyl-phenoxide, toluene, Isosorbide-5-Nitrae-dioxane, 1, one or both in 2-ethylene dichloride, acetonitrile, tetrahydrofuran (THF), methyl alcohol, acetone, methylene dichloride; The consumption of solvent is every mmole reactant 3-azepine-1,20 milliliters of solvent 5 – for 5-eneyne (1);
Temperature of reaction is 140 ℃ of 20 –.
3. according to the method described in claim 1 or 2, it is characterized in that:
Concrete operation step is as follows:
In reactor, react, reactor vacuumizes rear logical argon replaces, adds 3-azepine-1, and 5-eneyne (1), then adds solvent, reacts 12 to 96 hours at 20 ℃-140 ℃; After reaction finishes, with Rotary Evaporators, take out solvent, solid is dissolved in methylene dichloride loading and carries out silica gel column chromatography, obtains Cycloene derivate (2).
4. in accordance with the method for claim 1, it is characterized in that: building-up reactions thing 3-azepine-1, reaction formula and the step of 5-eneyne 1 are as follows:
R wherein
1, R
2, R
3, R
4for the phenyl of C1-C8 alkyl, pyridyl, phenyl or replacement, the substituting group on phenyl is C1-C8 alkyl, C1-C8 alkoxyl group, F, Cl, Br, I, NO
2in a kind of or two kinds or three kinds; R
ffor Polyfluoroalkyl: CF
3, CF
2cl, C
2f
5, C
3f
7or C
4f
9;
Concrete operation step is as follows:
In reactor, react, reactor vacuumizes after logical argon replaces, adds the new CH steaming of 40ml
2cl
2; Then add the N-alkylsulfonyl-allylamine of 5mmol formula 3 and the alkynes of 5.0-7.5mmol formula 4; The Cs that finally adds 5-20mol%
2cO
3, 0 ℃-stirring at room 1-24 hour; After reaction finishes, revolve and evaporate partial solvent to the 1/4-1/5 of liquor capacity for liquor capacity before not evaporating, loading is carried out 3-azepine-1 that silica gel column chromatography obtains formula 1,5-eneyne.
5. it is characterized in that in accordance with the method for claim 4:
N-alkylsulfonyl-allylamine 3 is 1:1-1.5 with the mol ratio of alkynes 4; The CH that N-alkylsulfonyl-allylamine 3 of every 1mmol adopts
2cl
2for 6-15ml.
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| CN105693593A (en) * | 2014-11-25 | 2016-06-22 | 中国科学院大连化学物理研究所 | Preparation method for 2-aza-dicyclo[3.2.0]-2-hexene derivative |
| CN114957097A (en) * | 2022-06-01 | 2022-08-30 | 中南大学 | Preparation method of indoline compound |
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| CN105693586A (en) * | 2014-11-25 | 2016-06-22 | 中国科学院大连化学物理研究所 | Process for preparing 1-trifluoromethyl-3-sulfonyl-methyl-pyrrole derivative |
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| CN105693593B (en) * | 2014-11-25 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of method for preparing 2- aza-bicyclos [3.2.0] -2- hexene derivatives |
| CN114957097A (en) * | 2022-06-01 | 2022-08-30 | 中南大学 | Preparation method of indoline compound |
| CN114957097B (en) * | 2022-06-01 | 2023-10-03 | 中南大学 | Preparation method of indoline compound |
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| CN104119255B (en) | 2015-12-23 |
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