CN104119255B - A kind of method preparing the Cycloene derivate of polyfluorinated alkyl - Google Patents

A kind of method preparing the Cycloene derivate of polyfluorinated alkyl Download PDF

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CN104119255B
CN104119255B CN201310143427.2A CN201310143427A CN104119255B CN 104119255 B CN104119255 B CN 104119255B CN 201310143427 A CN201310143427 A CN 201310143427A CN 104119255 B CN104119255 B CN 104119255B
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eneyne
azepine
phenyl
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alkyl
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CN104119255A (en
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万伯顺
信晓义
吴凡
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Dalian Institute of Chemical Physics of CAS
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Abstract

The present invention relates to a kind of method being prepared the Cycloene derivate of polyfluorinated alkyl by 3-azepine-1,5-eneyne derivative, specifically only under the condition of heating, just generate Cycloene derivate efficiently by 3-azepine-1,5-eneyne.The method that the present invention uses does not use transition-metal catalyst, just obtains through simple operation step the polysubstituted Cycloene derivate that other method is difficult to obtain.

Description

A kind of method preparing the Cycloene derivate of polyfluorinated alkyl
Technical field
The present invention relates to a kind of method being prepared the Cycloene derivate of polyfluorinated alkyl by 3-azepine-1,5-eneyne derivative.
Background technology
Cycloene derivate is the important carbocyclic ring of a class, be extensively present in natural product as important structural unit and to 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.).Synthesis 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 by cyclopropane derivative by ring expansion, A.; 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.; AbuSohel, 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.; ZhuZ. – 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 by eneyne cyclization isomerization reaction, A.; 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.ThermalElectrocyclicReactions through electrocyclic reaction by connection alkene-ene derivative; AcademicPress:NewYork, 1980; Pp145-146; (b) Schuster, H.F.; Coppola, G.M.AllenesinOrganicSynthesis; Wiley:NewYork, 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.TetrahedronLett.1967,1.Schneider, R.; Siegel, H.; Hopf, H.LiebigsAnn.Chem.1981,1812; (e) Rey, J.G.; Rodr1 ' rguez, J.; DeLera, A.R.TetrahedronLett.1993,34,6293; (f) Murakami, M.; Amii, H.; Itami, K.; Ito, Y.Angew.Chem., Int.Ed.Engl.1995,34,1476.).We have developed the novel method being prepared polyfluorinated alkyl Cycloene derivate by 3-azepine-1,5-eneyne derivative.Organic fluorocompound has unique physics and chemistry character, is thus widely used in key areas (document 7:Forrecentreviews, see:(a) Tomaschenko, the O.A. such as medicine, material, agricultural chemicals; 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) Muller, K.; Faeh, C.; Diederich, F.Science2007,317,1881; (d) Kirsch, P.ModernFluoroorganicChemistry:Synthesis, Reactivity, Applications; Wiley-VCH:Weinhiem, Germany, 2004; (e) Hiyama, T.OrganofluorineChemistry, Principles, andCommercialApplications; Banks, R.E., Smart, B.E., Tatlow, C.J., Eds.; Springer:NewYork, 1994; Pp237-262.).Cyclobutene product synthesized by present method contains the functional groups such as Polyfluoroalkyl, has potential physiologically active.Substituting group new style, is difficult to synthesize this compound by other method.The method does not use transition-metal catalyst, through simple operation step just can high yield obtain functionalized cyclobutene biologic.
Summary of the invention
The object of the present invention is to provide a kind of novel method of synthesizing polyfluorinated alkyl Cycloene derivate.
Reaction equation 1. synthesizes Cycloene derivate by 3-azepine-1,5-eneyne
Concrete operation step following (reaction equation 1):
React in reactor, reactor vacuumizes rear logical argon replaces, adds 3-azepine-1,5-eneyne 1, then adds solvent, reacts 12 to 96 hours at 20 DEG C-140 DEG C; After reaction terminates, take out solvent with Rotary Evaporators, solid is dissolved in methylene dichloride loading and carries out silica gel column chromatography, obtains Cycloene derivate 2.
Wherein R 1, R 2, R 3, R 4the phenyl being respectively C1-C8 alkyl, pyridyl, phenyl or replacing, the substituting group on phenyl is C1-C8 alkyl, C1-C8 alkoxyl group, F, Cl, Br, I, NO 2in one or two kinds or three kinds; R ffor Polyfluoroalkyl: CF 3, CF 2cl, C 2f 5, C 3f 7or C 4f 9.
Solvent is one or both in DMF, N,N-dimethylacetamide, methyl-phenoxide, toluene, Isosorbide-5-Nitrae-dioxane, 1,2-ethylene dichloride, acetonitrile, tetrahydrofuran (THF), methyl alcohol, acetone, methylene dichloride; The consumption of solvent is that every mmole reactant 3-azepine-1,5-eneyne (1) uses solvent 5 – 20 milliliters;
Reaction formula and the step of building-up reactions thing 3-azepine-1,5-eneyne 1 are as follows:
Wherein R 1, R 2, R 3, R 4for C1-C8 alkyl, pyridyl, phenyl or replace phenyl, the substituting group on phenyl is C1-C8 alkyl, C1-C8 alkoxyl group, F, Cl, Br, I, NO 2in one 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:
React in reactor, after reactor vacuumizes logical argon replaces, add the CH that 40ml newly steams 2cl 2; Then the N-alkylsulfonyl-allylamine of 5mmol formula 3 and the alkynes of 5.0-7.5mmol formula 4 is added; Finally add the Cs of 5-20mol% 2cO 3, 0 DEG C-stirring at room temperature 1-24 hour; After reaction terminates, revolve that to evaporate partial solvent be the 1/4-1/5 not evaporating front liquor capacity to liquor capacity, loading carries out 3-azepine-1, the 5-eneyne that silica gel column chromatography obtains formula 1.
N-alkylsulfonyl-allylamine 3 is 1:1-1.5 with the mol ratio of alkynes 4; The CH that the 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 cheaper starting materials is easy to get.
2. operation is simple; Do not use transition-metal catalyst, environmental friendliness.
3. cyclobutene product functional group enriches, and containing functional groups such as Polyfluoroalkyl, sulfoamido and exocyclic double bonds, is difficult to synthesize the Cycloene derivate with this substituting group pattern by other method.
Embodiment
In order to understand the present invention better, be described by following instance.
Embodiment 1
React in reactor, 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 24 hours at 100 DEG C.After reaction terminates, take out solvent under vacuo, then sample is dissolved in methylene dichloride loading and carries out silica gel column chromatography, eluent is sherwood oil: the mixed solvent of ethyl acetate=20:1, obtains the cyclobutene 2a of 93.2mg.Separation yield is 91%.
The characterization data of compound 1a is as follows:
1HNMR(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); 13CNMR(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; 19FNMR(471MHz,CDCl 3)δ-62.80;HRMScalcdforC 27H 22NO 4F 3NaS[M+Na] +536.1119,found536.1139.
The sign number of compound 2a is as follows:
1HNMR(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); 13CNMR(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; 19FNMR(471MHz,CDCl 3)δ-74.65;HRMScalcdforC 27H 22NO 4F 3NaS[M+Na] +536.1119,found536.1141.
Embodiment 2
React in reactor, 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 24 hours at 100 DEG C.After reaction terminates, take out solvent under vacuo, then sample is dissolved in methylene dichloride loading and carries out silica gel column chromatography, eluent is sherwood oil: the mixed solvent of ethyl acetate=20:1, obtains the cyclobutene 2b of 77.3mg.Separation yield is 73%.
The characterization data of compound 1b is as follows:
1HNMR(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); 13CNMR(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; 19FNMR(471MHz,CDCl 3)δ-48.40;HRMScalcdforC 27H 22NO 4F 2NaSCl[M+Na] +552.0824,found552.0834.
The sign number of compound 2b is as follows:
1HNMR(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); 19FNMR(471MHz,CDCl 3)δ-59.05(dd,J=610.6,165.4Hz);HRMScalcdforC 27H 22NO 4F 2NaSCl[M+Na] +552.0824,found552.0808.
Embodiment 3
React in reactor, 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 24 hours at 100 DEG C.After reaction terminates, take out solvent under vacuo, then sample is dissolved in methylene dichloride loading and carries out silica gel column chromatography, eluent is sherwood oil: the mixed solvent of ethyl acetate=20:1, obtains the cyclobutene 2c of 88.6mg.Separation yield is 92%.
The characterization data of compound 1c is as follows:
1HNMR(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); 13CNMR(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; 19FNMR(471MHz,CDCl 3)δ-62.83;HRMScalcdforC 24H 24NO 4F 3NaS[M+Na] +502.1276,found502.1278.
The sign number of compound 2c is as follows:
1HNMR(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); 13CNMR(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; 19FNMR(471MHz,CDCl 3)δ-74.92;HRMScalcdforC 24H 24NO 4F 3NaS[M+Na] +502.1276,found502.1274.

Claims (5)

1. prepare a method for the Cycloene derivate of polyfluorinated alkyl, it is characterized in that:
With 3-azepine-1,5-eneyne derivative (1) shown in following formula for raw material generates Cycloene derivate (2), reaction formula is as follows:
Wherein R 1, R 2, R 3, R 4the phenyl being respectively C1-C8 alkyl, pyridyl, phenyl or replacing, the substituting group on phenyl is C1-C8 alkyl, C1-C8 alkoxyl group, F, Cl, Br, I, NO 2in one or two kinds or three kinds; R ffor Polyfluoroalkyl: CF 3, CF 2cl, C 2f 5, C 3f 7or C 4f 9;
Solvent is one or both in DMF, N,N-dimethylacetamide, methyl-phenoxide, toluene, Isosorbide-5-Nitrae-dioxane, 1,2-ethylene dichloride, acetonitrile, tetrahydrofuran (THF), methyl alcohol, acetone, methylene dichloride; Temperature of reaction is 20 – 140 DEG C, and the reaction times is 12 to 96 hours.
2. in accordance with the method for claim 1, it is characterized in that:
The consumption of solvent is that every mmole reactant 3-azepine-1,5-eneyne (1) uses solvent 5 – 20 milliliters.
3., according to the method described in claim 1 or 2, it is characterized in that:
Concrete operation step is as follows:
React in reactor, reactor vacuumizes rear logical argon replaces, adds 3-azepine-1,5-eneyne (1), then adds solvent, reacts 12 to 96 hours at 20 DEG C-140 DEG C; After reaction terminates, take out solvent with Rotary Evaporators, 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: reaction formula and the step of building-up reactions thing 3-azepine-1,5-eneyne 1 are as follows:
Wherein R 1, R 2, R 3, R 4for C1-C8 alkyl, pyridyl, phenyl or replace phenyl, the substituting group on phenyl is C1-C8 alkyl, C1-C8 alkoxyl group, F, Cl, Br, I, NO 2in one 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:
React in reactor, after reactor vacuumizes logical argon replaces, add the CH that 40ml newly steams 2cl 2; Then the N-alkylsulfonyl-allylamine of 5mmol formula 3 and the alkynes of 5.0-7.5mmol formula 4 is added; Finally add the Cs of 5-20mol% 2cO 3, 0 DEG C-stirring at room temperature 1-24 hour; After reaction terminates, revolve that to evaporate partial solvent be the 1/4-1/5 not evaporating front liquor capacity to liquor capacity, loading carries out 3-azepine-1, the 5-eneyne that silica gel column chromatography obtains formula 1.
5. in accordance with the method for claim 4, it is characterized in that:
N-alkylsulfonyl-allylamine 3 is 1:1-1.5 with the mol ratio of alkynes 4; The CH that the N-alkylsulfonyl-allylamine 3 of every 1mmol adopts 2cl 2for 6-15ml.
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