CN106008433A - 2H-chromene derivative containing perfluoroalkyl group, and synthetic method thereof - Google Patents

2H-chromene derivative containing perfluoroalkyl group, and synthetic method thereof Download PDF

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CN106008433A
CN106008433A CN201610399446.5A CN201610399446A CN106008433A CN 106008433 A CN106008433 A CN 106008433A CN 201610399446 A CN201610399446 A CN 201610399446A CN 106008433 A CN106008433 A CN 106008433A
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chromene
cdcl
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严旭峰
韩靖
陈杰
张慧
曹卫国
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University of Shanghai for Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/12—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 3 and unsubstituted in position 7
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/14—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 6 and unsubstituted in position 7
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/18—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted otherwise than in position 3 or 7

Abstract

The invention relates to a 2H-chromene derivative containing a perfluoroalkyl group, and a synthetic method thereof. The structure of the 2H-chromene derivative containing the perfluoroalkyl group is as shown in a formula which is described in the specification; and in the formula, R is H, a methoxy group, a bromo group, a methyl group or a nitro group, and RF is a trifluoromethyl group or pentafluoroethyl group. The 2H-chromene derivative containing the perfluoroalkyl group is synthesized from the two components in a one-kettle way. Compared with the prior art, the method provided by the invention uses L-proline as a green mild organic catalyst for synthesis of the2H-chromene derivative containing the perfluoroalkyl group and has the advantages of high atom economy, environment friendliness, easiness in operation and mild conditions. Absolute methanol is used as a solvent in reaction, so environmental pollution is low. High regioselectivity and good yield are obtained. Thus, the synthetic method provided by the invention is a novel effective method for synthesis of the 2H-chromene derivative containing the perfluoroalkyl group.

Description

Containing perfluoroalkyl 2H-chromene derivative and synthetic method thereof
Technical field
The present invention relates to a kind of containing perfluoroalkyl 2H-chromene derivative and synthetic method thereof.
Background technology
Polyfunctional group substituted chromene (.alpha.-5:6-benzopyran) derivant is a very important compound of class, due to it widely Biology and pharmacologically active, such as solved spasm medicine, diuretic, anticoagulant, antitumor and antiallergic etc. so that it is by people Pay attention to widely.Wherein, 2H-chromene derivative is a series of to have potential source biomolecule and the natural product of pharmacologically active and medicine Basic framework, therefore design simple effective method synthesis 2H-chromene derivative has certain scientific meaning.
But, synthesize ring the most cost-effectively and be still that synthesis focus.From the achievement in research the most much delivered From the point of view of, although there is the polyfunctional group 2 of the most different novel structuresH-chromene is synthesized, but for fluorine-containing 2HGrinding of-chromene Studying carefully still at an early stage, synthetic method is less.This method, introduces 2 by perfluoroalkylHIn-chromene derivative, use novel The compound that method has synthesized a series of novel structure, regioselectivity is high.
The preparation 2 of report at presentH-chromene derivative synthetic method is listed below:
(1) alkynes reacts generation 2 with the addition compound product of benzyne derivant and DMFH-chromene and 4H-chromene:
(2) salicyl N-tosylhydrazone and Terminal Acetylenes are at CoIISynthesis 2 under the effect of catalystH-chromene:
(3) salicylaldehyde derivatives, Terminal Acetylenes and 2-nitrine acetonitrile react generation 2 under the catalysis of CuI and TEAH-chromene:
Summing up synthetic method so far, we are not difficult to find out, conventional 2HIn-chromene derivative synthetic method, often Need highly basic or metal as catalyst；Or raw material is difficult to obtain, it is necessary to first synthesis material, is carrying out next step reaction, making Reactions steps becomes loaded down with trivial details, operation complicates, and adds catalyst or stepwise reaction all has their weak point.
Summary of the invention
An object of the present invention is to provide one containing perfluoroalkyl 2H-chromene derivative.
The two of the purpose of the present invention are to provide the synthetic method of this compounds a kind of.
For reaching above-mentioned purpose, reaction equation of the present invention is:
According to above-mentioned reaction mechanism, the present invention adopts the following technical scheme that
A kind of containing perfluoroalkyl 2H-chromene, it is characterised in that the structure of this compound is:
Wherein, R is H, methoxyl group, bromo, methyl or nitro；RF is trifluoromethyl or pentafluoroethyl group.
A kind of synthesize above-mentioned containing perfluoroalkyl 2HThe method of-chromene derivative, it is characterised in that the concrete step of the method Suddenly be: by salicylaldehyde derivatives, perfluoroalkyl acetylenic acid ester andL-proline is dissolved in by the mol ratio of 1:1 ~ 1.2:0.1 ~ 0.3 In methanol, at 70 ~ 90 DEG C, stirring reaction is to salicylaldehyde derivatives reaction completely；After reaction terminates, remove solvent, more separated Purification obtains solid and is containing perfluoroalkyl 2H-chromene derivative；The structural formula of described salicylaldehyde derivatives is:；The structural formula of described perfluoroalkyl acetylenic acid ester is:。
This method uses two component one pot process, the method for the most original report, the method withL-proline is as green The organic catalyst of colour temperature sum synthesizes containing perfluoroalkyl 2H-chromene derivative, has Atom economy high, environmental friendliness, behaviour Make easy, the advantage of mild condition.In addition, the products collection efficiency obtained is good, and regioselectivity is high.
Detailed description of the invention
Embodiment one:
Addition salicylide (122 mg, 1 mmol) in round-bottomed flask, trifluoromethyl Methyl propiolate (152 ~ 182 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is solvent, is warming up to 70 ~ 90 DEG C reaction 18 ~ 30 hours after, be cooled to room temperature, solvent is spin-dried for, and column chromatography for separation obtains clean product.White solid.Productivity 82%.
Structural formula:
Chinese name: 2-hydroxyl-2-(trifluoromethyl)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 2-hydroxy-2-(trifluoromethyl)-2H -chromene-3-carboxylate
Molecular weight: 274.05
Outward appearance: white solid
Fusing point: 70.7.6-73.0 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 3.75 (s, 3H), 7.02 (d, J = 8.0 Hz, 1H), 7.06-7.09 (m, 1H), 7.40-7.44 (m, 1H), 7.52-7.54 (m, 1H), 7.97 (s, 1H), 9.05 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): δ: 53.1,95.3 (q,2 J C-F = 34.9 Hz), 114.5, 116.0, 117.5, 122.6 (q, 1 J C-F = 284.8 Hz), 122.8, 129.6, 134.1, 139.7, 152.6, 167.1 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-81.8 (s, CF3) ppm。
Embodiment two:
2-hydroxy 3-methoxybenzene formaldehyde (152 mg, 1 mmol), trifluoromethyl Methyl propiolate is added in round-bottomed flask (152 ~ 182 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is molten Agent, after being warming up to 70 ~ 90 DEG C of reactions 18 ~ 30 hours, is cooled to room temperature, and solvent is spin-dried for, and column chromatography for separation obtains clean product.Yellowish Color solid.Productivity 75%.
Structural formula:
Chinese name: 2-hydroxyl-8-methoxyl group-2-(trifluoromethyl)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 2-hydroxy-8-methoxy-2-(trifluoromethyl)-2H -chromene-3- carboxylate
Molecular weight: 304.06
Outward appearance: faint yellow solid
Fusing point: 85.4-97.0 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 3.75 (s, 3H), 3.81 (s, 3H), 7.00 (t, J = 7.8 Hz, 1H), 7.09-7.11 (m, 1H), 7.14-7.16 (m, 1H), 7.92 (s, 1H), 9.05 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): δ: 53.0,56.4,95.4 (q,2 J C-F = 34.8 Hz), 114.7, 117.1, 118.2, 121.2, 122.5, 122.6 (q, 1 J C-F = 290.6 Hz), 139.9, 142.0, 147.5, 167.0 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-81.7 (s, CF3) ppm。
Embodiment three:
Addition 2-hydroxyl-3-bromobenzaldehyde (200 mg, 1 mmol) in round-bottomed flask, trifluoromethyl Methyl propiolate (152 ~ 182 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is solvent, rises After temperature is reacted 18 ~ 30 hours to 70 ~ 90 DEG C, being cooled to room temperature, solvent is spin-dried for, and column chromatography for separation obtains clean product.Pale yellow colored solid Body.Productivity 66%.
Structural formula:
Chinese name: 8-bromo-2-hydroxyl-2-(trifluoromethyl)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 8-bromo-2-hydroxy-2-(trifluoromethyl)-2H -chromene-3- carboxylate
Molecular weight: 351.96
Outward appearance: faint yellow solid
Fusing point: 106.9-108.8 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 3.77 (s, 3H), 7.03 (t, J = 7.8 Hz, 1H), 7.56-7.57 (m, 1H), 7.69-7.71 (m, 1H), 8.00 (s, 1H), 9.38 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): 53.2,96.0 (q,2 J C-F = 35.3 Hz), 109.9, 115.7, 118.9, 122.6 (q, 1 J C-F = 290.3 Hz), 123.6, 128.7, 137.2, 139.1, 149.4, 166.7 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-82.1 (s, CF3) ppm。
Embodiment four:
2-hydroxy-3-methyl benzaldehyde (136 mg, 1 mmol), trifluoromethyl Methyl propiolate is added in round-bottomed flask (152 ~ 182 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is molten Agent, after being warming up to 70 ~ 90 DEG C of reactions 18 ~ 30 hours, is cooled to room temperature, and solvent is spin-dried for, and column chromatography for separation obtains clean product.Yellowish Color solid.Productivity 42%.
Structural formula:
Chinese name: 2-hydroxyl-8-methyl-2-(trifluoromethyl)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 2-hydroxy-8-methyl-2-(trifluoromethyl)-2H -chromene-3- carboxylate
Molecular weight: 288.06
Outward appearance: faint yellow solid
Fusing point: 112.1-113.8 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 2.19 (s, 3H), 3.75 (s, 3H), 6.97 (t, J = 7.5 Hz, 1H), 7.30 (d, J = 7.5 Hz, 1H), 7.35 (d, J = 7.5 Hz, 1H), 7. 94 (s, 1H), 8.99 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): 15.2,53.0,95.4 (q,2 J C-F = 34.7 Hz), 114.2, 117.2, 122.2, 122.7 (q, 1 J C-F = 290.9 Hz), 125.6, 127.3, 135.5, 140.3, 150.7, 167.3 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-82.0 (s, CF3) ppm。
Embodiment five:
2-hydroxyl-3-nitrobenzaldehyde (167 mg, 1 mmol), trifluoromethyl Methyl propiolate is added in round-bottomed flask (152 ~ 182 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is molten Agent, after being warming up to 70 ~ 90 DEG C of reactions 18 ~ 30 hours, is cooled to room temperature, and solvent is spin-dried for, and column chromatography for separation obtains clean product.Deep yellow Color solid.Productivity 60%.
Structural formula:
Chinese name: 2-hydroxyl-8-nitro-2-(trifluoromethyl)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 2-hydroxy-8-nitro-2-(trifluoromethyl)-2H -chromene-3- carboxylate
Molecular weight: 319.03
Outward appearance: dark yellow solid
Fusing point: 159.7-161.5 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 3.79 (s, 3H), 7.28 (t, J =8.0 Hz, 1H), 7.91-7.93 (m, 1H), 8.05-8.07 (m, 1H), 8.12 (s, 1H), 9.70 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): 52.8,97.5 (q,2 J C-F = 34.9 Hz), 120.3, 121.2, 122.2 (q, 1 J C-F = 287.6 Hz), 122.7, 128.5, 135.0, 137.7, 137.8, 145.1, 163.2 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-81.8 (s, CF3) ppm。
Embodiment six:
2-hydroxy-5-methyl epoxide benzaldehyde (152 mg, 1 mmol), trifluoromethyl Methyl propiolate is added in round-bottomed flask (152 ~ 182 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is molten Agent, after being warming up to 70 ~ 90 DEG C of reactions 18 ~ 30 hours, is cooled to room temperature, and solvent is spin-dried for, and column chromatography for separation obtains clean product.Yellowish Color solid.Productivity 60%.
Structural formula:
Chinese name: 2-hydroxyl-6-methoxyl group-2-(trifluoromethyl)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 2-hydroxy-6-methoxy-2-(trifluoromethyl)-2H -chromene-3- carboxylate
Molecular weight: 304.06
Outward appearance: faint yellow solid
Fusing point: 112.3-114.1 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 3.79 (s, 3H), 7.28 (t, J =8.0 Hz, 1H), 7.91-7.93 (m, 1H), 8.05-8.07 (m, 1H), 8.12 (s, 1H), 9.70 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): δ: 52.8,97.5 (q,2 J C-F = 34.9 Hz), 120.3, 121.2, 122.2 (q, 1 J C-F = 287.6 Hz), 122.7, 128.5, 135.0, 137.7, 137.8, 145.1, 163.2 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-81.8 (s, CF3) ppm。
Embodiment seven:
Addition 2-hydroxyl-5-bromobenzaldehyde (200 mg, 1 mmol) in round-bottomed flask, trifluoromethyl Methyl propiolate (152 ~ 182 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is solvent, rises After temperature is reacted 18 ~ 30 hours to 70 ~ 90 DEG C, being cooled to room temperature, solvent is spin-dried for, and column chromatography for separation obtains clean product.Pale yellow colored solid Body.Productivity 70%.
Structural formula:
Chinese name: 6-bromo-2-hydroxyl-2-(trifluoromethyl)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 6-bromo-2-hydroxy-2-(trifluoromethyl)-2H -chromene-3- carboxylate
Molecular weight: 351.96
Outward appearance: faint yellow solid
Fusing point: 104.9-106.5 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 3.73 (s, 3H), 3.75 (s, 3H), 6.95-7.01 (m, 2H), 7.16 (d, J= 3.0 Hz, 1H), 7.92 (s, 1H), 8.93 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): 53.0,55.7,95.3 (q,2 J C-F = 34.6 Hz), 113.1, 115.1, 116.7, 117.8, 120.2, 122.7 (q, 1 J C-F = 290.9 Hz), 139.8, 146.7, 154.8, 167.1 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-81.5 (s, CF3) ppm。
Embodiment eight:
2-hydroxy-5-methyl benzaldehyde (136 mg, 1 mmol), trifluoromethyl Methyl propiolate is added in round-bottomed flask (152 ~ 182 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is molten Agent, after being warming up to 70 ~ 90 DEG C of reactions 18 ~ 30 hours, is cooled to room temperature, and solvent is spin-dried for, and column chromatography for separation obtains clean product.Yellowish Color solid.Productivity 72%.
Structural formula:
Chinese name: 2-hydroxyl-6-methyl-2-(trifluoromethyl)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 2-hydroxy-6-methyl-2-(trifluoromethyl)-2H -chromene-3- carboxylate
Molecular weight: 288.06
Outward appearance: faint yellow solid
Fusing point: 70.9-73.1 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 2.25 (s, 3H), 3.75 (s, 3H), 6.91 (d, J = 8.0 Hz, 1H), 7.21-7.23 (m, 1H), 7.32 (d, J = 1.5 Hz, 1H), 7.89 (s, 1H), 8.97 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): 20.4,53.0,95.3 (q,2 J C-F = 34.7 Hz), 114.4, 115.7, 117.3, 122.7 (q, 1 J C-F = 290.8 Hz), 129.7, 132.2, 134.8, 140.0, 150.6, 167.2 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-81.9 (s, CF3) ppm。
Embodiment nine:
2-hydroxyl-5-nitrobenzaldehyde (167 mg, 1 mmol), trifluoromethyl Methyl propiolate is added in round-bottomed flask (152 ~ 182 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is molten Agent, after being warming up to 70 ~ 90 DEG C of reactions 18 ~ 30 hours, is cooled to room temperature, and solvent is spin-dried for, and column chromatography for separation obtains clean product.Deep yellow Color solid.Productivity 88%.
Structural formula:
Chinese name: 2-hydroxyl-6-nitro-2-(trifluoromethyl)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 2-hydroxy-6-nitro-2-(trifluoromethyl)-2H -chromene-3- carboxylate
Molecular weight: 319.03
Outward appearance: dark yellow solid
Fusing point: 104.2-106.1 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 3.79 (s, 3H), 7.27 (d, J =9.0 Hz, 1H), 8.19 (s, 1H), 8.26-8.28 (m, 1H), 8.59 (d, J =3.0 Hz, 1H), 9.97 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): 53.6,96.0 (q,2 J C-F = 35.4 Hz), 116.9, 117.1, 117.6, 122.1 (q, 1 J C-F = 289.9 Hz), 125.1, 129.0, 137.5, 142.9, 156.8, 166.3 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-82.1 (s, CF3) ppm。
Embodiment ten:
2-hydroxyl-3,5-dinitrobenzal-dehyde (212 mg, 1 mmol), trifluoromethyl acetylenecarboxylic acid first is added in round-bottomed flask Ester (152 ~ 182 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is Solvent, after being warming up to 70 ~ 90 DEG C of reactions 18 ~ 30 hours, is cooled to room temperature, and solvent is spin-dried for, and column chromatography for separation obtains clean product.Deeply Yellow solid.Productivity 77%.
Structural formula:
Chinese name: 2-hydroxyl-6,8-dinitro-2-(trifluoromethyl)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 2-hydroxy-6,8-dinitro-2-(trifluoromethyl)-2H -chromene-3- carboxylate
Molecular weight: 364.02
Outward appearance: dark yellow solid
Fusing point: 124.6-126.8 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 3.82 (s, 3H), 8.30 (s, 1H), 8.86 (d, J = 2.8 Hz, 1H), 8.89 (d, J= 2.8 Hz, 1H), 10.19 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): 53.9,97.2 (q,2 J C-F = 37.0 Hz), 119.2, 120.9, 121.6 (q, 1 J C-F = 289.4 Hz), 124.3, 128.1, 135.8, 137.2, 141.4, 149.8, 165.3 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-81.9 (s, CF3) ppm。
Embodiment 11:
2-hydroxyl-3,5-dibromo benzaldehyde (278 mg, 1 mmol), trifluoromethyl Methyl propiolate is added in round-bottomed flask (152 ~ 182 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is molten Agent, after being warming up to 70 ~ 90 DEG C of reactions 18 ~ 30 hours, is cooled to room temperature, and solvent is spin-dried for, and column chromatography for separation obtains clean product.Yellowish Color solid.Productivity 61%.
Structural formula:
Chinese name: 6,8-bis-bromo-2-hydroxyl-2-(trifluoromethyl)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 6,8-dibromo-2-hydroxy-2-(trifluoromethyl)-2H -chromene-3- carboxylate
Molecular weight: 429.86
Outward appearance: faint yellow solid
Fusing point: 114.6-117.2 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS): 3.78 (s, 3H), 7.85 (d,J = 2.3 Hz, 1H), 7.95 (d, J= 2.3 Hz, 1H), 7.97 (s, 1H), 9.53 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): 53.5,96.1 (q,2 J C-F = 35.5 Hz), 110.9, 114.8, 116.9, 120.1, 122.2 (q, 1 J C-F = 290.3 Hz), 130.8, 137.7, 139.0, 148.6, 166.3 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-81.9 (s, CF3) ppm。
Embodiment 12:
Addition 2-hydroxyl-4-bromobenzaldehyde (200 mg, 1 mmol) in round-bottomed flask, trifluoromethyl Methyl propiolate (152 ~ 182 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is solvent, rises After temperature is reacted 18 ~ 30 hours to 70 ~ 90 DEG C, being cooled to room temperature, solvent is spin-dried for, and column chromatography for separation obtains clean product.Pale yellow colored solid Body.Productivity 85%.
Structural formula:
Chinese name: 7-bromo-2-hydroxyl-2-(trifluoromethyl)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 7-bromo-2-hydroxy-2-(trifluoromethyl)-2H -chromene-3- carboxylate
Molecular weight: 351.96
Outward appearance: faint yellow solid
Fusing point: 99.8-100.1 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 3.76 (s, 3H), 7.28-7.31 (m, 2H), 7.50 (d, J= 8.0 Hz, 1H), 7. 99 (s, 1H), 9.27 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): 53.2,95.4 (q,2 J C-F = 35.0 Hz), 114.9, 116.5, 119.5, 122.4 (q, 1 J C-F = 290.3 Hz), 126.2, 127.7, 130.3, 138.7, 152.9, 166.9 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-82.0 (s, CF3) ppm。
Embodiment 13:
2-hydroxy-4-methyl benzaldehyde (136 mg, 1 mmol), trifluoromethyl Methyl propiolate is added in round-bottomed flask (152 ~ 182 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is molten Agent, after being warming up to 70 ~ 90 DEG C of reactions 18 ~ 30 hours, is cooled to room temperature, and solvent is spin-dried for, and column chromatography for separation obtains clean product.Yellowish Color solid.Productivity 63%.
Structural formula:
Chinese name: 2-hydroxyl-7-methyl-2-(trifluoromethyl)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 2-hydroxy-7-methyl-2-(trifluoromethyl)-2H -chromene-3- carboxylate
Molecular weight: 288.06
Outward appearance: faint yellow solid
Fusing point: 101.2-103.5 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 2.31 (s, 3H), 3.74 (s, 3H), 6.85 (s, 1H), 6.88-6.89 (m, 1H), 7.40 (d, J = 8.0 Hz, 1H), 7. 94 (s, 1H), 8.97 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): 21.9,52.9,95.3 (q,2 J C-F = 34.8 Hz), 113.2, 115.1, 116.4, 122.4 (q, 1 J C-F = 290.6 Hz), 123.8, 129.4, 139.9, 145.6, 152.7, 167.3 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-82.1 (s, CF3) ppm。
Embodiment 14:
2-hydroxyl-3,6-dimethylbenzaldehyde (150 mg, 1 mmol), trifluoromethyl acetylenecarboxylic acid first is added in round-bottomed flask Ester (152 ~ 182 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is Solvent, after being warming up to 70 ~ 90 DEG C of reactions 18 ~ 30 hours, is cooled to room temperature, and solvent is spin-dried for, and column chromatography for separation obtains clean product.In vain Color solid.Productivity 31%.
Structural formula:
Chinese name: 2-hydroxyl-5,8-dimethyl-2-(trifluoromethyl)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 2-hydroxy-5,8-dimethyl-2-(trifluoromethyl)-2H -chromene- 3-carboxylate
Molecular weight: 302.08
Outward appearance: white solid
Fusing point: 153.6-154.1 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 2.15 (s, 3H),2.36 (s, 3H), 3.76 (s, 3H), 6.82 (d, J =7.5 Hz, 1H), 7.18 (d, J =7.5 Hz, 1H), 7.94 (s, 1H), 8.92 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): 15.2,18.1,53.0,94.9 (q,2 J C-F = 34.6 Hz), 113.5, 116.1, 122.8 (q, 1 J C-F = 290.9 Hz), 123.2, 123.7, 135.0, 135.1, 137.3, 151.0, 167.4 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-81.7 (s, CF3) ppm。
Embodiment 15:
2-hydroxyl-3,6-dimethylbenzaldehyde (182 mg, 1 mmol), trifluoromethyl acetylenecarboxylic acid first is added in round-bottomed flask Ester (152 ~ 182 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is Solvent, after being warming up to 70 ~ 90 DEG C of reactions 18 ~ 30 hours, is cooled to room temperature, and solvent is spin-dried for, and column chromatography for separation obtains clean product.Light Yellow solid.Productivity 31%.
Structural formula:
Chinese name: 2-hydroxyl-5,7-dimethoxy-2-(trifluoromethyl)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 2-hydroxy-5,8-dimethoxy-2-(trifluoromethyl)-2H -chromene- 3-carboxylate
Molecular weight: 334.07
Outward appearance: yellowish solid
147.3 ° of C of fusing point: 146.2-
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 3.73 (s, 3H), 3.82 (s, 3H), 3.86 (s, 3H), 6.25 (d, J =2.0 Hz, 1H), 6.28 (d, J =2.0 Hz, 1H), 7.98 (s, 1H), 8.92 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): 52.6,55.7,55.8,92.9,93.1,95.6 (q, 2 J C-F = 34.9 Hz), 101.8, 108.4, 122.9 (q, 1 J C-F = 290.7 Hz), 135.3, 155.1, 158.5, 165.7, 167.8 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-81.3 (s, CF3) ppm。
Embodiment 16:
Addition salicylide (122 mg, 1 mmol) in round-bottomed flask, pentafluoroethyl group tetrolic acid methyl ester (202 ~ 242 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is solvent, is warming up to 70 ~ 90 DEG C reaction 18 ~ 30 hours after, be cooled to room temperature, solvent is spin-dried for, and column chromatography for separation obtains clean product.Faint yellow solid.Productivity 27%。
Structural formula:
Chinese name: 2-hydroxyl-2-(pentafluoroethyl group)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 2-hydroxy-2-(perfluoroethyl)-2H -chromene-3-carboxylate
Molecular weight: 224.04
Outward appearance: faint yellow solid
Fusing point: 112.5-114.6 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 3.76 (s, 3H), 6.95 (d, J = 8.5 Hz, 1H), 7.05-7.08 (m, 1H), 7.40-7.43 (m, 1H), 7.52-7.54 (m, 1H), 8.00 (s, 1H), 9.17 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): δ: 53.1,97.1 (t,2 J C-F = 29.1 Hz), 112.5 (tq, 1 J C-F = 265.1 Hz, 2 J C-F = 35.1 Hz), 114.1, 116.0, 117.7, 118.7 (qt,1 J C-F = 286.3 Hz, 2 J C-F = 34.7 Hz), 122.8, 129.5, 134.0, 139.8, 152.6, 167.5 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-78.1 (s, CF3), -123.4 (s, CF2) ppm。
Embodiment 17:
2-hydroxy-5-methyl epoxide benzaldehyde (152 mg, 1 mmol), pentafluoroethyl group tetrolic acid methyl ester is added in round-bottomed flask (202 ~ 242 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is molten Agent, after being warming up to 70 ~ 90 DEG C of reactions 18 ~ 30 hours, is cooled to room temperature, and solvent is spin-dried for, and column chromatography for separation obtains clean product.Yellowish Color solid.Productivity 28%.
Structural formula:
Chinese name: 2-hydroxyl-6-methoxyl group-2-(pentafluoroethyl group)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 2-hydroxy-6-methoxy-2-(perfluoroethyl)-2H -chromene-3- carboxylate
Molecular weight: 354.05
Outward appearance: faint yellow solid
Fusing point: 97.4-99.5 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 3.73 (s, 3H), 3.75 (s, 3H), 6.89 (d, J = 9.0 Hz, 1H), 6.98-7.00 (m, 1H), 7.16 (s, 1H), 7.96 (s, 1H), 9.06 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): δ: 53.1,55.7,97.1 (q,2 J C-F = 28.8 Hz), 112.8 (tq, 1 J C-F = 265.4 Hz, 2 J C-F = 34.7 Hz), 113.1, 114.7, 116.8, 117.9, 118.7 (qt, 1 J C-F = 289.5 Hz, 2 J C-F = 34.6 Hz), 120.1, 139.8, 146.6, 154.8, 167.4 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-78.1 (s, CF3), -123.4 (d, J =33.4 Hz, CF2) ppm。
Embodiment 18:
2-hydroxy-5-methyl benzaldehyde (136 mg, 1 mmol), pentafluoroethyl group tetrolic acid methyl ester is added in round-bottomed flask (202 ~ 242 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is molten Agent, after being warming up to 70 ~ 90 DEG C of reactions 18 ~ 30 hours, is cooled to room temperature, and solvent is spin-dried for, and column chromatography for separation obtains clean product.Yellowish Color solid.Productivity 25%.
Structural formula:
Chinese name: 2-hydroxyl-6-methyl-2-(pentafluoroethyl group)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 2-hydroxy-6-methyl-2-(perfluoroethyl)-2H -chromene-3- carboxylate
Molecular weight: 338.06
Outward appearance: faint yellow solid
Fusing point: 91.0-92.9 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 2.25 (s, 3H), 3.75 (s, 3H), 6.85 (d, J = 8.0 Hz, 1H), 7.20-7.23 (m, 1H), 7.31 (d, J = 1.5 Hz, 1H), 7.93 (s, 1H), 9.08 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): δ: 20.4,53.0,97.1 (q,2 J C-F = 28.9 Hz), 112.5 (tq, 1 J C-F = 265.1 Hz, 2 J C-F = 34.9 Hz), 114.0, 115.7, 117.9, 118.7 (qt, 1 J C-F = 286.3 Hz, 2 J C-F = 34.6 Hz), 129.6, 132.3, 134.7, 140.0, 150.5, 167.6 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-78.2 (s, CF3), -123.4 (d, J =18.3 Hz, CF2) ppm。
Embodiment 19:
2-hydroxyl-5-nitrobenzaldehyde (167 mg, 1 mmol), pentafluoroethyl group tetrolic acid methyl ester is added in round-bottomed flask (202 ~ 242 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is molten Agent, after being warming up to 70 ~ 90 DEG C of reactions 18 ~ 30 hours, is cooled to room temperature, and solvent is spin-dried for, and column chromatography for separation obtains clean product.Deep yellow Color solid.Productivity 30%.
Structural formula:
Chinese name: 2-hydroxyl-6-nitro-2-(pentafluoroethyl group)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 2-hydroxy-6-nitro-2-(perfluoroethyl)-2H -chromene-3- carboxylate
Molecular weight: 369.03
Outward appearance: dark yellow solid
Fusing point: 73.6-75.1 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 3.79 (s, 3H), 7.20 (d, J =9.0 Hz, 1H), 8.22 (s, 1H), 8.26-8.28 (m, 1H), 8.59 (d, J =3.0 Hz, 1H), 9.74 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): δ: 53.6,97.8 (t,2 J C-F = 29.4 Hz), 112.2 (tq, 1 J C-F = 265.4 Hz, 2 J C-F = 35.6 Hz), 116.9, 117.8, 118.4 (qt, 1 J C-F = 286.2 Hz, 2 J C-F = 34.4 Hz), 119.0, 125.0, 129.0, 137.5, 143.0, 156.7, 166.7 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-78.2 (s, CF3), -123.7 (d, J =9.4 Hz, CF2) ppm。
Embodiment 20:
Addition 2-hydroxyl-4-bromobenzaldehyde (200 mg, 1 mmol) in round-bottomed flask, pentafluoroethyl group tetrolic acid methyl ester (202 ~ 242 mg, 1 ~ 1.2 mmol),L-proline (11.5 ~ 34.5 mg, 0.1 ~ 0.3 mmol), methanol (3 mL) is solvent, rises After temperature is reacted 18 ~ 30 hours to 70 ~ 90 DEG C, being cooled to room temperature, solvent is spin-dried for, and column chromatography for separation obtains clean product.Pale yellow colored solid Body.Productivity 35%.
Structural formula:
Chinese name: 7-bromo-2-hydroxyl-2-(pentafluoroethyl group)-2H-chromene-3-carboxylate methyl ester
English name: Methyl 7-bromo-2-hydroxy-2-(perfluoroethyl)-2H -chromene-3- carboxylate
Molecular weight: 401.95
Outward appearance: faint yellow solid
Fusing point: 125.6-127.1 ° of C
Proton nmr spectra (500MHz, CDCl3, Internal standard: TMS):δ : 3.76 (s, 3H), 7.23 (d, J = 1.5 Hz, 1H), 7.28-7.30 (m, H), 7.51 (d, J = 8.0 Hz, 1H), 8.03 (s, 1H), 9.39 (s, 1H) ppm；
Carbon-13 nmr spectra (125MHz, CDCl3, internal standard: TMS): δ: 53.2,97.3 (t,2 J C-F = 29.2 Hz), 112.4 (tq, 1 J C-F = 264.9 Hz, 2 J C-F = 35.5 Hz), 114.4, 116.7, 118.6 (qt, 1 J C-F = 286.3 Hz, 2 J C-F = 34.7 Hz), 119.4, 126.3, 127.6, 130.2, 138.7, 152.8, 167.3 ppm;
Enantiomeric excess (470MHz, CDCl3, internal standard: C6F6) :-78.2 (s, CF3), -123.6 (s, CF2) ppm。

Claims (2)

1. one kind contains perfluoroalkyl 2H-chromene, it is characterised in that the structure of this compound is:
Wherein, R is H, methoxyl group, bromo, methyl or nitro；RF is trifluoromethyl or pentafluoroethyl group.
2. a synthesis is according to claim 1 containing perfluoroalkyl 2HThe method of-chromene derivative, it is characterised in that should Concretely comprising the following steps of method: by salicylaldehyde derivatives, perfluoroalkyl acetylenic acid ester andL-proline presses 1:1 ~ 1.2:0.1 ~ 0.3 Mol ratio be dissolved in methanol, at 70 ~ 90 DEG C, stirring reaction is to salicylaldehyde derivatives reaction completely；After reaction terminates, remove Solvent, more separated purification obtains solid and is containing perfluoroalkyl 2H-chromene derivative；The knot of described salicylaldehyde derivatives Structure formula is:；The structural formula of described perfluoroalkyl acetylenic acid ester is:。
CN201610399446.5A 2016-06-08 2016-06-08 2H-chromene derivative containing perfluoroalkyl group, and synthetic method thereof Pending CN106008433A (en)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN1234029A (en) * 1996-08-27 1999-11-03 盐野义制药株式会社 Chromene-3-carboxylate derivative
JP2009237199A (en) * 2008-03-27 2009-10-15 Kyocera Mita Corp Electrophotographic photoreceptor
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Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1234029A (en) * 1996-08-27 1999-11-03 盐野义制药株式会社 Chromene-3-carboxylate derivative
JP2009237199A (en) * 2008-03-27 2009-10-15 Kyocera Mita Corp Electrophotographic photoreceptor
US20140045121A1 (en) * 2012-08-09 2014-02-13 Samsung Display Co., Ltd. Photoresist composition and method of forming a black matrix using the same

Non-Patent Citations (3)

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Title
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LELE WEN，等: "A facile synthetic route to 2-trifluoromethyl-substituted polyfunctionalized chromenes and chromones", 《JOURNAL OF FLUORINE CHEMISTRY》 *
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Application publication date: 20161012