CN109879833A - 2- perfluoroalkyl benzo selenium azole compounds and preparation method thereof - Google Patents
2- perfluoroalkyl benzo selenium azole compounds and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 54
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 25
- -1 perfluoroalkyl iodides Chemical class 0.000 claims abstract description 19
- 150000003346 selenoethers Chemical class 0.000 claims abstract description 19
- 239000002585 base Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 230000004224 protection Effects 0.000 claims abstract description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000004440 column chromatography Methods 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000007858 starting material Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 230000005855 radiation Effects 0.000 claims abstract 2
- 238000005286 illumination Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract description 3
- 230000001939 inductive effect Effects 0.000 abstract description 3
- 239000003504 photosensitizing agent Substances 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000004293 19F NMR spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical class C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 229940065287 selenium compound Drugs 0.000 description 2
- 150000003343 selenium compounds Chemical class 0.000 description 2
- KWXGJTSJUKTDQU-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-8-iodooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I KWXGJTSJUKTDQU-UHFFFAOYSA-N 0.000 description 1
- BULLJMKUVKYZDJ-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-6-iodohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I BULLJMKUVKYZDJ-UHFFFAOYSA-N 0.000 description 1
- KCEJJSGJNCSQFI-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5-undecafluoro-5-iodopentane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I KCEJJSGJNCSQFI-UHFFFAOYSA-N 0.000 description 1
- PGRFXXCKHGIFSV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-iodobutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)I PGRFXXCKHGIFSV-UHFFFAOYSA-N 0.000 description 1
- XTGYEAXBNRVNQU-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-iodopropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)I XTGYEAXBNRVNQU-UHFFFAOYSA-N 0.000 description 1
- LMHCYRULPLGEEZ-UHFFFAOYSA-N 1-iodoheptane Chemical compound CCCCCCCI LMHCYRULPLGEEZ-UHFFFAOYSA-N 0.000 description 1
- CTCGHLVDQKKOCB-UHFFFAOYSA-N 2-[(2-aminophenyl)diselanyl]aniline Chemical class NC1=CC=CC=C1[Se][Se]C1=CC=CC=C1N CTCGHLVDQKKOCB-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910004879 Na2S2O5 Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000003386 histamine H2 receptor agonist Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- BITXABIVVURDNX-UHFFFAOYSA-N isoselenocyanic acid Chemical class N=C=[Se] BITXABIVVURDNX-UHFFFAOYSA-N 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JNLAWMGPPJLSMA-UHFFFAOYSA-N n-(2-iodophenyl)benzamide Chemical compound IC1=CC=CC=C1NC(=O)C1=CC=CC=C1 JNLAWMGPPJLSMA-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000010490 three component reaction Methods 0.000 description 1
Landscapes
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses 2- perfluoroalkyl benzo selenazoles classes to close object and preparation method thereof.This law is using 2- isonitrile base benzene first selenide and perfluoroalkyl iodides as starting material; N; N- tetramethylethylenediamine does alkali; tetrahydrofuran is solvent, 30 DEG C of reaction temperature, and under the conditions of nitrogen protection; radiation of visible light 12 hours; after consumption of raw materials is complete, solvent is removed in rotation, obtains a series of target products through column chromatography for separation --- and 2- perfluoroalkyl benzo selenazoles class closes object.The present invention provides a kind of visible light-inducing for the first time, and using 2- isonitrile base benzene first selenide and perfluoroalkyl iodides as starting material, synthesis 2- perfluoroalkyl benzo selenazoles class closes the new method of object.This law mild condition, environmentally protective, easy to operate, efficient quick.Because being avoided in reaction process using photosensitizer, in terms of light-catalyzed reaction constructs heterocyclic compound and field of medicine and chemical technology has huge application value.
Description
Technical field
The invention belongs to chemical technology fields, are related to chemical synthesis, especially 2- perfluoroalkyl benzo selenium azole compounds
Preparation method.
Background technique
The heterocyclic compound that organofluorine compound, especially perfluoroalkyl replace is in agriculture chemistry, materials chemistry, drug
Etc. fields, which have, to be extremely widely applied.Some organic micromolecule compounds can significantly improve life after connecting upper perfluoroalkyl
Object activity improves bioavilability, and enhancing is fat-soluble, influences its dynamic metabolism in vivo.Organic selenium compounds are
Particularly important Synthetic Organic Chemistry product attract attention because of its extensive use in pharmaceutical chemistry and materials science field.?
In numerous organic selenium compounds, 2- function dough benzo selenazoles analog derivative is the mother nucleus structure of many bioactive substances,
And possess many excellent pharmacological activity, such as: antiviral, anti-inflammatory, anti-oxidant, histamine H2Receptor stimulating agent etc..Therefore, it develops
The synthetic method of simple and effective synthesis 2- functionalization benzo selenazoles analog derivative will be one and be of great significance and huge challenge
Work.
The synthetic method of 2- function dough benzo selenium azole compounds reported at present is relatively limited, specifically includes that (1)
The 2- halogenophenyl isonitrile of Cu (I) catalysis, elemental selenium and nucleopilic reagent three component reactions (J.Org.Chem.2007,72,
8087-8090)；(2) cross-coupling reaction (Tetrahedron of the 2- halogenated aniline of Cu (II) catalysis and isoselenocyanates
Lett.2011,52,505-508)；(3)Na2S2O5The condensation reaction of bis- (2- aminophenyl) diselenides and aryl aldehyde that promote
(Tetrahedron 2013,69,1316-1321)；(4) N- (acetyl group) benzoyl -2- Iodoaniline and Woollins reagent
Microwave-assisted firing one kettle way (Tetrahedron Lett.2014,55,5052-5054)；(5) 2 halogenated anilines that Se is mediated
With Arylacetic acids/benzyl chloride compound condensation reaction (Tetrahedron Lett.2018,59,2835-2838).In view of perfluor
Potential significance in chemical biology of alkyls and benzo selenium azole compounds and synthetic method has been reported at present
Limitation needs the new method that development prepares 2- perfluoroalkyl benzo selenium azole compounds.
Summary of the invention
The present invention provides a kind of visible light-inducing for the first time, the 2- isonitrile base benzene first selenide easily to prepare and commercialization
Perfluoroalkyl iodides starting material synthesizes the new method that 2- perfluoroalkyl benzo selenazoles class closes object.This law mild condition, it is environmentally protective,
It is easy to operate, efficient quick.Because it avoids using rare earth metal or organic dyestuff in traditional light-catalyzed reaction during the reaction
As photosensitizer, so photocatalysis free radical series connection cyclization building heterocyclic compound in terms of and field of medicine and chemical technology tool
There is huge potential using value.
Realize the technical scheme is that
2- perfluoroalkyl benzo selenium azole compounds, it is characterised in that: structural formula is as follows
Wherein, the positive integer of n=3-8.
The preparation method of 2- perfluoroalkyl benzo selenium azole compounds, steps are as follows, by 2- isonitrile base benzene first selenide, perfluor
Alkyl iodide, N, N- tetramethylethylenediamine are mixed in tetrahydrofuran, under the conditions of 30 DEG C of nitrogen protections, it is seen that and light irradiates 1-6 hours,
After consumption of raw materials is complete, solvent is removed in rotation, obtains a series of target products through column chromatography for separation --- 2- perfluoroalkyl benzo selenium
Azole closes object.
Moreover, the 2- isonitrile base benzene first selenide structural formula is as follows:
Moreover, the perfluoroalkyl iodides structural formula is as follows:
I-CnF2n+1
(II),
The wherein positive integer of n=3-8.
Moreover, using 2- isonitrile base benzene first selenide and perfluoroalkyl iodides as starting material, N, N- tetramethylethylenediamine does alkali, four
Hydrogen furans be solvent, 30 DEG C of reaction temperature, under the conditions of nitrogen protection, it is seen that light irradiate 1-6 hours, after consumption of raw materials is complete,
Solvent is removed in rotation, obtains a series of target products through column chromatography for separation --- and 2- perfluoroalkyl benzo selenazoles class closes object.
Moreover, the 2- isonitrile base benzene first selenide, perfluoroalkyl iodides, N, the equivalent proportion of N- tetramethylethylenediamine is 1.0:
2.0:2.0, the concentration in tetrahydrofuran are 0.1M.
Moreover, the 2- perfluoroalkyl benzo selenium azole compounds prepare equation and method is as follows:
The 2- isonitrile base benzene first selenide of 1.0equiv. and the perfluoroalkyl iodides of 2.0equiv. are starting material,
The N of 2.0equiv., N- tetramethylethylenediamine do alkali, and the tetrahydrofuran of 0.1M is solvent, and 30 DEG C of reaction temperature, and protected in nitrogen
Under the conditions of shield, it is seen that light irradiates 1-6 hours, and after consumption of raw materials is complete, solvent is removed in rotation, obtains a series of mesh through column chromatography for separation
Mark product --- 2- perfluoroalkyl benzo selenazoles class closes object；Wherein, the positive integer of n=3-8.
Advantages of the present invention effect is:
It is free that the present invention provides a kind of visible light-inducing perfluoroalkylation based on electron donor-acceptor complex for the first time
Fundamental series joins cyclization, a series of with potential source biomolecule activity 2- perfluoroalkyl benzo selenazoles class conjunction object to synthesize.This law is enough
It avoids using high-valency metal or peroxide as radical initiator completely.It is freely anti-compared to traditional photocatalysis simultaneously
Answer, the reaction without use rare earth metal or organic dyestuff as photosensitizer, thus accomplish to greatest extent it is environmentally protective, side
Just efficiently.It will be further appreciated that this law has greatly novelty in synthesis methodology and molecular structure, it is that synthesis 2- is complete
Fluoroalkyl benzo selenazoles class closes object unique method.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's every other embodiment obtained under that premise of not paying creative labor, belongs to this hair
The range of bright protection.
Embodiment 1
The preparation method of 2- perfluoroalkyl benzo selenazoles compound 1, steps are as follows:
By 2- isonitrile base benzene first selenide (0.2mmol), perfluoro propyl iodine (0.4mmol), N, N- tetramethylethylenediamine
(0.4mmol) is mixed in 2mL tetrahydrofuran, under the conditions of 30 DEG C of nitrogen protections, it is seen that light irradiates 1 hour, complete to consumption of raw materials
Quan Hou, rotation remove solvent, obtain target product 1 through column chromatography for separation.
Concrete outcome is as follows:
Colorless oil (38.6mg, 55%yield)1H NMR(400MHz,Chloroform-d)δ8.32(d,J
=8.2Hz, 1H), 8.06 (d, J=8.1Hz, 1H), 7.67-7.48 (m, 2H)13C NMR(101MHz,Chloroform-d)δ
159.82 (t, J=31.8Hz), 154.15,139.37,127.35,127.24,126.87,124.92.19F NMR(376MHz,
Chloroform-d)δ-79.98–-80.04(m,3F),-104.97–-105.06(m,2F),-125.52(s,2F).
Embodiment 2
The preparation method of 2- perfluoroalkyl benzo selenazoles compound 2, steps are as follows:
By 2- isonitrile base benzene first selenide (0.2mmol), perfluoro butyl iodine (0.4mmol), N, N- tetramethylethylenediamine
(0.4mmol) is mixed in 2mL tetrahydrofuran, under the conditions of 30 DEG C of nitrogen protections, it is seen that light irradiates 1 hour, complete to consumption of raw materials
Quan Hou, rotation remove solvent, obtain target product 2 through column chromatography for separation.
Concrete outcome is as follows:
57.1-58.5 DEG C of of White solid (44.9mg, 56%yield), mp1H NMR(400MHz,
Chloroform-d) δ 8.32 (d, J=8.2Hz, 1H), 8.06 (d, J=8.0Hz, 1H), 7.66-7.48 (m, 2H)13C NMR
(101MHz, Chloroform-d) δ 160.07 (t, J=31.8Hz), 154.15,139.37,127.31,127.19,126.87,
124.88.19F NMR (376MHz, Chloroform-d) δ-81.23 (t, J=9.8Hz, 3F) ,-104.29-- 104.36 (m,
2F),-121.96–-122.04(m,2F),-125.54–-125.67(m,2F).
Embodiment 3
The preparation method of 2- perfluoroalkyl benzo selenazoles compound 3, steps are as follows:
By 2- isonitrile base benzene first selenide (0.2mmol), perfluoropentyl iodine (0.4mmol), N, N- tetramethylethylenediamine
(0.4mmol) is mixed in 2mL tetrahydrofuran, under the conditions of 30 DEG C of nitrogen protections, it is seen that light irradiates 3 hours, complete to consumption of raw materials
Quan Hou, rotation remove solvent, obtain target product 3 through column chromatography for separation.
Concrete outcome is as follows:
73.9-75.8 DEG C of of White solid (44.2mg, 49%yield), mp1H NMR(400MHz,
Chloroform-d) δ 8.32 (d, J=8.1Hz, 1H), 8.06 (d, J=8.1Hz, 1H), 7.57 (dt, J=46.8,7.6Hz,
2H).13C NMR (101MHz, Chloroform-d) δ 160.03 (t, J=31.7Hz), 154.15,139.38,127.34,
127.22,126.88,124.90.19F NMR(376MHz,Chloroform-d)δ-80.79–-80.86(m,3F),-
104.11–-104.20(m,2F),-121.16–-121.26(m,2F),-122.02–-122.18(m,2F),-126.17–-
126.27(m,2F).
Embodiment 4
The preparation method of 2- perfluoroalkyl benzo selenazoles compound 4, steps are as follows:
By 2- isonitrile base benzene first selenide (0.2mmol), perfluoro-hexyl iodide (0.4mmol), N, N- tetramethylethylenediamine
(0.4mmol) is mixed in 2mL tetrahydrofuran, under the conditions of 30 DEG C of nitrogen protections, it is seen that light irradiates 6 hours, complete to consumption of raw materials
Quan Hou, rotation remove solvent, obtain target product 4 through column chromatography for separation.
Concrete outcome is as follows:
82.5-84.2 DEG C of of White solid (41.1mg, 41%yield), mp1H NMR(400MHz,
Chloroform-d) δ 8.32 (d, J=8.1Hz, 1H), 8.07 (d, J=8.1Hz, 1H), 7.58 (dt, J=47.2,8.1Hz,
2H).13C NMR (101MHz, Chloroform-d) δ 160.06 (t, J=31.3Hz), 154.14,139.38,127.35,
127.24,126.89,124.92.19F NMR(376MHz,Chloroform-d)δ-81.24–-81.36(m,3F),-
104.55–-104.65(m,2F),-121.43–-121.55(m,2F),-121.67–-121.83(m,2F),-123.25–-
123.30(m,2F),-126.57–-126.70(m,2F).
Embodiment 5
The preparation method of 2- perfluoroalkyl benzo selenazoles compound 5, steps are as follows:
By 2- isonitrile base benzene first selenide (0.2mmol), perfluor heptyl iodine (0.4mmol), N, N- tetramethylethylenediamine
(0.4mmol) is mixed in 2mL tetrahydrofuran, under the conditions of 30 DEG C of nitrogen protections, it is seen that light irradiates 3 hours, complete to consumption of raw materials
Quan Hou, rotation remove solvent, obtain target product 5 through column chromatography for separation.
Concrete outcome is as follows:
94.9-96.2 DEG C of of White solid (48.5mg, 44%yield), mp1H NMR(400MHz,
Chloroform-d) δ 8.32 (d, J=8.2Hz, 1H), 8.07 (d, J=8.0Hz, 1H), 7.58 (dt, J=46.6,7.7Hz,
2H).13C NMR (101MHz, Chloroform-d) δ 160.07 (t, J=31.4Hz), 154.15,139.38,127.34,
127.22,126.89,124.90.19F NMR(376MHz,Chloroform-d)δ-80.64–-80.69(m,3F),-
103.92–-103.99(m,2F),-120.78–-121.00(m,4F),-121.80–-121.83(m,2F),-122.55–-
123.57(m,2F),-125.97–-126.06(m,2F).
Embodiment 6
The preparation method of 2- perfluoroalkyl benzo selenazoles compound 6, steps are as follows:
By 2- isonitrile base benzene first selenide (0.2mmol), perfluoro octyl iodide (0.4mmol), N, N- tetramethylethylenediamine
(0.4mmol) is mixed in 2mL tetrahydrofuran, under the conditions of 30 DEG C of nitrogen protections, it is seen that light irradiates 6 hours, complete to consumption of raw materials
Quan Hou, rotation remove solvent, obtain target product 6 through column chromatography for separation.
Concrete outcome is as follows:
103.5-105.0 DEG C of of White solid (74.5mg, 62%yield), mp1H NMR(400MHz,
Chloroform-d) δ 8.32 (d, J=8.2Hz, 1H), 8.06 (d, J=8.0Hz, 1H), 7.66-7.48 (m, 2H)13C NMR
(101MHz, Chloroform-d) δ 160.07 (t, J=31.8Hz), 154.15,139.37,127.31,127.19,126.87,
124.88.19F NMR (376MHz, Chloroform-d) δ -80.92 (t, J=9.9Hz, 3F), -104.13 (t, J=13.9Hz,
2F),-120.94–-121.10(m,4F),-121.85–-121.97(m,4F),-122.73–-122.89(m,2F),-
126.19–-126.29(m,2F).
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1.2- perfluoroalkyl benzo selenium azole compounds, it is characterised in that: structural formula is as follows
Wherein, the positive integer of n=3-8.
The preparation method of 2.2- perfluoroalkyl benzo selenium azole compounds, it is characterised in that: steps are as follows, by 2- isonitrile Ji Benjia
Selenide, perfluoroalkyl iodides, N, N- tetramethylethylenediamine are mixed in tetrahydrofuran, under the conditions of 30 DEG C of nitrogen protections, it is seen that illumination
It penetrates 1-6 hours, after consumption of raw materials is complete, solvent is removed in rotation, a series of target products are obtained through column chromatography for separation --- 2- perfluor
Alkyl benzo selenazoles class closes object.
3. the preparation method of 2- perfluoroalkyl benzo selenium azole compounds according to claim 2, it is characterised in that: described
2- isonitrile base benzene first selenide structural formula it is as follows:
4. the preparation method of 2- perfluoroalkyl benzo selenium azole compounds according to claim 2, it is characterised in that: described
Perfluoroalkyl iodides structural formula it is as follows:
The wherein positive integer of n=3-8.
5. the preparation method of 2- perfluoroalkyl benzo selenium azole compounds according to claim 2, it is characterised in that: with 2-
Isonitrile base benzene first selenide and perfluoroalkyl iodides are starting material, N, and N- tetramethylethylenediamine does alkali, and tetrahydrofuran is solvent, reaction
30 DEG C of temperature, under the conditions of nitrogen protection, it is seen that light irradiates 1-6 hours, and after consumption of raw materials is complete, solvent is removed in rotation, chromatographs through column
A series of isolated target products --- 2- perfluoroalkyl benzo selenazoles class closes object.
6. the preparation method of 2- perfluoroalkyl benzo selenium azole compounds according to claim 2, it is characterised in that: described
The equivalent proportion of 2- isonitrile base benzene first selenide, perfluoroalkyl iodides, N, N- tetramethylethylenediamine is 1.0:2.0:2.0, in tetrahydrofuran
In concentration be 0.1M.
7. according to the preparation method of the described in any item 2- perfluoroalkyl benzo selenium azole compounds of claim 2-6, feature
Be: the 2- perfluoroalkyl benzo selenium azole compounds prepare equation and method is as follows:
The 2- isonitrile base benzene first selenide of 1.0 equiv. and the perfluoroalkyl iodides of 2.0 equiv. are starting material, 2.0 equiv.
N, N- tetramethylethylenediamine does alkali, and the tetrahydrofuran of 0.1M is solvent, 30 DEG C of reaction temperature, and under the conditions of nitrogen protection,
Radiation of visible light 1-6 hours, after consumption of raw materials is complete, solvent was removed in rotation, obtains a series of targets through column chromatography for separation and produces
Object --- 2- perfluoroalkyl benzo selenazoles class closes object；Wherein, the positive integer of n=3-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910247587.9A CN109879833A (en) | 2019-03-29 | 2019-03-29 | 2- perfluoroalkyl benzo selenium azole compounds and preparation method thereof |
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| CN112635827A (en) * | 2020-12-04 | 2021-04-09 | 上海应用技术大学 | Electrolyte additive, electrolyte containing additive and lithium ion battery |
| CN115677621A (en) * | 2022-10-24 | 2023-02-03 | 广州医科大学 | Synthesis method of benzothioselenazole-1-ketone compound and enantiomer thereof |
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| CN108863985A (en) * | 2018-08-01 | 2018-11-23 | 武汉大学 | Benzo selenium azole compounds and the preparation method and application thereof |
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| CN108863985A (en) * | 2018-08-01 | 2018-11-23 | 武汉大学 | Benzo selenium azole compounds and the preparation method and application thereof |
Non-Patent Citations (1)
| Title |
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| RENATA A. BALAGUEZ: "Synthesis of benzoselenazoles and benzoselenazolines by cyclization of 2-amino-benzeneselenol with β-dicarbonyl compounds", 《TETRAHEDRON LETTERS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112635827A (en) * | 2020-12-04 | 2021-04-09 | 上海应用技术大学 | Electrolyte additive, electrolyte containing additive and lithium ion battery |
| CN115677621A (en) * | 2022-10-24 | 2023-02-03 | 广州医科大学 | Synthesis method of benzothioselenazole-1-ketone compound and enantiomer thereof |
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