CN102503747A - Synthetic method of polyfluorinated aromatic hydrocarbon-hetero-aromatic ring building block - Google Patents
Synthetic method of polyfluorinated aromatic hydrocarbon-hetero-aromatic ring building block Download PDFInfo
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- CN102503747A CN102503747A CN2011102957767A CN201110295776A CN102503747A CN 102503747 A CN102503747 A CN 102503747A CN 2011102957767 A CN2011102957767 A CN 2011102957767A CN 201110295776 A CN201110295776 A CN 201110295776A CN 102503747 A CN102503747 A CN 102503747A
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- NHCLUGDRJDXSKT-UHFFFAOYSA-N CC(c1ccc(-c(c(F)c(c(F)c2F)F)c2F)[s]1)=O Chemical compound CC(c1ccc(-c(c(F)c(c(F)c2F)F)c2F)[s]1)=O NHCLUGDRJDXSKT-UHFFFAOYSA-N 0.000 description 4
- UPBYJZXQEWSFCO-UHFFFAOYSA-N CC(c1ccc(-c(c(F)c(nc2F)F)c2F)[s]1)=O Chemical compound CC(c1ccc(-c(c(F)c(nc2F)F)c2F)[s]1)=O UPBYJZXQEWSFCO-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a method for synthesizing a polyfluorinated aromatic hydrocarbon and a derivative thereof, i.e., a hetero-aromatic ring building block under a simple and convenient condition. The invention specifically provides a method for obtaining various polyfluorinated aromatic hydrocarbons and derivatives thereof, i.e., hetero-aromatic ring compounds at high yields based on a simple polyfluorinated aromatic hydrocarbon and a derivative and a hetero-aromatic ring compound thereof under the catalytic action of a palladium salt by taking a catalytic amount of silver salt and oxygen as oxidants and taking a catalytic amount of protonic acid as an additive. In the method, the simple polyfluorinated aromatic hydrocarbon and the derivative and the hetero-aromatic ring compound thereof are taken as raw materials; and the method has the advantages of small using amount of a catalyst, wide substrate application range, easiness and convenience for operating, high reaction efficiency, and the like. The obtained polyfluorinated aromatic hydrocarbon and the derivative thereof, i.e, the hetero-aromatic ring building block are widely applied on the aspects of photoelectric materials and solar cells.
Description
Technical field
The present invention relates to the short-cut method of a kind of synthetic polyfluoro aromatic hydrocarbons-hetero-aromatic ring building block
Background technology
Polyfluoro aromatic hydrocarbons-hetero-aromatic ring building block is at organic electronic devices, like organic luminescent material, play a part particularly importantly in the field-effect semiconductor, and the method for therefore exploring a kind of easy synthetic polyfluoro aromatic hydrocarbons-hetero-aromatic ring building block has significant meaning.Traditional method general use preactivated aromatic hydrocarbons metal reagent (aryl boron cpd, tin aryl SnAr2 compound) and halogenated aryl hydrocarbon are raw material ((a) Yoon, M.-H.; Facchetti, A.; Stern, C.E.; Marks, T.J.J.Am.Chem.Soc.2006,128,5792. (b) Takimiya, K.; Niihara, N.; Otsubo, T.Synthesis, 2005,1589. (c) Crouch, D.J.; Skabara, P.J.; Heeney, M.; McCulloch, I.; Coles, S.J.; Hursthouse, M.B.Chem.Commun.2005,1465. (d) Facchetti, A.; Yoon, M.-H.; Stern, C.L.; Katz, H.E.; Marks, T.J.Angew.Chem.Int.Ed.2003,42,3900.), be raw material ((a) Lafrance, M. perhaps with polyfluoro aromatic hydrocarbons and aryl halides; Rowley, C.N.; Woo, T.K.; Fagnou, K.J.; Am.Chem.Soc.2006,128,8754. (b) Lafrance, M.; Shore, D.; Fagnou, K.Org.Lett.2006,8,5097. (c) Do, H.-Q.; Daugulis, O.J.Am.Chem.Soc.2008,130,1128. (d) Do, H.-Q.; Khan, R.M.K.; Daugulis O.J.Am.Chem.Soc.2008,130,15185. (e) Do, H.-Q.; Daugulis, O.Chem.Commun.2009,6433. (f) Rene, O.; Fagnou, K.Org.Lett.2010,12,2116. (g) Wei, Y.; Kan, J.; Wang, M.; Su, W.; Hong, M.Org.Lett.2009, the common reactions step of 11,3346. these methods is tediously long, and functional group's compatibility is bad, and some reaction needed is used some hypertoxic metallic compounds (tin reagent).2010, our group developed the dehydrogenation linked reaction of palladium catalysis polyfluoro aromatic ring and hetero-aromatic ring first: He, C.-Y.; Fan, S.; Zhang, X
*.J.Am.Chem.Soc.2010,132,12850. we are catalyzer with the palladium in this reaction, and 1.5 times of normal silver carbonates are oxygenant, have realized the synthetic of polyfluoro aromatic hydrocarbons-hetero-aromatic ring building block, and shortcoming then is that the amount consumption of silver is many.
It is oxygenant with oxygen that the inventor has invented a kind of, and the simple and easy method through the synthetic polyfluoro aromatic hydrocarbons of two direct functionalizations of hydrocarbon key-hetero-aromatic ring building block compound has more economy than the method that develops in the past.
Summary of the invention
The short-cut method that the purpose of this invention is to provide a kind of synthetic polyfluoro aromatic hydrocarbons and verivate thereof-assorted aromatic hydrocarbons building block.
The purpose of this invention is to provide and a kind ofly set out, the short-cut method of synthetic polyfluoro aromatic hydrocarbons-assorted aromatic hydrocarbons building block by polyfluoro aromatic hydrocarbons and verivate thereof.
The purpose of this invention is to provide a kind ofly by polyfluoro aromatic hydrocarbons and verivate thereof, assorted aromatic hydroxy compound sets out, the short-cut method of synthetic polyfluoro aromatic hydrocarbons-assorted aromatic hydrocarbons building block.
The purpose of this invention is to provide a kind of is catalyzer with palladium salt, and by polyfluoro aromatic hydrocarbons and verivate thereof, assorted aromatic hydroxy compound sets out, the short-cut method of synthetic polyfluoro aromatic hydrocarbons and verivate thereof-assorted aromatic hydrocarbons building block.
Method of the present invention further be described as in the presence of organic solvent with 60 ℃ of-180 ℃ of scopes in; With polyfluoro aromatic hydrocarbons and verivate thereof; Assorted aromatic hydroxy compound is a raw material; As catalyzer, is oxidant reaction 3-9 hour to generate the short-cut method of polyfluoro aromatic hydrocarbons and verivate-assorted aromatic hydrocarbons building block thereof with silver salt and oxygen with palladium salt;
Described polyfluoro aromatic hydrocarbons and verivate thereof, palladium salt, silver salt, assorted arene compounds, protonic acid, the mol ratio of oxygen is 1-3: 0.01-1: 0-1: 1-3.0: 0-2: 0.2-48.
Described palladium salt structure is: Pd (OAc)
2, Pd (PPh
3)
4Or Pd
2(dba)
3Wherein, PPh
3Be triphenylphosphine, dba is a dibenzalacetone.
Described silver salt is tachyol, silver acetate, Silver Trifluoroacetate, silver carbonate, silver trifluoromethanesulfonate, Silver Nitrate or silver suboxide;
Described polyfluoro aromatic hydrocarbons and verivate thereof have the R of following structural formula
1-R
3Substituted polyfluoro benzene or R
1-R
2Substituted polyfluoro pyridine:
Described hetero-aromatic ring compounds has the R that is of following structural formula
4Perhaps R
5The five yuan of hetero-aromatic rings of the substituted O of containing, N or S or the substituted five yuan of hetero-aromatic rings that contain O, N or S of benzo base:
R wherein
1-R
3Take from hydrogen, C
1-4Perfluoroalkyl, C
1-4Alkyl, halogen, phenyl, C
1-4Alkoxyl group, C
1-4The substituted phenyl of alkoxyl group, COOC
1-4H
3-9, C=COO C
1-6H
3-13Perhaps adjacent group is the benzo base;
R
4Perhaps R
5The five yuan of hetero-aromatic rings of the substituted O of containing, N or S or the substituted five yuan of hetero-aromatic rings that contain O, N or S of benzo base; Wherein, R
4Perhaps R
5Take from halogen, CN, C (O) H, C (O) C
1-4H
3-9, COOC
1-4H
3-9, C
1-4The substituted phenyl of alkoxyl group, the substituted phenyl of nitro, C=COO C
1-6H
3-13, CON (C
1-4H
3-9)
2Or trimethyl silicon based (TMS-) or thienyl; Described R
6Be C
1-4Alkyl or benzyl.
Further recommend described polyfluoro aromatic hydroxy compound to have following structural formula:
Further recommending assorted aromatic hydroxy compound is to have following structural formula:
The palladium salt catalyst of related use further is recommended as palladium .. in the inventive method
Polyfluoro aromatic hydrocarbons described in the inventive method and verivate thereof, palladium salt, silver salt, assorted arene compounds, protonic acid, the mol ratio of oxygen further is recommended as 1-3: 0.02-0.1: 0.02-0.1: 1-3.0: 0-1: 1-48; Do not have protonic acid good result can be arranged from embodiment yet, and replace silver to have a little reaction yet, add and the amount of oxygen can be tried one's best in certain volume with other alkali because saturated oxygen atmosphere down or pressurization can be more favourable to reaction.
In the inventive method employed thiophene structure as stated, the alkyl of being mentioned, further recommending carbon number is 1-8, especially to recommend carbon number be 1-4's; The thiazolinyl of being mentioned, further recommending carbon number is 2-8, especially to recommend carbon number be 2-4's; R
6Further be recommended as methyl or benzyl.
The per-cent of employed palladium salt catalyst is 1%-100% in the inventive method, and the recommendation ratio is 2-10%.
Range of reaction temperature is 60 ℃-160 ℃ in the Ben Fabenming method, and further recommended temperature is 120 ℃-140 ℃.
Employed organic solvent is N-Methyl pyrrolidone (NMP), N in the inventive method, dinethylformamide, DMSO 99.8MIN., 1,3-dimethyl--3; 4,5,6-tetrahydrochysene-2-pyrimidone (DMPU), 1; 4-dioxane, N; The N-N,N-DIMETHYLACETAMIDE, further to recommend solvent be N, and dinethylformamide and DMSO 99.8MIN. ratio are 1: 1 mixed solvent, and DMSO 99.8MIN. is with ground 4A molecular sieve drying.The reaction density scope is that the further recommended density of 0.01mmol/mL-1mmol/mL. is 0.3-0.5mmol/mL.
Adopt the inventive method products therefrom can pass through recrystallization, thin-layer chromatography, column chromatography separates etc. method.
As when using recrystallization method, recommending solvent is the mixed solvent of polar solvent and non-polar solvent, and the recommendation solvent can be ETHYLE ACETATE-sherwood oil, mixed solvent such as ethanol-sherwood oil.When using thin-layer chromatography and column chromatography method, used developping agent is a mixed solvent.The recommendation solvent is a sherwood oil, ETHYLE ACETATE-sherwood oil.
Adopt method of the present invention can obtain the polyfluoro aromatic hydrocarbons-assorted aromatic hydrocarbons building block of following structural formula:
Wherein, R
1-R
6As previously mentioned, ArFn representes foregoing R
1-R
3Substituted polyfluoro benzene or R
1-R
2Substituted polyfluoro pyridine:
The invention provides a kind of by simple polyfluoro aromatic hydrocarbons and verivate thereof; Under the catalysis of palladium salt; Directly utilize the silver salt and the oxygen of catalytic amount to be oxygenant and various assorted aromatic hydrocarbons reaction, obtain the method for various polyfluoro aromatic hydrocarbons and verivate thereof-assorted aromatic hydrocarbons building block with high yield.Compare with existing method, this method is used simple raw material, and catalyst levels is few, and wide application range of substrates is easy and simple to handle, the reaction efficiency advantages of higher
Embodiment
To help to understand the present invention through following embodiment, but not limit content of the present invention.
Embodiment 1
In the tube sealing of 25mL, add 3.5mg (10mol%) Ag
2After O substitutes oxygen three times; Add 0.5mL DMSO 99.8MIN. (DMSO), 0.5mL N (DMF) is injected 100 μ L (0.90mmol) penta fluoro benzenes with microsyringe again; 34 μ L (0.3mmol) 2-acetyl thiophenes; 120 ℃ were stirred down after 9 hours, and adding fluorobenzene is interior mark, did fluorine spectrum monitoring reaction.
19F-NMR is 0.
Embodiment 2
In the tube sealing of 25mL, add 3.4 (5mol%) Pd (OAc)
2After substituting oxygen three times, add 0.5mL DMSO, 0.5mLDMF injects 100 μ L (0.90mmol) penta fluoro benzenes with microsyringe again, 34 μ L (0.3mmol) 2-acetyl thiophenes, and 120 ℃ were stirred down after 9 hours, and adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is a trace.
Embodiment 3
In the tube sealing of 25mL, add 3.4 (5mol%) Pd (OAc)
2, 3.5mg (10mol%) Ag
2After O substitutes nitrogen three times, add 0.5mL DMSO, 0.5mLDMF injects 100 μ L (0.90mmol) penta fluoro benzenes with microsyringe again, 34 μ L (0.3mmol) 2-acetyl thiophenes, and 120 ℃ were stirred down after 9 hours, and adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is a trace.
Embodiment 4
In the tube sealing of 25mL, add 3.4mg (5mol%) Pd (OAc)
2And 3.5mg (5mol%) Ag
2O,
5.4mg Buddha's warrior attendant is sour, substitute oxygen three times after, add 0.5mL DMSO; 0.5mL DMF is a solvent, injects 100 μ L (0.90mmol) penta fluoro benzenes with microsyringe again, 34 μ L (0.3mmol) 2-acetyl thiophenes; 120 ℃ were stirred down after 9 hours, and adding fluorobenzene is interior mark, did fluorine spectrum monitoring reaction.
19F-NMR is 71%.
Embodiment 5
In the tube sealing of 25mL, add 6.7mg (10mol%) Pd (OAc)
2And 10mg (20mol%) Ag
2O,
After substituting oxygen three times, add 1mL DMSO, 1mL DMF is a solvent; Inject acetate 9 μ L (50%mmol) 100 μ L (0.90mmol) penta fluoro benzenes with microsyringe again, 34 μ L (0.3mmol) 2-acetyl thiophenes, 120 ℃ are stirred after 9 hours down; Adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is 61%.
Embodiment 6
In the tube sealing of 25mL, add 6.7mg (10mol%) Pd (OAc)
2And 7mg (10mol%) Ag
2O,
After substituting oxygen three times, add 1mL DMSO, 1mL DMF is a solvent; Inject 100 μ L (0.90mmol) penta fluoro benzenes with microsyringe again, 34 μ L (0.3mmol) 2-acetyl thiophenes, 120 ℃ are stirred after 9 hours down; Adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is 80%.
Embodiment 7
In the tube sealing of 25mL, add 6.7mg (10mol%) Pd (OAc)
2And 8mg (20mol%) AgF,
After substituting oxygen three times, add 1mL DMSO, 1mL DMF is a solvent; Inject 100 μ L (0.90mmol) penta fluoro benzenes with microsyringe again, 34 μ L (0.3mmol) 2-acetyl thiophenes, 120 ℃ are stirred after 9 hours down; Adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is 61%.
Embodiment 8
In the tube sealing of 25mL, add 6.7mg (10mol%) Pd (OAc)
2And 10mg (10mol%) AgOAc,
After substituting oxygen three times, add 1mL DMSO, 1mL DMA is a solvent; Inject 100 μ L (0.90mmol) penta fluoro benzenes with microsyringe again, 34 μ L (0.3mmol) 2-acetyl thiophenes, 120 ℃ are stirred after 9 hours down; Adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is 63%.
Embodiment 9
In the tube sealing of 25mL, add 6.7mg (10mol%) Pd (OAc)
2And 3.2g (5mol%) K
3PO
4,
After substituting oxygen three times, add 0.5mL DMSO, 0.5mL DMF is a solvent; Inject 15 μ L (0.12mmol) PivOH (trimethylacetic acid) with microsyringe again; 100 μ L (0.90mmol) penta fluoro benzenes, 34 μ L (0.3mmol) 2-acetyl thiophenes, 120 ℃ are stirred after 9 hours down; Adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is 29%.
Embodiment 10
In the tube sealing of 25mL, add 6.7mg (10mol%) Pd (OAc)
2And 5g (5mol%) Cs
2CO
3,
After substituting oxygen three times, add 0.5mL DMSO, 0.5mL DMF is a solvent; Inject 15 μ L (0.12mmol) PivOH (trimethylacetic acid) with microsyringe again; 100 μ L (0.90mmol) penta fluoro benzenes, 34 μ L (0.3mmol) 2-acetyl thiophenes, 120 ℃ are stirred after 9 hours down; Adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is 29%.
Embodiment 11
In the tube sealing of 25mL, add 3.4mg (5mol%) Pd (OAc)
2And 5.1mg (5mol%) AgNO
3After substituting oxygen three times, add 0.5mL DMSO, 0.5mL DMF is a solvent; Inject 15 μ L (0.12mmol) PivOH (trimethylacetic acid) with microsyringe again; 100 μ L (0.90mmol) penta fluoro benzenes, 34 μ L (0.3mmol) 2-acetyl thiophenes, 120 ℃ are stirred after 9 hours down; Adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is 50%.
Embodiment 12
In the tube sealing of 25mL, add 3.4mg (5mol%) Pd (OAc)
2And 7.7mg (5mol%) silver trifluoromethanesulfonate, substitute oxygen three times after, add 0.5mL DMSO; 0.5mL DMF is a solvent, injects 15 μ L (0.12mmol) PivOH (trimethylacetic acid) with microsyringe again, 100 μ L (0.90mmol) penta fluoro benzenes; 34 μ L (0.3mmol) 2-acetyl thiophenes; 120 ℃ were stirred down after 9 hours, and adding fluorobenzene is interior mark, did fluorine spectrum monitoring reaction.
19F-NMR is 5%.
Embodiment 13
In the tube sealing of 25mL, add 13mg (2.5mol%) Pd
2(dba)
3And 3.5mg (5mol%) silver suboxide, substitute oxygen three times after, add 0.5mL DMSO; 0.5mL DMF is a solvent, injects 15 μ L (0.12mmol) PivOH (trimethylacetic acid) with microsyringe again, 100 μ L (0.90mmol) penta fluoro benzenes; 34 μ L (0.3mmol) 2-acetyl thiophenes; 120 ℃ were stirred down after 9 hours, and adding fluorobenzene is interior mark, did fluorine spectrum monitoring reaction.
19F-NMR is 35%.
Embodiment 14
In the tube sealing of 25mL, add 17mg (2.5mol%) Pd (PPh
3)
4And 3.5mg (5mol%) silver suboxide, substitute oxygen three times after, add 0.5mL DMSO; 0.5mL DMF is a solvent, injects 15 μ L (0.12mmol) PivOH (trimethylacetic acid) with microsyringe again, 100 μ L (0.90mmol) penta fluoro benzenes; 34 μ L (0.3mmol) 2-acetyl thiophenes; 120 ℃ were stirred down after 9 hours, and adding fluorobenzene is interior mark, did fluorine spectrum monitoring reaction.
19F-NMR is 45%.
Embodiment 15
In the tube sealing of 25mL, add 11mg (2.5mol%) Pd (PPh
3)
2Cl
2And 3.5mg (5mol%) silver suboxide, substitute oxygen three times after, add 0.5mL DMSO; 0.5mL DMF is a solvent, injects 15 μ L (0.12mmol) PivOH (trimethylacetic acid) with microsyringe again, 100 μ L (0.90mmol) penta fluoro benzenes; 34 μ L (0.3mmol) 2-acetyl thiophenes; 120 ℃ were stirred down after 9 hours, and adding fluorobenzene is interior mark, did fluorine spectrum monitoring reaction.
19F-NMR is 4%.
Embodiment 16
In the tube sealing of 25mL, add 3.4mg (5mol%) Pd (OAc)
2And 3.5mg (5mol%) Ag
2After O substitutes oxygen three times, add 0.5mL DMSO, 0.5mL DMF is a solvent; Inject 15mg (0.12mmol) propionic acid with microsyringe again; 100 μ L (0.90mmol) penta fluoro benzenes, 34 μ L (0.3mmol) 2-acetyl thiophenes, 120 ℃ are stirred after 9 hours down; Adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is 60%.
Embodiment 17
In the tube sealing of 25mL, add 3.4mg (5mol%) Pd (OAc)
2And 3.5mg (5mol%) Ag
2After O substitutes oxygen three times, add 0.5mL DMSO, 0.5mL DMF is a solvent; Inject 14mg (0.12mmol) trifluoroacetic acid with microsyringe again; 100 μ L (0.90mmol) penta fluoro benzenes, 34 μ L (0.3mmol) 2-acetyl thiophenes, 120 ℃ are stirred after 9 hours down; Adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is 6%.
Embodiment 18
In the tube sealing of 25mL, add 3.4mg (5mol%) Pd (OAc)
2And 3.5mg (5mol%) Ag
2O, 15mg (0.12mmol) phenylformic acid, substitute oxygen three times after; Add 0.5mL DMSO, 0.5mL DMF is a solvent, injects 100 μ L (0.90mmol) penta fluoro benzenes with microsyringe again; 34 μ L (0.3mmol) 2-acetyl thiophenes; 120 ℃ were stirred down after 9 hours, and adding fluorobenzene is interior mark, did fluorine spectrum monitoring reaction.
19F-NMR is 20%.
Embodiment 19
In the tube sealing of 25mL, add 3.4mg (5mol%) Pd (OAc)
2And 3.5mg (5mol%) Ag
2O, 22.8mg (0.12mmol) p-methyl benzenesulfonic acid, substitute oxygen three times after; Add 0.5mL DMSO, 0.5mL DMF is a solvent, injects 100 μ L (0.90mmol) penta fluoro benzenes with microsyringe again; 34 μ L (0.3mmol) 2-acetyl thiophenes; 120 ℃ were stirred down after 9 hours, and adding fluorobenzene is interior mark, did fluorine spectrum monitoring reaction.
19F-NMR is 8%.
Embodiment 20
In the tube sealing of 25mL, add 6.7mg (10mol%) Pd (OAc)
2And 8mg (10mol%) Ag
2CO
3After substituting oxygen three times, add 2mL DMSO, inject 100 μ L (0.90mmol) penta fluoro benzenes with microsyringe again, 34 μ L (0.3mmol) 2-acetyl thiophenes, 120 ℃ were stirred down after 9 hours, and adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is 56%.
Embodiment 21
In the tube sealing of 25mL, add 6.7mg (10mol%) Pd (OAc)
2And 8mg (10mol%) Ag
2CO
3After substituting oxygen three times, add 1mL DMSO, 1mL DMF is a solvent; Inject 100 μ L (0.90mmol) penta fluoro benzenes with microsyringe again, 34 μ L (0.3mmol) 2-acetyl thiophenes, 120 ℃ are stirred after 9 hours down; Adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is 67%.
Embodiment 22
In the tube sealing of 25mL, add 6.7mg (10mol%) Pd (OAc)
2And after 10mg (20mol%) AgOAc substitutes oxygen three times; Add 1mL DMSO, 1mL DMF is a solvent, injects 100 μ L (0.90mmol) penta fluoro benzenes with microsyringe again; 34 μ L (0.3mmol) 2-acetyl thiophenes; 120 ℃ were stirred down after 9 hours, and adding fluorobenzene is interior mark, did fluorine spectrum monitoring reaction.
19F-NMR is 69%.
Embodiment 23
In the tube sealing of 25mL, add 6.7mg (10mol%) Pd (OAc)
2And 7mg (10mol%) Ag
2After O substitutes oxygen three times, add 1mL DMSO, 1mL DMF is a solvent; Inject 100 μ L (0.90mmol) penta fluoro benzenes with microsyringe again, 34 μ L (0.3mmol) 2-acetyl thiophenes, 120 ℃ are stirred after 9 hours down; Adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is 80%, and system is with 100mL ETHYLE ACETATE dilution, and water (25mL) after saturated aqueous common salt (25mL) washing, is crossed post and separated, petrol ether/ethyl acetate=100/1 obtain product 63.0mg (72% productive rate, 0.21mmol).
1H NMR (300MHz, CDCl
3) δ 7.73 (d, J=4.2Hz, 1H), 7.52 (d, J=4.2Hz, 1H), 2.61 (s, 3H).
13C NMR (75.4MHz, CDCl
3) δ 190.5,145.9,144.2 (dm, J=249.1Hz), 140.6 (dm, J=256.8Hz), 138.0 (dm, J=253.4Hz), 133.9,131.9,130.8 (t, J=4.9Hz), 109.1 (m), 26.7.
19F NMR (282MHz, CDCl
3) δ-139.2 (dd, J=22.0Hz, 5.9Hz, 2F) ,-153.6 (t, J=20.8Hz, 1F) ,-161.6 (m, 2F) .IR (film thin film): v
Max3105,1663cm
-1.MS (EI): m/z (%) 292 (M
+), 277 (100), 205.HRMS: calculated value (Calculated for) C
12H
5OF
5S:291.9981; Measured value (Found): 291.9982.
Embodiment 24
In the tube sealing of 25mL, add 6.7mg (10mol%) Pd (OAc)
2And 7mg (10mol%) Ag
2After O substitutes oxygen three times, add 1mL DMSO, 1mL DMF is a solvent; Inject 15 μ L (0.12mmol) PivOH (trimethylacetic acid) with microsyringe again; 100 μ L (0.90mmol) penta fluoro benzenes, 34 μ L (0.3mmol) 2-acetyl thiophenes, 120 ℃ are stirred after 9 hours down; Adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is 85%, and system is with 100mL ETHYLE ACETATE dilution, and water (25mL) after saturated aqueous common salt (25mL) washing, is crossed post and separated, petrol ether/ethyl acetate=100/1 obtain product 67.0mg (76% yield, 0.23mmol).
Embodiment 25
In the tube sealing of 25mL, add 3.4mg (5mol%) Pd (OAc)
2And 7mg (10mol%) Ag
2After O substitutes oxygen three times, add 1mL DMSO, 1mL DMF is a solvent; Inject 15 μ L (0.12mmol) PivOH (trimethylacetic acid) with microsyringe again; 100 μ L (0.90mmol) penta fluoro benzenes, 34 μ L (0.3mmol) 2-acetyl thiophenes, 120 ℃ are stirred after 9 hours down; Adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is 70%, and system is with 100mL ETHYLE ACETATE dilution, and water (25mL) after saturated aqueous common salt (25mL) washing, is crossed post and separated, petrol ether/ethyl acetate=100/1 obtain product 59.0mg (67% yield, 0.20mmol).
Embodiment 26
In the tube sealing of 25mL, add 3.4mg (5mol%) Pd (OAc)
2And 3.5mg (5mol%) Ag
2After O substitutes oxygen three times, add 1mL DMSO, 1mL DMF is a solvent; Inject 15 μ L (0.12mmol) PivOH (trimethylacetic acid) with microsyringe again; 100 μ L (0.90mmol) penta fluoro benzenes, 34 μ L (0.3mmol) 2-acetyl thiophenes, 120 ℃ are stirred after 9 hours down; Adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is 74%, and system is with 100mL ETHYLE ACETATE dilution, and water (25mL) after saturated aqueous common salt (25mL) washing, is crossed post and separated, petrol ether/ethyl acetate=100/1 obtain product 61.0mg (69% yield, 0.21mmol).
Embodiment 27
In the tube sealing of 25mL, add 3.4mg (5mol%) Pd (OAc)
2And 3.5mg (5mol%) Ag
2After O substitutes oxygen three times, add 0.5mL DMSO, 0.5mL DMF is a solvent; Inject 15 μ L (0.12mmol) PivOH (trimethylacetic acid) with microsyringe again; 100 μ L (0.90mmol) penta fluoro benzenes, 34 μ L (0.3mmol) 2-acetyl thiophenes, 120 ℃ are stirred after 9 hours down; Adding fluorobenzene is interior mark, does fluorine spectrum monitoring reaction.
19F-NMR is 88%, and system is with 100mL ETHYLE ACETATE dilution, water (25mL), after saturated aqueous common salt (25mL) washing,, cross post and separate, petrol ether/ethyl acetate=100/1 obtain product 71.0mg (81% yield, 0.24mmol).
Adopt the same terms, the result is following for change hetero-aromatic ring compounds raw material:
P2
White solid.90% yield.
1H NMR (300MHz, CDCl
3) δ 7.84 (d, J=3.9Hz, 1H), 7.50 (d, J=3.9Hz, 1H), 3.93 (s, 3H),
13C NMR (100MHz, CDCl
3) δ 162.1,144.2 (dm, J=250.0Hz), 140.6 (dm, J=255.0Hz), 138.0 (dm, J=256.7Hz), 135.4,133.1,132.8,130.4 (t, J=4.9Hz), 109.1 (m), 52.4.
19F NMR (282MHz, CDCl
3) δ-139.4 (dd, J=21.9Hz, 6.0Hz, 2F) ,-153.9 (t, J=20.4Hz, 1F) ,-161.6 (m, 2F) .IR (film): v
Max1716,1647,1538, cm
-1.MS (EI): m/z (%) 309 (M
++ H
+), 308 (M
+), 277 (100), 205.HRMS: calculated value C
12H
5O
2F
5S:307.9930; Experimental value: 307.9935.
P3
Light yellow solid.68% yield.
1H NMR (300MHz, CDCl3) δ 9.99 (s, 1H), 7.83 (d, J=3.9Hz, 1H); 7.61 (d, J=3.9Hz, 1H) .13C NMR (75.4MHz, CDCl3) δ 182.8,145.1,144.2 (dm; J=248.5Hz), 140.9 (dm, J=257.5Hz), 138.1 (dm, J=256.7Hz), 135.6; 130.9 (t, J=4.8Hz), 108.8 (m) .19F NMR (282MHz, CDCl3) δ .-138.9 (dd,, J=21.4; 7.1Hz, 2F) ,-152.8 (t, J=20.6Hz, 1F) ,-161.2 (m; 2F) .IR (film): vmax 3141,1656,1488cm-1.MS (EI): m/z (%) 279 (M++H+), 278 (M+), 277 (100), 205.HRMS: calculated value C11H3OF5S:277.9825; Trial value: 277.9823.
P4
White solid.94% yield.
1H NMR (300MHz, CDCl3) δ 7.45 (d, 1H, J=4.0Hz), 7.40 (d, 1H, J=4.0Hz); 3.22 (s, 6H) .13C NMR (75.4MHz, CDCl3) δ 163.4,143.9 (dm, J=251.1Hz), 140.3,140.7 (dm; J=255.8Hz), 137.9 (dm, J=253.0Hz), 129.6 (t, J=5.4Hz), 129.4,128.9; 109.2 (m), 39.3,36.6.19F NMR (282MHz, CDCl3) δ .-139.2 (dd, J=21.7Hz, 6.2Hz, 2F);-154.3 (t, J=21.4Hz, 1F) ,-161.5 (m, 2F) .IR (film): vmax2927,1601,1560; 1536,1490cm-1.MS (EI): m/z (%) 322 (M++H+), 321 (M+), 278,277 (100), 205.HRMS: calculated value C13H8NOSF5:321.0247; Trial value: 321.0250.
P5
White solid.60% yield.
1H NMR (300MHz, CDCl3) δ 7.32 (d, J=3.9Hz, 1H), 7.00 (d, J=3.9Hz, 1H) .13C NMR (100MHz; CDCl3) δ 144.3 (dm, J=253.3Hz), 140.3 (dm, J=254.3Hz), 138.3 (dm, J=251.9Hz); 133.6 (t, J=4.8Hz), 130.0 (t, J=5.5Hz), 126.7,125.3; 109.5 (m) .19F NMR (282MHz, CDCl3) δ-140.5 (dd, J=20.6Hz, 6.5Hz, 2F) ,-155.5 (t; J=21.7Hz, 1F) ,-162.0 (m, 2F) .IR (film): vmax 3145,1771, and 1653; 1606,1536cm-1.MS (EI): m/z (%) 286 (M+, 37), 284 (M+, 100), 205.HRMS: calculated value C10H2F5SCl:283.9487; Trial value: 283.9486.
P6
White solid.93% yield.
1H NMR (300MHz, CDCl3) δ 7.89 (d, J=8.4Hz, 1H), 7.87 (d, J=8.4Hz; 1H), 7.72 (s, 1H) .7.42 (m, 2H) .19F NMR (282MHz, CDCl3) δ .-139.1 (dd, J=20.3Hz; 6.5Hz, 2F) ,-154.2 (t, J=20.8Hz, 1F) ,-161.6 (m; 2F) .IR (film): vmax 1530,1510,1488cm-1.MS (EI): m/z (%) 301 (M++H+), 300 (M+, 100) .HRMS: calculated value C14H5F5S:300.0032; Trial value: 300.0033.
P7
White solid.55% yield.
1H NMR (300MHz, CDCl3) δ 7.32 (d, J=3.9Hz, 1H), 7.00 (d, J=3.9Hz, 1H); 2.56 (s, 3H) .13C NMR (100MHz, CDCl3) δ 186.8,153.1,144.1,144.0 (dm, J=254.7Hz); 141.1 (dm, J=251.5Hz), 138.1 (dm, J=252.2Hz), 117.3,115.4 (t; J=5.6Hz), 105.7 (m), 26.0.19F NMR (282MHz, CDCl3) δ .-140.1 (dd, J=20.0Hz, 7.3Hz; 2F) ,-153.1 (1F) ,-161.7 (m.2F) .IR (film): vmax 3332,3161 for t, J=20.0Hz; 2929,1786,1678,1569cm-1.MS (EI): m/z (%) 276 (M+), 261 (100), 205.HRMS: calculated value C12H5O2F5:276.0210; Trial value: 276.0206.
P8
White solid.87% yield.
1H NMR (400MHz, CDCl3) δ 7.51 (dm, J=7.6Hz, 1H), 7.40 (dm, J=8.4Hz, 1H), 7.31 (td, J=7.5Hz; 1.6Hz, 1H), 7.28 (s, 1H), 7.21 (tm, J=7.5Hz, 1H), 3.85 (s, 3H) .13C NMR (100MHz; CDCl3) δ 144.2 (dm, J=241.0Hz), 139.4 (dm, J=250.7Hz), 138.0 (dm, J=240.0Hz), 136.8,130.0,126.3; 122.4,120.4,120.3 (t, J=3.4Hz), 110.2 (m), 109.7,99.8,33.1.
19F NMR (282MHz, CDCl3) δ-141.0 (dd, J=21.1Hz, 5.4Hz, 2F);-158.5 (t, J=21.1Hz, 1F) ,-163.3 (td, J=21.1Hz; 8.5Hz 2F) .IR (film): vmax 2940,1545, and 1516; 1498cm-1.MS (EI): m/z (%) 298 (M++H+), 297 (M+, 100), 296 (M+-H+).
P9
Yellow solid.98% yield.
1H NMR (300MHz, CDCl
3): δ 8.49 (t, J=1.8Hz, 1H), 8.19 (ddd, J=8.0Hz, 2.1Hz, 0.6Hz, 1H), 7.95 (ddd, J=8.0Hz, 1.8Hz, 0.9Hz, 1H), 7.61 (t, J=8.1Hz, 1H), 7.57 (d, J=3.6Hz, 1H), 7.50 (d, J=3.6Hz, 1H).
13C NMR (100MHz, CDCl
3) δ 148.8,143.9 (m), 143.9 (dm, J=249.7Hz), 140.1 (dm, J=254.5Hz), 138.1 (dm; J=251.8Hz), 135.1,131.5,131.4 (t, J=5.5Hz), 130.1,127.3; 124.9,122.6,120.5,109.4 (td, J=15.1Hz, 4.2Hz).
19F NMR (282MHz, CDCl
3) δ .-139.9 (dd, J=21.7Hz, 6.2Hz, 2F) ,-155.2 (t, J=20.2Hz, 1F) ,-162.0 (m.2F) .IR (film): v
Max1652,1543,1522,1495,1348cm
-1.MS (EI): m/z (%) 372 (M
++ 1), 371 (M
+), 325,306,281.HRMS: calculated value C
12H
5O
2F
5: 371.0039; Trial value: 371.0040.
P10
Yellow solid.88% yield.
1H NMR (300MHz, CDCl
3) δ 7.56 (d, J=8.2Hz, 1H), 7.47 (d, J=3.8Hz, 1H), δ 7.23 (d, J=3.8Hz, 1H), 6.93 (d, J=8.2Hz, 1H), 3.84 (s, 3H).
13C NMR (100MHz, CDCl
3) δ 159.8,147.2,143.9 (dm, J=249.0Hz), 139.6 (dm, J=253.2Hz), 138.0 (dm, J=246.8Hz), 131.2 (t, J=5.5Hz), 127.3,126.2,124.4,122.2,114.4,110.1 (m), 55.4.
19F NMR (282MHz, CDCl
3) δ-140.4 (dd, J=21.8Hz, 7.2Hz, 2F) ,-157.0 (t, J=20.7Hz, 1F) ,-163.2 (td, J=21.1Hz, 7.2Hz, 2F) .IR (film): v
Max2918,2849,1607,1572,1522,1540cm
-1.MS (EI): m/z (%) 357 (M
++ 1), 356 (M
+, 100), 341,313.HRMS: calculated value C
12H
5O
2F
5: 356.0297; Trial value: 356.0294.
P11
White solid.50% yield.
(300MHz, CDCl3) (1H), 7.54 (1H) (282MHz, CDCl3) (m, 2F) ,-154.5 (m, 1F) ,-162.0 (m, 2F) .IR (film): vmax 2276,1606,1536cm-1. for δ-139.5 for ..19F NMR for d, J=3.9Hz for d, J=3.9Hz for δ 7.70 for 1H NMR
P12
White solid.50% yield.
1H NMR (300MHz, CDCl3) δ 7.82 (d, J=3.9Hz, 1H), 7.48 (d, J=3.9Hz, 1H), 6.93 (m; 1H), 3.92 (s, 3H) .13C NMR (100MHz, CDCl3) δ 162.3,154.1 (dm, J=258.4Hz), 150.0 (dm, J=263.9Hz); 148.8 (dm, J=253.7Hz), 137.7 (dm, J=253.3Hz), 134.7,134.1,133.4,133.1; 129.9 (m), 109.2 (m), 101.4 (m), 52.3.19FNMR (282MHz, CDCl3) δ-113.4 (t, J=9.8Hz 1F) ,-131.5 (d; J=20.6Hz, 2F), s, 1F) ,-164.1 (m, 1F) .IR (film): vmax 3096,2957; 1704,1644,1606,1534cm-1.MS (EI): m/z (%) 291 (M++H+), 290 (M+), 259 (100), 187.HRMS: calculated value C12H6O2F4S:290.0025; Trial value: 290.0022.
P13
White solid.50% yield.
1H NMR (300MHz, CDCl3) δ 7.83 (d, J=4.2Hz, 1H), 7.57 (d, J=4.2Hz, 1H); 7.09 (m, 1H), 3.93 (s, 3H) .13C NMR (100MHz, CDCl3) δ 162.5,146.6 (dm; J=246.5Hz), 143.9 (dm, J=249.8Hz), 135.7 (t, J=4.0Hz), 134.3 (t; J=3.1Hz), 133.3,130.9 (t, J=6.0Hz), 114.5 (m), 105.6 (t; J=22.7Hz), 52.7.19F NMR (282MHz, CDCl3) δ-138.7 (m, 2F) ,-139.9 (m, 2F) .IR (film): vmax 3047; 1711,1604,1537cm-1.MS (EI): m/z (%) 291 (M++H+), 290 (M+), 259 (100), 187.HRMS: calculated value C12H6O2F4S:290.0025; Trial value: 290.0030.
P14
White solid.77% yield.
1H NMR (300MHz, CDCl3) δ 7.70 (d, J=3.6Hz, 1H), 7.10 (d, J=3.6Hz; 1H) .13C NMR (75.4MHz, CDCl3) δ 144.3 (dm, J=244.0Hz), 138.2 (dm, J=260.9Hz), 137.0 (m); 132.4 (t, J=7.8Hz), 127.0,125.2 (m) .19F NMR (282MHz, CDCl3) δ-91.1 (m; 2F) ,-142.3 (m, 2F) .IR (film): vmax 3122,1643, and 1618; 1426cm-1.MS (EI): m/z (%) 269 (M+, 38), 267 (M+, 100), 188.HRMS: calculated value C9H2ClF4NS:266.9533; Trial value: 266.9527.
P15
Yellow solid.88% yield.
1H NMR (300MHz, CDCl
3) δ 7.84 (d, J=4.2Hz, 1H), 7.78 (d, J=4.2Hz, 1H), 2.65 (s, 3H).
13C NMR (75.4MHz, CDCl
3) δ 190.5,147.8 (t, J=4.3Hz), 144.2 (dm, J=244.4Hz), 138.6 (dd, J=262.3Hz, 35.2Hz), 133.0 (t, J=6.9Hz), 131.8,27.0.
19F NMR (282MHz, CDCl
3) δ .-90.4 (m, 2F) ,-140.9 (m, 2F) .IR (film): v
Max1670,1643,1461cm
-1.MS (EI): m/z (%) 276 (M
++ H
+), 275 (M
+), 260 (100), 188.HRMS: calculated value C
11H
5NOF
4S:275.0028; Trial value: 275.0029.
P16
White solid.80% yield.
1H NMR (300MHz, CDCl3) δ 7.82 (d, J=4.0Hz, 1H), 7.48 (d, J=4.0Hz, 1H), 4.14 (s; 3H), 3.92 (s, 3H) .13C NMR (75.4MHz, CDCl3) δ 162.3,144.4 (dm, J=248.9Hz), 141.1 (dm; J=251.6Hz), 138.0 (m), 134.5 (m), 134.1 (m), 133.1,129.8 (t, J=5.7Hz); 106.9 (t, J=15.2Hz), 62.1 (t, J=4.0Hz), 52.3.19F NMR (282MHz, CDCl3) δ-140.5 (m, 2F);-157.5 (5.9Hz, 2F) .IR (film): vmax 1714 for dd, J=20.0Hz, 1649cm-1.MS (EI): m/z (%) 321 (M++H+), 320 (M+), 289 (100) .HRMS: calculated value C
13H
8F
4O
3S:320.0130; Trial value: 320.0134.
P17
White solid.91% yield.
1H NMR (300MHz, CDCl3) δ 7.87 (d, J=4.0Hz, 1H), 7.67 (d, J=4.0Hz, 1H); 3.95 (s, 3H) .13C NMR (100MHz, CDCl3) δ 161.9,144.5 (dm, J=252.2Hz), 143.9 (dm, J=253.1Hz); 136.8 (m), 133.1,132.3,131.7 (t, J=6.4Hz), 120.6 (q, J=275.1Hz); 117.5 (m), 108.6 (m), 52.6.19F NMR (282MHz, CDCl3) δ .-56.0 (t, J=20.2Hz, 3F) ,-137.7 (m; 2F) ,-140.4 (m, 2F) .IR (film): vmax 3095,2968, and 2850,1728,1655; 1621,1535,1475cm-1.MS (EI): m/z (%) 359 (M++H+), 358 (M+), 327 (100), 255.HRMS: calculated value C13H5O2F7S:357.9898; Trial value: 357.9900.
P18
White solid.77% yield
1H NMR (300MHz, CDCl3) δ 7.54 (d, J=4.2Hz, 1H), 7.05 (d, J=4.2Hz, 1H) .13C NMR (100MHz; CDCl3) δ 144.6 (dd, J=248.2Hz, 16Hz), 143.4 (dm, J=247.1Hz), 135.4 (t, J=6.1Hz); 131.3 (t, J=7.2Hz), 126.8,125.1,120.7 (q, J=273.2Hz), 117.6 (t; J=14Hz), 107.6 (m) .19F NMR (282MHz, CDCl3) δ .-56.6 (t, J=22.4Hz, 3F) ,-138.9 (m, 2F);-140.1 (m, 2F) .IR (film): vmax 2919,1652, and 1622,1615,1563,1558; 1479cm-1.MS (EI): m/z (%) 336 (M+, 37), 334 (M+, 100), 315,255.HRMS: calculated value C11H2F7SCl:333.9454; Trial value: 333.9457.
P19
Light yellow solid.78% yield.
1H NMR (300MHz, CDCl3) δ 7.85 (d, J=4.2Hz, 1H), 7.65 (m, 2H), 6.75 (d, J=16.5Hz; 1H), 3.94 (s, 3H), 1.55 (s, 9H) .13C NMR (75.4MHz, CDCl3) δ 165.2,162.1,145.5 (dm; J=242.1Hz), 143.7 (dm, J=245.4Hz), 135.7 (t, J=4.6Hz), 133.8 (m), 133.1,130.9 (t; J=6.6Hz), 128.7 (t, J=8.5Hz), 127.5,113.7 (t, J=14.0Hz), 81.5; 52.4,28.0.19F NMR (282MHz, CDCl3) δ-140.1 (m, 2F) ,-140.6 (m, 2F) .IR (film): vmax 3128,2981; 1718,1631cm-1.MS (EI): m/z (%) 416 (M++H+), 416 (M+), 360 (100), 343,329,57.HRMS: calculated value C19H16F4O4S:416.0705; Trial value: 416.0707.
P20
White solid.50% yield.
1H NMR (300MHz, CDCl3) δ 7.81 (d, J=4.0Hz, 1H), 7.45 (d, J=4.0Hz, 1H); 6.81 (t, J=8.7Hz, 2H), 3.92 (s, 3H) .13C NMR (100MHz, CDCl3) δ 162.5; 161.9 (dt, J=250.9Hz, 15.5Hz), 160.1 (ddd, J=252.1Hz, 14.0Hz; 9.2Hz), 135.3,134.0,133.1,129.4 (t, J=5.2Hz); 108.2 (m), 101.1 (m), 52.3.19F NMR (282MHz, CDCl3) δ-106.7 (t, J=7.9Hz, 2F);-107.2 (m, 1F) .IR (film): vmax 1713,1638,1593cm-1.MS (EI): m/z (%) 272 (M+), 241 (100), 169.HRMS: calculated value C12H7F3O2S:272.0119; Trial value: 272.0120.
P21
White solid.52% yield
1H NMR (300MHz, CDCl3) δ 7.84 (d, J=3.9Hz, 1H), 7.60 (d, J=3,9Hz, 1H); 7.45 (d, J=8.6Hz, 2H), 7.03 (d, J=8.6Hz, 2H), 3.93 (s, 3H); 3.87 (s, 3H) .13CNMR (100MHz, CDCl3) δ 162.3,160.3,144.1 (dm, J=250.0Hz), 135.0 (m), 134.5; 133.2,131.4,130.3 (t, J=6.1Hz), 120.0 (t, J=16.6Hz), 119.0,114.2; 111.7 (t, J=14.7Hz), 55.3,52.4.19F NMR (282MHz, CDCl3) δ-140.4 (dd, J=22.2Hz, 13.3Hz; 2F) ,-141.1 (11.0Hz, 2F) .IR (film): vmax 2960,2919 for dd, J=22.2Hz, and 1716; 1651,1610,1522,1471cm-1.MS (EI): m/z (%) 397 (M++H+), 396 (M+, 100), 365293.HRMS: calculated value C19H12O3F4S:396.0443; Trial value: 396.0443.
P22
White solid.85% yield.
1H NMR (300MHz, CDCl
3) δ 7.85 (d, J=3.9Hz, 1H), 7.62 (d, J=3.9Hz, 1H), 7.51 (s, 5H), 3.93 (s, 3H).
13C NMR (100MHz, CDCl
3) δ 162.3,144.2 (dm, J=248.5Hz), 135.2 (t, J=4.3Hz), 134.3,133.2,130.5 (t, J=6.0Hz), 130.1,129.4,128.7,127.0,120.2 (t, J=16.9Hz), 112.4 (t, J=14.7Hz), 52.4.
19F NMR (282MHz, CDCl
3) δ .-140.2 (dd, J=21.4Hz, 8.7Hz, 2F) ,-144.1 (dd, J=21.4Hz, 11.0Hz, 2F) .IR (film): v
Max3056,2953,1723,1538,1480,1438cm
-1.MS (EI): m/z (%) 367 (M
++ H
+), 366 (M
+), 335 (100), 263.HRMS: calculated value C
18H
10O
2F
4S:366.0338; Trial value: 366.0342.
P23
White solid, 50% yield.
1H NMR (300MHz, CDCl
3) δ 7.84 (d, J=3.8Hz, 1H), 7.57 (d, J=3.8Hz, 1H), 3.94 (s, 3H).
13C NMR (100MHz, CDCl
3) δ 162.4,145.7 (dm, J=243.1Hz), 144.1 (dm, J=253.6Hz), 136.0 (t, J=4.0Hz), 133.7 (m), 133.4,131.0 (t, J=6.0Hz), 113.3 (t, J=15.1Hz), 99.7 (t, J=22.5Hz), 52.7.
19F NMR (282MHz, CDCl
3) δ .-133.1 (m, 2F) ,-138.3 (dd, J=21.2Hz, 10.4Hz, 2F) .IR (film): v
Max1712,1533,1478cm
-1.MS (EI): m/z (%) 370 (M
+, 57), 368 (M
+, 58), 339 (100), 337 (99), 267 (51), 265 (52), 186.HRMS: calculated value C
12H
5BrF
4O
2S:367.9130; Trial value: 367.9127.
P24
White solid.60% yield.
1H NMR (300MHz, CDCl3) δ 7.82 (d, J=3.9Hz, 1H), 7.53 (d, J=3.9Hz; 1H), 3.94 (s, 3H), 2.32 (t, J=2.0Hz, 3H) .19F NMR (282MHz; CDCl3) (m, 2F) ,-143.7 (m, 2F) .IR (film): vmax 1751,1632cm-1 for δ-141.5
P25
White solid.40% yield.
1H?NMR(300MHz，CDCl3)δ7.57(d，J＝3.6Hz，1H)，7.29(d，J＝3.6Hz，1H)，0.37(s，9H)19F?NMR(282MHz，CDCl3)δ-140.2(m，2F)，-156.6(t，J＝22.2Hz，2F)，-162.7(m，2F).
、
P26
White solid.87% yield.
1H?NMR(300MHz，CDCl
3)δ7.60(s，2H).
19F?NMR(282MHz，CDCl
3)δ.-139.6(dd，J＝20.6Hz，6.6Hz，2F)，-154.7(t，J＝20.6Hz，1F)，-161.8(m，2F).
P27
Yellow solid 52% yield
1H?NMR(300MHz，CDCl
3)δ7.50(d，J＝3.5Hz，2H)，7.30(d，J＝3.5Hz，2H).
19F?NMR(282MHz，CDCl
3)δ-140.0(dd，J＝22.0Hz，6.2Hz，2F)，-155.7(t，J＝20.6，1F)，-162.1(td，J＝20.6，5.6Hz，2F).
Claims (7)
1. the compound method of a polyfluoro aromatic hydrocarbons and verivate-heterocycle building block thereof; It is characterized in that in the presence of organic solvent with 100 ℃ of-140 ℃ of scopes in; With polyfluoro aromatic hydrocarbons and verivate thereof is raw material, with palladium salt as catalyzer, with silver salt and oxygen as oxygenant; Reacted 3-9 hour as additive and hetero-aromatic ring compounds with protonic acid, generate polyfluoro aromatic hydrocarbons and verivate-hetero-aromatic ring building block thereof;
Described polyfluoro aromatic hydrocarbons and verivate thereof, palladium salt, silver salt, assorted arene compounds, protonic acid, the mol ratio of oxygen is 1-3: 0.01-1: 0.01-1: 1-3.0: 0-1: 0.2-48;
Described palladium salt structure is: PdX
2,, Pd (PPh
3)
4Or Pd
2(dba)
3Wherein, the negatively charged ion of X representative is acetate or trifluoracetic acid root; PPh
3Be triphenylphosphine; Dba is a dibenzalacetone;
Described silver salt is tachyol, Silver monoacetate, Silver Trifluoroacetate, silver carbonate, silver trifluoromethanesulfonate, Silver Nitrate or silver suboxide;
Described polyfluoro aromatic hydrocarbons and verivate thereof have the R of following structural formula
1-R
3Substituted polyfluoro benzene or R
1-R
2Substituted polyfluoro pyridine:
Described hetero-aromatic ring compounds has the R that is of following structural formula
4Perhaps R
5The five yuan of hetero-aromatic rings of the substituted O of containing, N or S or the substituted five yuan of hetero-aromatic rings that contain O, N or S of benzo base:
R wherein
1-R
3Take from hydrogen, C
1-4Perfluoroalkyl, C
1-4Alkyl, halogen, phenyl, C
1-4Alkoxyl group, C
1-4The substituted phenyl of alkoxyl group, COOC
1-4H
3-9, C=COO C
1-6H
3-13Perhaps adjacent group benzo base each other;
R
4Perhaps R
5The five yuan of hetero-aromatic rings of the substituted O of containing, N or S or the substituted five yuan of hetero-aromatic rings that contain O, N or S of benzo base; Wherein, R
4Perhaps R
5Take from halogen, CN, C (O) H, C (O) C
1-4H
3-9, COOC
1-4H
3-9, C
1-4The substituted phenyl of alkoxyl group, the substituted phenyl of nitro, C=COO C
1-6H
3-13, CON (C
1-4H
3-9), trimethyl silicon based or thienyl; Described R
6Be C
1-4Alkyl or benzyl.
2. the method for synthetic polyfluoro aromatic hydrocarbons according to claim 1-assorted aromatic hydrocarbons is characterized in that described polyfluoro aromatic hydroxy compound has following structural formula:
3. the method for synthetic polyfluoro aromatic hydrocarbons according to claim 1-assorted aromatic hydrocarbons is characterized in that described assorted aromatic hydroxy compound has following structural formula:
4. the method for synthetic polyfluoro aromatic hydrocarbons according to claim 1-assorted aromatic hydrocarbons; It is characterized in that described polyfluoro aromatic hydrocarbons and verivate thereof, palladium salt, silver salt, assorted arene compounds; Protonic acid, the mol ratio of oxygen are 1-3: 0.05-0.1: 0.05-0.5: 1-3.0: 0-0.6: 1-48..
5. the method for synthetic polyfluoro aromatic hydrocarbons according to claim 1 and verivate thereof-assorted aromatic hydrocarbons is characterized in that institute with an organic solvent is N-Methyl pyrrolidone, N, dinethylformamide, DMSO 99.8MIN., 1; 3-dimethyl--3; 4,5,6-tetrahydrochysene-2-pyrimidone, 1; 4-dioxane or DMAC N,N.
6. the method for synthetic polyfluoro aromatic hydrocarbons according to claim 1-assorted aromatic hydrocarbons is characterized in that described protonic acid is acetate, formic acid, propionic acid, Buddha's warrior attendant acid, trimethylacetic acid or phenylformic acid.
7. the method for synthetic polyfluoro aromatic hydrocarbons according to claim 1-assorted aromatic hydrocarbons is characterized in that described polyfluoro aromatic hydrocarbons-assorted aromatic hydrocarbons building block has following structural formula:
Wherein, R
1-R
6According to claim 1; Polyfluoro aromatic hydrocarbons ArFn representes with the described R of claim 1
1-R
3Substituted polyfluoro benzene or R
1-R
2Substituted polyfluoro pyridine.
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| CN103030627A (en) * | 2013-01-07 | 2013-04-10 | 中国科学院上海有机化学研究所 | Synthesis method for thiophene ring/furan ring-heteroaromatic ring structure |
| CN104672221A (en) * | 2013-11-29 | 2015-06-03 | 中国科学院上海有机化学研究所 | Synthetic method of fluorobenzoheterocycle-heteroaromatic ring structure |
| CN114956924A (en) * | 2022-06-29 | 2022-08-30 | 河南科技学院 | Method for synthesizing polyfluoro biaryl through series/coupling reaction |
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| CHUN-YANG HE,ET AL.: "《Pd-Catalyzed Oxidative Cross-Coupling of Perfluoroarenes with Aromatic Heterocycles》", 《J.AM.CHEM.SOC.》 * |
| YE WEI AND WEIPING SU: "《Pd(OAc)2-Catalyzed Oxidative C-H/C-H Cross-Coupling of Electron-Deficient Polyfluoroarenes with Simple Arenes》", 《J.AM.CHEM.SOC.》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030627A (en) * | 2013-01-07 | 2013-04-10 | 中国科学院上海有机化学研究所 | Synthesis method for thiophene ring/furan ring-heteroaromatic ring structure |
| CN103030627B (en) * | 2013-01-07 | 2017-11-10 | 中国科学院上海有机化学研究所 | A kind of synthetic method of thiphene ring/furan nucleus Heteroaryl ring structures |
| CN104672221A (en) * | 2013-11-29 | 2015-06-03 | 中国科学院上海有机化学研究所 | Synthetic method of fluorobenzoheterocycle-heteroaromatic ring structure |
| CN104672221B (en) * | 2013-11-29 | 2018-01-23 | 中国科学院上海有机化学研究所 | A kind of synthetic method of fluoro benzheterocycle Heteroaryl ring structures |
| CN114956924A (en) * | 2022-06-29 | 2022-08-30 | 河南科技学院 | Method for synthesizing polyfluoro biaryl through series/coupling reaction |
| CN114956924B (en) * | 2022-06-29 | 2024-01-30 | 河南科技学院 | Method for synthesizing polyfluorinated biaryl through series connection/coupling reaction |
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