CN103910591A - Boron removal method of phenyl and heterocyclic borate catalyzed by monovalent silver and application thereof - Google Patents
Boron removal method of phenyl and heterocyclic borate catalyzed by monovalent silver and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of organic synthesis chemistry, and the method provides a hydrolytic boron removal reaction of phenyl and heterocyclic borate catalyzed by monovalent silver with certain catalytic amount. The method provided by the invention has the advantages that phenyl and heterocyclic borate substrates are wide, the functional groups have high durability and the reagent has commercial availability. The method not only provides the hydrolytic boron removal of the phenyl and heterocyclic borate to obtain aromatic and heterocyclic compounds, but also can be applied to preparation of selective deuterated products.
Description
technical field
The invention belongs to Synthetic Organic Chemistry technical field, the present invention relates to is under the catalysis of monovalence silver, from phenyl, heterocyclic boronic acids, and the method for the de-boronation product of preparation.
Background technology
Nearly decades, organoboron reagent is widely used in [E. R. Burkhardt, K. Matos in organic synthesis; Chem. Rev.2006,106,2617 – 2650.N. Miyaura; A. Suzuki, Chem. Rev. 1995,95; 2457 – 2483.M. Suginome, J. Synth. Org. Chem. Jpn. 2007,65; 1048 – 1059.M. Yamashita; Angew. Chem. 2010,122,2524 – 2526; Angew. Chem. Int. Ed.2010,49,2474 – 2475.P.G. Campbell, A.J.V. Marwitz, S.-Y. Liu, Angew. Chem. Int. Ed.2012,51,6074 – 6092].Organic boronic compounds is owing to being easy to get, and high reactivity is also used widely in organic chemistry.The boric acid of a series of aryl and heterocycle is produced and participates in organic reaction, as crosslinking reaction, the protecting group of glycol and diamines, [the N.Miyaura such as the de-boron halogenating reaction of regioselectivity, A.J.Suzuki, Chem. Soc., Chem. Commun. (19): 866. N. A.Petasis, I. A.Xavialov, J. Am. Chem. Soc. 119 (2): 445. M.Sakai, H.Hayashi, N. Miyaura, Angew. Chem. Int. Ed. 37 (23): 3279. A. D.Ainley, F.J. Challenger, Chem. Soc.:2171.].But in many target products, boron is not functional groups in final product, need to remove.Therefore,, in organic chemistry, selective removal boric acid base group is a huge challenge.At present, only there is little de-boron glycosylation reaction of a few example report boric acid.But the severe reaction conditions using, as stoichiometric metal reagents such as uses, [Ainley, Challenger, the J. Chem. SOC. such as the ammonia solution of hafnium halide, zinc halide and Silver Nitrate, 2171 (1930) .Michaelis, Becker, Ber., 15,181 (1882)], and above-mentioned reaction conditions tend to affect the group of some chemically unstables on aromatic ring and heterocycle.Therefore be, to make us very much thirsting in the method for a kind of gentleness of development, selective removal boronate.
The present invention overcomes existing methods shortcoming, under mild conditions, uses the monovalence silver catalysis phenyl of catalytic amount, the de-boronation reaction of hydrolysis of heterocyclic boronic acids.The advantage of this reaction is phenyl, heterocyclic boronic acids substrate widely, the wearing quality of high functional group, the business availability of reagent.Meanwhile, the method can, in sloughing boric acid base group, optionally be introduced deuterated atom on aromatic ring and heterocycle.In organic compound, selectivity is introduced D atom for isotopic compound research, c h bond Study of Activation, and the aspects such as mechanism of catalytic reaction research are very important.At present, by fracture C-B key, selectivity is introduced D atom, and never someone reported especially.
Summary of the invention
Present method provides in one under mild conditions, the monovalence silver catalysis phenyl of catalytic amount, the de-boronation reaction of hydrolysis of heterocyclic boronic acids.The advantage of this reaction is phenyl, heterocyclic boronic acids substrate widely, the wearing quality of high functional group, the business availability of reagent.Present method not only provides the hydrolysis of phenyl, heterocyclic boronic acids de-boronation, obtains aryl and heterogeneous ring compound, and can be applied in the preparation of the deuterated product of selectivity.
The reaction equation of the phenyl the present invention relates to, the de-boronation reaction of the hydrolysis of heterocyclic boronic acids and the deuterated product of preparation selectivity:
By boric acid, potassiumphosphate 2.0eq-4.0eq, silver carbonate 0.1eq-0.5eq adds DMF successively, and quality is than in the mixture of 0.1-1:0.1-1,20-100
oc stirs, and detects raw material disappear to TLC, and shrend is gone out, and ether extraction three times merges organic layer, washing, and dry, silica gel column chromatography obtains product.
Accompanying drawing explanation
The reduction of accompanying drawing 1:2-naphthalene boronic acids
1h spectrogram;
The reduction of accompanying drawing 2:2-naphthalene boronic acids
13c spectrogram;
Accompanying drawing 3:2-naphthalene boronic acids is deuterated
1h spectrogram;
Accompanying drawing 4:2-naphthalene boronic acids is deuterated
13c spectrogram.
Present method advantage is mild condition, and the monovalence silver of catalytic amount is catalyzer, and functional group's tolerance level is high, applied widely, with low cost, and raw material is easy to get, and can be widely used in the deuterated product of preparation selectivity, has very high practical value.
embodiment:
Aforesaid method will further describe by concrete example, but the method being to provide can not be served as the restriction to present method.
Embodiment 1 prepares benzene by phenylo boric acid
By phenylo boric acid (122mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, and quality is than in the mixture of 1:1 (0.5ml:0.5ml), and 60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains compound benzene (58mg, 74%)
Colourless liquid; 1H-NMR (500 MHz, CDCl3) δ 7.34 (s, 6H); 13C-NMR (CDCl3,125 MHz) δ 128.3.
Embodiment 2 is by methoxyphenylboronic acid is prepared to methyl-phenoxide
By 2-methoxyl group-phenylo boric acid (152mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, and quality is than in the mixture of 1:1 (0.5ml:0.5ml), and 60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains compound methyl-phenoxide (95mg, 88%)
Colourless liquid; 1H-NMR (500 MHz, CDCl3) δ 7.29 (t, J=8.0 Hz, 2H); 7.94 (t, J=7.0 Hz, 1H), 6.90 (d; J=8.5 Hz, 2H), 3.80 (s, 3H); 13C-NMR (CDCl3,500 MHz) δ 159.5,129.4,120.6,113.8,55.1.
Embodiment 3 prepares phenol by para hydroxybenzene boric acid
By para hydroxybenzene boric acid (138mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, and quality is than in the mixture of 1:1 (0.5ml:0.5ml), and 60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains compound phenol (40mg, 43%)
White solid; 1H-NMR (500 MHz, CDCl3) δ 7.27-7.24 (m, 2H), 6.94 (t; J=7.5 Hz, 1H), 6.84 (dd, J=2.0 Hz; J=8.5 Hz, 2H), 4.72 (s, 1H); 13C-NMR (CDCl3,125 MHz) δ 155.3,129.7,120.8,115.3.
Embodiment 4 is by fluorobenzoic boric acid is prepared to fluorobenzene
Will be to fluorobenzoic boric acid (140mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains compound fluorobenzene (42mg, 44%)
Liquid; 1H-NMR (500 MHz, CDCl3) δ 7.36-7.29 (m, 2H), 7.12 (t, J=7.5 Hz, 1H), 7.08-7.02 (m, 2H); 13C-NMR (CDCl3,125 MHz) δ 162.8 (d, J=15.6 Hz), 129.9 (d, J=0.5 Hz), 123.9,115.3 (d, J=1.3 Hz).
Embodiment 5 prepares fluorobenzene by adjacent fluorobenzoic boric acid
By adjacent fluorobenzoic boric acid (149mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains compound fluorobenzene (64mg, 67%)
Liquid; 1H-NMR (500 MHz, CDCl3) δ 7.36-7.29 (m, 2H), 7.12 (t, J=7.5 Hz, 1H), 7.08-7.02 (m, 2H); 13C-NMR (CDCl3,125 MHz) δ 162.8 (d, J=15.6 Hz), 129.9 (d, J=0.5 Hz), 123.9,115.3 (d, J=1.3 Hz).
Embodiment 6 prepares fluorobenzene by a fluorobenzoic boric acid
Fluorobenzoic boric acid (149mg, 1.0mmol) between inciting somebody to action, potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.6ml:0.6ml) of water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains compound fluorobenzene (51mg, 53%)
Liquid; 1H-NMR (500 MHz, CDCl3) δ 7.36-7.29 (m, 2H), 7.12 (t, J=7.5 Hz, 1H), 7.08-7.02 (m, 2H); 13C-NMR (CDCl3,125 MHz) δ 162.8 (d, J=15.6 Hz), 129.9 (d, J=0.5 Hz), 123.9,115.3 (d, J=1.3 Hz).
Embodiment 7 is by formylphenylboronic acid is prepared to phenyl aldehyde
Will be to formylphenylboronic acid (150mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (1ml:1ml) of water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains compound phenyl aldehyde (50mg, 47%)
Colourless liquid; 1H-NMR (500 MHz, CDCl3) δ 10.02 (s, 1H), 7.89-7.87 (m, 2H), 7.65-7.61 (m, 1H), 7.53 (t, J=8.0 Hz, 2H); 13C-NMR (CDCl3,125 MHz) δ 192.4,136.3,134.4,129.7,129.0.
Embodiment 8 is by acetylbenzene boric acid is prepared to methyl phenyl ketone
Will be to acetylbenzene boric acid (164mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains compound methyl phenyl ketone (91mg, 76%)
Yellow liquid; 1H-NMR (500 MHz, CDCl3) δ 7.98-7.95 (m, 2H), 7.59-7.55 (m, 1H), 7.48-7.45 (m, 2H), 2.61 (s, 3H); 13C-NMR (CDCl3,125 MHz) δ 198.1 .137.0,133.1,128.5,128.3,26.6.
Embodiment 9 is by borono-phenylformic acid is prepared to phenylformic acid
Will be to borono-phenylformic acid (166mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains compound phenylformic acid (76mg, 62%)
White solid; 1H-NMR (500 MHz, CDCl3) δ 8.13 (dd, J=1.0 Hz, J=8.0 Hz, 2H) 7.63 (t, J=7.5 Hz, 1H), 7.49 (t, J=8.0 Hz, 2H); 13C-NMR (CDCl3,125 MHz) δ 172.0,133.8,130.2,129.2,128.5.
Embodiment 10 is by 1,1
,-phenylbenzene-4-phenylo boric acid is prepared biphenyl
By 1,1 ,-phenylbenzene-4-phenylo boric acid (198mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains compound biphenyl (135.5mg, 88%)
White solid; 1H-NMR (500 MHz, CDCl3) δ 7.60-7.56 (m, 4H), 7.45-7.42 (m, 4H), 7.36-7.22 (m, 2H); 13C-NMR (CDCl3,125 MHz) δ 141.2,128.7,127.2,127.1.
Embodiment 11 is by cyanophenylboronic acid is prepared to benzonitrile
Will be to cyanophenylboronic acid (147mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains compound benzonitrile (52mg, 50%)
Liquid; 1H-NMR (500 MHz, CDCl3) δ 7.66 (dd, J=1.0 Hz, J=8.0Hz, 2H), 7.63 (t, J=2.0 Hz, 1H), 7.48 (t, J=8.0 Hz, 2H); 13C-NMR (CDCl3,125 MHz) δ 132.7,132.0,129.0,118.8,112.3.
Embodiment 12 prepares naphthalene by 2-naphthalene boronic acids
By 2-naphthalene boronic acids (172mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains compound naphthalene (102mg, 80%)
White solid; 1H-NMR (500 MHz, CDCl3) δ 7.86-7.79 (m, 4H), 7.50-7.41 (m, 4H); 13C-NMR (CDCl3,125 MHz) δ 133.4,126.8,125.8.
Embodiment 13 prepares pyridine by 3-pyridine boric acid
By 3-pyridine boric acid (123mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains compound pyridine (49mg, 62%)
Liquid; 1H-NMR (500 MHz, CDCl3) δ 8.61 (d, J=4.0 Hz, 2H), 7.69-7.63 (m, 1H), 7.29-7.24 (m, 2H); 13C-NMR (CDCl3,125 MHz) δ 149.6,135.7,123.5.
Embodiment 14 prepares thiophene by 3 thienylboronic acid
By 3 thienylboronic acid (128mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains compound thiophene (70mg, 83%)
Liquid; 1H-NMR (500 MHz, CDCl3) δ 7.35-7.34 (m, 2H), 7.13-7.12 (m, 2H); 13C-NMR (CDCl3,125 MHz) δ 126.8,125.1.
Embodiment 15 prepares m-difluorobenzene by 2,6-difluorobenzene boric acid
By 2,6-difluorobenzene boric acid (158mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains compound m-difluorobenzene (98mg, 86%)
Liquid; 1H-NMR (500 MHz, CDCl3) δ 7.33-7.26 (m, 1H), 6.91-6.85 (m, 2H), 6.82-6.78 (m, 1H); 13C-NMR (CDCl3,125 MHz) δ 163.2 (d, J=15.8 Hz), 163.1 (d, J=15.8), 130.6 (t, J=0.6 Hz), 111.2 (d, J=1.2 Hz), 103.9 (t, J=1.7 Hz).
Embodiment 16 is by being prepared by fluorobenzoic boric acid to the deuterated fluorobenzene of contraposition
Will be to fluorobenzoic boric acid (149mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of deuterated heavy water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains the deuterated fluorobenzene of compound contraposition (75mg, 78%)
Liquid; 1H-NMR (500 MHz, CDCl3) δ 7.36-7.30 (t, 2H), 7.13 (t, J=7.5 Hz, 0.2H), 7.05 (t, J=8.5 Hz, 2H); 13C-NMR (CDCl3,125 MHz) δ 163.8,161.8,130.0,129.9,129.8,129.8,123.9,115.4,115.2.
Embodiment 17 prepares the deuterated fluorobenzene in ortho position by adjacent fluorobenzoic boric acid
By adjacent fluorobenzoic boric acid (149mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of deuterated heavy water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains the deuterated fluorobenzene in compound ortho position (76mg, 79%)
Liquid; 1H-NMR (500 MHz, CDCl3) δ 7.36-7.28 (m, 2H), 7.12 (t, J=7.0 Hz, 1H), 7.05 (t, J=9.0 Hz, 1.3H); 13C-NMR (CDCl3,125 MHz) δ 163.7,163.7,129.9,129.9,129.8,129.8,129.8,123.9,115.3,115.2.
Embodiment 18 is by the deuterated fluorobenzene in position between a fluorobenzoic boric acid preparation
Fluorobenzoic boric acid (149mg, 1.0mmol) between inciting somebody to action, potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of deuterated heavy water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, and washing is dry, and silica gel column chromatography (sherwood oil) obtains the deuterated fluorobenzene (75mg, 78%) in position between compound
Liquid; 1H-NMR (500 MHz, CDCl3) δ 7.35-7.31 (m, 1H), 7.13 (d, J=7.5 Hz, 1H), 7.06 (t, J=6.5 Hz, 2H); 13C-NMR (CDCl3,125 MHz) δ 163.8,161.8,130.0,129.9,123.8,115.4,115.3,115.2,115.1.
Embodiment 19 is by 1,1, and-phenylbenzene-4-phenylo boric acid is prepared the deuterated biphenyl of contraposition
By 1,1 ,-phenylbenzene-4-phenylo boric acid (198mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of deuterated heavy water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains the deuterated biphenyl of compound contraposition (135.5mg, 88%)
White solid; 1H-NMR (500 MHz, CDCl3) δ 7.59 (d, J=7.5Hz, 4H), 7.47-7.41 (m, 4H), 7.34 (t, J=7.0 Hz, 1H); 13C-NMR (CDCl3,125 MHz) δ 141.2,128.7,128.6,127.2,127.1.
Embodiment 20 prepares the deuterated naphthalene of 2-by 2-naphthalene boronic acids
By 2-naphthalene boronic acids (172mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of deuterated heavy water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains the deuterated naphthalene of compound 2-(108mg, 84%)
White solid; 1H-NMR (500 MHz, CDCl3) δ 7.85-7.80 (m, 4H), 7.48-7.44 (m, 3H); 13C-NMR (CDCl3,125 MHz) δ 133.4,127.8,127.7,125.8,125.7.
Embodiment 21 prepares the deuterated naphthalene of 1-by 1-naphthalene boronic acids
By 1-naphthalene boronic acids (172mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of deuterated heavy water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains the deuterated naphthalene of compound 1-(96mg, 75%)
White solid; 1H-NMR (500 MHz, CDCl3) δ 7.85-7.80 (m, 3H), 7.50-7.43 (m, 4H); 13C-NMR (CDCl3,125 MHz) δ 133.4,127.8,127.8,125.8,125.7.
Embodiment 22 prepares deuterated benzene by phenylo boric acid
By phenylo boric acid (122mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of deuterated heavy water 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, washing, and dry, silica gel column chromatography (sherwood oil) obtains the deuterated benzene of compound (48mg, 62%)
Liquid; 1H-NMR (500 MHz, CDCl3) δ 7.37-7.33 (s, 5H); 13C-NMR (CDCl3,125 MHz) δ 128.3,128.2.
It is deuterated-1 that embodiment 23 prepares 6-by 2,4 difluorobenzene boric acid, 3-difluorobenzene
By 2,4 difluorobenzene boric acid (158mg, 1.0mmol), potassiumphosphate (423mg, 2.0mmol), silver carbonate (27.4mg, 0.1mmol) adds DMF successively, in the mixture (0.5ml:0.5ml) of deuterated heavy water mass ratio 1:1,60
oc stirs, and detects raw material disappear to TLC.Shrend is gone out, and ether extraction three times (3*10 mL) merges organic layer, and washing is dry, and it is deuterated-1 that silica gel column chromatography (sherwood oil) obtains compound 6-, 3-difluorobenzene (73mg, 64%)
Liquid; 1H-NMR (500 MHz, CDCl3) δ 7.33-7.26 (m, 1H), 6.89-6.84 (m, 1.3H), 6.83-6.77 (m, 1H); 13C-NMR (CDCl3,125 MHz) δ 164.1,164.0,162.1,162.0,130.6,130.5,130.5,130.4,130.6,111.2,111.0,104.1,103.9,103.7.
Claims (3)
1. the method for the de-boronation of monovalence silver catalysis phenyl, heterocyclic boronic acids, is characterized in that boric acid, potassiumphosphate 2.0eq-4.0eq, and silver carbonate 0.1eq-0.5eq adds DMF successively, and quality is than in the mixture of 0.1-1:0.1-1,20-100
oc stirs, and detects raw material disappear to TLC, and shrend is gone out, and ether extraction three times merges organic layer, washing, and dry, silica gel column chromatography obtains product.
2. by method claimed in claim 1, it is characterized in that 2,4 difluorobenzene boric acid 1.0mmol, potassiumphosphate 2.0mmol, silver carbonate 0.1mmol adds DMF successively, in the mixture of deuterated heavy water mass ratio 1:1,60
oc stirs, and detects raw material disappearance shrend go out to TLC, and three 3*10 mL of ether extraction, merge organic layer, and washing is dry, silica gel column chromatography obtains compound 6-deuterated-1,3-difluorobenzene 73mg, 64%.
3. apply in the deuterated product of preparation selectivity by method claimed in claim 1.
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| CN113149801A (en) * | 2021-01-27 | 2021-07-23 | 南京工业大学 | Deuterated polyhalogen aromatic compound, preparation method thereof and organic intermediate |
| CN114105736A (en) * | 2021-11-30 | 2022-03-01 | 天津济坤医药科技有限公司 | Preparation method of deuterated aromatic compound |
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| CN103617260A (en) * | 2013-11-29 | 2014-03-05 | 华为技术有限公司 | Index generation method and device for repeated data deletion |
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| CN103617260A (en) * | 2013-11-29 | 2014-03-05 | 华为技术有限公司 | Index generation method and device for repeated data deletion |
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| 吴永花: "银催化芳香化合物的脱硼反应和脱羧反应", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113149801A (en) * | 2021-01-27 | 2021-07-23 | 南京工业大学 | Deuterated polyhalogen aromatic compound, preparation method thereof and organic intermediate |
| CN114105736A (en) * | 2021-11-30 | 2022-03-01 | 天津济坤医药科技有限公司 | Preparation method of deuterated aromatic compound |
| CN114105736B (en) * | 2021-11-30 | 2023-12-15 | 天津济坤医药科技有限公司 | Preparation method of deuterated aromatic compound |
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