CN109021002A - A kind of preparation method of two amido aryl boron amide of naphthalene -1,8- - Google Patents
A kind of preparation method of two amido aryl boron amide of naphthalene -1,8- Download PDFInfo
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- CN109021002A CN109021002A CN201810993799.7A CN201810993799A CN109021002A CN 109021002 A CN109021002 A CN 109021002A CN 201810993799 A CN201810993799 A CN 201810993799A CN 109021002 A CN109021002 A CN 109021002A
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- naphthalene
- aryl boron
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- 229910052796 boron Inorganic materials 0.000 title claims abstract description 21
- -1 amido aryl boron amide Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title claims description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 9
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 9
- 239000001632 sodium acetate Substances 0.000 claims abstract description 9
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000004440 column chromatography Methods 0.000 claims abstract description 7
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- 125000000524 functional group Chemical group 0.000 abstract description 7
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 125000004185 ester group Chemical group 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract 1
- 150000002790 naphthalenes Chemical class 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 0 C*c1ccc(*)cc1 Chemical compound C*c1ccc(*)cc1 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000004607 11B NMR spectroscopy Methods 0.000 description 2
- 150000001499 aryl bromides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZZPNDIHOQDQVNU-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(O)OC1(C)C ZZPNDIHOQDQVNU-UHFFFAOYSA-N 0.000 description 1
- QZVQQUVWFIZUBQ-UHFFFAOYSA-N 3-fluoroaniline Chemical compound NC1=CC=CC(F)=C1 QZVQQUVWFIZUBQ-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- NKGYQJVDGSWXFR-UHFFFAOYSA-N Brc1ccc(B(N2)Nc3cccc4c3c2ccc4)cc1 Chemical compound Brc1ccc(B(N2)Nc3cccc4c3c2ccc4)cc1 NKGYQJVDGSWXFR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001503 aryl iodides Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical compound [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- AZAKMLHUDVIDFN-UHFFFAOYSA-N tert-butyl nitrate Chemical compound CC(C)(C)O[N+]([O-])=O AZAKMLHUDVIDFN-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of naphthalenes -1, the preparation method of bis- amido aryl boron amide of 8-, by sequentially adding Bpin-Bdan, tetrabutylammonium iodide, sodium acetate, dibenzoyl peroxide and nitrite tert-butyl in the reaction vessel, arylamine and acetonitrile are added in nitrogen environment, reaction is heated and be vigorously stirred, reaction solution filtering will be obtained, be spin-dried for solvent, it is separated by column chromatography chromatogram to get target product is arrived.The method of the present invention is reacted quickly and efficiently, and functional group's tolerance is preferable, can be compatible with halogen, ester group, hydroxyl, cyano, amino etc..
Description
Technical field
The invention belongs to technical field of compound preparation, and in particular to a kind of system of bis- amido aryl boron amide of naphthalene -1,8-
Preparation Method.
Background technique
Currently, because organoboron compound is widely used in synthesis chemistry, medicament research and development and materials chemistry synthesis,
Increasingly by the concern of chemist, so chemists are devoted to explore and a variety of different efficiently synthesize organoboron compound
Method.Other than aryl boric acid, stability is higher, reactivity is stronger and the better aryl-boric acid ester of controllable reaction and
Aryl boron amide all shows better application prospect.Organoboron compound as highly useful synthon, can with it is very much
Functional group reactions form new carbon-carbon bond or carbon heterodesmic.One of method of most common synthesizing aryl boric acid is to utilize aryl halogenation
Object is translated into aryl grignard reagent or aryl lithium as starting material first, then reacts with trimethylborate, finally
Corresponding aryl boric acid is obtained by hydrolyzing post-processing；Another method is using aryl bromide or aryl iodide in metal
Coupling reaction occurs to obtain corresponding aryl boric acid ester derivant with connection boric acid pinacol ester under the catalysis of palladium or metallic copper.
2015, Li Peng flew professor seminar and reports aryl bromide and asymmetric double boron compound Bpin- under catalyzing by metal palladium
The method that Bdan reaction prepares aryl boron amide compound.Above method all comes with some shortcomings place, such as to air and wet
Gas is very sensitive, functional group's tolerance difference etc..
As a kind of cheap and biggish starting material of amount of storage, amino can be reacted by Sandmeyer to be turned arylamine
Turn to a variety of functional groups such as hydroxyl, halogen, cyano.Under normal conditions, its amino is optionally substituted by halogen first in arylamine, then passes through lattice
Family name's reagent method or palladium chtalyst boronation method are converted into corresponding aryl boric acid and its derivative.It is clear that this method needs two steps
It can complete, undoubtedly reaction efficiency be reduced.The method also faces that such as yield is lower, the more complex drawback of post-processing.
Summary of the invention
For all disadvantages of the above-mentioned prior art, the present invention is using arylamine as starting material, asymmetric double borane reagent Bpin-
Bdan is as boron source, under no metal catalyzed conditions, reacts a step by Sandmeyer and is translated into corresponding aryl boron acyl
Amine.Quickly and efficiently, and functional group's tolerance is preferable for method of the present invention reaction, can with halogen, ester group, hydroxyl, cyano,
Amino etc. is compatible.
In order to reach above-mentioned technical purpose, the present invention is realized especially by following technical scheme:
A kind of preparation method of bis- amido aryl boron amide of naphthalene -1,8-, specifically includes the following steps:
1) Bpin-Bdan, tetrabutylammonium iodide, sodium acetate, dibenzoyl peroxide and Asia are sequentially added in the reactor
The nitric acid tert-butyl ester empties gas reactor, and arylamine and acetonitrile, sealing are added in nitrogen environment；
2) it heats and is vigorously stirred, completion to be reacted obtains reaction solution；
3) reaction solution is filtered, is spin-dried for solvent, separated by column chromatography chromatogram to get target product is arrived.
Further, the Bpin-Bdan be aryl boron amide derivatives, general structure Ar-Bdan:
In formula, Ar base is One of kind；
The R1For MeO, Br, CF3, one of OH, NC or COOMe kind.
The R2For Me, OMe, OCF3, Br, F, COOMe or CONH2One of kind.
The R3For Br or F.
The R4For CH3Or COOMe.
Reactant arylamine, Bpin-Bdan, tetrabutylammonium iodide, sodium acetate, dibenzoyl peroxide and the nitrous acid
The dosage of the tert-butyl ester is measured with molar ratio as 2:1:0.1:1.5:0.1:2.
The acetonitrile is as solvent, concentration 6mL/mmol.
The invention has the benefit that
1) present invention makes one step of arylamine be converted into corresponding aryl boron amide derivatives using no metal catalytic；
2) reaction condition of the present invention is mild, and reaction conversion ratio is high；
3) functional group's tolerance of the present invention is preferable, can be compatible with a variety of functional groups such as hydroxyl, ester group, amide groups；
4) arylamine that the present invention uses, it is cheap, it is easy to get.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance spectroscopy of 1 product of the embodiment of the present invention；
Fig. 2 is the carbon-13 nmr spectra figure of 1 product of the embodiment of the present invention；
Fig. 3 is the nuclear magnetic resonance spectroscopy of 2 product of the embodiment of the present invention；
Fig. 4 is the carbon-13 nmr spectra figure of 2 product of the embodiment of the present invention；
Fig. 5 is the nuclear magnetic resonance spectroscopy of 3 product of the embodiment of the present invention；
Fig. 6 is the carbon-13 nmr spectra figure of 3 product of the embodiment of the present invention；
Fig. 7 is the nuclear magnetic resonance spectroscopy of 4 product of the embodiment of the present invention；
Fig. 8 is the carbon-13 nmr spectra figure of 4 product of the embodiment of the present invention.
Specific embodiment
Below in conjunction with specific embodiment of the present invention, technical solution of the present invention is clearly and completely described, is shown
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
4- aminoanisole (24.6mg, 0.2mmol, 2.0eq.), Bpin- are sequentially added in dry 10mL reaction tube
Bdan (29.4mg, 0.1mmol, 1.0eq.), tetrabutylammonium iodide (3.7mg, 0.01mmol, 0.1eq.), sodium acetate
(12.3mg, 0.15mmol, 1.5eq.), dibenzoyl peroxide (2.4mg, 0.01mmol, 0.1eq.) and nitrite tert-butyl
(20.6mg, 0.2mmol, 2.0eq.) substitutes nitrogen three times, injects 0.6mL acetonitrile, rotation into reaction tube under nitrogen stream environment
Tight reaction lid is vigorously stirred 8 hours at 80 DEG C, is stopped reaction, is down to room temperature to reaction solution.Reaction solution uses diatomite first
Reaction residues are filtered out, filter cake is washed three times with ethyl acetate, and merging filtrate is separated after being spin-dried for solvent by column chromatography chromatogram
To 20.6 milligrams of target white solid, yield 75%.
The mechanism type of target product are as follows:
Fusing point, the analysis of infrared and nucleus n-ness spectrum are carried out to target product, as a result as follows:
Fusing point: 163.2~165.6 DEG C；
IR(cm-1):3407,1594,1495,1407,1224,1181,1029；
1H NMR(400MHz,CDCl3) δ 7.59 (d, J=8.8Hz, 2H), 7.15 (t, J=8.0Hz, 2H), 7.05 (d, J
=8.0Hz, 2H), 6.98 (d, J=8.4Hz, 2H), 6.42 (d, J=7.2Hz, 2H), 5.99 (s, 2H), 3.86 (s, 3H)；
13C NMR(100MHz,CDCl3)δ161.5,141.3,136.5,133.1,127.8,119.8,117.8,114.0,
106.1,55.3；
11B NMR(128MHz,CDCl3)δ29.1；
HRMS(APCI)m/z calcd for C17H14BN2O(M-):273.1205,found:273.1203。
Embodiment 2
4- bromaniline (34.2mg, 0.2mmol, 2.0eq.), Bpin-Bdan are sequentially added in dry 10mL reaction tube
(29.4mg, 0.1mmol, 1.0eq.), tetrabutylammonium iodide (3.7mg, 0.01mmol, 0.1eq.), sodium acetate (12.3mg,
0.15mmol, 1.5eq.), dibenzoyl peroxide (2.4mg, 0.01mmol, 0.1eq.) and nitrite tert-butyl (20.6mg,
0.2mmol, 2.0eq.), it substitutes nitrogen three times, injects 0.6mL acetonitrile into reaction tube under nitrogen stream environment, screw reaction tube
Lid, is vigorously stirred 8 hours at 80 DEG C, stops reaction, is down to room temperature to reaction solution.Reaction solution is filtered out instead with diatomite first
Residue is answered, filter cake is washed three times with ethyl acetate, merging filtrate, is spin-dried for after solvent through the isolated white of column chromatography chromatogram admittedly
20.0 milligrams of body, yield 62%.
The mechanism type of target product are as follows:
The analysis of infrared and nucleus n-ness spectrum is carried out to target product, as a result as follows:
IR(cm-1):3408.9,2921.3,2851.4,2362.0,2342.0,1596.0,1511.4,1400.3,
1373.3,817.5,752.2,690.0；
1H NMR(400MHz,CDCl3) δ 7.58 (d, J=8.0Hz, 2H), 7.51 (d, J=8.0Hz, 2H), 7.14 (t, J
=7.8Hz, 2H), 7.06 (d, J=7.2Hz, 2H), 6.41 (d, J=7.2Hz, 2H), 5.98 (s, 2H)；
13C NMR(100MHz,CDCl3)δ140.8,136.3,133.0,131.5,127.6,124.9,124.8,118.1,
106.2；
HRMS(APCI)m/z calcd for C16H12BBrN2(M-):322.0282,found:322.0279。
Embodiment 3
2-aminotoluene (21.4mg, 0.2mmol, 2.0eq.), Bpin-Bdan are sequentially added in dry 10mL reaction tube
(29.4mg, 0.1mmol, 1.0eq.), tetrabutylammonium iodide (3.7mg, 0.01mmol, 0.1eq.), sodium acetate (12.3mg,
0.15mmol, 1.5eq.), dibenzoyl peroxide (2.4mg, 0.01mmol, 0.1eq.) and nitrite tert-butyl (20.6mg,
0.2mmol, 2.0eq.), it substitutes nitrogen three times, injects 0.6mL acetonitrile into reaction tube under nitrogen stream environment, screw reaction tube
Lid, is vigorously stirred 8 hours at 80 DEG C, stops reaction, is down to room temperature to reaction solution.Reaction solution is filtered out instead with diatomite first
Residue is answered, filter cake is washed three times with ethyl acetate, merging filtrate, is spin-dried for after solvent through the isolated white of column chromatography chromatogram admittedly
11.6 milligrams of body, yield 45%.
The mechanism type of target product are as follows:
Fusing point, the analysis of infrared and nucleus n-ness spectrum are carried out to target product, as a result as follows:
Fusing point: 73.2~75.1 DEG C；
IR(cm-1):3420.1,3404.9,2360.8,2341.0,1594.1,1506.1,1325.8,1318.1,
1077.9,818.4,656.0；
1H NMR(400MHz,CDCl3) δ 7.44 (d, J=7.3Hz, 1H), 7.31 (t, J=7.5Hz, 1H), 7.21 (m,
2H), 7.12 (t, J=7.8Hz, 2H), 7.11 (d, J=8.5Hz, 2H), 6.33 (d, J=7.2Hz, 2H), 5.80 (s, 2H),
2.49(s,3H)；
13C NMR(100MHz,CDCl3)δ141.1,140.7,136.4,132.3,129.7,129.3,127.7,125.3,
119.8,117.9,105.9,22.4；
11B NMR(128MHz,CDCl3)δ30.0；
HRMS(APCI)m/z calcd for C17H14BN2(M-):257.1256,found:257.1257。
Embodiment 4
3- fluoroaniline (22.2mg, 0.2mmol, 2.0eq.), Bpin-Bdan are sequentially added in dry 10mL reaction tube
(29.4mg, 0.1mmol, 1.0eq.), tetrabutylammonium iodide (3.7mg, 0.01mmol, 0.1eq.), sodium acetate (12.3mg,
0.15mmol, 1.5eq.), dibenzoyl peroxide (2.4mg, 0.01mmol, 0.1eq.) and nitrite tert-butyl (20.6mg,
0.2mmol, 2.0eq.), it substitutes nitrogen three times, injects 0.6mL acetonitrile into reaction tube under nitrogen stream environment, screw reaction tube
Lid, is vigorously stirred 8 hours at 80 DEG C, stops reaction, is down to room temperature to reaction solution.Reaction solution is filtered out instead with diatomite first
Residue is answered, filter cake is washed three times with ethyl acetate, merging filtrate, is spin-dried for after solvent through the isolated white of column chromatography chromatogram admittedly
21.3 milligrams of body, yield 60%.
The mechanism type of target product are as follows:
The analysis of infrared and nucleus n-ness spectrum is carried out to target product, as a result as follows:
IR(cm-1):3442.7,3435.4,3032.2,1595.8,1520.5,1371.4,757.1,749.4,686.3；
1H NMR(400MHz,CDCl3) δ 7.41 (m, 2H), 7.33 (dd, J=2.4,9.2Hz, 1H), 7.14 (m, 3H),
7.06 (d, J=8.0Hz, 2H), 6.41 (d, J=7.3Hz, 2H), 5.97 (s, 2H)；
13C NMR(100MHz,CDCl3)δ164.1,161.7,140.8,136.3,130.2,130.1,127.7,127.1,
127.0,118.1,118.1,117.3,117.0,106.2；
HRMS(APCI)m/z calcd for C16H12BFN2(M-):262.1083,found:262.1080。
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understand without departing from the principles and spirit of the present invention can to these examples carry out it is a variety of variation, modification, replacement and
Modification, the scope of the present invention is defined by the appended.
Claims (9)
1. a kind of preparation method of bis- amido aryl boron amide of naphthalene -1,8-, which comprises the following steps:
1) Bpin-Bdan, tetrabutylammonium iodide, sodium acetate, dibenzoyl peroxide and nitrous acid are sequentially added in the reactor
The tert-butyl ester empties gas reactor, and arylamine and acetonitrile, sealing are added in nitrogen environment；
2) it heats and is vigorously stirred, completion to be reacted obtains reaction solution；
3) reaction solution is filtered, is spin-dried for solvent, separated by column chromatography chromatogram to get target product is arrived.
2. a kind of preparation method of bis- amido aryl boron amide of naphthalene -1,8- according to claim 1, which is characterized in that institute
The Bpin-Bdan stated is aryl boron amide derivatives, general structure Ar-Bdan.
3. a kind of preparation method of bis- amido aryl boron amide of naphthalene -1,8- according to claim 2, which is characterized in that institute
The Ar base stated is One of kind.
4. a kind of preparation method of bis- amido aryl boron amide of naphthalene -1,8- according to claim 3, which is characterized in that institute
The R stated1For MeO, Br, CF3, one of OH, NC or COOMe kind.
5. a kind of preparation method of bis- amido aryl boron amide of naphthalene -1,8- according to claim 3, which is characterized in that institute
The R stated2For Me, OMe, OCF3, Br, F, COOMe or CONH2One of kind.
6. a kind of preparation method of bis- amido aryl boron amide of naphthalene -1,8- according to claim 3, which is characterized in that institute
The R stated3For Br or F.
7. a kind of preparation method of bis- amido aryl boron amide of naphthalene -1,8- according to claim 3, which is characterized in that institute
The R stated4For CH3Or COOMe.
8. a kind of preparation method of bis- amido aryl boron amide of naphthalene -1,8- according to claim 1, which is characterized in that institute
The use of reactant arylamine, Bpin-Bdan, tetrabutylammonium iodide, sodium acetate, dibenzoyl peroxide and the nitrite tert-butyl stated
Amount is measured with molar ratio as 2:1:0.1:1.5:0.1:2.
9. a kind of preparation method of bis- amido aryl boron amide of naphthalene -1,8- according to claim 1, which is characterized in that institute
The acetonitrile stated is as solvent, concentration 6mL/mmol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810993799.7A CN109021002B (en) | 2018-08-29 | 2018-08-29 | Preparation method of naphthalene-1, 8-diamino aryl boron amide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810993799.7A CN109021002B (en) | 2018-08-29 | 2018-08-29 | Preparation method of naphthalene-1, 8-diamino aryl boron amide |
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| Publication Number | Publication Date |
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| US20110245538A1 (en) * | 2010-03-30 | 2011-10-06 | Fujifilm Corporation | Squarylium compound, method for producing the same and infrared absorbent |
| CN106946916A (en) * | 2017-03-20 | 2017-07-14 | 西京学院 | A kind of new method for preparing asymmetric borane reagent Bpin Bdan |
| JP2017165857A (en) * | 2016-03-16 | 2017-09-21 | 東洋インキＳｃホールディングス株式会社 | Near-infrared absorption dye and its use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110245538A1 (en) * | 2010-03-30 | 2011-10-06 | Fujifilm Corporation | Squarylium compound, method for producing the same and infrared absorbent |
| JP2017165857A (en) * | 2016-03-16 | 2017-09-21 | 東洋インキＳｃホールディングス株式会社 | Near-infrared absorption dye and its use |
| CN106946916A (en) * | 2017-03-20 | 2017-07-14 | 西京学院 | A kind of new method for preparing asymmetric borane reagent Bpin Bdan |
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