CN105367442B - A kind of method of the deaminizating of aromatic compound containing amino - Google Patents
A kind of method of the deaminizating of aromatic compound containing amino Download PDFInfo
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- CN105367442B CN105367442B CN201410432347.3A CN201410432347A CN105367442B CN 105367442 B CN105367442 B CN 105367442B CN 201410432347 A CN201410432347 A CN 201410432347A CN 105367442 B CN105367442 B CN 105367442B
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- aromatic compound
- containing amino
- compound containing
- deaminizating
- nitrite
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 18
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000002904 solvent Substances 0.000 claims abstract description 20
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 7
- -1 amino aromatic compound Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 239000003208 petroleum Substances 0.000 claims description 16
- 239000003480 eluent Substances 0.000 claims description 11
- 238000004440 column chromatography Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 235000010289 potassium nitrite Nutrition 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical class NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 239000004304 potassium nitrite Substances 0.000 claims description 2
- KKKDGYXNGYJJRX-UHFFFAOYSA-M silver nitrite Chemical compound [Ag+].[O-]N=O KKKDGYXNGYJJRX-UHFFFAOYSA-M 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 12
- 239000002253 acid Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000009615 deamination Effects 0.000 abstract description 4
- 238000006481 deamination reaction Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 40
- 239000000243 solution Substances 0.000 description 12
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 11
- 230000006837 decompression Effects 0.000 description 11
- 238000000967 suction filtration Methods 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- AIBQGOMAISTKSR-UHFFFAOYSA-N 6-chloro-1,3-benzothiazole Chemical class ClC1=CC=C2N=CSC2=C1 AIBQGOMAISTKSR-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- BXNHTSHTPBPRFX-UHFFFAOYSA-M potassium nitrite Chemical class [K+].[O-]N=O BXNHTSHTPBPRFX-UHFFFAOYSA-M 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- VZEBSJIOUMDNLY-UHFFFAOYSA-N 6-bromo-1,3-benzothiazol-2-amine Chemical class C1=C(Br)C=C2SC(N)=NC2=C1 VZEBSJIOUMDNLY-UHFFFAOYSA-N 0.000 description 1
- VMNXKIDUTPOHPO-UHFFFAOYSA-N 6-chloro-1,3-benzothiazol-2-amine Chemical class C1=C(Cl)C=C2SC(N)=NC2=C1 VMNXKIDUTPOHPO-UHFFFAOYSA-N 0.000 description 1
- CJLUXPZQUXVJNF-UHFFFAOYSA-N 6-fluoro-1,3-benzothiazol-2-amine Chemical class C1=C(F)C=C2SC(N)=NC2=C1 CJLUXPZQUXVJNF-UHFFFAOYSA-N 0.000 description 1
- JKQDAIVDZXQKCT-UHFFFAOYSA-N 6-propan-2-yl-1,3-benzothiazol-2-amine Chemical class CC(C)C1=CC=C2N=C(N)SC2=C1 JKQDAIVDZXQKCT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to technical field of organic synthesis, to solve the problem of deamination based method conventional at present is accurately controlled in the presence of the temperature needs due to being polluted and reacted to environment using strong acid, is unfavorable for production, the present invention proposes a kind of method of the deaminizating of aromatic compound containing amino, it will contain after amino aromatic compound, nitrite, solvent mixing, it is put into pressure pipe, at 80 ~ 130 DEG C, stirring reaction 12 ~ 72 hours, the isolated aromatic compound for sloughing amino, the method of the present invention is efficient, it is easy to operate, polluted in the absence of spent acid.
Description
Technical field
The present invention relates to technical field of organic synthesis, a kind of deamination based method containing amino-compound is related in particular to.
Background technology
The desamination reaction of the aromatic compound containing amino is the important chemical reaction of a class, raw in organic synthesis or industry
In production, it is often necessary to the amino on aromatic ring is changed into hydrogen so as to obtain the compound without amino, at present conventional deaminizating
Method is that amino first is converted into diazol by diazo-reaction, then is acted on by reducing agents such as hypophosphorous acid or ethanol by amino
Slough and be changed into hydrogen, but the strong acid that the diazotation step that is related to of this method is used can be polluted to environment, and the temperature reacted
Degree needs are accurately controlled, and are unfavorable for production.Therefore, develop a kind of efficient, it is easy to operate, without using the deamination based method of strong acid
Significant and application value.
The content of the invention
Exist to solve deamination based method conventional at present due to the temperature for being polluted and being reacted to environment using strong acid
The problem of degree needs are accurately controlled, are unfavorable for production, the present invention proposes a kind of deaminizating of aromatic compound containing amino
Method, method of the invention is efficiently, easy to operate, is polluted in the absence of spent acid.
The present invention is to be achieved through the following technical solutions：A kind of method of the deaminizating of aromatic compound containing amino is to contain
After amino aromatic compound, nitrite, solvent mixing, it is put into pressure pipe, at 80 ~ 130 DEG C, stirring reaction 12 ~ 72 is small
When, the isolated aromatic compound for sloughing amino.
Described aromatic compound containing amino is one in 4- aminoazabenzols or 2- aminobenzothiazole class compounds
Kind.Reaction expression is as follows：
,
,
In formula, one or more of the R in H, methyl, fluorine, chlorine, bromine, iodine, methoxyl group, nitro, ethyl, phenyl.
The one kind of described nitrite in potassium nitrite, natrium nitrosum, silver nitrite, nitrite is with containing amino
The mol ratio of aromatic compound is 1 ~ 4：1, preferably 2：1.
Described solvent is selected from low polar organic solvent, preferably, solvent elects 1,2- dichloroethanes as.The use of solvent
Measure to make the amount that solute dissolves.
Preferably, reaction temperature is 100 ~ 120 DEG C, more preferably 110 DEG C, the reaction time is 48 hours.
Preferably, after reaction stops, being cooled in room temperature, reaction solution and adding dchloromethane, taken off after decompression suction filtration
Solvent is removed, residue is column chromatography or recrystallization through separating-purifying, described separation process.Preferably, washing in column chromatography
De- agent is the mixed solution of petroleum ether and ethyl acetate, and wherein the volume ratio of petroleum ether and ethyl acetate is 6：1.Preferably,
Recrystallization solvent used is the one or more in methanol, ethanol, petroleum ether.
Compared with prior art, the beneficial effects of the invention are as follows：
（1）The characteristics of present invention has efficient, easy to operate；
（2）The present invention does not result in spent acid pollution compared with the conventional method without using strong acid；
（3）The reagent used is cheap, it is adaptable to industrialized production.
Embodiment
The present invention is described in further detail with reference to specific embodiment, protection scope of the present invention not limited to this.
Embodiment 1：
0.3 mmol 4- amino -2,6- dimethyl -4 '-chlorine azobenzenes, 0.6 are added in a closed reaction vessel
Mmol natrium nitrosums, 3 mL 1,2- dichloroethanes, reactant mixture stirring reaction 48 hours under the conditions of 110 DEG C.Reaction stops
Afterwards, it is cooled in room temperature, reaction solution and adds 10 mL dchloromethanes, solvent is sloughed after decompression suction filtration, residue is through post layer
Separating-purifying is analysed, eluant, eluent is V (petroleum ether)/V (ethyl acetate)=6/1, obtains 2,6- dimethyl -4 '-chlorine azobenzenes, is produced
Rate is 88%.
Brown solid; mp 132-134 ºC; 1H NMR (CDCl3, 500 MHz): δ 7.86 (d, J = 5
Hz, 2H), 7.52 (d, J = 10 Hz, 2H), 7.19-7.14 (m,3H), 2.38 (s, 6H); 13C NMR
(CDCl3, 125 MHz): δ 151.16, 136.96, 130.96, 129.34, 129.21, 128.75, 128.48,
128.38, 126.83, 125.14, 123.74, 122.63, 18.93; GC-MS (EI, 70 eV): m/z = 244
[M+].
Embodiment 2：
0.3 mmol 4- amino -2,6- dimethyl -4 '-fluorine azobenzenes, 0.6 are added in a closed reaction vessel
Mmol potassium nitrites, 3 mL 1,2- dichloroethanes, reactant mixture stirring reaction 24 hours under the conditions of 110 DEG C.Reaction stops
Afterwards, it is cooled in room temperature, reaction solution and adds 10 mL dchloromethanes, solvent is sloughed after decompression suction filtration, residue is through post layer
Separating-purifying is analysed, eluant, eluent is V (petroleum ether)/V (ethyl acetate)=6/1, obtains 2,6- dimethyl -4 '-fluorine azobenzenes, is produced
Rate is 68%.
Brown solid; mp 128-130 ºC; 1H NMR (CDCl3, 500 MHz): δ 7.83 (d, J = 5
Hz, 2H), 7.50 (d, J = 10 Hz, 2H), 7.20-7.13 (m,3H), 2.36 (s, 6H); 13C NMR
(CDCl3, 125 MHz): δ 151.59, 151.09, 132.37, 131.03, 129.31, 129.25, 128.56,
124.00, 18.96; GC-MS (EI, 70 eV): m/z = 228 [M+].
Embodiment 3：
0.3 mmol 4- amino -2,6- dimethyl -4 '-bromine azobenzenes, 0.3 are added in a closed reaction vessel
Mmol natrium nitrosums, 3 mL 1,2- dichloroethanes, reactant mixture stirring reaction 48 hours under the conditions of 110 DEG C.Reaction stops
Afterwards, it is cooled in room temperature, reaction solution and adds 10 mL dchloromethanes, solvent is sloughed after decompression suction filtration, residue is through post layer
Separating-purifying is analysed, eluant, eluent is V (petroleum ether)/V (ethyl acetate)=6/1, obtains 2,6- dimethyl -4 '-bromine azobenzenes, is produced
Rate is 62%.
Brown solid; mp 129-132 ºC; 1H NMR (CDCl3, 500 MHz): δ 7.79 (d, J = 5
Hz, 2H), 7.48 (d, J = 10 Hz, 2H), 7.17-7.10 (m,3H), 2.42 (s, 6H); 13C NMR
(CDCl3, 125 MHz): δ 152.55, 151.18, 133.25, 131.19, 130.05, 129.17, 128.49,
124.21, 17.62; GC-MS (EI, 70 eV): m/z = 288 [M+].
Embodiment 4：
0.3 mmol 4- amino -2,6- dimethyl -2 '-chlorine azobenzenes, 0.5 are added in a closed reaction vessel
Mmol potassium nitrites, 4 mL 1,2- dichloroethanes, reactant mixture stirring reaction 48 hours under the conditions of 90 DEG C.Reaction stops
Afterwards, it is cooled in room temperature, reaction solution and adds 10 mL dchloromethanes, solvent is sloughed after decompression suction filtration, residue is through post layer
Separating-purifying is analysed, eluant, eluent is V (petroleum ether)/V (ethyl acetate)=6/1, obtains 2,6- dimethyl -2 '-chlorine azobenzenes, is produced
Rate is 76%.
Brown solid;; mp 130-133 ºC; 1H NMR (CDCl3, 500 MHz): δ 7.67 (t, J = 5
Hz, 1H), 7.60 (d, J = 5 Hz, 1H), 7.50 (s, 1H), 7.39-7.36 (m, 1H), 7.17-7.13
(m, 2H), 6.15 (d, J = 5 Hz, 1H), 2.50 (s, 6H); 13C NMR (CDCl3, 125 MHz): δ
150.64, 149.32, 135.34, 134.39, 132.12, 131.73, 131.47, 130.74, 129.18,
129.15, 128.63, 127.99, 126.86, 19.62; GC-MS (EI, 70 eV): m/z = 244 [M+].
Embodiment 5：
0.3 mmol 4- amino -2,6- dimethyl -4 '-iodine azobenzenes, 0.6 are added in a closed reaction vessel
Mmol natrium nitrosums, 3 mL 1,2- dichloroethanes, reactant mixture stirring reaction 48 hours under the conditions of 110 DEG C.Reaction stops
Afterwards, it is cooled in room temperature, reaction solution and adds 10 mL dchloromethanes, solvent is sloughed after decompression suction filtration, residue is through post layer
Separating-purifying is analysed, eluant, eluent is V (petroleum ether)/V (ethyl acetate)=6/1, obtains 2,6- dimethyl -4 '-iodine azobenzenes, is produced
Rate is 62%.
Brown solid; mp 132-134 ºC; 1H NMR (CDCl3, 500 MHz): δ 7.98 (d, J = 5
Hz, 2H), 7.77 (d, J = 10 Hz, 2H), 7.24-7.20 (m,3H), 2.34 (s, 6H); 13C NMR
(CDCl3, 125 MHz): δ 152.17, 152.10, 150.41, 139.37, 138.40, 138.03, 133.35,
131.05, 129.25, 129.11, 128.59, 124.12, 18.98; GC-MS (EI, 70 eV): m/z = 336
[M+].
Embodiment 6：
0.3 mmol 2- amino -6- chloro benzothiazoles, 0.6 mmol nitrous acid are added in a closed reaction vessel
Sodium, 3 mL 1,2- dichloroethanes, reactant mixture stirring reaction 60 hours under the conditions of 110 DEG C.After reaction stops, it is cooled to
Solvent is sloughed after 10 mL dchloromethanes, decompression suction filtration are added in room temperature, reaction solution, residue is carried through column chromatography for separation
Pure, eluant, eluent is V (petroleum ether)/V (ethyl acetate)=6/1, obtains 6- chloro benzothiazoles, yield is 89%.
Yellow solid;; mp 43-44 ºC; 1H NMR (CDCl3, 500 MHz): δ 8.99 (s, 1H),
8.05 (d, J = 5 Hz, 1H), 7.94 (d, J = 5 Hz, 1H), 7.50-7.48 (m, 1H); 13C NMR
(CDCl3, 125 MHz): δ 154.28, 151.81, 134.97, 131.70, 127.09, 124.36, 121.48;
GC-MS (EI, 70 eV): m/z = 169 [M+].
Embodiment 7:
0.3 mmol 2- amino -6- bromo benzothiazoles, 0.9 mmol nitrous acid are added in a closed reaction vessel
Silver, 3 mL 1,2- dichloroethanes, reactant mixture stirring reaction 72 hours under the conditions of 80 DEG C.After reaction stops, room is cooled to
Solvent is sloughed after 10 mL dchloromethanes, decompression suction filtration are added in temperature, reaction solution, residue is purified through column chromatography for separation,
Eluant, eluent is V (petroleum ether)/V (ethyl acetate)=6/1, obtains 6- chloro benzothiazoles, yield is 79%.
Brown solid; mp 57-59 ºC; 1H NMR (CDCl3, 500 MHz): δ 9.02 (s, 1H),
8.12 (d, J = 5 Hz, 1H), 8.02 (d, J = 5 Hz, 1H), 7.55-7.53 (m, 1H); 13C NMR
(CDCl3, 125 MHz): δ 154.52, 151.93, 129.86, 128.84, 124.65, 124.48; GC-MS
(EI, 70 eV): m/z = 215 [M+].
Embodiment 8：
0.3 mmol 2- amino -6- isopropyl benzothiazoles, 1.2 mmol nitrous are added in a closed reaction vessel
Sour silver, 4 mL 1,2- dichloroethanes, reactant mixture stirring reaction 20 hours under the conditions of 130 DEG C.After reaction stops, cooling
To room temperature, solvent is sloughed after 10 mL dchloromethanes, decompression suction filtration are added in reaction solution, residue is carried through column chromatography for separation
Pure, eluant, eluent is V (petroleum ether)/V (ethyl acetate)=6/1, obtains 6- chloro benzothiazoles, yield is 56%.
Yellow solid;; mp 79-82 ºC; 1H NMR (CDCl3, 500 MHz): δ 8.94 (s, 1H),
8.06 (d, J = 5 Hz, 1H), 7.82-7.72 (m, 1H), 7.73-7.41 (m, 1H); 13C NMR (CDCl3,
125 MHz): δ 153.02, 130.89, 128.84, 125.48, 123.22, 118.88, 34.25, 24.19; GC-
MS (EI, 70 eV): m/z = 177 [M+].
Embodiment 9：
0.3 mmol 2- amino -6- ester group benzothiazoles, 0.6 mmol nitrous acid are added in a closed reaction vessel
Silver, 4 mL 1,2- dichloroethanes, reactant mixture stirring reaction 36 hours under the conditions of 100 DEG C.After reaction stops, it is cooled to
Solvent is sloughed after 10 mL dchloromethanes, decompression suction filtration are added in room temperature, reaction solution, residue is carried through column chromatography for separation
Pure, eluant, eluent is V (petroleum ether)/V (ethyl acetate)=6/1, obtains 6- ester group benzothiazoles, yield is 62%.
Yellow solid; mp 78-80 ºC; 1H NMR (CDCl3, 500 MHz): δ 9.15 (s, 1H),
8.70 (s, 1H), 8.21-8.16 (m, 2H), 4.44 (q, J = 10 Hz, 2H), 1.44 (t, J = 5 Hz,
3H); 13C NMR (CDCl3, 125 MHz): δ 166.02, 157.14, 155.96, 133.80, 127.88,
127.30, 124.13, 123.34; GC-MS (EI, 70 eV): m/z = 207 [M+].
Embodiment 10：
0.3 mmol 2- amino -6- fluoro benzothiazoles, 0.6 mmol nitrous acid are added in a closed reaction vessel
Silver, 4 mL 1,2- dichloroethanes, reactant mixture stirring reaction 12 hours under the conditions of 130 DEG C.After reaction stops, it is cooled to
Solvent is sloughed after 10 mL dchloromethanes, decompression suction filtration are added in room temperature, reaction solution, residue is carried through column chromatography for separation
Pure, eluant, eluent is V (petroleum ether)/V (ethyl acetate)=6/1, obtains 6- ester group benzothiazoles, yield is 81%.
Yellow solid; mp 56-58 ºC; 1H NMR (CDCl3, 500 MHz): δ 9.23 (s, 1H),
8.03 (d, J = 5 Hz, 1H), 7.73 (d, J = 5 Hz, 1H), 7.26-7.24 (m, 1H); 13C NMR
(CDCl3, 125 MHz): δ 158.58, 155.81, 149.17, 134.60, 123.29, 113.96, 108.98;
GC-MS (EI, 70 eV): m/z = 153 [M+].
Claims (4)
1. a kind of method of the deaminizating of aromatic compound containing amino, it is characterised in that described method is fragrant for that will contain amino
After compounds of group, nitrite, solvent mixing, it is put into pressure pipe, at 80 ~ 130 DEG C, reacts 12 ~ 72 hours, it is isolated de-
The aromatic compound deaminized,
Described aromatic compound containing amino is a kind of in 4- aminoazabenzols or 2- aminobenzothiazole class compounds；
Reaction expression is as follows：
In formula, one or more of the R in H, methyl, fluorine, chlorine, bromine, iodine, methoxyl group, nitro, ethyl, phenyl；
The one kind of described nitrite in potassium nitrite, natrium nitrosum, silver nitrite, nitrite is with containing amino fragrance
The mol ratio of compounds of group is 1 ~ 4：1；
Described solvent is selected from low polar organic solvent.
2. the method for a kind of deaminizating of aromatic compound containing amino according to claim 1, it is characterised in that described
Separation process is column chromatography or recrystallization.
3. a kind of method of deaminizating of aromatic compound containing amino according to claim 2, it is characterised in that column chromatography
In eluant, eluent be the mixed solution of petroleum ether and ethyl acetate, the wherein volume ratio of petroleum ether and ethyl acetate is 6：1.
4. a kind of method of deaminizating of aromatic compound containing amino according to claim 2, it is characterised in that recrystallization
Solvent used is the one or more in methanol, ethanol, petroleum ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410432347.3A CN105367442B (en) | 2014-08-29 | 2014-08-29 | A kind of method of the deaminizating of aromatic compound containing amino |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410432347.3A CN105367442B (en) | 2014-08-29 | 2014-08-29 | A kind of method of the deaminizating of aromatic compound containing amino |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105367442A CN105367442A (en) | 2016-03-02 |
| CN105367442B true CN105367442B (en) | 2017-07-28 |
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Family Applications (1)
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| US11976023B1 (en) | 2023-12-18 | 2024-05-07 | King Faisal University | Synthetic route to 2,2',6,6'-tetraisopropyl-4,4'-diiodoazobenzene via homo-oxidative cross-coupling of aryl diazonium salt using cu-catalyzed sandmeyer-style reaction |
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| CN101157597A (en) * | 2007-11-14 | 2008-04-09 | 高邮市光明化工厂 | Preparation technique of 3-fluorine -5 bromine benzotrifluoride |
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| CN101157597A (en) * | 2007-11-14 | 2008-04-09 | 高邮市光明化工厂 | Preparation technique of 3-fluorine -5 bromine benzotrifluoride |
Non-Patent Citations (2)
| Title |
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| "Deamination of 2-aminothiazoles and 3-amino-1,2,4-triazines with nitric oxide in the presence of a catalytic amount of oxygen";Takashi ITOH，et al.;《Chem.Pharm.Bull.》;19970930;第45卷(第9期);1547-1549 * |
| "乙酸乙酯介质中脱氨基反应";孟晓燕等;《江苏化工》;20050630;第33卷;101-103 * |
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