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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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.
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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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| "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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