CN101525304A - Preparation method for nitrogen-chloro acetanilide containing halogenated functional group - Google Patents
Preparation method for nitrogen-chloro acetanilide containing halogenated functional group Download PDFInfo
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- CN101525304A CN101525304A CN200910061467A CN200910061467A CN101525304A CN 101525304 A CN101525304 A CN 101525304A CN 200910061467 A CN200910061467 A CN 200910061467A CN 200910061467 A CN200910061467 A CN 200910061467A CN 101525304 A CN101525304 A CN 101525304A
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- acetanilide
- nitrogen
- halogenated
- organic phase
- water
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Abstract
The invention discloses a preparation method for nitrogen-chloro acetanilide containing halogenated functional groups, which comprises the following steps: halogenated acetanilide, sodium bicarbonate, aether and water are blended till organic phase formed by the halogenated acetanilide being dissolved in the aether and the aqueous phase formed by the sodium bicarbonate being dissolved in the water are both clarifying solutions; in the condition of ice-water bath and stirring, calcium hypochlorite white turbid liquid, halogenated acetanilide, sodium bicarbonate and calcium hypochlorite are slowly added into a reaction vessel according to the quantity relative ratio of the substance of 1:3-4:1.5-3, after the mixture fully reacts, the organic phase is collected, the aqueous phase is leached with aether or ethyl acetate, the organic phase is combined, dried and dehydrated, and then in the condition of ice-water bath, solvent in the organic phase is rotated to be dry, thus obtaining nitrogen-chloro acetanilide containing halogenated functional group. The method is simple and convenient to be operated; the used raw materials are cheap, has high yield and is easy to be industrialized; therefore, the method has great application potential in pharmaceutical synthesis intermediate, natural products, opto-electrical functional materials and dyestuff synthesis.
Description
Technical field
The present invention relates to contain the preparation method of the nitrogen-nitrogen-chloro acetanilide of halogenated functional group, belong to the synthetic chemistry field.
Background technology
Nitrogen-containing organic compound extensively is present in nature, is the very important compound of a class, occupies very big proportion in the total amount of organic compound.Many nitrogen-containing organic compound biologically actives are as alkaloid; Some is the indispensable material of vital movement, as amino acid, polypeptide, protein etc.; Many medicines, dyestuff etc. also are nitrogen-containing organic compounds.Therefore, become a focus in the organic chemistry methodology for the synthetic production research of nitrogen-containing organic compound in recent years.
Become the key field at carbon nitrogen, Buchwald-Hartwig reaction, Chan-Evans-Lam carbon nitrogen oxidative coupling reaction that early stage Ullmann reaction, past 10 years have been obtained quantum jump, the nitrogenous source of use all is R
1R
2N
-Synthon wherein mainly is to use arylamines, acid amides as nitrogenous source.
And this R of nitrogen-nitrogen-chloro acetanilide
1R
2N
+Synthon equally also is nitrogen-nitrogen-chloro acetanilide that a kind of potential can carry out containing on the nitrogenous source, particularly phenyl ring of carbon-nitrogen binding reaction bromine, iodine halogenated functional group, and very important synthetic meaning is arranged.But in the bibliographical information this preparation method who contains the nitrogen-nitrogen-chloro acetanilide of halogenated functional group does not appear as yet at present.
Summary of the invention
The objective of the invention is to remedy the deficiencies in the prior art, the preparation method of the nitrogen-nitrogen-chloro acetanilide that contains halogenated functional group is provided.
For achieving the above object, the technical solution used in the present invention is: the preparation method who contains the nitrogen-nitrogen-chloro acetanilide of halogenated functional group, may further comprise the steps: halogenated acetanilide being, sodium bicarbonate, ether and water are mixed, be dissolved in organic phase that ether forms and sodium bicarbonate up to halogenated acetanilide being and be dissolved in till water that water forms is clear liquor; Under ice-water bath, agitation condition, in this reaction vessel, slowly add Losantin white suspension liquid, the amount of substance ratio of halogenated acetanilide being, sodium bicarbonate and Losantin is 1: 3～4: 1.5～3, fully after the reaction, collect organic phase and, merge organic phase with ether or ethyl acetate extraction water, drying dewaters, under the ice-water bath condition, be spin-dried for the solvent in the organic phase then, promptly obtain containing the nitrogen-nitrogen-chloro acetanilide of halogenated functional group.
Halogenated acetanilide being described in the above-mentioned steps is neighbour-bromo Acetanilide, right-the bromo Acetanilide, neighbour-iodo Acetanilide or right-iodo Acetanilide; The described reaction times is 1～4 hour.
The inventive method is simple, is convenient to operation, and raw material is cheap, and the yield height is easy to industrialization, in medicinal intermediates, natural product, photoelectric functional material and dyestuff synthetic very big application potential is arranged.
Embodiment
The invention will be further described below by specific embodiment, and its purpose is to help to understand content of the present invention better, but the protection domain that these specific embodiments do not limit the present invention in any way.
The raw materials used known compound that is of the present invention can be buied by market, maybe can adopt methods known in the art synthetic.
Embodiment 1
Synthesizing of the adjacent acetobromanilide of nitrogen-chloro
Adjacent acetobromanilide of 10mmol and 30mmol sodium bicarbonate are put into the 250mL reaction vessel,, make organic phase and water be clear liquor then to wherein adding 35mL ether and 16mL water.The 22mmol Losantin is mixed with 40mL water, stir and make it to become white suspension liquid.Under ice-water bath, agitation condition, slowly add the Losantin suspension liquid in the above-mentioned 250mL reaction vessel, reacted 1～4 hour, and collected organic phase behind the sufficient reacting, and with a small amount of extracted with diethyl ether water for several times, merge organic phase, use anhydrous sodium sulfate drying, under the ice-water bath condition, be spin-dried for the solvent in the organic phase then, obtain product, productive rate is 85%.By mass spectral characteristi, confirm that this product is the adjacent acetobromanilide of nitrogen-chloro.MS(EI)m/e(％)：248.8(15.1)[M
++2]，246.8(12.1)[M
+]，206.9(100)[C
6H
4BrClN
++2]，205.1(64.9)[C
6H
4BrClN
+]，170.0(11.0)[M
++2-Br]，168.2(33.0)[M
+-Br]，126.0(16.7)[C
6H
4ClN
+]，90.0(13.0)[C
6H
4N
+]，63.0(25.0)[C
5H
3 +]，43.0(38.6)[C
2H
3O
+].
Embodiment 2
Synthesizing of nitrogen-chloro asepsin
10mmol asepsin and 33mmol sodium bicarbonate are put into the 250mL reaction vessel,, make organic phase and water be clear liquor then to wherein adding 35mL ether and 18mL water.The 24mmol Losantin is mixed with 40mL water, stir and make it to become white suspension liquid.Under ice-water bath, agitation condition, the Losantin suspension liquid is slowly added in the above-mentioned 250mL reaction vessel, reacted 1～4 hour, collect organic phase behind the sufficient reacting, and with a small amount of extracted with diethyl ether water for several times, merge organic phase, use anhydrous magnesium sulfate drying.Under the ice-water bath condition, be spin-dried for the solvent in the organic phase, obtain product, productive rate is 83%.By mass spectral characteristi, confirm that this product is nitrogen-chloro asepsin.MS(EI)m/e(％)：249.0(14.6)[M
++2]，247.0(12.0)[M
+]，214.2(23.7)[M
++2-Cl]，212.2(25.6)[M
+-Cl]，207.2(100)[C
6H
4BrClN
++2]，205.3(68.8)[C
6H
4BrClN
+]，126.2(17.9)[C
6H
4ClN
+]，90.0(29.4)[C
6H
4N
+]，63.1(26.2)[C
5H
3 +]，43.0(44.2)[C
2H
3O
+].
Embodiment 3
Synthesizing of the adjacent iodantifebrin of nitrogen-chloro
10mmol asepsin and 36mmol sodium bicarbonate are put into the 250mL reaction vessel,, make organic phase and water be clear liquor then to wherein adding 35mL ether and 20mL water.The 28mmol Losantin is mixed with 45mL water, stir and make it to become white suspension liquid.Under ice-water bath, agitation condition, the Losantin suspension liquid is slowly added in the above-mentioned 250mL reaction vessel, fully organic phase is collected in the reaction back, and with a small amount of extracted with diethyl ether water for several times, merges organic phase, uses anhydrous sodium sulfate drying.Under the ice-water bath condition, be spin-dried for the solvent in the organic phase, obtain product, productive rate is 92%.By mass spectral characteristi, confirm that this product is the adjacent iodantifebrin of nitrogen-chloro.MS(EI)m/e(％)：295.0(14.3)[M
+]，255.2(29.2)[C
6H
4IClN
++2]，253.2(100)[C
6H
4IClN
+]，170.2(19.2)[M
++2-I]，168.3(64.2)[M
+-I]，127.2(24.6)[I
+]，126.2(31.6)[C
6H
4ClN
+]，90.0(21.1)[C
6H
4N
+]，63.1(25.0)[C
5H
3 +]，43.0(38.2)[C
2H
3O
+].
Embodiment 4
Nitrogen-chloro is synthetic to iodantifebrin
10mmol is put into the 250mL reaction vessel to iodantifebrin and 35mmol sodium bicarbonate,, make organic phase and water be clear liquor then to wherein adding 35mL ether and 18mL water.The 26mmol Losantin is mixed with 45mL water, stir and make it to become white suspension liquid.Under ice-water bath, agitation condition, the Losantin suspension liquid is slowly added in the above-mentioned 250mL reaction vessel, fully organic phase is collected in the reaction back, and with a small amount of extracted with diethyl ether water for several times, merges organic phase, uses anhydrous sodium sulfate drying.Under the ice-water bath condition, be spin-dried for the solvent in the organic phase, obtain product, productive rate is 90%.By mass spectral characteristi, confirm that this product is that nitrogen-chloro is to iodantifebrin.MS(EI)m/e(％)：294.9(24.2)[M
+]，260.2(86.3)[M
+-Cl]，255.2(32.7)[C
6H
4IClN
++2]，253.4(100)[C
6H
4IClN
+]，127.2(15.9)[I
+]，126.2(19.8)[C
6H
4ClN
+]，90.1(32.1)[C
6H
4N
+]，63.1(30.8)[C
5H
3 +]，43.0(29.9)[C
2H
3O
+].
In the embodiment of the invention, be to adopt the extracted with diethyl ether organic phase, can also adopt ethyl acetate; Merging after the organic phase, is with anhydrous sodium sulphate or anhydrous magnesium sulfate drying, also can adopt other siccative, as long as used siccative can play the effect of dewatering and not react with organic phase and the nitrogen that contains halo functional group wherein-nitrogen-chloro acetanilide.Water in the embodiment of the invention can be clean tap water, pure water, ultrapure water, deionized water, distilled water, redistilled water etc.
Claims (3)
1. the preparation method who contains the nitrogen-nitrogen-chloro acetanilide of halogenated functional group, it is characterized in that may further comprise the steps: halogenated acetanilide being, sodium bicarbonate, ether and water are mixed, be dissolved in organic phase that ether forms and sodium bicarbonate up to halogenated acetanilide being and be dissolved in till water that water forms is clear liquor; Under ice-water bath, agitation condition, in this reaction vessel, slowly add Losantin white suspension liquid, the amount of substance ratio of halogenated acetanilide being, sodium bicarbonate and Losantin is 1: 3～4: 1.5～3, fully after the reaction, collect organic phase and, merge organic phase with ether or ethyl acetate extraction water, drying dewaters, under the ice-water bath condition, be spin-dried for the solvent in the organic phase then, promptly obtain containing the nitrogen-nitrogen-chloro acetanilide of halogenated functional group.
2. the preparation method who contains the nitrogen-nitrogen-chloro acetanilide of halogenated functional group according to claim 1 is characterized in that: described halogenated acetanilide being is neighbour-bromo Acetanilide, right-the bromo Acetanilide, neighbour-iodo Acetanilide or right-iodo Acetanilide.
3. the preparation method who contains the nitrogen-nitrogen-chloro acetanilide of halogenated functional group according to claim 1 is characterized in that: the reaction times is 1～4 hour.
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|---|---|---|---|
| CN2009100614676A CN101525304B (en) | 2009-04-08 | 2009-04-08 | Preparation method for nitrogen-chloro acetanilide containing halogenated functional group |
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|---|---|---|---|
| CN2009100614676A CN101525304B (en) | 2009-04-08 | 2009-04-08 | Preparation method for nitrogen-chloro acetanilide containing halogenated functional group |
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| CN101525304A true CN101525304A (en) | 2009-09-09 |
| CN101525304B CN101525304B (en) | 2012-07-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400495A (en) * | 2018-12-22 | 2019-03-01 | 山东国邦药业股份有限公司 | A kind of preparation method of acetochloroanilide |
-
2009
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400495A (en) * | 2018-12-22 | 2019-03-01 | 山东国邦药业股份有限公司 | A kind of preparation method of acetochloroanilide |
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