CN101525304B - 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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- CN101525304B CN101525304B CN2009100614676A CN200910061467A CN101525304B CN 101525304 B CN101525304 B CN 101525304B CN 2009100614676 A CN2009100614676 A CN 2009100614676A CN 200910061467 A CN200910061467 A CN 200910061467A CN 101525304 B CN101525304 B CN 101525304B
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- acetanilide
- nitrogen
- organic phase
- halogenated
- 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 one type of very important compound, in the total amount of organic cpds, occupies very big proportion.Many nitrogen-containing organic compound biologically actives are like vegeto-alkali; Some is the indispensable material of vital movement, like 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 deficiency of prior art, the preparation method of the nitrogen-nitrogen-chloro acetanilide that contains halogenated functional group is provided.
For realizing above-mentioned purpose; The technical scheme that the present invention adopts is: the preparation method who contains the nitrogen-nitrogen-chloro acetanilide of halogenated functional group; May further comprise the steps: halogenated acetanilide being, sodium hydrogencarbonate, ether and water are mixed, be dissolved in till water that organic phase that ether forms and sodium hydrogencarbonate be dissolved in water formation is clear liquor up to halogenated acetanilide being; 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 hydrogencarbonate 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, revolve the solvent of doing 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 said reaction times is 1～4 hour.
The inventive method is simple, is convenient to operation, and raw material is cheap, and yield is high, is easy to industrialization, in medicinal intermediates, natural product, photoelectric functional material and dyestuff synthetic, very big application potential is arranged.
Embodiment
Through specific embodiment the present invention is described further below, 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 hydrogencarbonate 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, 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 sodium sulfate drying, under the ice-water bath condition, revolve the solvent of doing in the organic phase then; Obtain product, productive rate is 85%.Through 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 hydrogencarbonate 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, revolve the solvent of doing in the organic phase, obtain product, productive rate is 83%.Through 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 hydrogencarbonate 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, revolve the solvent of doing in the organic phase, obtain product, productive rate is 92%.Through 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 hydrogencarbonate,, 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, revolve the solvent of doing in the organic phase, obtain product, productive rate is 90%.Through 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 ETHYLE ACETATE; Merging after the organic phase, is with SODIUM SULPHATE ANHYDROUS 99PCT 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, zero(ppm) water, redistilled water etc.
Claims (1)
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 hydrogencarbonate, ether and water are mixed, be dissolved in till water that organic phase that ether forms and sodium hydrogencarbonate be dissolved in water formation is clear liquor up to halogenated acetanilide being; 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 hydrogencarbonate 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, revolve the solvent of doing in the organic phase then, promptly obtain containing the nitrogen-nitrogen-chloro acetanilide of halogenated functional group; Wherein said halogenated acetanilide being is neighbour-bromo Acetanilide, right-the bromo Acetanilide, neighbour-iodo Acetanilide or right-iodo Acetanilide, and the said reaction times is 1～4 hour.
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Non-Patent Citations (3)
| Title |
|---|
| Chuan He et al.Aryl Halide Tolerated Electrophilic Amination of Arylboronic Acids with N-Chloroamides Catalyzed by CuCl at Room Temperature.《Angew.Chem.Int.Ed.》.2008,第47卷6414 –6417. * |
| F. D. CHATTAW et al.CIV.—A series of substituted nitrogen chlorides and their relation to the substitution of halogen in anilides and anilines.《Journal of the chemical society,Transations》.1899,1046-1054. * |
| Yong-Li Zhong et al.Practical and efficient synthesis of N-halo compounds.《Tetrahedron Letters》.2005,第46卷1099-1101. * |
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