CN105622570A - Method for preparing 2-amino-5-nitrothiophene compound from Cu<2+> - Google Patents
Method for preparing 2-amino-5-nitrothiophene compound from Cu<2+> Download PDFInfo
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- CN105622570A CN105622570A CN201610077426.6A CN201610077426A CN105622570A CN 105622570 A CN105622570 A CN 105622570A CN 201610077426 A CN201610077426 A CN 201610077426A CN 105622570 A CN105622570 A CN 105622570A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/42—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms with nitro or nitroso radicals directly attached to ring carbon atoms
- C07D333/44—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms with nitro or nitroso radicals directly attached to ring carbon atoms attached in position 5
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
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Abstract
The invention belongs to the field of organic synthesis and relates to a method for preparing a 2-amino-5-nitrothiophene compound from Cu<2+>. The method includes adding a 2-acylamino thiophene compound into an acetic anhydride-Cu<2+>/NO3<-> compound salt system, stirring, performing nitration to obtain a 2-acylamino-5-nitrothiophene compound, and subjecting the 2-acylamino-5-nitrothiophene compound to hydrolysis so as to obtain the 2-amino-5-nitrothiophene compound, namely a target product. The method for preparing the 2-amino-5-nitrothiophene compound from the Cu<2+> has the advantages that nitration is conducted in the acetic anhydride-Cu<2+>/NO3<-> compound salt system, mild reaction conditions, easiness in system reaction temperature control, little environmental pollution and high product purity are achieved, copper salt can be recycled after use, and accordingly the method is applicable to large-scale industrial production.
Description
Technical field
The invention belongs to organic synthesis field, relate to a kind of Cu2+The method of 2-amino-5-nitrothiophene compounds is prepared in catalysis.
Background technology
Thiophene heterocyclic azo dye is one important in thiophene heterocyclic disperse dyes, and the azo component in thiophene heterocyclic azo dye is 2-amino-5-nitrothiophene ring. Thiophene heterocyclic azo dye structural formula is as follows:
Wherein, R1For-CN ,-COR ,-CONH2,-COOR, or-COOH; R2And R3For-CH3,-CH2CH3, or-CH2CH2CN��
2-amino-5-nitrothiophene ring structure unit, as the key intermediate of thiophene heterocyclic azo dye, derives from the nitration reaction of 2-aminothiophene compounds.
The nitration method with aromatic ring structure compound is mainly nitric acid-sulfuric acid mixed acid process, nitric-acetic acid anhydride method and trifluoroacetic anhydride-nitrate method. Wherein, nitric acid-sulfuric acid mixed acid process report at most, but also exists the defects such as oxidisability is strong, condition is difficult to control to; Although nitric-acetic acid anhydride method avoids using concentrated sulphuric acid, but the oxidation of the strong oxidizing property of concentrated nitric acid is still unavoidable from aromatic rings oxidizable group or atom (such as sulphur atom in thiphene ring); And trifluoroacetic anhydride is expensive, make large-scale production limited.
Summary of the invention
In order to solve the problems referred to above, the present invention provides a kind of Cu2+The method of 2-amino-5-nitrothiophene compounds is prepared in catalysis, and the method is easy to operation, and environmental pollution is little, and product purity is high, and the reaction condition of nitrated system is relatively mild controlled.
The present invention is achieved by the following technical solutions:
A kind of Cu2+The method of 2-amino-5-nitrothiophene compounds is prepared in catalysis, and the 2-amide groups thiophenes of formula I structure is joined acetic anhydride-Cu by described method2+/NO3 -Composite salt system in, stirring, carry out nitration reaction, obtain the 2-acylamino--5-nitrothiophene compounds of formula II structure, described 2-acylamino--5-nitrothiophene compounds is hydrolyzed and is obtained by reacting the 2-amino-5-nitrothiophene compounds of formula III structure, i.e. target product;
Wherein, R1For-CN ,-COR ,-COOH ,-CONH2Or-COOR, wherein R is-CnH2n+1, the value of n is 1-30.
Further, described acetic anhydride-Cu2+/NO3 -The preparation method of composite salt system be: at 0-10 DEG C, with acetic anhydride for solvent, add mantoquita and nitrate, obtain after stirring.
Further, at the described acetic anhydride-Cu prepared2+/NO3 -Composite salt system in, Cu2+It is 1:5 with the mol ratio of acetic anhydride.
Further, described mantoquita is copper nitrate or copper sulfate; Described nitrate is any one in copper nitrate, potassium nitrate and magnesium nitrate.
Further, described method specifically includes following steps:
(1) nitration reaction: described 2-amide groups thiophenes is joined described acetic anhydride-Cu2+/NO3 -Composite salt system in, stir, carry out nitration reaction, filter after reacting completely, collect containing Cu2+Filtrate standby, and the solid being filtrated to get is carried out recrystallization, namely obtains described 2-acylamino--5-nitrothiophene compounds;
(2) hydrolysis: described 2-acylamino--5-nitrothiophene compounds step (1) obtained joins in acid solution according to solid-liquid ratio 1:2-3 and mixes, back flow reaction, freezing, precipitate out solid, carry out recrystallization, namely 2-amino-5-nitrothiophene compounds, i.e. target product are obtained.
Further, nitration reaction condition described in step (1) is: control mole and the acetic anhydride-Cu of the 2-amide groups thiophenes of addition2+/NO3 -Composite salt system in Cu2+The ratio of mole be 1:5, the reaction temperature of nitration reaction is 0-10 DEG C.
Further, the hydrochloric acid solution of to be molar concentration the be 5-12.5mol/L of acid solution described in step (2) or mass percent are the sulfuric acid solution of 30-80%.
Further, described in collecting, Cu is contained2+Filtrate carry out recycling and can obtain mantoquita, described recycling includes alkalization and obtains solid precipitation, reclaims solid, and acidifying obtains mantoquita.
The Advantageous Effects of the present invention:
(1) present invention utilizes acetic anhydride-Cu2+/NO3 -Composite salt system carries out nitration reaction, and compared with the nitric acid-sulfuric acid mixed acid process in traditional handicraft, acetic anhydride-nitric acid mantoquita compound system reaction is relatively mild, and the reaction temperature of system is easier to control, and significantly reduces hazard index.
(2) the nitric acid-sulfuric acid nitration mixture that utilizes in traditional handicraft carries out nitration reaction, and wherein nitric acid-sulfuric acid nitration mixture has strong oxidisability, it is easy to the sulphur atom on oxidation of thiophene ring; And the described acetic anhydride-Cu of the present invention2+/NO3 -Composite salt system can be effectively prevented from the oxidation of sulphur atom so that product purity improves, and through Liquid Detection, product purity is more than 98%.
(3) mantoquita can be regenerated and reuse by the present invention, it is to avoid the pollution of heavy metal copper ion pair environment.
(4) acetic anhydride-nitric acid mantoquita compound system that the present invention adopts, being the nitration method of a kind of brand-new 2-aminothiophene compounds, operation is simple and easy to do, and environmental pollution is little, and the product purity obtained is high, and the reaction condition of nitrated system is relatively mild controlled.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearly understand, the present invention is explained in further detail by following example. Should be appreciated that specific embodiment described herein is used only for explaining the present invention, be not intended to limit the present invention.
On the contrary, the present invention contains any replacement made in the spirit and scope of the present invention, amendment, equivalent method and scheme being defined by the claims. Further, in order to make the public that the present invention to be had a better understanding, in below the details of the present invention being described, detailed describe some specific detail sections. The description not having these detail sections for a person skilled in the art can also understand the present invention completely.
Embodiment 1
A kind of Cu2+The method of 2-Amino 3 cyano-5-nitrothiophene is prepared in catalysis.
Preparation method is as follows:
(1) acetic anhydride-Cu2+/NO3 -The preparation of composite salt system: in there-necked flask, add acetic anhydride 23ml (0.25mol) and Cu (NO3)2��3H2O (12.08g, 0.05mol), temperature control is 0 DEG C, namely obtains described acetic anhydride-Cu after stirring 30min2+/NO3 -Composite salt system;
(2) nitration reaction: the described acetic anhydride-Cu prepared toward step (1)2+/NO3 -Composite salt system in be slowly added to 2-benzamide-3-cyano thiophene (11.4g, 0.05mol), control temperature range and be 0-10 DEG C, stirring is to after react, being poured into by reactant liquor in a large amount of frozen water, filter, collect and contain Cu2+Filtrate standby, and obtain dark solid, activated carbon decolorizing is added after dissolving with ethanol, continue to use after elimination activated carbon and state alcoholic solution and carry out recrystallization, precipitate out buff crystal, filter and dried, obtain 2-benzamide-3-cyano group-5-nitrothiophene (11.84g, yield 86.7%). Described 2-benzamide-3-cyano group-5-the nitrothiophene obtained is carried out magnetic resonance detection, and testing result is as follows:1HNMR (400MHz, CDCl3), ��: 7.82 (m, 1H, CH), 7.54 (m, 2H, CH), 7.95 (d, 2H, CH), 8.29 (s, 1H, CH), 11.9 (s, 1H, NH);13CNMR (400MHz, CDCl3), �� (ppm): 142.7,158.2,97.1,130.4,134.2,127.5,128.8,132.1,164.7,115.3; MS (ESI+), m/z:274; Purity 98.0%.
(3) hydrolysis: above-mentioned product 2-benzamide-3-cyano group-5-nitrothiophene 11.84g is scattered in 20ml methanol (analytical pure), and it being slowly added dropwise 20ml (0.25mol) concentrated hydrochloric acid, after back flow reaction 12h, reaction completes, system color burn, after being cooled to room temperature, freeze overnight, precipitate out dark solid, after filtration, carry out recrystallization with 95% ethanol, obtain 2-Amino 3 cyano-5-nitrothiophene 6.89g, yield 94%. The described 2-Amino 3 cyano-5-nitrothiophene obtained is carried out magnetic resonance detection, and testing result is as follows:1HNMR (400MHz, CDCl3), �� (ppm): 6.89 (s, 1H, CH), 7.46 (s, 2H, NH2);13CNMR (400MHz, CDCl3), �� (ppm): 154.7,159.9,83.4,131.9,115.3; MS (ESI+), m/z:170; Purity 98.2%.
What be filtrated to get in step (1) contains Cu2+Filtrate be adjusted to about pH=10 with 0.1mol/L sodium hydroxide solution, be stirred at room temperature to precipitation completely, filter, obtain blue solid, be adjusted to about pH6, evaporating water with dust technology, obtain copper nitrate solid, recycle.
Embodiment 2
A kind of Cu2+The method of 2-amino-3-acetyl group-5-nitrothiophene is prepared in catalysis.
Preparation method is as follows:
(1) acetic anhydride-Cu2+/NO3 -The preparation of composite salt system: with embodiment 1.
(2) nitration reaction: the described acetic anhydride-Cu prepared toward step (1)2+/NO3 -Composite salt system in be slowly added to 2-acetylaminohydroxyphenylarsonic acid 3-acetyl thiophene (9.15g, 0.05mol), controlling temperature range is 10 DEG C, and stirring is to after react, being poured into by reactant liquor in a large amount of frozen water, filter, collect and contain Cu2+Filtrate standby, and obtain yellow solid, after dissolving with methanol solution, add activated carbon decolorizing; continue to use after elimination activated carbon and state methanol solution and carry out recrystallization, precipitate out buff crystal, filter and dried; obtain 2-ammonia acetyl group-3-acetyl group-5-nitrothiophene 10.20g, yield 89.5%. The described 2-ammonia acetyl group-3-acetyl group-5-nitrothiophene obtained is carried out magnetic resonance detection, and testing result is as follows:1HNMR (400MHz, DMSO) �� (ppm): 11.96 (s, 1H), 8.56 (s, 1H), 2.59 (s, 3H), 2.38 (s, 3H);13CNMR(DMSO)��(ppm):196.11,170.66,151.93,140.31,129.73,120.17,29.12,23.58.EI-MS(m/z):228��
(3) hydrolysis: above-mentioned product 2-ammonia acetyl group-3-acetyl group-5-nitrothiophene 10.20g is scattered in 30ml concentrated hydrochloric acid or sulfuric acid solution that 30ml mass percent is 30%; after back flow reaction 10h; freeze overnight; precipitate out solid; after filtration, carry out recrystallization with methanol, obtain 2-amino-3-acetyl group-5-nitrothiophene crystal 7.74g; yield 93%, testing result is as follows:1HNMR (400MHz, DMSO) ��: 9.13 (s, 2H), 8.31 (s, 1H), 2.40 (s, 3H);13CNMR (DMSO) �� (ppm): 194.72,168.85,133.92,130.23,115.05,28.35.ESI-MS (m/z): 186.09 (M+H); Purity 98.67%.
Embodiment 3
A kind of Cu2+The method of 2-acetylaminohydroxyphenylarsonic acid 3-acetamide-5-nitrothiophene is prepared in catalysis.
Preparation method is as follows:
(1) acetic anhydride-Cu2+/NO3 -The preparation of composite salt system: in there-necked flask, add acetic anhydride 23ml (0.25mol), CuSO4(7.98g, 0.05mol) and KNO3(5.06g, 0.05mol), temperature control is 0 DEG C, namely obtains described acetic anhydride-Cu after stirring 30min2+/NO3 -Composite salt system;
(2) nitration reaction: the described acetic anhydride-Cu prepared toward step (1)2+/NO3 -Composite salt system in be slowly added to 2-acetylaminohydroxyphenylarsonic acid 3-acetamide thiophene (9.20g, 0.05mol), controlling temperature range is 5 DEG C, and stirring is to after react, being poured into by reactant liquor in a large amount of frozen water, filter, collect and contain Cu2+Filtrate standby, and obtain yellow solid, after dissolving with methanol solution, add activated carbon decolorizing, continue to use after elimination activated carbon and state methanol solution and carry out recrystallization, precipitate out buff crystal, filter and dried, obtain 2-acetylaminohydroxyphenylarsonic acid 3-acetamide-5-nitrothiophene 10.31g, yield 90%.1HNMR (400MHz, CDCl3), �� (ppm): 2.28 (s, 3H, CH3), 7.80 (s, 2H, NH2), 11.08 (s, 1H, NH), 8.54 (s, 1H, CH);13CNMR (400MHz, CDCl3), �� (ppm): 141.9,192.2,118.5,126.2,167.9,168.9,24.8; MS (ESI+), m/z:230; Purity 98.0%.
Embodiment 4
A kind of Cu2+The method of 2-acetylaminohydroxyphenylarsonic acid 3-ethoxycarbonyl-5-nitrothiophene is prepared in catalysis.
Preparation method is as follows:
(1) acetic anhydride-Cu2+/NO3 -The preparation of composite salt system: in there-necked flask, add acetic anhydride 23ml (0.25mol), CuSO4(7.98g, 0.05mol) and NaNO3(4.25,0.05mol), temperature control is 0 DEG C, namely obtains described acetic anhydride-Cu after stirring 30min2+/NO3 -Composite salt system;
(2) nitration reaction: the described acetic anhydride-Cu prepared toward step (1)2+/NO3 -Composite salt system in be slowly added to 2-acetylaminohydroxyphenylarsonic acid 3-ethoxycarbonyl thiophene (9.95g, 0.05mol), controlling temperature range is 8 DEG C, and stirring is to after react, being poured into by reactant liquor in a large amount of frozen water, filter, collect and contain Cu2+Filtrate standby, and obtain yellow solid, activated carbon decolorizing is added after dissolving with the alcoholic solution that concentration is 95%, continue to use after elimination activated carbon and state alcoholic solution and carry out recrystallization, precipitate out buff crystal, filter and dried, obtain 2-acetylaminohydroxyphenylarsonic acid 3-ethoxycarbonyl-5-nitrothiophene 10.86g, yield 89%.1HNMR (400MHz, CDCl3), �� (ppm): 2.28 (s, 3H, CH3), 3.90 (s, 3H, CH3), 11.08 (s, 1H, NH), 8.49 (s, 1H, CH);13CNMR (400MHz, CDCl3), �� (ppm): 140.2,187.8,120.5,129.2,159.9,168.9,51.5,24.0; MS (ESI+), m/z:245; Purity 99.1%.
Embodiment 5
A kind of Cu2+The method of 2-acetylaminohydroxyphenylarsonic acid 3-carboxyl-5-nitrothiophene is prepared in catalysis.
Preparation method is as follows:
(1) acetic anhydride-Cu2+/NO3 -The preparation of composite salt system: with embodiment 4;
(2) nitration reaction: the described acetic anhydride-Cu prepared toward step (1)2+/NO3 -Composite salt system in be slowly added to 2-acetylaminohydroxyphenylarsonic acid 3-carboxy thiophene (9.25g, 0.05mol), controlling temperature range is 8 DEG C, and stirring is to after react, being poured into by reactant liquor in a large amount of frozen water, filter, collect and contain Cu2+Filtrate standby, and obtain yellow solid, activated carbon decolorizing is added after dissolving with the alcoholic solution that concentration is 95%, continue to use after elimination activated carbon and state alcoholic solution and carry out recrystallization, precipitate out buff crystal, filter and dried, 2-acetylaminohydroxyphenylarsonic acid 3-carboxyl-5-nitrothiophene 10.47g, yield 91%.1HNMR (400MHz, CDCl3), �� (ppm): 2.28 (s, 3H, CH3), 11.08 (s, 1H, NH), 12.75 (s, 1H, COOH), 8.57 (s, 1H, CH);13CNMR (400MHz, CDCl3), �� (ppm): 140.9,189.1,120.5,129.2,163.3,168.9,24.0; MS (ESI+), m/z:231; Purity 98.46%.
Claims (8)
1. a Cu2+The method of 2-amino-5-nitrothiophene compounds is prepared in catalysis, it is characterised in that the 2-amide groups thiophenes of formula I structure is joined acetic anhydride-Cu by described method2+/NO3 -Composite salt system in, stirring, carry out nitration reaction, obtain the 2-acylamino--5-nitrothiophene compounds of formula II structure, described 2-acylamino--5-nitrothiophene compounds is hydrolyzed and is obtained by reacting the 2-amino-5-nitrothiophene compounds of formula III structure, i.e. target product;
Wherein, R1For-CN ,-COR ,-COOH ,-CONH2Or-COOR, wherein R is-CnH2n+1, the value of n is 1-30.
2. a kind of Cu according to claim 12+The method of 2-amino-5-nitrothiophene compounds is prepared in catalysis, it is characterised in that described acetic anhydride-Cu2+/NO3 -The preparation method of composite salt system be: at 0-10 DEG C, with acetic anhydride for solvent, add mantoquita and nitrate, obtain after stirring.
3. a kind of Cu according to claim 22+The method of 2-amino-5-nitrothiophene compounds is prepared in catalysis, it is characterised in that at the described acetic anhydride-Cu prepared2+/NO3 -Composite salt system in, Cu2+It is 1:5 with the mol ratio of acetic anhydride.
4. a kind of Cu according to claim 22+The method of 2-amino-5-nitrothiophene compounds is prepared in catalysis, it is characterised in that described mantoquita is copper nitrate or copper sulfate; Described nitrate is any one in copper nitrate, potassium nitrate and magnesium nitrate.
5. a kind of Cu according to claim 12+The method of 2-amino-5-nitrothiophene compounds is prepared in catalysis, it is characterised in that described method specifically includes following steps:
(1) nitration reaction: described 2-amide groups thiophenes is joined described acetic anhydride-Cu2+/NO3 -Composite salt system in, stir, carry out nitration reaction, filter after reacting completely, collect containing Cu2+Filtrate standby, and the solid being filtrated to get is carried out recrystallization, namely obtains described 2-acylamino--5-nitrothiophene compounds;
(2) hydrolysis: described 2-acylamino--5-nitrothiophene compounds step (1) obtained joins in acid solution according to solid-liquid ratio 1:2-3 and mixes, back flow reaction, freezing, precipitate out solid, carry out recrystallization, namely 2-amino-5-nitrothiophene compounds, i.e. target product are obtained.
6. a kind of Cu according to claim 52+The method of 2-amino-5-nitrothiophene compounds is prepared in catalysis, it is characterised in that nitration reaction condition described in step (1) is: control mole and the acetic anhydride-Cu of the 2-amide groups thiophenes of addition2+/NO3 -Composite salt system in Cu2+The ratio of mole be 1:5, the reaction temperature of nitration reaction is 0-10 DEG C.
7. a kind of Cu according to claim 52+The method of 2-amino-5-nitrothiophene compounds is prepared in catalysis, it is characterised in that acid solution described in step (2) is molar concentration is the hydrochloric acid solution of 5-12.5mol/L or mass percent is the sulfuric acid solution of 30-80%.
8. a kind of Cu according to claim 52+The method of 2-amino-5-nitrothiophene compounds is prepared in catalysis, it is characterised in that contain Cu described in collecting2+Filtrate carry out recycling and can obtain mantoquita, described recycling includes alkalization and obtains solid precipitation, reclaims solid, and acidifying obtains mantoquita.
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| CN114874182A (en) * | 2022-06-08 | 2022-08-09 | 青海施丹弗化工有限责任公司 | Method for thiophene continuous nitration reaction |
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| Title |
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| GERNOT A. ELLER，ET AL.，: "First Synthesis of 3-Acetyl-2-aminothiophenes Using the Gewald Reaction", 《MOLECULES》 * |
| 谢朝阳: "硝酸銅—矽膠擔體試劑與間—苯二酚之硝化反應研究", 《博硕士论文》 * |
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| CN114874182A (en) * | 2022-06-08 | 2022-08-09 | 青海施丹弗化工有限责任公司 | Method for thiophene continuous nitration reaction |
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