CN105622570B - A kind of Cu2+It is catalyzed the method for preparing 2- amino -5- nitrothiophene class compounds - Google Patents
A kind of Cu2+It is catalyzed the method for preparing 2- amino -5- nitrothiophene class compounds Download PDFInfo
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
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- 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 organic synthesis fields, are related to a kind of Cu2+The method that catalysis prepares 2 amino, 5 nitrothiophene class compound.2 amide groups thiophenes are added to acetic anhydride Cu by the method2+/NO3 ‑Composite salt system in, stirring, carry out nitration reaction, obtain 2 acylamino-, 5 nitrothiophene class compound, 2 acylamino-, 5 nitrothiophene class compound be hydrolyzed, 2 amino, 5 nitrothiophene class compound, i.e. target product is obtained by the reaction.The present invention utilizes acetic anhydride Cu2+/NO3 ‑Composite salt system in carry out nitration reaction, condition is relatively mild, and the reaction temperature of system is easier to control, and environmental pollution is small, and product purity is high, and mantoquita uses rear recyclable regeneration, is suitable for large-scale industrial production.
Description
Technical field
The invention belongs to organic synthesis fields, are related to a kind of Cu2+Catalysis prepares 2- amino -5- nitrothiophene class compounds
Method.
Background technology
Thiophene heterocyclic azo dyes is one kind important in thiophene heterocycle type disperse dye, thiophene heterocyclic azo dyes
In azo component be 2- amino -5- nitrothiophene rings.Thiophene heterocyclic azo dyes structural formula is as follows：
Wherein, R1For-CN ,-COR ,-CONH2,-COOR, or-COOH；R2And R3For-CH3,-CH2CH3, or-CH2CH2CN。
Key intermediate of the 2- amino -5- nitrothiophene ring structure units as thiophene heterocyclic azo dyes, derives from
The nitration reaction of 2- aminothiophene class compounds.
Nitration method with aromatic ring structure compound is mainly nitric acid-sulfuric acid mixed acid process, nitric-acetic acid anhydride method and three
Fluoroacetic acid acid anhydride-nitrate method.Wherein, nitric acid-sulfuric acid mixed acid process report is most, but there is oxidisability that strong, condition is difficult to control
The defects of；Although nitric-acetic acid anhydride method avoids using the concentrated sulfuric acid, but the strong oxidizing property of concentrated nitric acid is still unavoidable from aromatic rings
The oxidation of upper oxidizable group or atom (sulphur atom in such as thiphene ring)；And trifluoroacetic anhydride is expensive, makes large-scale production
It is limited.
Invention content
To solve the above-mentioned problems, the present invention provides a kind of Cu2+Catalysis prepares 2- amino -5- nitrothiophene class compounds
Method, this method is easy to operation, and environmental pollution is small, and product purity is high, nitrify system reaction condition it is relatively mild can
Control.
The present invention is achieved by the following technical solutions：
A kind of Cu2+It is catalyzed the method for preparing 2- amino -5- nitrothiophene class compounds, the method is by formula (I) structure
2- amide groups thiophenes are added to acetic anhydride-Cu2+/NO3 -Composite salt system in, stirring, carry out nitration reaction, obtain
To the 2- acylamino- -5- nitrothiophene class compounds of formula (II) structure, by the 2- acylamino-s -5- nitrothiophene class compounds into
Row hydrolysis obtains the 2- amino -5- nitrothiophene class compounds of formula (III) structure, i.e. target product；
Wherein, R1For-CN ,-COR ,-COOH ,-CONH2Or-COOR, wherein R are-CnH2n+1, the value of n is 1-30.
Further, the acetic anhydride-Cu2+/NO3 -The preparation method of composite salt system be：At 0-10 DEG C, with second
Acid anhydrides is solvent, adds mantoquita and nitrate, is obtained after stirring evenly.
Further, in the acetic anhydride-Cu prepared2+/NO3 -Composite salt system in, Cu2+With acetic anhydride
Molar ratio is 1:5.
Further, the mantoquita is copper nitrate or copper sulphate；The nitrate is in copper nitrate, potassium nitrate and magnesium nitrate
Any one.
Further, the method specifically includes following steps：
(1) nitration reaction：The 2- amide groups thiophenes are added to the acetic anhydride-Cu2+/NO3 -It is compound
It in salt system, stirs evenly, carries out nitration reaction, filtering after the reaction was complete, collection contains Cu2+Filtrate it is spare, and will filtering
Obtained solid is recrystallized to get to the 2- acylamino-s -5- nitrothiophene class compounds；
(2) hydrolysis：2- acylamino-s -5- nitrothiophene class the compounds that step (1) is obtained are according to solid-liquid ratio
1:2-3 is added in acid solution and is mixed, back flow reaction, and solid is precipitated in freezing, is recrystallized to get to 2- amino -5-
Nitrothiophene class compound, i.e. target product.
Further, nitration reaction condition described in step (1) is：Control the 2- amide groups thiophenes being added
Mole and acetic anhydride-Cu2+/NO3 -Composite salt system in Cu2+Mole ratio be 1:5, the reaction temperature of nitration reaction
Degree is 0-10 DEG C.
Further, acid solution described in step (2) is the hydrochloric acid solution or quality that molar concentration is 5-12.5mol/L
Percentage is the sulfuric acid solution of 30-80%.
Further, Cu will be contained described in collection2+Filtrate carry out being recycled available mantoquita, the recovery processing
Solid precipitation is obtained including alkalization, recycles solid, acidification obtains mantoquita.
The advantageous effects of the present invention：
(1) present invention utilizes acetic anhydride-Cu2+/NO3 -Composite salt system carries out the nitre in nitration reaction, with traditional handicraft
Acid-sulfuric acid mixed acid process is compared, and acetic anhydride-nitric acid mantoquita compound system reaction is relatively mild, and the reaction temperature of system is easier to
Control, significantly reduces hazard index.
(2) nitration reaction is carried out using nitric acid-sulfuric acid nitration mixture in traditional handicraft, wherein nitric acid-sulfuric acid nitration mixture has strong
Strong oxidisability, the sulphur atom being easy on oxidation of thiophene ring；And acetic anhydride-the Cu of the present invention2+/NO3 -Composite salt system
The oxidation of sulphur atom can be effectively prevented from so that product purity improves, and is detected through liquid phase, product purity is 98% or more.
(3) present invention can be regenerated and be reused to mantoquita, avoid the pollution of heavy metal copper ion pair environment.
(4) acetic anhydride-nitric acid mantoquita compound system that the present invention uses, is a kind of completely new 2- aminothiophene class chemical combination
The nitration method of object, operation is simple and easy to do, and environmental pollution is small, and the product purity obtained is high, nitrifies the anti-of system
Answer condition relatively mild controllable.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, following embodiment carries out the present invention
It is described in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, it is not used to limit
The present invention.
On the contrary, the present invention covers any replacement done in the spirit and scope of the present invention being defined by the claims, repaiies
Change, equivalent method and scheme.Further, in order to make the public have a better understanding the present invention, below to the thin of the present invention
It is detailed to describe some specific detail sections in section description.Part without these details for a person skilled in the art
Description can also understand the present invention completely.
Embodiment 1
A kind of Cu2+It is catalyzed the method for preparing 2- Amino 3 cyano -5- nitrothiophenes.
Preparation method is as follows：
(1) acetic anhydride-Cu2+/NO3 -Composite salt system preparation：Acetic anhydride 23ml is added in three-necked flask
(0.25mol) and Cu (NO3)2·3H2O (12.08g, 0.05mol), temperature control are 0 DEG C, and the acetic acid is obtained after stirring 30min
Acid anhydride-Cu2+/NO3 -Composite salt system；
(2) nitration reaction：Acetic anhydride-the Cu prepared toward step (1)2+/NO3 -Composite salt system in slowly
2-benzamide -3- cyano thiophenes (11.4g, 0.05mol) are added, control temperature range is 0-10 DEG C, and stirring to reaction is completed
Afterwards, reaction solution is poured into a large amount of ice water, is filtered, collection contains Cu2+Filtrate it is spare, and obtain dark solid, it is molten with ethyl alcohol
After solution plus activated carbon decolorizing, filters off to continue to use after activated carbon and state ethanol solution and recrystallized, buff crystal, filtering is precipitated
And after drying, 2-benzamide -3- cyano -5- nitrothiophenes (11.84g, yield 86.7%) are obtained.To the obtained 2- benzene first
Amide -3- cyano -5- nitrothiophenes carry out magnetic resonance detection, and testing result is as follows：1HNMR (400MHz, CDCl3), δ: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)；13C NMR
(400MHz, CDCl3), δ (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 -5- nitrothiophenes 11.84g is scattered in 20ml first
In alcohol (analysis pure), and it is slowly added dropwise 20ml (0.25mol) concentrated hydrochloric acid, after back flow reaction 12h, reaction is completed, and system color adds
Deep, after being cooled to room temperature, freeze overnight is precipitated dark solid, after filtering, is recrystallized with 95% ethyl alcohol, obtain 2- ammonia
Base -3- cyano -5- nitrothiophene 6.89g, yield 94%.The obtained 2- amino -3- cyano -5- nitrothiophenes are carried out
Magnetic resonance detection, testing result are as follows：1HNMR (400MHz, CDCl3), δ (ppm):6.89 (s, 1H, CH), 7.46 (s, 2H,
NH2)；13C NMR (400 MHz, CDCl3), δ (ppm):154.7,159.9,83.4,131.9,115.3；MS (ESI+), m/z:
170；Purity 98.2%.
What is be obtained by filtration in step (1) contains Cu2+Filtrate be adjusted to pH=10 or so with 0.1mol/L sodium hydroxide solutions,
It being stirred at room temperature to precipitation completely, filtering obtains blue solid, pH6 or so is adjusted to dust technology, and evaporating water obtains copper nitrate solid,
It recycles.
Embodiment 2
A kind of Cu2+It is catalyzed the method for preparing 2- amino -3- acetyl group -5- nitrothiophenes.
Preparation method is as follows：
(1) acetic anhydride-Cu2+/NO3 -Composite salt system preparation：With embodiment 1.
(2) nitration reaction：Acetic anhydride-the Cu prepared toward step (1)2+/NO3 -Composite salt system in slowly
2- acetylaminohydroxyphenylarsonic acid 3- acetyl thiophenes (9.15g, 0.05mol) are added, control temperature range is 10 DEG C, and stirring to reaction is completed
Afterwards, reaction solution is poured into a large amount of ice water, is filtered, collection contains Cu2+Filtrate it is spare, and obtain yellow solid, it is molten with methanol
After liquid dissolving plus activated carbon decolorizing, filters off to continue to use after activated carbon and states methanol solution and recrystallized, buff crystal is precipitated,
After filtering and drying, 2- ammonia acetyl group -3- acetyl group -5- nitrothiophene 10.20g, yield 89.5% are obtained.Described in obtaining
2- ammonia acetyl group -3- acetyl group -5- nitrothiophenes carry out magnetic resonance detection, and testing result is as follows：1H NMR(400MHz,
DMSO)δ(ppm):11.96(s,1H),8.56(s,1H),2.59(s,3H),2.38 (s,3H)；13C NMR(DMSO)δ(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- nitrothiophenes 10.20g is scattered in 30ml
In the sulfuric acid solution that concentrated hydrochloric acid or 30ml mass percents are 30%, after back flow reaction 10h, solid, mistake is precipitated in freeze overnight
It after filter, is recrystallized with methanol, obtains 2- amino -3- acetyl group -5- nitrothiophene crystal 7.74g, yield 93%, detection knot
Fruit is as follows：1H NMR(400MHz,DMSO)δ:9.13(s,2H),8.31(s, 1H),2.40(s,3H)；13C NMR(DMSO)δ
(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+It is catalyzed the method for preparing 2- acetylaminohydroxyphenylarsonic acid 3- acetamide -5- nitrothiophenes.
Preparation method is as follows：
(1) acetic anhydride-Cu2+/NO3 -Composite salt system preparation：Acetic anhydride 23ml is added in three-necked flask
(0.25mol)、CuSO4(7.98g, 0.05mol) and KNO3(5.06g, 0.05mol), temperature control are 0 DEG C, are after stirring 30min
Obtain the acetic anhydride-Cu2+/NO3 -Composite salt system；
(2) nitration reaction：Acetic anhydride-the Cu prepared toward step (1)2+/NO3 -Composite salt system in slowly
2- acetylaminohydroxyphenylarsonic acid 3- acetamides thiophene (9.20g, 0.05mol) is added, control temperature range is 5 DEG C, and stirring to reaction is completed
Afterwards, reaction solution is poured into a large amount of ice water, is filtered, collection contains Cu2+Filtrate it is spare, and obtain yellow solid, it is molten with methanol
After liquid dissolving plus activated carbon decolorizing, filters off to continue to use after activated carbon and states methanol solution and recrystallized, buff crystal is precipitated,
After filtering and drying, 2- acetylaminohydroxyphenylarsonic acid 3- acetamide -5- nitrothiophene 10.31g, yield 90% are obtained.1H NMR (400MHz,
CDCl3), δ (ppm):2.28 (s, 3H, CH3), 7.80 (s, 2H, NH2), 11.08 (s, 1H, NH), 8.54 (s, 1H, CH)；13C
NMR (400MHz, CDCl3), δ (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+It is catalyzed the method for preparing 2- acetylaminohydroxyphenylarsonic acid 3- ethoxycarbonyl -5- nitrothiophenes.
Preparation method is as follows：
(1) acetic anhydride-Cu2+/NO3 -Composite salt system preparation：Acetic anhydride 23ml is added in three-necked flask
(0.25mol)、CuSO4(7.98g, 0.05mol) and NaNO3(4.25,0.05mol), temperature control are 0 DEG C, are after stirring 30min
Obtain the acetic anhydride-Cu2+/NO3 -Composite salt system；
(2) nitration reaction：Acetic anhydride-the Cu prepared toward step (1)2+/NO3 -Composite salt system in slowly
2- acetylaminohydroxyphenylarsonic acid 3- ethoxycarbonyies thiophene (9.95g, 0.05mol) is added, control temperature range is 8 DEG C, and stirring to reaction is completed
Afterwards, reaction solution is poured into a large amount of ice water, is filtered, collection contains Cu2+Filtrate it is spare, and obtain yellow solid, use is a concentration of
After 95% ethanol solution dissolving plus activated carbon decolorizing, filters off to continue to use after activated carbon and state ethanol solution and recrystallized, analyse
Go out buff crystal, after filtering and drying, obtains 2- acetylaminohydroxyphenylarsonic acid 3- ethoxycarbonyl -5- nitrothiophene 10.86g, yield 89%.1H
NMR (400MHz, CDCl3), δ (ppm):2.28 (s, 3H, CH3), 3.90 (s, 3H, CH3), 11.08 (s, 1H, NH), 8.49
(s, 1H, CH)；13C NMR (400MHz, CDCl3), δ (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+It is catalyzed the method for preparing 2- acetylaminohydroxyphenylarsonic acid 3- carboxyl -5- nitrothiophenes.
Preparation method is as follows：
(1) acetic anhydride-Cu2+/NO3 -Composite salt system preparation：With embodiment 4；
(2) nitration reaction：Acetic anhydride-the Cu prepared toward step (1)2+/NO3 -Composite salt system in slowly
2- acetylaminohydroxyphenylarsonic acid 3- carboxy thiophenes (9.25g, 0.05mol) are added, control temperature range is 8 DEG C, after the completion of stirring is extremely reacted,
Reaction solution is poured into a large amount of ice water, is filtered, collection contains Cu2+Filtrate it is spare, and yellow solid is obtained, with a concentration of 95%
Ethanol solution dissolving after plus activated carbon decolorizing, filter off to continue to use after activated carbon and state ethanol solution and recrystallized, be precipitated deep
Yellow crystals, after filtering and drying, 2- acetylaminohydroxyphenylarsonic acid 3- carboxyl -5- nitrothiophene 10.47g, yield 91%.1H NMR
(400MHz, CDCl3), δ (ppm):2.28 (s, 3H, CH3), 11.08 (s, 1H, NH), 12.75 (s, 1H, COOH), 8.57 (s,
1H, CH)；13C NMR (400MHz, CDCl3), δ (ppm):140.9,189.1,120.5,129.2,163.3,168.9,24.0；
MS(ESI+), m/z:231；Purity 98.46%.
Claims (7)
1. a kind of Cu2+It is catalyzed the method for preparing 2- amino -5- nitrothiophene class compounds, which is characterized in that the method is by formula
（Ⅰ）The 2- amide groups thiophenes of structure are added to acetic anhydride-Cu2+/NO3 -Composite salt system in, stirring, carry out nitre
Change reaction, obtains formula（Ⅱ）2- acylamino- -5- nitrothiophene class the compounds of structure, by the 2- acylamino-s -5- nitrothiophenes
The formula of being obtained by the reaction is hydrolyzed in class compound（Ⅲ）2- amino -5- nitrothiophene class the compounds of structure, i.e. target product；
Wherein, R1For-CN ,-COR ,-COOH ,-CONH2Or-COOR, wherein R are-CnH2n+1, the value of n is 1-30；
Acetic anhydride-the Cu2+/NO3 -The preparation method of composite salt system be：At 0-10 DEG C, using acetic anhydride as solvent, add
Add mantoquita and nitrate, is obtained after stirring evenly.
2. a kind of Cu according to claim 12+It is catalyzed the method for preparing 2- amino -5- nitrothiophene class compounds, feature
It is, in the acetic anhydride-Cu prepared2+/NO3 -Composite salt system in, Cu2+Molar ratio with acetic anhydride is 1:5.
3. a kind of Cu according to claim 12+It is catalyzed the method for preparing 2- amino -5- nitrothiophene class compounds, feature
It is, the mantoquita is copper nitrate or copper sulphate；The nitrate is any one in copper nitrate, potassium nitrate and magnesium nitrate.
4. a kind of Cu according to claim 12+It is catalyzed the method for preparing 2- amino -5- nitrothiophene class compounds, feature
It is, the method specifically includes following steps：
（1）Nitration reaction：The 2- amide groups thiophenes are added to the acetic anhydride-Cu2+/NO3 -Complex salt body
It in system, stirs evenly, carries out nitration reaction, filtering after the reaction was complete, collection contains Cu2+Filtrate it is spare, and will be obtained by filtration
Solid recrystallized to get to the 2- acylamino-s -5- nitrothiophene class compounds；
（2）Hydrolysis：By step（1）The obtained 2- acylamino-s -5- nitrothiophene class compounds are according to solid-liquid ratio 1:2-3
It is added in acid solution and is mixed, solid is precipitated in back flow reaction, freezing, is recrystallized to get to 2- amino -5- nitros
Thiophenes, i.e. target product.
5. a kind of Cu according to claim 42+It is catalyzed the method for preparing 2- amino -5- nitrothiophene class compounds, feature
It is, step（1）Described in nitration reaction condition be：Control the mole and acetic acid of the 2- amide groups thiophenes being added
Acid anhydride-Cu2+/NO3 -Composite salt system in Cu2+Mole ratio be 1:5, the reaction temperature of nitration reaction is 0-10 DEG C.
6. a kind of Cu according to claim 42+It is catalyzed the method for preparing 2- amino -5- nitrothiophene class compounds, feature
It is, step（2）Described in acid solution be hydrochloric acid solution that molar concentration is 5-12.5mol/L or mass percent is 30-80%
Sulfuric acid solution.
7. a kind of Cu according to claim 42+It is catalyzed the method for preparing 2- amino -5- nitrothiophene class compounds, feature
It is, Cu will be contained described in collection2+Filtrate be recycled available mantoquita, the recovery processing includes alkalization acquisition
Solid precipitates, and recycles solid, and acidification obtains mantoquita.
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| First Synthesis of 3-Acetyl-2-aminothiophenes Using the Gewald Reaction;Gernot A. Eller，et al.，;《Molecules》;20060516;第11卷;第371-376页 * |
| 硝酸銅—矽膠擔體試劑與間—苯二酚之硝化反應研究;谢朝阳;《博硕士论文》;20140505;摘要 * |
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