CN103880711A - Method for preparing aldehyde semicarbazone Schiff base - Google Patents
Method for preparing aldehyde semicarbazone Schiff base Download PDFInfo
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- CN103880711A CN103880711A CN201410081659.4A CN201410081659A CN103880711A CN 103880711 A CN103880711 A CN 103880711A CN 201410081659 A CN201410081659 A CN 201410081659A CN 103880711 A CN103880711 A CN 103880711A
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- phenyl
- aldehyde
- semicarbazone
- schiff alkali
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Abstract
The invention provides a method for preparing an aldehyde semicarbazone Schiff base. The method comprises the steps of adding a mol of aldehyde, b mol of semicarbazide hydrochloride and c mol of p-aminobenzene sulfonic acid to a dried reactor; uniformly mixing the raw materials and reacting the raw materials, wherein a ratio of a: b: c is 1: (1-1.2): (0.1-0.3); implementing TLC detection until the reaction is complete; preserving heat of the reactor in an oven; cooling the reactor to room temperature, washing, and carrying suction filtering; concentrating filtrate to be dry to obtain a target product, i.e., the aldehyde semicarbazone Schiff base, wherein yield of the Schiff base is higher than 95%. The aldehyde semicarbazone Schiff base is prepared through a solvent-free method; the preparation method is simple in experiment operation, short in reaction time, simple in post-treatment and high in yield; moreover, a catalyst adopted is recoverable and reusable; the method is an economic, efficient, green and environment-friendly synthesis method.
Description
Technical field
The invention belongs to the field of chemical synthesis, particularly a kind of method of preparing aldehyde semicarbazone Schiff alkali.
Background technology
In organic reaction, aldehyde and primary amine condensation form the important organic compound of a class, be Schiff's base (Schiff Bases), report that it is synthetic more with the document of application, be one of focus of research at present, the Schiff's base semicarbazone that aldehyde and Urea,amino-reaction generate is a kind of important fine-chemical intermediate.Schiff's base semicarbazone is mainly used in synthetic nitrofural, furadantin, Nifurtoinol, nifurfoline, nifurmazole, nitre furan profit pine etc., also can be used as agricultural chemicals, dyestuff intermediate, chemical reagent, metal ligand reagent etc., in new drug research and exploitation, be subject to paying attention to widely, had vast potential for future development.The shortcomings such as the traditional high and low productive rate of methodology of organic synthesis energy consumption, environmental pollution is serious, do not meet the requirement of people to " Green Chemistry " in recent years.
Summary of the invention
The invention provides a kind of method of preparing aldehyde semicarbazone Schiff alkali, adopt solventless method to prepare semicarbazone, experimental implementation is simple, the reaction times is short, aftertreatment is simple, productive rate is high, and its catalyzer used is recyclable, reusable, it is the synthetic method of a kind of economy, green, environmental protection.
For achieving the above object, the technical solution used in the present invention comprises the following steps:
1) in dry reaction vessel, add a mol aldehyde, b mol semicarbazide hydrochloride and c mol Sulphanilic Acid, then raw material is mixed, and raw material is reacted, TLC detects until reaction is carried out completely, obtain mixture, wherein a:b:c=1:(1～1.2): (0.1～0.3);
2) mixture is incubated at the temperature of 80～100 ℃, is then cooled to room temperature, then washs, decompress filter, filtrate is concentrated into dry, obtains target product aldehyde semicarbazone Schiff alkali.
The structural formula of described aldehyde is: R-CHO,
Wherein, R=H ,-CH
3,-C
2h
5, n-C
3h
7, phenyl, furyl, thienyl, 3-nitrophenyl, 4-nitrophenyl, 4-hydroxy phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-aminophenyl, 4-dimethylamino phenyl, 2-hydroxy phenyl, 2-hydroxyl-3,5-dinitrophenyl, 3,5-3,5-dimethylphenyl, 3-aminomethyl phenyl or 2,4-dibromo phenyl.
Described step 1) is at room temperature carried out.
Described reaction vessel is mortar, by grinding, raw material is mixed, and raw material is reacted in described step 1).
Described be ground to reaction and carry out that the required time is 10～20min completely.
Described TLC detects until reaction refers to the raw material point disappearance that aldehyde detected completely, and wherein the developping agent of TLC is that volume ratio is the ethyl acetate of 1:3 and the mixed solvent of sherwood oil.
Described step 2) in soaking time be 30～60min.
Described step 2) in insulation in baking oven, carry out.
Cleaning solvent in described step 3) is dehydrated alcohol or anhydrous methanol.
The structural formula of the aldehyde semicarbazone Schiff alkali making is:
Wherein, R=H ,-CH
3,-C
2h
5, n-C
3h
7, phenyl, furyl, thienyl, 3-nitrophenyl, 4-nitrophenyl, 4-hydroxy phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-aminophenyl, 4-dimethylamino phenyl, 2-hydroxy phenyl, 2-hydroxyl-3,5-dinitrophenyl, 3,5-3,5-dimethylphenyl, 3-aminomethyl phenyl or 2,4-dibromo phenyl.
Compared with prior art, the present invention has following beneficial effect:
The invention provides a kind of method of preparing aldehyde semicarbazone Schiff alkali, take aldehyde and semicarbazide hydrochloride as raw material, take Sulphanilic Acid as catalyzer, reaction generates aldehyde semicarbazone Schiff alkali, the method experimental implementation is simple, desired raw material is cheap and easy to get, required experimental installation is simple, reaction times is short, temperature of reaction is lower, aftertreatment is simple, the productive rate of target product is high, environmental protection, and its catalyzer used is recyclable, reusable, the filter cake of decompress filter is the catalyzer of recovery, the invention provides a kind of economical, green, the method of the synthetic aldehyde semicarbazone Schiff alkali of environmental protection, can meet industrial needs.
Further, the present invention puts into mortar by aldehyde and semicarbazide hydrochloride and at room temperature grinds evenly, the heat producing in process of lapping gets final product so that raw material starts to react, simple to operate, raw material is put into baking oven by mortar after being easy to reaction and grinding evenly, at 80～100 ℃, being incubated 30～60min can make product be fully dried, finally product is purified, make the productive rate of final aldehyde semicarbazone Schiff alkali can be up to more than 95%.
Embodiment
Synthetic route of the present invention is:
Wherein R=H ,-CH
3,-C
2h
5, n-C
3h
7, phenyl, furyl, thienyl, 3-nitrophenyl, 4-nitrophenyl, 4-hydroxy phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-aminophenyl, 4-dimethylamino phenyl, 2-hydroxy phenyl, 2-hydroxyl-3,5-dinitrophenyl, 3,5-3,5-dimethylphenyl, 3-aminomethyl phenyl, 2,4-dibromo phenyl.
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1:
1) in dry mortar, add 1mol aldehyde (R=H), 1mol semicarbazide hydrochloride and 0.1mol Sulphanilic Acid, at room temperature grind, raw material is mixed, and raw material is reacted, being ground to reaction, to carry out the completely required time be 20min, and now TLC detects the raw material point disappearance of finding aldehyde, and the developping agent of TLC is that volume ratio is the ethyl acetate of 1:3 and the mixed solvent of sherwood oil;
2) mortar is placed in to baking oven, at the temperature of 80 ℃, is incubated 30min; Then be cooled to room temperature, with absolute ethanol washing, decompress filter, filtrate is concentrated into dry, obtains target product 2-methene amido urea.Its productive rate reaches more than 95%, and structural formula is:
M.p.(fusing point)=120～123 ℃; IR(KBr, ν/cm
-1): 3458.23,3065.38,1648.10,1624.33,993.28.
Embodiment 2:
1) in dry mortar, add 1mol aldehyde (R=CH
3), 1mol semicarbazide hydrochloride and 0.2mol Sulphanilic Acid, at room temperature grind, raw material is mixed, and raw material is reacted, being ground to reaction, to carry out the completely required time be 12min, and now TLC detects the raw material point disappearance of finding aldehyde, and the developping agent of TLC is that volume ratio is the ethyl acetate of 1:3 and the mixed solvent of sherwood oil;
2) mortar is placed in to baking oven, at the temperature of 85 ℃, is incubated 50min; Then be cooled to room temperature, with absolute ethanol washing, decompress filter, filtrate is concentrated into dry, obtains target product 2-ethyleneimino urea.Its productive rate reaches more than 95%, and structural formula is:
M.p.=175～176℃；IR（KBr，ν/cm
-1）：3412.47，3283.62，3121.83，1679.49，402.71，325.25。
Embodiment 3:
1) in dry mortar, add 1mol aldehyde (R=phenyl), 1.1mol semicarbazide hydrochloride and 0.2mol Sulphanilic Acid, at room temperature grind, raw material is mixed, and raw material is reacted, being ground to reaction, to carry out the completely required time be 10min, and now TLC detects the raw material point disappearance of finding aldehyde, and the developping agent of TLC is that volume ratio is the ethyl acetate of 1:3 and the mixed solvent of sherwood oil;
2) mortar is placed in to baking oven, at the temperature of 80 ℃, is incubated 60min; Then be cooled to room temperature, with absolute ethanol washing, decompress filter, filtrate is concentrated into dry, obtains target product 2-(phenylmethylene)-Urea,amino-.Its productive rate reaches more than 95%, and structural formula is:
M.p.=220～222℃；IR（KBr，ν/cm
-1）：3401.89，3298.90，3059.38,1689.42，603.71，758.08，689.40。
Embodiment 4
1) in dry mortar, add 1mol aldehyde (R=C
2h
5), 1.2mol semicarbazide hydrochloride and 0.3mol Sulphanilic Acid, at room temperature grind, raw material is mixed, and raw material is reacted, being ground to reaction, to carry out the completely required time be 20min, and now TLC detects the raw material point disappearance of finding aldehyde, and the developping agent of TLC is that volume ratio is the ethyl acetate of 1:3 and the mixed solvent of sherwood oil;
2) mortar is placed in to baking oven, at the temperature of 100 ℃, is incubated 30min; Then be cooled to room temperature, with anhydrous methanol washing, decompress filter, filtrate is concentrated into dry, obtains target product 2-propionaldehyde semicarbazone.Its productive rate reaches more than 95%, and structural formula is:
Embodiment 5
1) in dry mortar, add 1mol aldehyde (R=furyl), 1.2mol semicarbazide hydrochloride and 0.1mol Sulphanilic Acid, at room temperature grind, raw material is mixed, and raw material is reacted, being ground to reaction, to carry out the completely required time be 15min, and now TLC detects the raw material point disappearance of finding aldehyde, and the developping agent of TLC is that volume ratio is the ethyl acetate of 1:3 and the mixed solvent of sherwood oil;
2) mortar is placed in to baking oven, at the temperature of 90 ℃, is incubated 40min; Then be cooled to room temperature, with anhydrous methanol washing, decompress filter, filtrate is concentrated into dry, obtains target product 2-(furfurylidene)-Urea,amino-.Its productive rate reaches more than 95%, and structural formula is:
Embodiment 6～22 is identical with step and the operating parameters of embodiment 1, and the raw material aldehyde that it adds and the product aldehyde semicarbazone Schiff alkali obtaining are specifically as shown in table 1.
Table 1
Claims (10)
1. a method of preparing aldehyde semicarbazone Schiff alkali, is characterized in that, comprises the following steps:
1) in dry reaction vessel, add a mol aldehyde, b mol semicarbazide hydrochloride and c mol Sulphanilic Acid, then raw material is mixed, and raw material is reacted, TLC detects until reaction is carried out completely, obtain mixture, wherein a:b:c=1:(1～1.2): (0.1～0.3);
2) mixture is incubated at the temperature of 80～100 ℃, is then cooled to room temperature, then washs, decompress filter, filtrate is concentrated into dry, obtains target product aldehyde semicarbazone Schiff alkali.
2. the method for preparing aldehyde semicarbazone Schiff alkali according to claim 1, is characterized in that: the structural formula of described aldehyde is: R-CHO,
Wherein, R=H ,-CH
3,-C
2h
5, n-C
3h
7, phenyl, furyl, thienyl, 3-nitrophenyl, 4-nitrophenyl, 4-hydroxy phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-aminophenyl, 4-dimethylamino phenyl, 2-hydroxy phenyl, 2-hydroxyl-3,5-dinitrophenyl, 3,5-3,5-dimethylphenyl, 3-aminomethyl phenyl or 2,4-dibromo phenyl.
3. the method for preparing aldehyde semicarbazone Schiff alkali according to claim 1 and 2, is characterized in that: described step 1) is at room temperature carried out.
4. the method for preparing aldehyde semicarbazone Schiff alkali according to claim 1 and 2, is characterized in that: described reaction vessel is mortar, by grinding, raw material is mixed, and raw material is reacted in described step 1).
5. the method for preparing aldehyde semicarbazone Schiff alkali according to claim 4, is characterized in that: described be ground to reaction and carry out that the required time is 10～20min completely.
6. the method for preparing aldehyde semicarbazone Schiff alkali according to claim 1 and 2, it is characterized in that: described TLC detects until reaction refers to the raw material point disappearance that aldehyde detected completely, and wherein the developping agent of TLC is that volume ratio is the ethyl acetate of 1:3 and the mixed solvent of sherwood oil.
7. the method for preparing aldehyde semicarbazone Schiff alkali according to claim 1 and 2, is characterized in that: described step 2) in soaking time be 30～60min.
8. the method for preparing aldehyde semicarbazone Schiff alkali according to claim 1 and 2, is characterized in that: described step 2) in insulation in baking oven, carry out.
9. the method for preparing aldehyde semicarbazone Schiff alkali according to claim 1 and 2, is characterized in that: the cleaning solvent in described step 3) is dehydrated alcohol or anhydrous methanol.
10. the method for preparing aldehyde semicarbazone Schiff alkali according to claim 1 and 2, is characterized in that: the structural formula of the aldehyde semicarbazone Schiff alkali making is:
Wherein, R=H ,-CH
3,-C
2h
5, n-C
3h
7, phenyl, furyl, thienyl, 3-nitrophenyl, 4-nitrophenyl, 4-hydroxy phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-aminophenyl, 4-dimethylamino phenyl, 2-hydroxy phenyl, 2-hydroxyl-3,5-dinitrophenyl, 3,5-3,5-dimethylphenyl, 3-aminomethyl phenyl or 2,4-dibromo phenyl.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175312A (en) * | 2015-08-28 | 2015-12-23 | 陕西科技大学 | 1-substituted-2-(carbazole-9-yl-acetic acid)-hydrazide Schiff base and preparation method thereof |
| CN107024473A (en) * | 2017-05-15 | 2017-08-08 | 北京长江脉医药科技有限责任公司 | A kind of O-phthalaldehyde disinfectant concentration quick detection test paper and preparation method and application |
| CN115974728A (en) * | 2022-12-29 | 2023-04-18 | 陕西科技大学 | Synthesis of phenyl semicarbazone and identification of hexavalent chromium ions by phenyl semicarbazone |
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| WO1994006758A1 (en) * | 1992-09-21 | 1994-03-31 | University Of Saskatchewan | Aryl semicarbazone anticonvulsants |
| CN1220988A (en) * | 1997-12-24 | 1999-06-30 | 南京大学 | Method for synthesising schiff base in the absence of solvent |
| CN101050192A (en) * | 2007-05-11 | 2007-10-10 | 江南大学 | Method for synthesizing semicarbazide c,p - aldehyde group benzoic acid of derivative of semicarbazide |
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2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4727024A (en) * | 1986-05-12 | 1988-02-23 | Martin Koocher | Binding assays involving formation and detection of light scattering crystals |
| WO1994006758A1 (en) * | 1992-09-21 | 1994-03-31 | University Of Saskatchewan | Aryl semicarbazone anticonvulsants |
| CN1220988A (en) * | 1997-12-24 | 1999-06-30 | 南京大学 | Method for synthesising schiff base in the absence of solvent |
| CN101050192A (en) * | 2007-05-11 | 2007-10-10 | 江南大学 | Method for synthesizing semicarbazide c,p - aldehyde group benzoic acid of derivative of semicarbazide |
Non-Patent Citations (2)
| Title |
|---|
| KIASAT, ALI REZA ET AL: "Synthesis of semicarbazones from carbonyl compounds under solvent free conditions", 《ASIAN JOURNAL OF CHEMISTRY》 * |
| 贤景春等: "5-溴水杨醛缩氨基脲及其钴配合物的合成", 《泉州师范学院学报自然科学版》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175312A (en) * | 2015-08-28 | 2015-12-23 | 陕西科技大学 | 1-substituted-2-(carbazole-9-yl-acetic acid)-hydrazide Schiff base and preparation method thereof |
| CN107024473A (en) * | 2017-05-15 | 2017-08-08 | 北京长江脉医药科技有限责任公司 | A kind of O-phthalaldehyde disinfectant concentration quick detection test paper and preparation method and application |
| CN107024473B (en) * | 2017-05-15 | 2019-06-25 | 北京长江脉医药科技有限责任公司 | A kind of O-phthalaldehyde disinfectant concentration quick detection test paper and the preparation method and application thereof |
| CN115974728A (en) * | 2022-12-29 | 2023-04-18 | 陕西科技大学 | Synthesis of phenyl semicarbazone and identification of hexavalent chromium ions by phenyl semicarbazone |
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Application publication date: 20140625 |