CN106478742A - A kind of bisoxazoline containing ferrocenyl and preparation method thereof - Google Patents
A kind of bisoxazoline containing ferrocenyl and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of bisoxazoline containing ferrocenyl and preparation method thereof.Add A mol ferrocenyl semicarbazides Schiff and B mL glacial acetic acid in the there-necked flask with reflux condensing tube being dried, and add manganese dioxide as catalyst, back flow reaction is complete to reaction, wherein A:B=1:(60～100), reaction terminates rear sucking filtration and removes catalyst, and filtrate is cooled to room temperature, sucking filtration again after standing, obtains acicular crystal, as bisoxazoline containing ferrocenyl after the filtration cakes torrefaction of secondary sucking filtration.The present invention is simple to operate, and the response time is short, and reaction condition is gentle, and equipment requirements are low, and post processing is simple, and catalyst is cheap and easy to get simultaneously.The present invention is prepared for a series of heterocyclic compound of bisoxazoline containing ferrocenyl of brand news, provides more more options for finding such compound with biological activity, the development and application to such compound provides beneficial help.
Description
Technical field
The invention belongs to the field of chemical synthesis, particularly to a kind of bisoxazoline containing ferrocenyl and preparation method thereof.
Background technology
Ferrocene has preferable biological activity in itself, has preferably antibacterial, anticancer and hypotoxicity, therefore in medicine neck
Domain has important effect.Ferrocene derivatives also have the features such as armaticity, hypotoxicity, stability, are good liquid crystal materials
Material, conductive material and magnetic material, particularly cause people very big in materials chemistry, electrochemistry, asymmetric synthesis chemistry
Interest.Schiff cyclic compound containing heterocycle not only has the biological activitys such as anticancer, antiviral, sterilization, and is also
The good extractant of the metal ions such as rare earth, thus about to the synthesis of new Schiff cyclic compound and performance study being
One of most active object of study at present.
Bisoxazoline class compound is widely used in the fields such as medicine, pesticide due to its good biological activity, by two
Oxazoline heterocycle is introduced in other compounds, tends to generate a series of noval chemical compounds with extensive biological activity.Therefore, new
In medicine design, bisoxazoline heterocycle is commonly used for the structural modification of compound.But the synthesis bisoxazoline of report is closed at present
One-tenth method, its catalyst is relatively costly, relatively low containing heavy metal, pollution environment, yield, is partly synthesized using acyl chlorides, harm
Larger, also electrochemically synthesized, its cost is also higher.
Content of the invention
It is an object of the invention to provide a kind of bisoxazoline containing ferrocenyl and preparation method thereof, the method has operation
Simply, reaction condition is gentle, and the response time is short, and post processing is simple, the advantages of yield is higher.
For reaching above-mentioned purpose, the technical solution used in the present invention is：
A kind of bisoxazoline containing ferrocenyl, shown in its general structure such as formula (1)：
Wherein, R be phenyl, o-hydroxy-phenyl, a hydroxy phenyl, p-hydroxybenzene, to N, N- dimethylaminophenyl, right
Fluorophenyl, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl, a bromophenyl, p-bromophenyl, 2,4- dibromobenzene
Base, adjacent aminophenyl, m-aminophenyl base, p-aminophenyl, O-Nitrophenylfluorone, m-nitro base, p-nitrophenyl, 3,5- dinitro
Base phenyl, o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, to methoxybenzene
Base, furyl, thienyl, 3- pyridine radicals or 4- pyridine radicals.
A kind of preparation method containing ferrocenyl bisoxazoline, comprises the following steps that：
A mol ferrocenyl semicarbazides Schiff and B mL glacial acetic acid, A is added in reaction vessel:B=1:(60～
100), and add manganese dioxide as catalyst, it is heated to reflux to reaction completely, then sucking filtration, remove catalyst, filtrate cools down
Carry out standing sucking filtration again to room temperature, obtain acicular crystal by after the filtration cakes torrefaction of secondary sucking filtration, as containing ferrocenyl
Bisoxazoline.
Shown in the general structure such as formula (2) of described ferrocenyl semicarbazides Schiff：
Wherein, R be phenyl, o-hydroxy-phenyl, a hydroxy phenyl, p-hydroxybenzene, to N, N- dimethylaminophenyl, right
Fluorophenyl, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl, a bromophenyl, p-bromophenyl, 2,4- dibromobenzene
Base, adjacent aminophenyl, m-aminophenyl base, p-aminophenyl, O-Nitrophenylfluorone, m-nitro base, p-nitrophenyl, 3,5- dinitro
Base phenyl, o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, to methoxybenzene
Base, furyl, thienyl, 3- pyridine radicals or 4- pyridine radicals.
The preparation method of described ferrocenyl semicarbazides Schiff comprises the following steps：
1) weigh a mol ferrocenyl methyl ketone to be placed in mortar, add b mol NaOH solid, mix homogeneously, add c
Mol aldehyde compound, mixed grinding is reacted, and with TLC board monitoring to reacting completely, the solid that reaction is obtained washs, takes out
Filter, filter cake is dried, that is, obtain biferrocenyl chalcone class compound；Wherein a:b:C=1:(1.7～2.2):(0.9～
1.2)；The structural formula of aldehyde compound is RCHO, and wherein R is phenyl, o-hydroxy-phenyl, a hydroxy phenyl, p-hydroxybenzene, right
N, N- dimethylaminophenyl, to fluorophenyl, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl, a bromophenyl,
P-bromophenyl, 2,4- dibromo phenyl, adjacent aminophenyl, m-aminophenyl base, p-aminophenyl, O-Nitrophenylfluorone, m-nitro base,
P-nitrophenyl, 3,5- dinitrophenyl, o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, a first
Phenyl, p-methoxyphenyl, furyl, thienyl, 3- pyridine radicals or 4- pyridine radicals；
2) d mol biferrocenyl chalcone, e mol semicarbazides and f mL are added in the there-necked flask with reflux condensing tube
Dehydrated alcohol, is subsequently adding glacial acetic acid and adjusts pH=4, carry out heating reflux reaction, reacted with TLC board monitoring, after reaction 6～8h
Cooling separates out solid, sucking filtration, and filter cake is vacuum dried, that is, obtain ferrocenyl semicarbazides Schiff；Wherein d:E=1:(1.2～
1.6), d:F=1:(50～100).
The consumption of described catalyst is C mol, A:C=1:(0.2～0.5).
The temperature of described back flow reaction is 115～125 DEG C, and the time reacting completely required is 1～1.2h.
Described back flow reaction process is monitored with TLC, when the raw material point of ferrocenyl semicarbazides Schiff disappears
When represent reaction completely, the developing solvent of described TLC is volume ratio is 10:1 dichloromethane and the mixed liquor of methanol.
With respect to prior art, beneficial effects of the present invention are：
The preparation method containing ferrocenyl bisoxazoline that the present invention provides, with ferrocenyl semicarbazides Schiff and ice
Acetic acid is raw material, using common manganese dioxide as catalyst, containing ferrocenyl diazole is obtained by the way of being heated to reflux
Quinoline., compared with traditional methodology of organic synthesis, reaction condition is gentle for the present invention, and operating process is simple, and the response time is short, after reaction
Process simple, yield is higher, and environmental pollution is little, and catalyst is cheap and easy to get.
The present invention is prepared for a series of heterocyclic compound of bisoxazoline containing ferrocenyl of brand news, has life for finding
Such compound of thing activity provides more more options, and the development and application to such compound provides beneficial help.
Brief description
Fig. 1 is the infrared spectrum of the diphenylphosphino ferrocene base bisoxazoline that embodiment 1 is obtained；
Fig. 2 is the infrared spectrum of the o-hydroxy-phenyl ferrocenyl bisoxazoline that embodiment 2 is obtained；
Fig. 3 is the infrared spectrum to dimethylamino phenyl ferrocenyl bisoxazoline that embodiment 3 is obtained；
Fig. 4 is the infrared spectrum of the rubigan ferrocenyl bisoxazoline that embodiment 4 is obtained；
Fig. 5 is the infrared spectrum of the p-bromophenyl ferrocenyl bisoxazoline that embodiment 5 is obtained.
Specific embodiment
With reference to the accompanying drawings and examples the present invention is described in further details.
The present invention is with ferrocenyl semicarbazides Schiff and glacial acetic acid as raw material, with manganese dioxide as catalyst, plus
Hot reflux, prepares a series of bisoxazoline containing ferrocenyl, shown in its reaction equation such as formula (3).
Wherein, R be phenyl, o-hydroxy-phenyl, a hydroxy phenyl, p-hydroxybenzene, to N, N- dimethylaminophenyl, right
Fluorophenyl, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl, a bromophenyl, p-bromophenyl, 2,4- dibromobenzene
Base, adjacent aminophenyl, m-aminophenyl base, p-aminophenyl, O-Nitrophenylfluorone, m-nitro base, p-nitrophenyl, 3,5- dinitro
Base phenyl, o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, to methoxybenzene
Base, furyl, thienyl, 3- pyridine radicals or 4- pyridine radicals.
Embodiment 1
The synthesis of 1- ferrocenyl -3- phenyl -2- propenone semicarbazides Schiff：
1) weigh 0.5mmol ferrocenyl methyl ketone to be placed in mortar, addition 1mmol NaOH solid, mix homogeneously, then plus
Enter 0.5mmol aldehyde compound RCHO (R is phenyl), mixed grinding, be monitored with TLC plate, to reacting completely, by gained
Solids washed with water, sucking filtration, filter cake is dried, obtains biferrocenyl chalcone class compound；
2) add 0.4mmol biferrocenyl chalcone class compound in the there-necked flask with reflux condensing tube,
0.56mmol semicarbazides and 30mL dehydrated alcohol, add glacial acetic acid to adjust pH=4, are heated to reflux, reacted with TLC board monitoring, instead
After answering 7h, cooling separates out solid, sucking filtration, and filter cake is vacuum dried, and obtains 1- ferrocenyl -3- phenyl -2- propenone semicarbazides
Schiff.
The synthesis of diphenylphosphino ferrocene base bisoxazoline：
To be dried the 250mL there-necked flask with reflux condensing tube in add 0.35mmol 1- ferrocenyl -3- phenyl -
2- propenone semicarbazides Schiff, the glacial acetic acid of 25mL and 0.14mmol manganese dioxide, after three's mix homogeneously, are warming up to
With test reaction whether completely 120 DEG C carry out back flow reaction, carry out TLC point plate every half an hour, reaction takes 1h completely.Instead
Sucking filtration after should terminating, removes catalyst, and filtrate is cooled to room temperature, stands sucking filtration, filter cake obtains orange after being dried at room temperature for
Color acicular crystal, as diphenylphosphino ferrocene base bisoxazoline.
IR(KBr,v/cm-1):3403.10(N-H)；(2927.26,2856.06 saturation C-H)；1579.27 (unsaturated C=
C vibrates)；(1418.81 phenyl ring skeletal vibration)；(1343.84 methyl C-H bending vibration)；1188.26,1037.85 (luxuriant ring shakes
Dynamic absworption peak)；(1126.11 C-O-C stretching vibration)；814.96 (monosubstituted phenyl ring C-H bending vibrations).
Fig. 1 is the diphenylphosphino ferrocene base bisoxazoline IR spectrogram that embodiment 1 is obtained, as shown in Figure 1：3403.10cm-1Place can
Can be the vibration absorption peak of N-H, and in 2927.26cm-1, 2856.06cm-1Place may be the absorption of saturation C-H stretching vibration
Peak, 1579.27cm-1The peak at place may be unsaturated C=C absworption peak, 1418.81cm-1The peak at place may be the absorption of Ar-H
Peak, 1343.84cm-1Place may be methyl C-H bending vibration absworption peak, 1188.26cm-1And 1037.85cm-1Place may be cyclopentadienyl
Ring vibration absworption peak, 1126.11cm-1Place may be diazole C-O-C stretching vibration absworption peak, 814.96cm-1Place may be for taking
For phenyl ring C-H bending vibration absworption peak.In sum it can be verified that synthesis has obtained diphenylphosphino ferrocene base bisoxazoline.
Embodiment 2
The synthesis of 1- ferrocenyl -3- (2- hydroxy phenyl) -2- propenone semicarbazides Schiff：
1) weigh 0.5mmol ferrocenyl methyl ketone to be placed in mortar, addition 1mmol NaOH solid, mix homogeneously, then plus
Enter 0.5mmol aldehyde compound RCHO (R is 2- hydroxy phenyl), mixed grinding, be monitored with TLC plate, to reacting completely, will
The solids washed with water of gained, sucking filtration, filter cake is dried, obtains biferrocenyl chalcone class compound；
2) add 0.4mmol biferrocenyl chalcone class compound in the there-necked flask with reflux condensing tube,
0.56mmol semicarbazides and 30mL dehydrated alcohol, add glacial acetic acid to adjust pH=4, are heated to reflux, reacted with TLC board monitoring, instead
After answering 7h, cooling separates out solid, sucking filtration, and filter cake is vacuum dried, and obtains 1- ferrocenyl -3- (2- hydroxy phenyl) -2- propenone ammonia
Base urea Schiff.
The synthesis of o-hydroxy-phenyl ferrocenyl bisoxazoline：
1- ferrocenyl -3- (the 2- hydroxyl of 0.26mmol is added in the 250mL there-necked flask with reflux condensing tube being dried
Base phenyl) -2- propenone semicarbazides Schiff, the glacial acetic acid of 25mL and 0.104mmol manganese dioxide, treat three's mix homogeneously
Afterwards, it is warming up to 120 DEG C and carries out back flow reaction, with test reaction whether completely to carry out TLC point plate every half an hour, reaction is completely
Time-consuming 1h.Reaction terminates rear sucking filtration, removes catalyst, and filtrate is cooled to room temperature, stands sucking filtration, after filter cake is dried at room temperature for
Obtain brown color acicular crystal, as o-hydroxy-phenyl ferrocenyl bisoxazoline.
IR(KBr,v/cm-1):3399.93(O-H)；(2929.79,2857.44 saturation C-H)；1557.84 (unsaturated C=
C vibrates)；(1396.48 phenyl ring skeletal vibration)；(1343.63 methyl C-H bending vibration)；1188.15,1035.19 (luxuriant ring shakes
Dynamic absworption peak)；(1126.56 C-O-C stretching vibration)；764.04 (1,2- substituted benzene ring C-H bending vibrations).
Fig. 2 is the o-hydroxy-phenyl ferrocenyl bisoxazoline IR spectrogram that embodiment 2 is obtained, as shown in Figure 2：
3399.93cm-1Place may be the vibration absorption peak of O-H, and in 2929.79cm-1, 2857.44cm-1Place may stretch for saturation C-H
The absworption peak of contracting vibration, 1557.84cm-1The peak at place may be unsaturated C=C absworption peak, 1396.48cm-1The peak at place may be
The absworption peak of Ar-H, 1343.63cm-1Place may be methyl C-H bending vibration absworption peak, 1188.15cm-1And 1035.19cm-1
Place may be luxuriant ring vibration absworption peak, 1126.56cm-1Place may be diazole C-O-C stretching vibration absworption peak, 764.04cm-1
Place may be 1,2- substituted benzene ring C-H bending vibration absworption peak.In sum it can be verified that synthesis has obtained adjacent hydroxyl ferrocene
Base bisoxazoline.
Embodiment 3
The synthesis of 1- ferrocenyl -3- (4-N, N- dimethylamino phenyl) -2- propenone semicarbazides Schiff：
1) weigh 0.5mmol ferrocenyl methyl ketone to be placed in mortar, addition 1mmol NaOH solid, mix homogeneously, then plus
Enter 0.5mmol aldehyde compound RCHO (R be 4-N, N- dimethylamino phenyl), mixed grinding, be monitored with TLC plate, to anti-
Completely by the solids washed with water of gained, sucking filtration, filter cake should be dried, obtain biferrocenyl chalcone class compound；
2) add 0.4mmol biferrocenyl chalcone class compound in the there-necked flask with reflux condensing tube,
0.56mmol semicarbazides and 30mL dehydrated alcohol, add glacial acetic acid to adjust pH=4, are heated to reflux, reacted with TLC board monitoring, instead
After answering 7h, cooling separates out solid, sucking filtration, and filter cake is vacuum dried, and obtains 1- ferrocenyl -3- (4-N, N- dimethylamino phenyl) -2-
Propenone semicarbazides Schiff.
Synthesis to dimethylamino phenyl ferrocenyl bisoxazoline：
To be dried the 250mL there-necked flask with reflux condensing tube in add 0.29mmol 1- ferrocenyl -3- (4-N,
N- dimethylamino phenyl) -2- propenone semicarbazides Schiff, the glacial acetic acid of 25mL and 0.116mmol manganese dioxide, treat three
After mix homogeneously, it is warming up to 120 DEG C and carries out back flow reaction, with test reaction whether completely to carry out TLC point plate every half an hour,
Reaction takes 1h completely.Reaction terminates rear sucking filtration, removes catalyst, and filtrate is cooled to room temperature, stands sucking filtration, filter cake is in room temperature
Orange-yellow acicular crystal is obtained, as to dimethylamino phenyl ferrocenyl bisoxazoline after lower drying.
IR(KBr,v/cm-1):3397.72(N-H)；(1572.54 unsaturated C=C vibration)；1417.16 (phenyl ring skeleton shakes
Dynamic)；(1343.59 methyl C-H bending vibration)；(1189.61,1035.32 luxuriant ring vibration absworption peak)；1125.47 (C-O-C stretches
Contracting vibration)；814.06 (1,4- substituted benzene ring C-H bending vibrations).
Fig. 3 be embodiment 3 be obtained to dimethylamino phenyl ferrocenyl bisoxazoline IR spectrogram, as shown in Figure 3：
3397.72cm-1Place may be the vibration absorption peak of N-H, 1572.54cm-1The peak at place may be unsaturated C=C absworption peak,
1417.16cm-1The peak at place may be the absworption peak of Ar-H, 1343.59cm-1Place may be methyl C-H bending vibration absworption peak,
1189.61cm-1And 1035.32cm-1Place may be luxuriant ring vibration absworption peak, 1125.47cm-1Place may stretch for diazole C-O-C
Contracting vibration absorption peak, 814.06cm-1Place may be 1,4- substituted benzene ring C-H bending vibration absworption peak.In sum it can be verified that
Synthesis has obtained to dimethylamino ferrocenyl bisoxazoline.
Embodiment 4
The synthesis of 1- ferrocenyl -3- (4- chlorphenyl) -2- propenone semicarbazides Schiff：
1) weigh 0.5mmol ferrocenyl methyl ketone to be placed in mortar, addition 1mmol NaOH solid, mix homogeneously, then plus
Enter 0.5mmol aldehyde compound RCHO (R is rubigan), mixed grinding, be monitored with TLC plate, to reacting completely, by institute
The solids washed with water obtaining, sucking filtration, filter cake is dried, obtains biferrocenyl chalcone class compound；
2) add 0.4mmol biferrocenyl chalcone class compound in the there-necked flask with reflux condensing tube,
0.56mmol semicarbazides and 30mL dehydrated alcohol, add glacial acetic acid to adjust pH=4, are heated to reflux, reacted with TLC board monitoring, instead
After answering 7h, cooling separates out solid, sucking filtration, and filter cake is vacuum dried, and obtains 1- ferrocenyl -3- (4- chlorphenyl) -2- propenone amino
Urea Schiff.
The synthesis of rubigan ferrocenyl bisoxazoline：
1- ferrocenyl -3- (the 4- chlorine of 0.26mmol is added in the 250mL there-necked flask with reflux condensing tube being dried
Phenyl) -2- propenone semicarbazides Schiff, the glacial acetic acid of 25mL and 0.104mmol manganese dioxide, treat three's mix homogeneously
Afterwards, it is warming up to 120 DEG C and carries out back flow reaction, with test reaction whether completely to carry out TLC point plate every half an hour, reaction is completely
Time-consuming 1h.Reaction terminates rear sucking filtration, removes catalyst, and filtrate is cooled to room temperature, stands sucking filtration, after filter cake is dried at room temperature for
Obtain brown color acicular crystal, as rubigan ferrocenyl bisoxazoline.
IR(KBr,v/cm-1):3248.93(N-H)；(2926.80,2855.72 saturation C-H)；1611.82 (unsaturated C=
C vibrates)；(1396.22 phenyl ring skeletal vibration)；(1342.44 methyl C-H bending vibration)；1180.46,1032.84 (luxuriant ring shakes
Dynamic absworption peak)；(1124.34 C-O-C stretching vibration)；814.99 (1,4- substituted benzene ring C-H bending vibrations)；730.10(C-
Cl).
Fig. 4 is the rubigan ferrocenyl bisoxazoline IR spectrogram that embodiment 4 is obtained, as shown in Figure 4：3248.93cm-1
Place may be the vibration absorption peak of N-H, and in 2926.80cm-1, 2855.72cm-1Place may be the suction of saturation C-H stretching vibration
Receive peak, 1611.82cm-1The peak at place may be unsaturated C=C absworption peak, 1396.22cm-1The peak at place may be the absorption of Ar-H
Peak, 1342.44cm-1Place may be methyl C-H bending vibration absworption peak, 1180.46cm-1And 1032.84cm-1Place may be cyclopentadienyl
Ring vibration absworption peak, 1124.34cm-1Place may be diazole C-O-C stretching vibration absworption peak, 814.99cm-1Place may be 1,
4- substituted benzene ring C-H bending vibration absworption peak, 730.10cm-1Place may be C-Cl absworption peak.In sum it can be verified that synthesizing
Obtain rubigan ferrocenyl bisoxazoline.
Embodiment 5
The synthesis of 1- ferrocenyl -3- (4- bromophenyl) -2- propenone semicarbazides Schiff：
1) weigh 0.5mmol ferrocenyl methyl ketone to be placed in mortar, addition 1mmol NaOH solid, mix homogeneously, then plus
Enter 0.5mmol aldehyde compound RCHO (R is p-bromophenyl), mixed grinding, be monitored with TLC plate, to reacting completely, by institute
The solids washed with water obtaining, sucking filtration, filter cake is dried, obtains biferrocenyl chalcone class compound；
2) add 0.4mmol biferrocenyl chalcone class compound in the there-necked flask with reflux condensing tube,
0.56mmol semicarbazides and 30mL dehydrated alcohol, add glacial acetic acid to adjust pH=4, are heated to reflux, reacted with TLC board monitoring, instead
After answering 7h, cooling separates out solid, sucking filtration, and filter cake is vacuum dried, and obtains 1- ferrocenyl -3- (4- bromophenyl) -2- propenone amino
Urea Schiff.
The synthesis of p-bromophenyl ferrocenyl bisoxazoline：
1- ferrocenyl -3- (the 4- bromine of 0.37mmol is added in the 250mL there-necked flask with reflux condensing tube being dried
Phenyl) -2- propenone semicarbazides Schiff, the glacial acetic acid of 25mL and 0.148mmol manganese dioxide, treat three's mix homogeneously
Afterwards, it is warming up to 120 DEG C and carries out back flow reaction, with test reaction whether completely to carry out TLC point plate every half an hour, reaction is completely
Time-consuming 1h.Reaction terminates rear sucking filtration, removes catalyst, and filtrate is cooled to room temperature, stands sucking filtration, after filter cake is dried at room temperature for
Obtain orange-yellow acicular crystal, as p-bromophenyl ferrocenyl bisoxazoline.
IR(KBr,v/cm-1):3407.07(N-H)；(2929.88 saturation C-H)；(1594.61 unsaturated C=C vibration)；
(1410.66 phenyl ring skeletal vibration)；(1345.81 methyl C-H bending vibration)；1188.75,1038.88 (luxuriant ring vibration absorbs
Peak)；(1126.29 C-O-C stretching vibration)；815.24 (1,4- substituted benzene ring C-H bending vibrations)；568.43(C-Br).
Fig. 5 is the p-bromophenyl ferrocenyl bisoxazoline IR spectrogram that embodiment 5 is obtained, as shown in Figure 5：3407.07cm-1
Place may be the vibration absorption peak of N-H, and in 2929.88cm-1Place may be the absworption peak of saturation C-H stretching vibration,
1594.61cm-1The peak at place may be unsaturated C=C absworption peak, 1410.66cm-1The peak at place may be the absworption peak of Ar-H,
1345.81cm-1Place may be methyl C-H bending vibration absworption peak, 1188.75cm-1And 1038.88cm-1Place may shake for luxuriant ring
Dynamic absworption peak, 1126.29cm-1Place may be diazole C-O-C stretching vibration absworption peak, 815.24cm-1Place may take for 1,4-
For phenyl ring C-H bending vibration absworption peak, 568.43cm-1Place may be C-Br absworption peak.In sum it can be verified that synthesis obtains
P-bromophenyl ferrocenyl bisoxazoline.
Embodiment 6
The synthesis of 1- ferrocenyl -3- (2- aminophenyl) -2- propenone semicarbazides Schiff：
1) weigh 0.5mmol ferrocenyl methyl ketone to be placed in mortar, addition 0.85mmol NaOH solid, mix homogeneously, then
Add 0.45mmol aldehyde compound RCHO (R be adjacent aminophenyl), mixed grinding, be monitored with TLC plate, to having reacted
Entirely, by the solids washed with water of gained, sucking filtration, filter cake is dried, obtains biferrocenyl chalcone class compound；
2) add 0.4mmol biferrocenyl chalcone class compound in the there-necked flask with reflux condensing tube,
0.48mmol semicarbazides and 20mL dehydrated alcohol, add glacial acetic acid to adjust pH=4, are heated to reflux, reacted with TLC board monitoring, instead
After answering 6h, cooling separates out solid, sucking filtration, and filter cake is vacuum dried, and obtains 1- ferrocenyl -3- (2- aminophenyl) -2- propenone ammonia
Base urea Schiff.
The synthesis of adjacent aminophenyl ferrocenyl bisoxazoline：
1- ferrocenyl -3- (the 2- ammonia of 0.3mmol is added in the 250mL there-necked flask with reflux condensing tube being dried
Base phenyl) -2- propenone semicarbazides Schiff, the glacial acetic acid of 18mL and 0.06mmol manganese dioxide, treat three's mix homogeneously
Afterwards, it is warming up to 115 DEG C and carries out back flow reaction, with test reaction whether completely to carry out TLC point plate every half an hour, reaction is completely
Time-consuming 1.1h.Reaction terminates rear sucking filtration, removes catalyst, and filtrate is cooled to room temperature, stands sucking filtration, and filter cake is dried at room temperature for
After obtain adjacent aminophenyl ferrocenyl bisoxazoline.
Embodiment 7
The synthesis of 1- ferrocenyl -3- (2- nitrobenzophenone) -2- propenone semicarbazides Schiff：
1) weigh 0.5mmol ferrocenyl methyl ketone to be placed in mortar, addition 1.1mmol NaOH solid, mix homogeneously, then
Add 0.6mmol aldehyde compound RCHO (R is O-Nitrophenylfluorone), mixed grinding, be monitored with TLC plate, complete to reacting,
By the solids washed with water of gained, sucking filtration, filter cake is dried, obtains biferrocenyl chalcone class compound；
2) add 0.4mmol biferrocenyl chalcone class compound in the there-necked flask with reflux condensing tube,
0.64mmol semicarbazides and 40mL dehydrated alcohol, add glacial acetic acid to adjust pH=4, are heated to reflux, reacted with TLC board monitoring, instead
After answering 8h, cooling separates out solid, sucking filtration, and filter cake is vacuum dried, and obtains 1- ferrocenyl -3- (2- nitrobenzophenone) -2- propenone ammonia
Base urea Schiff.
Synthesis to O-Nitrophenylfluorone ferrocenyl bisoxazoline：
1- ferrocenyl -3- (the 2- nitre of 0.3mmol is added in the 250mL there-necked flask with reflux condensing tube being dried
Base phenyl) -2- propenone semicarbazides Schiff, the glacial acetic acid of 30mL and 0.15mmol manganese dioxide, treat three's mix homogeneously
Afterwards, it is warming up to 125 DEG C and carries out back flow reaction, with test reaction whether completely to carry out TLC point plate every half an hour, reaction is completely
Time-consuming 1.2h.Reaction terminates rear sucking filtration, removes catalyst, and filtrate is cooled to room temperature, stands sucking filtration, and filter cake is dried at room temperature for
After obtain to O-Nitrophenylfluorone ferrocenyl bisoxazoline.
Embodiment 8
The synthesis of 1- ferrocenyl -3- (3- methoxyphenyl) -2- propenone semicarbazides Schiff：
1) weigh 0.5mmol ferrocenyl methyl ketone to be placed in mortar, addition 0.95mmol NaOH solid, mix homogeneously, then
Add 0.55mmol aldehyde compound RCHO (R be m-methoxyphenyl), mixed grinding, be monitored with TLC plate, to having reacted
Entirely, by the solids washed with water of gained, sucking filtration, filter cake is dried, obtains biferrocenyl chalcone class compound；
2) add 0.4mmol biferrocenyl chalcone class compound in the there-necked flask with reflux condensing tube,
0.52mmol semicarbazides and 25mL dehydrated alcohol, add glacial acetic acid to adjust pH=4, are heated to reflux, reacted with TLC board monitoring, instead
After answering 6.5h, cooling separates out solid, sucking filtration, and filter cake is vacuum dried, and obtains 1- ferrocenyl -3- (3- methoxyphenyl) -2- propylene
Ketone semicarbazides Schiff.
The synthesis of m-methoxyphenyl ferrocenyl bisoxazoline：
1- ferrocenyl -3- (the 3- first of 0.3mmol is added in the 250mL there-necked flask with reflux condensing tube being dried
Phenyl) -2- propenone semicarbazides Schiff, the glacial acetic acid of 22mL and 0.08mmol manganese dioxide, treat three's mixing all
After even, it be warming up to 118 DEG C and carry out back flow reaction, with test reaction whether completely to carry out TLC point plate every half an hour, reacted
Entirely take 1.05h.Reaction terminates rear sucking filtration, removes catalyst, and filtrate is cooled to room temperature, stands sucking filtration, filter cake is at room temperature
M-methoxyphenyl ferrocenyl bisoxazoline is obtained after drying.
Embodiment 9
The synthesis of 1- ferrocenyl -3- (4- aminomethyl phenyl) -2- propenone semicarbazides Schiff：
1) weigh 0.5mmol ferrocenyl methyl ketone to be placed in mortar, addition 1.05mmol NaOH solid, mix homogeneously, then
Add 0.52mmol aldehyde compound RCHO (R be p-methylphenyl), mixed grinding, be monitored with TLC plate, to having reacted
Entirely, by the solids washed with water of gained, sucking filtration, filter cake is dried, obtains biferrocenyl chalcone class compound；
2) 0.4mmol biferrocenyl chalcone class compound, 0.6mmol are added in the there-necked flask with reflux condensing tube
Semicarbazides and 35mL dehydrated alcohol, add glacial acetic acid to adjust pH=4, are heated to reflux, reacted with TLC board monitoring, after reaction 7.5h,
Cooling separates out solid, sucking filtration, and filter cake is vacuum dried, and obtains 1- ferrocenyl -3- (4- aminomethyl phenyl) -2- propenone semicarbazides
Schiff.
The synthesis of p-methylphenyl ferrocenyl bisoxazoline：
1- ferrocenyl -3- (the 4- first of 0.3mmol is added in the 250mL there-necked flask with reflux condensing tube being dried
Base phenyl) -2- propenone semicarbazides Schiff, the glacial acetic acid of 27mL and 0.1mmol manganese dioxide, treat three's mix homogeneously
Afterwards, it is warming up to 122 DEG C and carries out back flow reaction, with test reaction whether completely to carry out TLC point plate every half an hour, reaction is completely
Time-consuming 1.15h.Reaction terminates rear sucking filtration, removes catalyst, and filtrate is cooled to room temperature, stands sucking filtration, and filter cake is done at room temperature
P-methylphenyl ferrocenyl bisoxazoline is obtained after dry.
The above, be only presently preferred embodiments of the present invention, not the present invention imposed any restrictions, every according to the present invention
Any simple modification, change and equivalent structure transformation that technical spirit is made to above example, all still fall within skill of the present invention
In the protection domain of art scheme.
Claims (7)
1. a kind of bisoxazoline containing ferrocenyl it is characterised in that：Shown in its general structure such as formula (1)：
Wherein, R be phenyl, o-hydroxy-phenyl, a hydroxy phenyl, p-hydroxybenzene, to N, N- dimethylaminophenyl, to fluorobenzene
Base, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl, a bromophenyl, p-bromophenyl, 2,4- dibromo phenyl, neighbour
Aminophenyl, m-aminophenyl base, p-aminophenyl, O-Nitrophenylfluorone, m-nitro base, p-nitrophenyl, 3,5- dinitro benzene
Base, o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, furan
Mutter base, thienyl, 3- pyridine radicals or 4- pyridine radicals.
2. a kind of preparation method containing ferrocenyl bisoxazoline is it is characterised in that comprise the following steps that：
A mol ferrocenyl semicarbazides Schiff and B mL glacial acetic acid, A is added in reaction vessel:B=1:(60～100),
And add manganese dioxide as catalyst, and it is heated to reflux to reaction completely, then sucking filtration, remove catalyst, filtrate is cooled to room
Carry out standing sucking filtration again after temperature, obtain acicular crystal by after the filtration cakes torrefaction of secondary sucking filtration, as containing ferrocenyl two
Oxazoline.
3. the preparation method containing ferrocenyl bisoxazoline according to claim 2 it is characterised in that：Described ferrocene
Shown in the general structure such as formula (2) of base semicarbazides Schiff：
Wherein, R be phenyl, o-hydroxy-phenyl, a hydroxy phenyl, p-hydroxybenzene, to N, N- dimethylaminophenyl, to fluorobenzene
Base, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl, a bromophenyl, p-bromophenyl, 2,4- dibromo phenyl, neighbour
Aminophenyl, m-aminophenyl base, p-aminophenyl, O-Nitrophenylfluorone, m-nitro base, p-nitrophenyl, 3,5- dinitro benzene
Base, o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, furan
Mutter base, thienyl, 3- pyridine radicals or 4- pyridine radicals.
4. the preparation method containing ferrocenyl bisoxazoline according to claim 2 it is characterised in that：Described ferrocene
The preparation method of base semicarbazides Schiff comprises the following steps：
1) weigh a mol ferrocenyl methyl ketone to be placed in mortar, add b mol NaOH solid, mix homogeneously, add c mol
Aldehyde compound, mixed grinding is reacted, and with TLC board monitoring to reacting completely, the solid that reaction is obtained washs, sucking filtration,
Filter cake is dried, that is, obtain biferrocenyl chalcone class compound；Wherein a:b:C=1:(1.7～2.2):(0.9～1.2)；
The structural formula of aldehyde compound be RCHO, wherein R be phenyl, o-hydroxy-phenyl, a hydroxy phenyl, p-hydroxybenzene, to N, N-
Dimethylaminophenyl, to fluorophenyl, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl, a bromophenyl, to bromine
Phenyl, 2,4- dibromo phenyl, adjacent aminophenyl, m-aminophenyl base, p-aminophenyl, O-Nitrophenylfluorone, m-nitro base, to nitre
Base phenyl, 3,5- dinitrophenyl, o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, meta-methoxy
Phenyl, p-methoxyphenyl, furyl, thienyl, 3- pyridine radicals or 4- pyridine radicals；
2) add d mol biferrocenyl chalcone, e mol semicarbazides and f mL anhydrous in the there-necked flask with reflux condensing tube
Ethanol, is subsequently adding glacial acetic acid and adjusts pH=4, carry out heating reflux reaction, with TLC board monitoring reaction, lowers the temperature after reaction 6～8h
Separate out solid, sucking filtration, filter cake is vacuum dried, that is, obtain ferrocenyl semicarbazides Schiff；Wherein d:E=1:(1.2～
1.6), d:F=1:(50～100).
5. the preparation method containing ferrocenyl bisoxazoline according to claim 2 it is characterised in that：Described catalyst
Consumption be C mol, A:C=1:(0.2～0.5).
6. the preparation method containing ferrocenyl bisoxazoline according to claim 2 it is characterised in that：Described backflow is anti-
The temperature answered is 115～125 DEG C, and the time reacting completely required is 1～1.2h.
7. the preparation method containing ferrocenyl bisoxazoline according to claim 2 it is characterised in that：Described backflow is anti-
The process TLC of answering is monitored, and represents reaction when the raw material point of ferrocenyl semicarbazides Schiff disappears completely, described
The developing solvent of TLC is volume ratio is 10:1 dichloromethane and the mixed liquor of methanol.
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| CN107602624A (en) * | 2017-10-16 | 2018-01-19 | 陕西科技大学 | A kind of class compound of Thiadiazoline containing ferrocenyl and preparation method thereof |
| CN114044795A (en) * | 2021-09-28 | 2022-02-15 | 陕西科技大学 | Preparation method and application of ferrocenyl chalcone amino (thio) urea Schiff base |
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| CN104059109A (en) * | 2014-06-26 | 2014-09-24 | 陕西科技大学 | 3-[4-(2-amino-5-substituted-[1,3,4]thiadiazolyl)-phenyl]-1-ferrocenyl-acrylketone and preparation method thereof |
| CN104098609A (en) * | 2014-07-28 | 2014-10-15 | 陕西科技大学 | Imidazole and [2,1-b]-1,3,4-thiadiazole containing ferrocene, preparation method and application thereof |
| CN104231006A (en) * | 2014-09-03 | 2014-12-24 | 陕西科技大学 | Amino (thio) urea Schiff base containing ferrocenyl chalcone and preparation method and application thereof |
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| CN104059109A (en) * | 2014-06-26 | 2014-09-24 | 陕西科技大学 | 3-[4-(2-amino-5-substituted-[1,3,4]thiadiazolyl)-phenyl]-1-ferrocenyl-acrylketone and preparation method thereof |
| CN104098609A (en) * | 2014-07-28 | 2014-10-15 | 陕西科技大学 | Imidazole and [2,1-b]-1,3,4-thiadiazole containing ferrocene, preparation method and application thereof |
| CN104231006A (en) * | 2014-09-03 | 2014-12-24 | 陕西科技大学 | Amino (thio) urea Schiff base containing ferrocenyl chalcone and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107602624A (en) * | 2017-10-16 | 2018-01-19 | 陕西科技大学 | A kind of class compound of Thiadiazoline containing ferrocenyl and preparation method thereof |
| CN107602624B (en) * | 2017-10-16 | 2019-11-19 | 陕西科技大学 | One kind class compound of Thiadiazoline containing ferrocenyl and preparation method thereof |
| CN114044795A (en) * | 2021-09-28 | 2022-02-15 | 陕西科技大学 | Preparation method and application of ferrocenyl chalcone amino (thio) urea Schiff base |
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