CN106478742B - One kind oxadiazoline containing ferrocenyl and preparation method thereof - Google Patents
One kind oxadiazoline containing ferrocenyl and preparation method thereof Download PDFInfo
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- CN106478742B CN106478742B CN201610864916.0A CN201610864916A CN106478742B CN 106478742 B CN106478742 B CN 106478742B CN 201610864916 A CN201610864916 A CN 201610864916A CN 106478742 B CN106478742 B CN 106478742B
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Abstract
The present invention provides a kind of oxadiazolines containing ferrocenyl and preparation method thereof.A mol ferrocenyl semicarbazides Schiff and B mL glacial acetic acid are added into the dry three-necked flask with reflux condensing tube, and manganese dioxide is added as catalyst, back flow reaction is to fully reacting, wherein A:B=1:(60~100), it filters after reaction and removes catalyst, filtrate is cooled to room temperature, filters again after standing, acicular crystal, as oxadiazoline containing ferrocenyl are obtained after the filtration cakes torrefaction of secondary suction filtration.Operation of the present invention is simple, and the reaction time is short, and reaction condition is mild, and equipment requirement is low, and post-processing is simple, while catalyst is cheap and easy to get.The present invention is prepared for a series of heterocyclic compound of oxadiazoline containing ferrocenyl of brand news, provides more more options to find such biologically active compound, beneficial help is provided to the development and application of such compound.
Description
Technical field
The invention belongs to the field of chemical synthesis, in particular to a kind of oxadiazoline containing ferrocenyl and preparation method thereof.
Background technique
Ferrocene itself has preferable bioactivity, has preferable antibacterial, anticancer and hypotoxicity, therefore lead in medicine
Domain plays an important role.Ferrocene derivatives also have many characteristics, such as armaticity, hypotoxicity, stability, are good liquid crystal materials
It is very big especially to cause people in materials chemistry, electrochemistry, asymmetric syntheses chemistry for material, conductive material and magnetic material
Interest.Schiff cyclic compound containing heterocycle not only has the bioactivity such as anticancer, antiviral, sterilization, but also is also
The good extractant of the metal ions such as rare earth, thus in relation to novel Schiff cyclic compound synthesis and performance study be
One of current most active research object.
Oxadiazoline class compound will dislike two since its good bioactivity is widely used in the fields such as medicine, pesticide
Oxazoline heterocycle is introduced into other compounds, tends to generate a series of noval chemical compounds with extensive bioactivity.Therefore, new
In medicine design, oxadiazoline heterocycle is commonly used for the structural modification of compound.But synthesis oxadiazoline reported at present closes
It is catalyst higher cost, lower containing heavy metal, pollution environment, yield at method, it is partially synthesized, is endangered using acyl chlorides
Larger, there are also electrochemically being synthesized, cost is also higher.
Summary of the invention
The purpose of the present invention is to provide a kind of oxadiazolines containing ferrocenyl and preparation method thereof, and this method has operation
Simply, the advantages that reaction condition is mild, and the reaction time is short, and post-processing is simple, and yield is higher.
In order to achieve the above objectives, the technical solution adopted by the present invention are as follows:
A kind of oxadiazoline containing ferrocenyl, shown in general structure such as formula (1):
Wherein, R be phenyl, o-hydroxy-phenyl, hydroxy phenyl, p-hydroxybenzene, to N, it is N- dimethylaminophenyl, right
Fluorophenyl, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl, m-bromophenyl, p-bromophenyl, 2,4- dibromobenzene
Base, o-aminophenyl, m-aminophenyl base, p-aminophenyl, O-Nitrophenylfluorone, m-nitro base, p-nitrophenyl, 3,5- dinitro
Base phenyl, o-methyl-phenyl, aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, to methoxybenzene
Base, furyl, thienyl, 3- pyridyl group or 4- pyridyl group.
A kind of preparation method of the oxadiazoline containing ferrocenyl, the specific steps are as follows:
Addition A mol ferrocenyl semicarbazides Schiff and B mL glacial acetic acid into reaction vessel, A:B=1:(60~
100), and manganese dioxide is added as catalyst, is heated to reflux to fully reacting, then filters, remove catalyst, filtrate is cooling
It is stood after to room temperature and is filtered again, acicular crystal will be obtained after the filtration cakes torrefaction of secondary suction filtration, as contain ferrocenyl
Oxadiazoline.
Shown in the general structure such as formula (2) of the ferrocenyl semicarbazides Schiff:
Wherein, R be phenyl, o-hydroxy-phenyl, hydroxy phenyl, p-hydroxybenzene, to N, it is N- dimethylaminophenyl, right
Fluorophenyl, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl, m-bromophenyl, p-bromophenyl, 2,4- dibromobenzene
Base, o-aminophenyl, m-aminophenyl base, p-aminophenyl, O-Nitrophenylfluorone, m-nitro base, p-nitrophenyl, 3,5- dinitro
Base phenyl, o-methyl-phenyl, aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, to methoxybenzene
Base, furyl, thienyl, 3- pyridyl group or 4- pyridyl group.
The preparation method of the ferrocenyl semicarbazides Schiff the following steps are included:
1) it weighs a mol ferrocenyl methyl ketone to be placed in mortar, b mol NaOH solid is added, be uniformly mixed, add c
Mol aldehyde compound, mixed grinding are reacted, and with TLC board monitoring to fully reacting, the solid washing that reaction is obtained is taken out
Filter, filter cake are dried to arrive 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, wherein R be phenyl, it is o-hydroxy-phenyl, hydroxy phenyl, p-hydroxybenzene, right
N, N- dimethylaminophenyl, p-fluorophenyl, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl, m-bromophenyl,
P-bromophenyl, 2,4- dibromo phenyl, o-aminophenyl, m-aminophenyl base, p-aminophenyl, O-Nitrophenylfluorone, m-nitro base,
P-nitrophenyl, 3,5- dinitrophenyl, o-methyl-phenyl, aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, first
Phenyl, p-methoxyphenyl, furyl, thienyl, 3- pyridyl group or 4- pyridyl group；
2) d mol biferrocenyl chalcone, e mol semicarbazides and f mL are added into the there-necked flask with reflux condensing tube
Then dehydrated alcohol is added glacial acetic acid and adjusts pH=4, carries out heating reflux reaction, reacted with TLC board monitoring, after reacting 6~8h
Solid is precipitated in cooling, filters, and filter cake is dried in vacuo to arrive ferrocenyl semicarbazides Schiff；Wherein d:e=1:(1.2~
1.6), d:f=1:(50~100).
The dosage of the catalyst is C mol, A:C=1:(0.2~0.5).
The temperature of the back flow reaction is 115~125 DEG C, and the time needed for fully reacting is 1~1.2h.
The back flow reaction process is monitored with TLC, when the raw material point of ferrocenyl semicarbazides Schiff disappears
When indicate fully reacting, the solvent of the TLC is the mixed liquor of the methylene chloride that volume ratio is 10:1 and methanol.
Compared with the existing technology, the invention has the benefit that
The preparation method of the oxadiazoline provided by the invention containing ferrocenyl, with ferrocenyl semicarbazides Schiff and ice
Acetic acid is raw material, and using common manganese dioxide as catalyst, oxadiazoles containing ferrocenyl is made by the way of being heated to reflux
Quinoline.For the present invention compared with traditional methodology of organic synthesis, reaction condition is mild, and operating process is simple, and the reaction time is short, after reaction
Processing is simple, and yield is higher, and environmental pollution is small, and catalyst is cheap and easy to get.
The present invention is prepared for a series of heterocyclic compound of oxadiazoline containing ferrocenyl of brand news, has life to find
Such active compound of object provides more more options, and beneficial help is provided to the development and application of such compound.
Detailed description of the invention
Fig. 1 is the infrared spectrum of diphenylphosphino ferrocene base oxadiazoline made from embodiment 1；
Fig. 2 is the infrared spectrum of o-hydroxy-phenyl ferrocenyl oxadiazoline made from embodiment 2；
Fig. 3 is the infrared spectrum obtained to dimethylamino phenyl ferrocenyl oxadiazoline of embodiment 3；
Fig. 4 is the infrared spectrum of rubigan ferrocenyl oxadiazoline made from embodiment 4；
Fig. 5 is the infrared spectrum of p-bromophenyl ferrocenyl oxadiazoline made from embodiment 5.
Specific embodiment
The present invention is described in further details with reference to the accompanying drawings and examples.
The present invention, using manganese dioxide as catalyst, is added using ferrocenyl semicarbazides Schiff and glacial acetic acid as raw material
Heat reflux prepares a series of oxadiazolines containing ferrocenyl, shown in reaction equation such as formula (3).
Wherein, R be phenyl, o-hydroxy-phenyl, hydroxy phenyl, p-hydroxybenzene, to N, it is N- dimethylaminophenyl, right
Fluorophenyl, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl, m-bromophenyl, p-bromophenyl, 2,4- dibromobenzene
Base, o-aminophenyl, m-aminophenyl base, p-aminophenyl, O-Nitrophenylfluorone, m-nitro base, p-nitrophenyl, 3,5- dinitro
Base phenyl, o-methyl-phenyl, aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, to methoxybenzene
Base, furyl, thienyl, 3- pyridyl group or 4- pyridyl group.
Embodiment 1
The synthesis of 1- ferrocenyl -3- phenyl -2- propenone semicarbazides Schiff:
1) it weighs 0.5mmol ferrocenyl methyl ketone to be placed in mortar, 1mmol NaOH solid is added, be uniformly mixed, then plus
Entering 0.5mmol aldehyde compound RCHO (R is phenyl), mixed grinding is monitored with TLC plate, until fully reacting, it will be resulting
Solid is washed with water, and filters, filter cake is dried, biferrocenyl chalcone class compound is obtained；
2) 0.4mmol biferrocenyl chalcone class compound is added into the there-necked flask with reflux condensing tube,
0.56mmol semicarbazides and 30mL dehydrated alcohol are added glacial acetic acid and adjust pH=4, be heated to reflux, reacted with TLC board monitoring, instead
After answering 7h, solid is precipitated in cooling, is filtered, and filter cake vacuum drying obtains 1- ferrocenyl -3- phenyl -2- propenone semicarbazides
Schiff.
The synthesis of diphenylphosphino ferrocene base oxadiazoline:
1- ferrocenyl -3- the phenyl-of 0.35mmol is added into the dry 250mL there-necked flask with reflux condensing tube
2- propenone semicarbazides Schiff, the glacial acetic acid of 25mL and 0.14mmol manganese dioxide after mixing to three are warming up to
120 DEG C of progress back flow reactions, fully reacting time-consuming 1h whether complete with test reaction every half an hour progress TLC contact plate.Instead
It is filtered after answering, removes catalyst, filtrate is cooled to room temperature, stood and filter, filter cake obtains orange after being dried at room temperature for
Color acicular crystal, as diphenylphosphino ferrocene base oxadiazoline.
IR(KBr,v/cm-1):3403.10(N-H)；(2927.26,2856.06 saturation C-H)；1579.27 (unsaturated C=
C vibration)；(1418.81 phenyl ring skeletal vibration)；(1343.84 methyl C-H bending vibration)；1188.26,1037.85 (luxuriant ring vibration
Dynamic absorption peak)；(1126.11 C-O-C stretching vibration)；814.96 (monosubstituted phenyl ring C-H bending vibrations).
Fig. 1 is diphenylphosphino ferrocene base oxadiazoline IR spectrogram made from embodiment 1, as shown in Figure 1: 3403.10cm-1It place can
It 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 unsaturation C=C absorption 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 absorption peak, 1188.26cm-1And 1037.85cm-1Place may be cyclopentadienyl
Ring vibration absorption peak, 1126.11cm-1Place may be oxadiazoles C-O-C stretching vibration absworption peak, 814.96cm-1Place may be to take
For phenyl ring C-H bending vibration absorption peak.In summary, it can be verified that synthesis has obtained diphenylphosphino ferrocene base oxadiazoline.
Embodiment 2
The synthesis of 1- ferrocenyl -3- (2- hydroxy phenyl) -2- propenone semicarbazides Schiff:
1) it weighs 0.5mmol ferrocenyl methyl ketone to be placed in mortar, 1mmol NaOH solid is added, be uniformly mixed, then plus
Entering 0.5mmol aldehyde compound RCHO (R is 2- hydroxy phenyl), mixed grinding is monitored with TLC plate, until fully reacting, it will
Resulting solid is washed with water, and filters, filter cake is dried, biferrocenyl chalcone class compound is obtained；
2) 0.4mmol biferrocenyl chalcone class compound is added into the there-necked flask with reflux condensing tube,
0.56mmol semicarbazides and 30mL dehydrated alcohol are added glacial acetic acid and adjust pH=4, be heated to reflux, reacted with TLC board monitoring, instead
After answering 7h, solid is precipitated in cooling, is filtered, and filter cake vacuum drying obtains 1- ferrocenyl -3- (2- hydroxy phenyl) -2- propenone ammonia
Base urea Schiff.
The synthesis of o-hydroxy-phenyl ferrocenyl oxadiazoline:
1- ferrocenyl -3- (the 2- hydroxyl of 0.26mmol is added into the dry 250mL there-necked flask with reflux condensing tube
Base phenyl) -2- propenone semicarbazides Schiff, 25mL glacial acetic acid and 0.104mmol manganese dioxide, to three be uniformly mixed
Afterwards, 120 DEG C of progress back flow reactions are warming up to, carry out whether complete, the fully reacting with test reaction of TLC contact plate every half an hour
Time-consuming 1h.It filters after reaction, removes catalyst, filtrate is cooled to room temperature, stand and filter, after filter cake is dried at room temperature for
Obtain brown color acicular crystal, as o-hydroxy-phenyl ferrocenyl oxadiazoline.
IR(KBr,v/cm-1):3399.93(O-H)；(2929.79,2857.44 saturation C-H)；1557.84 (unsaturated C=
C vibration)；(1396.48 phenyl ring skeletal vibration)；(1343.63 methyl C-H bending vibration)；1188.15,1035.19 (luxuriant ring vibration
Dynamic absorption peak)；(1126.56 C-O-C stretching vibration)；764.04 (1,2- substituted benzene ring C-H bending vibrations).
Fig. 2 is o-hydroxy-phenyl ferrocenyl oxadiazoline IR spectrogram made from embodiment 2, 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
Contract the absorption peak vibrated, 1557.84cm-1The peak at place may be unsaturation C=C absorption peak, 1396.48cm-1The peak at place may be
The absorption peak of Ar-H, 1343.63cm-1Place may be methyl C-H bending vibration absorption peak, 1188.15cm-1And 1035.19cm-1
Place may be luxuriant ring vibration absorption peak, 1126.56cm-1Place may be oxadiazoles C-O-C stretching vibration absworption peak, 764.04cm-1
Place may be 1,2- substituted benzene ring C-H bending vibration absorption peak.In summary, it can be verified that synthesis has obtained adjacent hydroxyl Ferrocene
Base oxadiazoline.
Embodiment 3
The synthesis of 1- ferrocenyl -3- (4-N, N- dimethylamino phenyl) -2- propenone semicarbazides Schiff:
1) it weighs 0.5mmol ferrocenyl methyl ketone to be placed in mortar, 1mmol NaOH solid is added, be uniformly mixed, then plus
Enter 0.5mmol aldehyde compound RCHO (R 4-N, N- dimethylamino phenyl), mixed grinding is monitored with TLC plate, until anti-
Resulting solid should be washed with water completely, filter, filter cake is dried, biferrocenyl chalcone class compound is obtained；
2) 0.4mmol biferrocenyl chalcone class compound is added into the there-necked flask with reflux condensing tube,
0.56mmol semicarbazides and 30mL dehydrated alcohol are added glacial acetic acid and adjust pH=4, be heated to reflux, reacted with TLC board monitoring, instead
After answering 7h, solid is precipitated in cooling, is filtered, and filter cake vacuum drying obtains 1- ferrocenyl -3- (4-N, N- dimethylamino phenyl) -2-
Propenone semicarbazides Schiff.
Synthesis to dimethylamino phenyl ferrocenyl oxadiazoline:
Into the dry 250mL there-necked flask with reflux condensing tube be added 0.29mmol 1- ferrocenyl -3- (4-N,
N- dimethylamino phenyl) -2- propenone semicarbazides Schiff, 25mL glacial acetic acid and 0.116mmol manganese dioxide, to three
After mixing, 120 DEG C of progress back flow reactions are warming up to, it is whether complete with test reaction every half an hour progress TLC contact plate,
Fully reacting time-consuming 1h.It filters after reaction, removes catalyst, filtrate is cooled to room temperature, stand and filter, filter cake is in room temperature
Orange-yellow acicular crystal is obtained after lower drying, as to dimethylamino phenyl ferrocenyl oxadiazoline.
IR(KBr,v/cm-1):3397.72(N-H)；(1572.54 unsaturated C=C vibration)；1417.16 (phenyl ring skeleton vibration
It is dynamic)；(1343.59 methyl C-H bending vibration)；(1189.61,1035.32 luxuriant ring vibration absorption peak)；1125.47 (C-O-C stretches
Contracting vibration)；814.06 (1,4- substituted benzene ring C-H bending vibrations).
Fig. 3 is that embodiment 3 is obtained to dimethylamino phenyl ferrocenyl oxadiazoline 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 unsaturation C=C absorption peak,
1417.16cm-1The peak at place may be the absorption peak of Ar-H, 1343.59cm-1Place may be methyl C-H bending vibration absorption peak,
1189.61cm-1And 1035.32cm-1Place may be luxuriant ring vibration absorption peak, 1125.47cm-1Place may stretch for oxadiazoles C-O-C
Contracting vibration absorption peak, 814.06cm-1Place may be 1,4- substituted benzene ring C-H bending vibration absorption peak.In summary, it can be verified that
Synthesis has been obtained to dimethylamino ferrocenyl oxadiazoline.
Embodiment 4
The synthesis of 1- ferrocenyl -3- (4- chlorphenyl) -2- propenone semicarbazides Schiff:
1) it weighs 0.5mmol ferrocenyl methyl ketone to be placed in mortar, 1mmol NaOH solid is added, be uniformly mixed, then plus
Entering 0.5mmol aldehyde compound RCHO (R is rubigan), mixed grinding is monitored with TLC plate, until fully reacting, by institute
The solid obtained is washed with water, and filters, filter cake is dried, biferrocenyl chalcone class compound is obtained；
2) 0.4mmol biferrocenyl chalcone class compound is added into the there-necked flask with reflux condensing tube,
0.56mmol semicarbazides and 30mL dehydrated alcohol are added glacial acetic acid and adjust pH=4, be heated to reflux, reacted with TLC board monitoring, instead
After answering 7h, solid is precipitated in cooling, is filtered, and filter cake vacuum drying obtains 1- ferrocenyl -3- (4- chlorphenyl) -2- propenone amino
Urea Schiff.
The synthesis of rubigan ferrocenyl oxadiazoline:
1- ferrocenyl -3- (the 4- chlorine of 0.26mmol is added into the dry 250mL there-necked flask with reflux condensing tube
Phenyl) -2- propenone semicarbazides Schiff, 25mL glacial acetic acid and 0.104mmol manganese dioxide, to three be uniformly mixed
Afterwards, 120 DEG C of progress back flow reactions are warming up to, carry out whether complete, the fully reacting with test reaction of TLC contact plate every half an hour
Time-consuming 1h.It filters after reaction, removes catalyst, filtrate is cooled to room temperature, stand and filter, after filter cake is dried at room temperature for
Obtain brown color acicular crystal, as rubigan ferrocenyl oxadiazoline.
IR(KBr,v/cm-1):3248.93(N-H)；(2926.80,2855.72 saturation C-H)；1611.82 (unsaturated C=
C vibration)；(1396.22 phenyl ring skeletal vibration)；(1342.44 methyl C-H bending vibration)；1180.46,1032.84 (luxuriant ring vibration
Dynamic absorption 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 rubigan ferrocenyl oxadiazoline IR spectrogram made from embodiment 4, 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 unsaturation C=C absorption 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 absorption peak, 1180.46cm-1And 1032.84cm-1Place may be cyclopentadienyl
Ring vibration absorption peak, 1124.34cm-1Place may be oxadiazoles C-O-C stretching vibration absworption peak, 814.99cm-1Place may be 1,
4- substituted benzene ring C-H bending vibration absorption peak, 730.10cm-1Place may be C-Cl absorption peak.In summary, it can be verified that synthesis
Rubigan ferrocenyl oxadiazoline is obtained.
Embodiment 5
The synthesis of 1- ferrocenyl -3- (4- bromophenyl) -2- propenone semicarbazides Schiff:
1) it weighs 0.5mmol ferrocenyl methyl ketone to be placed in mortar, 1mmol NaOH solid is added, be uniformly mixed, then plus
Entering 0.5mmol aldehyde compound RCHO (R is p-bromophenyl), mixed grinding is monitored with TLC plate, until fully reacting, by institute
The solid obtained is washed with water, and filters, filter cake is dried, biferrocenyl chalcone class compound is obtained；
2) 0.4mmol biferrocenyl chalcone class compound is added into the there-necked flask with reflux condensing tube,
0.56mmol semicarbazides and 30mL dehydrated alcohol are added glacial acetic acid and adjust pH=4, be heated to reflux, reacted with TLC board monitoring, instead
After answering 7h, solid is precipitated in cooling, is filtered, and filter cake vacuum drying obtains 1- ferrocenyl -3- (4- bromophenyl) -2- propenone amino
Urea Schiff.
The synthesis of p-bromophenyl ferrocenyl oxadiazoline:
1- ferrocenyl -3- (the 4- bromine of 0.37mmol is added into the dry 250mL there-necked flask with reflux condensing tube
Phenyl) -2- propenone semicarbazides Schiff, 25mL glacial acetic acid and 0.148mmol manganese dioxide, to three be uniformly mixed
Afterwards, 120 DEG C of progress back flow reactions are warming up to, carry out whether complete, the fully reacting with test reaction of TLC contact plate every half an hour
Time-consuming 1h.It filters after reaction, removes catalyst, filtrate is cooled to room temperature, stand and filter, after filter cake is dried at room temperature for
Obtain orange-yellow acicular crystal, as p-bromophenyl ferrocenyl oxadiazoline.
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 p-bromophenyl ferrocenyl oxadiazoline IR spectrogram made from embodiment 5, 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 absorption peak of saturation C-H stretching vibration,
1594.61cm-1The peak at place may be unsaturation C=C absorption peak, 1410.66cm-1The peak at place may be the absorption peak of Ar-H,
1345.81cm-1Place may be methyl C-H bending vibration absorption peak, 1188.75cm-1And 1038.88cm-1Place may be luxuriant ring vibration
Dynamic absorption peak, 1126.29cm-1Place may be oxadiazoles C-O-C stretching vibration absworption peak, 815.24cm-1Place may take for 1,4-
For phenyl ring C-H bending vibration absorption peak, 568.43cm-1Place may be C-Br absorption peak.In summary, it can be verified that synthesis obtains
P-bromophenyl ferrocenyl oxadiazoline.
Embodiment 6
The synthesis of 1- ferrocenyl -3- (2- aminophenyl) -2- propenone semicarbazides Schiff:
1) it weighs 0.5mmol ferrocenyl methyl ketone to be placed in mortar, 0.85mmol NaOH solid is added, be uniformly mixed, then
It is added 0.45mmol aldehyde compound RCHO (R is o-aminophenyl), mixed grinding is monitored with TLC plate, until having reacted
Entirely, resulting solid is washed with water, filters, filter cake is dried, biferrocenyl chalcone class compound is obtained；
2) 0.4mmol biferrocenyl chalcone class compound is added into the there-necked flask with reflux condensing tube,
0.48mmol semicarbazides and 20mL dehydrated alcohol are added glacial acetic acid and adjust pH=4, be heated to reflux, reacted with TLC board monitoring, instead
After answering 6h, solid is precipitated in cooling, is filtered, and filter cake vacuum drying obtains 1- ferrocenyl -3- (2- aminophenyl) -2- propenone ammonia
Base urea Schiff.
The synthesis of o-aminophenyl ferrocenyl oxadiazoline:
1- ferrocenyl -3- (the 2- ammonia of 0.3mmol is added into the dry 250mL there-necked flask with reflux condensing tube
Base phenyl) -2- propenone semicarbazides Schiff, 18mL glacial acetic acid and 0.06mmol manganese dioxide, to three be uniformly mixed
Afterwards, 115 DEG C of progress back flow reactions are warming up to, carry out whether complete, the fully reacting with test reaction of TLC contact plate every half an hour
Time-consuming 1.1h.It filters after reaction, removes catalyst, filtrate is cooled to room temperature, stand and filter, filter cake is dried at room temperature for
After obtain o-aminophenyl ferrocenyl oxadiazoline.
Embodiment 7
The synthesis of 1- ferrocenyl -3- (2- nitrobenzophenone) -2- propenone semicarbazides Schiff:
1) it weighs 0.5mmol ferrocenyl methyl ketone to be placed in mortar, 1.1mmol NaOH solid is added, be uniformly mixed, then
It being added 0.6mmol aldehyde compound RCHO (R is O-Nitrophenylfluorone), mixed grinding is monitored with TLC plate, until fully reacting,
Resulting solid is washed with water, filters, filter cake is dried, biferrocenyl chalcone class compound is obtained；
2) 0.4mmol biferrocenyl chalcone class compound is added into the there-necked flask with reflux condensing tube,
0.64mmol semicarbazides and 40mL dehydrated alcohol are added glacial acetic acid and adjust pH=4, be heated to reflux, reacted with TLC board monitoring, instead
After answering 8h, solid is precipitated in cooling, is filtered, and filter cake vacuum drying obtains 1- ferrocenyl -3- (2- nitrobenzophenone) -2- propenone ammonia
Base urea Schiff.
Synthesis to O-Nitrophenylfluorone ferrocenyl oxadiazoline:
1- ferrocenyl -3- (the 2- nitre of 0.3mmol is added into the dry 250mL there-necked flask with reflux condensing tube
Base phenyl) -2- propenone semicarbazides Schiff, 30mL glacial acetic acid and 0.15mmol manganese dioxide, to three be uniformly mixed
Afterwards, 125 DEG C of progress back flow reactions are warming up to, carry out whether complete, the fully reacting with test reaction of TLC contact plate every half an hour
Time-consuming 1.2h.It filters after reaction, removes catalyst, filtrate is cooled to room temperature, stand and filter, filter cake is dried at room temperature for
After obtain to O-Nitrophenylfluorone ferrocenyl oxadiazoline.
Embodiment 8
The synthesis of 1- ferrocenyl -3- (3- methoxyphenyl) -2- propenone semicarbazides Schiff:
1) it weighs 0.5mmol ferrocenyl methyl ketone to be placed in mortar, 0.95mmol NaOH solid is added, be uniformly mixed, then
It is added 0.55mmol aldehyde compound RCHO (R is m-methoxyphenyl), mixed grinding is monitored with TLC plate, until having reacted
Entirely, resulting solid is washed with water, filters, filter cake is dried, biferrocenyl chalcone class compound is obtained；
2) 0.4mmol biferrocenyl chalcone class compound is added into the there-necked flask with reflux condensing tube,
0.52mmol semicarbazides and 25mL dehydrated alcohol are added glacial acetic acid and adjust pH=4, be heated to reflux, reacted with TLC board monitoring, instead
After answering 6.5h, solid is precipitated in cooling, is filtered, and filter cake vacuum drying obtains 1- ferrocenyl -3- (3- methoxyphenyl) -2- propylene
Ketone semicarbazides Schiff.
The synthesis of m-methoxyphenyl ferrocenyl oxadiazoline:
1- ferrocenyl -3- (the 3- first of 0.3mmol is added into the dry 250mL there-necked flask with reflux condensing tube
Phenyl) -2- propenone semicarbazides Schiff, 22mL glacial acetic acid and 0.08mmol manganese dioxide, it is equal to three's mixing
After even, 118 DEG C of progress back flow reactions are warming up to, it is whether complete with test reaction every half an hour progress TLC contact plate, it has reacted
Full time-consuming 1.05h.It filters after reaction, removes catalyst, filtrate is cooled to room temperature, stand and filter, filter cake is at room temperature
M-methoxyphenyl ferrocenyl oxadiazoline is obtained after drying.
Embodiment 9
The synthesis of 1- ferrocenyl -3- (4- aminomethyl phenyl) -2- propenone semicarbazides Schiff:
1) it weighs 0.5mmol ferrocenyl methyl ketone to be placed in mortar, 1.05mmol NaOH solid is added, be uniformly mixed, then
It is added 0.52mmol aldehyde compound RCHO (R is p-methylphenyl), mixed grinding is monitored with TLC plate, until having reacted
Entirely, resulting solid is washed with water, filters, filter cake is dried, biferrocenyl chalcone class compound is obtained；
2) 0.4mmol biferrocenyl chalcone class compound, 0.6mmol are added into the there-necked flask with reflux condensing tube
Semicarbazides and 35mL dehydrated alcohol are added glacial acetic acid and adjust pH=4, be heated to reflux, reacted with TLC board monitoring, after reacting 7.5h,
Solid is precipitated in cooling, filters, and filter cake vacuum drying obtains 1- ferrocenyl -3- (4- aminomethyl phenyl) -2- propenone semicarbazides
Schiff.
The synthesis of p-methylphenyl ferrocenyl oxadiazoline:
1- ferrocenyl -3- (the 4- first of 0.3mmol is added into the dry 250mL there-necked flask with reflux condensing tube
Base phenyl) -2- propenone semicarbazides Schiff, 27mL glacial acetic acid and 0.1mmol manganese dioxide, to three be uniformly mixed
Afterwards, 122 DEG C of progress back flow reactions are warming up to, carry out whether complete, the fully reacting with test reaction of TLC contact plate every half an hour
Time-consuming 1.15h.It filters after reaction, removes catalyst, filtrate is cooled to room temperature, stand and filter, filter cake is done at room temperature
P-methylphenyl ferrocenyl oxadiazoline is obtained after dry.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent structure transformation to the above embodiments, still fall within skill of the present invention
In the protection scope of art scheme.
Claims (6)
1. a kind of preparation method of oxadiazoline containing ferrocenyl, which is characterized in that specific step is as follows:
Amol ferrocenyl semicarbazides Schiff and BmL glacial acetic acid, A:B=1:(60~100 are added into reaction vessel), and
Manganese dioxide is added as catalyst, is heated to reflux to fully reacting, then filters, removes catalyst, filtrate is cooled to room temperature
After stood and filtered again, acicular crystal, as oxadiazoles containing ferrocenyl will be obtained after the filtration cakes torrefaction of secondary suction filtration
Quinoline.
2. the preparation method of the oxadiazoline according to claim 1 containing ferrocenyl, it is characterised in that: the ferrocene
Shown in the general structure such as formula (2) of base semicarbazides Schiff:
Wherein, R be phenyl, o-hydroxy-phenyl, hydroxy phenyl, p-hydroxybenzene, to N, N- dimethylaminophenyl, to fluorobenzene
Base, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl, m-bromophenyl, p-bromophenyl, 2,4- dibromo phenyl, neighbour
Aminophenyl, m-aminophenyl base, p-aminophenyl, O-Nitrophenylfluorone, m-nitro base, p-nitrophenyl, 3,5- dinitrobenzene
Base, o-methyl-phenyl, aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, furan
It mutters base, thienyl, 3- pyridyl group or 4- pyridyl group.
3. the preparation method of the oxadiazoline according to claim 1 containing ferrocenyl, it is characterised in that: the ferrocene
The preparation method of base semicarbazides Schiff the following steps are included:
1) it weighs amol ferrocenyl methyl ketone to be placed in mortar, bmol NaOH solid is added, be uniformly mixed, add cmol aldehyde
Class compound, mixed grinding are reacted, and with TLC board monitoring to fully reacting, the solid washing that reaction is obtained is filtered, filter
Cake is dried to arrive biferrocenyl chalcone class compound；Wherein a:b:c=1:(1.7~2.2): (0.9~1.2)；Aldehyde
The structural formula of class compound be RCHO, wherein R be phenyl, o-hydroxy-phenyl, hydroxy phenyl, p-hydroxybenzene, to N, N- bis-
Methylamino phenyl, p-fluorophenyl, Chloro-O-Phenyl, rubigan, 2,4 dichloro benzene base, o-bromophenyl, m-bromophenyl, to bromobenzene
Base, 2,4- dibromo phenyl, o-aminophenyl, m-aminophenyl base, p-aminophenyl, O-Nitrophenylfluorone, m-nitro base, to nitro
Phenyl, 3,5- dinitrophenyl, o-methyl-phenyl, aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, meta-methoxy benzene
Base, p-methoxyphenyl, furyl, thienyl, 3- pyridyl group or 4- pyridyl group；
2) to reflux condensing tube there-necked flask in be added dmol biferrocenyl chalcone class compound, emol semicarbazides and
Then fmL dehydrated alcohol is added glacial acetic acid and adjusts pH=4, carries out heating reflux reaction, reacted with TLC board monitoring, and reaction 6~
Solid is precipitated in cooling after 8h, filters, and filter cake is dried in vacuo to arrive ferrocenyl semicarbazides Schiff；Wherein d:e=1:
(1.2~1.6), d:f=1:(50~100).
4. the preparation method of the oxadiazoline according to claim 1 containing ferrocenyl, it is characterised in that: the catalyst
Dosage be Cmol, A:C=1:(0.2~0.5).
5. the preparation method of the oxadiazoline according to claim 1 containing ferrocenyl, it is characterised in that: the reflux is anti-
The temperature answered is 115~125 DEG C, and the time needed for fully reacting is 1~1.2h.
6. the preparation method of the oxadiazoline according to claim 1 containing ferrocenyl, it is characterised in that: the reflux is anti-
It answers process to be monitored with TLC, indicates fully reacting when the raw material point of ferrocenyl semicarbazides Schiff disappears, it is described
The solvent of TLC is the mixed liquor of the methylene chloride that volume ratio is 10:1 and methanol.
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