CN107188889A - Acetyl butyryl of 4 acetyl group of a kind of 1 phenothiazinyl, 3 aryl 1,5 and preparation method thereof - Google Patents
Acetyl butyryl of 4 acetyl group of a kind of 1 phenothiazinyl, 3 aryl 1,5 and preparation method thereof Download PDFInfo
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- CN107188889A CN107188889A CN201710386947.4A CN201710386947A CN107188889A CN 107188889 A CN107188889 A CN 107188889A CN 201710386947 A CN201710386947 A CN 201710386947A CN 107188889 A CN107188889 A CN 107188889A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
- C07D279/30—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom with acyl radicals attached to the ring nitrogen atom
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Abstract
The invention provides a kind of acetyl butyryl of 1 phenothiazinyl, 3 aryl, 4 acetyl group 1,5 and preparation method thereof, its structural formula is：
Description
Technical field
The invention belongs to the field of chemical synthesis, more particularly to a kind of 1- phenothiazinyls -3- aryl -4- acetyl group -1,5- oneself
Diketone and preparation method thereof.
Background technology
N- phenothiazinyls chalcone contains an a, β-unsaturated double-bond due to it, so on N- phenothiazinyl chalcones
Reaction more than around Michael addition reactions or cyclization reaction carry out.It can with hydrazine, nitrile, active methylene compound or
The materials such as amine carry out Michael addition reactions, generate a series of derivatives containing phenothiazinyl, the analog derivative in antibacterial,
There is good application in the field such as antiviral.
Michael addition reactions are the organic reactions of the important formation carbon-carbon key of a class, and most directly application is exactly for it
Increase carbochain, compound of the synthesis containing multiple functional groups, these compounds are respectively provided with the ability further reacted, generated various
The organic compound of type.But traditional Michael reactions are carried out in organic solvent with strong alkali as a catalyst mostly, catalysis
The agent alkalescence too strong or reaction time is longer, has many accessory substances and produces, so that yield is undesirable.
The content of the invention
It is an object of the invention to provide a kind of 1- phenothiazinyls -3- aryl -4- acetyl group -1,5- acetyl butyryls and its preparation
Method, using solid-phase sequencing, has synthesized a series of new Michael addition compound products for having no document report, this method reaction
Time is short, without solvent, green, environmental protection, economy and simple to operate, reaction condition is gentle, and post processing is simple, yield is high.
To reach above-mentioned purpose, the present invention uses following technical scheme：
A kind of 1- phenothiazinyls -3- aryl -4- acetyl group -1,5- acetyl butyryls, its general structure is as follows：
Wherein Ar is phenyl, substituted-phenyl or heterocyclic radical.
The substituted-phenyl is rubigan, p-bromophenyl, p-fluorophenyl, aminomethyl phenyl, methoxyphenyl, p-nitrophenyl
Base, m-nitro base, O-Nitrophenylfluorone, dimethylamino phenyl, hydroxy phenyl, styryl；
The heterocyclic radical is furyl, thienyl or pyridine radicals.
The preparation method of described 1- phenothiazinyl -3- aryl -4- acetyl group -1,5- acetyl butyryls, it is comprised the following steps that：
A mol 1- phenothiazinyls -3- aryl-propenone, B mol catalyst, C mol second is added into dry mortar
Acyl acetone, grinding is reacted it, and TLC tracing detections are complete up to reaction, then washing, suction filtration, will be after filtration cakes torrefaction
Obtain 1- phenothiazinyl -3- aryl -4- acetyl group -1,5- acetyl butyryls, wherein A:B:C=1:(1~1.5):(1~2.0).
The general structure of the 1- phenothiazinyls -3- aryl-propenone is as follows：
Wherein Ar is phenyl, rubigan, p-bromophenyl, p-fluorophenyl, aminomethyl phenyl, methoxyphenyl, p-nitrophenyl
Base, m-nitro base, O-Nitrophenylfluorone, dimethylamino phenyl, hydroxy phenyl, styryl, furyl, thienyl or pyridine
Base.
The catalyst is solid NaOH or anhydrous K2CO3。
The time of the griding reaction is 30~40min.
Represent that raw material reaction is complete when the raw material point of 1- phenothiazinyls -3- aryl-propenone disappears；TLC detections are used
Solvent be that volume ratio is 1:5 ethyl acetate and the mixed solvent of petroleum ether.
During suction filtration, filter cake is repeatedly washed, until the pH of filtrate is in neutrality.
Compared with prior art, the invention has the advantages that：
The present invention uses solid-phase sequencing, by acetylacetone,2,4-pentanedione and 1- phenothiazinyls -3- aryl-propylene reactive ketone, synthesis
A series of new Michael addition compound products for having no document report, i.e. 1- phenothiazinyls -3- aryl -4- acetyl group -1,5- oneself two
Ketone, and its preparation method is explored, while optimizing experiment condition, the reaction time is shortened, is that green syt is made that contribution.
1- phenothiazinyl -3- aryl -4- acetyl group -1,5- the acetyl butyryls that the present invention is provided are a series of brand-new containing phenothiazinyl
Ketones derivant, with sterilization, it is antibacterial the effects such as, have good application prospect in the field such as antibacterial, antiviral.
The preparation method for 1- phenothiazinyl -3- aryl -4- acetyl group -1,5- acetyl butyryls that the present invention is provided, by 1- fen thiophenes
Piperazine base -3- aryl-propenone, catalyst and acetylacetone,2,4-pentanedione add rapid grinding in dry mortar and reacted, process of lapping
In, raw material is thick as the progress of reaction is begun to change into then to gradually become solid, and TLC tracing detections are produced to reacting complete
Thing is through washing, suction filtration, drying to obtain 1- phenothiazinyl -3- aryl -4- acetyl group -1,5- acetyl butyryls.With prior synthesizing method
Compare, the present invention uses solid-phase sequencing, course of reaction is simple, reacting phenomenon substantially, the reaction time is short, without solvent, green,
Environmentally friendly, economic and simple to operate, reaction condition is gentle, and equipment requirement is low, and the post processing of this method is simple, accessory substance is few, production
Rate is high.Overcome that the prior synthesizing method reaction time is long, accessory substance is more, the shortcomings of low yield, with it is economical, conveniently, it is efficient, green
The advantage of color.
Further, the present invention uses TLC monitoring reaction courses, solvent used is that volume ratio is in preparation process
1:5 ethyl acetate and petroleum ether, monitoring is accurate, beneficial to control extent of reaction and end.Catalyst used in simultaneously of the invention
For solid NaOH or anhydrous K2CO3, cheap and easy to get, catalytic effect is good, makes reaction more rapid and complete, and post processing is simple.
Brief description of the drawings
Fig. 1 is the infared spectrum of product made from embodiment 1；
Fig. 2 is the infared spectrum of product made from embodiment 2；
Fig. 3 is the infared spectrum of product made from embodiment 3；
Fig. 4 is product made from embodiment 11HNMR collection of illustrative plates；
Fig. 5 is product made from embodiment 21HNMR collection of illustrative plates；
Fig. 6 is product made from embodiment 31HNMR collection of illustrative plates.
Embodiment
The reaction equation for the 1- phenothiazinyl -3- aryl -4- acetyl group -1,5- acetyl butyryls that the present invention is provided is as follows：
Wherein Ar is phenyl, rubigan, p-bromophenyl, p-fluorophenyl, aminomethyl phenyl, methoxyphenyl, p-nitrophenyl
Base, m-nitro base, O-Nitrophenylfluorone, dimethylamino phenyl, hydroxy phenyl, styryl, furyl, thienyl or pyridine
Base.
The present invention is described in further details below in conjunction with preferred embodiments of the present invention.
Embodiment 1
Weigh 0.002mol acetylacetone,2,4-pentanediones and 0.0015mol anhydrous Ks2CO3In dry mortar, it is mixed rapidly
It is even, 0.001mol 1- phenothiazinyl -3- phenyl-acryloyl ketone is added, 35min is ground.In process of lapping, mixture can be gradually
Become glutinous, continue to grind until material no longer changes, using TLC tracking and monitoring reaction process, solvent used is volume
Than for 1:5 ethyl acetate and the mixed solvent of petroleum ether, after question response terminates, carry out repeatedly washing to product with pure water and take out
Filter, until the pH of filtrate is in neutrality, then by filter cake natural air drying, obtains celadon powder, as 1- phenothiazinyls -3- phenyl -
4- acetyl group -1,5- acetyl butyryls.Yield is：85.6%, m.p.112 DEG C~114 DEG C.
Fig. 1 is the infrared figure of 1- phenothiazinyl -3- phenyl -4- acetyl group -1,5- acetyl butyryls prepared by the embodiment of the present invention 1
Spectrum, as shown in Figure 1：3057cm-1Locate the vibration absorption peak for Ar-H, and in 2954cm-1、1381cm-1Locate as-CH3Absorption
Peak, in 2921cm-1、1438cm-1Locate as-CH2Absworption peak, in 1734cm-1、1654cm-1The peak at place is C=O characteristic absorption
Peak, 1589cm-1And 1464cm-1The peak at place is the breathing vibration absworption peak of phenyl ring, 742cm-1For adjacent dibasic suction on phenyl ring
Receive peak.In summary, it can be verified that synthesis has obtained 1- phenothiazinyl -3- phenyl -4- acetyl group -1,5- acetyl butyryls.
Fig. 4 is 1- phenothiazinyl -3- phenyl -4- acetyl group -1,5- acetyl butyryls prepared by the embodiment of the present invention 11HNMR
Collection of illustrative plates, as shown in Figure 4：1HNMR:6.52-7.16(m,13H,Ar-H),2.76-2.82(d,2H,COCH2),3.80-3.97(m,
1H,CH),2.15(s,3H,COCH3).
Embodiment 2
Weigh 0.002mol acetylacetone,2,4-pentanediones and 0.0015mol anhydrous Ks2CO3In dry mortar, it is mixed rapidly
It is even, 0.001mol 1- phenothiazinyls -3- (4- chlorphenyls)-propenone is added, 37min is ground.In process of lapping, mixture
Meeting gradually becomes glutinous, continues to grind up to material no longer changes, uses TLC tracking and monitoring reaction process, solvent used
It is 1 for volume ratio:5 ethyl acetate and the mixed solvent of petroleum ether, after question response terminates, are carried out repeatedly with pure water to product
Suction filtration is washed, until the pH of filtrate is in neutrality, then by filter cake natural air drying, brown ceramic powder, as 1- phenothiazinyls -3- is obtained
(4- chlorphenyls) -4- acetyl group -1,5- acetyl butyryls.Yield is：87.4%, m.p.108 DEG C~112 DEG C.
Fig. 2 is 1- phenothiazinyls -3- (4- chlorphenyls) -4- acetyl group -1,5- acetyl butyryls prepared by the embodiment of the present invention 2
Infared spectrum, as shown in Figure 2：3050cm-1Locate the vibration absorption peak for Ar-H, and in 2976cm-1、1383cm-1Locate as-CH3's
Absworption peak, in 2933cm-1、1455cm-1Locate as-CH2Absworption peak, in 1708cm-1、1666cm-1The peak at place is C=O feature
Absworption peak, 1591cm-1And 1488cm-1The peak at place is the breathing vibration absworption peak of phenyl ring, 750cm-1Replace for the neighbour two on phenyl ring
Absworption peak, 810cm-1To align substituted absworption peak on phenyl ring.In summary, it can be verified that synthesis has obtained 1- phenthazine
Base -3- (4- chlorphenyls) -4- acetyl group -1,5- acetyl butyryls.
Fig. 5 is 1- phenothiazinyls -3- (4- chlorphenyls) -4- acetyl group -1,5- acetyl butyryls prepared by the embodiment of the present invention 2
's1HNMR collection of illustrative plates, as shown in Figure 5：1HNMR:6.66-7.19(m,12H,Ar-H),2.60-2.62(d,2H,COCH2),3.62-
3.67(m,1H,CH),2.11(s,3H,COCH3).
Embodiment 3
Weigh 0.002mol acetylacetone,2,4-pentanediones and 0.0015mol anhydrous Ks2CO3In dry mortar, it is mixed rapidly
It is even, 0.001mol 1- phenothiazinyls -3- (4- bromophenyls)-propenone is added, 33min is ground.In process of lapping, mixture
Meeting gradually becomes glutinous, continues to grind up to material no longer changes, uses TLC tracking and monitoring reaction process, solvent used
It is 1 for volume ratio:5 ethyl acetate and the mixed solvent of petroleum ether, after question response terminates, are carried out repeatedly with pure water to product
Suction filtration is washed, until the pH of filtrate is in neutrality, then by filter cake natural air drying, celadon powder, as 1- phenothiazinyls -3- is obtained
(4- bromophenyls) -4- acetyl group -1,5- acetyl butyryls.Yield is：86.5%, m.p.173 DEG C~176 DEG C.
Fig. 3 is 1- phenothiazinyls -3- (4- bromophenyls) -4- acetyl group -1,5- acetyl butyryls prepared by the embodiment of the present invention 3
Infared spectrum, as shown in Figure 3：3051cm-1Locate the vibration absorption peak for Ar-H, and in 2976cm-1、1383cm-1Locate as-CH3's
Absworption peak, in 2934cm-1、1442cm-1Locate as-CH2Absworption peak, in 1716cm-1、1650cm-1The peak at place is C=O feature
Absworption peak, 1558cm-1And 1471cm-1The peak at place is the breathing vibration absworption peak of phenyl ring, 736cm-1Replace for the neighbour two on phenyl ring
Absworption peak, 805cm-1To align substituted absworption peak on phenyl ring.In summary, it can be verified that synthesis has obtained 1- phenthazine
Base -3- (4- bromophenyls) -4- acetyl group -1,5- acetyl butyryls.
Fig. 6 is 1- phenothiazinyls -3- (4- bromophenyls) -4- acetyl group -1,5- acetyl butyryls prepared by the embodiment of the present invention 3
's1HNMR collection of illustrative plates, as shown in Figure 6：1HNMR:6.30-7.42(m,12H,Ar-H),2.60-2.66(d,2H,COCH2),3.54-
3.71(m,1H,CH),2.05(s,3H,COCH3).
Embodiment 4
Weigh 0.002mol acetylacetone,2,4-pentanediones and 0.0015mol anhydrous Ks2CO3In dry mortar, it is mixed rapidly
It is even, 0.001mol 1- phenothiazinyls -3- (4- dimethylamino phenyls)-propenone is added, 36min is ground.In process of lapping,
Mixture can gradually become glutinous, continue to grind up to material no longer changes, used using TLC tracking and monitoring reaction process
Solvent is that volume ratio is 1:5 ethyl acetate and the mixed solvent of petroleum ether, after question response terminates, are entered with pure water to product
Row repeatedly washes suction filtration, until the pH of filtrate is in neutrality, then by filter cake natural air drying, obtains yellow powder, as 1- phenthazine
Base -3- (4- dimethylamino phenyls) -4- acetyl group -1,5- acetyl butyryls.Yield is：85.3%, m.p.152 DEG C~155 DEG C.
IR(KBr)ν(cm-1):3068 (=C-H, Ar-H), 2981,1385 (- CH3), 1733,1708 (C=O), 1595,
1468 (Ar), 738 (neighbour two replaces on phenyl ring), 817 (substitution is aligned on phenyl ring)
1HNMR:6.51-7.04(m,12H,Ar-H),2.64-2.66(d,2H,COCH2),3.50-3.72(m,1H,CH),
2.12(s,3H,COCH3),2.90(s,3H,NCH3).
Embodiment 5
Weigh 0.002mol acetylacetone,2,4-pentanediones and 0.0015mol anhydrous Ks2CO3In dry mortar, it is mixed rapidly
It is even, 0.001mol 1- phenothiazinyls -3- (4- methoxyphenyls)-propenone is added, 34min is ground.In process of lapping, mix
Compound can gradually become glutinous, continue to grind up to material no longer changes, use TLC tracking and monitoring reaction process, exhibition used
It is that volume ratio is 1 to open agent:5 ethyl acetate and the mixed solvent of petroleum ether, after question response terminates, are carried out with pure water to product
Repeatedly washing suction filtration, until the pH of filtrate is in neutrality, then by filter cake natural air drying, obtains buff powder, as 1- phenthazine
Base -3- (4- methoxyphenyls) -4- acetyl group -1,5- acetyl butyryls.Yield is 85.7%, m.p.116 DEG C~118 DEG C.
IR(KBr)ν(cm-1):3057 (=C-H, Ar-H), 2975,1395 (- CH3),2934,1439(-CH2),1738,
1653 (C=O), 1591,1463 (Ar), 742 (neighbour two replaces on phenyl ring), 815 (substitution is aligned on phenyl ring)
1HNMR:6.47-7.11(m,12H,Ar-H),2.62-2.64(d,2H,COCH2),3.53-3.82(m,1H,CH),
2.11(s,3H,COCH3),3.82(s,3H,OCH3)
Embodiment 6
Weigh 0.002mol acetylacetone,2,4-pentanediones and 0.0015mol anhydrous Ks2CO3In dry mortar, it is mixed rapidly
It is even, 0.001mol 1- phenothiazinyls -3- (4- aminomethyl phenyls)-propenone is added, 32min is ground.In process of lapping, mixing
Thing can gradually become glutinous, continue to grind up to material no longer changes, use TLC tracking and monitoring reaction process, expansion used
Agent is that volume ratio is 1:5 ethyl acetate and the mixed solvent of petroleum ether, after question response terminates, are carried out many with pure water to product
Secondary washing suction filtration, until the pH of filtrate is in neutrality, then by filter cake natural air drying, obtains brown ceramic powder, as 1- phenothiazinyls -3-
(4- aminomethyl phenyls) -4- acetyl group -1,5- acetyl butyryls.Yield is：85.8%, m.p.114 DEG C~116 DEG C.
IR(KBr)ν(cm-1):3057 (=C-H, Ar-H), 2981,1394 (- CH3), 1697,1668 (C=O), 1593,
1463 (Ar), 743 (neighbour two replaces on phenyl ring), 817 (substitution is aligned on phenyl ring)
1HNMR:6.63-7.12(m,12H,Ar-H),2.63-2.65(d,2H,COCH2),3.52-3.76(m,1H,CH),
2.08(s,3H,COCH3),2.45(s,3H,CH3).
Embodiment 7
Weigh 0.0018mol acetylacetone,2,4-pentanediones and 0.0014mol anhydrous Ks2CO3In dry mortar, it is mixed rapidly
It is even, 0.001mol 1- phenothiazinyls -3- (4- nitrobenzophenones)-propenone is added, 38min is ground.In process of lapping, mixing
Thing can gradually become glutinous, continue to grind up to material no longer changes, use TLC tracking and monitoring reaction process, expansion used
Agent is that volume ratio is 1:5 ethyl acetate and the mixed solvent of petroleum ether, after question response terminates, are carried out many with pure water to product
Secondary washing suction filtration, until the pH of filtrate is in neutrality, then by filter cake natural air drying, obtains pale yellow powder, as 1- phenothiazinyls-
3- (4- nitrobenzophenones) -4- acetyl group -1,5- acetyl butyryls.Yield is 89.2%, m.p.108 DEG C~110 DEG C.
IR(KBr)ν(cm-1):3058 (=C-H, Ar-H), 2982,1383 (- CH3), 1705,1665 (C=O), 1591,
1462 (Ar), 742 (neighbour two replaces on phenyl ring), 818 (substitution is aligned on phenyl ring)
1HNMR:6.56-8.00(m,12H,Ar-H),2.65-2.68(d,2H,COCH2),3.61-3.76(m,1H,CH),
2.14(s,3H,COCH3).
Embodiment 8
Weigh 0.0012mol acetylacetone,2,4-pentanediones and 0.0011mol anhydrous Ks2CO3In dry mortar, it is mixed rapidly
It is even, 0.001mol 1- phenothiazinyls -3- (4- fluorophenyls)-propenone is added, 31min is ground.In process of lapping, mixture
Meeting gradually becomes glutinous, continues to grind up to material no longer changes, uses TLC tracking and monitoring reaction process, solvent used
It is 1 for volume ratio:5 ethyl acetate and the mixed solvent of petroleum ether, after question response terminates, are carried out repeatedly with pure water to product
Suction filtration is washed, until the pH of filtrate is in neutrality, then by filter cake natural air drying, pale yellow powder, as 1- phenothiazinyls -3- is obtained
(4- fluorophenyls) -4- acetyl group -1,5- acetyl butyryls.Yield is：87.8%, m.p.162 DEG C~164 DEG C.
IR(KBr)ν(cm-1):3059 (=C-H, Ar-H), 2972,1380 (- CH3),2931,1440(-CH2),1706,
1662 (C=O), 1593,1462 (Ar), 748 (neighbour two replaces on phenyl ring), 816 (substitution is aligned on phenyl ring)
1HNMR:6.57-7.12(m,12H,Ar-H),2.58-2.61(d,2H,COCH2),3.72-3.80(m,1H,CH),
2.12(s,3H,COCH3).
Embodiment 9
Weigh 0.002mol acetylacetone,2,4-pentanediones and 0.0015mol NaOH be mixed uniformly in dry mortar, rapidly,
0.001mol 1- phenothiazinyls -3- (2- thienyls)-propenone is added, 39min is ground.In process of lapping, mixture can be by
Gradual change is sticked, and continues to grind until material no longer changes, using TLC tracking and monitoring reaction process, solvent used is body
Product is than being 1:5 ethyl acetate and the mixed solvent of petroleum ether, after question response terminates, are repeatedly washed with pure water to product
Suction filtration, until the pH of filtrate is in neutrality, then by filter cake natural air drying, obtains pale yellow powder, as 1- phenothiazinyls -3- (2-
Thienyl) -4- acetyl group -1,5- acetyl butyryls.Yield is：86.0%, m.p.120 DEG C~123 DEG C.
IR(KBr)ν(cm-1):3050 (=C-H, Ar-H), 2976,1382 (- CH3),2930,1452(-CH2),1702,
1650 (C=O), 1593,1476 (Ar), 750 (neighbour two replaces on phenyl ring)
1HNMR:6.57-7.01(m,8H,Ar-H),2.65-2.66(d,2H,COCH2),3.62-3.76(m,1H,CH),
2.08(s,3H,COCH3),7.01(d,1H,Thy-H),6.73(m,1H,Thy-H).
Embodiment 10
Weigh 0.002mol acetylacetone,2,4-pentanediones and 0.0013mol NaOH be mixed uniformly in dry mortar, rapidly,
0.001mol 1- phenothiazinyls -3- (2- pyridine radicals)-propenone is added, 30min is ground.In process of lapping, mixture can be by
Gradual change is sticked, and continues to grind until material no longer changes, using TLC tracking and monitoring reaction process, solvent used is body
Product is than being 1:5 ethyl acetate and the mixed solvent of petroleum ether, after question response terminates, are repeatedly washed with pure water to product
Suction filtration, until the pH of filtrate is in neutrality, then by filter cake natural air drying, obtains brown ceramic powder, as 1- phenothiazinyls -3- (2- pyrroles
Piperidinyl) -4- acetyl group -1,5- acetyl butyryls.Yield is 87.5%, m.p.125 DEG C~127 DEG C.
IR(KBr)ν(cm-1):3053 (=C-H, Ar-H), 2976,1385 (- CH3),2931,1442(-CH2),1714,
1669 (C=O), 1583,1471 (Ar), 738 (neighbour two replaces on phenyl ring)
1HNMR:6.58-6.93(m,8H,Ar-H),2.61-2.64(d,2H,COCH2),3.57-3.77(m,1H,CH),
2.07(s,3H,COCH3),7.28-7.54(d,1H,Py-H),7.70-7.76(m,2H,Py-H),7.92-7.94(d,1H,Py-
H).
Embodiment 11
Weigh 0.0015mol acetylacetone,2,4-pentanediones and 0.0012mol NaOH be mixed uniformly in dry mortar, rapidly,
0.001mol 1- phenothiazinyls -3- (2- furyls)-propenone is added, 40min is ground.In process of lapping, mixture can be by
Gradual change is sticked, and continues to grind until material no longer changes, using TLC tracking and monitoring reaction process, solvent used is body
Product is than being 1:5 ethyl acetate and the mixed solvent of petroleum ether, after question response terminates, are repeatedly washed with pure water to product
Suction filtration, until the pH of filtrate is in neutrality, then by filter cake natural air drying, obtains brown ceramic powder, as 1- phenothiazinyls -3- (2- furans
Mutter base) -4- acetyl group -1,5- acetyl butyryls.Yield is：86.2%, m.p.122 DEG C~124 DEG C.
IR(KBr)ν(cm-1):3058 (=C-H, Ar-H), 2872,1388 (- CH3),2925,1437(-CH2),1714,
1680 (C=O), 1591,1463 (Ar), 1126,1039 (C-O-C), 743 (neighbour two replaces on phenyl ring)
1HNMR:6.58-7.01(m,8H,Ar-H),2.58-2.62(d,2H,COCH2),3.51-3.76(m,1H,CH),
2.09(s,3H,COCH3),5.83-5.90(d,1H,Fu-H),6.29-6.32(m,1H,Fu-H),7.22-7.28(d,1H,Fu-
H).
Embodiment 12
Weigh 0.001mol acetylacetone,2,4-pentanediones and 0.001mol NaOH are mixed uniformly in dry mortar, rapidly, then
0.001mol 1- phenothiazinyls -3- (3- nitrobenzophenones)-propenone is added, 35min is ground.In process of lapping, mixture can be by
Gradual change is sticked, and continues to grind until material no longer changes, using TLC tracking and monitoring reaction process, solvent used is body
Product is than being 1:5 ethyl acetate and the mixed solvent of petroleum ether, after question response terminates, are repeatedly washed with pure water to product
Suction filtration, until the pH of filtrate is in neutrality, then by filter cake natural air drying, obtains grey powder, as 1- phenothiazinyls -3- (3- nitre
Base phenyl) -4- acetyl group -1,5- acetyl butyryls.Yield is 88.3%, m.p.114 DEG C~117 DEG C.
IR(KBr)ν(cm-1):3057 (=C-H, Ar-H), 2973,1387 (- CH3),2927,1440(-CH2),1708,
1648 (C=O), 1593,1463 (Ar), 743 (neighbour two replaces on phenyl ring)
1HNMR:6.56-8.02(m,12H,Ar-H),2.65-2.68(d,2H,COCH2),3.57-3.89(m,1H,CH),
2.08(s,3H,COCH3).
In addition to the implementation, raw material 1- phenothiazinyls -3- aryl-propenone can also use following material, and wherein Ar is
O-Nitrophenylfluorone, hydroxy phenyl, styryl etc.；It is numerous to list herein.
In addition, 1- phenothiazinyls -3- aryl-propenone in the present invention can be prepared using following methods：
10- acetyl phenothiazines (1.21g, 0.005mol), NaOH particles are added in the three-necked flask dried to 250mL
(0.24g, 0.006mol) and absolute methanol 15mL, stirs 10min at room temperature, and the absolute methanol of aromatic aldehyde (0.006mol) is added dropwise
Solution 10mL, back flow reaction 30min (TLC monitors the reaction process).Reaction is cooled to room temperature after terminating, by gained reaction solution
All solids are separated out in 40mL frozen water, suction filtration, filter cake is washed with frozen water, natural air drying, then it is carried out again with absolute methanol
Crystallization, that is, obtain obtaining 1- phenothiazinyls -3- aryl-propenone.Its reaction equation is as follows：
Wherein Ar is phenyl, rubigan, p-bromophenyl, p-fluorophenyl, aminomethyl phenyl, methoxyphenyl, p-nitrophenyl
Base, m-nitro base, O-Nitrophenylfluorone, dimethylamino phenyl, hydroxy phenyl, styryl, furyl, thienyl or pyridine
Base.
The present invention uses solid-phase sequencing, by acetylacetone,2,4-pentanedione and 1- phenothiazinyls -3- aryl-propylene reactive ketone, synthesis
A series of new Michael addition compound products for having no document report, i.e. 1- phenothiazinyls -3- aryl -4- acetyl group -1,5- oneself two
Ketone, and its preparation method is explored, while optimizing experiment condition, the reaction time is shortened, is that green syt is made that contribution.
1- phenothiazinyl -3- aryl -4- acetyl group -1,5- the acetyl butyryls that the present invention is provided are a series of brand-new containing phenothiazinyl
Ketones derivant, with sterilization, it is antibacterial the effects such as, have good application prospect in the field such as antibacterial, antiviral.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions, it is every according to the present invention
Any simple modification, change and equivalent structure transformation that technical spirit is made to above example, still fall within skill of the present invention
In the protection domain of art scheme.
Claims (8)
1. a kind of 1- phenothiazinyls -3- aryl -4- acetyl group -1,5- acetyl butyryls, it is characterised in that its general structure is as follows：
Wherein Ar is phenyl, substituted-phenyl or heterocyclic radical.
2. 1- phenothiazinyls -3- aryl -4- acetyl group -1,5- acetyl butyryls according to claim 1, it is characterised in that：Institute
Substituted-phenyl is stated for rubigan, p-bromophenyl, p-fluorophenyl, aminomethyl phenyl, methoxyphenyl, p-nitrophenyl, a nitro
Phenyl, O-Nitrophenylfluorone, dimethylamino phenyl, hydroxy phenyl, styryl；
The heterocyclic radical is furyl, thienyl or pyridine radicals.
3. the preparation method of 1- phenothiazinyl -3- aryl -4- acetyl group -1,5- acetyl butyryls described in claim 1 or 2, it is special
Levy and be, it is comprised the following steps that：
Amol 1- phenothiazinyls -3- aryl-propenone, B mol catalyst, C mol levulinics is added into dry mortar
Ketone, grinding is reacted it, and TLC tracing detections are until reaction is complete, and then washing, suction filtration, will be obtained after filtration cakes torrefaction
1- phenothiazinyl -3- aryl -4- acetyl group -1,5- acetyl butyryls, wherein A:B:C=1:(1~1.5):(1~2.0).
4. the preparation method of 1- phenothiazinyls -3- aryl -4- acetyl group -1,5- acetyl butyryls according to claim 3, it is special
Levy and be：The general structure of the 1- phenothiazinyls -3- aryl-propenone is as follows：
Wherein Ar be phenyl, rubigan, p-bromophenyl, p-fluorophenyl, aminomethyl phenyl, methoxyphenyl, p-nitrophenyl,
Nitrobenzophenone, O-Nitrophenylfluorone, dimethylamino phenyl, hydroxy phenyl, styryl, furyl, thienyl or pyridine radicals.
5. the preparation method of 1- phenothiazinyls -3- aryl -4- acetyl group -1,5- acetyl butyryls according to claim 3, it is special
Levy and be：The catalyst is solid NaOH or anhydrous K2CO3。
6. the preparation method of 1- phenothiazinyls -3- aryl -4- acetyl group -1,5- acetyl butyryls according to claim 3, it is special
Levy and be：The time of the griding reaction is 30~40min.
7. the preparation method of 1- phenothiazinyls -3- aryl -4- acetyl group -1,5- acetyl butyryls according to claim 3, it is special
Levy and be：Represent that raw material reaction is complete when the raw material point of 1- phenothiazinyls -3- aryl-propenone disappears；Used in TLC detections
Solvent is that volume ratio is 1:5 ethyl acetate and the mixed solvent of petroleum ether.
8. the preparation method of 1- phenothiazinyls -3- aryl -4- acetyl group -1,5- acetyl butyryls according to claim 3, it is special
Levy and be：During suction filtration, filter cake is repeatedly washed, until the pH of filtrate is in neutrality.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130742A (en) * | 2013-02-27 | 2013-06-05 | 陕西科技大学 | N-phenothiazinylchalcone preparation method |
| CN103214429A (en) * | 2013-04-11 | 2013-07-24 | 陕西科技大学 | 1-substituted phenyl-3-(N-phenothiazinyl)propyl-2-ene-1-ketone as well as preparation method and application thereof |
| CN104311607A (en) * | 2014-09-17 | 2015-01-28 | 陕西科技大学 | 1-Ferrocenyl-3-aryl-3-diacetylmethylene-acetone and preparation method thereof |
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2017
- 2017-05-26 CN CN201710386947.4A patent/CN107188889A/en active Pending
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|---|---|---|---|---|
| CN103130742A (en) * | 2013-02-27 | 2013-06-05 | 陕西科技大学 | N-phenothiazinylchalcone preparation method |
| CN103214429A (en) * | 2013-04-11 | 2013-07-24 | 陕西科技大学 | 1-substituted phenyl-3-(N-phenothiazinyl)propyl-2-ene-1-ketone as well as preparation method and application thereof |
| CN104311607A (en) * | 2014-09-17 | 2015-01-28 | 陕西科技大学 | 1-Ferrocenyl-3-aryl-3-diacetylmethylene-acetone and preparation method thereof |
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