CN103360395B - A kind of indole carbazole compound and its preparation method and application - Google Patents
A kind of indole carbazole compound and its preparation method and application Download PDFInfo
- Publication number
- CN103360395B CN103360395B CN201210104960.3A CN201210104960A CN103360395B CN 103360395 B CN103360395 B CN 103360395B CN 201210104960 A CN201210104960 A CN 201210104960A CN 103360395 B CN103360395 B CN 103360395B
- Authority
- CN
- China
- Prior art keywords
- compound
- organic solvent
- dmso
- nmr
- indole carbazole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 O=C(*1)C=CC1=O Chemical compound O=C(*1)C=CC1=O 0.000 description 1
- JXDYKVIHCLTXOP-UHFFFAOYSA-N O=C(c1ccccc1N1)C1=O Chemical compound O=C(c1ccccc1N1)C1=O JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 1
- LLSIEQLHMGACNA-UHFFFAOYSA-N OC(c1c[nH]c2ccccc12)(c(cccc1)c1N1)C1=O Chemical compound OC(c1c[nH]c2ccccc12)(c(cccc1)c1N1)C1=O LLSIEQLHMGACNA-UHFFFAOYSA-N 0.000 description 1
- WHJMXLYLQPXPSY-UHFFFAOYSA-N c1c(-c2c[nH]c3c2cccc3)c2ccccc2[nH]1 Chemical compound c1c(-c2c[nH]c3c2cccc3)c2ccccc2[nH]1 WHJMXLYLQPXPSY-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N c1c[nH]c2ccccc12 Chemical compound c1c[nH]c2ccccc12 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Indole Compounds (AREA)
Abstract
The invention discloses a kind of indole carbazole compound, it is characterised in that this indole carbazole compound has the structure as shown in Formulas I, II, III or IV,Formulas I,Formula II,Formula III,
Description
Technical field
The present invention relates to a kind of indole carbazole compound and preparation method thereof, and this indole carbazole class
Application in resisting tobacco mosaic virus (TMV) for the compound.
Background technology
Tobacco mosaic virus (TMV) (Tobacco mosaic virus, TMV) causes planting of being widely present in the world
Thing disease, and its control is still challenging.It is a kind of widely studied model virus, simultaneously
It is also strong, very big to the agricultural production harm plant virus of a kind of infectivity.Tobacco mosaic virus (TMV) contains
Article one, single RNA positive-sense strand of 6395 nucleotides, RNA is by 2130 identical glutelin subunit institutes
Parcel, each subunit contains 158 amino acid residues.The disk originating in glutelin is reacted in assembling of virus
The specific recognition effect to TMV RNA the preceding paragraph special sequence for the aggregation, this section of sequence has been referred to as
Begin to assemble site (assembly origin of TMV RNA).The general process that TMV assembles is RNA's
Assembling homing sequence protein-bonded 20S disk aggregation, then protein masses is continuously added and promotes disease
Poison is constantly extended.
Tylophora alkaloids is the derivative of phenanthroindolizididerivative pyridine, and it is biological alive that this compounds is showed
Property includes antibacterial, antiviral, antitumor and anticancer etc..Wherein, antofine has significant Tobacco mosaic
HIV suppression activity, it is 1 × 10-6TMV inhibiting rate under the concentration of g/mL is 60%.Same
Under experiment condition, reference commercialization antiviral drugs DHT is 5 × 10-4Suppression under the concentration of g/mL
Rate is only 50%.Early-stage Study shows, the assembling initiation site (oriRNA) to TMV RNA for the antofine
Having higher compatibility, its antiviral property will likely depend on the combination with oriRNA and assembles initial
Interference.
Indole carbazole is that a class has extensive bioactive natural alkaloid, and its biologically active includes killing
Bacterium, antiviral, anti-hypertension and antitumor etc..Wherein studying most commonly used is Staurosporine
And Rebeccamycin.Staurosporine is considered as a kind of great potential, typical cyclin
White dependant kinase (CDKs) and the inhibitor of protein kinase C (PKC).And Rebeccamycin makees
For DNA and suppression topoisomerase I, there is good active anticancer.It can stably be opened up effectively
Flutter isomerase I-DNA shearing compound and DNA otch that suppression is produced by topoisomerase I
Connect and repair.Owing to Rebeccamycin has good topoisomerase I inhibitory activity and anticancer work
Property, it has been applied to clinical testing treatment liver cancer, leukaemia etc..
Antofine (Antofine) is an almost plane molecule containing aromatic rings, and the molecule of this structure is easy
In the noncovalent interaction forming insertion type with nucleic acid.Experimental study also indicates that, antofine antiviral
Activity is that the virus assembly inhibitory action being target with TMV RNA is caused[5]。
At present, the compound of the anti-TMV of Devoting Major Efforts To Developing should be needed.
Content of the invention
It is an object of the invention to provide the indole carbazole compound of a kind of new anti-TMV.
On the one hand, the invention provides a kind of indole carbazole compound, it is characterised in that this indoles click
Azole compounds has the structure as shown in Formulas I, II, III or IV,
Formulas I,
Formula II,
Formula III,
Formula IV,
Wherein, R1、R2, X, Y, Z, M and N be separate group, R1And R2It is respectively
-the H of different numbers and the position of substitution, alkyl, aryl, hydroxyl, alkoxyl, aryloxy group, ester group, sulphur
At least one in perester radical, azido, amino, halogen, nitro and cyano group, X for-O-,-S-,
One in substituted or unsubstituted alkylidene and substituted or unsubstituted imido grpup, Y and Z respectively-H,
One in alkyl, aryl, hydroxyl, alkoxyl, aryloxy group, carbonyl and thiocarbonyl group, M and N divides
Wei-H, alkyl, aryl, hydroxyl, alkoxyl, aryloxy group, aldehyde radical, ester group, sulfonate group, folded
At least one in nitrogen base, amino, halogen, nitro and cyano group.
Preferably, X be-O-or-NH, it is further preferred that in Y and Z one be-H, another
For-H or carbonyl.
Preferably, M and N is respectively-CH2OH。
Preferably, described indole carbazole compound is
On the other hand, the invention provides the preparation method of a kind of indole carbazole compound, comprising:
(1) by substituted or unsubstituted
At Me2NH and EtOH exists
Under, reaction obtains the first product；
(2) the first product step (1) being obtained and NaBH4、BF3Et2O and DME contacts,
Obtain the second product；
(3) the second product that step (2) is obtained with
React in the presence of AcOH.
Preferably, X is-H in-O-or-NH, Y and Z one, and another is-H or carbonyl.
Preferably, described method also includes:
Under boron-Hization sodium reduction reaction condition, the product that obtain step (3) and the first organic solvent
Contact, the first product obtaining, wherein, X is that O, Y and Z are carbonyl, described first organic molten
Agent for be dried four-H furans, dimethylformamide, methyl alcohol, ethanol, Isosorbide-5-Nitrae-dioxane, chloroform, four
At least one in chlorination carbon；Or
Under-Hization aluminium lithium reduction reaction conditions, the product that obtain step (3) and the second organic solvent
Contact, the second product obtaining, wherein, X is that O, Y and Z are carbonyl, described second organic molten
Agent for be dried four-H furans, methyl alcohol, ethanol, Isosorbide-5-Nitrae-dioxane, chloroform, in carbon tetrachloride at least
A kind of；Or
Under zinc granule, concentrated hydrochloric acid reduction reaction conditions, the product and the 3 that obtain step (3) are organic
Solvent contacts, the third product obtaining, and wherein, X is that NH, Y and Z are carbonyl, and the described 3rd
Organic solvent is DMF, chloroform, at least one in carbon tetrachloride；Or
Under boron-Hization sodium, BFEE reduction reaction conditions, product that step (3) is obtained
With the 4th organic solvent exposure, the 4th product obtaining, wherein, X is that NH, Y and Z are carbonyl,
Described 4th organic solvent for be dried four-H furans, methyl alcohol, ethanol, Isosorbide-5-Nitrae-dioxane, chloroform, four
At least one in chlorination carbon.
The third aspect, the invention provides indole carbazole compound as above at resisting tobacco mosaic disease
Application in Du.
The indole carbazole compound that the present invention provides has anti-TMV activity.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of indole carbazole compound, this indole carbazole compound has
Just like the structure shown in Formulas I, II, III or IV,
Formulas I,
Formula II,
Formula III,
Formula IV,
Wherein, R1、R2, X, Y, Z, M and N be separate group, R1And R2It is respectively
-the H of different numbers and the position of substitution, alkyl, aryl, hydroxyl, alkoxyl, aryloxy group, ester group, sulphur
At least one in perester radical, azido, amino, halogen, nitro and cyano group, X for-O-,-S-,
One in substituted or unsubstituted alkylidene and substituted or unsubstituted imido grpup, Y and Z respectively-H,
One in alkyl, aryl, hydroxyl, alkoxyl, aryloxy group, carbonyl and thiocarbonyl group, M and N divides
Wei-H, alkyl, aryl, hydroxyl, alkoxyl, aryloxy group, aldehyde radical, ester group, sulfonate group, folded
At least one in nitrogen base, amino, halogen, nitro and cyano group.
In the present invention, alkyl is preferably C1-C20Alkyl, more preferably C1-C10Alkyl；Alkoxyl
It is preferably C1-C20Alkoxyl, more preferably C1-C10Alkoxyl；Aryloxy group is preferably C6-C20
Aryloxy group, more preferably C6-C10Aryloxy group；Ester group is preferably C1-C10Alkoxyl,
More preferably C1-C5Alkoxyl；Sulfonate group is preferably C1-C10Alkoxyl, more preferably C1-C5
Alkoxyl, amino is preferably C0-C20Amino, more preferably C0-C10Amino.
Preferably, X be-O-or-NH, it is further preferred that in Y and Z one be-H, another
For-H or carbonyl.
Preferably, M and N is respectively-CH2OH。
Preferably, R1And R2It is respectively-H, the C of different number and the position of substitution1-C10Alkyl, C6-C10
Aryl, C1-C10Alkoxyl, C6-C10Aryloxy group, C1-C5Ester group, C1-C5Sulphonic acid ester
Base, C0-C10Amino, hydroxyl, azido, at least one in halogen nitro and cyano group, further
Preferably, R1And R2It is respectively-H, the C of different number and the position of substitution1-C10Alkoxyl, C6-C10
Aryloxy group and C0-C10Amino at least one.
Indole carbazole compound of the present invention is still more preferably
On the other hand, the invention provides the preparation method of a kind of indole carbazole compound, comprising:
(1) by substituted or unsubstituted
At Me2NH and EtOH exists
Under, reaction obtains the first product；
(2) the first product step (1) being obtained and NaBH4、BF3Et2O and DME contacts,
Obtain the second product；
(3) the second product that step (2) is obtained with
React in the presence of AcOH.
In the inventive method, the reaction condition of step (1) includes: temperature 15-30 DEG C, time 22-26h.
In the inventive method, the contact conditions of step (2) includes: temperature 15-30 DEG C, time 1-3h.
In the inventive method, the reaction condition of step (3) includes: temperature 90-100 DEG C, the time according to
The difference of X is different, and for example, X is-O-, and the reaction time is 45-50h；X is-NH, during reaction
Between be 22-26h.
In the inventive method, X be preferably-O-or-NH, it is further preferred that in Y and Z one be-H,
Another is-H or carbonyl.
Method is exemplified below:
The inventive method preferably also includes:
Under boron-Hization sodium reduction reaction condition, the product that obtain step (3) and the first organic solvent
Contact, the first product obtaining, wherein, X is that O, Y and Z are carbonyl, described first organic molten
Agent for be dried four-H furans, dimethylformamide, methyl alcohol, ethanol, Isosorbide-5-Nitrae-dioxane, chloroform, four
At least one in chlorination carbon；Or
Under-Hization aluminium lithium reduction reaction conditions, the product that obtain step (3) and the second organic solvent
Contact, the second product obtaining, wherein, X is that O, Y and Z are carbonyl, described second organic molten
Agent for be dried four-H furans, methyl alcohol, ethanol, Isosorbide-5-Nitrae-dioxane, chloroform, in carbon tetrachloride at least
A kind of；Or
Under zinc granule, concentrated hydrochloric acid reduction reaction conditions, the product and the 3 that obtain step (3) are organic
Solvent contacts, the third product obtaining, and wherein, X is that NH, Y and Z are carbonyl, and the described 3rd
Organic solvent is DMF, chloroform, at least one in carbon tetrachloride；Or
Under boron-Hization sodium, BFEE reduction reaction conditions, product that step (3) is obtained
With the 4th organic solvent exposure, the 4th product obtaining, wherein, X is that NH, Y and Z are carbonyl,
Described 4th organic solvent for be dried four-H furans, methyl alcohol, ethanol, Isosorbide-5-Nitrae-dioxane, chloroform, four
At least one in chlorination carbon.
Reaction is exemplified below:
In the present invention, boron-Hization sodium reduction reaction condition includes, temperature is room temperature, and the time is 3 hours.
In the present invention ,-Hization aluminium lithium reduction reaction conditions includes, temperature is room temperature, and the time is 3 hours.
In the present invention, zinc granule, concentrated hydrochloric acid reduction reaction conditions include, temperature is 100 DEG C, and the time is 3
Hour.
In the present invention, boron-Hization sodium, BFEE reduction reaction conditions include, temperature is 80 DEG C,
Time is 3 hours.
Fourth aspect, the invention provides indole carbazole compound as above at resisting tobacco mosaic disease
Application in Du.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, various possible combinations are no longer illustrated by the present invention separately.
Additionally, also can be combined between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Embodiment
Prepare following compound:
Compound 1 (3,3 '-biindolyl):
Indoles (11.72g, 100mmol), isatin (14.71g, 100mmol), the diformazan aqueous amine of 40%
The heating stirring reaction 1 under the conditions of 45 DEG C in the flask of 250mL of solution (1mL) and 150mL ethanol
It after little Shi, is stirred overnight at room temperature.Then in system, water is added until system is muddy (150-200mL water),
After several minutes, having gray solid to separate out, suction filtration obtains intermediate (23.78g, 90%) with directly after being dried
Tap into next step reaction of row.13.22g midbody compound (50 is added in the flask of 250mL
Mmol), boron-Hization sodium (5.68g, 150mmol) and 75mL glycol dimethyl ether.Then by perseverance
Pressure dropping funel is slowly dropped into the 25mL of BFEE (28.38g, 200mmol) in system
The dropping of ethylene glycol dimethyl ether solution, about 30min finishes.After being stirred at room temperature one hour, use constant pressure addition
Funnel is added dropwise to the 6N HCl of 50mL in system, adds thereafter water.Suction filtration obtains white after being dried
Solid 8.60g, productivity is 74%, mp:285-287 DEG C.1H NMR (400MHz, DMSO d6): δ
7.07 (t, J=7.2Hz, 2H), 7.15 (t, J=7.2Hz, 2H), 7.46 (d, J=8.0Hz, 2H), 7.65 (d, J=
2.4Hz, 2H), 7.79 (d, J=7.8Hz, 2H), 11.18 (s, 2H)；13C NMR (400MHz, DMSO
d6): δ 109.7 (s), 111.5 (s), 118.8 (s), 119.6 (s), 121.2 (s), 121.8 (s), 126.0 (s),
136.3(s)。
Compound 2:
Add 3 in 50mL flask, 3 '-biindolyl (0.12g, 0.50mmol), maleimide (0.10
G, 1.00mmol) and 15mL glacial acetic acid heat under the conditions of 90-100 DEG C reaction 24 hours after, take out
Be filtered dry dry after obtain red solid 0.10g (60%), mp ＞ 300 DEG C.1H NMR (400MHz, DMSO
d6): δ 7.42 (t, J=7.2Hz, 2H), 7.59 (t, J=7.2Hz, 2H), 7.80 (d, J=8.0Hz, 2H),
8.83 (d, J=8.0Hz, 2H), 11.12 (s, 1H), 12.08 (s, 2H)；13C NMR (400MHz, DMSO
d6): δ 111.5 (s), 112.4 (s), 119.7 (s), 120.7 (s), 122.5 (s), 123.4 (s), 127.0 (s), 128.5 (s),
142.4 (s), 170.0 (s).
Compound 3:
Add 3 in 50mL flask, 3 '-biindolyl (0.12g, 0.50mmol), maleic anhydride (0.10
G, 1.00mmol) and 15mL glacial acetic acid heat under the conditions of 90-100 DEG C reaction 24 hours after, take out
Be filtered dry dry after obtain dark red solid 0.07g (60%), mp ＞ 300 DEG C.1H NMR (400MHz,
DMSO d6): δ 7.45 (t, J=7.2Hz, 2H), 7.65 (t, J=7.2Hz, 2H), 7.80 (d, J=8.0Hz,
2H), 8.83 (d, J=8.0Hz, 2H), 12.40 (s, 2H)；13C NMR (400MHz, DMSO d6): δ
109.3 (s), 112.5 (s), 120.3 (d), 123.8 (d), 127.9 (s), 129.1 (s), 142.6 (s), 163.6 (s).
Compound 4 (5-methoxyl group-3,3 '-biindolyl):
Synthetic method is with 3, and 3 '-biindolyl 1, white solid, productivity is 73%, mp:183-185 DEG C.1H NMR (400MHz, DMSO d6): δ 3.79 (s, 3H), 6.82 (d, J=8.0Hz, 1H), 7.07 (t, J=
7.2Hz, 1H), 7.16 (t, J=7.2Hz, 1H), 7.22 (s, 1H), 7.36 (d, J=8.0Hz, 1H), 7.47 (d, J
=8.0Hz, 1H), 7.60 (s, 1H), 7.65 (s, 1H), 7.78 (d, J=8.0Hz, 1H), 11.02 (s, 1H),
11.15 (s, 1H)；13C NMR (400MHz, DMSO d6): δ 55.3 (s), 101.3 (s), 109.5 (s),
109.8 (s), 111.3 (s), 111.5 (s), 111.2 (s), 118.7 (s), 119.5 (s), 121.2 (s), 121.7 (s),
122.6 (s), 126.1 (s), 126.3 (s), 131.5 (s), 136.4 (s), 153.4 (s).
Compound 5:
Synthetic method is 54% with compound 2, red solid, productivity, mp ＞ 300 DEG C.1H NMR(400
MHz, DMSO d6): δ 3.79 (s, 3H), 6.82 (d, J=8.0Hz, 1H), 7.07 (t, J=7.2Hz, 1H),
7.16 (t, J=7.2Hz, 1H), 7.22 (s, 1H), 7.36 (d, J=8.0Hz, 1H), 7.47 (d, J=8.0Hz,
1H), 7.60 (s, 1H), 7.65 (s, 1H), 7.78 (d, J=8.0Hz, 1H), 11.02 (s, 1H), 11.15 (s, 1H)；13C NMR (400MHz, DMSO d6): δ 55.3 (s), 101.3 (s), 109.5 (s), 109.8 (s), 111.3 (s),
111.5 (s), 111.2 (s), 118.7 (s), 119.5 (s), 121.2 (s), 121.7 (s), 122.6 (s), 126.1 (s),
126.3 (s), 131.5 (s), 136.4 (s), 153.4 (s).
Compound 6:
Synthetic method is 54% with compound 3, red solid, productivity, mp ＞ 300 DEG C.1H NMR(400
MHz, DMSO d6): δ 3.98 (s, 3H), 7.31 (d, J=8.8Hz, 1H), 7.44 (t, J=7.2Hz, 1H),
7.62 (t, J=7.2Hz, 1H), 7.69 (d, J=8.8Hz, 1H), 7.78 (d, J=8.0Hz, 1H), 8.12 (s,
1H), 8.68 (d, J=8.8Hz, 1H), 12.19 (s, 1H), 11.34 (s, 1H)；13C NMR (400MHz,
DMSO d6): δ 55.4 (s), 105.4 (s), 108.8 (s), 112.4 (s), 113.0 (s), 117.1 (s), 120.0 (s),
120.1 (s), 120.3 (s), 123.2 (s), 123.4 (s), 127.5 (s), 128.6 (s), 129.4 (s), 137.4 (s),
142.3 (s), 142.4 (s), 153.3 (s), 163.4 (s), 163.5 (s).
Compound 7 (5,5 '-dimethoxy-3,3 '-biindolyl):
Synthetic method same 3,3 '-biindolyl 1, white solid, productivity 39%, mp:211-214 DEG C.1H NMR
(400MHz, DMSO d6): δ 3.78 (s, 6H), 6.80 (dd, J=1.6Hz, J=8.0Hz, 2H), 7.18 (d,
J=1.2Hz, 2H), 7.34 (d, J=8.0Hz, 2H), 7.56 (d, J=1.6Hz, 2H), 10.98 (s, 2H)；13C
NMR (400MHz, DMSO d6): δ 55.3 (s), 101.1 (s), 109.6 (s), 111.4 (s), 112.2 (s),
122.5 (s), 126.3 (s), 131.5 (s), 153.3 (s).
Compound 8:
Synthetic method is 61% with compound 2, red solid, productivity, mp ＞ 300 DEG C.1H NMR(400
MHz, DMSO d6): δ 4.00 (s, 6H), 7.23 (d, J=8.0Hz, 2H), 7.69 (d, J=8.0Hz, 2H),
8.16 (s, 2H), 11.04 (s, 1H), 11.84 (s, 2H)；13C NMR (400MHz, DMSO d6): δ
55.2 (s), 104.5 (s), 111.6 (s), 113.2 (s), 117.0 (s), 120.6 (s), 122.2 (s), 128.6 (s),
137.3 (s), 153.2 (s), 170.1 (s).
Compound 9 (5,7-dimethoxy-1H, 1 ' H-3,3 '-biindolyl):
Synthetic method is with 3, and 3 '-biindolyl 1, white solid, productivity is 51%.1H NMR (400MHz,
DMSO d6): δ 3.76 (s, 3H), 3.92 (s, 3H), 6.39 (s, 1H), 6.78 (s, 1H), 7.05 (t, J=7.2Hz,
1H), 7.14 (t, J=7.2Hz, 1H), 7.44 (d, J=8.0Hz, 2H), 7.60 (s, 1H), 7.72 (d, J=
8.0Hz, 1H), 11.09 (s, 1H), 11.12 (s, 1H)；13C NMR (400MHz, DMSO d6): δ
55.2 (s), 55.3 (s), 93.1 (s), 93.7 (s), 109.8 (s), 110.1 (s), 111.5 (s), 118.7 (s), 119.4 (s),
121.1 (s), 121.7 (s), 121.8 (s), 126.0 (s), 126.8 (s), 136.3 (s), 146.4 (s), 154.1 (s).
Compound 10:
Synthetic method is 61% with compound 2, red solid, productivity, mp ＞ 300 DEG C.1H NMR(400
MHz, DMSO d6): δ 4.01 (s, 3H), 4.03 (s, 3H), 6.87 (s, 1H), 7.41 (t, J=7.2Hz, 1H),
7.57 (t, J=7.2Hz, 1H), 7.75 (s, 1H), 7.79 (d, J=8.0Hz, 1H), 8.69 (d, J=8.0Hz,
1H), 10.91 (s, 1H), 11.06 (s, 1H), 12.02 (s, 1H)；13C NMR (400MHz, DMSO d6): δ
55.8 (d), 97.0 (s), 98.9 (s), 111.8 (s), 112.5 (s), 119.8 (s), 120.5 (s), 121.5 (s), 122.1 (s),
123.1 (s), 123.2 (d), 126.9 (s), 127.7 (s), 128.3 (s), 129.3 (s), 142.3 (s), 146.6 (s),
154.4 (s), 169.6 (s), 170.0 (s).
Compound 11 (5,5 ', 7-trimethoxy-1H, 1 ' H-3,3 '-biindolyl):
Synthetic method is with 3, and 3 '-biindolyl 1, white solid, productivity is 28%.1H NMR (400MHz,
DMSO d6): δ 3.77 (s, 6H), 3.93 (s, 3H), 6.40 (d, J=2.0Hz, 1H), 6.77 (d, J=1.6Hz,
1H), 6.80 (dd, J=2.4Hz, J=4.8Hz, 1H), 7.15 (d, J=2.0Hz, 1H), 7.35 (d, J=
7.8Hz, 1H), 7.43 (d, J=2.4Hz, 1H), 7.54 (d, J=2.4Hz, 1H), 10.97 (s, 1H), 11.08 (s,
1H)；13C NMR (400MHz, DMSO d6): δ 55.2 (d), 55.3 (s), 93.0 (s), 93.8 (s),
101.0 (s), 109.6 (s), 110.2 (s), 111.4 (s), 112.2 (s), 121.7 (s), 122.6 (s), 126.4 (s),
126.8 (s), 131.5 (s), 146.5 (s), 153.3 (s), 154.1 (s).
Compound 12:
Synthetic method is 50% with compound 2, red solid, productivity, mp ＞ 300 DEG C.1H NMR(400
MHz, DMSO d6): δ 3.88 (s, 3H), 3.89 (s, 3H), 3.98 (s, 3H), 6.66 (s, 1H), 7.14 (d, J=
7.2Hz, 1H), 7.38 (s, 1H), 7.61 (d, J=7.2Hz, 1H), 7.83 (s, 1H), 10.19 (s, 1H),
10.91 (s, 1H), 11.64 (s, 1H)；13C NMR (400MHz, DMSO d6): δ 54.9 (s), 55.0 (s),
55.6 (s), 95.6 (s), 98.6 (s), 104.0 (s), 111.5 (s), 111.8 (s), 113.0 (s), 116.8 (s), 120.4 (s),
121.1 (s), 121.9 (s), 122.6 (s), 127.2 (s), 128.0 (d), 128.6 (s), 137.1 (s), 146.3 (s),
153.0 (s), 154.0 (s), 169.7 (s), 169.9 (s).
Compound 13 (2-nitro-3,3 '-biindolyl):
Synthetic method is with 3, and 3 '-biindolyl 1, red solid, productivity is 80%.1H NMR (400MHz,
DMSO d6): δ 7.10 (t, J=7.2Hz, 1H), 7.19 (t, J=7.2Hz, 1H), 7.50 (d, J=8.0Hz,
1H), 7.63 (d, J=8.0Hz, 1H), 7.78 (d, J=8.0Hz, 2H), 7.92 (d, J=8.0Hz, 1H),
8.07 (dd, J=2.0Hz, J=8.0Hz, 1H), 8.69 (d, J=2.0Hz, 1H), 11.35 (s, 1H), 11.99 (s,
1H)；13C NMR (400MHz, DMSO d6): δ 108.00 (s), 111.8 (s), 112.0 (s), 112.6 (s),
116.7 (s), 119.2 (d), 121.5 (s), 122.7 (s), 125.4 (s), 125.5 (s), 125.8 (s), 136.4 (s),
139.4 (s), 140.6 (s).
Compound 14:
Synthetic method is 59% with compound 2, red solid, productivity, mp ＞ 300 DEG C.1H NMR(400
MHz, DMSO d6): δ 7.33 (t, J=7.2Hz, 1H), 7.53 (t, J=7.2Hz, 1H), 7.69 (t, J=
7.2Hz, 2H), 8.28 (t, J=7.2Hz, 2H), 9.16 (s, 1H), 11.12 (s, 1H), 11.98 (s, 1H),
12.49 (s, 1H).
Compound 15:
In 100mL flask, compound 3 (163mg, 0.50mmol) is dissolved in 20mL and is dried
THF in, under condition of ice bath, be slowly added to boron-Hization sodium (38mg, 1.00mmol)).Add
After finishing, reaction 3 hour being stirred at room temperature, being then acidified to pH with 3N HCl is 1-2.System stirs
After half an hour, ethyl acetate extracts (3 × 20mL), the washing of organic layer saturated sodium-chloride and anhydrous sulphur
Acid sodium is dried.Column chromatography (ethyl acetate/petroleum ether=1/2) obtains yellow solid 83mg, and productivity is
53%.1H NMR (400MHz, DMSO d6): δ 5.20 (s, 2H), 7.31 (d, J=7.2Hz, 2H),
7.40 (t, J=7.2Hz, 1H), 7.47 (t, J=7.2Hz, 1H), 7.66 (d, J=7.6Hz, 1H), 7.73 (d, J
=7.6Hz, 1H), 8.74 (t, J=8.0Hz, 2H), 11.52 (s, 1H), 11.57 (s, 1H)；13C NMR(400
MHz, DMSO d6): δ 58.2 (s), 111.2 (s), 111.3 (s), 114.5 (s), 116.3 (s), 118.1 (s),
118.2 (s), 121.7 (s), 121.8 (s), 122.3 (s), 122.8 (s), 124.2 (s), 124.8 (s), 133.5 (s),
135.2.2 (s), 138.8 (s), 140.2 (s), 172.8 (s).
Compound 16:
In 100mL flask, compound 3 (261mg, 0.80mmol) is dissolved in 30mL and is dried
THF in, under condition of ice bath, be slowly added to-Hization aluminium lithium (121mg, 3.20mmol).Add
After finishing, reaction 3 hour being stirred at room temperature, being then acidified to pH with 3N HCl is 1-2.System stirs
After half an hour, ethyl acetate extracts (3 × 20mL), and organic layer saturated sodium-chloride washs and anhydrous
Sodium sulphate is dried.Column chromatography obtains gray solid 110mg after (ethanol/methylene=1/30), produces
Rate is 43%.1H NMR (400MHz, DMSO d6): δ 5.16 (s, 6H), 7.31 (t, J=7.2Hz, 2H),
7.44 (t, J=7.2Hz, 2H), 7.69 (d, J=8.0Hz, 2H), 8.72 (d, J=7.6Hz, 2H), 11.31 (s,
2H)；13C NMR (400MHz, DMSO d6): δ 56.7 (s), 111.3 (s), 114.7 (s), 118.1 (s),
121.6 (s), 122.0 (s), 122.3 (s), 124.2 (s), 134.1 (s), 139.6 (s).
Compound 17:
Diol compound 16 (32mg, 0.10mmol) is dissolved in 10mL in 25mL flask to do
In dry THF solution, under condition of ice bath, add 435mg manganese dioxide.Then constant pressure funnel is used
It is added dropwise to triethylamine (0.72ml, 4.5mmol) and trifluoroacetic acid (1.2ml, 15mmol) respectively.
After the bath of reaction system cryosel and room temperature stir 1 hour respectively, add 5mL water, by reaction system diatom
After soil filters, dichloromethane extracts (3 × 10mL), and anhydrous sodium sulfate is dried.Concentration, direct suction filtration
Obtaining red solid 11mg, productivity is 35%.1H NMR (400MHz, DMSO d6): δ 7.46 (d,
J=7.6Hz, 2H), 7.64 (t, J=7.6Hz, 2H), 7.98 (d, J=8.0Hz, 2H), 8.89 (d, J=8.0Hz,
2H), 11.38 (s, 2H), 12.18 (s, 2H)；13C NMR (400MHz, DMSO d6): δ 112.8 (s),
116.1 (s), 119.9 (s), 120.0 (s), 122.4 (s), 123.8 (s), 127.5 (s), 132.6 (s),
142.8 (s), 191.8 (s).
Compound 18 and compound 19:
Nitrogen is protected, in 50mL flask by diol compound 16 (190mg, 0.10mmol) and
DMAP (24mg, 0.20mmol) is dissolved in 20mL dry THF solution.Then constant pressure addition is used
Funnel is added dropwise to the 10mL THF solution of acetic anhydride (57 μ L, 61mg, 0.60mmol) respectively.
After reaction system is stirred at room temperature 1 hour, after concentration, column chromatography (ethyl acetate/petroleum ether=1/4)
To yellow solid (compound 18) 103mg, productivity is 48%；Yellow solid (compound 19) 63mg,
Productivity is 26%.Compound 18,1H NMR (400MHz, DMSO d6): δ 2.06 (s, 3H), 5.10 (d,
J=4.8Hz, 2H), 5.26 (d, J=4.8Hz, 1H), 5.70 (s, 2H), 7.32 (t, J=7.6Hz, 2H), 7.46 (t,
J=7.6Hz, 2H), 7.68 (m, 2H), 8.73 (d, J=8.0Hz, 2H), 11.40 (s, 1H), 11.47 (s, 1H)；13C NMR (400MHz, DMSO d6): δ 20.9 (s), 56.5 (s), 60.0 (s), 111.2 (s), 111.4 (s),
114.8 (s), 115.1 (s), 115.7 (s), 118.3 (s), 118.4 (s), 121.8 (s), 121.9 (s), 122.5 (s),
122.6 (s), 122.8 (s), 124.5 (s), 124.7 (s), 133.8 (s), 134.4 (s) 139.6 (s), 139.8 (s),
170.8(s).Compound 19,1H NMR (400MHz, DMSO d6): δ 2.06 (s, 6H), 5.69 (s, 2H),
7.36 (t, J=7.6Hz, 2H), 7.51 (t, J=7.6Hz, 2H), 7.68 (d, J=8.0Hz, 2H), 8.77 (d, J=
8.0Hz, 2H), 11.59 (s, 2H)；13C NMR (400MHz, DMSO d6): δ 20.8 (s), 59.7 (s),
111.4 (s), 115.9 (s), 116.4 (s), 118.6 (s), 121.7 (s), 122.7 (s), 125.0 (s), 134.3 (s),
139.9 (s), 170.5 (s).
Compound 20:
Compound 2 (2.00g, 6.15mmoles) zinc granule (18.00g) is added in 250mL two-mouth bottle
With 100mL DMF.Adding system after 100 DEG C, constant pressure funnel is slowly added dropwise into 45mL
Concentrated hydrochloric acid, dropping in about 1 hour finishes.Reaction system is continued at heating reaction 1 hour at 100 DEG C,
Ethyl acetate extraction (4 × 40mL) after concentration, organic layer saturated sodium-chloride washing and anhydrous slufuric acid
Sodium is dried.Column chromatography obtains yellow solid 1.01g after (ethanol/methylene=1/30), and productivity is
53%.1H NMR (400MHz, DMSO d6): δ 4.81 (s, 2H), 7.38 (m, 2H), 7.48 (t, J=
7.2Hz, 1H), 7.54 (t, J=7.2Hz, 1H), 7.70 (d, J=8.0Hz, 1H), 7.82 (d, J=8.0Hz,
1H), 8.59 (s, 1H), 8.78 (d, J=8.0Hz, 1H), 8.84 (d, J=8.0Hz, 1H), 11.74 (s, 1H),
11.86 (s, 1H)；13C NMR (400MHz, DMSO d6): δ 44.4 (s), 111.5 (s), 112.2 (s),
114.3 (s), 115.4 (s), 118.4 (s), 118.8 (s), 118.9 (s), 121.3 (s), 121.9 (s), 122.2 (s),
123.2 (s), 124.4 (s), 125.5 (s), 127.2 (s), 128.8 (s), 129.4 (s), 139.8 (s), 140.4 (s),
171.0(s)。
Compound 21:
In 100mL flask add compound 2 (325mg, 1mmol), boron-Hization sodium (567mg,
15mmol) the THF being dried with 30mL.Under the conditions of ice-water bath, slowly add borontrifluoride to system
Borate ether (2.5mL, 20mmol), then reaction system heating reflux reaction 3 hours.After cooling,
Frozen water stopped reaction, adds 50mL ethyl acetate, 6N-H sodium hydroxide solution alkalization to pH=to system
10.Separating organic layer, water layer ethyl acetate extracts (2 × 30mL), organic layer saturated sodium-chloride
Washing and anhydrous sodium sulfate are dried.Obtaining white solid 150mg after direct suction filtration after concentration, productivity is
50%.1H NMR (400MHz, DMSO d6): δ 4.54 (s, 4H), 7.30 (t, J=7.2Hz, 2H),
7.42 (t, J=7.2Hz, 2H), 7.60 (d, J=8.0Hz, 2H), 8.71 (d, J=8.0Hz, 2H), 11.43 (s,
2H)；13C NMR (400MHz, DMSO d6): δ 51.7 (s), 111.1 (s), 114.5 (s), 118.3 (s),
122.3 (s), 122.4 (s), 123.6 (s), 123.9 (s), 129.8 (s), 139.3 (s).
Compound 22:
Synthetic method is with compound 21, gray solid, productivity 62%.1H NMR (400MHz, DMSO
d6): δ 3.99 (s, 3H), 4.53 (s, 4H), 7.12 (d, J=8.4Hz, 1H), 7.33 (t, J=7.2Hz, 1H),
7.42 (t, J=7.2Hz, 1H), 7.53 (d, J=8.2Hz, 1H), 7.61 (d, J=8.0Hz, 1H), 8.17 (s,
1H), 8.65 (d, J=8.0Hz, 1H), 11.27 (s, 1H), 11.46 (s, 1H)；13C NMR (400MHz,
DMSO d6): δ 51.7 (s), 55.8 (s), 105.4 (s), 111.2 (s), 111.7 (s), 112.8 (s), 114.3 (s),
114.5 (s), 118.4 (s), 122.0 (s), 122.4 (s), 122.7 (s), 123.8 (s), 129.6 (s), 130.7 (s),
134.4 (s), 139.3 (s), 152.6 (s).
Compound 23:
Synthetic method is with compound 21, gray solid, productivity 50%.1H NMR (400MHz, DMSO
d6): δ 4.00 (s, 6H), 4.58 (s, 2H), 5.01 (s, 2H), 7.10 (t, J=7.2Hz, 2H), 7.53 (d, J=
8.4Hz, 2H), 8.18 (s, 2H), 7.53 (d, J=8.2Hz, 1H), 7.61 (d, J=8.0Hz, 1H), 8.17 (s,
1H), 8.65 (d, J=8.0Hz, 1H), 11.27 (s, 1H), 11.31 (s, 1H), 11.40 (s, 1H)；13C
NMR (400MHz, DMSO d6): δ 51.4 (s), 55.2 (s), 104.2 (s), 111.9 (s), 113.5 (s),
112.8 (s), 113.8 (s), 114.5 (s), 118.9 (s), 122.4 (s), 122.8 (s), 130.3 (s), 134.3 (s),
152.5 (s), 152.6 (s).
Compound 24:
Synthetic method is with compound 21, gray solid, productivity 50%.1H NMR (400MHz, DMSO
d6): δ 4.02 (s, 3H), 4.04 (s, 3H), 4.60 (s, 4H), 6.76 (s, 1H), 7.33 (t, J=7.2Hz, 1H),
7.42 (t, J=7.2Hz, 1H), 7.61 (d, J=8.0Hz, 1H), 7.77 (s, 1H), 8.66 (d, J=8.2Hz,
1H), 11.33 (s, 1H), 11.51 (s, 1H)；13C NMR (400MHz, DMSO d6): δ 51.1 (s),
51.5 (s), 55.4 (s), 55.8 (s), 95.9 (s), 96.7 (s), 111.3 (s), 114.3 (s), 115.3 (s), 118.4 (s),
122.0 (s), 122.3 (d), 122.6 (s), 123.1 (s), 123.8 (s), 124.7 (s), 129.5 (s), 130.1 (s),
139.3 (s), 146.3 (s), 153.4 (s).
Compound 25 (1H, 1 ' H-2,3 '-biindolyl):
It in the flask of 100mL, is dissolved in 2.00g indoles in 10mL absolute ether, then uses constant voltage
Dropping funel 30min is added dropwise to the saturated chlorination-H diethyl ether solution 20mL of precooling.By reaction system room
After temperature stirring 18 hours, direct suction filtration, absolute ether washing, be dried after be dissolved in ethyl acetate, full
With the washing of carbonic acid-H sodium solution, saturated aqueous common salt washing, anhydrous sodium sulfate direct concentrated by rotary evaporation after being dried.
The product obtaining is resuspended in 20mL toluene, adds the palladium carbon of 0.40g 5%, system back flow reaction
2.5 hour.Add the palladium carbon of 0.20g 5%, continue back flow reaction 0.5 hour.Reactant is tied to form heat
Filtering, and with the washing of a small amount of hot toluene, having white solid to separate out after filtrate cooling, suction filtration has obtained product.
Filtrate and ethyl acetate washing palladium carbon after suction filtration filtrate merge, concentrate, column chromatography (ethyl acetate/
Petroleum ether=1/3) after there are white solid product 1.25g, gross production rate 63%.1H NMR (400MHz,
DMSO d6): δ 6.77 (d, J=1.6Hz, 1H), 6.97 (m, 1H), 7.04 (m, 1H), 7.18 (m, 2H),
7.36 (d, J=7.6Hz, 1H), 7.47 (d, J=7.2Hz, 1H), 7.51 (d, J=7.6Hz, 1H), 7.87 (d, J
=2.4Hz, 1H), 8.01 (d, J=7.6Hz, 1H), 11.21 (s, 1H), 11.40 (s, 1H)；13C NMR(400
MHz, DMSO d6): δ 96.8 (s), 108.4 (s), 110.4 (s), 111.9 (s), 118.8 (s), 119.0 (s),
119.6 (s), 119.8 (s), 120.3 (s), 121.7 (s), 123.1 (s), 124.6 (s), 129.2 (s), 134.1 (s),
136.0 (s), 136.6 (s).
Compound 26:
Synthetic method is 49% with compound 2, red solid, productivity, mp ＞ 300 DEG C.1H NMR (400
MHz, DMSO d6):1H NMR (400MHz, DMSO d6): δ 7.36 (t, J=7.2Hz, 1H),
7.42 (t, J=7.2Hz, 1H), 7.55 (m, 2H), 7.76 (t, J=2.4Hz, 2H), 8.79 (d, J=3.6Hz,
1H), 8.94 (d, J=3.6Hz, 1H), 11.07 (s, 1H), 12.20 (s, 1H), 12.34 (s, 1H)；13C
NMR (400MHz, DMSO d6): δ 107.4 (s), 110.8 (s), 111.5 (s), 111.8 (s), 112.2 (s),
120.1 (s), 120.3 (s), 121.2 (s), 121.7 (s), 123.7 (s), 124.6 (s), 126.2 (d), 132.4 (s),
138.2 (s), 141.0 (s), 170.2 (s), 171.0 (s).
Test case
Choose compound obtained above 2nd, compound the 20th, compound the 21st, compound the 3rd, compound the 15th,
Compound the 16th, compound the 17th, compound the 18th, compound 19 carries out following determination of activity.
Test case 1
The live body protection determination of activity of anti-TMV
Select the Nicotiana glutinosa that growing way is consistent, with phosphate buffer, TMV crude extract is diluted to concentration 6 × 10-3
Mg/mL, spreads compound solution at Zuo Banye, and the solvent that right half leaf spreads matched doses compares.12
After little Shi, with the artificial frictional inoculation of writing brush on the of the right age blade sprinkled with diamond dust (full leaf virus inoculation,
Every blade manually smears virus once gently, and left and right half leaf is smeared dynamics and accomplished uniformly as far as possible), after inoculation
Rinse with clear water.In illumination box, moisturizing is cultivated subsequently, observes and record the number of withered spot after 3～4d
Mesh.Every chemicals treatment sets 3 strains, 3～4 leaves of every strain.Every medicament carries out 3 repetitions as stated above.
When presenting obvious withered spot on half leaf of blank, about can investigate after test 3～4d, respectively
Record the withered spot number of left and right half leaf of every leaf, be calculated as follows out test compound and plant virus is pressed down
Rate processed, i.e. relative efficacy.Representation: Y=(C-A)/C × 100%.Wherein: Y is compound pair
The inhibiting rate of plant virus, C is control group (right half leaf) withered spot number, and A is compound treatment group (left half
Leaf) withered spot number.Wherein control group (right half leaf) withered spot number and compound treatment group (Zuo Banye) withered spot number are all
The withered spot sum repeating by each group of average repeating or each group can be joined.Each is processed is with oneself
Second half is as comparison, then arranges the process of one group of commercially available medicine virazole as a comparison.The results are shown in Table 1.
Test case 2
The live body therapeutic activity of anti-TMV measures
Select the Nicotiana glutinosa that growing way is consistent, with phosphate buffer, TMV crude extract is diluted to concentration 6 × 10-3
Mg/mL, with the artificial frictional inoculation of writing brush on the of the right age blade sprinkled with diamond dust (full leaf virus inoculation, often
Blade manually smears virus once gently, and left and right half leaf is smeared dynamics and accomplished uniformly as far as possible), use after inoculation
Clear water rinses.After blade is dry, spreading compound solution at Zuo Banye, right half leaf spreads matched doses
Solvent compares.In illumination box, moisturizing is cultivated subsequently, observes and record the number of withered spot after 3～4d
Mesh.Every chemicals treatment sets 3 strains, 3～4 leaves of every strain.Every medicament carries out 3 repetitions as stated above.
When presenting obvious withered spot on half leaf of blank, about can investigate after test 3～4d, record respectively
The withered spot number of left and right half leaf of every leaf, is calculated as follows out the suppression to plant virus for the test compound
Rate, i.e. relative efficacy.Representation: Y=(C-A)/C × 100%.Wherein: Y is compound to planting
The inhibiting rate of thing virus, C is control group (right half leaf) withered spot number, and A is compound treatment group (Zuo Banye)
Withered spot number.Wherein control group (right half leaf) withered spot number and compound treatment group (Zuo Banye) withered spot number all may be used
The withered spot sum repeating by each group of average repeating or each group with ginseng.Each is processed is another with oneself
Half is as comparison, then arranges the process of one group of commercially available medicine virazole as a comparison.Determination of activity experiment knot
Fruit is shown in Table 1.
Table 1
| Test compound | Concentration (μ g/mL) | Live body protection activity (%) | Live body therapeutic activity (%) |
| Compound 2 | 500 | NotTest | 16.1 |
| Compound 20 | 500 | 29.5 | 35.8 |
| Compound 21 | 500 | 33.3 | 40.5 |
| Compound 3 | 500 | 20.8 | 34.4 |
| Compound 15 | 500 | 26.8 | 32.4 |
| Compound 16 | 500 | 17.9 | 25.3 |
| Compound 17 | 500 | 27.2 | 30.1 |
| Compound 18 | 500 | 20.5 | 28.3 |
| Compound 19 | 500 | 7.6 | 20.4 |
| Virazole | 500 | 32.8 | 36.2 |
As it can be seen from table 1 the indole carbazole compound that the present invention provides has certain anti-TMV
Activity.
Claims (4)
1. an indole carbazole compound, it is characterised in that this indole carbazole compound have as
Structure shown in Formulas I or II,
Wherein, R1、R2, X, Y, Z, M and N be separate group, R1And R2For-H, X is-O-or-NH,
In Y and Z, one is-H, and another is-H or carbonyl；M and N is respectively aldehyde radical and-CH2At least one in OH.
2. indole carbazole compound according to claim 1, wherein, described indole carbazole class
Compound is
3. the preparation method of the indole carbazole compound described in a claim 1 or 2, comprising:
(1) willAt Me2In the presence of NH and EtOH, reaction obtains
(2) step (1) is obtainedWith NaBH4、BF3·Et2O and DME connects
Touch, obtain
(3) step (2) is obtainedWithEnter in the presence of AcOH
Row reaction, obtainsOrWherein, X is-O-or-NH, Y
It is carbonyl with Z；
Described method also includes:
(a) under sodium borohydride reduction reaction condition, product that step (3) is obtained
With the first organic solvent exposure, the X obtaining in-O-, Y and Z one be-H and another be carbonyl
The compound shown in Formulas I, described first organic solvent be dry tetrahydrofuran, dimethylformamide,
At least one in methyl alcohol, ethanol, 1,4-dioxane, chloroform, carbon tetrachloride；Or
(b) under lithium aluminium hydride reduction reaction condition, product that step (3) is obtained
With the second organic solvent exposure, M and N obtaining is-CH2Compound shown in the Formula II of OH, its
In, described second organic solvent be dry tetrahydrofuran, methyl alcohol, ethanol, Isosorbide-5-Nitrae-dioxane, chloroform,
At least one in carbon tetrachloride；Or
(c) under zinc granule, concentrated hydrochloric acid reduction reaction conditions, product that step (3) is obtainedWith the 3rd organic solvent exposure, obtain X in-NH, Y and Z one be-H and
Another compound shown in the Formulas I of carbonyl, described 3rd organic solvent is DMF, chloroform, tetrachloro
Change at least one in carbon；Or
D step (3), under sodium borohydride, BFEE reduction reaction conditions, is obtained by ()
ProductWith the 4th organic solvent exposure, the X obtaining is H's for-NH, Y and Z
Compound shown in Formulas I, described 4th organic solvent be dry tetrahydrofuran, methyl alcohol, ethanol, Isosorbide-5-Nitrae-
At least one in dioxane, chloroform, carbon tetrachloride.
4. the answering in resisting tobacco mosaic virus of the indole carbazole compound described in claim 1 or 2
With.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210104960.3A CN103360395B (en) | 2012-04-11 | 2012-04-11 | A kind of indole carbazole compound and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210104960.3A CN103360395B (en) | 2012-04-11 | 2012-04-11 | A kind of indole carbazole compound and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103360395A CN103360395A (en) | 2013-10-23 |
| CN103360395B true CN103360395B (en) | 2016-10-05 |
Family
ID=49362740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210104960.3A Active CN103360395B (en) | 2012-04-11 | 2012-04-11 | A kind of indole carbazole compound and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103360395B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111218A (en) * | 2015-09-10 | 2015-12-02 | 东华大学 | Preparing method for 5H-indole[3,2-a]pyrrole[3,4-c]carbazole-6,8(7H,13H)-diketone compound |
| CN105145109B (en) * | 2015-10-26 | 2017-09-29 | 赤峰和润农业高新科技产业开发有限公司 | A kind of greenhouse tomato method of overwintering cultivation suitable for cold area in north |
| CN105272611B (en) * | 2015-10-26 | 2019-01-11 | 赤峰和润农业高新科技产业开发有限公司 | A kind of formula and its production method of garden crop cultivation matrix |
| CN105669516B (en) * | 2016-03-09 | 2018-08-03 | 中山大学 | A kind of preparation method of 3,3 '-bis-benzazolyl compounds |
| CN110041338B (en) * | 2018-10-30 | 2021-11-30 | 贵州省中国科学院天然产物化学重点实验室 | Bis-indole maleimide compound with anti-tumor activity and application thereof |
| CN113045556B (en) * | 2019-12-26 | 2022-08-23 | 天津师范大学 | Alkaloid streptandole derivative, preparation thereof and application thereof in preventing and treating plant virus and bacterial diseases |
| CN112375029B (en) * | 2020-11-11 | 2022-03-18 | 湖北省生物农药工程研究中心 | Carbazole alkaloid derivative and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544669A (en) * | 2009-05-06 | 2009-09-30 | 贵州大学 | Phenyl cyanoacrylate derivatives containing alpha-amino phosphonate ester and preparation method and application thereof |
| WO2011055933A2 (en) * | 2009-11-03 | 2011-05-12 | 제일모직 주식회사 | Composition for an organic photoelectric device, organic photoelectric device using same, and display device comprising same |
-
2012
- 2012-04-11 CN CN201210104960.3A patent/CN103360395B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544669A (en) * | 2009-05-06 | 2009-09-30 | 贵州大学 | Phenyl cyanoacrylate derivatives containing alpha-amino phosphonate ester and preparation method and application thereof |
| WO2011055933A2 (en) * | 2009-11-03 | 2011-05-12 | 제일모직 주식회사 | Composition for an organic photoelectric device, organic photoelectric device using same, and display device comprising same |
Non-Patent Citations (4)
| Title |
|---|
| 100. Experiments on the Preparation of Indolocurbaxoles. Part III.;P. V. Clifton，S. G. P. Plant;《Journal of the Chemical Society》;19511231;第461-466页 * |
| Aline Voldoire，等.Rebeccamycin Analogues from Indolo[2,3-c]carbazole.《Bioorganic & Medicinal Chemistry》.2001,第9卷(第2期),第357-365页. * |
| Eric Desarbre，Jan Bergman.Synthesis of symmetric and non-symmetric indolo[2,3-c]carbazole derivatives: preparation of indolo[2,3-c]pyrrolo[3,4-a]carbazoles.《J. Chem. Soc., Perkin Trans. 1》.1998,(第13期),第2009-2016页. * |
| Larisa N. Yudina，Jan Bergman.Synthesis and alkylation of indolo[3,2-b]carbazoles.《Tetrahedron》.2003,第59卷(第8期),第1265-1275页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103360395A (en) | 2013-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103360395B (en) | A kind of indole carbazole compound and its preparation method and application | |
| Cao et al. | Design, synthesis and in vitro and in vivo antitumor activities of novel β-carboline derivatives | |
| JP2010519337A (en) | Carbamate compounds | |
| WO2000003990A1 (en) | Pharmaceutical compositions comprising 2-quinolones | |
| CN105153142A (en) | Furazan derivative of coumarin parent nucleus and antineoplastic activity | |
| Rasheed et al. | Ultrasound‐Assisted Synthesis of Novel α‐Aminophosphonates and Their Biological Activity | |
| CN106083879A (en) | Norcantharidin mono-acid monoester derivates and antitumor application thereof | |
| CA3218824A1 (en) | Stapled peptides and methods thereof | |
| CN101307038B (en) | 4- benzyl piperazi ethyliminumacyl (formimidoyl benzol)hydrazine compounds, preparation method thereof, pharmaceutical compositions and use | |
| CN105073731A (en) | Plant growth regulating compounds | |
| CN106831799B (en) | Hydroxy styrenes pyridine Mannich alkaloid compound, preparation method and use | |
| CN105418610B (en) | A kind of 10 hydroxyevodiamine anti-tumor compounds and its preparation method and application | |
| CN100540550C (en) | The stabilization method of macrolides compound | |
| Naureen et al. | Iron (III) and zinc (II) metal alkaloid complexes: Synthesis, characterization and biological activities | |
| CN109422744A (en) | Matrine derivative and its synthesis and the application in terms of preventing and treating plant pest | |
| EP1202971A2 (en) | Pharmaceutical compositions comprising 4-quinolones | |
| CN111393318A (en) | Synthesis of novel sildenafil acid amide derivative and application of novel sildenafil acid amide derivative in antitumor drugs | |
| CN107459536B (en) | A kind of green synthesis method of 4- ferrocenyl quinoline | |
| CA2376681A1 (en) | Novel xanthone compounds, their preparation and use as medicament | |
| CN103749456A (en) | Application of diterpene alkaloid compound and preparation to prevention of crop virus diseases | |
| CN104262130B (en) | A kind of naphthoquinone compound of ocean microorganism, preparation method and its usage | |
| CN107857791B (en) | Oleanolic acid derivative, preparation method and application | |
| Ahmad et al. | Oppositinines A and B: new vasorelaxant β-carboline alkaloids from Neisosperma oppositifolia | |
| CN106977518B (en) | A kind of N- substituted pyrazolecarboxylic simultaneously [3,4-d] pyrimidinones and preparation method and application | |
| CN106478692A (en) | Copper-nitrate complex and its synthetic method and application with 1 (2 pyridine) 9 benzyl β carboline as part |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |