CN108484611B - A kind of method of simple synthesis Caulerpin - Google Patents
A kind of method of simple synthesis Caulerpin Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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Abstract
The invention belongs to organic chemical synthesis fields, disclose a kind of method of simple synthesis Caulerpin.This method is using indoles as raw material, without protecting to amino on indoles, No. 2 positions of indoles is carried out with the affine substitution of methyl acetate, generates indoles -2- methyl acetate；Then formylation reaction being carried out in No. 3 positions of indoles -2- methyl acetate again and obtaining 3- formoxyl -2- heteroauxin methyl esters, Caulerpin finally is can be obtained by two intermolecular cyclizations in 3- formoxyl -2- heteroauxin methyl esters.Compared to the prior art, method synthesis cycle of the invention greatly shortens, and simple process, cost of material is low, and reaction condition is mild, is easy to industrialization, has very high medical value and vast market prospect.
Description
Technical field
The invention belongs to organic chemical synthesis field, in particular to a kind of method of simple synthesis Caulerpin.
Background technique
Caulerpin is a kind of secondary metabolites extracted from seaweed, belongs to bisindole alkaloid, is had a variety of efficient
Bioactivity and anti-tumor activity.Its molecular formula is C24H18N2O4, structural formula is as follows:
Caulerpin can be used as auxin.Cen Yingzhou etc. is with 5 × 10-6~10 × 10-6The caulerpa of mol/L concentration
Red pigment spray solution finds that it can promote 30% or more Chinese cabbage leaf growth on Chinese cabbage blade face；With the caulerpa of above-mentioned same concentrations
Red pigment solution carries out seed soaking to wheat, corn, and can also significantly improving germination percentage, (Lv Yang, Lu wait Caulerpin more
(Caulerpin) structural analysis structural chemistry .1994,13 (6): 472-476).(Xu Xiaohua, the Su Jing joy such as Xu Xiaohua
.Caulerpin separation identification and bioactivity Zhongshan University journal (natural science edition) .1996,35 (2): 64) to caulerpa
Red pigment carries out plant and increases active measurement, and Caulerpin takes root to cucumber cotyledons, expands and the promotion hundred of Wheat coleoptile growth
Point rate is respectively 68%, 45%, 42%, shows that Caulerpin has the function of being obviously promoted growth.
The pharmacological action of Caulerpin.Roberto Martínez(Roberto Martínezet al.Marine
Drugs 12 (4): 1757-1772) report Caulerpin has the function for the treatment of pulmonery tuberculosis, has than conventional medicament rifampin more preferable
Effect.NasrinMovahhedina(NasrinMovahhedina et al.Iranian Journal of
Pharmaceutical Research.2014,12 (2): 515-521) Caulerpin is carried out in the lethal experiment of progress artemia
General toxicity detection, the results showed that it does not show toxicity；To the DPPH characterization of Caulerpin, it is a kind of right to show that Caulerpin can be used as
The nontoxic natural food of human body.(the AlessandraFerramosca et such as Alessandra Ferramosca
Al.Biochemical and Biophysical ResearchCommunications.2016:1133-1138) use rat line
Plastochondria studies Caulerpin and its derivative caulerpinic acid to the shadow of mammalian mitochondria as experimental subjects
It rings.The experimental results showed that two kinds of seaweed metabolins can be used as the medicine of the cancer cell to defective Mitochondria complex I
Object, such as oophoroma cisplatinresistant cell.This for always using along platinum-containing anticancer drug treatment oophoroma provide
Potential researches on natural drugs direction.Nathália Regina Porto Vieira Macedo(Nathália Regina
Porto Vieira Macedo et al.RevistaBrasileira de Farmacognosia.2012,22(4):861-
867) report can be used as a potential effective antiviral drugs (EC for herpe simplex 1 type virus, Caulerpin50For 1.29 μ
M, SI 904).
Other effects of Caulerpin.(the Chennappan Kamal et such as Chennappan Kamal
Al.Industrial&Engineering Chemistry Research.2012,51:10399-10407) report Caulerpin
Interface can be extracted in mild steel/acid and inhibit low-carbon steel corrosion, show that Caulerpin can be used as potential green anti-corrosion material.
In conclusion Caulerpin has broad application prospects, but the extracted amount of natural plants is few at present, and chemistry closes
It is low at the more yields of method by-product, more it can not be studied and be tested.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that providing a kind of simple synthesis
The method of Caulerpin.This method is raw materials used cheap, and synthesis cycle greatly shortens, and reaction condition is mild, operating procedure
Simplicity is easy to industrialization, has very high medical value and vast market prospect.
The purpose of the present invention is realized by following proposal:
A kind of method of simple synthesis Caulerpin, mainly comprises the steps that using indoles as raw material, without on indoles
Amino is protected, and No. 2 positions of indoles are carried out with the nucleophilic displacement of fluorine of methyl acetate, generates indoles -2- methyl acetate；Then again in Yin
No. 3 positions of diindyl -2- methyl acetate carry out formylation reaction and obtain 3- formoxyl -2- heteroauxin methyl esters, finally by 3- formoxyl -
Caulerpin can be obtained by two intermolecular cyclizations in 2- heteroauxin methyl esters.
Preferably, the method for above-mentioned simple synthesis Caulerpin, specifically includes the following steps:
(1) ethyl xanthate is dissolved in organic solvent and obtains solution A；Halogenated acetic acids methyl esters is dissolved in of the same race organic molten
It in agent, is stirring evenly and then adding into solution A and is reacted, be evaporated under reduced pressure after reaction, purifying obtains 2- xanthogen-second
Sour methyl esters；
(2) indoles and the double lauroyl of peroxidating are dissolved in organic solvent, the 2- xanthogen-that step (1) obtains is added
Methyl acetate is reacted, and reaction terminates to purify gained reaction solution to obtain indoles -2- methyl acetate；
(3) N- N-formyl morpholine N is dissolved in organic solvent and obtains solution B；Mineral acid chloride is dissolved in of the same race organic molten
It in agent, is stirring evenly and then adding into solution B and is reacted, obtaining solid through vacuum distillation after reaction is morpholine imines
Salt；
(4) indoles -2- methyl acetate that step (2) obtains is dissolved in organic solvent, it is sub- that the morpholine that step (3) obtain is added
Amine salt carries out formylation reaction, and filtering solid be precipitated is 3- formoxyl -2- heteroauxin methyl esters；
(5) the 3- formoxyl -2- heteroauxin methyl esters for taking step (4) to obtain is dissolved in organic solvent, and piperidines and acetic acid is added
Two intermolecular cyclization reactions occur, obtain red material, as Caulerpin with chromatography after reaction；
Organic solvent described in step (1) be at least one of methylene chloride, acetone, dichloroethanes, tetrahydrofuran,
Preferably acetone；
Ethyl xanthate described in step (1) be one of ehtyl potassium xanthate or sodium ethylxanthate, preferably
Ehtyl potassium xanthate.
Halogenated acetic acids methyl esters described in step (1) is one of methyl bromoacetate or methyl chloroacetate, preferably bromine second
Sour methyl esters.
The concentration of solution A described in step (1) is 0.5-3.0mol/L, preferably 1.0~2.0mol/L, and described is halogenated
The concentration that methyl acetate is dissolved in halogenated acetic acids methyl esters in the solution obtained when organic solvent of the same race is 0.5-5.0mol/L, preferably
2.0~4.0mol/L；
The molar ratio of halogenated acetic acids methyl esters used in step (1) and ethyl xanthate is 1:0.5~5；
It is added in solution A and is reacted described in step (1), wherein the temperature of solution A is 0~25 DEG C when being added,
Preferably 0 DEG C；Reaction described in step (1) refers in 0~40 DEG C of 0.5~8h of reaction, preferably in 25 DEG C of reaction 4h.
Purifying described in step (1) is directed to add water and ethyl acetate to be extracted in the product after vacuum distillation, so
After be dried over anhydrous sodium sulfate after merge organic phase, vacuum distillation removes solvent, and obtaining pale yellow oily liquid is 2- xanthan
Acidic group-methyl acetate；
Organic solvent described in step (2) be methylene chloride, chloroform, tetrahydrofuran, acetone at least one, preferably third
Ketone；
Indoles described in step (2), 2- xanthogen-methyl acetate, the double lauroyl of peroxidating molar ratio be 1:1~
5:1~5, when amplifying reaction, i.e., indoles is more than 5g, and to react raw material more sufficiently, the double lauroyl additions of peroxidating can
The mode being added portionwise on a small quantity is taken, i.e., using indoles as equivalent, 0.3eq is added every time, the time interval being added every time is in 0.5-
1h, until the double lauroyl of peroxidating that plan is added are added completely into；
Reaction described in step (2) refer to 0~100 DEG C react 3~for 24 hours, preferably at 80 DEG C；React 12h；
Purifying described in step (2) refers to utilizes reaction solution after reaction after vacuum distillation removes solvent
It is indoles -2- methyl acetate that column chromatography, which obtains faint yellow solid,；
Organic solvent described in step (3) be methylene chloride, acetonitrile, tetrahydrofuran, acetone at least one, preferably two
Chloromethanes；
Mineral acid chloride described in step (3) be phosphorus oxychloride, oxalyl chloride, thionyl chloride, sulfonic acid chloride at least
One kind, preferably oxalyl chloride.
The concentration of solution B described in step (3) is 0.5~3.0mol/L, preferably 1.0~2.0mol/L, the nothing
When machine acid chloride is dissolved in organic solvent of the same race the concentration of mineral acid chloride be 0.5~7.0mol/L, preferably 2.0~
5.0mol/L；
The molar ratio of mineral acid chloride described in step (3) and N- N-formyl morpholine N is 0.8~5:1；
Reaction described in step (3) refers to that reaction temperature is -10~40 DEG C, preferably 0 DEG C；Reaction time be 0.25~
8h, preferably 4h；
Organic solvent described in step (4) is at least one of dimethyl sulfoxide, chloroform, tetrahydrofuran, acetonitrile, preferably
Acetonitrile；
The molar ratio of indoles -2- methyl acetate described in step (4) and morpholine inferior amine salt is 1:1~8；
Reaction described in step (4) refer to reaction temperature be 0~120 DEG C, preferably 25 DEG C, the reaction time be 0.25~
10h, preferably 1h；
Organic solvent described in step (5) is at least one of dimethyl sulfoxide, chloroform, tetrahydrofuran, acetonitrile, preferably
Acetonitrile；
3- formoxyl -2- heteroauxin methyl esters described in step (5), piperidines, acetic acid molar ratio be 1:1~20:1~
20；
Cyclization reaction described in step (5) refers to that reaction temperature is 50~120 DEG C, preferably 100 DEG C；Reaction time is
3~10h, preferably 7h.
The synthetic route of above-mentioned method is as follows:
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
Synthetic method of the invention is using indoles as raw material, without protecting to amino on indoles, directly to No. 2 positions of indoles
The nucleophilic displacement of fluorine for carrying out methyl acetate, is then acylated to obtain 3- formoxyl -2- heteroauxin methyl esters in its No. 3 positions, most
Caulerpin can be obtained by two intermolecular cyclizations afterwards.The method for the synthesis Caulerpin published is compared, this hair
Bright method synthesis cycle greatly shortens, and simple process, cost of material is low, and reaction condition is mild, is easy to industrialization, has very high
Medical value and vast market prospect.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Agents useful for same can routinely be bought unless otherwise specified from market in embodiment.
Embodiment 1
(1) in ice-water bath, ehtyl potassium xanthate (4g) 2- xanthogen-methyl acetate synthesis: is dissolved in 25mL third
In ketone.Methyl bromoacetate (2.36mL) is dissolved in 10mL acetone, is stirring evenly and then adding into containing ehtyl potassium xanthate
It is reacted in acetone soln, is gradually increased to room temperature and continues extremely to react completion in stirring 4 hours.Decompression steaming is being carried out to reaction system
After evaporating, water being added and ethyl acetate is extracted, three times, each 50mL merges organic phase after being dried over anhydrous sodium sulfate for extraction,
Vacuum distillation removal solvent, obtains pale yellow oily liquid i.e. 2- xanthogen-methyl acetate.
(2) substitution of methyl acetate: indoles (1.0g) is dissolved in 10mL acetone, and the double lauroyl of peroxidating are added
2- xanthogen-methyl acetate (2.4g) back flow reaction 12 hours at 80 DEG C that step (1) obtains are added in (4.1g), reaction
End is evaporated under reduced pressure to reaction system, is obtained bronzing oily liquids, is chromatographed to obtain faint yellow solid using column, is passed through
Identification, confirmation are indoles -2- methyl acetate.
(3) synthesis of morpholine inferior amine salt: in ice-water bath, N- N-formyl morpholine N (2mL) is dissolved in 20mL methylene chloride.?
In ice-water bath, oxalyl chloride (1.7mL) is dissolved in 8mL methylene chloride, two containing N- N-formyl morpholine N are stirring evenly and then adding into
0 DEG C is kept in chloromethanes solution to react 4 hours, reaction terminates gained faint yellow solid after being evaporated under reduced pressure to reaction system,
Identified, confirmation is morpholine inferior amine salt.
(4) hydrolysis is acylated: the indoles -2- methyl acetate (0.6g) that step (2) obtains being dissolved in 20mL acetonitrile, is added
The morpholine inferior amine salt (0.8g) that step (3) obtains is hydrolyzed, and completes to reaction within normal-temperature reaction 1 hour, filtering is precipitated light
Brown solid, identified, confirmation is 3- formoxyl -2- heteroauxin methyl esters.
(5) two intermolecular cyclizations: the 3- formoxyl -2- heteroauxin methyl esters (0.2g) for taking step (4) to obtain is dissolved in
In 20mL anhydrous acetonitrile, piperidines (0.4mL) is added and acetic acid (0.1mL) carries out two intermolecular cyclization dimerization reactions, at 100 DEG C
Reaction 7 hours obtains red material with column chromatography after reaction, identified, is confirmed as Caulerpin,1H NMR
(300MHz, Chloroform-d) δ 9.23 (s, 2H), 8.08 (s, 2H), 7.47-7.43 (m, 2H), 7.33 (dt, J=8.1,
1.0Hz, 2H), 7.21 (ddd, J=8.2,7.0,1.3Hz, 2H), 7.12 (ddd, J=8.1,7.0,1.1Hz, 2H), 3.93 (s,
6H).13C NMR(75MHz,CDCl3)δ166.65,142.78,137.72,132.86,128.16,125.47,123.38,
120.74,118.04,112.49,111.52,52.52.
Embodiment 2
(1) in 10 DEG C of water-baths, ehtyl potassium xanthate (6g) 2- xanthogen-methyl acetate synthesis: is dissolved in 25mL
In acetone.Methyl bromoacetate (3.54mL) is dissolved in 10mL acetone, is stirring evenly and then adding into containing ehtyl potassium xanthate
Acetone soln in reacted, be gradually increased to room temperature continue stirring 6 hours to reaction complete.It is depressurized to reaction system
After distillation, water is added and ethyl acetate is extracted, three times, each 50mL merges organic after being dried over anhydrous sodium sulfate for extraction
Phase, vacuum distillation removal solvent, obtains pale yellow oily liquid i.e. 2- xanthogen-methyl acetate.
(2) substitution of methyl acetate: indoles (1.5g) is dissolved in 10mL acetone, and the double lauroyl of peroxidating are added
2- xanthogen-methyl acetate (5.0g) back flow reaction 16 hours at 55 DEG C that step (1) obtains are added in (10.0g), reaction
End is evaporated under reduced pressure to reaction system, is obtained bronzing oily liquids, is chromatographed to obtain faint yellow solid using column, is passed through
Identification, confirmation are indoles -2- methyl acetate.
(3) in 10 DEG C of water-baths, N- N-formyl morpholine N (4.0mL) synthesis of morpholine inferior amine salt: is dissolved in 20mL methylene chloride
In.In 10 DEG C of baths, oxalyl chloride (3.4mL) is dissolved in 8mL methylene chloride, is stirring evenly and then adding into containing N- N-formyl morpholine N
Dichloromethane solution in keep 10 DEG C react 3 hours, reaction terminate reaction system is evaporated under reduced pressure after gained it is faint yellow
Solid, identified, confirmation is morpholine inferior amine salt.
(4) hydrolysis is acylated: the indoles -2- methyl acetate (0.6g) that step (2) obtains being dissolved in 20mL acetonitrile, is added
The morpholine inferior amine salt (1.8g) that step (3) obtains is hydrolyzed, and 80 DEG C are completed for reaction 3 hours to reaction, and filtering is precipitated light
Brown solid, identified, confirmation is 3- formoxyl -2- heteroauxin methyl esters.
(5) two intermolecular cyclizations: the 3- formoxyl -2- heteroauxin methyl esters (0.2g) for taking step (4) to obtain is dissolved in
In 20mL anhydrous acetonitrile, piperidines (0.6mL) is added and acetic acid (0.2mL) carries out two intermolecular cyclization dimerization reactions, at 60 DEG C
Reaction 10 hours obtains red material with column chromatography after reaction, identified, is confirmed as Caulerpin,1H NMR
(300MHz, Chloroform-d) δ 9.23 (s, 2H), 8.08 (s, 2H), 7.47-7.43 (m, 2H), 7.33 (dt, J=8.1,
1.0Hz, 2H), 7.21 (ddd, J=8.2,7.0,1.3Hz, 2H), 7.12 (ddd, J=8.1,7.0,1.1Hz, 2H), 3.93 (s,
6H).13C NMR(75MHz,CDCl3)δ166.65,142.78,137.72,132.86,128.16,125.47,123.38,
120.74,118.04,112.49,111.52,52.52.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (8)
1. a kind of method of simple synthesis Caulerpin, it is characterised in that mainly comprise the steps that using indoles as raw material, to Yin
No. 2 positions of diindyl carry out the nucleophilic displacement of fluorine of methyl acetate, generate indoles -2- methyl acetate；Then again the 3 of indoles -2- methyl acetate
Number position carries out formylation reaction and obtains 3- formoxyl -2- heteroauxin methyl esters, finally passes through 3- formoxyl -2- heteroauxin methyl esters
It crosses two intermolecular cyclizations and obtains Caulerpin；
Specifically includes the following steps:
(1) ethyl xanthate is dissolved in organic solvent and obtains solution A；Halogenated acetic acids methyl esters is dissolved in organic solvent of the same race
In, it is stirring evenly and then adding into solution A and is reacted, is evaporated under reduced pressure after reaction, purifying obtains 2- xanthogen-acetic acid
Methyl esters；
(2) indoles and the double lauroyl of peroxidating are dissolved in organic solvent, 2- xanthogen-acetic acid that step (1) obtains is added
Methyl esters is reacted, and reaction terminates to purify gained reaction solution to obtain indoles -2- methyl acetate；
(3) N- N-formyl morpholine N is dissolved in organic solvent and obtains solution B；Mineral acid chloride is dissolved in organic solvent of the same race
In, it is stirring evenly and then adding into solution B and is reacted, obtaining solid through vacuum distillation after reaction is morpholine imines
Salt；
(4) indoles -2- methyl acetate that step (2) obtains is dissolved in organic solvent, the morpholine inferior amine salt that step (3) obtain is added
Formylation reaction is carried out, filtering solid be precipitated is 3- formoxyl -2- heteroauxin methyl esters；
(5) the 3- formoxyl -2- heteroauxin methyl esters for taking step (4) to obtain is dissolved in organic solvent, and piperidines is added and acetic acid occurs
Two intermolecular cyclization reactions obtain red material, as Caulerpin with chromatography after reaction；
Organic solvent described in step (5) is acetonitrile.
2. the method for simple synthesis Caulerpin according to claim 1, it is characterised in that:
Organic solvent as described in step (1) is at least one of methylene chloride, acetone, dichloroethanes, tetrahydrofuran；
Ethyl xanthate as described in step (1) is one of ehtyl potassium xanthate or sodium ethylxanthate；
Halogenated acetic acids methyl esters as described in step (1) is one of methyl bromoacetate or methyl chloroacetate；
The concentration of solution A as described in step (1) is 0.5 ~ 3.0mol/L, and the halogenated acetic acids methyl esters is dissolved in of the same race organic molten
The concentration of halogenated acetic acids methyl esters is 0.5 ~ 5.0mol/L in the solution obtained when agent；
The molar ratio of halogenated acetic acids methyl esters used in step (1) and ethyl xanthate is 1:0.5 ~ 5.
3. the method for simple synthesis Caulerpin according to claim 1, it is characterised in that:
As described in step (1) to be added to when being reacted in solution A, the temperature of solution A is 0 ~ 25 DEG C；Described in step (1)
Reaction refer in 0 ~ 40 DEG C of 0.5 ~ 8h of reaction；
Purifying as described in step (1) is directed to add water and ethyl acetate to be extracted in the product after vacuum distillation, then passes through
Merge organic phase after anhydrous sodium sulfate is dry, vacuum distillation removes solvent, and obtaining pale yellow oily liquid is 2- xanthogen-
Methyl acetate.
4. the method for simple synthesis Caulerpin according to claim 1, it is characterised in that:
Organic solvent described in step (2) is at least one of methylene chloride, chloroform, tetrahydrofuran, acetone；
Indoles described in step (2), 2- xanthogen-methyl acetate, the double lauroyl of peroxidating molar ratio be 1:1 ~ 5:1 ~
5。
5. the method for simple synthesis Caulerpin according to claim 1, it is characterised in that:
Reaction temperature described in step (2) be 0 ~ 100 DEG C, the reaction temperature be 3 ~ for 24 hours；
Purifying described in step (2), which refers to, utilizes column layer after vacuum distillation removes solvent for reaction solution after reaction
It is indoles -2- methyl acetate that analysis, which obtains faint yellow solid,.
6. the method for simple synthesis Caulerpin according to claim 1, it is characterised in that:
Organic solvent described in step (3) is at least one of methylene chloride, acetonitrile, tetrahydrofuran, acetone；
Mineral acid chloride described in step (3) is phosphorus oxychloride, at least one of oxalyl chloride, thionyl chloride, sulfonic acid chloride；
The concentration of solution B described in step (3) is 0.5 ~ 3.0mol/L, and the mineral acid chloride is dissolved in of the same race organic
The concentration of mineral acid chloride is 0.5 ~ 7.0mol/L when solvent；
The molar ratio of mineral acid chloride described in step (3) and N- N-formyl morpholine N is 0.8 ~ 5:1；
Reaction described in step (3) refers to that reaction temperature is -10 ~ 40 DEG C, and the reaction time is 0.25 ~ 8h.
7. the method for simple synthesis Caulerpin according to claim 1, it is characterised in that:
Organic solvent described in step (4) is at least one of dimethyl sulfoxide, chloroform, tetrahydrofuran, acetonitrile；
The molar ratio of indoles -2- methyl acetate described in step (4) and morpholine inferior amine salt is 1:1 ~ 8；
Reaction described in step (4) refers to that reaction temperature is 0 ~ 120 DEG C, and the reaction time is 0.25 ~ 10h.
8. the method for simple synthesis Caulerpin according to claim 1, it is characterised in that:
3- formoxyl -2- heteroauxin methyl esters described in step (5), piperidines, acetic acid molar ratio be 1:1 ~ 20:1 ~ 20；
Cyclization reaction described in step (5) refers to that reaction temperature is 50 ~ 120 DEG C, and the reaction time is 3 ~ 10h.
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| Title |
|---|
| CAULERPIN;Bhim C. Maiti et al.;《NATO Conference Series IV: Marine Sciences》;19771231;第159-163页 |
| Cyclization of N-Acylanthranilic Acids with Vilsmeier Reagents. Chemical and Structural Studies;Jan Bergnmn et al.;《Tetrahedron》;19961231;第52卷(第3期);第753-770页 |
| Efficient, intermolecular, oxidative radical alkylation of heteroaromatic systems under "tin-free" conditions;Yazmin M. Osornio et al.;《Chem.commun.》;20031231;第2316-2317页 |
| Expeditious synthesis of 1-substituted taurines with diverse functionalized side-chains;Saeed Kakaei et al.;《Tetrahedron》;20121016;第69卷;第302-309页 |
| Jan Bergman et al..Synthesis of indolocarbazole quinines |
| potent aryl hydrocarbon receptor ligands.《Tetrahedron》.2002,第58卷第1443-1452页. |
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