CN104151227A - Preparation method for compound Dabsyl-L-tryptophan - Google Patents
Preparation method for compound Dabsyl-L-tryptophan Download PDFInfo
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- CN104151227A CN104151227A CN201310179624.XA CN201310179624A CN104151227A CN 104151227 A CN104151227 A CN 104151227A CN 201310179624 A CN201310179624 A CN 201310179624A CN 104151227 A CN104151227 A CN 104151227A
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- compound
- dimethylaminophenyl
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- methyl ester
- absyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D209/20—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals substituted additionally by nitrogen atoms, e.g. tryptophane
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- Organic Chemistry (AREA)
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Abstract
The invention relates to a method for synthesizing and purifying a compound Dabsyl-L-tryptophan. 4-dimethylamino phenyl azobenzene-4'- sodium sulfonate, phosphorus oxychloride, L-tryptophan methyl ester hydrochloride and the like are taken as raw materials; the yield of the prepared final product reaches requirements; the purification degree is high; and the preparation method is scientific and reasonable, so that detailed theory and practice guidance is provided for subsequent expanded production.
Description
Technical field
The invention belongs to compound preparation field, especially a kind of preparation method of Dabsyl-L-tryptophane.
Background technology
At present, because Bioexperiment makes new breakthroughs, make us in treatment and find in the process of the cause of disease, means are more, result is more accurate, property pharmaceutical requirements is also increased gradually for the various diseases for the treatment of so, therefore, the various compounds with new function are in a large amount of being developed, the whole world all has the new compound of the various difficult and complicated cases of opposing in searching, so in the process of these new compound exploitations, can produce the compound of numerous new textures and new configuration, and then in these numerous new compounds, find useful, there is the molecule for the treatment of use, therefore developing new compound is one and important process.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of Compound D absyl-L-tryptophane, and this compound of purifying, make its purity reach certain requirement, can further test or application it.
The technical scheme of object of the present invention is as follows:
(1) compound 4-dimethylaminophenyl nitrogen benzide-4'-SULPHURYL CHLORIDE is synthetic:
4-dimethylaminophenyl nitrogen benzide-4'-sodium sulfonate is added in reaction flask, add phosphorus oxychloride, back flow reaction at 100 DEG C.TLC detection reaction completely after, reaction solution is spin-dried for, the shrend on the rocks phosphorus oxychloride of going out, filters and obtains solid, dries and obtains compound 4-dimethylaminophenyl nitrogen benzide-4'-SULPHURYL CHLORIDE.
(2) Compound D absyl-L-tryptophan methyl ester is synthetic:
4-dimethylaminophenyl nitrogen benzide-4'-SULPHURYL CHLORIDE and L-Trp methyl ester hydrochloride are joined in reaction flask, add methylene dichloride, 0 DEG C drips triethylamine, and room temperature reaction spends the night.TLC detection reaction completely after, reaction solution is spin-dried for, after add ethyl acetate, filter, filtrate is spin-dried for by methanol wash, dries solid, obtains Compound D absyl-L-tryptophan methyl ester.
(3) Compound D absyl-L-tryptophane is synthetic:
Dabsyl-L-tryptophan methyl ester is added in reaction flask, add methyl alcohol, 0 DEG C drips the aqueous solution of KOH, and back flow reaction is spent the night.TLC detection reaction completely after, methyl alcohol in reaction solution is spin-dried for, filter, after add water, adjusting pH with the hydrochloric acid of 2N is 3, filter, filter cake washing with acetone, oven dry obtains Compound D absyl-L-tryptophane.
And the ratio of the described 4-dimethylaminophenyl nitrogen benzide-4'-of step (1) sodium sulfonate, phosphorus oxychloride is 46mmol:100ml.
And the ratio of the described 4-dimethylaminophenyl nitrogen benzide-4'-of step (2) SULPHURYL CHLORIDE, L-Trp methyl ester hydrochloride, methylene dichloride, triethylamine, ethyl acetate, methyl alcohol is 46.3mmol:60mmol:500ml:140mmol:1000ml:100ml.
And the described Dabsyl-L-tryptophan methyl ester of step (3), methyl alcohol, KOH, water are than being 24.3mmol:100ml:121.6mmol:100ml.
Advantage of the present invention and positively effect are:
1, the invention provides method and the purification process thereof of the synthetic Dabsyl-L-tryptophanes of raw material such as using 4-dimethylaminophenyl nitrogen benzide-4'-sodium sulfonate, phosphorus oxychloride, L-Trp methyl ester hydrochloride, prepare end product productive rate and reach requirement, degree of purification is high, production method science, reasonable, instructs for follow-up expanding production provides detailed theory and practice.
2, the invention provides synthesis condition, the raw material of each step in Dabsyl-L-tryptophane building-up process, and the nuclear magnetic spectrum of synthetic after product, for the analysis and identification of synthetic product provides detailed support.
Embodiment
Below in conjunction with embodiment, the present invention is further described, and following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
Reaction scheme of the present invention is as follows:
Raw material
4-dimethylaminophenyl nitrogen benzide-4'-sodium sulfonate, phosphorus oxychloride, L-Trp methyl ester hydrochloride etc.
The synthetic method of this compound is as follows:
(1) compound 4-dimethylaminophenyl nitrogen benzide-4'-SULPHURYL CHLORIDE is synthetic:
Take 4-dimethylaminophenyl nitrogen benzide-4'-sodium sulfonate (90g, 92mmol) in 500mL single port bottle, add phosphorus oxychloride (200mL), back flow reaction (100 DEG C).TLC detection reaction completely after, reaction solution is spin-dried for, the rear shrend on the rocks phosphorus oxychloride of going out, filters and obtains solid, dries and obtains compound 4-dimethylaminophenyl nitrogen benzide-4'-SULPHURYL CHLORIDE (70g).
(2) Compound D absyl-L-tryptophan methyl ester is synthetic:
Take 4-dimethylaminophenyl nitrogen benzide-4'-SULPHURYL CHLORIDE (15g, 46.3mmol) and L-Trp methyl ester hydrochloride (24g, 92.6mmol) in 1000mL single port bottle, add 500mL methylene dichloride, 0 DEG C drips triethylamine (14g, 140mmol), and room temperature reaction (25 DEG C) spends the night.TLC detection reaction completely after, reaction solution is spin-dried for, after add ethyl acetate (1000mL), filter, filtrate is spin-dried for methyl alcohol (100mL) washing, dries solid, obtains Compound D absyl-L-tryptophan methyl ester (9g).
(3) Compound D absyl-L-tryptophane is synthetic:
Take Dabsyl-L-tryptophan methyl ester (12.3g, 24.3mmol)) in 250mL single port bottle, add 100mL methyl alcohol, 0 DEG C drip KOH(6.8g, 121.6mmol) aqueous solution 100mL, back flow reaction is spent the night.TLC detection reaction completely after, methyl alcohol in reaction solution is spin-dried for, filter, after add water (100mL), adjusting pH with the hydrochloric acid of 2N is 3, filter, filter cake washing with acetone, oven dry obtains Compound D absyl-L-tryptophane (8.7g).
Claims (4)
1. a preparation method for Compound D absyl-L-tryptophane, is characterized in that: step is as follows:
(1) compound 4-dimethylaminophenyl nitrogen benzide-4'-SULPHURYL CHLORIDE is synthetic:
4-dimethylaminophenyl nitrogen benzide-4'-sodium sulfonate is added in reaction flask, add phosphorus oxychloride, back flow reaction at 100 DEG C.TLC detection reaction completely after, reaction solution is spin-dried for, the shrend on the rocks phosphorus oxychloride of going out, filters and obtains solid, dries and obtains compound 4-dimethylaminophenyl nitrogen benzide-4'-SULPHURYL CHLORIDE.
(2) Compound D absyl-L-tryptophan methyl ester is synthetic:
4-dimethylaminophenyl nitrogen benzide-4'-SULPHURYL CHLORIDE and L-Trp methyl ester hydrochloride are joined in reaction flask, add methylene dichloride, 0 DEG C drips triethylamine, and room temperature reaction spends the night.TLC detection reaction completely after, reaction solution is spin-dried for, after add ethyl acetate, filter, filtrate is spin-dried for by methanol wash, dries solid, obtains Compound D absyl-L-tryptophan methyl ester.
(3) Compound D absyl-L-tryptophane is synthetic:
Dabsyl-L-tryptophan methyl ester is added in reaction flask, add methyl alcohol, 0 DEG C drips the aqueous solution of KOH, and back flow reaction is spent the night.TLC detection reaction completely after, methyl alcohol in reaction solution is spin-dried for, filter, after add water, adjusting pH with the hydrochloric acid of 2N is 3, filter, filter cake washing with acetone, oven dry obtains Compound D absyl-L-tryptophane.
2. preparation method according to claim 1, is characterized in that: the ratio of the described 4-dimethylaminophenyl nitrogen benzide-4'-of step (1) sodium sulfonate, phosphorus oxychloride is 23mmol:50ml.
3. preparation method according to claim 1, is characterized in that: the ratio of the described 4-dimethylaminophenyl nitrogen benzide-4'-of step (2) SULPHURYL CHLORIDE, L-Trp methyl ester hydrochloride, methylene dichloride, triethylamine, ethyl acetate, methyl alcohol is 46.3mmol:92.6mmol:500ml:140mmol:1000ml:100ml.
4. preparation method according to claim 1, is characterized in that: the described Dabsyl-L-tryptophan methyl ester of step (3), methyl alcohol, KOH, water are than being 24.3mmol:100ml:121.6mmol:100ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310179624.XA CN104151227A (en) | 2013-05-15 | 2013-05-15 | Preparation method for compound Dabsyl-L-tryptophan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310179624.XA CN104151227A (en) | 2013-05-15 | 2013-05-15 | Preparation method for compound Dabsyl-L-tryptophan |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104151227A true CN104151227A (en) | 2014-11-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310179624.XA Pending CN104151227A (en) | 2013-05-15 | 2013-05-15 | Preparation method for compound Dabsyl-L-tryptophan |
Country Status (1)
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| CN (1) | CN104151227A (en) |
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2013
- 2013-05-15 CN CN201310179624.XA patent/CN104151227A/en active Pending
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Application publication date: 20141119 |