CN106632395B - A kind of loop coil amino acid esters compound and its preparation method and application - Google Patents
A kind of loop coil amino acid esters compound and its preparation method and application Download PDFInfo
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- CN106632395B CN106632395B CN201611079165.8A CN201611079165A CN106632395B CN 106632395 B CN106632395 B CN 106632395B CN 201611079165 A CN201611079165 A CN 201611079165A CN 106632395 B CN106632395 B CN 106632395B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/10—Spiro-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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Abstract
The present invention relates to a kind of loop coil amino acid esters compounds and its preparation method and application.The technical solution adopted by the present invention is：Loop coil amino acid esters compound, the structural formula with formula (I).Preparation method is as follows：With benzylamine, carbonate, tetrabromo season amylalcohol be raw material, in polar solvent, condensing reflux at 130 150 DEG C obtains target product.The present invention, with benzylamine, potassium carbonate and tetrabromo season amylalcohol as raw material, through one pot reaction, it can be obtained target product, this compound had not only had spirane structure but also had contained amino-acid ester group, was a kind of novel loop coil amino acid esters compound, the method for the present invention is easy to operate, the production cycle is relatively short, is easy to purify, it is expected in industry, agricultural, medicine aspect is used widely.
Description
Technical field
The invention belongs to organic chemical synthesis fields, and in particular to a kind of loop coil amino acid esters compound and its preparation side
Method.
Background technology
The polycyclic compound that two monocycles share a carbon atom is known as spiro-compound, and shared carbon atom is known as spiral shell original
Son.There are many method of synthesizing spiro compound, and simple spiro-compound synthesizes generally use 1,3- Dipolar Cycloadditions, acetal
Ketone method, malonate are reacted with penta tetrabromo of season (chlorine), acid anhydrides and reacting for di Grignard reagent etc..Spiro-compound has rigidity
Rock-steady structure, especially chiral spiro compound have larger specific rotatory power, in asymmetry catalysis, medicine, luminescent material, pesticide
Etc. have important application.Such as, Srivastava and Kumar is reported is repaiied with optical activity spiral shell [4.4] nonane -1,6- glycol
It is used for equivalent reduction of aromatic ketone after adoring tetra lithium aluminium hydride, ee values to be up to 98%, fully show excellent not right of spirocyclic ring scaffold
Claim inducing effect.Goekjian et al. is reacted using methylene glucosan derivative with fragrant nitrile oxide, and loop coil grape is prepared for
Sugar derivatives.Such compound can be used as the antibody of glucose phosphate glycosides.Tominaga in 2007 etc. has synthesized a series of loop coils
Structural compounds find that the substance relative molecular mass is more than 600, and substance of the fusing point higher than 150 DEG C has preferable thermostabilization
Performance and photochromic properties.Baker etc. has found that in sexually matured female drosophila sexual gland secretion include spiro ketal compound,
In addition, in the male body of gland of drosophila, there is also spiro ketals.Spiro ketal serves not only as sex pheromone component and is present in many
In drosophila body of gland, and as structural unit there are in the natural products for having strong physiological activity of many complexity, such as antibiosis
All contain spiro ketal structural unit in plain Okadaic acid and potential anti-cancer substance Spongistatin.Nunzio in 1979
R et al. is prepared for spiral shell [1- cyclopropane base -1'- indenyls] -2- formic acid-alpha-cyano -3,3 dimethyl (3- benzyloxy phenoxies base) ester, should
Compound is mixed with PVC, has apparent except mite effect, and have hypotoxicity to mammal.
For amino acid esters compound, its synthesis is usually acid catalyzed process, ester-interchange method, triphosgene etc..Amino acid
Ester type compound has special physicochemical property, in an increasingly wide range of applications in chemical industry, medicine, pesticide etc..Sun Jian
Army etc. is using glutamic acid and laruyl alcohol as raw material, with solid super-strong acid ZrO2-SO4 2-Make catalyst synthesis glutamic acid lauryl alcohol ester table
Face activating agent；Zeng Yiliang etc. screens a kind of N- methyl alkyls substituted-phenyl carbamate compounds, and the compound is to more
Kind prevention and control of aphids drug effect is excellent, and to mammal low toxicity, safe to use, raw material is easy to get, at low cost；B.Ramamurthy is reported
Amino acid ester derivative has anti-tubercular.However, having the compound report of amino-acid ester group again very for existing loop coil
Lack, especially target product：Have whorled bis-amino acid ester group, yet there are no be reported so far.
Invention content
The object of the present invention is to provide a kind of method is simple, through one pot reaction, you can obtain not only there is spirane structure but also
New-type spiro amino acid esters compound containing amino-acid ester group.
To achieve the above object, the technical solution adopted by the present invention is：A kind of loop coil amino acid esters compound has formula
(I) structural formula：
The preparation method of above-mentioned loop coil amino acid esters compound, method are as follows：With benzylamine, carbonate, tetrabromo season penta
Alcohol is raw material, and in polar solvent, condensing reflux at 130-150 DEG C obtains target product.
The preparation method of above-mentioned loop coil amino acid esters compound, the polar solvent is DMF.
The preparation method of above-mentioned loop coil amino acid esters compound, the carbonate is potassium carbonate.
The preparation method of above-mentioned loop coil amino acid esters compound, by molar ratio, benzylamine:Carbonate:Tetrabromo season
Amylalcohol=4:1.5:2.
The preparation method of above-mentioned loop coil amino acid esters compound, condensing reflux 12-16 hours.
The beneficial effects of the invention are as follows：
1. the present invention, with benzylamine, potassium carbonate and tetrabromo season amylalcohol as raw material, through one pot reaction, you can obtain target
Product, this compound had not only had spirane structure but also had contained amino-acid ester group, were a kind of novel loop coil amino acid esters
Close object.
2. the loop coil amino acid esters compound that the present invention synthesizes is the compound of -3- nitrogen -2- ketone structural units of oxygen containing 1-,
The structure class compound has extensive bioactivity, by the intermediate as synthesizing activity drug, the active medicine can by with
In treatment senile dementia.
3. the loop coil amino acid esters compound that the present invention synthesizes is the compound of -3- nitrogen -2- ketone structural units of oxygen containing 1-,
The structure class compound is widely used in the herbicide of various crops, and not only herbicidal effect is notable, but also has good crop
Weeds selectivity, is especially used as rice weeding.
4. the loop coil amino acid esters compound that the present invention synthesizes is the compound of -3- nitrogen -2- ketone structural units of oxygen containing 1-,
The structure class compound is the inhibitor of 11- beta-hydroxysteroid dehydrogenases 1, for treating metabolism class disease, is such as metabolized comprehensive
Close disease, diabetes, obesity and dyslipidemia.
5. the method for the present invention is easy to operate, the production cycle is relatively short, is easy to purify, it is expected in industry, agricultural, medicine side
It is used widely in face.
Description of the drawings
Fig. 1 is the MS (CH of target product prepared by embodiment2Cl2) figure.
Fig. 2 is target product prepared by embodiment1HNMR(CDCl3) figure.
Fig. 3 is IR (KBr) figure of target product prepared by embodiment.
Fig. 4 is the hot ellipsoid figure of monocrystalline of target product prepared by embodiment.
Specific implementation mode
In order to better understand the present invention, below by embodiment, the present invention will be further described.
Embodiment
(1) preparation method：
0.776g (2mmol) four bromo seasons amylalcohol, 0.429g (4mmol) benzylamine, 0.207g are added in 100ml there-necked flasks
The DMF of (1.5mmol) potassium carbonate and 10ml, condensing reflux 12h under the conditions of 140 °.After reaction, inorganic salts are filtered out, then depressurize steaming
Distillate DMF.Absolute ethyl alcohol is added, crystallization obtains white needle-like crystals 0.099g.
(2) result
1. 190-191 DEG C of the fusing point of product.
2. Fig. 1 is the MS (CH of target product2Cl2) figure.As shown in Figure 1, the ESI-MS of target product：Calculated M：
366.4Found[M+Na]+：389.3.
3. Fig. 2 is target product1HNMR(CDCl3) figure, from Figure 2 it can be seen that1H NMR(CDCl3,300MHz)δ:2.96
(2H,d,CH2),3.10(2H,d,CH2),3.97(2H,d,CH2),4.09(2H,d,CH2),4.44(4H,t,CH2),7.35
(10H,m,Ar-H)。
4. Fig. 3 is IR (KBr) figure of target product, as seen from Figure 3, IR (KBr), λ max/cm-1：3367.59cm-1,
3032.67cm-1, 2921.28cm-1, 1689.59cm-1, 1492.44cm-1, 1437.25cm-1, 1369.44cm-1,
1266.93cm-1, 1229.08cm-1, 1184.92cm-1, 1095.02cm-1, 1031.94cm-1, 749.64cm-1,713.37cm-1, 694.45cm-1。
5. Fig. 4 is the hot ellipsoid figure of monocrystalline of target product, the structural analysis of target product is as follows：Crystal belongs to monoclinic crystal
System, Cc space groups, cell parameter is,β=96.157
(5)°。 Z=4, empirical formula C20H20NO2, relative molecular mass 306.37, the crystal calculated
Density is Dc=1.110g/cm-3.Mainly bond distance's bond angle is： ∠ O2-C6-N1=119.60 °, ∠ C6-N1-C3=123.97 °, ∠ C6-O2-C2=118.78 °. ∠ C4-N2-C7=123.55 °, ∠ N2-C7-O4=
119.73 °, ∠ C7-O4-C5=120.30 °.
Claims (5)
1. the preparation method of loop coil amino acid esters compound, it is characterised in that：Method is as follows：With benzylamine, carbonate, tetrabromo season
Amylalcohol is raw material, and in polar solvent, condensing reflux at 130-150 DEG C obtains target product；The loop coil amino acid esters
Compound, the structural formula with formula (I)：
2. the preparation method of loop coil amino acid esters compound as described in claim 1, it is characterised in that：The polarity is molten
Agent is DMF.
3. the preparation method of loop coil amino acid esters compound as described in claim 1, it is characterised in that：The carbonate
It is potassium carbonate.
4. the preparation method of loop coil amino acid esters compound as described in claim 1, it is characterised in that：By feeding intake mole
Than benzylamine:Carbonate:Tetrabromo season amylalcohol=4:1.5:2.
5. the preparation method of loop coil amino acid esters compound as described in claim 1, it is characterised in that：Condensing reflux 12-
16 hours.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4665197A (en) * | 1984-06-19 | 1987-05-12 | Shell Oil Company | Process for preparing azetidine derivatives and intermediates thereof |
| US4701534A (en) * | 1984-06-19 | 1987-10-20 | Shell Oil Company | Azetidine derivative |
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2016
- 2016-11-30 CN CN201611079165.8A patent/CN106632395B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4665197A (en) * | 1984-06-19 | 1987-05-12 | Shell Oil Company | Process for preparing azetidine derivatives and intermediates thereof |
| US4701534A (en) * | 1984-06-19 | 1987-10-20 | Shell Oil Company | Azetidine derivative |
Non-Patent Citations (1)
| Title |
|---|
| Natural Product-Like Virtual Libraries: Recursive Atom-Based Enumeration;Melvin J. Yu;《Journal of Chemical Information and Modeling》;20110509;第51卷(第3期);541-557 * |
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