CN105218369A - The new synthetic method of one class bromo unsaturated fatty acid ester - Google Patents
The new synthetic method of one class bromo unsaturated fatty acid ester Download PDFInfo
- Publication number
- CN105218369A CN105218369A CN201410235574.7A CN201410235574A CN105218369A CN 105218369 A CN105218369 A CN 105218369A CN 201410235574 A CN201410235574 A CN 201410235574A CN 105218369 A CN105218369 A CN 105218369A
- Authority
- CN
- China
- Prior art keywords
- compound
- solvent
- reaction
- formula
- temperature
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to pharmaceutical synthesis field.Particularly, the present invention relates to the new preparation process of the long-chain bromination yne compounds with hypolipidemic activity.
Description
Technical field
The invention belongs to pharmaceutical synthesis field.Particularly, the present invention relates to the new preparation process of the long-chain bromination yne compounds with hypolipidemic activity.
Background technology
About there are 1.2 hundred million people to suffer from obesity in current world wide, have 2.1 hundred million people overweight in addition.Along with the rapid lifting of China's economic level, the mode of life of people also changes thereupon.Day by day common unhealthy diet and the generally decline of physical activity level, make the overweight incidence of China's rural and urban population in rapid rising, obesity morbidity is also in rising trend in recent years.Data display according to investigations, rate that China resident is overweight is 17.6%, obesity rates is 5.6%, and sum of the two is 23.2%.Fat and the disease serious threat brought out and affect human life's safety and quality of life, it is very urgent therefore to prevent, control and treat obesity.
Developing the Living marine resources of China, therefrom finding has in the process of the marine natural product of biological activity and prospect in medicine, a kind of long-chain bromination eneyne unsaturated fatty acids compound obtained is separated: E from marine organisms sponge XestospongiaTsstudinaria, E-22-bromo-9,11,19-tri-alkynes-17,21-diene methyl behenate, its structural formula is as follows:
This compound of research display has remarkable steapsase inhibit activities (be the Chinese patent application of 201110180360.0 see application number), and the long-chain bromination eneyne unsaturated fatty acids compound of other similar also probably has similar activity.But this compounds content in natural product is rare, biogenetic derivation difficulty, constrains it and further develops, and prepare by synthetic method the effective way that this compounds carrys out source problem.Therefore, need to develop that a kind of route is novel, new preparation method easy and simple to handle prepares this compounds simply, efficiently.
Summary of the invention
The object of the present invention is to provide the preparation method of the long-chain bromination unsaturated fatty acids with formula 1 structure:
Wherein, n
1and n
2be 1,2,3,4 or 5 independently of one another; R is C1-C5 alkyl;
Preferably, R is methyl, ethyl, n-propyl or sec.-propyl.
Described method is undertaken by following reaction process:
A. in a solvent, formula 2 compound reacts with trimethylsilyl acetylene under palladium reagent, cuproine, the catalysis of amine reagent, production 3 compound;
B. in a solvent, formula 3 compound obtains formula 4 compound under tosic acid or para-methylbenzenepyridinsulfonate sulfonate effect;
C. in a solvent, formula 4 compound obtains formula 5 compound through oxidizing;
D. in a solvent, formula 5 compound and triphenyl phosphorus and carbon tetrabromide are obtained by reacting formula 6 compound;
E. in a solvent, formula 6 compound obtains formula 7 compound under alkali effect;
F. in a solvent, formula 7 compound is obtained by reacting formula 8 compound with bromo acetylenic acid ester under cuprous, oxammonium hydrochloride and amine catalysis;
G. in a solvent, formula 8 compound sloughs protecting group Me under fluorine reagent effect
3si-obtains formula 9 compound;
H. in a solvent, formula 9 compound is obtained by reacting formula 1 compound with 1,2-sym-dibromoethane under cuprous, palladium reagent and amine catalysis.
Wherein, the synthesis reference literature J.Chin.Chem.Soc. of formula 2 compound, (Taipei), 1999,46,87-90.
A. the synthesis of formula 3 alkynes ene compound:
In a solvent, formula 2 compound is obtained by reacting formula 3 compound with trimethylsilyl acetylene under palladium reagent, cuproine, the catalysis of amine reagent, and described palladium reagent is tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride; Described cuproine is cuprous chloride, cuprous bromide or cuprous iodide; Described solvent is methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, dipropyl amine, dibutylamine, Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine or Diisopropylamine; Temperature of reaction is room temperature.
B. the synthesis of formula 4 alkyne enol compound:
In a solvent, formula 3 compound obtains formula 4 compound under tosic acid or para-methylbenzenepyridinsulfonate sulfonate effect, and described solvent is methyl alcohol, ethanol or Virahol; Temperature of reaction is that room temperature arrives backflow.
C. the synthesis of formula 5 alkynes olefine aldehydr compound:
In a solvent, formula 4 compound obtains formula 5 compound through oxidizing, described oxygenant is PCC (Pyridiniumchlorochromate, pyridinium chlorochromate drone salt), PDC (Pyridiniumdichromate, pyridinium dichromate) or chromium trioxide pyridine; Described solvent is methylene dichloride or chloroform; Temperature of reaction is that room temperature arrives backflow.
D. the synthesis of formula 6 sym-dibromoethane compound:
In a solvent, formula 5 compound and triphenyl phosphorus and carbon tetrabromide are obtained by reacting formula 6 compound, and described solvent is methylene dichloride or chloroform; Temperature of reaction be-78 DEG C to room temperature.
E. the synthesis of formula 7 acetylene compound:
In a solvent, formula 6 obtains formula 7 compound under alkali effect, and described solvent is tetrahydrofuran (THF) or ether; Described alkali is n-Butyl Lithium, tert-butyl lithium, phenyl lithium or lithium diisopropylamine; Temperature of reaction be-78 DEG C to room temperature.
F. the synthesis of formula 8 trimethyl silicane alkynes enoic acid ester compounds:
In a solvent, formula 7 compound is obtained by reacting formula 8 compound with bromo acetylenic acid ester under amine, oxammonium hydrochloride and amine catalysis, and described amine is methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, dipropyl amine, dibutylamine, Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine or Diisopropylamine; Described cuproine is cuprous chloride, cuprous bromide or cuprous iodide; Described solvent is methyl alcohol or ethanol; Temperature of reaction is that room temperature arrives backflow.
G. the synthesis of formula 9 alkynes enoic acid ester compounds:
In a solvent, formula 8 compound obtains formula 9 compound under fluorine reagent effect, and described fluorine reagent is hydrogen fluoride, Potassium monofluoride or tetrabutyl ammonium fluoride; Described solvent is tetrahydrofuran (THF) or ether; Temperature of reaction is room temperature.
H. the synthesis of formula 1 compound:
Formula 9 compound is obtained by reacting formula 1 compound with sym-dibromoethane under palladium reagent, cuproine and amine effect, and described amine is methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, dipropyl amine, dibutylamine, Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine or Diisopropylamine; Described cuproine is cuprous chloride, cuprous bromide or cuprous iodide; Described palladium reagent is tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride; Temperature of reaction is that room temperature arrives backflow.
Preferably, the reagent and the condition that respectively walk reaction are:
In step a, described palladium reagent is bi triphenyl phosphorus palladium chloride, and described cuproine is cuprous iodide; Described solvent is diethylamine; Temperature of reaction is room temperature;
In stepb, described solvent is methyl alcohol; Temperature of reaction is room temperature;
In step c, described oxygenant is PCC or PDC; Described solvent is methylene dichloride; Temperature of reaction is room temperature;
In steps d, described solvent is methylene dichloride; Temperature of reaction is room temperature;
In step e, described solvent is tetrahydrofuran (THF); Alkali is n-Butyl Lithium; Temperature of reaction be-78 DEG C to room temperature;
In step f, described amine is ethamine; Described cuproine is cuprous chloride; Described solvent is methyl alcohol; Temperature of reaction is room temperature;
In step g, described fluorine reagent is tetrabutyl ammonium fluoride; Described solvent is tetrahydrofuran (THF); Temperature of reaction is room temperature;
In step h, described amine is triethylamine; Described cuproine is cuprous iodide; Described palladium reagent is tetrakis triphenylphosphine palladium; Temperature of reaction is room temperature.
Embodiment
Embodiment 1:(E) synthesis of-1-trimethyl silicane-9-(2-the tetrahydro-pyran oxy)-ninth of the ten Heavenly Stems-3-alkene-1-alkynes
In the reaction flask of nitrogen protection; the 10 grams of iodo-7-of (E)-1-(2-tetrahydro-pyran oxy)-1-heptene are dissolved in 10 milliliters of diethylamine; add 428 milligrams of bi triphenyl phosphorus palladium chlorides; 1.5 grams of cuprous iodides and 3 grams of trimethylsilyl acetylenes, stirring at room temperature added water after 5 hours, ether extraction; dried over mgso; filtering and concentrating, through column chromatography give light yellow oil 6.25 grams, yield 70%.
1HNMR(400MHz,CDCl
3):δ0.17(s,9H),1.24-1.82(m,12H),2.09(t,2H),3.33-3.40(m,1H),3.47-3.51(m,1H),3.68-3.76(m,1H),3.82-3.88(m,1H),4.55(s,1H),5.49(d,J=15.9Hz,1H),6.20(dt,J=15.9,7.2Hz,1H);
13CNMR(125MHz,CDCl
3):0.46,19.26,25.04,25.27,27.99,29.07,30.32,32.55,61.94,67.01,92.12,98.44,103.68,109.23,145.69;ESI-MSm/z:294.2[M]
+.
Embodiment 2:(E) synthesis of-9-trimethyl silicane-6-alkene-8-alkynes-1 nonyl alcohol
5 grams of (E)-1-trimethyl silicanes-9-(2-the tetrahydro-pyran oxy)-ninth of the ten Heavenly Stems-3-alkene-1-alkynes is dissolved in 150 ml methanol, add 3.9 grams of tosic acid, stirring at room temperature 2 hours, pressure reducing and steaming solvent, adds water, ether extraction, dried over mgso, filtering and concentrating, through column chromatography give light yellow oil 3.13 grams, yield 87%.
1HNMR(400MHz,CDCl
3):δ0.17(s,9H),1.35-1.43(m,4H),1.54-1.48(m,2H),2.08-2.12(m,2H),3.62(dt,J=6.8,2.9Hz,2H),5.50(dt,J=15.9,1.6Hz,1H),6.20(dt,J=15.9,7.2Hz,1H);
13CNMR(125MHz,CDCl
3):0.46,24.77,27.94,29.07,32.08,32.57,62.41,92.22,103.62,109.34,145.53;ESI-MSm/z:210.1[M]
+.
Embodiment 3:(E) synthesis of-9-trimethyl silicane-6-alkene-8-alkynes aldehyde C-9
30 milliliters of methylene dichloride are added in the reaction flask of drying nitrogen protection; 3.1 grams of oxalyl chlorides; cool to-78 DEG C; add the 2.4 grams of methyl-sulphoxides being dissolved in 3 milliliters of methylene dichloride; add rear stirring 10 minutes; add 2.6 grams of (the E)-9-trimethyl silicane-6-alkene-8-alkynes-1 nonyl alcohols being dissolved in 6 milliliters of methylene dichloride, continue stirring 10 minutes, add 10 milliliters of triethylamines; rise to room temperature; add water, separate dichloromethane layer, washing; dried over mgso; filtering and concentrating, through column chromatography give light yellow oil 2.2 grams, yield 82%.
1HNMR(400MHz,CDCl
3):δ0.20(s,9H),1.41-1.49(m,2H),1.64-1.70(m,2H),2.14-2.16(m,2H),2.43-2.47(m,2H),5.53(dt,J=16.0,1.2Hz,1H),6.20(dt,J=16.0,7.2Hz,1H),9.78(t,J=1.6Hz,1H);
13CNMR(125MHz,CDCl
3):0.48,21.00,27.61,32.30,43.20,92.50,103.40,109.79,144.75,201.92;ESI-MSm/z:208.1[M]
+.
Embodiment 5:(E) synthesis of-1-trimethyl silicane-10,10-bis--1-alkynes-3,9-diene in the bromo-last of the ten Heavenly stems
2.5 grams of (E)-9-trimethyl silicane-6-alkene-8-alkynes aldehyde C-9s are added successively in reaction flask, 4.5 grams of carbon tetrabromides, 7.6 grams of triphenyl phosphorus and 20 milliliters of methylene dichloride, stirring at room temperature 2 hours, adds water, separates dichloromethane layer, dried over mgso, filtering and concentrating, obtains colourless liquid 3.7 grams through column chromatography, yield 83%.
1HNMR(400MHz,CDCl
3):δ0.17(s,9H),1.40-1.46(m,4H),2.08-2.15(m,4H),5.51(d,J=15.9Hz,1H),6.19(dt,J=15.9,7.2Hz,1H),6.36(t,J=7.2Hz,1H);
13CNMR(125MHz,CDCl
3):0.01,27.18,27.92,32.74,88.90,92.87,103,94,110.08,138.41,145.51;ESI-MSm/z:362.0[M]
+.
Embodiment 6:(E) the synthesis of-1-trimethyl silicane-last of the ten Heavenly stems-3-alkene-1,9-diine
3.7 grams of (E)-1-trimethyl silicane-10,10-bis--1-alkynes-3,9-diene in the bromo-last of the ten Heavenly stems are added in the reaction flask of drying nitrogen protection; be dissolved in 100 milliliters of anhydrous tetrahydro furans; cool to-78 DEG C, slowly add the n-Butyl Lithium of 14 milliliters of 1M, add rear stirring 2 hours; add water; ether extraction, organic phase dried over mgso, filtering and concentrating; colourless liquid 1.8 grams is obtained, yield 85% through column chromatography.
1HNMR(400MHz,CDCl
3):δ0.17(s,9H),1.51-1.54(m,4H),1.94(t,3H),2.11-2.18(m,4H),5.50(d,J=15.9Hz,1H),6.20(dt,J=15.9,7.2Hz,1H);
13CNMR(125MHz,CDCl
3):0.02,18.21,27.60,27.72,32.49,68.43,84.22,92.79,103,98,110.02,145.57;ESI-MSm/z:204.1[M]
+.
Embodiment 7:(E) synthesis of the sour methyl esters of-20-trimethyl silicane-17-alkene-9,11,19-tri-alkynes 20
65 milligrams of oxammonium hydrochlorides are dissolved in 20 milliliters of ethamine, add 90 milligrams of cuprous chlorides, add 2.9 grams of (E)-1-trimethyl silicanes the being dissolved in 20 ml methanol-last of the ten Heavenly stems-3-alkene-1,9-diine, 3.7 grams of 10-bromine methyl caprates, stirring at room temperature 12 hours, adds water, ether extraction, there is basic unit's saturated common salt water washing, dried over mgso, filtering and concentrating, colorless oil 1.4 grams is obtained, yield 52% through column chromatography.
1HNMR(300MHz,CDCl
3):δ0.19(s,9H),1.27-1.33(m,6H),1.50-1.62(m,8H),2.12-2.15(m,2H),2.24-2.34(m,6H),3.68(s,3H),5.51(d,J=16.0Hz,1H),6.20(dt,J=16.0,7.2Hz,1H);
13CNMR(125MHz,CDCl
3):0.08,18.9,19.1,24.8,27.5,27.6,28.1,28.5,28.6,28.9,32.4,34.0,51.2,65.1,65.5,76.9,77.5,92.7,103.9,110.0,145.4,174.2;EI-MSm/z:384.0[M]
+.
The synthesis of the sour methyl esters of embodiment 8:E-17-alkene-9,11,19-tri-alkynes 20
1.4 grams of E-20-trimethyl silicane-17-alkene-9,11, the sour methyl esters of 19-tri-alkynes 20 is dissolved in 35 milliliters of tetrahydrofuran (THF)s, adds 1.4 grams of tetrabutyl ammonium fluorides, stirring at room temperature 2 hours, add water, ether extraction, dried over mgso, filtering and concentrating, resistates obtains colourless liquid 1.1 grams through column chromatography, yield 96%.
1HNMR(300MHz,CDCl
3):δ0.17(s,9H),1.27-1.42(m,6H),1.49-1.65(m,8H),2.09-2.15(m,2H),2.24-2.34(m,6H),2.80(s,1H),3.65(s,3H),5.7(d,J=15.8Hz,1H),6.25(dt,J=15.8,7.2Hz,1H);
13CNMR(125MHz,CDCl
3):18.9,19.1,24.8,27.6,27.7,28.2,28.6,28.7,28.9,32.4,34.0,51.4,65.2,65.5,75.8,76.9,77.6,82.3,108.9,146.0,174.2;ESI-MSm/z:313[M+1]
+.
Embodiment 9:(17E, 21E) synthesis of bromo-9,11,19-tri-alkynes-17, the 21-diene methyl behenates of-22-
The sour methyl esters of 1 gram of E-17-alkene-9,11,19-tri-alkynes 20 is added in the reaction flask of nitrogen protection; 40 milliliters of triethylamines; add 1 gram of 1,2-sym-dibromoethane more successively, 0.2 gram of four (triphenyl phosphorus) palladium; 0.2 gram of cuprous iodide; stirring at room temperature 16 hours, filters, and filtrate concentrates; resistates obtains colourless liquid 0.76 gram through column chromatography, yield: 58%
1HNMR(300MHz,CDCl
3):δ1.27-1.40(m,6H),1.49-1.65(m,8H),2.05-2.16(m,2H),2.24-2.34(m,6H),3.68(s,3H),5.57(d,J=16.1Hz,1H),6.18(dt,J=16.1,7.2Hz,1H),6.32(d,J=14.0Hz,1H,1H),6.66(d,J=14.0Hz,1H,1H);13CNMR(125MHz,CDCl
3):19.0,19.1,24.8,27.6,28.2,28.6,28.7,28.9,29.7,32.6,34.0,51.4,65.2,65.5,76.9,77.6,84.6,90.6,109.5,117.5,145.3,174.2;EI-MSm/z:165,337,415,417[M-1]
+。
Claims (4)
1. prepare the method for the long-chain bromination unsaturated fatty acids with formula 1 structure for one kind:
Wherein, n
1and n
2be 1,2,3,4 or 5 independently of one another; R is C1-C5 alkyl;
Described method is undertaken by following reaction process:
In a solvent, formula 2 compound reacts with trimethylsilyl acetylene step a. under palladium reagent, cuproine, the catalysis of amine reagent, production 3 compound;
In a solvent, formula 3 compound obtains formula 4 compound to step b. under tosic acid or para-methylbenzenepyridinsulfonate sulfonate effect;
In a solvent, formula 4 compound obtains formula 5 compound through oxidizing to step c;
Steps d. in a solvent, formula 5 compound and triphenyl phosphorus and carbon tetrabromide are obtained by reacting formula 6 compound;
In a solvent, formula 6 compound obtains formula 7 compound to step e. under alkali effect;
In a solvent, formula 7 compound is obtained by reacting formula 8 compound with bromo acetylenic acid ester to step f. under cuprous, oxammonium hydrochloride and amine catalysis;
Step g. in a solvent, formula 8 compound sloughs protecting group Me under fluorine reagent effect
3si-obtains formula 9 compound;
In a solvent, formula 9 compound is obtained by reacting formula 1 compound with 1,2-sym-dibromoethane to step h. under cuprous, palladium reagent and amine catalysis.
2. method according to claim 1, wherein
R is methyl, ethyl, n-propyl or sec.-propyl.
3. method according to claim 1 and 2, wherein,
In step a, described palladium reagent is tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride; Described cuproine is cuprous chloride, cuprous bromide or cuprous iodide; Described solvent is methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, dipropyl amine, dibutylamine, Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine or Diisopropylamine; Temperature of reaction is room temperature;
In stepb, described solvent is methyl alcohol, ethanol or Virahol; Temperature of reaction is that room temperature arrives backflow;
In step c, described oxygenant is PCC, PDC or chromium trioxide pyridine; Described solvent is methylene dichloride or chloroform; Temperature of reaction is that room temperature arrives backflow;
In steps d, described solvent is methylene dichloride or chloroform; Temperature of reaction be-78 DEG C to room temperature;
In step e, described solvent is tetrahydrofuran (THF) or ether, and described alkali is n-Butyl Lithium, tert-butyl lithium, phenyl lithium or lithium diisopropylamine; Temperature of reaction be-78 DEG C to room temperature;
In step f, described amine is methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, dipropyl amine, dibutylamine, Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine or Diisopropylamine; Described cuproine is cuprous chloride, cuprous bromide or cuprous iodide; Described solvent is methyl alcohol or ethanol; Temperature of reaction is that room temperature arrives backflow;
In step g, described fluorine reagent is hydrogen fluoride, Potassium monofluoride or tetrabutyl ammonium fluoride; Described solvent is tetrahydrofuran (THF) or ether; Temperature of reaction is room temperature;
In step h, described amine is methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, dipropyl amine, dibutylamine, Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine or Diisopropylamine; Described cuproine is cuprous chloride, cuprous bromide or cuprous iodide; Described palladium reagent is tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride; Temperature of reaction is that room temperature arrives backflow.
4. method according to claim 1 and 2, wherein,
In step a, described palladium reagent is bi triphenyl phosphorus palladium chloride, and described cuproine is cuprous iodide; Described solvent is diethylamine; Temperature of reaction is room temperature;
In stepb, described solvent is methyl alcohol; Temperature of reaction is room temperature;
In step c, described oxygenant is PCC or PDC; Described solvent is methylene dichloride; Temperature of reaction is room temperature;
In steps d, described solvent is methylene dichloride; Temperature of reaction is room temperature;
In step e, described solvent is tetrahydrofuran (THF); Alkali is n-Butyl Lithium; Temperature of reaction be-78 DEG C to room temperature;
In step f, described amine is ethamine; Described cuproine is cuprous chloride; Described solvent is methyl alcohol; Temperature of reaction is room temperature;
In step g, described fluorine reagent is tetrabutyl ammonium fluoride; Described solvent is tetrahydrofuran (THF); Temperature of reaction is room temperature;
In step h, described amine is triethylamine; Described cuproine is cuprous iodide; Described palladium reagent is tetrakis triphenylphosphine palladium; Temperature of reaction is room temperature.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410235574.7A CN105218369B (en) | 2014-05-29 | 2014-05-29 | The new synthetic method of a kind of bromo unsaturated fatty acid ester |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410235574.7A CN105218369B (en) | 2014-05-29 | 2014-05-29 | The new synthetic method of a kind of bromo unsaturated fatty acid ester |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105218369A true CN105218369A (en) | 2016-01-06 |
CN105218369B CN105218369B (en) | 2018-04-17 |
Family
ID=54987714
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410235574.7A Expired - Fee Related CN105218369B (en) | 2014-05-29 | 2014-05-29 | The new synthetic method of a kind of bromo unsaturated fatty acid ester |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105218369B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107033178A (en) * | 2017-04-01 | 2017-08-11 | 三峡大学 | A kind of trimethyl silicon substrate yne compounds and its synthetic method |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101230126A (en) * | 2007-12-29 | 2008-07-30 | 中国科学院长春应用化学研究所 | Soluble conjugated polymer using 9,10-diaryl anthracene as repeating units and preparation method thereof |
CN101654431A (en) * | 2008-08-22 | 2010-02-24 | 上海药明康德新药开发有限公司 | Method for synthesizing pyridine propiolic acid ester |
CN101798297A (en) * | 2009-02-11 | 2010-08-11 | 中国科学院上海药物研究所 | Chemical synthesis method of laetispicine |
WO2014040476A1 (en) * | 2012-09-17 | 2014-03-20 | 中国科学院上海药物研究所 | Process for synthesising brominated eneyne compound e, e-22-bromo-9,11,19-triyne-17,21-diene docosanoic acid ester |
CN103664605A (en) * | 2012-09-17 | 2014-03-26 | 中国科学院上海药物研究所 | Preparation method of brominated eneyne compound E-18-bromo-5,7,15-trialkynyl-17-ene stearate |
-
2014
- 2014-05-29 CN CN201410235574.7A patent/CN105218369B/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101230126A (en) * | 2007-12-29 | 2008-07-30 | 中国科学院长春应用化学研究所 | Soluble conjugated polymer using 9,10-diaryl anthracene as repeating units and preparation method thereof |
CN101654431A (en) * | 2008-08-22 | 2010-02-24 | 上海药明康德新药开发有限公司 | Method for synthesizing pyridine propiolic acid ester |
CN101798297A (en) * | 2009-02-11 | 2010-08-11 | 中国科学院上海药物研究所 | Chemical synthesis method of laetispicine |
WO2014040476A1 (en) * | 2012-09-17 | 2014-03-20 | 中国科学院上海药物研究所 | Process for synthesising brominated eneyne compound e, e-22-bromo-9,11,19-triyne-17,21-diene docosanoic acid ester |
CN103664605A (en) * | 2012-09-17 | 2014-03-26 | 中国科学院上海药物研究所 | Preparation method of brominated eneyne compound E-18-bromo-5,7,15-trialkynyl-17-ene stearate |
Non-Patent Citations (2)
Title |
---|
HISASHI YAMAMOTO 等: "Stereo- and regioselective organic transformations based on main group organometallic reagentsapplication to the stereocontrolled Claisen rearrangements", 《PURE & APPL. CHEM》 * |
徐叔军: "5(Z),14(Z)-二十碳二烯-1-醇的合成研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107033178A (en) * | 2017-04-01 | 2017-08-11 | 三峡大学 | A kind of trimethyl silicon substrate yne compounds and its synthetic method |
Also Published As
Publication number | Publication date |
---|---|
CN105218369B (en) | 2018-04-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6980648B2 (en) | Production of 3-hydroxy-3,6-dimethylhexahydrobenzofuran-2-one and its derivatives | |
Miyamoto et al. | Selective Reduction of Carboxylic Acids to Aldehydes by a Ruthenium-catalyzed Reaction with 1, 2-Bis (dimethylsilyl) benzene | |
CN107417505A (en) | α halo tetramethyl-ring hexanones and its with(2,3,4,4 tetramethyl-ring amyl groups)The preparation method of methyl carboxylic acids ester | |
CN105218369A (en) | The new synthetic method of one class bromo unsaturated fatty acid ester | |
JP5680009B2 (en) | Process for producing (E3) -3-alkenyl acetate using 5-acetoxy- (E3) -3-pentenyl-methoxymethyl ether | |
CN104592017B (en) | The method for preparing 2- isopropylidene -5- methyl -4- hexenyl butyrate | |
CN109956850B (en) | Process for producing 3, 7-dimethyl-7-octenyl alcohol and 3, 7-dimethyl-7-octenyl carboxylate compound | |
Yamada et al. | Fluorine–copper exchange reaction of α, β, γ, γ, γ-pentafluorocrotonates with organocuprates: Generation and cross-coupling reactions of β-metallated α, γ, γ, γ-tetrafluorocrotonates | |
CN103664604B (en) | Bromo-9,11,19-tri-alkynes-17, the 21-diene behenic acid Lipase absobed methods of bromination yne compounds E, E-22- | |
CN104974017A (en) | Preparation method of (1R,2S)-2-(3,4-difluorophenyl) rolicyprine.D-mandelate | |
CN105198692A (en) | Method for asymmetrically catalyzing and synthesizing (S)-curcumene | |
JP7254665B2 (en) | Method for producing 4-pentene-2-ynal | |
CN103664605B (en) | The preparation method of bromo-5,7, the 15-tri-alkynes-17-alkene stearic acid esters of bromination yne compounds E-18- | |
Prokhorevich et al. | The synthesis of the insect pheromone (2S, 3R, 7R)-3, 7-dimethyltridec-2-yl acetate from racemic 3, 4-dimethyl-γ-butyrolactone by diastereoselective chiral resolution | |
JP6424153B2 (en) | Process for producing 2-isopropenyl-5-methyl-4-hexen-1-yl 3-methyl-2-butenoate | |
EP3789376B1 (en) | Dialkoxyalkadienyne compound and a process for preparing the same and a process for preparing a dienynal compound | |
CN109699646B (en) | Preparation method of rice stem borer pheromone component | |
CN108164403A (en) | 7- methyl -3- methylene -7- octenals acetal compound and the method with its production aldehydes and ester type compound | |
JP2007291044A (en) | Method for producing fluorine-containing alcohol derivative | |
CN105420285A (en) | Method for producing (z)-2-benzoyloxy-12-heptadecene and (2s,12z)-2- hydroxy-12-heptadecene and method for producing (2s,12z)-2-acetoxy-12- heptadecene | |
FR2565968A1 (en) | PROCESS FOR OBTAINING INTERMEDIATES FROM THE PREPARATION OF PYRETHROIDS | |
JP3878701B2 (en) | Process for producing 4-hydroxy-1-alkynes | |
JP2022151723A (en) | Method of producing 11-halo-1,1-dialkoxy-7-undecene compound, and 11,11-dialkoxy-4-undecenyltriarylphosphonium=halide compound, trienal comound, and dienal compound from the same | |
JP2007238528A (en) | Method of manufacturing fluorine-containing allyl alcohol | |
JP2554265B2 (en) | New alcohol and its manufacturing method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180417 Termination date: 20210529 |