CN105218369B - The new synthetic method of a kind of bromo unsaturated fatty acid ester - Google Patents
The new synthetic method of a kind of bromo unsaturated fatty acid ester Download PDFInfo
- Publication number
- CN105218369B CN105218369B CN201410235574.7A CN201410235574A CN105218369B CN 105218369 B CN105218369 B CN 105218369B CN 201410235574 A CN201410235574 A CN 201410235574A CN 105218369 B CN105218369 B CN 105218369B
- Authority
- CN
- China
- Prior art keywords
- solvent
- compound
- formula
- room temperature
- amine
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to pharmaceutical synthesis field.In particular it 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.In particular it relates to the long-chain bromination eneyne with hypolipidemic activity
The new preparation process of compound.
Background technology
1.2 hundred million people are there are about in world wide at present and suffer from obesity, in addition there are 2.1 hundred million people overweight.With China's economic level
Rapid lifting, the life style of people also changes therewith.Increasingly common unhealthy diet and physical activity level it is universal
Decline so that incidence that China's rural and urban population is overweight is rising rapidly, and obesity illness rate is also in rising trend in recent years.According to tune
Consult reference materials display, and rate that China resident is overweight is 17.6%, obesity rates 5.6%, sum of the two 23.2%.Fat and its induction
Disease serious threat and affect human life's safety and quality of life, therefore prevent, control and treatment obesity carved not
Rong Huan.
Living marine resources in utilization China, therefrom find the marine natural with bioactivity and prospect in medicine
During product, isolated a kind of long-chain bromination from marine organisms sponge Xestospongia Tsstudinaria
Eneyne unsaturated fatty acids compound：Bromo- 9,11,19- tri- alkynes -17,21- diene methyl behenate of E, E-22-, its structure
Formula is as follows：
Researches show that this compound has notable pancreatic lipase inhibitory activity (referring to Application No. 201110180360.0
Chinese patent application), and the similar long-chain bromination eneyne unsaturated fatty acids compound of other structures is also likely to have
Similar activity.But such compound content in natural products is rare, and biological source is difficult, constrains it and further opens
Hair, and such compound is prepared come the effective way of source problem by synthetic method.It is new therefore, it is necessary to develop a kind of route
It is clever, new preparation method simply, efficiently prepares this kind of compound easily to operate.
The content of the invention
It is an object of the invention to provide the preparation method of the long-chain bromination unrighted acid with 1 structure of formula：
Wherein, n1And n2It is each independently 1,2,3,4 or 5；R is C1-C5 alkyl；
Preferably, R is methyl, ethyl, n-propyl or isopropyl.
The method is carried out by following reaction process：
A. in a solvent, 2 compound of formula is reacted under palladium reagent, cuproine, the catalysis of amine reagent with trimethylsilyl acetylene,
3 compound of production；
B. in a solvent, 3 compound of formula obtains 4 chemical combination of formula under p-methyl benzenesulfonic acid or para-methylbenzenepyridinsulfonate sulfonate effect
Thing；
C. in a solvent, oxidized dose of oxidation of 4 compound of formula obtains 5 compound of formula；
D. in a solvent, 5 compound of formula reacts to obtain 6 compound of formula with triphenyl phosphorus and carbon tetrabromide；
E. in a solvent, 6 compound of formula obtains 7 compound of formula under alkali effect；
F. in a solvent, 7 compound of formula reacts to obtain formula 8 under cuprous, hydroxylamine hydrochloride and amine catalysis with bromo acetylenic acid ester
Compound；
G. in a solvent, 8 compound of formula sloughs protection group Me under fluorine reagent effect3Si- obtains 9 compound of formula；
H. in a solvent, 9 compound of formula reacts to obtain formula 1 under cuprous, palladium reagent and amine catalysis with 1,2- dibromoethylenes
Compound.
Wherein, the synthesis reference literature J.Chin.Chem.Soc. of 2 compound of formula, (Taipei), 1999,46,87-90.
A. the synthesis of 3 ene-alkyne compound of formula：
In a solvent, 2 compound of formula is reacted under palladium reagent, cuproine, the catalysis of amine reagent with trimethylsilyl acetylene
To 3 compound of formula, the palladium reagent is tetrakis triphenylphosphine palladium or double (triphenylphosphine) palladium chlorides；The cuproine is chlorine
Change cuprous, cuprous bromide or cuprous iodide；The solvent for methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, di-n-propylamine,
Dibutyl amine, trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine or diisopropylamine；Reaction temperature is room temperature.
B. the synthesis of 4 ene-alkyne alcoholic compound of formula：
In a solvent, 3 compound of formula obtains 4 compound of formula under p-methyl benzenesulfonic acid or para-methylbenzenepyridinsulfonate sulfonate effect,
The solvent is methanol, ethanol or isopropanol；Reaction temperature is room temperature to reflux.
C. the synthesis of 5 ene-alkyne aldehyde compound of formula：
In a solvent, oxidized dose of oxidation of 4 compound of formula obtains 5 compound of formula, and the oxidant is PCC
(Pyridinium chlorochromate, pyridine chlorochromate drone salt), PDC (Pyridinium dichromate, dichromic acid pyrrole
Pyridine salt) or chromium trioxide pyridine；The solvent is dichloromethane or chloroform；Reaction temperature is room temperature to reflux.
D. the synthesis of 6 dibromoethylene compound of formula：
In a solvent, 5 compound of formula reacts to obtain 6 compound of formula with triphenyl phosphorus and carbon tetrabromide, and the solvent is two
Chloromethanes or chloroform；Reaction temperature is -78 DEG C to room temperature.
E. the synthesis of 7 acetylene compound of formula：
In a solvent, formula 6 obtains 7 compound of formula under alkali effect, and the solvent is tetrahydrofuran or ether；The alkali is
N-BuLi, tert-butyl lithium, phenyl lithium or lithium diisopropylamine；Reaction temperature is -78 DEG C to room temperature.
F. the synthesis of 8 trimethyl silicane ene-alkyne ester compound of formula：
In a solvent, 7 compound of formula reacts to obtain 8 chemical combination of formula under the catalysis of amine, hydroxylamine hydrochloride and amine with bromo acetylenic acid ester
Thing, the amine are methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, di-n-propylamine, dibutyl amine, trimethylamine, triethylamine, 3 third
Amine, tri-n-butylamine or diisopropylamine；The cuproine is stannous chloride, cuprous bromide or cuprous iodide；The solvent is methanol
Or ethanol；Reaction temperature is room temperature to reflux.
G. the synthesis of 9 ene-alkyne ester compound of formula：
In a solvent, 8 compound of formula obtains 9 compound of formula under fluorine reagent effect, and the fluorine reagent is hydrogen fluoride, fluorination
Potassium or tetrabutyl ammonium fluoride；The solvent is tetrahydrofuran or ether；Reaction temperature is room temperature.
H. the synthesis of 1 compound of formula：
9 compound of formula reacts to obtain 1 compound of formula under the effect of palladium reagent, cuproine and amine with dibromoethylene, described
Amine is methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, di-n-propylamine, dibutyl amine, trimethylamine, triethylamine, tripropyl amine (TPA), three fourths
Amine or diisopropylamine；The cuproine is stannous chloride, cuprous bromide or cuprous iodide；The palladium reagent is four (triphenyls
Phosphine) palladium or double (triphenylphosphine) palladium chlorides；Reaction temperature is room temperature to reflux.
Preferably, the reagent of each step reaction and condition are：
In step a, the palladium reagent is bi triphenyl phosphorus palladium chloride, and the cuproine is cuprous iodide；It is described
Solvent is diethylamine；Reaction temperature is room temperature；
In stepb, the solvent is methanol；Reaction temperature is room temperature；
In step c, the oxidant is PCC or PDC；The solvent is dichloromethane；Reaction temperature is room temperature；
In step d, the solvent is dichloromethane；Reaction temperature is room temperature；
In step e, the solvent is tetrahydrofuran；Alkali is n-BuLi；Reaction temperature is -78 DEG C to room temperature；
In step f, the amine is ethamine；The cuproine is stannous chloride；The solvent is methanol；Reaction temperature
For room temperature；
In step g, the fluorine reagent is tetrabutyl ammonium fluoride；The solvent is tetrahydrofuran；Reaction temperature is room temperature；
In step h, the amine is triethylamine；The cuproine is cuprous iodide；The palladium reagent is four (triphenyls
Phosphine) palladium；Reaction temperature is room temperature.
Embodiment
Embodiment 1：(E) synthesis of -1- trimethyl silicanes -9- (2- tetrahydro-pyran oxies)-nonyl- 3- alkene -1- alkynes
In the reaction bulb of nitrogen protection, 10 grams of (E) -1- iodo- 7- (2- tetrahydro-pyran oxies) -1- heptene are dissolved in 10 millis
Diethylamine is risen, adds 428 milligrams of bi triphenyl phosphorus palladium chlorides, 1.5 grams of cuprous iodides and 3 grams of trimethylsilyl acetylenes, room temperature are stirred
Mix 5 it is small when after plus water, extracted by ether, magnesium sulfate drying, filtering and concentrating, through 6.25 grams of column chromatography give light yellow oil, yield
70%.1H NMR(400MHz,CDCl3):δ 0.17 (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)；13C NMR(125MHz,CDCl3):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-MS m/z:294.2[M]+.
Embodiment 2：(E) synthesis of -9- trimethyl silicanes -6- alkene -8- alkynes -1 nonyl alcohol
5 grams of (E) -1- trimethyl silicanes -9- (2- tetrahydro-pyran oxies)-nonyl- 3- alkene -1- alkynes is dissolved in 150 ml methanols, adds
Enter 3.9 grams of p-methyl benzenesulfonic acid, be stirred at room temperature 2 it is small when, decompression boils off solvent, adds water, extracted by ether, magnesium sulfate drying, and filtering is dense
Contracting, through 3.13 grams of column chromatography give light yellow oil, yield 87%.1H NMR(400MHz,CDCl3):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)；13C NMR(125MHz,CDCl3):0.46,
24.77,27.94,29.07,32.08,32.57,62.41,92.22,103.62,109.34,145.53；ESI-MS m/z:
210.1[M]+.
Embodiment 3：(E) synthesis of -9- trimethyl silicanes -6- alkene -8- alkynes aldehyde C-9s
30 milliliters of dichloromethane are added in the reaction bulb of drying nitrogen protection, 3.1 grams of oxalyl chlorides, cool to -78 DEG C, add
Enter to be dissolved in 2.4 grams of dimethyl sulfoxides of 3 milliliters of dichloromethane, stirred 10 minutes after adding, addition is dissolved in 6 milliliters of dichloromethane
2.6 grams of (E) -9- trimethyl silicane -6- alkene -8- alkynes -1 nonyl alcohols, continue stirring 10 minutes, add 10 milliliters of triethylamines, rise to room
Temperature, adds water, separates dichloromethane layer, washing, magnesium sulfate drying, filtering and concentrating, through 2.2 grams of column chromatography give light yellow oil,
Yield 82%.1H NMR(400MHz,CDCl3):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)；13C NMR(125MHz,CDCl3):0.48,21.00,27.61,32.30,
43.20,92.50,103.40,109.79,144.75,201.92；ESI-MS m/z:208.1[M]+.
Embodiment 5：(E) synthesis of the bromo- decyl- 1- alkynes -3,9- diene of -1- trimethyl silicanes -10,10- two
Sequentially add 2.5 grams of (E) -9- trimethyl silicane -6- alkene -8- alkynes aldehyde C-9s in reaction bulb, 4.5 grams of carbon tetrabromides, 7.6
Gram triphenyl phosphorus and 20 milliliters of dichloromethane, be stirred at room temperature 2 it is small when, add water, separate dichloromethane layer, magnesium sulfate drying, filtering
Concentration, 3.7 grams of colourless liquid, yield 83% are obtained through column chromatography.1H NMR(400MHz,CDCl3):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)；13C NMR(125MHz,CDCl3):0.01,27.18,27.92,32.74,88.90,92.87,
103,94,110.08,138.41,145.51；ESI-MS m/z:362.0[M]+.
Embodiment 6：(E) synthesis of -1- trimethyl silicanes-decyl- 3- alkene -1,9- diines
3.7 grams of bis- bromo- decyl- 1- alkynes -3 of (E) -1- trimethyl silicanes -10,10- are added in the reaction bulb of drying nitrogen protection,
9- diene, is dissolved in 100 milliliters of anhydrous tetrahydro furans, cools to -78 DEG C, be slowly added to the n-BuLi of 14 milliliters of 1M, add
When stirring 2 is small after complete, add water, extracted by ether, organic phase is dried with magnesium sulfate, filtering and concentrating, and colourless liquid 1.8 is obtained through column chromatography
Gram, yield 85%.
1H NMR(400MHz,CDCl3):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)；13C NMR(125MHz,CDCl3):
0.02,18.21,27.60,27.72,32.49,68.43,84.22,92.79,103,98,110.02,145.57；ESI-MS m/
z:204.1[M]+.
Embodiment 7：(E) synthesis of the sour methyl esters of three alkynes of -20- trimethyl silicanes -17- alkene -9,11,19- 20
65 milligrams of hydroxylamine hydrochlorides are dissolved in 20 milliliters of ethamine, add 90 milligrams of stannous chlorides, and addition is dissolved in 20 milliliters
2.9 grams of (E) -1- trimethyl silicanes-decyl- 3- alkene -1,9- diines of methanol, the bromo- 9- alkynes methyl caprates of 3.7 grams of 10-, are stirred at room temperature 12
Hour, add water, extracted by ether, has basic unit's saturated common salt water washing, magnesium sulfate drying, filtering and concentrating, obtains colourless through column chromatography
1.4 grams of grease, yield 52%.1H NMR(300MHz,CDCl3):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)；13C NMR(125MHz,CDCl3):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-MS m/z:384.0[M]+.
Embodiment 8：The synthesis of the sour methyl esters of three alkynes of E-17- alkene -9,11,19- 20
The sour methyl esters of 1.4 grams of three alkynes of E-20- trimethyl silicane -17- alkene -9,11,19- 20 is dissolved in 35 milliliters of tetrahydrofurans
In, add 1.4 grams of tetrabutyl ammonium fluorides, be stirred at room temperature 2 it is small when, add water, extracted by ether, magnesium sulfate drying, filtering and concentrating is remaining
Thing obtains 1.1 grams of colourless liquid, yield 96% through column chromatography.1H NMR(300MHz,CDCl3):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)；13C NMR(125MHz,CDCl3):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-MS m/z:313[M+1]+.
Embodiment 9：The synthesis of bromo- 9,11,19- tri- alkynes -17,21- diene methyl behenates of (17E, 21E) -22-
1 gram of E-17- alkene -9,11, the sour methyl esters of tri- alkynes of 19- 20,40 milliliter of three second are added in the reaction bulb of nitrogen protection
Amine, sequentially adds 1 gram of 1,2- dibromoethylene, 0.2 gram of four (triphenyl phosphorus) palladium, 0.2 gram of cuprous iodide, it is small to be stirred at room temperature 16
When, filtering, filtrate concentrates, and residue obtains 0.76 gram of colourless liquid, yield through column chromatography：58%
1H NMR(300MHz,CDCl3):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)；13C NMR(125MHz,CDCl3):
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-MS m/z:165,337,415,417[M-1]+。
Claims (3)
- A kind of 1. method for preparing the long-chain bromination unrighted acid with 1 structure of formula：Wherein, n1For 4, n2For 6；R is methyl；The method is carried out by following reaction process：Step a. in a solvent, under palladium reagent, cuproine, the catalysis of amine reagent with trimethylsilyl acetylene react by 2 compound of formula, 3 compound of production；In a solvent, 3 compound of formula obtains 4 chemical combination of formula to step b. under p-methyl benzenesulfonic acid or para-methylbenzenepyridinsulfonate sulfonate effect Thing；In a solvent, the oxidized dose of oxidation of 4 compound of formula obtains 5 compound of formula to step c., wherein, the oxidant is sub- for diformazan The combination of sulfone and oxalyl chloride, reaction temperature are -78 DEG C；Step d. in a solvent, with triphenyl phosphorus and carbon tetrabromide react to obtain 6 compound of formula by 5 compound of formula；In a solvent, 6 compound of formula obtains 7 compound of formula to step e. under alkali effect；Step f. in a solvent, under cuprous, hydroxylamine hydrochloride and amine catalysis with bromo acetylenic acid ester react to obtain formula 8 by 7 compound of formula Compound；In a solvent, 8 compound of formula sloughs protection group Me to step g. under fluorine reagent effect3Si- obtains 9 compound of formula；Step h. in a solvent, react to obtain formula 1 with 1,2- dibromoethylenes under cuprous, palladium reagent and amine catalysis by 9 compound of formula Compound.
- 2. according to the method described in claim 1, wherein,In step a, the palladium reagent is tetrakis triphenylphosphine palladium or double (triphenylphosphine) palladium chlorides；The cuproine is Stannous chloride, cuprous bromide or cuprous iodide；The solvent is methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, dipropyl Amine, dibutyl amine, trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine or diisopropylamine；Reaction temperature is room temperature；In stepb, the solvent is methanol, ethanol or isopropanol；Reaction temperature is room temperature to reflux；In step d, the solvent is dichloromethane or chloroform；Reaction temperature is -78 DEG C to room temperature；In step e, the solvent is tetrahydrofuran or ether, and the alkali is that n-BuLi, tert-butyl lithium, phenyl lithium or two are different Propylcarbamic lithium；Reaction temperature is -78 DEG C to room temperature；In step f, the amine for methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, di-n-propylamine, dibutyl amine, trimethylamine, Triethylamine, tripropyl amine (TPA), tri-n-butylamine or diisopropylamine；The cuproine is stannous chloride, cuprous bromide or cuprous iodide；It is described Solvent is methanol or ethanol；Reaction temperature is room temperature to reflux；In step g, the fluorine reagent is hydrogen fluoride, potassium fluoride or tetrabutyl ammonium fluoride；The solvent is tetrahydrofuran or second Ether；Reaction temperature is room temperature；In step h, the amine for methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, di-n-propylamine, dibutyl amine, trimethylamine, Triethylamine, tripropyl amine (TPA), tri-n-butylamine or diisopropylamine；The cuproine is stannous chloride, cuprous bromide or cuprous iodide；It is described Palladium reagent is tetrakis triphenylphosphine palladium or double (triphenylphosphine) palladium chlorides；Reaction temperature is room temperature to reflux.
- 3. according to the method described in claim 1, wherein,In step a, the palladium reagent is bi triphenyl phosphorus palladium chloride, and the cuproine is cuprous iodide；The solvent For diethylamine；Reaction temperature is room temperature；In stepb, the solvent is methanol；Reaction temperature is room temperature；In step d, the solvent is dichloromethane；Reaction temperature is room temperature；In step e, the solvent is tetrahydrofuran；Alkali is n-BuLi；Reaction temperature is -78 DEG C to room temperature；In step f, the amine is ethamine；The cuproine is stannous chloride；The solvent is methanol；Reaction temperature is room Temperature；In step g, the fluorine reagent is tetrabutyl ammonium fluoride；The solvent is tetrahydrofuran；Reaction temperature is room temperature；In step h, the amine is triethylamine；The cuproine is cuprous iodide；The palladium reagent is four (triphenylphosphines) Palladium；Reaction temperature 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 CN105218369A (en) | 2016-01-06 |
| CN105218369B true 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) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107033178B (en) * | 2017-04-01 | 2019-10-08 | 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 |
|---|
| 5（Z），14（Z）-二十碳二烯-1-醇的合成研究;徐叔军;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20070615;第12-34页 * |
| Stereo- and regioselective organic transformations based on main group organometallic reagentsapplication to the stereocontrolled Claisen rearrangements;Hisashi Yamamoto 等;《Pure & Appl. Chem》;19901231;第62卷(第10期);2063-2068 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105218369A (en) | 2016-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6980648B2 (en) | Production of 3-hydroxy-3,6-dimethylhexahydrobenzofuran-2-one and its derivatives | |
| 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 | |
| Yoshino et al. | Fluorination with ionic liquid EMIMF (HF) 2.3 as mild HF source | |
| CN105218369B (en) | The new synthetic method of a kind of bromo unsaturated fatty acid ester | |
| Honda et al. | Reaction of acylsilanes with α-sulfinyl carbanions: Regioselective synthesis of silyl enol ethers | |
| CASON et al. | The Preparation of Cyclobutanecarboxylic Acid | |
| Inoue et al. | Synthesis of ethyl 3, 3, 3-trifluoropropionate from 2-bromo-3, 3, 3-trifluoropropene | |
| CN109796332A (en) | A kind of 2- bis-fluoro ethyls -1- indenone derivative and preparation method | |
| Yajima et al. | Substitution of both chloro and sulfinyl groups of aryl 1-chlorocyclopropyl sulfoxides in one-pot via cyclopropylmagnesium carbenoids: a synthesis of multi-substituted cyclopropanes | |
| Patrick et al. | Heck reaction with 3-fluoro-3-buten-2-one | |
| CN105085190B (en) | Preparing method of 2,6-difluoro-4-bromophenol | |
| Singh et al. | Synthesis and characterization of novel trifluoromethyl-containing alcohols with Ruppert's reagent | |
| Yoshida et al. | Stereoselective synthesis of (Z)-β-fluoro-α, β-unsaturated esters from (Z)-2-fluoro-1-alkenyliodonium salts | |
| Fordred et al. | Tandem hydroboration/reduction of trisubstituted β, γ-unsaturated esters for the asymmetric synthesis of chiral 1, 3-diols | |
| Pajkert et al. | TiCl4 and Grignard reagent-promoted ring-opening reactions of various epoxides: synthesis of γ-hydroxy-α, α-difluoromethylenephosphonates | |
| Araki et al. | Allylgallation of cyclopropenes. Crystal structure of a novel cyclopropylgallium compound prepared by allylgallation of hydroxy-bearing cyclopropene | |
| Umezu et al. | α-Substituent effect on olefination of ester carbonyl groups with ynolates | |
| Li et al. | A new approach to the synthesis of α-chlorocycloalkanones | |
| CN107445880B (en) | A kind of trifluoromethyl modification AβThe synthetic method of -42 inhibitor structure analogs | |
| Sakai et al. | Stereoselective synthesis of 4-fluoro-1, 3-alkadienylboronates and their application in the stereoselective synthesis of fluoropolyenes | |
| Yamada et al. | Easy access to CF 2-containing molecules based on the reaction of 2, 2, 3, 3-tetrafluorooxetane with various nucleophiles | |
| CN103664604B (en) | Bromo-9,11,19-tri-alkynes-17, the 21-diene behenic acid Lipase absobed methods of bromination yne compounds E, E-22- | |
| Ishino et al. | Metal zinc-promoted gem-bisallylation of acid chlorides with allyl chlorides in the presence of chlorotrimethylsilane | |
| Karama et al. | A facile one-pot synthesis of (Z)-α-chloro-α, β-unsaturated esters from alcohols | |
| Lee et al. | Synthesis of (15S, 16S, 21R)-4-deoxyrollicosin analog |
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 |
Granted publication date: 20180417 Termination date: 20210529 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |