CN106496087B - A kind of method by the decarboxylation coupling reaction one pot process compound of class containing selenium - Google Patents
A kind of method by the decarboxylation coupling reaction one pot process compound of class containing selenium Download PDFInfo
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- C07C391/00—Compounds containing selenium
- C07C391/02—Compounds containing selenium having selenium atoms bound to carbon atoms of six-membered aromatic rings
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Abstract
The invention discloses a kind of method by decarboxylation coupling reaction one pot process selenium class compound, synthesis universal method comprises the following steps：0.5mmol carboxylic acid, the selenide of 1.5 equivalents, 5% Cu catalyst, the alkali and 10mL N methyl pyrrolidone solvents of 1.2 equivalents, 90 are added in 25mL round-bottomed flasko6h, TLC tracking reactions are reacted under C；After question response is complete, room temperature is cooled to, reactant is poured into 15mL water, and is extracted 3 times with 20 30mL ethyl acetate, then with saturated common salt water washing 1 time, finally uses anhydrous Na2SO4Dry, filtering, removal of solvent under reduced pressure, purified through Flash silica column chromatography, make eluant, eluent with petroleum ether, eluent solvent evaporated, produce product.It is simple to operate particular by organic selenium compounds of the decarboxylation coupling reaction one pot process with two or three carbon selenium keys, the preparation method the invention provides a kind of new method for synthesizing organic selenium compounds, raw material is easy to get, reactions steps are few, and yield is high, and application prospect is extensive.
Description
Technical field
The present invention relates to organic synthesis field, is specifically that one kind passes through decarboxylation coupling reaction one pot process selenium class compound
Method.
Background technology
In document report, Guo Li etc., which reports phenyl aminoethyl selenium (PAESe), has antihypertensive effect（《It is Chinese new
Medicine magazine》, 2000,9,155-158）.Song Xiaoyu etc. reports selenium compound and vincristine（VCR）Drug combination can strengthen
Antitumous effect, and selenium compound can also reduce VCR cytotoxicity（《China Agricultural University's journal》, 2007,12,14-
18）.Teacher the research such as enters and finds new selenium-containing compound BBSKE (1,2- [two ((the 2H)-ketone of 1,2- benzisoxa selenazoles -3)]
Ethane) in-vitro multiplication of PC-3 prostate gland cancer cells can be suppressed and induce its apoptosis, it is anti-in vivo that zoopery also demonstrates it
Tumor promotion（《Chinese Medical Journal》, 2003,83,1984-1988）.The seleno morpholine of the Feng Juhong synthesis of Central China Normal University
Derivative has preferably antibacterial to gibberella saubinetii, beet Cercospora bacterium, cotton wilt fusarium, Rhizoctonia solani and apple wheel line bacterium
Effect.（《World pesticide》, 2013,35,15-19）.Zhao Wei light of Elements and Organic Chemistry Inst., Nankai Univ. etc. is by selenium atom
1,2,3- Thiadiazoles are introduced, design has synthesized the l for having good inhibitory activity to the rice blast, -5- formamides of 2,3- selenium two
Class compound（《Organic chemistry》, 23 (supplementary issues)；173）.
Increasing evidence shows that malignant tumour (such as liver cancer, stomach cancer, lung cancer, prostate can be reduced by increasing selenium intake
Cancer etc.) and disease of cardiovascular system (such as coronary heart disease, atherosclerosis) incidence；Improving immunocompetence；It can hinder
Only viral (such as HBV, HIV) infection；And HIV can be delayed to develop into AIDS process.But even to this day, general selenium-supply
Method is still that oral formulations are made with inorganic selenium, and studies have shown that organic selenium compounds toxicity is low and immune anti-exciting
Should on it is more notable than inorganic selenium.In addition, organic selenium compounds also play an important roll in the exploitation and development of agricultural chemicals.But Organic Selenium
Limited source, therefore it is an important research topic to develop more new methods synthesis organic selenium compounds.
The content of the invention
It is an object of the invention to provide a kind of new method for synthesizing organic selenium compounds, is specifically that one kind is coupled by decarboxylation
React the method for one pot process selenium class compound.
A kind of method by decarboxylation coupling reaction one pot process selenium class compound, synthesis universal method include following step
Suddenly：
（1）0.5 mmol carboxylic acid, the selenide of 1.5 equivalents are added in 25 mL round-bottomed flask, 5% Cu is urged
Agent, the alkali of 1.2 equivalents and 10 mL 1-METHYLPYRROLIDONE solvents, 90o6 h, TLC tracking reactions are reacted under C；
（2）After question response is complete, room temperature is cooled to, reactant is poured into 15 mL water, and with 20-30 mL ethyl acetate
Extraction 3 times, then with saturated common salt water washing 1 time, finally use anhydrous Na2SO4Dry, filtering, removal of solvent under reduced pressure, through quick
Silica gel column chromatography purifies, and makees eluant, eluent with petroleum ether, eluent solvent evaporated, produces product；
Synthetic method formula is as follows：
Wherein, Cu catalyst：Copper acetate, copper chloride, stannous chloride or cuprous iodide；
Alkali：Sodium carbonate, sodium acid carbonate, potassium phosphate, potassium carbonate or cesium carbonate.
Step（1）Carboxylic acid be phenylpropiolic acid, to methyl phenylpropiolic acid, a methyl phenylpropiolic acid, o-methyl-benzene propiolic acid,
To fluorobenzene propiolic acid or phenylacetic acid.
Step（1）Selenide be diphenyl disenenide ether or 1,2- double（4- bromophenyls）Diselenide.
The invention provides a kind of new method for synthesizing organic selenium compounds is provided, particular by decarboxylation coupling reaction one
Organic selenium compounds of the pot method synthesis with two or three carbon selenium keys, the preparation method is simple to operate, and raw material is easy to get, reaction step
Rapid few, yield is high, and application prospect is extensive.
Embodiment
Present invention is further described with reference to embodiment, but is not limitation of the invention.
Embodiment 1
Synthesis（The bases of 2- phenylethylenes -1,1,2- three）Three（Phenyl selenide）, its chemical equation is：
Synthetic method is：Add 0.5 mmol phenylpropiolic acid in 25 mL round-bottomed flask, the two of 1.5 equivalents
Phenyl diselenide, 5% copper acetate, the sodium carbonate of 1.2 equivalents and 10 mL 1-METHYLPYRROLIDONEs, 90o6 are reacted under C
H, TLC tracking reaction；
After question response is complete, room temperature is cooled to, reactant is poured into 15 mL water, and is extracted with 20-30 mL ethyl acetate
Take 3 times, then with saturated common salt water washing 1 time, finally use anhydrous Na2SO4Dry, filtering, removal of solvent under reduced pressure, through quick silicon
It is gel column chromatography eluting, make eluant, eluent with petroleum ether, eluent solvent evaporated produces yellow oily liquid 1a yields 81%.
1H NMR (400 MHz, CDCl3) δ 7.78 (dd, J = 7.3, 1.8 Hz, 1H), 7.64 – 7.58
(m, 2H), 7.44 (dd, J = 6.6, 4.6 Hz, 6H), 7.36 (d, J = 7.3 Hz, 3H), 7.33 –
7.27 (m, 3H), 7.22 – 7.16 (m, 5H); 13C NMR (100 MHz, CDCl3) δ 149.1, 140.5,
135.9, 133.4, 132.7, 132.3, 131.8, 130.6, 129.0 (2C), 128.5 (2C), 127.9,
127.5, 127.4 (2C), 127.3, 117.2。
Embodiment 2
Synthesis（2-（P-methylphenyl）The bases of ethene -1,1,2- three）Three（Phenyl selenide）, its chemical equation is：
Synthetic method is：Working as to methyl phenylpropiolic acid, 1.5 for 0.5 mmol is added in 25 mL round-bottomed flask
The diphenyl disenenide ether of amount, 5% copper chloride, the sodium acid carbonate of 1.2 equivalents and 10 mL 1-METHYLPYRROLIDONEs, 90oUnder C
React 6 h, TLC tracking reactions；
After question response is complete, room temperature is cooled to, reactant is poured into 15 mL water, and is extracted with 20-30 mL ethyl acetate
Take 3 times, then with saturated common salt water washing 1 time, finally use anhydrous Na2SO4Dry, filtering, removal of solvent under reduced pressure, through quick silicon
It is gel column chromatography eluting, make eluant, eluent with petroleum ether, eluent solvent evaporated produces yellow oily liquid 2a yields 83%.
1H NMR (400 MHz, CDCl3) δ 7.40 (dd, J = 7.3, 2.0 Hz, 2H), 7.28 – 7.21
(m, 5H), 7.19 – 7.14 (m, 3H), 7.13 – 7.06 (m, 3H), 7.00 (t, J = 7.3 Hz, 2H),
6.92 (d, J = 8.0 Hz, 2H), 6.85 (d, J = 7.9 Hz, 2H), 2.16 (s, 3H); 13C NMR (100
MHz, CDCl3) δ 148.9, 137.7, 137.1, 135.5, 133.3, 132.6, 132.3, 131.9, 130.7,
128.8 (2C), 128.4 (2C), 128.1, 127.7, 127.20 (2C), 117.4, 21.2。
Embodiment 3
Synthesis（2-（Between tolyl）The bases of ethene -1,1,2- three）Three（Phenyl selenide）, its chemical equation is：
Synthetic method is：Methyl phenylpropiolic acid between 0.5 mmol is added in 25 mL round-bottomed flask, 1.5 work as
The diphenyl disenenide ether of amount, 5% stannous chloride, the potassium carbonate of 1.2 equivalents and 10 mL 1-METHYLPYRROLIDONEs, 90oUnder C
React 6 h, TLC tracking reactions；
After question response is complete, room temperature is cooled to, reactant is poured into 15 mL water, and is extracted with 20-30 mL ethyl acetate
Take 3 times, then with saturated common salt water washing 1 time, finally use anhydrous Na2SO4Dry, filtering, removal of solvent under reduced pressure, through quick silicon
It is gel column chromatography eluting, make eluant, eluent with petroleum ether, eluent solvent evaporated produces yellow oily liquid 3a yields 79%.
1H NMR (400 MHz, CDCl3) δ 7.33 (s, 2H), 7.18 – 7.04 (m, 8H), 7.03 –
6.95 (m, 3H), 6.93 – 6.79 (m, 3H), 6.72 (m, 2H), 6.61 (d, J = 13.6 Hz, 1H),
2.00 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 149.2, 140.1, 136.8, 135.8, 133.4,
132.5, 132.3, 131.7, 131.4, 130.7, 129.7, 129.1, 128.8, 128.5, 128.2, 128.0,
127.8, 127.2, 126.0, 116.6, 21.1。
Embodiment 4
Synthesis（2-（O-tolyl）The bases of ethene -1,1,2- three）Three（Phenyl selenide）, its chemical equation is：
Synthetic method is：0.5 mmol o-methyl-benzene propiolic acid is added in 25 mL round-bottomed flask, 1.5 work as
The diphenyl disenenide ether of amount, 5% stannous chloride, the potassium phosphate of 1.2 equivalents and 10 mL 1-METHYLPYRROLIDONEs, 90oUnder C
React 6 h, TLC tracking reactions；
After question response is complete, room temperature is cooled to, reactant is poured into 15 mL water, and is extracted with 20-30 mL ethyl acetate
Take 3 times, then with saturated common salt water washing 1 time, finally use anhydrous Na2SO4Dry, filtering, removal of solvent under reduced pressure, through quick silicon
It is gel column chromatography eluting, make eluant, eluent with petroleum ether, eluent solvent evaporated produces yellow oily liquid 4a yields 82%.
1H NMR (400 MHz, CDCl3) δ 7.55 – 7.50 (m, 2H), δ 7.34 – 7.28 (m, 8H),
7.22 – 7.14 (m, 3H), 7.06 – 6.90 (m, 6H), 2.29 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 149.8, 139.3, 136.7, 134.9, 134.3, 132.1, 131.6 (2C), 129.6 (2C),
129.2, 128.9, 128.5, 128.2 (2C), 127.8, 127.5, 127.2, 125.0, 114.3, 19.6。
Embodiment 5
Synthesis（2-（4- fluorophenyls）The bases of ethene -1,1,2- three）Three（Phenyl selenide）, its chemical equation is：
Synthetic method is：Added in 25 mL round-bottomed flask 0.5 mmol to fluorobenzene propiolic acid, 1.5 equivalents
Diphenyl disenenide ether, 5% cuprous iodide, the potassium phosphate of 1.2 equivalents and 10 mL 1-METHYLPYRROLIDONEs, 90oUnder C
React 6 h, TLC tracking reactions；
After question response is complete, room temperature is cooled to, reactant is poured into 15 mL water, and is extracted with 20 ~ 30 mL ethyl acetate
Take 3 times, then with saturated common salt water washing 1 time, finally use anhydrous Na2SO4Dry, filtering, removal of solvent under reduced pressure, through quick silicon
It is gel column chromatography eluting, make eluant, eluent with petroleum ether, eluent solvent evaporated produces yellow oily liquid 5a yields 80%.
1H NMR (400 MHz, CDCl3) δ 7.52 – 7.40 (m, 2H), 7.31 – 7.06 (m, 11H),
7.05 – 6.92 (m, 4H), 6.76 – 6.67 (m, 2H); 13C NMR (100MHz, CDCl3) δ 162.8,
160.4, 147.4, 136.5, 135.8, 133.2, 132.8, 132.1, 131.6, 131.4, 130.8, 130.7,
130.4, 128.8, 128.6, 128.5, 128.0, 127.5, 127.3 , 118.0, 114.4, 114.2。
Embodiment 6
Synthesis（The bases of 2- phenylethylenes -1,1,2- three）Three（（4- bromophenyls）Selenide）, its chemical equation is：
Synthetic method is：Add 0.5 mmol phenylpropiolic acid in 25 mL round-bottomed flask, the 1 of 1.5 equivalents,
2- is double（4- bromophenyls）Diselenide, 5% copper chloride, the cesium carbonate of 1.2 equivalents and 10 mL 1-METHYLPYRROLIDONEs, 90o6 h, TLC tracking reactions are reacted under C；
After question response is complete, room temperature is cooled to, reactant is poured into 15 mL water, and is extracted with 20-30 mL ethyl acetate
Take 3 times, then with saturated common salt water washing 1 time, finally use anhydrous Na2SO4Dry, filtering, removal of solvent under reduced pressure, through quick silicon
It is gel column chromatography eluting, make eluant, eluent with petroleum ether, eluent solvent evaporated produces yellow solid 6a yields 85%.
1H NMR (400 MHz, CDCl3) δ 7.49 (d, J = 0.5 Hz, 1H), 7.48 – 7.38 (m,
7H), 7.28 – 7.15 (m, 9H); 13C NMR (100 MHz, CDCl3) δ 139.9, 135.5, 134.7,
132.4 (2C), 132.2, 131.8, 129.6, 129.1, 128.4, 127.8, 127.2, 122.3, 120.9。
Embodiment 7
Synthesis（Phenylmethylene）It is double（Phenyl selenide）, its chemical equation is：
Synthetic method is：0.5 mmol phenylacetic acid, the hexichol of 1.5 equivalents are added in 25 mL round-bottomed flask
Base diselenide, 5% cuprous iodide, the cesium carbonate of 1.2 equivalents and 10 mL 1-METHYLPYRROLIDONEs, 90o6 are reacted under C
H, TLC tracking reaction；
After question response is complete, room temperature is cooled to, reactant is poured into 15 mL water, and is extracted with 20-30 mL ethyl acetate
Take 3 times, then with saturated common salt water washing 1 time, finally use anhydrous Na2SO4Dry, filtering, removal of solvent under reduced pressure, through quick silicon
Gel column chromatography eluting petroleum ether makees eluant, eluent, and eluent solvent evaporated produces yellow oily liquid 7a yields 84%.
1H NMR (400 MHz, CDCl3) δ 7.42 (d, J = 7.0 Hz,4H), 7.28 – 7.12 (m,
11H), 5.48 (s,1H)；13C NMR (100 MHz, CDCl3) δ 141.2, 134.5, 131.0, 129.0,
128.7, 128.2, 128.0, 127.5, 43.8。
Claims (3)
1. a kind of method by decarboxylation coupling reaction one pot process selenium class compound, it is characterized in that, synthesize universal method bag
Include following steps：
（1）Add 0.5 mmol carboxylic acid in 25 mL round-bottomed flask, the selenide of 1.5 equivalents, 5% Cu catalyst,
The alkali of 1.2 equivalents and 10 mL 1-METHYLPYRROLIDONE solvents, 90o6 h, TLC tracking reactions are reacted under C；
（2）After question response is complete, room temperature is cooled to, reactant is poured into 15 mL water, and is extracted with 20-30 mL ethyl acetate
3 times, then with saturated common salt water washing 1 time, finally use anhydrous Na2SO4Dry, filtering, removal of solvent under reduced pressure, through Flash silica
Column chromatography purifies, and makees eluant, eluent with petroleum ether, eluent solvent evaporated, produces product；
Synthetic method formula is as follows：
Wherein, Cu catalyst：Copper acetate, copper chloride, stannous chloride or cuprous iodide；
Alkali：Sodium carbonate, sodium acid carbonate, potassium phosphate, potassium carbonate or cesium carbonate.
2. the method according to claim 1 by decarboxylation coupling reaction one pot process selenium class compound, it is characterized in that：
Step（1）Carboxylic acid be phenylpropiolic acid, to methyl phenylpropiolic acid, a methyl phenylpropiolic acid, o-methyl-benzene propiolic acid, to fluorobenzene third
Acetylenic acid or phenylacetic acid.
3. the method according to claim 1 by decarboxylation coupling reaction one pot process selenium class compound, it is characterized in that：
Step（1）Selenide be diphenyl disenenide ether or 1,2- double（4- bromophenyls）Diselenide.
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| CN103086935A (en) * | 2011-10-28 | 2013-05-08 | 沈阳药科大学 | Diphenyl selenide, diphenyl selenoxide, diphenyl selenone compounds and uses thereof |
| CN103724246A (en) * | 2013-12-04 | 2014-04-16 | 温州大学 | Aryl elemental selenium compound synthesis method |
| CN104370785A (en) * | 2014-12-03 | 2015-02-25 | 温州大学 | Synthetic method of Beta-hydroxyl selenide compound |
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Patent Citations (3)
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| CN103086935A (en) * | 2011-10-28 | 2013-05-08 | 沈阳药科大学 | Diphenyl selenide, diphenyl selenoxide, diphenyl selenone compounds and uses thereof |
| CN103724246A (en) * | 2013-12-04 | 2014-04-16 | 温州大学 | Aryl elemental selenium compound synthesis method |
| CN104370785A (en) * | 2014-12-03 | 2015-02-25 | 温州大学 | Synthetic method of Beta-hydroxyl selenide compound |
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| Reaction of diorganyl diselenides with organyl 2,2-dichlorovinyl sulfides via phase-transfer catalysis as a method for preparation of organylthio(organylseleno)acetylenes and 1-organylthio-1,2-bis(organylseleno)-2-chloroethenes;Martynov, A. V. 等;《Zhurnal Organicheskoi Khimii》;19951231;第31卷(第4期);第512-520页 * |
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