CN108341761A - The preparation method of Organic Selenium cyano compound - Google Patents
The preparation method of Organic Selenium cyano compound Download PDFInfo
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- CN108341761A CN108341761A CN201810088954.0A CN201810088954A CN108341761A CN 108341761 A CN108341761 A CN 108341761A CN 201810088954 A CN201810088954 A CN 201810088954A CN 108341761 A CN108341761 A CN 108341761A
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- C07C391/00—Compounds containing selenium
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- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J51/00—Normal steroids with unmodified cyclopenta(a)hydrophenanthrene skeleton not provided for in groups C07J1/00 - C07J43/00
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- C07—ORGANIC CHEMISTRY
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- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
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Abstract
The invention discloses a kind of preparation methods of Organic Selenium cyano compound, and under the conditions of being included in existing for hydrochloric acid, organic solvent and nitrite, selenium cyanate is reacted with ketone compounds generates Organic Selenium cyano compound.The present invention has the characteristics that reaction condition is mild, operating procedure is simple, efficiency of pcr product is high.
Description
Technical field
The present invention relates to chemosynthesis technical fields.It is more particularly related to a kind of Organic Selenium cyano compound
Preparation method.
Background technology
Selenium is micro- necessary to animal body, is there are two types of existing way in nature tool：Inorganic selenium and Organic Selenium.
Compared with inorganic selenium, Organic Selenium have that bioavilability is high, bioactivity is strong, toxicity is low, environmental pollution is small and it is anti-oxidant,
The features such as anti-inflammatory, cancer-resisting.In organic matter introduce selenium cyano functional group, the prior art using：First by having
Machine object carries out halogenating reaction, generates organochlorine, bromine or iodine compound, and then organohalogen compounds further take with selenium Zassol
Generation reaction, obtains Organic Selenium cyano compound.Fern á ndez-Herrera M A etc. have synthesized a steroid nucleus branch using method of substitution
There are one the steroidal compounds of selenium cyano functional group, it is preferable that biological activity test shows that the compound has for the positions the 26- connection of chain
Inhibition growth of tumour cell proliferation activity, the IC50 values to cervical cancer cell HeLa, CaSki and ViBo are respectively 10,15 and
18 μM, however this method need by multistep reaction carry out and yield it is relatively low the features such as.
Invention content
As various extensive and careful research and experiment as a result, it has been found by the inventor that methyl ketone or
Selenium cyano functional group can draw cyclic ketones within specified temperatures in the acidic environment containing specific nitrite and organic solvent
Enter the alpha-position to carbonyl in methyl ketone or cyclic ketones.Based on this discovery, the present invention is completed.
It is excellent it is an object of the invention to solve at least the above and/or defect, and provide at least to will be described later
Point.
It is a still further object of the present invention to provide the preparation methods of Organic Selenium cyano compound, can pass through single step reaction
Selenium cyano functional group is introduced on the alpha-position of general formula I or general formula II.
In order to realize these purposes and other advantages according to the present invention, a kind of system of Organic Selenium cyano compound is provided
Preparation Method, under the conditions of existing for hydrochloric acid, organic solvent and nitrite, selenium cyanate, which reacts generation with ketone compounds, to be had
Machine selenium cyano compound,
Wherein, the ketone compounds have following general formula structure：
General formula I：Or general formula II：
R indicates steroid nucleus, cyclopenta, cyclohexyl, alkyl, phenyl ring or naphthalene nucleus；
X indicates that hydrogen, methyl, methoxyl group, hydroxyl or halogen, the position of substitution of X on phenyl ring are alpha-position or β-position；
N indicates 1 or 2.
Preferably, the preparation method of the Organic Selenium cyano compound includes the following steps：
1) hydrochloric acid and organic solvent, 10~30min of ice bath stirring are added into reaction vessel；
2) nitrite solution is added into the reaction vessel, and selenium cyanate is added after 10~30min；
3) ketone compounds are added into the reaction vessel, are reacted in a certain temperature conditions；
4) liquid in the reaction bulb is isolated and purified, obtains required Organic Selenium cyano class compound.
Preferably, in step 1), the mass fraction of the hydrochloric acid is 3~20%, 1~10 parts by volume of the hydrochloric acid, institute
It is 20~50 parts by volume to state organic solvent.
Preferably, the organic solvent is ethyl alcohol, methanol or acetonitrile.
Preferably, in step 2), the quality of the nitrite in nitrite solution is 50~150 parts by weight, selenium cyanogen
The additive amount of hydrochlorate is 100~300 parts by weight.
Preferably, in step 2), the nitrite solution is sodium nitrite solution or potassium nitrite solution, the selenium
Cyanate is selenium Zassol or Potassium Selenocyanate.
Preferably, in step 3), the ketone compounds are 200~500 parts by weight, and reaction temperature is 40~60 DEG C；
Preferably, the isolation and purification method includes the following steps：
A) it uses extractant to the liquid extraction in the reaction vessel, obtains extract liquor；
B) water washing is carried out to extract liquor described in step a) and saturated nacl aqueous solution washs, the extraction after being washed
Liquid；
C) extract liquor after the washing described in step b) is dried using anhydrous sodium sulfate, obtains dry liquid；
D) to dry liquid vacuum distillation is to remove solvent described in step c), to obtain crude extract；
E) to crude extract column chromatography for separation described in step d), Organic Selenium cyano compound is obtained.
Preferably, the extractant is ethyl acetate.
The present invention includes at least following advantageous effect：Directly use methyl ketone, that is, general formula I or cyclic ketones, that is, general formula II as former
Material, under the conditions of existing for nitrite, hydrochloric acid, selenium cyanate, by single step reaction can in methyl ketone or cyclic ketones carbonyl
Alpha-position introduce selenium cyano functional group；Selenium cyano efficiency of pcr product is introduced in methyl ketone or cyclic ketones be higher than 87% by one-step method.
The present invention has preparation process simple, and reaction condition is mild, is easily isolated purifying and without using spies such as oxidizing species
Point.
Part is illustrated to embody by further advantage, target and the feature of the present invention by following, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Specific implementation mode
The present invention is described in further detail below, to enable those skilled in the art being capable of evidence with reference to specification word
To implement.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of a other elements or combinations thereof.
<Example 1>
A kind of preparation method of Organic Selenium cyano compound, the condition existing for hydrochloric acid, organic solvent and nitrite
Under, selenium cyanate is reacted with ketone compounds generates Organic Selenium cyano compound,
Wherein, the ketone compounds have following general formula structure：
General formula I：Or general formula II：
R indicates steroid nucleus, cyclopenta, cyclohexyl, alkyl, phenyl ring or naphthalene nucleus；
X indicates that hydrogen, methyl, methoxyl group, hydroxyl or halogen, the position of substitution of X on phenyl ring are alpha-position or β-position；
N indicates 1 or 2.
<Example 2>
A kind of preparation method of Organic Selenium cyano compound, specifically includes following steps：
1) hydrochloric acid and organic solvent, ice bath stirring 10min are added into reaction vessel；
2) nitrite solution is added into the reaction vessel, and selenium cyanate is added after 10min；
3) ketone compounds of the addition with general formula II into the reaction vessel, TLC track to raw material point disappearance
Reaction is terminated afterwards；
4) liquid in the reaction bulb is isolated and purified, obtains required Organic Selenium cyano class compound.
<Example 3>
A kind of preparation method of Organic Selenium cyano compound, includes the following steps：
1) hydrochloric acid and ethyl alcohol are added into reaction vessel, the mass fraction of the hydrochloric acid is 20%, the hydrochloric acid 1mL, institute
It is 20mL, ice bath stirring 15min to state ethyl alcohol；
2) nitrite solution is added into the reaction vessel, and selenium cyanate is added after 30min；
3) ketone compounds of the addition with general formula I into the reaction vessel, after TLC tracks to raw material point disappearance
Terminate reaction；
4) liquid in the reaction bulb is isolated and purified, obtains required Organic Selenium cyano class compound.
<Example 4>
A kind of preparation method of Organic Selenium cyano compound, includes the following steps：
1) hydrochloric acid and methanol are added into reaction vessel, the mass fraction of the hydrochloric acid is 3%, the hydrochloric acid 10mL, institute
It is 50mL, ice bath stirring 30min to state methanol；
2) sodium nitrite solution is added into the reaction vessel, and 50mg sodium nitrites are contained in solution, are added after 30min
The selenium Zassol of 100mg；
3) the ketone compounds 500mg of the addition with general formula II into the reaction vessel, in 60 DEG C of temperature strip
It is reacted under part, TLC is tracked to after raw material point disappears and terminated reaction；
4) liquid in the reaction bulb is isolated and purified, obtains required Organic Selenium cyano class compound.
<Example 5>
A kind of preparation method of Organic Selenium cyano compound, includes the following steps：
1) hydrochloric acid and methanol are added into reaction vessel, the mass fraction of the hydrochloric acid is 10%, the hydrochloric acid 5mL, institute
It is 30mL, ice bath stirring 20min to state methanol；
2) sodium nitrite solution is added into the reaction vessel, and 150mg sodium nitrites are contained in solution, are added after 20min
Add the selenium Zassol of 300mg；
3) the ketone compounds 300mg of the addition with general formula II into the reaction vessel, in 40 DEG C of temperature strip
It is reacted under part, TLC is tracked to after raw material point disappears and terminated reaction；
4) liquid in the reaction bulb is isolated and purified, the isolation and purification method includes the following steps：
A) it uses extractant to the liquid extraction in the reaction vessel, obtains extract liquor；
B) water washing is carried out to extract liquor described in step a) and saturated nacl aqueous solution washs, the extraction after being washed
Liquid；
C) extract liquor after the washing described in step b) is dried using anhydrous sodium sulfate, obtains dry liquid；
D) to dry liquid vacuum distillation is to remove solvent described in step c), to obtain crude extract；
E) to crude extract column chromatography for separation described in step d), Organic Selenium cyano compound is obtained.
<Example 6>
A kind of preparation method of Organic Selenium cyano compound, includes the following steps：
1) hydrochloric acid and acetonitrile are added into reaction vessel, the mass fraction of the hydrochloric acid is 15%, the hydrochloric acid 10mL, institute
It is 40mL, ice bath stirring 20min to state acetonitrile；
2) sodium nitrite solution is added into the reaction vessel, and 100mg sodium nitrites are contained in solution, are added after 20min
Add the selenium Zassol of 200mg；
3) pregnenolone is added into the reaction vessel, is reacted under 50 DEG C of temperature condition, TLC tracks to raw material point
Reaction is terminated after disappearance；
4) liquid in the reaction bulb is isolated and purified, the isolation and purification method includes the following steps：
A) it uses ethyl acetate to the liquid extraction in the reaction vessel, obtains extract liquor；
B) water washing is carried out to extract liquor described in step a) and saturated nacl aqueous solution washs, the extraction after being washed
Liquid liquid；
C) extract liquor after the washing described in step b) is dried using anhydrous sodium sulfate, obtains dry liquid；
D) to dry liquid vacuum distillation is to remove solvent described in step c), to obtain crude extract；
E) to crude extract column chromatography for separation described in step d), Organic Selenium cyano compound is obtained, efficiency of pcr product is
91.4%, product is determined as 21- selenium cyano pregnenolones and 17- selenium cyano pregnenolones through structure through IR, NMR and MS analysis.
<Example 7>
A kind of preparation method of Organic Selenium cyano compound, includes the following steps：
1) hydrochloric acid and ethyl alcohol are added into reaction vessel, the mass fraction of the hydrochloric acid is 10%, the hydrochloric acid 5mL, institute
It is 30mL, ice bath stirring 10min to state ethyl alcohol；
2) potassium nitrite solution is added into the reaction vessel, and selenium Zassol is added after 30min；
3) progesterone is added into the reaction vessel, is reacted under 55 DEG C of temperature condition, TLC tracks to raw material point and disappears
Reaction is terminated after mistake；
4) liquid in the reaction bulb is isolated and purified, the isolation and purification method includes the following steps：
A) it uses ethyl acetate to the liquid extraction in the reaction vessel, obtains extract liquor；
B) water washing is carried out to extract liquor described in step a) and saturated nacl aqueous solution washs, the extraction after being washed
Liquid；
C) extract liquor after the washing described in step b) is dried using anhydrous sodium sulfate, obtains dry liquid；
D) to dry liquid vacuum distillation is to remove solvent described in step c), to obtain crude extract；
E) to crude extract column chromatography for separation described in step d), Organic Selenium cyano compound is obtained, efficiency of pcr product is
86.7%, product is determined as 21- selenium cyano progesterone and 17- selenium cyano progesterone through structure through IR, NMR and MS analysis.
<Example 8>
A kind of preparation method of Organic Selenium cyano compound, includes the following steps：
1) hydrochloric acid and ethyl alcohol are added into reaction vessel, the mass fraction of the hydrochloric acid is 3%, the hydrochloric acid 8mL, described
Ethyl alcohol is 50mL, ice bath stirring 15min；
2) potassium nitrite solution is added into the reaction vessel, and 150mg potassium nitrites are contained in solution, are added after 20min
Add the selenium Zassol of 150mg；
3) acetophenone is added into the reaction vessel, is reacted under 45 DEG C of temperature condition, TLC tracks to raw material point and disappears
Reaction is terminated after mistake；
4) liquid in the reaction bulb is isolated and purified, the isolation and purification method includes the following steps：
A) it uses ethyl acetate to the liquid extraction in the reaction vessel, obtains extract liquor；
B) water washing is carried out to extract liquor described in step a) and saturated nacl aqueous solution washs, the extraction after being washed
Liquid；
C) extract liquor after the washing described in step b) is dried using anhydrous sodium sulfate, obtains dry liquid；
D) to dry liquid vacuum distillation is to remove solvent described in step c), to obtain crude extract；
E) to crude extract column chromatography for separation described in step d), Organic Selenium cyano compound is obtained, efficiency of pcr product is
89.8%, product is determined as α-selenium cyano-acetophenone through structure through IR, NMR and MS analysis.
<Example 9>
A kind of preparation method of Organic Selenium cyano compound, includes the following steps：
1) hydrochloric acid and ethyl alcohol are added into reaction vessel, the mass fraction of the hydrochloric acid is 3%, the hydrochloric acid 4mL, described
Ethyl alcohol is 50mL, ice bath stirring 30min；
2) potassium nitrite solution is added into the reaction vessel, and 150mg potassium nitrites are contained in solution, are added after 20min
Add the selenium Zassol of 300mg；
3) 1-tetralone is added into the reaction vessel, is reacted under 50 DEG C of temperature condition, TLC tracks to raw material
Point terminates reaction after disappearing；
4) liquid in the reaction bulb is isolated and purified, the isolation and purification method includes the following steps：
A) it uses ethyl acetate to the liquid extraction in the reaction vessel, obtains extract liquor；
B) water washing is carried out to extract liquor described in step a) and saturated nacl aqueous solution washs, the extraction after being washed
Liquid；
C) extract liquor after the washing described in step b) is dried using anhydrous sodium sulfate, obtains dry liquid；
D) to dry liquid vacuum distillation is to remove solvent described in step c), to obtain crude extract；
E) to crude extract column chromatography for separation described in step d), Organic Selenium cyano compound is obtained, efficiency of pcr product is
88.4%, product is determined as 2- selenium cyano -1-tetralone through structure through IR, NMR and MS analysis.
<Example 10>
A kind of preparation method of Organic Selenium cyano compound, includes the following steps：
1) hydrochloric acid and ethyl alcohol are added into reaction vessel, the mass fraction of the hydrochloric acid is 20%, the hydrochloric acid 1mL, institute
It is 20mL, ice bath stirring 30min to state ethyl alcohol；
2) potassium nitrite solution is added into the reaction vessel, and 150mg potassium nitrites are contained in solution, are added after 20min
Add the selenium Zassol of 250mg；
3) 1- indones are added into the reaction vessel, are reacted under 50 DEG C of temperature condition, TLC tracks to raw material point and disappears
Reaction is terminated after mistake；
4) liquid in the reaction bulb is isolated and purified, the isolation and purification method includes the following steps：
A) it uses ethyl acetate to the liquid extraction in the reaction vessel, obtains extract liquor；
B) water washing is carried out to extract liquor described in step a) and saturated nacl aqueous solution washs, the extraction after being washed
Liquid；
C) extract liquor after the washing described in step b) is dried using anhydrous sodium sulfate, obtains dry liquid；
D) to dry liquid vacuum distillation is to remove solvent described in step c), to obtain crude extract；
E) to crude extract column chromatography for separation described in step d), Organic Selenium cyano compound is obtained, efficiency of pcr product is
90.3%, product is determined as 2- selenium cyano -1- indones through structure through IR, NMR and MS analysis.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With.It can be applied to various suitable the field of the invention completely.It for those skilled in the art, can be easily
Realize other modification.Therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details.
Claims (9)
1. a kind of preparation method of Organic Selenium cyano compound, which is characterized in that deposited in hydrochloric acid, organic solvent and nitrite
Under the conditions, selenium cyanate is reacted with ketone compounds generates Organic Selenium cyano compound,
Wherein, the ketone compounds have following general formula structure：
General formula I：Or general formula II：
R indicates steroid nucleus, cyclopenta, cyclohexyl, alkyl, phenyl ring or naphthalene nucleus；
X indicates that hydrogen, methyl, methoxyl group, hydroxyl or halogen, the position of substitution of X on phenyl ring are alpha-position or β-position；
N indicates 1 or 2.
2. the preparation method of Organic Selenium cyano compound according to claim 1, which is characterized in that specifically include following step
Suddenly：
1) hydrochloric acid and organic solvent, 10~30min of ice bath stirring are added into reaction vessel；
2) nitrite solution is added into the reaction vessel, and selenium cyanate is added after 10~30min；
3) ketone compounds are added into the reaction vessel, are reacted in a certain temperature conditions；
4) liquid in step 3) reaction bulb is isolated and purified, obtains the Organic Selenium cyano class compound.
3. the preparation method of Organic Selenium cyano compound according to claim 2, which is characterized in that described in step 1)
The mass fraction of hydrochloric acid is 3~20%, 1~10 parts by volume of the hydrochloric acid, and the organic solvent is 20~50 parts by volume.
4. according to the preparation method of claim 1-3 any one of them Organic Selenium cyano compounds, which is characterized in that described to have
Solvent is ethyl alcohol, methanol or acetonitrile.
5. the preparation method of Organic Selenium cyano compound according to claim 2, which is characterized in that in step 2), nitrous
The quality of nitrite in acid salt solution is 50~150 parts by weight, and the additive amount of selenium cyanate is 100~300 parts by weight.
6. the preparation method of Organic Selenium cyano compound according to claim 5, which is characterized in that described in step 2)
Nitrite solution is sodium nitrite solution or potassium nitrite solution, and the selenium cyanate is selenium Zassol or Potassium Selenocyanate.
7. the preparation method of Organic Selenium cyano compound according to claim 2, which is characterized in that described in step 3)
Ketone compounds are 200~500 parts by weight, and reaction temperature is 40~60 DEG C.
8. the preparation method of Organic Selenium cyano compound according to claim 2, which is characterized in that the side of isolating and purifying
Method includes the following steps：
A) it uses extractant to the liquid extraction in the reaction vessel, obtains extract liquor；
B) water washing is carried out to extract liquor described in step a) and saturated nacl aqueous solution washs, the extract liquor after being washed；
C) extract liquor after the washing described in step b) is dried using anhydrous sodium sulfate, obtains dry liquid；
D) to dry liquid vacuum distillation is to remove solvent described in step c), to obtain crude extract；
E) to crude extract column chromatography for separation described in step d), Organic Selenium cyano compound is obtained.
9. the preparation method of Organic Selenium cyano compound according to claim 8, which is characterized in that the extractant is
Ethyl acetate.
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| CN111879904A (en) * | 2020-07-07 | 2020-11-03 | 武汉市农业科学院 | Method for determining organic selenium in tea |
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| CN111879904A (en) * | 2020-07-07 | 2020-11-03 | 武汉市农业科学院 | Method for determining organic selenium in tea |
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