CN105646311B - The method that one kind prepares the carrot aldehyde of β Apos 8 ' - Google Patents
The method that one kind prepares the carrot aldehyde of β Apos 8 ' Download PDFInfo
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- C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
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Abstract
The invention discloses the method that one kind prepares the carrot aldehyde of β Apos 8 ', comprise the following steps：(1) with 2, the cyclohexene methanol of 6,6 trimethyl 1 and triphenylphosphine are raw material, and the cyclohexene methyl triphenyl quaternary alkylphosphonium salt of 2,6,6 trimethyl 1 is synthesized under the conditions of concentrated hydrochloric acid or the concentrated sulfuric acid；(2) by the obtained cyclohexene methyl triphenyl quaternary alkylphosphonium salt of 2,6,6 trimethyl 1 and 2,6,11 in step (1), 15 tetramethyls 2,4,6,8,10,12, the 14 ten six alkene dialdehyde of carbon seven react by Wittig, produce the carrot aldehyde of β Apos 8 '.This method is with the cyclohexene methanol of 2,6,6 trimethyl 1 for raw material, and course of reaction is safe, and no danger is a kind of new method for preparing β Apo 8' carrot aldehyde.
Description
Technical field
The present invention relates to organic synthesis field, β-Apo -8 is prepared more specifically to one kind ' side of-carrot aldehyde
Method.
Background technology
β-Apo -8'- carrot aldehyde (structural formula I), is one kind of carotenoid, has been widely used in feed industry
In.β-Apo -8'- carrot aldehyde can also be used to synthesize other carotenoid simultaneously.Therefore, β-Apo -8'- carrot aldehyde is studied
Synthetic method there is practical value.
The method of existing synthesis β-Apo -8'- carrot aldehyde is as follows：
1. document (Xu, Pingjun Chengdu Keji Daxue Xuebao, (3), 77-84；1992) β-Ah is reported
The preparation method of Piao's -8'- carrot aldehyde, its synthetic route such as reaction equation one：
Beta carotene oxidation scission containing 40 carbon atoms into β-Apo -8'- carrot aldehyde, is generated one by this method in addition
A little accessory substances, without economy.
2. patent (Ruttimann Eur.Pat.Appl.07 Jan 1998) is described with β-Apo -12'- carrotene
Dimethylacetal prepares the method for β-Apo -8'- carrot aldehyde, its synthetic route such as reaction equation two：
This method β-Apo -12'- carrotene dimethylacetal and 1- methoxyl group -2- methyl isophthalic acids, the condensation of 3- butadiene,
BFEE compound is used, β-Apo -8'- carrot aldehyde is obtained.
In summary, the above-mentioned method 1 for preparing β-Apo -8'- carrot aldehyde uses existing carrotene product, and oxidation is removed
A part of structure, and accessory substance is generated, without economy；Method 2 uses BFEE compound, and the compound is in sky
Middle chance moisture is hydrolyzed immediately, and the hydrogen fluoride smog of severe toxicity is generated during decomposition, is unfavorable for industrialization, therefore nor preferably square
Method.A kind of new method for preparing β-Apo -8'- carrot aldehyde of research has actual application value.
The content of the invention
The technical problem to be solved in the present invention is, for prior art drawbacks described above there is provided one kind synthesis β-Apo-
The method of 8'- carrot aldehyde, this method is with 2,6,6- trimethyl -1- cyclohexene methanol for raw material, and course of reaction is safe, no danger
Property, it is a kind of new method for preparing β-Apo -8'- carrot aldehyde.
The technical solution adopted for the present invention to solve the technical problems is：One kind is provided and prepares β-Apo -8 '-carrot aldehyde
Method, comprise the following steps：
(1) with 2,6,6- trimethyl -1- cyclohexene methanol and triphenylphosphine are raw material, under the conditions of concentrated hydrochloric acid or the concentrated sulfuric acid
Synthesize 2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts；
(2) by obtained 2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts and 2,6,11,15- in step (1)
Tetramethyl -2,4,6,8,10,12, the 14- ten six alkene dialdehyde of carbon seven react by Wittig, produce β-Apo -8 '-carrot aldehyde.
It is of the present invention to prepare β-Apo -8 ' method of-carrot aldehyde, wherein, preparation β-Apo -8 '-carrot aldehyde
Method also include the process that is purified respectively to the product of step (1), concrete operations are as follows：Treat that step (1) reaction is finished
Afterwards, room temperature is cooled to, water is added, water layer is extracted three times with dichloromethane, merges organic layer, then with n-hexane extraction twice
Use anhydrous Na2SO4Dry, removal of solvent under reduced pressure, remove impurity with hexamethylene or petroleum ether, or separate through silica gel column chromatography
Obtain thick solid, i.e., 2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts.
It is of the present invention to prepare β-Apo -8 ' method of-carrot aldehyde, wherein, preparation β-Apo -8 '-carrot aldehyde
Method also include the process that is purified respectively to the product of step (2), concrete operations are as follows：After step (2) reaction, plus it is full
And ammonium chloride solution, CH2Cl2Extraction three times, merges organic layer, uses anhydrous Na2SO4Dry organic layer, removal of solvent under reduced pressure, warp
Silica gel column chromatography or recrystallization, obtain β-Apo -8 '-carrot aldehyde.
It is of the present invention to prepare β-Apo -8 ' method of-carrot aldehyde, wherein, the elution system in the silica gel column chromatography
Unite as petroleum ether：Ethyl acetate=10：1.
It is of the present invention to prepare β-Apo -8 ' method of-carrot aldehyde, wherein, the concrete operations of the step (1) are such as
Under：Methanol is added in reaction bulb, 2,6,6- trimethyls -1- cyclohexene methanol and triphenylphosphine is added, after being mixed evenly,
It is heated to reflux under nitrogen protection 6-10 hours after concentrated hydrochloric acid or the concentrated sulfuric acid, completion of dropping is added dropwise at less than 15 DEG C, produces 2,
6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts.
It is of the present invention to prepare β-Apo -8 ' method of-carrot aldehyde, wherein, the ring lemon alcohol and triphenylphosphine
Mol ratio is 1:(1-1.5).
It is of the present invention to prepare β-Apo -8 ' method of-carrot aldehyde, wherein, 2,6,6- front threes in the step (1)
The mol ratio of base -1- cyclohexene methanol and concentrated hydrochloric acid or the concentrated sulfuric acid is 1：(1-1.5).
It is of the present invention to prepare β-Apo -8 ' method of-carrot aldehyde, wherein, the concrete operations of the step (2) are such as
Under：By obtained 2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts in step (1), stir at ambient temperature, plus
0.5-1h is stirred under nitrogen protection after entering the methanol solution of sodium methoxide, completion of dropping, is added followed by 2,6,11,15- tetramethyls
Base -2,4,6,8,10,12, the 14- ten six alkene dialdehyde of carbon seven, is reacted at room temperature 1-4 hours.
It is of the present invention to prepare β-Apo -8 ' method of-carrot aldehyde, wherein, described 2,6,6- trimethyl -1- hexamethylenes
Alkene methyl triphenyl quaternary alkylphosphonium salt, sodium methoxide and the alkene dialdehyde of 16 carbon of 2,6,11,15- tetramethyls -2,4,6,8,10,12,14- seven
Mol ratio is 1:(1-2):(1-1.5).
That implements the present invention prepares β-Apo -8 ' method of-carrot aldehyde, have the advantages that：
The present invention by, for raw material, first synthesizing corresponding 2 with 2,6,6- trimethyl -1- cyclohexene methanol and triphenylphosphine,
6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts, recycle 2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary phosphines
Salt and 2,6,11,15- tetramethyls -2,4,6,8,10,12, the 14- ten six alkene dialdehyde of carbon seven react by Wittig, produce β-Ah
Plain -8 '-carrot aldehyde.
Embodiment
Below, with reference to embodiment, the present invention is described further：
One kind prepares β-Apo -8 ' method of-carrot aldehyde, comprise the following steps：
(1) with 2,6,6- trimethyl -1- cyclohexene methanol and triphenylphosphine are raw material, under the conditions of concentrated hydrochloric acid or the concentrated sulfuric acid
Synthesize 2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts；Methanol is added in reaction bulb, 2,6,6- tri- is added
The mol ratio of methyl isophthalic acid-cyclohexene methanol and triphenylphosphine, 2,6,6- trimethyl -1- cyclohexene methanol and triphenylphosphine is 1:
(1-1.5)；After being mixed evenly, concentrated hydrochloric acid or the concentrated sulfuric acid are added dropwise at less than 15 DEG C, wherein, ring lemon alcohol and concentrated hydrochloric acid or
The mol ratio of the concentrated sulfuric acid is 1：(1-1.5).It is heated to reflux under nitrogen protection after completion of dropping 6-10 hours.Treat that step (1) is anti-
After should finishing, room temperature is cooled to, water is added, water layer is extracted three times with dichloromethane, merges organic with n-hexane extraction twice
Layer, then uses anhydrous Na2SO4Dry, removal of solvent under reduced pressure, impurity is removed with hexamethylene or petroleum ether, or through silica gel column layer
Analyse isolated thick solid, i.e., 2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts.
(2) by obtained 2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts and 2,6,11,15- in step (1)
Tetramethyl -2,4,6,8,10,12, the 14- ten six alkene dialdehyde of carbon seven react by Wittig, produce β-Apo -8 '-carrot aldehyde.I.e.
By obtained 2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts in step (1), stir, add at ambient temperature
Stir 0.5-1h under nitrogen protection after the methanol solution of sodium methoxide, completion of dropping, be added followed by 2,6,11,15- tetramethyls-
2,4,6,8,10,12, the 14- ten six alkene dialdehyde of carbon seven, are reacted at room temperature 1-4 hours.2,6,6- trimethyls -1- cyclohexene the methyl
The mol ratio of triphenyl quaternary alkylphosphonium salt, sodium methoxide and the alkene dialdehyde of 16 carbon of 2,6,11,15- tetramethyls -2,4,6,8,10,12,14- seven
For 1:(1-2):(1-1.5).After step (2) reaction, plus saturated ammonium chloride solution, CH2Cl2Extraction three times, merges organic layer, uses
Anhydrous Na2SO4Organic layer is dried, removal of solvent under reduced pressure, through silica gel column chromatography or recrystallization, obtains β-Apo -8 '-carrot aldehyde.
Wherein, the elution system in the silica gel column chromatography is petroleum ether：Ethyl acetate=10：1.
The present invention β-Apo -8 '-carrot aldehyde synthetic route it is as follows：
In all embodiments,1H-NMR、13C-NMR is by Bruker AV-400 type nmr determinations, with deuterochloroform
(CDCl3) it is solvent, tetramethylsilane (TMS) is internal standard；Mass spectrum is determined with Agilent 6210 (DOF-MAS) mass spectrograph.
Embodiment 1The preparation of β-Apo -8 '-carrot aldehyde：
Methanol (50mL), 2,6,6- trimethyl -1- cyclohexene methanol (1.54g, 10mmol) are added in 100mL reaction bulbs
With triphenylphosphine (3.14g, 12mmol), after being mixed evenly.It is added dropwise at less than 15 DEG C after 1.5g concentrated hydrochloric acids, completion of dropping
It is heated to reflux under nitrogen protection 8 hours.TLC (petroleum ethers：Ethyl acetate=5：1) reaction end is detected.After question response is finished
But to room temperature, 20mL water is added, with n-hexane extraction (25mL × 2), water layer extracts (25mL × 3) with dichloromethane, is associated with
Machine layer, anhydrous Na2SO4Dry, removal of solvent under reduced pressure, removing impurity is washed with hexamethylene (or petroleum ether), or through silica gel column chromatography
(ethanol) isolated thick solid, as 2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts, yield 50%.
2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts (4.34g, 10mmol) and first are added in reaction bulb
Alcohol (20mL).Sodium methoxide (0.81g, 15mmol) is dissolved in 20mL methanol, is stirred at room temperature down and is added in reaction bulb, completion of dropping
Stir 0.5h under nitrogen protection afterwards, then add 2,6,11,15- tetramethyls -2,4,6,8,10,12,14- ten six alkene of carbon seven
Dialdehyde (2.96g, 10mmol), reacts at room temperature 4h.Saturated ammonium chloride solution 40mL, CH are added after the completion of reaction2Cl2Extract (25mL
× 3), removal of solvent under reduced pressure after organic layer anhydrous sodium sulfate drying, through silica gel column chromatography (petroleum ether：Ethyl acetate=10：1)
Or recrystallization, obtain β-Apo -8 '-carrot aldehyde, yield 38%.
Embodiment 2The preparation of β-Apo -8 '-carrot aldehyde：
Methanol (50mL), 2,6,6- trimethyl -1- cyclohexene methanol (1.54g, 10mmol) are added in 100mL reaction bulbs
With triphenylphosphine (2.62g, 10mmol), after being mixed evenly.It is added dropwise at less than 15 DEG C after 1.5g concentrated hydrochloric acids, completion of dropping
It is heated to reflux under nitrogen protection 6 hours.TLC (petroleum ethers：Ethyl acetate=5：1) reaction end is detected.After question response is finished
But to room temperature, 20mL water is added, with n-hexane extraction (25mL × 2), water layer extracts (25mL × 3) with dichloromethane, is associated with
Machine layer, anhydrous Na2SO4Dry, removal of solvent under reduced pressure, removing impurity is washed with hexamethylene (or petroleum ether), or through silica gel column chromatography
(ethanol) isolated thick solid, as 2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts, yield 45%.
2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts (4.34g, 10mmol) and first are added in reaction bulb
Alcohol (20mL).Sodium methoxide (0.54g, 10mmol) is dissolved in 20mL methanol, is stirred at room temperature down and is added in reaction bulb, completion of dropping
Stir 0.5h under nitrogen protection afterwards, then add 2,6,11,15- tetramethyls -2,4,6,8,10,12,14- ten six alkene of carbon seven
Dialdehyde (2.96g, 10mmol), reacts at room temperature 1h.Saturated ammonium chloride solution 40mL, CH are added after the completion of reaction2Cl2Extract (25mL
× 3), removal of solvent under reduced pressure after organic layer anhydrous sodium sulfate drying, through silica gel column chromatography (petroleum ether：Ethyl acetate=10：1)
Or recrystallization, obtain β-Apo -8 '-carrot aldehyde, yield 23%.
Embodiment 3The preparation of β-Apo -8 '-carrot aldehyde：
Methanol (50mL), 2,6,6- trimethyl -1- cyclohexene methanol (1.54g, 10mmol) are added in 100mL reaction bulbs
With triphenylphosphine (3.85g, 15mmol), after being mixed evenly.It is added dropwise at less than 15 DEG C after 1.5g concentrated hydrochloric acids, completion of dropping
It is heated to reflux under nitrogen protection 10 hours.TLC (petroleum ethers：Ethyl acetate=5：1) reaction end is detected.After question response is finished
But to room temperature, 20mL water is added, with n-hexane extraction (25mL × 2), water layer extracts (25mL × 3) with dichloromethane, is associated with
Machine layer, anhydrous Na2SO4Dry, removal of solvent under reduced pressure, removing impurity is washed with hexamethylene (or petroleum ether), or through silica gel column chromatography
(ethanol) isolated thick solid, as 2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts, yield 52%.
2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts (4.34g, 10mmol) and first are added in reaction bulb
Alcohol (20mL).Sodium methoxide (1.08g, 20mmol) is dissolved in 20mL methanol, is stirred at room temperature down and is added in reaction bulb, completion of dropping
Stir 0.5h under nitrogen protection afterwards, then add 2,6,11,15- tetramethyls -2,4,6,8,10,12,14- ten six alkene of carbon seven
Dialdehyde (4.44g, 15mmol), reacts at room temperature 2h.Saturated ammonium chloride solution 40mL, CH are added after the completion of reaction2Cl2Extract (25mL
× 3), removal of solvent under reduced pressure after organic layer anhydrous sodium sulfate drying, through silica gel column chromatography (petroleum ether：Ethyl acetate=10：1)
Or recrystallization, obtain β-Apo -8 '-carrot aldehyde, yield 35%.
β-Apo -8 that Example 1-3 is prepared '-carrot aldehyde identified, the following is the data of its various spectrum
As a result：
Product β-Apo -8 '-carrot aldehyde spectroscopic data:
1H-NMR(400MHz,CDCl3):δ9.45(s,1H),6.12-6.96(m,12H),2.06-2.02(m,2H),2.00
(s,9H),1.90(s,3H),1.72(s,3H),1.60-1.64(m,2H),1.45-1.49(m,2H),1.03(s,6H)；
13C-NMR(100MHz,CDCl3)δ194.6,149.4,138.7,137.7,136.9,135.2,133.1,131.9,
130.7,129.6,129.1,127.2,126.2,122.7,39.6,34.3,33.2,29.0,21.8,19.3,13.0,12.8,
9.7。
HRMS-ESI:Calcd.For:C30H40O[M+Na]+:439.2977；Found:439.2972.
It will be apparent to those skilled in the art that technical scheme that can be as described above and design, make other various
It is corresponding to change and deformation, and all these change and deformation should all belong to the protection domain of the claims in the present invention
Within.
Claims (4)
1. one kind prepares β-Apo -8 ' method of-carrot aldehyde, it is characterised in that comprise the following steps：
（1）With 2,6,6- trimethyl -1- cyclohexene methanol and triphenylphosphine for raw material, synthesized under the conditions of concentrated hydrochloric acid or the concentrated sulfuric acid
For 2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts；The step（1）Concrete operations it is as follows：In reaction bulb
Methanol is added, ring lemon alcohol and triphenylphosphine is added, after being mixed evenly, concentrated hydrochloric acid or sulfuric acid are added dropwise at less than 15 DEG C,
It is heated to reflux under nitrogen protection after completion of dropping 6-10 hours, produced for 2,6,6- trimethyl -1- cyclohexene methyl triphenyl seasons
Phosphonium salt；The mol ratio of the ring lemon alcohol and triphenylphosphine is 1:（1-1.5）；The ring lemon alcohol and concentrated hydrochloric acid or the concentrated sulfuric acid
Mol ratio is 1：（1-1.5）；
（2）By step（1）In obtained 2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts and 2,6,11,15- tetramethyls
Base -2,4,6,8,10,12, the 14- ten six alkene dialdehyde of carbon seven react by Wittig, produce β-Apo -8 '-carrot aldehyde；The step
Suddenly（2）Concrete operations it is as follows：By step（1）In obtained 2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts,
Stirred under room temperature condition, 0.5-1h is stirred under nitrogen protection after adding the methanol solution of sodium methoxide, completion of dropping, then added again
Enter 2,6,11,15- tetramethyls -2,4,6,8,10,12, the 14- ten six alkene dialdehyde of carbon seven are reacted at room temperature 1-4 hours；Described 2,6,
6- trimethyl -1- cyclohexene methyl triphenyls quaternary alkylphosphonium salt, sodium methoxide and 2,6,11,15- tetramethyls -2,4,6,8,10,12,14-
The mol ratio of the alkene dialdehyde of 16 carbon seven is 1:（1-2）:（1-1.5）.
2. according to claim 1 prepare β-Apo -8 ' method of-carrot aldehyde, it is characterised in that preparation β-Apos -
The method of 8 '-carrot aldehyde also includes respectively to step（1）The process that is purified of product, concrete operations are as follows：Treat step
（1）After completion of the reaction, room temperature is cooled to, water is added, water layer is extracted three times with dichloromethane, merges with n-hexane extraction twice
Organic layer, then uses anhydrous Na2SO4Dry, removal of solvent under reduced pressure, impurity is removed with hexamethylene or petroleum ether, or through silica gel
Column chromatography for separation obtains thick solid, i.e., 2,6,6- trimethyl -1- cyclohexene methyl triphenyl quaternary alkylphosphonium salts.
3. according to claim 1 prepare β-Apo -8 ' method of-carrot aldehyde, it is characterised in that preparation β-Apos -
The method of 8 '-carrot aldehyde also includes respectively to step（2）The process that is purified of product, concrete operations are as follows：Step（2）
After reaction, plus saturated ammonium chloride solution, CH2Cl2Extraction three times, merges organic layer, uses anhydrous Na2SO4Dry organic layer, decompression
Solvent is removed, through silica gel column chromatography or recrystallization, β-Apo -8 is obtained '-carrot aldehyde.
4. according to claim 3 prepare β-Apo -8 ' method of-carrot aldehyde, it is characterised in that the silica gel column layer
Elution system in analysis is petroleum ether：Ethyl acetate=10：1.
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