CN101070270B - Method for synthesizing (E,E) Geranyl linalool - Google Patents
Method for synthesizing (E,E) Geranyl linalool Download PDFInfo
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- CN101070270B CN101070270B CN2007100492608A CN200710049260A CN101070270B CN 101070270 B CN101070270 B CN 101070270B CN 2007100492608 A CN2007100492608 A CN 2007100492608A CN 200710049260 A CN200710049260 A CN 200710049260A CN 101070270 B CN101070270 B CN 101070270B
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Abstract
This invention relates to synthetic method of a (E, E) - geranyl linalool. The invention takes (E) - nerolidol as raw material. The hydroxyl is shield by dihydropyrane, gain (E) - nerolidol tetrahydropyrane aether; selenium dioxide and teri-butyl hydroperoxide selectively oxidize the anti-form methyl of (E) - nerolidol tetrahydropyrane aether to gain anti-form allyl position hydroxylated oxidative product (E, E) - 12 - hydroxy nerolidol tetrahydropyrane aether, transit halogenating reaction to gain (E, E) - 12 - halogeno- nerolidol tetrahydropyrane aether, then take reaction with isopropyl methyl ketone that is selectively divested one proton by diisopropyl amido lithium, generate (6E, 10E) - 2, 6, 10, 14 - tetramethyl - 14 - (tetrahydropyrane - 2 - oxygen) -16 - 6, 10, 15 - triene - 3 - ketone, use sodium borohydride to reduce to gain (6E, 10E) - 2, 6, 10, 14 - tetramethyl-14-(tetrahydropyrane-2- oxygen) -16 - 6, 10, 15 - triene - 3 - alcohol, takes reaction with sulfonyl chloride or sulphonic acid ester with alkali presence to gain (6E, 10E) - 2, 6, 10, 14 - tetramethyl - 14 - (tetrahydropyrane - 2 oxygen) -16 - 6, 10, 15 - triene - 3 - alcoholic sulphonic acid ester, then divide sulphonic acid ester group under base catalysis to gain (E, E) - geranyl linalool tetrahydropyrane aether, and by deprotection to gain (E, E) - geranyl linalool. For the configuration of (E) - nerolidol 3 position tertiary carbon is not influenced in the course of reaction, if use (E) - nerolidol that has optical activity as raw material, should gain optical active (E, E) - geranyl linalool. (E, E)-geranyl linalool can replace Teprenone and such type medicament intermediate, natural product intermediate, insect pheromone and spice etc.
Description
Technical field
The present invention relates to a kind of (E, E)-geranyl linalool synthetic method.
Background technology
(E, E)-geranyl linalool is a kind of straight chain diterpene-kind compound, its molecular structural formula is:
(E, E)-geranyl linalool is important intermediate, bioactive compounds and the spices fixation composition of chain diterpenes medicine and natural product.
(E, E)-geranyl linalool just obtains the gastric mucosa protectant teprenone with the methyl acetoacetate single step reaction under aluminum isopropylate catalysis, this will be the synthetic method of convenient synthetic teprenone.Geranyl linalool is reset through a step and is obtained the geranyl nerolidol.(E, E)-geranyl linalool can also be as insect pheromone and insect natural insecticide.It also is the fixation composition of senior spices.Thereby, (E, E)-geranyl linalool has important economic value (forest chemical engineering communication 2005,39 (5): 34-38).
(E, E)-geranyl linalool has a small amount of existence, is difficult to separation and Extraction in some biology of occurring in nature.
(E, E)-geranyl linalool mainly adopts the method for chemosynthesis to prepare, but reported method is also fewer.
It is raw material that USSR (Union of Soviet Socialist Republics) Nazarov research group adopts 3-methyl-1-butene-3-alcohol, with the hydrogen halide reaction isomerization taking place obtains allyl halide, then the sodium salt with methyl aceto acetate reacts, decarboxylation obtains isopentene group acetone under alkaline condition, under highly basic (potassium hydroxide) condition ethynylation takes place with acetylene then, acetylide hydrogenation under palladium catalysis, obtain increasing a unitary compound 3 of isopentene group, 7-dimethyl-3-hydroxyl-1,6-octadiene.Just can obtain the constantly isoprene alcohols series compound of prolongation of carbochain by repeatedly repeating this several steps reaction, comprise geranyl linalool, obtain be cis-trans isomerism (RussianChem.Bull.1957,6 (10), 1294-1297).
SciFinder retrieves (but we do not find) on the State Intellectual Property Office website, patent of invention (application publication number 1660731,20058.31) in the presence of highly basic, react the generation acetylide with farnesyl acetone and acetylene, obtain geranyl linalool at the palladium catalyzed hydrogenation alkynyl that quinoline poisons then.Soviet Union Nazarov reported method is basic identical in front of this method.
More common method is from phantol now, under aluminum isopropylate catalysis with methyl acetoacetate the geranyl acetone that the Carroll reaction generates cis-trans isomerism takes place, obtain (E)-geranyl acetone through rectifying separation, obtain (E) nerolidol with vinyl chlorination reactive magnesium then.(E)-the Carroll reaction takes place with methyl acetoacetate and obtains (5E in nerolidol under aluminum isopropylate catalysis, 9E)-and (5Z, 9E)-isomeric compound of farnesyl acetone, adopt rectifying column to separate (but because the cis-trans-isomer boiling point differs very little, difficulty is very big, and this is a key step).Obtain (5E, 9E)-farnesyl acetone and vinyl chlorination reactive magnesium obtain (E, E)-geranyl linalool.Step is few, but will separate through twice cis-trans-isomer, and each rectifying will be removed the closely cis-isomeride of half, more trouble is that the cis-trans-isomer boiling point differs very little, cause separating difficulty very big, to general enterprise be difficult to accomplish (JP2003238463,2003.8.27).
Recently, Svatos is from geranyl bromine and L configuration or D configuration citromalic acid, through 7 step reactions synthetic (3R)-and (3S)-geranyl linalool, but this method use in a large number cuprous cyanide, double cyclopentenyl zirconium chloride, butyllithium, 2-thiophene lithium, borine etc. easily (certainly) fire, explosive, hypertoxic hazardous substance, lack actual application value (Coll.Czech.Chem.Commun.2002,67 (1): 83-90).
Because (E)-configuration of 3 tertiary carbons of nerolidol is unaffected in reaction process, thereby, have optically active (E)-nerolidol to make raw material if use, will obtain optically active (E, E)-geranyl linalool.
Synthetic route of the present invention had only for 7 steps, and wherein two steps be respectively the very high dihydropyrane of productive rate go up protection and deprotection, (E, E)-isomer purity height, raw material is cheap and easy to get, the reaction conditions gentleness, productive rate is higher, is hopeful to realize suitability for industrialized production.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of geranyl linalool.
Synthesis step is as follows:
1) is raw material with (E)-nerolidol, under the catalysis of tosic acid pyridinium salt, protects hydroxyl, obtain (E)-nerolidol tetrahydropyranyl ethers with dihydropyrane.
2) (E)-the nerolidol tetrahydropyranyl ethers carries out the selectivity allylic oxidation with tin anhydride and tertbutyl peroxide to the trans methyl of (E)-nerolidol tetrahydropyranyl ethers, obtain the hydroxylated oxidation products of trans allylic (E, E)-12-hydroxyl nerolidol tetrahydropyranyl ethers.If the by product of excessively oxidated some the trans allylic carbonylations of generation of reaction becomes needed alcohol to crude product with sodium borohydride reduction.
3) (E, E)-12-hydroxyl nerolidol tetrahydropyranyl ethers is with the halide reagent effect, obtain hydroxyl by halogen ask for generation compound (E, E)-12-halo nerolidol tetrahydropyranyl ethers.Under low temperature and protection of inert gas, this halides and lithium diisopropyl amido selectivity are seized the isopropyl methyl reactive ketone of a proton, obtain (6E; 10E)-2,6,10; 14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10,15-triolefin-3-ketone.
4) (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10,15-triolefin-3-ketone with sodium borohydride reduction obtain (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10,15-triolefin-3-alcohol.
5) in the presence of alkali, (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10,15-triolefin-3-alcohol and SULPHURYL CHLORIDE or sulphonic acid anhydride reaction generation (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10, the sulphonate of 15-triolefin-3-alcohol.
6) under base catalysis, (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10, the sulphonate of 15-triolefin-3-alcohol takes place to eliminate reaction, obtain (E, E)-the geranyl linalool tetrahydropyranyl ethers.
7) (E, E)-geranyl linalool tetrahydropyranyl ethers deprotection in the alcohol of acid-salt or the aqueous solution, obtain (E, E)-geranyl linalool.
The present invention uses for reference Sharpless second step and has obtained (E with the trans methyl of tin anhydride and tertbutyl peroxide regioselectivity ground oxidation nerolidol, E)-Important Thought (J.Am.Chem.Soc.1977 of 12-hydroxyl nerolidol acetic ester, 99,5526), further research (Tetrahedron Lett.2001,42 (11): 2205-2208) have been done by this method Dickinson group.
The present invention the 3rd step, (Synthesis 1994,267-269) with reference to the synthetic method of the abundant woods of Lee group.
The present invention is at present synthetic (E, E)-geranyl linalool need be through requiring the isolating important technology innovation of extra high cis-trans-isomer to rectification process, the present invention seeks to the separation that synthetic route need not the process cis-trans-isomer, all ingredients is cheap and easy to get, reaction conditions is gentle, makes this synthetic method have suitability for industrialized production and is worth.
(E by synthetic method preparation disclosed by the invention; E)-geranyl linalool; can be used as intermediate, insect pheromone, spices of medicine and natural product or the like; particularly from (E; E)-geranyl linalool sets out only to be needed just can synthesize gastric mucosa protectant teprenone medicine through single step reaction, has important economic value.
Set forth the present invention in more detail in conjunction with the following examples, do not think that they limit the scope of the present invention.
Embodiment
Embodiment 1
1) (E)-nerolidol tetrahydropyranyl ethers synthetic
With (E)-nerolidol (20.0 grams, 90 mmoles) with tosic acid pyridinium salt (0.75 gram, 3 mmoles) join in the exsiccant methylene dichloride (90 milliliters), under agitation be added dropwise to dihydropyrane (10.10 grams, 120 mmoles), dropwise in room temperature continuation stirring and spend the night, pour separating funnel into, add the water concussion, leave standstill, tell organic phase, water merges organic phase, the organic phase anhydrous magnesium sulfate drying with methylene dichloride (60 milliliters) extraction three times, concentrating under reduced pressure removes and desolvates yield 97%.Infrared spectrum and nuclear magnetic spectrogram show that product structure is correct.
2) (E, E)-12-hydroxyl nerolidol tetrahydropyranyl ethers
With tin anhydride (0.666 gram, 6 mmoles) and 75% tertbutyl peroxide (7.2 the gram, 60 mmoles) be dissolved in 30 milliliters the methylene dichloride, slowly drip the dichloromethane solution (40 milliliters) of Geraniol tetrahydropyranyl ethers (15.3 grams, 50 mmoles), added afterreaction 5 hours, extract with the ether dilution then, the ether layer of merging is through saturated sodium bicarbonate solution, water and saturated common salt water washing, anhydrous magnesium sulfate drying, filter concentrating under reduced pressure.The oily liquid of gained gets colorless oil product (9.98 gram) and raw material (3.12 gram), productive rate 62% through column chromatography for separation.Infrared spectrum and nuclear magnetic spectrogram show that product structure is correct.
3) (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10,15-triolefin-3-ketone
(E, E)-12-hydroxyl nerolidol tetrahydropyranyl ethers (8.64 gram, 20 mmoles), triphenyl phosphorus (7.95 grams, 30 mmoles) and imidazoles (2.40 restrain 35 mmoles) are dissolved in 30 milliliters of acetonitriles and the 40 milliliters of ether.Ice-water bath and stirring add elemental iodine (8.90 grams, 35 mmoles) in batches in following 20 minutes.Remove ice-water bath after adding, continue to stir 3 hours,, filter with the ether dilution.Filtrate is used anhydrous magnesium sulfate drying with saturated sodium thiosulfate solution, copper-bath, water, saturated salt washing, filters.30 ℃ of following concentrating under reduced pressure remove and desolvate, and obtain that thick (E E)-12-iodo nerolidol tetrahydropyranyl ethers, need not to be further purified, and it is to be used directly to be dissolved in anhydrous tetrahydro furan.
2.0M the tetrahydrofuran solution of diisopropylamine (20 milliliters, 40 mmoles) is driven in tetrahydrofuran (THF) (10 milliliters) solution of the 3-methyl-2-butanone (3.30 grams, 38 mmoles) under cryosel bath and the stirring by syringe.After half an hour, add by syringe toward this solution for continuous that (E E)-tetrahydrofuran solution of 12-iodo nerolidol tetrahydropyranyl ethers, continues to keep 3 hours, intensifications of giving free rein to then, and stirring is spent the night under cryosel is bathed.Add saturated ammonium chloride solution (50 milliliters) cancellation reaction, stirred 20 minutes, then separatory, water merges organic phase and water, saturated salt washing successively, anhydrous magnesium sulfate drying with ether (100 milliliters) extraction four times, filter, concentrating under reduced pressure obtains oily liquid, makes the eluent column chromatography with sherwood oil and ethyl acetate and obtains colorless oil liquid (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10,15-triolefin-3-ketone, productive rate 76%.Infrared spectrum and nuclear magnetic spectrogram show that product structure is correct.
4) (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10,15-triolefin-3-alcohol
(6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10,15-triolefin-3-ketone (3.90 grams, 10 mmoles) be dissolved in 40 milliliters of anhydrous methanols, add sodium borohydride (0.57 gram, 15 mmoles) under 0 ℃, the thin-layer chromatography demonstration reacts completely in batches, add saturated ammonium chloride (3 milliliters) cancellation reaction, concentrating under reduced pressure is removed methyl alcohol, adds 10 ml waters, ethyl acetate (20 milliliters) extraction three times, the organic phase water, the saturated brine washing, anhydrous magnesium sulfate drying filters concentrating under reduced pressure, crude product gets colorless oil through column chromatography purification, productive rate 95%.Infrared spectrum and nuclear magnetic spectrogram show that product structure is correct.
5) (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10,15-triolefin-3-alcohol p-toluenesulfonic esters
(6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10,15-triolefin-3-alcohol, triethylamine are dissolved in the methylene dichloride, and the ice-water bath cooling adds Tosyl chloride down, and stirring is spent the night.The mixed liquid of reaction water, saturated nacl aqueous solution is successively washed, and anhydrous magnesium sulfate drying filters, and filtrate decompression concentrates, and obtains colorless oil, productive rate 97%.Infrared spectrum and nuclear magnetic spectrogram show that product structure is correct.This crude product is directly used in next step reaction.
6) (E, E)-the geranyl linalool tetrahydropyranyl ethers
Under the nitrogen protection; (6E; 10E)-2; 6; 10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10; the anhydrous dimethyl sulfoxide solution of 15-triolefin-3-alcohol p-toluenesulfonic esters slowly is added drop-wise in anhydrous dimethyl sulfoxide (20 milliliters) solution of 70 ℃ of potassium tert.-butoxides that stir fast down (3.36 grams, 30 mmoles).After being added dropwise to complete, continuing to remain on 70 ℃ and stirred 3 hours down.After the cooling, add 30 ml waters, mix solvent extraction three times with ethyl acetate and sherwood oil, merge organic phase and wash twice, saturated nacl aqueous solution successively with water and wash once, anhydrous magnesium sulfate drying filters, filtrate decompression concentrates, resulting oily liquid column chromatography purification obtains colorless oil liquid, productive rate 72%.Infrared spectrum and nuclear magnetic spectrogram show that product structure is correct.
7) (E, E)-geranyl linalool
With (E, E)-geranyl linalool tetrahydropyranyl ethers (1.50 grams, 4 mmoles) and tosic acid (0.02 the gram, 0.08 mmole) join in the exsiccant methyl alcohol (30 milliliters), stirred 5 hours in 55 ℃, the reaction of thin-layer chromatography tracing display is finished, steam and add entry behind the solvent and fully stir, with ethyl acetate extraction three times, merge organic phase, wash with saturated nacl aqueous solution, use anhydrous sodium sulfate drying, filter, make the short silica gel column chromatography separating purification of eluent, yield 92% with ethyl acetate and sherwood oil behind the concentrating under reduced pressure.Infrared spectrum and nuclear magnetic spectrogram show that product structure is correct, and consistent with standard spectrum.
Claims (8)
1. the synthetic method of a geranyl linalool is characterized in that synthesis step is as follows:
1) is raw material with (E)-nerolidol, under the catalysis of tosic acid pyridinium salt, protects hydroxyl, obtain (E)-nerolidol tetrahydropyranyl ethers with dihydropyrane;
2) (E)-the nerolidol tetrahydropyranyl ethers carries out the selectivity allylic oxidation with tin anhydride and tertbutyl peroxide to the trans methyl of (E)-nerolidol tetrahydropyranyl ethers, obtain the hydroxylated oxidation products of trans allylic (E, E)-12-hydroxyl nerolidol tetrahydropyranyl ethers;
3) (E, E)-12-hydroxyl nerolidol tetrahydropyranyl ethers is with the halide reagent effect, obtain hydroxyl by halogen substituted compounds (E, E)-12-halo nerolidol tetrahydropyranyl ethers; Under low temperature and protection of inert gas, this halides and lithium diisopropyl amido selectivity are seized the isopropyl methyl reactive ketone of a proton, obtain (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10,15-triolefin-3-ketone;
4) (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10,15-triolefin-3-ketone with sodium borohydride reduction obtain (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10,15-triolefin-3-alcohol;
5) in the presence of alkali, (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10,15-triolefin-3-alcohol and SULPHURYL CHLORIDE or sulphonic acid anhydride reaction generation (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10, the sulphonate of 15-triolefin-3-alcohol;
6) under base catalysis, (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10, the sulphonate of 15-triolefin-3-alcohol takes place to eliminate reaction, obtain (E, E)-the geranyl linalool tetrahydropyranyl ethers;
7) (E, E)-geranyl linalool tetrahydropyranyl ethers deprotection in the alcohol of acid-salt or the aqueous solution, obtain (E, E)-geranyl linalool.
2. a kind of (E according to claim 1, E)-synthetic method of geranyl linalool, it is characterized in that said allylic selective oxidation preparation (E, E)-12-hydroxyl nerolidol tetrahydropyranyl ethers, employed oxygenant is tin anhydride and tertbutyl peroxide, wherein the mol ratio of tin anhydride and tertbutyl peroxide is 1: 1～20, oxygenant with (E)-mol ratio of nerolidol tetrahydropyranyl ethers is 1～10: 1; Oxidizing reaction temperature-15～50 ℃, 1～48 hour time.
3. according to claim 1 a kind of (E, E)-synthetic method of geranyl linalool, it is characterized in that said (E, E)-12-halo nerolidol tetrahydropyranyl ethers, employed halide reagent is the mixture of triphenyl phosphorus/elemental iodine/imidazoles; Halide reagent with (E, E)-mol ratio of 12-hydroxyl nerolidol tetrahydropyranyl ethers is 0.5～3: 1.
4. a kind of (E according to claim 1, E)-synthetic method of geranyl linalool, it is characterized in that said lithium diisopropyl amido selectivity seizes a proton of isopropyl methyl ketone, then with halides reaction generate (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10,15-triolefin-3-ketone; This be reflected at that cryosel is bathed or lower temperature under carry out; Isopropyl methyl ketone, lithium diisopropyl amido and with (E, E)-mol ratio of 12-halo nerolidol tetrahydropyranyl ethers is 1: 1～1.5: 0.8～1; Employed solvent is an ether solvent.
5. according to claim 1 a kind of (E, E)-synthetic method of geranyl linalool, it is characterized in that said (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10,15-triolefin-3-ketone sodium borohydride reduction; Employed solvent is an alcoholic solvent.
It is 6. according to claim 1 that a kind of (E E)-synthetic method of geranyl linalool, is characterized in that said (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10,15-triolefin-3-alcohol reacts with SULPHURYL CHLORIDE in the presence of alkali, generate (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10, the sulphonate of 15-triolefin-3-alcohol; Employed alkali is organic bases; (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10, the mol ratio of 15-triolefin-3-alcohol, SULPHURYL CHLORIDE, alkali is 1: 1～1.5: 1～2.
7. a kind of (E according to claim 1, E)-synthetic method of geranyl linalool, it is characterized in that said in the presence of alkali, (6E, 10E)-2,6,10,14-tetramethyl--14-(tetrahydropyrans-2-base oxygen)-16-6,10, the sulphonate of 15-triolefin-3-alcohol takes place to eliminate reaction, obtain (E, E)-the geranyl linalool tetrahydropyranyl ethers; Employed alkali is potassium tert.-butoxide; Temperature of reaction is-20～200 ℃.
8. according to claim 1 a kind of (E, E)-synthetic method of geranyl linalool, it is characterized in that said (E, E)-geranyl linalool tetrahydropyranyl ethers deprotection; Acid is tosic acid; Solvent is an alcohol; Temperature of reaction is 0～100 ℃.
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| CN105732340A (en) * | 2016-04-15 | 2016-07-06 | 四川墨凯科技有限公司 | Process for synthesizing teprenone |
| CN108250055B (en) * | 2016-12-28 | 2022-08-05 | 重庆医药工业研究院有限责任公司 | Preparation method of pyruvylgeranyl pyrophosphate intermediate |
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| CN115322072A (en) * | 2022-09-14 | 2022-11-11 | 浙江世佳科技股份有限公司 | Method for preparing enol by taking 4-pyridinium methyl benzenesulfonate as catalyst for deprotection |
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