CN101209968A - Improved synthesis method for tea caterpillar sex pheromone - Google Patents
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Abstract
The invention relates to an improved synthesis method for sex pheromone of euproctis pseudoconspersa, which is characterized in that 1, 7-heptanediol and 30-70 percent of hydrobromic acid solution react at the temperature of 50-130 DEG C and monobromide product 7-bromine-1-heptanol is obtained; the monobromide product 7-bromine-1-heptanol reacts with triphenyl phosphine in organic solvent I at the temperature of 50-130 DEG C, thus obtaining quaternary ammonium salt of triphenyl phosphine; with the function of organic base I or inorganic base, the obtained quaternary ammonium salt of triphenyl phosphine carries out Witting reaction with citral in organic solvent II and at the temperature of -20 DEG C-80 DEG C, and 10, 14-dimethyl-7, 9, 13-pentadec-1-triethylenic alcohols is produced; the triethylenic alcohols produced is reduced into 10, 14- dimethyl-1-pentadecanol in organic solvent III through catalysis and hydrogenation; finally, the 10, 14-dimethyl-1-pentadecanol obtained reacts with iso-butyryl chloride in the existence of the organic base II, so that 10, 14-dimethyl pentadec isobutyl is obtained. The invention has the advantages of easily obtained raw material, low cost, moderate reaction, suitability for scale production and high yield.
Description
Technical field
The present invention relates to a kind of synthetic method of Euproctis pseudoconspersa sex pheromone.
Background technology
Tealeaves has long plantation history in China, for many years, is one of important agricultural-food of China's foreign exchange earning always.Euproctis pseudoconspersa Euproctis pseudoconspersa (Strand) is one of primary pest in the tea growth process.It has caused grievous injury to the output and the quality of Tea Production.At present, the method for domestic this insect of control still depends on chemical pesticide.But the excessive use of chemical pesticide causes residual a large amount of agricultural chemicals in the tealeaves, has directly endangered the healthy of tealeaves human consumer, has also caused increasing dispute and financial loss in domain of international trade.Recently, European Union has increased substantially the examination criteria of pesticide residue in the tealeaves again, forces China Tea Production person to have to seek to use the insect protected new technology and the product of non-chemical pesticide.
Sex pheromone is a kind of highly sensitive, and safety non-toxic only at target pest, and does not does not kill and wound pest natural enemy and other beneficial insect and pest control product innovation free from environmental pollution.Before more than ten years, Japan [S.Wakamura, T.Yasuda, A.Ichikawa, T.Fukumoto, F.Mochizuki, Appl.Entomol.Zool.1994,29,403-411.] and China [C.H.Zhao, J.G.Millar, Z.Z.Wen, S.K.Wang, X.Y.Wang, Y.F.Zhu, Entomologia Sinica, 1996,3,58-69.] two research groups independently of one another isolation identification the main component of the sex pheromone that discharges of the female worm of Euproctis pseudoconspersa, its chemical structure is 10,14-dimethyl 15 carbon isobutyl esters.Nineteen ninety-five, people such as Ichikawa [A.Ichikawa, T.Yasuda, S.Wakamura, J.Chem.Ecol.1995,21,627-634.] have determined that the absolute configuration of C10 position methyl in this compound is the R configuration.Next year, this Japanology group [S.Wakamura, A.Ichikawa, T.Yasuda, N.Arakaki, T.Fukumoto, Appl.Entomol.Zool.1996,31,623-625.] report, the tentaculum electric potential (electroantennogram of Euproctis pseudoconspersa male worm, EAG) to (R)-10, the reaction of 14-dimethyl 15 carbon isobutyl esters is better than (S)-10,14-dimethyl 15 carbon isobutyl esters and racemization (racemic) 10,14-dimethyl 15 carbon isobutyl esters.
(R)-10,14-dimethyl 15 carbon isobutyl esters (S)-10,14-dimethyl 15 carbon isobutyl esters
Racemization 10,14-dimethyl 15 carbon isobutyl esters
People such as Ichikawa [A.Ichikawa, T.Yasuda, S.Wakamura, J.Chem.Ecol.1995,21,627-634.] be starting raw material with (S)-geraniol, through six-step process, synthesized about 21 milligrams of (R)-10,14-dimethyl 15 carbon isobutyl esters, overall yield is lower than 7%.Similarly, they are starting raw material with (R)-geraniol, have synthesized (S)-10,14-dimethyl 15 carbon isobutyl esters.People such as Zhao Chenghua [C.H.Zhao, J.G.Millar, K.H.Pan, C.S.Xu, J.Chem.Ecol.1998,24,1347-1353.] are key intermediate with (S)-lemongrass bromine, through six-step process, have synthesized (R)-10,14-dimethyl 15 carbon isobutyl esters.
But, Japanology group [S.Wakamura, A.Ichikawa, T.Yasuda, N.Arakaki, T.Fukumoto, Appl.Entomol.Zool.1996,31,623-625.] find, in field experiment, (R)-10,14-methyl 15 carbon isobutyl esters, (S)-10,14-dimethyl 15 carbon isobutyl esters and racemization 10,14-dimethyl 15 carbon isobutyl esters do not demonstrate difference, and they have same attractant effect to the Euproctis pseudoconspersa male worm.People such as Zhao Chenghua also find, (R)-10,14-dimethyl 15 carbon isobutyl esters and racemization 10,14-dimethyl 15 carbon isobutyl esters have the same worm ability that lures.Since it is so, with respect to (R)-10,14-dimethyl 15 carbon isobutyl esters, synthesising racemationization 10,14-dimethyl 15 carbon isobutyl esters should have significant practical value, because contain the raw material and the intermediate of chiral structure, price is all very expensive, causes the cost of chemosynthesis too high.For example, (S)-price of geraniol is 98 dollars (Aldrich prices) of 5 grams, (S)-price of lemongrass bromine is 155 dollars (Aldrich prices) of 25 grams.
People such as Fukumoto [T.Fukumoto, H.Suzuki, Jpn.Kodai Tokkyo Koho, JP08034752 (1996) .] react through twice grignard, have synthesized synthesising racemationization 10,14-dimethyl 15 carbon isobutyl esters.But the preparation of Grignard reagent and grignard reaction all require reaction conditions definitely anhydrous and anaerobic, for mass preparation production, have a lot of difficulties and restriction.People such as Zhao Chenghua are intermediate with the spiceleaf bromine, through six-step process, have synthesized racemization 10,14-dimethyl 15 carbon isobutyl esters.But they have also used harsh Grignard reagent and metallic copper lithium reagent on committed step.And, the price of spiceleaf bromine not cheap (98 dollars of 25 grams).
Summary of the invention
Technical problem to be solved by this invention provides that a kind of raw material is easy to get, with low cost, reaction temperature and, be fit to the improvement synthetic method of the higher Euproctis pseudoconspersa sex pheromone of scale production, productive rate.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of improvement synthetic method of Euproctis pseudoconspersa sex pheromone, it is characterized in that 1,7-heptanediol and mass concentration are that the hydrobromic acid aqueous solution of 30-70% reacts under 50 to 130 degree celsius temperature above freezing, have almost generated single brominated product 7-bromo-1-enanthol quantitatively; Single brominated product 7-bromo-1-enanthol and triphenyl phosphorus and react under 50 to 130 degree celsius temperature above freezing in organic solvent I, have obtained the triphenyl phosphorus quaternary ammonium salt; Under organic bases I or mineral alkali effect, resulting triphenyl phosphorus quaternary ammonium salt in organic solvent II, and subzero 20 degrees centigrade under 80 degree celsius temperature above freezing, with citral Wei Tige Wittig reaction taking place, generates 10,14-dimethyl-7,9,13-15 carbon-1-three enols; In the presence of catalyzer, through catalytic hydrogenation, normally under room temperature and normal pressure, three enols that generated are reduced to 10 in organic solvent II I, 14-dimethyl-1-pentadecanol; At last, in the presence of organic bases II, 10 of gained, 14-dimethyl-1-pentadecanol and isobutyl barefoot chlorine (isobutyrylchloride) effect normally at room temperature, obtain 10,14-dimethyl 15 carbon isobutyl esters.
Described 10,14-dimethyl-7,9,13-15 carbon-1-triolefin is pure and mild 10, and 14-dimethyl 15 carbon isobutyl esters need adopt column chromatographic isolation and purification.
Described hydrobromic acid aqueous solution concentration the best in quality is 48%.
Described organic solvent I adopts aromatic hydrocarbon, alkane, halogenated alkane, second cyanogen, ether, tetrahydrofuran (THF) or alcohol; But second cyanogen is proper.
Described organic bases I adopts potassium tert.-butoxide or sodium alkoxide.
Described mineral alkali adopts sodium amide, sodium hydride, sodium hydroxide or potassium hydroxide.
Described organic solvent II adopts aromatic hydrocarbon, alkane, halogenated alkane, second cyanogen, ether, tetrahydrofuran THF or alcohol, but tetrahydrofuran (THF) is proper.
Described Wei Tige Wittig react its temperature of reaction subzero 5 degrees centigrade to above freezing 30 degrees centigrade more suitable.
Described catalyzer adopts metallic nickel catalyzer, metal platinum catalyzer, metal palladium catalyst or Cu-Cr catalyst.
Described organic solvent II I adopts aromatic hydrocarbon, alkane, halogenated alkane, second cyanogen, ether, tetrahydrofuran (THF), ethyl acetate or alcohol.
Described organic bases II adopts triethylamine or arsenic pyridine.
Compared with prior art, the invention has the advantages that: the citral ($22/100g with cheap and easy to get, Aldrich) make key intermediate, with 1, the 7-heptanediol is a starting raw material, through the reaction of five steps, synthesized 10 of racemization smoothly, 14-dimethyl 15 carbon isobutyl esters, the overall yield of five steps reaction is 30-50%, thereby obtain following technique effect, 1, material is easy to get, cost is lower.Make key intermediate with citral cheap and easy to get first, reduced synthesis step.Other raw material and reagent are also more cheap.Like this, reduced by 10, the synthetic cost of 14-dimethyl 15 carbon isobutyl esters; 2, reaction conditions gentleness is fit to scale production.In whole synthesizing, avoided the use Grignard reagent, the reagent very harsh such as metallic copper lithium reagent and butyllithium to reaction conditions.Simultaneously, do not have special high temperature (more than 150 ℃) or special low temperature reaction conditionss such as (below 70 ℃) yet, be convenient to mass preparation production; 3, purifying is easy, and productive rate is higher.In the reaction of five steps, have only the product in the 3rd step and the 5th step to need column chromatographic isolation and purification.Use distillation under vacuum, might replace column chromatography for separation to come the purifying product in the 5th step.
Description of drawings
Fig. 1 is the reactions steps schematic flow sheet.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.
Examples of implementation 1
Step 1
In 500 milliliters of round-bottomed flasks, place 1,7-heptanediol (15 grams, 113 mmoles), toluene (analytical pure, 300 milliliters) and 48% hydrobromic acid aqueous solution (15.3 milliliters, 135.6 mmoles) (18-30 ℃), reaction mixture stirring and refluxing 28 hours.TLC analyzes demonstration, also has the part material unreacted.Add a spot of 48% hydrobromic acid aqueous solution again, continued stirring and refluxing 20 hours, disappear substantially until raw material.After reaction solution is chilled to room temperature, dilute with hexane.After organic phase is used saturated sodium bicarbonate aqueous solution and saturated common salt water washing respectively, anhydrous sodium sulfate drying.After removing solvent under reduced pressure, obtain 7-bromo-1-enanthol (22 grams, productive rate 99%).Products therefrom is enough pure, is directly used in next step reaction.
Step 2
In 200 milliliters of round-bottomed flasks, place 7-bromo-1-enanthol (19.5 grams, about 100 mmoles), triphenyl phosphorus (28.8 grams, 110 mmoles) and anhydrous second cyanogen (50 milliliters) (18-30 ℃), reaction mixture stirring and refluxing 24 hours under nitrogen protection.TLC analyzes demonstration, and raw material disappears substantially.After reaction solution is chilled to room temperature, remove solvent under reduced pressure.Gained residuum and anhydrous diethyl ether stir repeatedly, until a large amount of white depositions occurring.Behind the filtration under diminished pressure, vacuum-drying a few hours, promptly obtain triphenyl phosphorus bromination quaternary ammonium salt (43.5 grams, productive rate 95%).
Step 3
In 300 milliliters of round-bottomed flasks, place triphenyl phosphorus bromination quaternary ammonium salt (23 grams, 50 mmoles) and anhydrous tetrahydro furan (90 milliliters), after the ice-water bath cooling, to wherein dripping potassium tert.-butoxide tetrahydrofuran solution (100 milliliters, 100 mmoles).This mixture, cools off with ice-water bath after 1 hour once more in stirring at room.To the mixed solution that wherein drips citral (10.3 milliliters, 60 mmoles) and anhydrous tetrahydro furan (20 milliliters).Reaction mixture after 30 minutes, rises to room temperature 0 ℃ of stirring, continues to stir 1 hour, obtains the yellow suspension thing.With saturated ammonia chloride water solution termination reaction, mixture repeatedly extracts with hexane.After organic phase is used the saturated common salt water washing, anhydrous sodium sulfate drying.After removing solvent under reduced pressure, residuum is handled with hexane/ether, to remove most of triphenylphosphinc oxide.Crude product obtains 10 with quick silica gel column chromatography purifying (hexane/ethyl acetate system wash-out), 14-dimethyl-7,9,13-15 carbon-1-three enols (6.2 grams, productive rate 50%).
1H?NMR(300MHz，CDCl
3)：δ1.35-2.20(m，14H)，1.61(s，3H)，1.67(s，3H)，2.08(s，3H)，3.61(t，2H，J＝6.6Hz)，5.10(m，1H)，5.30(m，1H)，6.03-6.20(m，2H)；
13C?NMR(75MHz，CDCl
3)：δ25.86，25.89，26.90，27.03，27.60，27.66，29.28，29.90，32.94，40.48，63.14，120.14，124.33，124.96，130.06，131.79，138.71.
Step 4
In 200 milliliters of round-bottomed flasks, place 10,14-dimethyl-7,9,13-15 carbon-1-three enols (6 grams, 24 mmoles), hexane (80 milliliters) and 10% palladium-carbon catalyst (10%Pd/C) (0.7 gram) (18-30 ℃), catalytic hydrogenation 20 hours (TLC and GC monitoring reaction) under normal pressure.After filtering the removal solid catalyst, remove organic solvent under reduced pressure, obtain 10,14-dimethyl 15 carbon-1-alcohol (6.1 gram).Not purified, be directly used in next step reaction.
1H?NMR(300MHz，CDCl
3)：δ0.83(d，3H，J＝7.8Hz)，0.85(d，3H，J＝7.8Hz)，1.00-1.60(m，27H)，3.62(t，2H，J＝6.6Hz)；
13C?NMR(75MHz，CDCl
3)：δ19.91，22.83，22.92，25.01，25.96，27.29，28.19，29.67，29.85(2×C)，30.22，32.98，33.02，37.32，37.53，39.58，63.26.
Step 5
In 300 milliliters of round-bottomed flasks, place 10,14-dimethyl 15 carbon-1-alcohol (6.1 gram), anhydrous diethyl ether (150 milliliters) and anhydrous arsenic pyridine (4.24 milliliters, 52.4 mmoles).After the ice-water bath cooling, to wherein dripping isobutyryl chloride (3.76 milliliters, 35.7 mmoles).Reaction mixture after 30 minutes, rises to room temperature 0 ℃ of stirring, continues to stir 2 hours, obtains the white suspension thing.After filtering the removal white solid, filtrate is diluted with hexane.Organic phase is used saturated sodium bicarbonate aqueous solution respectively, diluted hydrochloric acid aqueous solution (0.01-2 mol), and after distilled water and the saturated common salt water washing, anhydrous sodium sulfate drying.After removing solvent under reduced pressure, crude product obtains 10 with quick silica gel column chromatography purifying (hexane/ethyl acetate system wash-out), 14-dimethyl 15 carbon isobutyl esters (5.5 grams, the overall yield of two-step reaction is 70%).
1H?NMR(300MHz，CDCl
3)：δ0.83(d，3H，J＝7.8Hz)，0.85(d，3H，J＝7.8Hz)，1.15(d，6H，J＝7.2Hz)，1.00-1.64(m，27H)，2.55(sept，1H，J＝6.9Hz)，4.04(t，2H，J＝6.6Hz)；
13C?NMR(75MHz，CDCl
3)：δ19.22(2×C)，19.92，22.83，22.92，25.01，26.12，27.28，28.19，28.87，29.47，29.74，29.81，30.19，32.97，34.26，37.31，37.53，39.58，64.61，177.45.
Examples of implementation 2
Step 1
In 500 milliliters of round-bottomed flasks, place 1,7-heptanediol (15 grams, 113 mmoles), toluene (300 milliliters) and 30% hydrobromic acid aqueous solution (15.3 milliliters, 84.5 mmoles) (18-30 ℃), reaction mixture stirring and refluxing 28 hours.TLC analyzes demonstration, also has the part material unreacted.Add a spot of 30% hydrobromic acid aqueous solution again, continued stirring and refluxing 20 hours, disappear substantially until raw material.After reaction solution is chilled to room temperature, dilute with hexane.After organic phase is used saturated sodium bicarbonate aqueous solution and saturated common salt water washing respectively, anhydrous sodium sulfate drying.After removing solvent under reduced pressure, obtain 7-bromo-1-enanthol (22 grams, productive rate 99%).Products therefrom is enough pure, is directly used in next step reaction.
Step 2
In 200 milliliters of round-bottomed flasks, place 7-bromo-1-enanthol (19.5 grams, about 100 mmoles), triphenyl phosphorus (28.8 grams, 110 mmoles) and anhydrous tetrahydro furan (50 milliliters) (18-30 ℃), reaction mixture stirring and refluxing 24 hours under nitrogen protection.TLC analyzes demonstration, and raw material disappears substantially.After reaction solution is chilled to room temperature, remove solvent under reduced pressure.Gained residuum and anhydrous diethyl ether stir repeatedly, until a large amount of white depositions occurring.Behind the filtration under diminished pressure, vacuum-drying a few hours, promptly obtain triphenyl phosphorus bromination quaternary ammonium salt (43.5 grams, productive rate 95%).
Step 3
In 300 milliliters of round-bottomed flasks, place triphenyl phosphorus bromination quaternary ammonium salt (23 grams, 50 mmoles) and anhydrous second cyanogen (90 milliliters), after the ice-water bath cooling, to wherein dripping the anhydrous second cyanogen of potassium tert.-butoxide solution (100 milliliters, 100 mmoles).This mixture, cools off with ice-water bath after 1 hour once more in stirring at room.To the mixed solution that wherein drips citral (10.3 milliliters, 60 mmoles) and anhydrous second cyanogen (20 milliliters).Reaction mixture after 30 minutes, rises to room temperature 0 ℃ of stirring, continues to stir 1 hour, obtains the yellow suspension thing.With saturated ammonia chloride water solution termination reaction, mixture repeatedly extracts with hexane.After organic phase is used the saturated common salt water washing, anhydrous sodium sulfate drying.After removing solvent under reduced pressure, residuum is handled with hexane/ether, to remove most of triphenylphosphinc oxide.Crude product obtains 10 with quick silica gel column chromatography purifying (hexane/ethyl acetate system wash-out), 14-dimethyl-7,9,13-15 carbon-1-three enols (6.2 grams, productive rate 50%).
1H?NMR(300MHz，CDCl
3)：δ1.35-2.20(m，14H)，1.61(s，3H)，1.67(s，3H)，2.08(s，3H)，3.61(t，2H，J＝6.6Hz)，5.10(m，1H)，5.30(m，1H)，6.03-6.20(m，2H)；
13C?NMR(75MHz，CDCl
3)：δ25.86，25.89，26.90，27.03，27.60，27.66，29.28，29.90，32.94，40.48，63.14，120.14，124.33，124.96，130.06，131.79，138.71.
Step 4
In 200 milliliters of round-bottomed flasks, place 10,14-dimethyl-7,9,13-15 carbon-1-three enols (6 grams, 24 mmoles), hexane (80 milliliters) and 10% nickel C catalyst (10%Ni/C) (0.7 gram) (15-30 ℃), catalytic hydrogenation 20 hours (TLC and GC monitoring reaction) under normal pressure.After filtering the removal solid catalyst, remove organic solvent under reduced pressure, obtain 10,14-dimethyl 15 carbon-1-alcohol (6.1 gram).Not purified, be directly used in next step reaction.
1H?NMR(300MHz，CDCl
3)：δ0.83(d，3H，J＝7.8Hz)，0.85(d，3H，J＝7.8Hz)，1.00-1.60(m，27H)，3.62(t，2H，J＝6.6Hz)；
13C?NMR(75MHz，CDCl
3)：δ19.91，22.83，22.92，25.01，25.96，27.29，28.19，29.67，29.85(2×C)，30.22，32.98，33.02，37.32，37.53，39.58，63.26.
Step 5
In 300 milliliters of round-bottomed flasks, place 10,14-dimethyl 15 carbon-1-alcohol (6.1 gram), anhydrous diethyl ether (150 milliliters) and anhydrous arsenic pyridine (4.24 milliliters, 52.4 mmoles).After the ice-water bath cooling, to wherein dripping isobutyryl chloride (3.76 milliliters, 35.7 mmoles).Reaction mixture after 30 minutes, rises to room temperature 0 ℃ of stirring, continues to stir 2 hours, obtains the white suspension thing.After filtering the removal white solid, filtrate is diluted with hexane.Organic phase is used saturated sodium bicarbonate aqueous solution respectively, diluted hydrochloric acid aqueous solution (0.01-2 mol), and after water and the saturated common salt water washing, anhydrous sodium sulfate drying.After removing solvent under reduced pressure, crude product obtains 10 with quick silica gel column chromatography purifying (hexane/ethyl acetate system wash-out), 14-dimethyl 15 carbon isobutyl esters (5.5 grams, the overall yield of two-step reaction is 70%).
1H?NMR(300MHz，CDCl
3)：δ0.83(d，3H，J＝7.8Hz)，0.85(d，3H，J＝7.8Hz)，1.15(d，6H，J＝7.2Hz)，1.00-1.64(m，27H)，2.55(sept，1H，J＝6.9Hz)，4.04(t，2H，J＝6.6Hz)；
13C?NMR(75MHz，CDCl
3)：δ19.22(2×C)，19.92，22.83，22.92，25.01，26.12，27.28，28.19，28.87，29.47，29.74，29.81，30.19，32.97，34.26，37.31，37.53，39.58，64.61，177.45.
Examples of implementation 3
Step 1
In 500 milliliters of round-bottomed flasks, place 1,7-heptanediol (15 grams, 113 mmoles), toluene (300 milliliters) and 70% hydrobromic acid aqueous solution (15.3 milliliters, 197.3 mmoles) (18-30 ℃), reaction mixture stirring and refluxing 28 hours.TLC analyzes demonstration, also has the part material unreacted.Add a spot of 70% hydrobromic acid aqueous solution again, continued stirring and refluxing 20 hours, disappear substantially until raw material.After reaction solution is chilled to room temperature, dilute with hexane.After organic phase is used saturated sodium bicarbonate aqueous solution and saturated common salt water washing respectively, anhydrous sodium sulfate drying.After removing solvent under reduced pressure, obtain 7-bromo-1-enanthol (22 grams, productive rate 99%).Products therefrom is enough pure, is directly used in next step reaction.
Step 2
In 200 milliliters of round-bottomed flasks, place 7-bromo-1-enanthol (19.5 grams, about 100 mmoles), triphenyl phosphorus (28.8 grams, 110 mmoles) and ether (50 milliliters) (18-30 ℃), reaction mixture stirring and refluxing 24 hours under nitrogen protection.TLC analyzes demonstration, and raw material disappears substantially.After reaction solution is chilled to room temperature, remove solvent under reduced pressure.Gained residuum and anhydrous diethyl ether stir repeatedly, until a large amount of white depositions occurring.Behind the filtration under diminished pressure, vacuum-drying a few hours, promptly obtain triphenyl phosphorus bromination quaternary ammonium salt (43.5 grams, productive rate 95%).
Step 3
In 300 milliliters of round-bottomed flasks, place triphenyl phosphorus bromination quaternary ammonium salt (23 grams, 50 mmoles) and ether (90 milliliters), after the ice-water bath cooling, to wherein dripping potassium tert.-butoxide diethyl ether solution (100 milliliters, 100 mmoles).This mixture, cools off with ice-water bath after 1 hour once more in stirring at room.To the mixed solution that wherein drips citral (10.3 milliliters, 60 mmoles) and ether (20 milliliters).Reaction mixture after 30 minutes, rises to room temperature 0 ℃ of stirring, continues to stir 1 hour, obtains the yellow suspension thing.With saturated ammonia chloride water solution termination reaction, mixture repeatedly extracts with hexane.After organic phase is used the saturated common salt water washing, anhydrous sodium sulfate drying.After removing solvent under reduced pressure, residuum is handled with hexane/ether, to remove most of triphenylphosphinc oxide.Crude product obtains 10 with quick silica gel column chromatography purifying (hexane/ethyl acetate system wash-out), 14-dimethyl-7,9,13-15 carbon-1-three enols (6.2 grams, productive rate 50%).
1H?NMR(300MHz，CDCl
3)：δ1.35-2.20(m，14H)，1.61(s，3H)，1.67(s，3H)，2.08(s，3H)，3.61(t，2H，J＝6.6Hz)，5.10(m，1H)，5.30(m，1H)，6.03-6.20(m，2H)；
13C?NMR(75MHz，CDCl
3)：δ25.86，25.89，26.90，27.03，27.60，27.66，29.28，29.90，32.94，40.48，63.14，120.14，124.33，124.96，130.06，131.79，138.71.
Step 4
In 200 milliliters of round-bottomed flasks, place 10,14-dimethyl-7,9,13-15 carbon-1-three enols (6 grams, 24 mmoles), hexane (80 milliliters) and 10% platinum C catalyst (10%Pt/C) (0.7 gram) (18-30 ℃), catalytic hydrogenation 20 hours (TLC and GC monitoring reaction) under normal pressure.After filtering the removal solid catalyst, remove organic solvent under reduced pressure, obtain 10,14-dimethyl 15 carbon-1-alcohol (6.1 gram).Not purified, be directly used in next step reaction.
1H?NMR(300MHz，CDCl
3)：δ0.83(d，3H，J＝7.8Hz)，0.85(d，3H，J＝7.8Hz)，1.00-1.60(m，27H)，3.62(t，2H，J＝6.6Hz)；
13C?NMR(75MHz，CDCl
3)：δ19.91，22.83，22.92，25.01，25.96，27.29，28.19，29.67，29.85(2×C)，30.22，32.98，33.02，37.32，37.53，39.58，63.26.
Step 5
In 300 milliliters of round-bottomed flasks, place 10,14-dimethyl 15 carbon-1-alcohol (6.1 gram), anhydrous diethyl ether (150 milliliters) and anhydrous arsenic pyridine (4.24 milliliters, 52.4 mmoles).After the ice-water bath cooling, to wherein dripping isobutyryl chloride (3.76 milliliters, 35.7 mmoles).Reaction mixture after 30 minutes, rises to room temperature 0 ℃ of stirring, continues to stir 2 hours, obtains the white suspension thing.After filtering the removal white solid, filtrate is diluted with hexane.Organic phase is used saturated sodium bicarbonate aqueous solution respectively, diluted hydrochloric acid aqueous solution (0.01-2 mol),, after water and the saturated common salt water washing, anhydrous sodium sulfate drying.After removing solvent under reduced pressure, crude product obtains 10 with quick silica gel column chromatography purifying (hexane/ethyl acetate system wash-out), 14-dimethyl 15 carbon isobutyl esters (5.5 grams, the overall yield of two-step reaction is 70%).
1H?NMR(300MHz，CDCl
3)：δ0.83(d，3H，J＝7.8Hz)，0.85(d，3H，J＝7.8Hz)，1.15(d，6H，J＝7.2Hz)，1.00-1.64(m，27H)，2.55(sept，1H，J＝6.9Hz)，4.04(t，2H，J＝6.6Hz)；
13C?NMR(75MHz，CDCl
3)：δ19.22(2×C)，19.92，22.83，22.92，25.01，26.12，27.28，28.19，28.87，29.47，29.74，29.81，30.19，32.97，34.26，37.31，37.53，39.58，64.61，177.45.
The field lures the worm test-results
We have synthesized (R)-10 according to people such as Zhao Chenghua [5] reported method, 14-dimethyl 15 carbon isobutyl esters, so that compare it and the racemization 10 that obtains according to our novel synthesis, the field of 14-dimethyl 15 carbon isobutyl esters lures the worm effect.In tea place, Ningbo and Shaoxing area, our simultaneous test both in the field to the trap effect of Euproctis pseudoconspersa male worm.Test-results shows that they have same attracting ability.
Claims (11)
1. the improvement synthetic method of an Euproctis pseudoconspersa sex pheromone is characterized in that 1, and 7-heptanediol and mass concentration are that the hydrobromic acid aqueous solution of 30-70% reacts under 50 to 130 degree celsius temperature above freezing, have generated single brominated product 7-bromo-1-enanthol; Single brominated product 7-bromo-1-enanthol and triphenyl phosphorus and react under 50 to 130 degree celsius temperature above freezing in organic solvent I, have obtained the triphenyl phosphorus quaternary ammonium salt; Under organic bases I or mineral alkali effect, resulting triphenyl phosphorus quaternary ammonium salt in organic solvent II, and subzero 20 degrees centigrade under 80 degree celsius temperature above freezing, with citral Wei Tige Wittig reaction taking place, generates 10,14-dimethyl-7,9,13-15 carbon-1-three enols; In the presence of catalyzer, through catalytic hydrogenation, three enols that generated are reduced to 10 in organic solvent II I, 14-dimethyl-1-pentadecanol; At last, in the presence of organic bases II, 10 of gained, 14-dimethyl 15 carbon-1-alcohol and isobutyryl chloride effect obtains 10,14-dimethyl 15 carbon isobutyl esters.
2. improvement synthetic method according to claim 1, it is characterized in that described 10,14-dimethyl-7,9,13-15 carbon-1-triolefin is pure and mild 10,14-dimethyl 15 carbon isobutyl esters need adopt column chromatographic isolation and purification.
3. improvement synthetic method according to claim 1 and 2 is characterized in that described hydrobromic acid aqueous solution mass concentration is 48%.
4. improvement synthetic method according to claim 1 and 2 is characterized in that described organic solvent I adopts aromatic hydrocarbon, alkane, halogenated alkane, second cyanogen, ether, tetrahydrofuran (THF) or alcohol.
5. improvement synthetic method according to claim 1 and 2 is characterized in that described organic bases I adopts potassium tert.-butoxide or sodium alkoxide.
6. improvement synthetic method according to claim 1 and 2 is characterized in that described mineral alkali adopts sodium amide, sodium hydride, sodium hydroxide or potassium hydroxide.
7. improvement synthetic method according to claim 1 and 2 is characterized in that described organic solvent II adopts aromatic hydrocarbon, alkane, halogenated alkane, second cyanogen, ether, tetrahydrofuran THF or alcohol.
8. improvement synthetic method according to claim 1 and 2 is characterized in that described Wei Tige Wittig reacts subzero 5 degrees centigrade to 30 degrees centigrade above freezing of its temperature of reaction.
9. improvement synthetic method according to claim 1 and 2 is characterized in that described catalyzer adopts metallic nickel catalyzer, metal platinum catalyzer, metal palladium catalyst or Cu-Cr catalyst.
10. improvement synthetic method according to claim 1 and 2 is characterized in that described organic solvent II I adopts aromatic hydrocarbon, alkane, halogenated alkane, second cyanogen, ether, tetrahydrofuran (THF), ethyl acetate or alcohol.
11. improvement synthetic method according to claim 1 and 2 is characterized in that described organic bases II adopts triethylamine or arsenic pyridine.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106946700A (en) * | 2017-04-17 | 2017-07-14 | 西北农林科技大学 | The synthetic method of tea caterpillar sex pheromone and its application |
| CN110724042A (en) * | 2019-12-09 | 2020-01-24 | 中国林业科学研究院森林生态环境与保护研究所 | Method for synthesizing sex pheromone active ingredient of populus canula |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106946700A (en) * | 2017-04-17 | 2017-07-14 | 西北农林科技大学 | The synthetic method of tea caterpillar sex pheromone and its application |
| CN106946700B (en) * | 2017-04-17 | 2019-06-07 | 西北农林科技大学 | The synthetic method and its application of tea caterpillar sex pheromone |
| CN110724042A (en) * | 2019-12-09 | 2020-01-24 | 中国林业科学研究院森林生态环境与保护研究所 | Method for synthesizing sex pheromone active ingredient of populus canula |
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