CN108484537A - A kind of preparation method of (R)-(+)-nonyl lactone and (S)-(-)-nonyl lactone - Google Patents
A kind of preparation method of (R)-(+)-nonyl lactone and (S)-(-)-nonyl lactone Download PDFInfo
- Publication number
- CN108484537A CN108484537A CN201810143535.2A CN201810143535A CN108484537A CN 108484537 A CN108484537 A CN 108484537A CN 201810143535 A CN201810143535 A CN 201810143535A CN 108484537 A CN108484537 A CN 108484537A
- Authority
- CN
- China
- Prior art keywords
- nonyl lactone
- added
- acid
- nonyl
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B57/00—Separation of optically-active compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods of (R) (+) γ nonalactones and (S) () γ nonalactones, include the following steps：（1）Racemic γ nonalactones are obtained into γ carboxylic acid aqueous solution of alkali metal salt with inorganic alkali solution open loop, organic solvent is then added, pH value is adjusted to faintly acid with inorganic acid, generation γ carboxylic acids is made to enter organic phase, separate organic phase drying；（2）(S) () α phenyl ethylamines or (R) (+) α phenyl ethylamines are added into obtained organic phase, the active γ carboxylic acids phenyl ethylamine salt of low optical is precipitated in crystallization；（3）Gained amine salt is added in resolution solvent, stirring and dissolving, inorganic acid is added in crystallization filtering, filter cake after being dissolved in water, be acidified after cyclization and (R) (+) γ decalactones or (S) () γ decalactones is obtained by extraction with organic solvent.Method for splitting operation using the present invention is easy, and can obtain two kinds of configuration chirality γ nonalactones, and aroma of pure is naturally, with easy to operate, mild condition, the advantage of high antimer excessive value.
Description
Technical field
The present invention relates to the preparation method of asymmetric lactone, specifically a kind of (R)-(+)-nonyl lactone and (S)-(-)-γ-
The preparation method of nonalactone.
Background technology
Nonyl lactone（4- amyl butyrolactone）Trade name arbricolin, be naturally occurring in beer, green tea, mango, apricot, strawberry,
In tomato, peach, passion fruit, barley, brandy, white wine, Rum.There are sweet tea, creamy, butter salted cake fried in sesame oil and strong coconut palm
Increment fragrance, tastes like fat sample.It is usually used in the allotment of food flavor, also can be used for perfumed soap, aromatizing agent, also serves as advanced makeup
The fragrance of product blending, while being also a kind of raw material of organic synthesis, it is one of kiloton kind rare in fragrance.
(R)-(+)-nonyl lactone has strong fragrant and sweet, soft coconut fragrant, the odor characteristic of the fat perfume with some milk,
Its specific rotatory power：[α]D 20=+51.8° （C=1.5 ~ 2.5, CH3OH）.And the fragrance ratio of (S)-(-)-nonyl lactone（R）Structure
Type isomers fragrance is weak, has fat perfume, musty, weak coconut perfume, specific rotatory power：[α]D 20=-51.6° （C=1.5 ~ 2.5,
CH3OH）.
Mostly using the racemic arbricolin of synthesis in present composition, fragrance fidelity is had a greatly reduced quality.Pursue naturally,
Advocate the natural modern times, the demand to asymmetric lactone with optical activation is a kind of trend of the times.
Currently, being compared to the method directly using chiral synthesis and biofermentation, list is prepared by the fractionation of racemic modification
One enantiomer is the industrial common and more economical method for obtaining chiral material.Japanese Soda Aroamtic Co., Ltd. is Japanese special
It has been delivered in sharp Patent Publication 2001-11063 and has split to obtain 4- (R)-(+)-using optically active (S)-(-)-α-phenylethylamine
The method of γ-decalactone, 4- (R)-(+)-gamma-undecalactone, 4- (R)-(+)-γ-dodecalactone.Like general fragrance in Shanghai
It is further split using (R)-(+)-α-phenylethylamine in state patent CN200510026464.0 and has successfully obtained 4- (S)-
(-)-γ-decalactone, 4- (S)-(-)-gamma-undecalactone, 4- (S)-(-)-γ-dodecalactone.Jingjiang Taida fragrance is in China
Patent CN201110327575.0 discloses a kind of hand of γ-dodecalactone based on (R)-(+)-α-phenylethylamine and double phosphine terpenes
Property method for splitting.Gamma lactone structure has similar place, and female ring is the same, but side chain lengths lengthen successively, and side chain is longer, splits
Easier, so γ-decalactone of side chain length, gamma-undecalactone, γ-dodecalactone, which is split, to be easy.It is non-below nonyl lactone
Normal difficulty is torn open, the fractionation of all not applicable nonyl lactone of the above method, and there has been no with racemic in existing open source literature
Nonyl lactone is the report that raw material prepares (R)-(+) -4- amyls butyrolactone and (S)-(-) -4- amyl butyrolactone using method for splitting
Road.
Invention content
To solve the above problems, the present invention provides a kind of system of (R)-(+)-nonyl lactone and (S)-(-)-nonyl lactone
Preparation Method, can obtain two kinds of configuration chirality nonyl lactones, and aroma of pure has easy to operate, mild condition, high antimer
The advantage of excessive value.
The technical solution adopted by the present invention is：A kind of preparation side of (R)-(+)-nonyl lactone and (S)-(-)-nonyl lactone
Method includes the following steps：
（1）Racemic nonyl lactone is obtained into γ-carboxylic acid aqueous solution of alkali metal salt with inorganic alkali solution open loop, is then added
Organic solvent adjusts pH value to faintly acid with inorganic acid, generation γ-carboxylic acid is made to enter organic phase, separates organic phase drying；
（2）To step（1）Optically active (S)-(-)-α-phenylethylamine is added in obtained organic phase, crystallization is precipitated low optical and lives
γ-carboxylic acid (S)-(-)-α-phenylethylamine salt of property（γ-carboxylic acid has two kinds of configurations of d-isomer and levo form, racemic Inner
Two kinds of configurations that ester is formed after γ-carboxylic acid all react to form amine salt with (S)-(-)-α-phenylethylamine, then crystallize precipitation
The amine salt amount of two kinds of configurations is similar, because referred to herein as low optical is active）；
（3）Gained amine salt is added in resolution solvent, stirring and dissolving, inorganic acid is added in crystallization filtering, filter cake after being dissolved in water, acid
(R)-(+)-nonyl lactone is obtained by extraction with organic solvent after change cyclization；（Levo form γ-carboxylic acid in mother liquor after crystallization
(S)-(-)-α-phenylethylamine salt holds advantage slightly, and can be acidified recycling, obtains (S)-(-)-nonyl lactone, enantiomeric excess value is not
Height can be used as and split (S)-(-)-nonyl lactone raw material, so it is to indicate to disregard recycling raw material partly to measure rate in embodiment
It calculates）；
（4）To step（1）Optically active (R)-(+)-α-phenylethylamine is added in obtained organic phase, crystallization is precipitated low optical and lives
γ-carboxylic acid (R)-(+)-α-phenylethylamine salt of property；
（5）Gained amine salt is added in resolution solvent, stirring and dissolving, inorganic acid is added in crystallization filtering, filter cake after being dissolved in water, acid
(S)-(-)-nonyl lactone is obtained by extraction with organic solvent after change cyclization；（D-isomer γ-carboxylic acid in mother liquor after crystallization
(R)-(+)-α-phenylethylamine salt holds advantage slightly, and can be acidified recycling, obtains (R)-(+)-nonyl lactone, enantiomeric excess value is not
Height can be used as and split (R)-(+)-nonyl lactone raw material）.
The step（1）In, inorganic base is sodium hydroxide or potassium hydroxide；Inorganic acid be sulfuric acid or hydrochloric acid, it is described weakly acidic
PH values are 5 ~ 6.
The step（2）In, the molar ratio of optically active (S)-(-)-α-phenylethylamine and racemic nonyl lactone is 0.9 ~
1.1:1；The step（4）In, the molar ratio of optically active (R)-(+)-α-phenylethylamine and racemic nonyl lactone is 0.9 ~
1.1:1, it is ensured that the nonyl lactone total overall reaction of required configuration.
The step（1）、（3）、（5）In, extraction solvent for use is petroleum ether, methyl tertiary butyl ether(MTBE), ethyl acetate, isopropyl acetate
The mixture of ester, dichloromethane or above-mentioned solvent, fractionation solvent for use are in methanol, ethyl alcohol, ethyl acetate, dichloromethane, water
At least one.
Preferably, the resolution solvent is the mixture of ethyl acetate and water, and the mass ratio of water and ethyl acetate is 2 ~ 6：100.
The step（3）And step（5）In, the mass ratio of amine salt and resolution solvent is 1:0.5~1:Between 6.
The step（3）And step（5）In, crystallization range is 0 DEG C ~ 50 DEG C, and the crystallization time is 2 ~ 8 hours, more conducively work
Industryization operates, and reduces production difficulty.
The beneficial effects of the invention are as follows：1, the method for the present invention is using first active γ-carboxylic acid (S)-(-)-α-of precipitation low optical
Phenyl ethylamine salt is not only smoothly split, but also recrystallization temperature is especially advantageous for industrial operation, usual factory substantially near room temperature
Low-temperature freezing facilities can only achieve -5 ~ -10 DEG C, reaches -15 ~ -30 DEG C of this low-temperature operations and wants particular arrangement, so this hair
Bright to be more advantageous to industrialization, general factory condition can be reached.2, method for splitting using the present invention operation is easy, can be with
Obtain two kinds of configuration chirality nonyl lactones, aroma of pure, with easy to operate, mild condition, high antimer excessive value it is excellent
Gesture.
Specific implementation mode
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, the embodiment
It is only used for explaining the present invention, be not intended to limit the scope of the present invention..
Embodiment one
（1）192g sodium hydroxides and 2000g water, stirring and dissolving are added in 5000ml there-necked flasks, continuously adds 500g racemics
Nonyl lactone, to 65 DEG C ~ 75 DEG C, insulation reaction to oil reservoir disappears warming-in-water, stops heating, is cooled to 20 DEG C, is added
1600g ethyl acetate, it is 50% sulfuric acid 320g that mass concentration, which is then added dropwise, adjusts pH value 5 ~ 6, and standing separates oil phase, and water phase is added
The extraction of 300g ethyl acetate is primary, merges organic phase, and the drying of 300g anhydrous sodium sulfates is added, racemic γ-hydroxyl is obtained by filtration
The ethyl acetate solution of acid；
（2）36 DEG C ~ 40 DEG C of temperature is controlled, (S)-is added dropwise into the ethyl acetate solution for the racemic γ-carboxylic acid being obtained by filtration
(-)-α-phenylethylamine 400g is added dropwise and continues to stir 0.5 h, cooling, -10 DEG C ~ 15 DEG C crystallization 8h, and filtering obtains filter cake
Active γ-carboxylic acid (S)-(-)-α-phenylethylamine salt of 780g, as low optical；
（3）Active γ-carboxylic acid (S)-(-)-α-phenylethylamine salt 150g of low optical is taken, ethyl acetate 750g and water 18g is added,
46 DEG C of dissolvings are heated to, then for slow cooling to 38 DEG C, crystalline amine salt is precipitated in heat preservation 6h（D-isomer γ-carboxylic acid s- phenyl ethylamines
Salt-mixture of the salt than levo form γ-carboxylic acid s- phenyl ethylamines salt dominances）Acetic acid is added in this crystalline amine salt filtered out in 70g
Ethyl ester 350g and water 8g is heated to 45 DEG C of dissolvings, then slow cooling to 39 DEG C, and heat preservation 3h is precipitated crystal（Mainly d-isomer γ-
Carboxylic acid s- phenyl ethylamine salt, levo form γ-carboxylic acid s- phenyl ethylamine salt are seldom）120g water, 48g is added in 33g, this crystal
Mass concentration is 50% sulfuric acid, and 90 DEG C are heated 30min, then are extracted with ethyl acetate, and gained oil phase is concentrated and dried to obtain product (R)-
17.1 g of (+)-nonyl lactone, chromatographic content 99.5%, optical activity [α]D 20=+48°（C=1.5 ~ 2.5, CH3OH）, partly measure
Rate 35.6%（Disregard recycling raw material nonyl lactone）, enantiomeric excess value 93.1%.
Embodiment two
（1）With embodiment one；
（2）With embodiment one；
（3）Active γ-carboxylic acid (S)-(-)-α-phenylethylamine salt 340g of low optical is taken, ethyl acetate 1000g and water is added
51g is heated to 60 DEG C of dissolvings, then slow cooling to the amine salt that+48 ° are added at 35 DEG C（The optical activity obtained in embodiment one
For the amine salt before+48 ° of (R)-(+)-nonyl lactone acidifications）As crystal seed, continues to be cooled to 32 DEG C, 400g is added in two batches
Ethyl acetate is cooled to 30 DEG C until 31 DEG C become more muddy, then add 100g ethyl acetate, keeps the temperature 2h, 124g is obtained by filtration
Amine salt, this amine salt rejoins ethyl acetate 600g and water 18g in 60 DEG C of dissolvings, then slow cooling, to 30 DEG C, heat preservation 4h is precipitated
Crystal obtains 60g, and 240g water is added in this crystal, 96g mass concentrations are 50% sulfuric acid, and 90 DEG C are heated 30min, then extracted with ethyl acetate
It takes, gained oil phase is concentrated and dried to obtain 31 g of product (R)-(+)-nonyl lactone, chromatographic content 99.4%, optical activity [α]D 20 =
+40°（C=1.5 ~ 2.5, CH3OH）, partly measure rate 28.4%（Disregard recycling raw material nonyl lactone）, enantiomeric excess value
77.2%。
Embodiment three
（1）68.9g sodium hydroxides and 875g water, stirring and dissolving are added in 2000ml there-necked flasks, continuously adds 175g racemics
Nonyl lactone, to 65 DEG C ~ 75 DEG C, insulation reaction to oil reservoir disappears warming-in-water, stops heating, is cooled to 20 DEG C, is added
700g ethyl acetate, it is 50% sulfuric acid 105g that mass concentration, which is then added dropwise, adjusts pH value 5 ~ 6, and standing separates oil phase, and water phase is added
The extraction of 175g ethyl acetate is primary, merges organic phase, and 200g saturated common salt water washing liquid separations are added；
（2）36 DEG C ~ 40 DEG C of temperature is controlled, (R)-(+)-α-phenylethylamine 140g is added dropwise to organic phase, is added dropwise and continues stirring 0.5
Hour, cooling, 10 DEG C of heat preservation 8h are precipitated crystal, and are filtered, are obtained filter cake 121g, the as active γ-carboxylic acid (R)-of low optical
(+)-α-phenylethylamine salt；
（3）Active γ-carboxylic acid (R)-(+)-α-phenylethylamine salt 20g of low optical is taken, ethyl acetate 100g and water 3.2g is added,
60 DEG C of dissolvings are heated to, then slow cooling is to 30 DEG C, and heat preservation 3h precipitates crystal to obtain 9.2g, this crystal rejoins ethyl acetate
150g and water 3g is heated to 60 DEG C of dissolvings, and slow cooling is to 35 DEG C, and heat preservation 2h precipitates crystal 3.4g, and 15g water is added in this crystal
It is 50% sulfuric acid with 6g mass concentrations, 90 DEG C of heating 30min, ethyl acetate extraction is dry to be concentrated to give product (S)-(-)-γ-nonyl
Lactone 1.7g, chromatographic content 99.3%, optical activity [α]D 20= -39°（C=1.5 ~ 2.5, CH3OH）, partly measure rate 11.8%（No
Meter recycling raw material nonyl lactone）, enantiomeric excess value 75.6%.
Example IV
（1）With embodiment three；
（2）With embodiment three；
（3）Active γ-carboxylic acid (R)-(+)-α-phenylethylamine salt 100g of low optical is taken, ethyl acetate 500g and water 15g is added,
60 DEG C of dissolvings are heated to, then slow cooling is to 25 DEG C, and heat preservation 4h precipitates crystal to obtain 41g, this crystal rejoins ethyl acetate
200g and water 6g is heated to 47 DEG C of dissolvings, and slow cooling degree (1 DEG C/h) is cooled to 35 DEG C, and heat preservation 3h precipitates crystal 20g, this is brilliant
80g water is added in body and 32g mass concentrations are 50% sulfuric acid, and 90 DEG C of heating 30min, ethyl acetate extraction is dry to be concentrated to give product
(S)-(-)-nonyl lactone 10.2g, chromatographic content 99.6%, optical activity [α]D 20= -43.9°（C=1.5 ~ 2.5, CH3OH）,
Partly measure rate 14.1%（Disregard recycling raw material nonyl lactone）, enantiomeric excess value 85.1%.
Claims (7)
1. a kind of preparation method of (R)-(+)-nonyl lactone and (S)-(-)-nonyl lactone, which is characterized in that including following
Step：
（1）Racemic nonyl lactone is obtained into γ-carboxylic acid aqueous solution of alkali metal salt with inorganic alkali solution open loop, is then added
Organic solvent adjusts pH value to faintly acid with inorganic acid, generation γ-carboxylic acid is made to enter organic phase, separates organic phase drying；
（2）To step（1）Optically active (S)-(-)-α-phenylethylamine is added in obtained organic phase, crystallization is precipitated low optical and lives
γ-carboxylic acid (S)-(-)-α-phenylethylamine salt of property；
（3）Gained amine salt is added in resolution solvent, stirring and dissolving, inorganic acid is added in crystallization filtering, filter cake after being dissolved in water, acid
(R)-(+)-nonyl lactone is obtained by extraction with organic solvent after change cyclization；
（4）To step（1）Optically active (R)-(+)-α-phenylethylamine is added in obtained organic phase, crystallization is precipitated low optical and lives
γ-carboxylic acid (R)-(+)-α-phenylethylamine salt of property；
（5）Gained amine salt is added in resolution solvent, stirring and dissolving, inorganic acid is added in crystallization filtering, filter cake after being dissolved in water, acid
(S)-(-)-nonyl lactone is obtained by extraction with organic solvent after change cyclization.
2. the preparation method of one kind (R)-(+)-nonyl lactone and (S)-(-)-nonyl lactone according to claim 1,
It is characterized in that, the step（1）In, inorganic base is sodium hydroxide or potassium hydroxide；Inorganic acid be sulfuric acid or hydrochloric acid, it is described weak
Acid PH values are 5 ~ 6.
3. the preparation method of one kind (R)-(+)-nonyl lactone and (S)-(-)-nonyl lactone according to claim 1,
It is characterized in that, the step（2）In, the molar ratio of optically active (S)-(-)-α-phenylethylamine and racemic nonyl lactone
It is 0.9 ~ 1.1:1；The step（4）In, the molar ratio of optically active (R)-(+)-α-phenylethylamine and racemic nonyl lactone
It is 0.9 ~ 1.1:1.
4. the preparation method of one kind (R)-(+)-nonyl lactone and (S)-(-)-nonyl lactone according to claim 1,
It is characterized in that, the step（1）、（3）、（5）In, extraction solvent for use be petroleum ether, methyl tertiary butyl ether(MTBE), ethyl acetate,
The mixture of isopropyl acetate, dichloromethane or above-mentioned solvent, resolution solvent be methanol, ethyl alcohol, ethyl acetate, dichloromethane,
At least one of water.
5. the preparation method of one kind (R)-(+)-nonyl lactone and (S)-(-)-nonyl lactone according to claim 4,
It is characterized in that, the resolution solvent is the mixture of ethyl acetate and water, the mass ratio of water and ethyl acetate is 2 ~ 6：100.
6. the preparation method of one kind (R)-(+)-nonyl lactone and (S)-(-)-nonyl lactone according to claim 4,
It is characterized in that, the step（3）And step（5）In, the mass ratio of amine salt and resolution solvent is 1:0.5~1:Between 6.
7. the preparation method of one kind (R)-(+)-nonyl lactone and (S)-(-)-nonyl lactone according to claim 1,
It is characterized in that, the step（3）And step（5）In, crystallization range is 0 DEG C ~ 50 DEG C, and the crystallization time is 2 ~ 8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810143535.2A CN108484537A (en) | 2018-02-12 | 2018-02-12 | A kind of preparation method of (R)-(+)-nonyl lactone and (S)-(-)-nonyl lactone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810143535.2A CN108484537A (en) | 2018-02-12 | 2018-02-12 | A kind of preparation method of (R)-(+)-nonyl lactone and (S)-(-)-nonyl lactone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108484537A true CN108484537A (en) | 2018-09-04 |
Family
ID=63340260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810143535.2A Pending CN108484537A (en) | 2018-02-12 | 2018-02-12 | A kind of preparation method of (R)-(+)-nonyl lactone and (S)-(-)-nonyl lactone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108484537A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400556A (en) * | 2018-12-29 | 2019-03-01 | 上海应用技术大学 | A kind of synthetic method of D- (-)-pantoic acid lactone |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5543502A (en) * | 1978-08-24 | 1980-03-27 | Konishiroku Photo Ind Co Ltd | Automatic film winding-up camera built-in with motor |
| JPH10251244A (en) * | 1997-03-11 | 1998-09-22 | Nippon Zeon Co Ltd | Production of delta-lactones of diastereomer hydroxycarboxylic acid amides |
| JP2001011063A (en) * | 1999-04-30 | 2001-01-16 | Soda Aromatic Co Ltd | Production of optically active gamma-lactone |
| CN103242169A (en) * | 2012-02-03 | 2013-08-14 | 爱普香料集团股份有限公司 | Recovery method for chiral amine resolution reagent |
-
2018
- 2018-02-12 CN CN201810143535.2A patent/CN108484537A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5543502A (en) * | 1978-08-24 | 1980-03-27 | Konishiroku Photo Ind Co Ltd | Automatic film winding-up camera built-in with motor |
| JPH10251244A (en) * | 1997-03-11 | 1998-09-22 | Nippon Zeon Co Ltd | Production of delta-lactones of diastereomer hydroxycarboxylic acid amides |
| JP2001011063A (en) * | 1999-04-30 | 2001-01-16 | Soda Aromatic Co Ltd | Production of optically active gamma-lactone |
| CN103242169A (en) * | 2012-02-03 | 2013-08-14 | 爱普香料集团股份有限公司 | Recovery method for chiral amine resolution reagent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400556A (en) * | 2018-12-29 | 2019-03-01 | 上海应用技术大学 | A kind of synthetic method of D- (-)-pantoic acid lactone |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110357853B (en) | Synthesis method of (R, S-) nicotine | |
| CN101440079B (en) | Process for the preparation of racemic citalopram and/or s- or r-citalopram | |
| JP2021527703A (en) | Bribalacetam intermediate, its manufacturing method and bribalacetam manufacturing method | |
| AU2003253120A1 (en) | A novel process for the manufacture of (+)-(s)-clopidogrel bisulfate form-i | |
| CN108484537A (en) | A kind of preparation method of (R)-(+)-nonyl lactone and (S)-(-)-nonyl lactone | |
| CN103288801B (en) | A kind of preparation method of high-purity esomeprazole sodium | |
| CN114213327A (en) | Synthesis method of (-) -huperzine A | |
| CN103864802A (en) | Preparation method of high-purity asenapine maleate | |
| KR102236806B1 (en) | Process for the preparation of enantiomerically enriched 3-aminopiperidine | |
| CN1872849B (en) | Method for synthesizing (S)(-)-gamma-lactone | |
| CN109369424A (en) | A kind of purification process of dapoxetine hydrochloride | |
| CN108314688B (en) | A kind of synthetic method of sitagliptin | |
| CN113880837A (en) | Preparation method of tadalafil | |
| KR20070024490A (en) | Process for the manufacture of lysergic acid | |
| EP1700851B1 (en) | Crystalline citalopram diol intermediate alkali | |
| CN108299346A (en) | A kind of preparation method of chirality γ-decalactone | |
| CA2408853C (en) | Process | |
| AU2009264395B2 (en) | Process for the preparation of clopidogrel hydrogen sulfate crystalline form I | |
| CN107108607A (en) | The method for preparing praziquantel | |
| CN102659639B (en) | Preparation technology of leonurine | |
| CN101715438A (en) | The method of stabilizing menthyl lactate | |
| CN103242117A (en) | Preparation method for (R)-(+)-gamma-lactone fragrance | |
| CN108069855B (en) | Method for recycling S-o-chloromandelic acid | |
| CN117447355B (en) | Preparation method of milbelin intermediate | |
| CN103242169A (en) | Recovery method for chiral amine resolution reagent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180904 |
|
| RJ01 | Rejection of invention patent application after publication |