JPH0286786A - Production of 3(r)-hydroxybutyric acid ester - Google Patents
Production of 3(r)-hydroxybutyric acid esterInfo
- Publication number
- JPH0286786A JPH0286786A JP63238081A JP23808188A JPH0286786A JP H0286786 A JPH0286786 A JP H0286786A JP 63238081 A JP63238081 A JP 63238081A JP 23808188 A JP23808188 A JP 23808188A JP H0286786 A JPH0286786 A JP H0286786A
- Authority
- JP
- Japan
- Prior art keywords
- alcohol
- mixed solvent
- acid ester
- dichloromethane
- acid
- 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.)
- Granted
Links
- -1 3(r)-hydroxybutyric acid ester Chemical class 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012046 mixed solvent Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims abstract description 4
- 239000005015 poly(hydroxybutyrate) Substances 0.000 claims abstract description 4
- 230000001580 bacterial effect Effects 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 5
- 230000000813 microbial effect Effects 0.000 abstract description 3
- 241000252867 Cupriavidus metallidurans Species 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000588986 Alcaligenes Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 241000589151 Azotobacter Species 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SJZRECIVHVDYJC-UHFFFAOYSA-M 4-hydroxybutyrate Chemical compound OCCCC([O-])=O SJZRECIVHVDYJC-UHFFFAOYSA-M 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000017788 Cydonia oblonga Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000607568 Photobacterium Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000607598 Vibrio Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000012470 diluted sample Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-L diphosphate(2-) Chemical compound OP([O-])(=O)OP(O)([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- HHXMXAQDOUCLDN-RXMQYKEDSA-N penem Chemical compound S1C=CN2C(=O)C[C@H]21 HHXMXAQDOUCLDN-RXMQYKEDSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野１
本発明はポリヒドロキジブヂレート（以後、Ｐ Ｉ（Ｂ
と略記Ｊ−ろ）を蓄積する菌体を直接アルコリンスして
３（１Ｎ）−ヒドロキシ酪酸エステルを製造する方法に
関するものである。この３（Ｒ）−ヒト［！キシ酪酸エ
ステルは、不斉炭素骨格を持ち、ペネム系抗生物質の側
鎖や光学活性物質の合成中間体として、有用性の高い物
質である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field 1 The present invention relates to polyhydroxybutyrate (hereinafter, P I (B
This invention relates to a method for producing 3(1N)-hydroxybutyric acid ester by directly subjecting bacterial cells that accumulate J-ro) to alcohol. This 3(R)-human [! Xybutyric acid ester has an asymmetric carbon skeleton and is a highly useful substance as a side chain of penem antibiotics and as a synthetic intermediate for optically active substances.
例えば、Ｄ、５ｅｅｂａｃｈ、 Ｍ、Ｆ、Ｚｕｇｅｒ、
［Ｉｅｌｖ、Ｃｈｉｍ。For example, D,5eebach, M,F,Zuger,
[Ielv, Chim.
Ａｃｔａ、６５，４９５ （１９８２）には、（１）ま
Ｊ”１）ＩＩＢを蓄積ｒる菌体からＰ ＩＩ Ｉ（をり
ａ 〔１；ｌ；ルム等の溶媒で抽出し、次に抽出単離さ
れたＰ ｔｌ ｌｉを１．２−ジクロルエタン／アルコ
ール系溶媒中でアルコリンスして該エステルを得る方法
（以後、２段階法と略記４−る）や（２）Ｐ ＨＢを蓄
積した菌体を１．２−ジク［１ルエタン／アルコール溶
媒中に分散させ直接アルコリシス反応を行って該エステ
ルを得る方法（以後、！段階法と略記する）の２方法が
記載されている。Acta. Method for obtaining the ester by alcohol-rinsing isolated P tl li in 1,2-dichloroethane/alcohol solvent (hereinafter abbreviated as two-step method) and (2) Bacteria that accumulate P HB Two methods are described: a method in which the ester is obtained by dispersing the ester in a 1,2-dichloroethane/alcohol solvent and carrying out a direct alcoholysis reaction (hereinafter abbreviated as the ! step method).
［発明が解決しようとする課題］
しかしながら、Ｉ） ＩＩ １３を何機溶剤に溶解した
時は溶液の濃度上昇と共に増粘がおこりがちであるため
、前記２段階法の場合、ｈｂ出操作及びアルコリシスの
いずれの工程においても撹拌等の操作上の問題が起こり
易い欠点がある。しかも抽出効率が最終目的物の収率に
も多大の影響を及ぼす難点がある。[Problems to be Solved by the Invention] However, when I) II 13 is dissolved in a solvent, thickening tends to occur as the concentration of the solution increases. Both of these steps have the disadvantage that operational problems such as stirring are likely to occur. Moreover, there is a drawback that the extraction efficiency greatly affects the yield of the final target product.
これに対して、■段階法の場合は菌体から抽出されるＰ
Ｈ８は直ちにアルコリシスに供せられるため、系内に
Ｐ Ｉ−Ｉ Ｂが高濃度に蓄積されることがないので、
上記の操作」二の問題は殆ど避けられろという利点があ
り、工業的な実施には期待か多い方法と考えられろが、
従来かかる１段階法で３（Ｒ）−ヒドロキシ酪酸エステ
ルを製造する場合の収率は菌体重量に対して８０重量％
未満てあり、更なる改善が望まれるところである。On the other hand, in the case of the step method, the P extracted from the bacterial cells is
Since H8 is immediately subjected to alcoholysis, P I-I B does not accumulate in the system at a high concentration.
It has the advantage that the second problem in the above operation can be avoided for the most part, and is considered to be a promising method for industrial implementation.
Conventionally, when producing 3(R)-hydroxybutyric acid ester using this one-step method, the yield was 80% by weight based on the bacterial weight.
However, further improvement is desired.
［課題を解決するだめの手段Ｊ
本発明者らは、上記の如き問題点を解決するため鋭意研
究を重ねた結果、体積比が１．５〜ＩＯであるジクロル
メタン／アルコール系混合溶媒に、ポリヒドロキンブチ
レートを蓄積する菌体を懸濁し、酸又はアルカリの存在
下でアルコリシス反応を行う場合、３（Ｒ）−ヒドロキ
シ酪酸エステルが収率よく得られることを見出し、本発
明を完成するに至った。[Means for Solving the Problems J] As a result of extensive research in order to solve the above-mentioned problems, the inventors of the present invention added polyethylene to a dichloromethane/alcohol mixed solvent with a volume ratio of 1.5 to IO. It was discovered that 3(R)-hydroxybutyric acid ester can be obtained in good yield when the bacterial cells that accumulate hydroquine butyrate are suspended and the alcoholysis reaction is carried out in the presence of acid or alkali, and in order to complete the present invention. It's arrived.
本発明の特徴点は、上述した如く混合溶媒の１成分にジ
クロルメタンを用いる点にある。このジクロルメタンを
用いることにより、３（Ｉえ）−ヒドロキシ酪酸エステ
ルが好収率で得られるのである。The feature of the present invention is that dichloromethane is used as one component of the mixed solvent as described above. By using this dichloromethane, 3(I)-hydroxybutyric acid ester can be obtained in good yield.
本発明で使用される菌体としては、アルカリゲネス（Ａ
ｌｃａｌｉｇｅｎｅｓ） ｆｉｆ＋、アゾトバクタ−（
Ａｚｏｔｏｂａｃｔｅｒ）属、バチルス（Ｂａｃｉｌｌ
ｕｓ）属、ｌ：／ ：ｔ−トモナス（Ｐｓｃｕｄｏｍｏ
ｎａｓ ）属、ビブリオ（Ｖｉｂｒｉｏ）属、フィート
バクテリウム（Ｐｈｏｔｏｂａｃｔｅｒｉｕｍ）属等に
属するＩ） Ｉ目３をＨｚ ｈ’ｔ ４−ろ任αの菌体
でよく、具体的には、例えばアルカリゲネス ニート〔
！ファス（Ａｌｃａｌｉｇｅｎｅｓ ｅｕｔｒｏｐｈｕ
ｓ Ａ ’Ｉ’ ＣＣｌ ７６９９）のようなＰＩＩ
Ｂを高濃度に蓄積する菌体か好ましい。The bacterial cells used in the present invention include Alcaligenes (A
fif+, Azotobacter (
Azotobacter genus, Bacillus
us) genus, l:/:t-tomonas (Pscudomo
Bacterial cells belonging to the genus Nas), the genus Vibrio, the genus Photobacterium, etc. may be used, and specifically, for example, alcaligenes neat
! Alcaligenes eutrophu
s A 'I' CCl 7699)
Bacterial cells that accumulate B at a high concentration are preferred.
該菌体は、通常、残余の水分で加水分解を起こさないよ
うに、水分を５重量％以下まで乾燥して使用１４−るの
か好ましい。It is usually preferable that the bacterial cells be dried to a moisture content of 5% by weight or less before use, so as not to cause hydrolysis due to residual moisture.
本発明で用いるジクロルメタン／アルコ−ル系混合溶媒
におｔ、するアルコールとしては、メタノール、エタノ
ール、ｎ−プロパツール、イソプロパツール、！＋−ブ
タノール、イソブタノール、ｔｅｒｔ−ブタノール、ベ
ンノルアルコール、２−メトキシアルコール専任、きの
らのが使用できるが、炭素数１〜８のものが実用的であ
る。又、該混合溶媒において、ジクロルメタンとアルコ
ールの混合割合は、体積比で、アルコールｌに対してジ
クロルメタン１．５〜１０倍、好ましくは２．０〜７．
５倍の割合か適当である。ジクロルメタンが１５１＆未
満の場合には菌体より混合溶媒中に抽出されるＩ） Ｉ
Ｉ ｒ３の（ｎが低下し、又、１０倍を越えるとアルコ
ールの量が少なくなり過ぎてアルコリンス反応が起こり
にくいため、いずれら収率が低下する。Examples of alcohols included in the dichloromethane/alcohol mixed solvent used in the present invention include methanol, ethanol, n-propanol, and isopropanol. +-butanol, isobutanol, tert-butanol, benol alcohol, 2-methoxy alcohol, and quince can be used, but those having 1 to 8 carbon atoms are practical. In the mixed solvent, the mixing ratio of dichloromethane and alcohol is 1.5 to 10 times, preferably 2.0 to 7.
A ratio of 5 times is appropriate. If dichloromethane is less than 151&, it is extracted from the bacterial cells into the mixed solvent I) I
(n of Ir3 decreases, and if it exceeds 10 times, the amount of alcohol becomes too small and the alcohol reaction is difficult to occur, resulting in a decrease in yield.
本発明で使用される酸としては、（濃）硫酸、塩酸、硝
酸、パラトルエンスルホン酸等、無機、有機の任意の酸
が挙げられ、アルカリとしては、苛性ソーダ、苛性カリ
等が挙げられろ。Examples of the acid used in the present invention include any inorganic or organic acid such as (concentrated) sulfuric acid, hydrochloric acid, nitric acid, and para-toluenesulfonic acid, and examples of the alkali include caustic soda and caustic potash.
本発明の反応を実施するに当たっては、通常、上記混合
溶媒に、酸又はアルカリを約１〜５０ｇ／Ｑ添加し、粉
末状の１）り記乾燥菌体を、好ましくは２０〜２００９
７ρ程度分散さけ、撹拌下にアルコリンスが行われろ。In carrying out the reaction of the present invention, usually about 1 to 50 g/Q of acid or alkali is added to the above mixed solvent, and the powdered dried bacterial cells described in 1) are added, preferably 20 to 2,009 g/Q.
Alcohol rinse should be performed while stirring to avoid dispersion of about 7ρ.
この時、反応温度は７０−１５０℃、好ましくは８０〜
ｌｌＯ℃、又、反応時間は１〜ＩＯ時間、好ましくは３
〜５時間が適当である。反応終了後は加水して、ａ機層
に目的物を、水槽に酸又はアルカリ及び菌体由来物を移
行さＵ゛、汀機層を分取後、濃縮し、真空蒸留を行い、
対応する３（Ｒ）ヒドロキシ酪酸エステルを得る。At this time, the reaction temperature is 70-150°C, preferably 80-150°C.
110°C, and the reaction time is 1 to IO hours, preferably 3
~5 hours is appropriate. After the reaction is completed, water is added to transfer the target substance to the a-layer and the acid or alkali and bacterial cell-derived substances to the water tank. After separating the strainer layer, it is concentrated and vacuum distilled.
The corresponding 3(R) hydroxybutyric acid ester is obtained.
［作 用］
本発明は、Ｐ ＩＩ １３をｂ債−＝Ｉ−る菌体を直接
アルコリンス反応して３（１１）−ヒト〔ｌキノ酪酸エ
ステルを製貰する際に、溶剤としてノクルロルメタン／
アルコール系混合溶媒を用いろことにより収率か向−に
慣ろという長所を６丁する。[Function] The present invention is directed to the production of 3(11)-human [l-quinobutyric acid ester] by direct alcoholinase reaction of bacterial cells containing P II 13, using noclorolmethane/nochlormethane as a solvent.
Using an alcohol-based mixed solvent has the advantage of improving yields.
［実施例及び対照例］
以下、実施例及び対照例を挙げて本発明を更に具体的に
説明する。[Examples and Comparative Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例１
アルカリゲネス ニー１− ［７フアス（Ａｌｃａｌｉ
ｇｃｎｃｓ ｅｕｔｒｏｐｈｕｓ ＡＴＣＣＩ ７．
６９９ ）を下記培地に接種し、３０℃、９時間本培養
を行−）た。Example 1 Alcaligenes nee 1-[7huas (Alcali
gcncs eutrophus ATCCI 7.
699) was inoculated into the following medium and main culture was carried out at 30°C for 9 hours.
培地ニリン酸二水素カリウノ、（Ｋｌ＋２１’０４）
１９硫酸マグネシウム（ＭｇＳＯ＝・７１１２０）０．
５ｇ酵母エキス ０，１７
硫酸鉄（１１）（ＦｅＳＯ４・７ＨｚＯ） ０．０１
ｇ塩化アンモニウム（ＮＩｌ、ＣＩ） 総量４．８
９フラクトース 総ｒｎ ９０
ｇ水 Ｉｏ。Medium Kariuno dihydrogen diphosphate, (Kl+21'04)
19 Magnesium sulfate (MgSO=・71120) 0.
5g yeast extract 0.17 Iron sulfate (11) (FeSO4・7HzO) 0.01
g Ammonium chloride (NIl, CI) Total amount 4.8
9 fructose total rn 90
g water Io.
但し、塩化アンモニウムとフラクトースは逐次に添加し
た。However, ammonium chloride and fructose were added sequentially.
倍径後、遠心分離にて集菌し、生菌体を得た。この生菌
体を１０５°Ｃで静置乾燥し、水分を５重！Ｈｔ％以下
とし、粉砕して粉末乾燥菌体をｊすた。After double diameter, bacteria were collected by centrifugation to obtain viable bacterial cells. This live bacterial body is left to dry at 105°C, and the moisture is removed 5 times! Ht% or less, and pulverized the powdered dry bacterial cells.
次に、２ρ容オートクレーブにジク〔ノルメタン７５０
ｍ１とメタノール２５０ｍ１を混合した混合溶媒にａ硫
酸２７ｇを加え、更に」二記扮末乾燥菌体１５０７を添
加して、１０ （１’Ｃ１３，５時間撹拌下にアルクリ
シス反応を行・）だ。（内圧的５ ｋｇ／ ａｍ’ ）
。反応終了後、水５００ｍ１を加えて撹拌し、放置後
２層分離させた３゜何機層を分取後、濃縮し、真空蒸留
を行った。３．２ｍｍ１４ｇ、留出温度３８℃の留分を
捕集して、ａ（ｒＢヒドロキシ酪酪酸メルル得た。Next, put the diluted sample into a 2ρ volume autoclave [normethane 750].
Add 27 g of a-sulfuric acid to a mixed solvent of 250 ml of methanol and 250 ml of methanol, and further add dried microbial cells 1507, and perform the alchrysis reaction under stirring for 5 hours. (internal pressure 5 kg/am')
. After the reaction was completed, 500 ml of water was added, stirred, and allowed to stand. Two layers were separated, a 3° layer was collected, concentrated, and vacuum distilled. A fraction of 3.2 mm, 14 g, and a distillation temperature of 38° C. was collected to obtain a(rB merle hydroxybutyrate).
以上の結果を第１表に示した。The above results are shown in Table 1.
実施例２〜６．対照例１〜４
実施例Ｉにおいて第１表に示す条件にかえた以外は回倒
と同様の反応を行った。その結果ら併Ｕて第１表に示す
。Examples 2-6. Control Examples 1 to 4 The same reaction as in Example I except that the conditions were changed to those shown in Table 1 was carried out. The results are also shown in Table 1.
［効 果］
本発明においては反応溶剤にジクロルメタン／アルコー
ル系混合溶媒を用いることによって、Ｉ） ＩＩ Ｌ（
を蓄積する菌体から直接３（１？）−とド〔！キノ醋酸
エステルが収率良く得られ、産業上極めて４丁用な方法
である。[Effect] In the present invention, by using a dichloromethane/alcohol mixed solvent as a reaction solvent, I) II L(
3(1?)- and de[!] directly from the bacterial cells that accumulate . Quinoacetic acid ester can be obtained in good yield, and this method is extremely useful in industry.
特許出願人 口本合成化学工業株式会社手 続 補 正 走 臼Patent applicant: Kuchimoto Gosei Kagaku Kogyo Co., Ltd. Continued Supplementary Positive Run mortar
Claims (1)
系混合溶媒に、ポリヒドロキシブチレートを蓄積する菌
体を懸濁し、酸又はアルカリの存在下でアルコリンス反
応を行うことを特徴とする３（Ｒ）−ヒドロキシ酪酸エ
ステルの製造法。3 (characterized by suspending bacterial cells that accumulate polyhydroxybutyrate in a dichloromethane/alcohol mixed solvent having a volume ratio of 1.5 to 10 and carrying out an alcoholic reaction in the presence of an acid or an alkali) R)-Production method of hydroxybutyric acid ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63238081A JP2707117B2 (en) | 1988-09-21 | 1988-09-21 | Method for producing 3 (R) -hydroxybutyrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63238081A JP2707117B2 (en) | 1988-09-21 | 1988-09-21 | Method for producing 3 (R) -hydroxybutyrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0286786A true JPH0286786A (en) | 1990-03-27 |
| JP2707117B2 JP2707117B2 (en) | 1998-01-28 |
Family
ID=17024876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63238081A Expired - Fee Related JP2707117B2 (en) | 1988-09-21 | 1988-09-21 | Method for producing 3 (R) -hydroxybutyrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2707117B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100392711B1 (en) * | 1998-02-14 | 2003-10-22 | 주식회사 엘지생명과학 | Method for manufacturing alkyl(d)-3-hydroxybutyrate by decomposition of biopolymer |
-
1988
- 1988-09-21 JP JP63238081A patent/JP2707117B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100392711B1 (en) * | 1998-02-14 | 2003-10-22 | 주식회사 엘지생명과학 | Method for manufacturing alkyl(d)-3-hydroxybutyrate by decomposition of biopolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2707117B2 (en) | 1998-01-28 |
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