JPH0413653A - Production of alpha-amino-beta-hydroxyvaleric acid - Google Patents
Production of alpha-amino-beta-hydroxyvaleric acidInfo
- Publication number
- JPH0413653A JPH0413653A JP11811690A JP11811690A JPH0413653A JP H0413653 A JPH0413653 A JP H0413653A JP 11811690 A JP11811690 A JP 11811690A JP 11811690 A JP11811690 A JP 11811690A JP H0413653 A JPH0413653 A JP H0413653A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- oxazoline
- alkali
- reaction
- ring
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- LGVJIYCMHMKTPB-UHFFFAOYSA-N 3-hydroxynorvaline Chemical compound CCC(O)C(N)C(O)=O LGVJIYCMHMKTPB-UHFFFAOYSA-N 0.000 title claims description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 15
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004473 Threonine Substances 0.000 abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000012948 isocyanate Substances 0.000 abstract description 4
- 150000002513 isocyanates Chemical class 0.000 abstract description 4
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 abstract description 3
- 238000009395 breeding Methods 0.000 abstract description 3
- 230000001488 breeding effect Effects 0.000 abstract description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 24
- 239000006227 byproduct Substances 0.000 description 14
- 239000004471 Glycine Substances 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229960001019 oxacillin Drugs 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OLEDFVABXXJJJP-MUWMCQJSSA-N (2S,3R)-2-amino-3-hydroxybutanoic acid butanoic acid Chemical compound C(CCC)(=O)O.N[C@@H]([C@H](O)C)C(=O)O OLEDFVABXXJJJP-MUWMCQJSSA-N 0.000 description 1
- MUVQIIBPDFTEKM-IUYQGCFVSA-N (2r,3s)-2-aminobutane-1,3-diol Chemical compound C[C@H](O)[C@H](N)CO MUVQIIBPDFTEKM-IUYQGCFVSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、スレオニン生産活性が高い菌株を育種するた
めに有用なα−アミノ−β−ヒドロキシ吉草酸の製造法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing α-amino-β-hydroxyvaleric acid, which is useful for breeding strains with high threonine-producing activity.
［従来の技術］
α−アミノ−β−ヒドロキシ吉草酸（以下ＡＨＶと略す
る）は、スレオニン生産活性が高い菌株を育種するため
の薬剤として有用である。[Prior Art] α-amino-β-hydroxyvaleric acid (hereinafter abbreviated as AHV) is useful as a drug for breeding bacterial strains with high threonine production activity.
即ち、ＡＨＶを加えた寒天培地で菌を増殖させると、ス
レオニン生産活性が高い菌株を得ることができる。That is, by growing the bacteria on an agar medium containing AHV, a strain with high threonine production activity can be obtained.
上記のＡＨＶ製造法としては殆ど文献はなく、例えばＮ
−ビリビリデングリンネート銅永和物とプロピオンアル
デヒドをナトリウムメトキンド触媒の存在下で反応させ
る方法（ＢｕＬ’Ｌ、ＣＨＥＭ、Ｓｏｃ、Ｊａｐ、 、
４７（５）、 １２９５（１９７４） ）か示されてい
る。There is almost no literature on the above AHV manufacturing method, for example, N
- A method for reacting bilibylidene grinnate copper ethosate with propionaldehyde in the presence of a sodium Metkind catalyst (BuL'L, CHEM, Soc, Jap,
47(5), 1295 (1974)).
又、Ａ）ＩＶと直接関連はしないがＡＨＶの類縁化合物
として、イソシアネートとアセトアルデヒドを反応させ
、５−メチル−４−アルコキンカルボニル−２−オキサ
シリンを得、これを室温においてオキサゾリン開環反応
させ、α−アミノ−β−ヒドロキン酪酸（スレオニン）
を製造する方法（Ａｇｒ、Ｂｉｏｌ、Ｃｈｅｍ、 、
４０．２０４５（１９７６） ）か示されている。Also, A) as a compound analogous to AHV but not directly related to IV, isocyanate and acetaldehyde are reacted to obtain 5-methyl-4-alcokynecarbonyl-2-oxacillin, which is subjected to an oxazoline ring-opening reaction at room temperature; α-amino-β-hydroquine butyric acid (threonine)
(Agr, Biol, Chem, ,
40.2045 (1976)).
［発明が解決しようとする課題］
しかし、従来の方法では副生成物としてグリシジが１０
％も混在する欠点がある。Ａ）ＩＶ中にグリシジが混入
するとスレオニン生産活性の高い菌の増殖が抑えられ、
スレオニン生産性が格段に落ちてしまった菌しか得られ
ないのである。[Problem to be solved by the invention] However, in the conventional method, glycidium is produced as a by-product.
% also has the disadvantage of being mixed. A) When glycidi is mixed into IV, the growth of bacteria with high threonine production activity is suppressed,
Only bacteria with significantly reduced threonine productivity can be obtained.
このためグリシンの副生のないＡＨＶの製造方法の開発
が要求されるのである。Therefore, there is a need to develop a method for producing AHV that does not produce glycine as a by-product.
［課題を解決するための手段］
そこで、本発明者は上記の課題を解決するために鋭意研
究を行った結果、５−エチル−４−アルコキシカルボニ
ル−２−オキサゾリンを酸又はアルカリによりオキサゾ
リン開環反応を行い、ＡＨＶを製造する際に、反応温度
を０−１０℃に保つことにより、グリシンの副生をほぼ
完全に抑えることが出来ることを見出し、本発明を完成
するに至った。[Means for Solving the Problems] Therefore, as a result of intensive research in order to solve the above problems, the present inventors conducted oxazoline ring-opening of 5-ethyl-4-alkoxycarbonyl-2-oxazoline with acid or alkali. The present inventors have discovered that the by-product of glycine can be almost completely suppressed by maintaining the reaction temperature at 0 to 10° C. during the reaction to produce AHV, and have completed the present invention.
本発明の合成法の特徴は、５−エチル−４−アルコキシ
カルボニル−２−オキサシリン（以下単にオキサゾリン
と略す）の開環温度を０〜ｌθ℃に保つという点である
。このことによりグリシンの副生を抑えることができる
のである。A feature of the synthesis method of the present invention is that the ring-opening temperature of 5-ethyl-4-alkoxycarbonyl-2-oxacillin (hereinafter simply referred to as oxazoline) is maintained at 0 to 1θ°C. This makes it possible to suppress the by-product of glycine.
以下、本発明の工程について詳細に説明する。Hereinafter, the steps of the present invention will be explained in detail.
まず、本発明の反応は次の如き反応式で示される。First, the reaction of the present invention is shown by the following reaction formula.
” （ｍｕ、Ｒ１よア２．。Ｉ。” (mu, R1 yo a2..I.
出発原料であるオキサゾリンは、イソシアネートとプロ
ピオンアルデヒドを反応させることにより合成され、こ
の際のイソシアネートとプロピオンアルデヒドの反応比
は１：１〜Ｉ：５であり、好ましくは１；２である。Oxazoline, which is a starting material, is synthesized by reacting isocyanate and propionaldehyde, and the reaction ratio of isocyanate and propionaldehyde is 1:1 to I:5, preferably 1:2.
オキサゾリンにおけるアルコキシル基とは、メトキシ基
、エトキシ基、プロポキシ基、ブトキシ基などであり、
通常炭素数が１〜４の範囲のものが好適である。The alkoxyl group in oxazoline includes methoxy group, ethoxy group, propoxy group, butoxy group, etc.
Generally, those having a carbon number of 1 to 4 are suitable.
上記のオキサゾリンを０〜１０℃の温度条件の下、酸又
はアルカリでオキサゾリンの開環反応を行う。開環温度
を０〜１０℃の範囲内に保つと、グリシンの副生は０．
３％以下とほぼ完全に抑えられるが、０℃以下では反応
速度が急激に遅くなり、又１０℃以上ではグリシンの副
生が大幅に増加するという欠点がある。The above-mentioned oxazoline is subjected to a ring-opening reaction with an acid or an alkali at a temperature of 0 to 10°C. When the ring-opening temperature is maintained within the range of 0 to 10°C, the amount of glycine by-product is 0.
Although it can be almost completely suppressed to 3% or less, there are disadvantages in that the reaction rate slows down rapidly below 0°C, and the amount of glycine by-product increases significantly above 10°C.
ここでの酸とは塩酸、硫酸、硝酸などの鉱酸であり、塩
酸が実用的である。オキサゾリンに対する酸の使用量は
２０１量％〜７０重量％であり、好ましくは４０重量％
〜５０重量％である。The acids used here are mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid, with hydrochloric acid being the most practical. The amount of acid used relative to oxazoline is 201% to 70% by weight, preferably 40% by weight.
~50% by weight.
又、アルカリとは水酸化ナトリウム、水酸化カリウム、
水酸化リチウムなどである。オキサゾリンに対するアル
カリの使用量は１０重量％〜７０重量％であり、好まし
くは４０重量％〜５０重量％である。Also, alkalis include sodium hydroxide, potassium hydroxide,
Lithium hydroxide, etc. The amount of alkali used relative to the oxazoline is 10% to 70% by weight, preferably 40% to 50% by weight.
酸とアルカリを比へるとＡＨＶの収率は酸の方が有利で
ある。When comparing acids and alkalis, acids are more advantageous in terms of AHV yield.
溶媒としては通常水が用いられるが、必要であれば反応
に影響しない含水溶液なども使用可能である。Water is usually used as the solvent, but if necessary, an aqueous solution that does not affect the reaction can also be used.
反応は酸又はアルカリを溶解した水溶液中にオキサゾリ
ンを加え、撹拌下に０〜１０℃に保つだけで良い。The reaction can be carried out simply by adding oxazoline to an aqueous solution containing an acid or alkali and maintaining the mixture at a temperature of 0 to 10° C. while stirring.
オキサゾリンは一括仕込みしても、分割仕込みしても、
連続仕込みしても良い。Oxazoline can be prepared all at once or divided into parts.
You can prepare it continuously.
反応時間は０．５〜３０時間が実用的であり、好ましく
は１〜５時間である。A practical reaction time is 0.5 to 30 hours, preferably 1 to 5 hours.
得られる反応生成液は、常法に従って単離される。例え
ば、陽イオン交換樹脂カラム（Ｈ”型）に生成液を通過
させてＡＨＶを樹脂に吸着させると共に、未反応物や不
純物を溶出除去する。吸着後、充分に水洗いしてからア
ンモニア水等のアルカリで吸着したＡＨＶを溶出させる
。溶出液を減圧下で濃縮した後、水−エタノールを加え
ることにより再結晶を行いＡＨＶを単離する。The resulting reaction product liquid is isolated according to a conventional method. For example, the product solution is passed through a cation exchange resin column (H" type) to adsorb AHV to the resin, and unreacted substances and impurities are eluted and removed. After adsorption, it is thoroughly washed with water, and then ammonia water etc. The adsorbed AHV is eluted with an alkali.The eluate is concentrated under reduced pressure, and then recrystallized by adding water-ethanol to isolate the AHV.
本発明の方法においては、オキサゾリンの開環の際に蟻
酸か副生されるが、これは反応生成液を濃縮する際に水
と共に留去される。In the method of the present invention, formic acid is produced as a by-product during ring opening of oxazoline, and this is distilled off together with water when the reaction product solution is concentrated.
かくして得られたＡＨＶは収率の点ではやや低めである
が、グリシンの副生率を０３％とほぼ完全に抑えること
が出来、スレオニン生産活性の高い菌株を育種するＡＨ
Ｖの有効性は充分に期待出来る。Although the yield of the AHV obtained in this way is somewhat low, the by-product rate of glycine can be almost completely suppressed to 0.3%, making it possible to breed AH strains with high threonine production activity.
The effectiveness of V can be fully expected.
［作 用コ
本発明ではＡＨＶを合成する際、オキサゾリンを開環す
る反応温度を０〜１０℃に保つことによって、副生成物
であるグリシンの副生率を抑えることが出来る。[Function] In the present invention, when synthesizing AHV, by keeping the reaction temperature for ring-opening oxazoline at 0 to 10°C, the rate of by-product glycine can be suppressed.
［実施例］ 以下、実施例を挙げて本発明を更に具体的に説明する。[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
２規定の塩酸２２０＋ｎｌを０〜５℃に冷却し、この温
度を保ちつつオキサゾリン４０９を徐々に添加した。更
に０〜５℃を保ちながら、３時間撹拌開環反応を行った
。Example 1 220+nl of 2N hydrochloric acid was cooled to 0 to 5°C, and oxazoline 409 was gradually added while maintaining this temperature. Further, the ring-opening reaction was carried out with stirring for 3 hours while maintaining the temperature at 0 to 5°C.
反応終了後、陽イオン交換樹脂カラム（Ｈ°型）に通過
させ、カラム内を水で充分洗浄した。次に５％アンモニ
ア水溶液で吸着したＡＨＶを溶出し、得られた溶出液を
減圧下で濃縮した。濃縮物に水−エタノール溶液５００
１を加え再結晶を行うと１１．３９のＡＨＶが得られた
。After the reaction was completed, the mixture was passed through a cation exchange resin column (H° type), and the inside of the column was thoroughly washed with water. Next, the adsorbed AHV was eluted with a 5% ammonia aqueous solution, and the resulting eluate was concentrated under reduced pressure. Concentrate water-ethanol solution 500%
When recrystallization was performed by adding 1, an AHV of 11.39 was obtained.
次にこのＡＨＶを高速液体クロマトグラフィーで分析し
たところ、グリシンの副生率は０，３％でしかなかった
。Next, this AHV was analyzed by high performance liquid chromatography, and the by-product rate of glycine was only 0.3%.
実施例２
実施例１において反応温度を５〜１０℃とした以外は同
じ条件下で反応を行った。グリシンの副生率は０．５％
であった。Example 2 The reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was 5 to 10°C. Glycine by-product rate is 0.5%
Met.
対照例１
実施例１において反応温度を１５℃とした以外は同じ条
件下で反応を行った。グリシンの副生率は５％であった
。Control Example 1 The reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was 15°C. The by-product rate of glycine was 5%.
対照例２
実施例Ｉにおいて反応温度を３０℃とした以外は同じ条
件下で反応を行った。グリシンの副生率は１０％であっ
た。Control Example 2 The reaction was carried out under the same conditions as in Example I except that the reaction temperature was 30°C. The by-product rate of glycine was 10%.
［効 果］
前記の如く、本発明の製造法はＡＨＶを製造する際、５
−エチル−４−エトキシカルボニル−２−オキサシリン
の開環温度を０〜１０℃に保つことにより、副生成物で
あるグリシンの生成が抑えられるという効果を有する。[Effect] As mentioned above, the production method of the present invention has 5 effects when producing AHV.
By keeping the ring-opening temperature of -ethyl-4-ethoxycarbonyl-2-oxacillin at 0 to 10°C, it has the effect of suppressing the production of glycine as a by-product.
Claims (1)
リンを酸又はアルカリによりオキサゾリン開環反応を行
う際、反応温度を０〜１０℃に保つことを特徴とするα
−アミノ−β−ヒドロキシ吉草酸の製造法。α characterized in that when carrying out the oxazoline ring-opening reaction of 5-ethyl-4-alkoxycarbonyl-2-oxazoline with an acid or alkali, the reaction temperature is maintained at 0 to 10°C.
-Production method of amino-β-hydroxyvaleric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11811690A JPH0413653A (en) | 1990-05-07 | 1990-05-07 | Production of alpha-amino-beta-hydroxyvaleric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11811690A JPH0413653A (en) | 1990-05-07 | 1990-05-07 | Production of alpha-amino-beta-hydroxyvaleric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0413653A true JPH0413653A (en) | 1992-01-17 |
Family
ID=14728427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11811690A Pending JPH0413653A (en) | 1990-05-07 | 1990-05-07 | Production of alpha-amino-beta-hydroxyvaleric acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0413653A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4858659B2 (en) * | 2010-01-28 | 2012-01-18 | 住友金属工業株式会社 | Heat treatment method for metal tube for nuclear power plant, batch type vacuum heat treatment furnace used therefor, and metal tube for nuclear power plant processed thereby |
| WO2013145583A1 (en) | 2012-03-26 | 2013-10-03 | 新日鐵住金株式会社 | Method for heat-treating metal pipes, metal pipe, and heat treatment furnace |
| US8739610B2 (en) | 2008-10-16 | 2014-06-03 | Shimadzu Corporation | Sample injection port and auto-sampler having the same |
-
1990
- 1990-05-07 JP JP11811690A patent/JPH0413653A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8739610B2 (en) | 2008-10-16 | 2014-06-03 | Shimadzu Corporation | Sample injection port and auto-sampler having the same |
| JP4858659B2 (en) * | 2010-01-28 | 2012-01-18 | 住友金属工業株式会社 | Heat treatment method for metal tube for nuclear power plant, batch type vacuum heat treatment furnace used therefor, and metal tube for nuclear power plant processed thereby |
| WO2013145583A1 (en) | 2012-03-26 | 2013-10-03 | 新日鐵住金株式会社 | Method for heat-treating metal pipes, metal pipe, and heat treatment furnace |
| KR20160113744A (en) | 2012-03-26 | 2016-09-30 | 신닛테츠스미킨 카부시키카이샤 | Method for heat-treating metal pipes, metal pipe, and heat treatment furnace |
| US9745642B2 (en) | 2012-03-26 | 2017-08-29 | Nippon Steel & Sumitomo Metal Corporation | Method for heat treating a metal tube or pipe, metal tube or pipe, and heat treatment furnace |
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