JPH068312B2 - New peptide manufacturing method - Google Patents
New peptide manufacturing methodInfo
- Publication number
- JPH068312B2 JPH068312B2 JP57014246A JP1424682A JPH068312B2 JP H068312 B2 JPH068312 B2 JP H068312B2 JP 57014246 A JP57014246 A JP 57014246A JP 1424682 A JP1424682 A JP 1424682A JP H068312 B2 JPH068312 B2 JP H068312B2
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- Japan
- Prior art keywords
- added
- glu
- methanol
- dap
- mixture
- Prior art date
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- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Peptides Or Proteins (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
Description
【発明の詳細な説明】 本発明は新規ペプチドの新規な製造方法に関し、詳細に
は薬理作用を有する新規ペプチド及びその医薬として許
容される塩の新規な製造方法に関するものである。The present invention relates to a novel method for producing a novel peptide, and more particularly to a novel method for producing a novel peptide having a pharmacological action and a pharmaceutically acceptable salt thereof.
この発明の反応は次式で示される。The reaction of the present invention is represented by the following formula.
（式中、Bzlはベンジルを、Ｚはベンジルオキシカルボ
ニルを、Ｒ１はメチルまたはエチルをそれぞれ意味す
る） この発明の目的化合物（Ｉ）は新規化合物であり、本発
明の発明者等や他の発明者によって以前に製造され、又
多くの国で出願がなされている（例えば、日本特許出
願、昭和55年特許願第106279号等）。 (In the formula, Bzl means benzyl, Z means benzyloxycarbonyl, and R 1 means methyl or ethyl, respectively.) The object compound (I) of the present invention is a novel compound, which has been previously produced by the inventors of the present invention and other inventors, and has been filed in many countries (for example, Japanese patent application, Showa 55). Patent application No. 106279, etc.)
その後、本発明の発明者らは該化合物の広汎な製造方法
について更に研究を続けた結果、工業的な製造において
より有用で且つ適切である新しい製造方法の確立に成功
した。After that, the inventors of the present invention further researched a wide range of production methods of the compound, and as a result, succeeded in establishing a new production method which is more useful and suitable for industrial production.
この発明の反応は、化合物（II）またはその塩を塩基の
存在下、加水分解およびパラジウム−炭素の存在下に接
触還元に付することによって化合物（Ｉ）またはその塩
を製造するものである。The reaction of the present invention is to produce the compound (I) or a salt thereof by subjecting the compound (II) or a salt thereof to hydrolysis and catalytic reduction in the presence of palladium-carbon in the presence of a base.
好適な塩基としては、アルカリ若しくはアルカリ土類金
属の水酸化物、炭酸塩若しくは重炭酸塩（例えば水酸化
ナトリム、水酸化カリウム、炭酸ナトリウム、炭酸カリ
ウム、炭酸リチウム、炭酸水素ナトリウム、水酸化カル
シウム、水酸化マグネシウム等）、水酸化アンモニウム
等の無機塩基、上記金属のアルコキシド若しくはフェノ
キシド（例えばナトリウムエトキシド、ナトリウムメト
キシド、リチウムフェノキシド等）、モノ、ジ又はトリ
アルキルアミン（例えばメチルアミン、エチルアミン、
プロピルアミン、イソプロピルアミン、ブチルアミン、
N,Ｎ−ジメチル−1,３−プロパンジアミン、トリメチル
アミン、トリエチルアミン等）、非置換又はモノ若しく
はジ置換アリールアミン（例えばアニリン、Ｎ−メチル
アニリン、N,Ｎ−ジメチルアニリン等）、複素環塩基
（例えばピロリジン、モルホリン、Ｎ−メチルモルホリ
ン、Ｎ−メチルピペリジン、N,Ｎ−ジメチルピペラジ
ン、ピリジン等）、ヒドラジン類（例えばヒドラジン、
メチルヒドラジン、エチルヒドラジン等）等の有機塩
基、及び塩基性イオン交換樹脂等が挙げられる。Suitable bases include alkali or alkaline earth metal hydroxides, carbonates or bicarbonates (for example sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate, calcium hydroxide, Magnesium hydroxide, etc.), inorganic bases such as ammonium hydroxide, alkoxides or phenoxides of the above metals (eg sodium ethoxide, sodium methoxide, lithium phenoxide etc.), mono-, di- or trialkylamines (eg methylamine, ethylamine,
Propylamine, isopropylamine, butylamine,
N, N-dimethyl-1,3-propanediamine, trimethylamine, triethylamine, etc.), unsubstituted or mono- or di-substituted arylamine (eg, aniline, N-methylaniline, N, N-dimethylaniline, etc.), heterocyclic base ( For example, pyrrolidine, morpholine, N-methylmorpholine, N-methylpiperidine, N, N-dimethylpiperazine, pyridine, etc.), hydrazines (eg, hydrazine,
Examples thereof include organic bases such as methylhydrazine and ethylhydrazine, and basic ion exchange resins.
加水分解は冷却若しくは加温の様な比較的穏やかな条件
で且つ反応に悪影響を及ぼさない溶媒［例えば水、アル
コール（例えばメタノール、エタノール、プロパノール
等）の様な親水性溶媒、アセトン、N,Ｎ−ジメチルホル
ムアミド、テトラヒドロフラン、ジオキサン、ジメチル
スルホキシド等またはこれらの混合溶媒またはベンゼ
ン、ジエチルエーテル等の様な疎水性溶媒］中において
行われる。更に上記のうち液状酸若しくは塩基は溶媒と
して兼用される。Hydrolysis is performed under relatively mild conditions such as cooling or heating, and a solvent that does not adversely influence the reaction [eg, hydrophilic solvent such as water or alcohol (eg, methanol, ethanol, propanol, etc.), acetone, N, N, etc.]. -Dimethylformamide, tetrahydrofuran, dioxane, dimethylsulfoxide and the like or a mixed solvent thereof or a hydrophobic solvent such as benzene and diethyl ether]. Further, among the above, the liquid acid or base is also used as a solvent.
更に接触還元に用いられる好ましい溶媒としては、上述
のもの以外に、ジエチルエーテル、ジオキサン、テトラ
ヒドロフラン等若しくはその混合物も使用される。Further, as a preferable solvent used for catalytic reduction, diethyl ether, dioxane, tetrahydrofuran or the like or a mixture thereof is used in addition to the above-mentioned ones.
反応は冷却若しくは加温等の比較的穏やかな条件下に速
やかに行われる。The reaction is rapidly performed under relatively mild conditions such as cooling or heating.
目的化合物（Ｉ）には、分子内の不斉炭素原子による１
又は２以上の異性体が含まれ、これら異性体は全て本発
明に含まれる。The target compound (I) contains 1 due to an asymmetric carbon atom in the molecule.
Alternatively, two or more isomers are included, and all these isomers are included in the present invention.
本発明の目的化合物（Ｉ）及びその塩は実験的感染症に
対する予防効果を有することが分かった。従って目的化
合物（Ｉ）及びその塩は病原微生物、例えばグラム陰性
菌、グラム陽性菌及びかび類による感染症の治療に有用
である。It was found that the object compound (I) of the present invention and its salt have a preventive effect against experimental infectious diseases. Therefore, the objective compound (I) and salts thereof are useful for treating infectious diseases caused by pathogenic microorganisms such as Gram-negative bacteria, Gram-positive bacteria and fungi.
次にこの発明の実施例を示す。Next, examples of the present invention will be described.
下記実施例において、出発物質及び目的化合物は下記の
略号を用いて表わす。In the following examples, starting materials and target compounds are represented by the following abbreviations.
Ｚ：ベンジルオキシカルボニル Et：エチル Bzl：ベンジル Al：アラニル DAP：α，ε−ジアミノピメリル Glu：グルタミル Me：メチル 参考例 トリフルオロ酢酸（100ml）にBoc−(L)−Ｚ−(D)−メゾ
DAP−(L)−(D)−OMe−(L)−Ｄ−AlaOMe(2)（19.0ｇ）を
加え、室温で２時間攪拌した。トリフルオロ酢酸を留去
した後、残留物を塩化メチレン（300ml）に溶解し、こ
れにトリエチルアミン（14.38ｇ）とステアロイル−Ｌ
−Ala−Ｄ−Glu(OSu)OBzl(3)（24.38ｇ）を加えた。反
応混合液にメタノール（250ml）とテトラヒドロフラン
（50ml）の混液を加え、室温で１晩攪拌した後、溶液の
pHが４になるまで水（300ml）と共に１Ｎ塩酸を加え
た。生成した沈殿物を集め水洗して得た粗製物を、シリ
カゲル（800ｇ）のカラムに展開し、クロロホルム−メ
タノール（50：１、容量比）を溶出液として精製する
と、ステアロイル−Ｌ−Ala−γ−Ｄ−Glu−(α-OBzl)
−(L)−Ｚ−(D)−メゾDAP−(D)−OMe−(L)−Ｄ−AlaOMe
(3)（21.13ｇ）が得られた。Z: benzyloxycarbonyl Et: ethyl Bzl: benzyl Al: alanyl DAP: α, ε-diaminopimeryl Glu: glutamyl Me: methyl Reference example Trifluoroacetic acid (100 ml) was added to Boc- (L) -Z- (D) -meso
DAP- (L)-(D) -OMe- (L) -D-AlaOMe (2) (19.0 g) was added, and the mixture was stirred at room temperature for 2 hours. After distilling off trifluoroacetic acid, the residue was dissolved in methylene chloride (300 ml), and triethylamine (14.38 g) and stearoyl-L were added thereto.
-Ala-D-Glu (OSu) OBzl (3) (24.38g) was added. A mixture of methanol (250 ml) and tetrahydrofuran (50 ml) was added to the reaction mixture, and the mixture was stirred overnight at room temperature.
1N hydrochloric acid was added with water (300 ml) until the pH was 4. The crude product obtained by collecting the collected precipitates and washing with water was developed on a column of silica gel (800 g) and purified with chloroform-methanol (50: 1, volume ratio) as an eluent to obtain stearoyl-L-Ala-γ. -D-Glu- (α-OBzl)
-(L) -Z- (D) -meso DAP- (D) -OMe- (L) -D-AlaOMe
(3) (21.13 g) was obtained.
mp：166-170゜C ［α］D-15.59゜［Ｃ＝0.30,CHCl3] IR(ヌジョ-ル)：3300,1730,1685,1635cm-1 NMR(CDCl3,δ）：0.88(3H,m),1.06-2.55(48H,m),3.66(3
H,s),3.71(3H,s),4.20-4.80(5H,m),5.10(2H,s),5.40(2
H,s),5.78(1H,d,J＝8Hz),6.50(1H,m),7.40(1H,d,J＝8H
z),7.30(10H,s), 実施例１ (1)工程１ 参考例と実質的に同じ様にして、ヘプタノイル−γ−Ｄ
−Glu−（α-OBzl)−(L)−Ｚ−(D)−メゾDAP−(D)−OMe
−(L)−Ｄ−AlaOH(3)を得た。mp: 166-170 ° C [α] D -15.59 ° [C = 0.30, CHCl 3 ] IR (nujoule): 3300, 1730, 1685, 1635 cm -1 NMR (CDCl 3 , δ): 0.88 (3H, m), 1.06-2.55 (48H, m), 3.66 (3
H, s), 3.71 (3H, s), 4.20-4.80 (5H, m), 5.10 (2H, s), 5.40 (2
H, s), 5.78 (1H, d, J = 8Hz), 6.50 (1H, m), 7.40 (1H, d, J = 8H
z), 7.30 (10H, s), Example 1 (1) Step 1 Substantially the same as the Reference Example, heptanoyl-γ-D
-Glu- (α-OBzl)-(L) -Z- (D) -meso DAP- (D) -OMe
-(L) -D-AlaOH (3) was obtained.
mp：114-116゜C ［α］D-12.26（Ｃ＝0.19,CHCl3) IR(ヌジョ-ル)：3300,1735,1685,1635cm-1 NMR(CDCl3,δ）：0.86(3H,m),1.05-2.45(23H,m),3.67(3
H,s),4.15-4.80(4H,m),5.05(2H,s),5.12(2H,s),7.29(10
H,s), (2)工程２ ヘプタノイル−γ−Ｄ−Glu−（α-OBzl)−(L)−Ｚ−
(D)−メゾDAP−(D)−OMe−(L)−Ｄ−AlaOH(3)(490mg)を
メタノール（5ml）に溶解し、これに、１Ｎ−水酸化ナ
トリウム水溶液（3ml）を加え、室温で2.5時間攪拌後、
濃縮した。残留物に0.1Ｎ塩酸（34ml）と酢酸エチル（5
0ml）を加え、水層に再度酢酸エチルを加えて抽出し
た。有機層を合わせ、ブラインで洗浄し硫酸マグネシウ
ムで乾燥した後、濃縮して油状残留物を得た。これを酢
酸（20ml）に溶解し、パラジウム−炭素（100mg）上に
おいて常圧下水素雰囲気中で水素化した。触媒を濾去し
た後、酢酸を減圧留去して得た残留物を、HP−20（15m
l）のカラムクロマトグラフィーに展開し水−メタノー
ル（７：３、容量比）を溶出液として精製し凍結乾燥さ
せると、ヘプタノイル−γ−Ｄ−Glu(α-OH)−(L)−メ
ゾ−DAP−(L)−Ｄ−AlaOH(4)(220mg)が得られた。mp: 114-116 ° C [α] D -12.26 (C = 0.19, CHCl 3 ) IR (nujoule): 3300, 1735, 1685, 1635 cm -1 NMR (CDCl 3 , δ): 0.86 (3H, m ), 1.05-2.45 (23H, m), 3.67 (3
H, s), 4.15-4.80 (4H, m), 5.05 (2H, s), 5.12 (2H, s), 7.29 (10
H, s), (2) Process 2 Heptanoyl-γ-D-Glu- (α-OBzl)-(L) -Z-
(D) -meso DAP- (D) -OMe- (L) -D-AlaOH (3) (490 mg) was dissolved in methanol (5 ml), 1N-sodium hydroxide aqueous solution (3 ml) was added thereto, After stirring for 2.5 hours at room temperature,
Concentrated. 0.1N hydrochloric acid (34 ml) and ethyl acetate (5
0 ml) was added, and ethyl acetate was added again to the aqueous layer for extraction. The organic layers were combined, washed with brine, dried over magnesium sulfate, and concentrated to give an oily residue. This was dissolved in acetic acid (20 ml) and hydrogenated over palladium-carbon (100 mg) under atmospheric pressure in a hydrogen atmosphere. After removing the catalyst by filtration, acetic acid was distilled off under reduced pressure to obtain a residue, which was converted to HP-20 (15 m
l) column chromatography and purified with water-methanol (7: 3, volume ratio) as eluent and lyophilized, heptanoyl-γ-D-Glu (α-OH)-(L) -meso- DAP- (L) -D-AlaOH (4) (220 mg) was obtained.
実施例２ 実施例１の工程２と実質的に同じ様にして、ヘプタノイ
ル−γ−Ｄ−Glu(α-OH)−(L)−メゾ−DAP−(L)−Ｄ−A
laOH(2)を得た。Example 2 Substantially the same as in Step 2 of Example 1, heptanoyl-γ-D-Glu (α-OH)-(L) -meso-DAP- (L) -DA.
got laOH (2).
実施例３ (1)工程１ ヘプタノイル−γ−Ｄ−Ｇｌｕ（α-OBzl)−(L)−Ｚ−
(D)−メゾDAP−(D)−OEt−(L)−Ｄ−AlaOH(1)（63.0
ｇ）を水（630ml）とエタノール（630ml）の混液に溶解
し、これに、１２％水酸化ナトリウム水溶液（100ml）
を加えた。１時間攪拌した後、ジオキサン(100ml)を加
え更に１時間攪拌した。次いで１８％塩酸（61ml）を加
え、減圧濃縮して得た油状残留物に水（500ml）を加え
酢酸エチル（500mlと300ml）で抽出した。抽出液をブラ
インで洗浄し硫酸マグネシウムで乾燥し更に減圧下に濃
縮した。油状残留物にジイソプロピルエーテルを加え、
得られた粉末を濾過によって集めると、ヘプタノイル−
γ−Ｄ−Glu(α-OH)−(L)−Ｚ−(D)−メゾDAP−(L)−Ｄ
−AlaOH(2)（57.6g）が得られた。Example 3 (1) Step 1 Heptanoyl-γ-D-Glu (α-OBzl)-(L) -Z-
(D) -meso DAP- (D) -OEt- (L) -D-AlaOH (1) (63.0
g) is dissolved in a mixture of water (630 ml) and ethanol (630 ml), and 12% sodium hydroxide aqueous solution (100 ml) is added to the solution.
Was added. After stirring for 1 hour, dioxane (100 ml) was added and the mixture was further stirred for 1 hour. Next, 18% hydrochloric acid (61 ml) was added, water (500 ml) was added to the oily residue obtained by concentration under reduced pressure, and the mixture was extracted with ethyl acetate (500 ml and 300 ml). The extract was washed with brine, dried over magnesium sulfate, and concentrated under reduced pressure. Diisopropyl ether was added to the oily residue,
The resulting powder was collected by filtration to give heptanoyl-
γ-D-Glu (α-OH)-(L) -Z- (D) -meso DAP- (L) -D
-AlaOH (2) (57.6g) was obtained.
［α］D-4.73（Ｃ＝0.3メタノ-ル) IR(ヌジョ-ル)：3300,1720,1630cm-1 NMR(CD3OD,δ）：0.88(3H,m),5.06(2H,s),7.30(5H,s), (2)工程２ ヘプタノイル−γ−Ｄ−Ｇｌｕ（α-OBzl)−(L)−Ｚ−
(D)−メゾDAP−(L)−Ｄ−AlaOH(2)（22.0ｇ）を、メタ
ノール（190ml）と水（10ml）の混液に溶解し、１０％
パラジウム−炭素（４ｇ）上において常圧下水素雰囲気
中で水素化した。触媒を濾去した後、溶媒を減圧留去し
て得た残留物を水（10ml）に溶解し、HP−20（250ml）
のカラムに展開した。水−メタノール（７：３）によっ
て溶出させ、溶出液を凍結乾燥させると非晶質粉末（9.
13ｇ）が得られた。この粉末をエタノール（72ml）とメ
タノール（21ml）の混液から結晶化させると、ヘプタノ
イル−γ−Ｄ−Glu（α-OH)−(L)−メゾDAP−(L)−Ｄ−
AlaOH(3)(9.10g)が得られた。[Α] D -4.73 (C = 0.3 methanol) IR (nujoule): 3300, 1720, 1630 cm -1 NMR (CD 3 OD, δ): 0.88 (3H, m), 5.06 (2H, s) , 7.30 (5H, s), (2) Step 2 Heptanoyl-γ-D-Glu (α-OBzl)-(L) -Z-
(D) -meso DAP- (L) -D-AlaOH (2) (22.0 g) was dissolved in a mixed solution of methanol (190 ml) and water (10 ml) to obtain 10%.
Hydrogenation over palladium on carbon (4g) under normal pressure in a hydrogen atmosphere. After removing the catalyst by filtration, the solvent was distilled off under reduced pressure and the obtained residue was dissolved in water (10 ml) to prepare HP-20 (250 ml).
Expanded to the column. Elution with water-methanol (7: 3) and freeze-drying of the eluate gave an amorphous powder (9.
13 g) was obtained. When this powder was crystallized from a mixture of ethanol (72 ml) and methanol (21 ml), heptanoyl-γ-D-Glu (α-OH)-(L) -meso DAP- (L) -D-
AlaOH (3) (9.10g) was obtained.
IR(ヌジョ-ル)：3250,1740,1666-1640(ブロ-ド)cm-1 NMR(D2O,δ）：0.82(3H,t,J＝6Hz),1.00-2.60(20H,m),
1.35(3H,d,J＝8Hz),3.81(1H,t,J＝7Hz),4.40-4.80(3H,
m),IR (nujoule): 3250,1740,1666-1640 (Broad) cm -1 NMR (D 2 O, δ): 0.82 (3H, t, J = 6Hz), 1.00-2.60 (20H, m) ,
1.35 (3H, d, J = 8Hz), 3.81 (1H, t, J = 7Hz), 4.40-4.80 (3H,
m),
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岡田 達 大阪府高槻市川添２丁目21−７ (72)発明者 余西 敏 大阪府門真市野里町39−10 (56)参考文献 特開 昭55−85552（ＪＰ，Ａ) 特開 昭55−76850（ＪＰ，Ａ) 特開 昭56−45447（ＪＰ，Ａ) 特開 昭56−36440（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tatsu Okada 2-21-7 Kawazoe, Takatsuki-shi, Osaka (72) Inventor Satoshi Yokanishi 39-10 Nosato-cho, Kadoma-shi, Osaka (56) Reference JP-A-55 -85552 (JP, A) JP 55-76850 (JP, A) JP 56-45447 (JP, A) JP 56-36440 (JP, A)
Claims (1)
れる化合物またはその塩を塩基の存在下、加水分解およ
びパラジウム−炭素の存在下、接触還元に付すことを特
徴とする式： で示される化合物またはその塩の製造法。1. A formula: (Wherein R 1 represents methyl or ethyl) or a salt thereof is subjected to catalytic reduction in the presence of a base, hydrolysis and palladium-carbon. A method for producing the compound represented by or a salt thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU18002/83A AU562632B2 (en) | 1982-01-29 | 1983-08-15 | Recombinant plasmid inserted with hepatitis beta virus gene and production of hepatitis beta surface antigen |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8102706 | 1981-01-29 | ||
| GB8109576 | 1981-03-26 | ||
| GB8102706 | 1981-03-26 | ||
| GB8109576 | 1981-03-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57145845A JPS57145845A (en) | 1982-09-09 |
| JPH068312B2 true JPH068312B2 (en) | 1994-02-02 |
Family
ID=26278263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57014246A Expired - Lifetime JPH068312B2 (en) | 1981-01-29 | 1982-01-29 | New peptide manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH068312B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0512853B1 (en) * | 1991-05-10 | 1996-08-21 | KIRIU MACHINE MFG. Co., Ltd. | Ventilated-type disc rotor |
| US20060258580A1 (en) * | 2003-05-14 | 2006-11-16 | Regents Of The University Of Michigan | Modulators of Nod1 signaling |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1431724A (en) * | 1973-01-08 | 1976-04-14 | Tektronix Inc | System for acquiring processing and displaying information |
| FR2442889A1 (en) * | 1978-10-19 | 1980-06-27 | Anvar | Immunostimulant and adjuvant N-acyl-peptide derivs. - produced by N-acylation of peptides from streptomyces stimulosus water-soluble extract (BE 17.4.80) |
| JPS5585552A (en) * | 1978-11-14 | 1980-06-27 | Fujisawa Pharmaceut Co Ltd | New lactyltetrapeptide |
| US4231910A (en) * | 1979-02-08 | 1980-11-04 | Dow Corning Corporation | Primer composition |
| FR2460290A1 (en) * | 1979-06-29 | 1981-01-23 | Rhone Poulenc Ind | NOVEL TETRA- OR PENTAPEPTIDES, THEIR PREPARATION AND THE MEDICINES THAT CONTAIN THEM |
| FR2460289A1 (en) * | 1979-06-29 | 1981-01-23 | Rhone Poulenc Ind | NEW TRIPEPTIDES, THEIR PREPARATION AND THE MEDICINES THAT CONTAIN THEM |
| JPH0668024B2 (en) * | 1986-07-15 | 1994-08-31 | 三井東圧化学株式会社 | Thermosetting resin composition |
| JPH0295412A (en) * | 1988-09-30 | 1990-04-06 | Toyobo Co Ltd | Gas separating film apparatus utilizing hollow yarn membrane |
| JPH0295413A (en) * | 1988-09-30 | 1990-04-06 | Shibaura Eng Works Co Ltd | Oxygen-enriched air moisture removal equipment |
-
1982
- 1982-01-29 JP JP57014246A patent/JPH068312B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57145845A (en) | 1982-09-09 |
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