JPS606957B2 - Method for producing antibiotic derivatives - Google Patents
Method for producing antibiotic derivativesInfo
- Publication number
- JPS606957B2 JPS606957B2 JP48040094A JP4009473A JPS606957B2 JP S606957 B2 JPS606957 B2 JP S606957B2 JP 48040094 A JP48040094 A JP 48040094A JP 4009473 A JP4009473 A JP 4009473A JP S606957 B2 JPS606957 B2 JP S606957B2
- Authority
- JP
- Japan
- Prior art keywords
- cephalexin
- water
- added
- butanol
- insoluble
- 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.)
- Expired
Links
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- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Cephalosporin Compounds (AREA)
Description
【発明の詳細な説明】
本発明はセフアロスポリンなる共通名を有する抗生物質
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing antibiotics having the common name cephalosporins.
セフレキシンは対人間治療用の抗生物質であ‐り、遊離
酸の１水和物の形で市販されている（すなわちｚｗＭｅ
ｒｉｏｎ）。Ceflexin is an antibiotic for human therapy and is commercially available in the form of the free acid monohydrate (i.e. zwMe
rion).
本物質に関しては例えばＪ．Ｍｅｄ．Ｃｈｅｍ．１２，
３１０〜一３１３（１９６９）Ｊ．Ｃｒｇ．Ｃｈｅｍ３
母９｝，１２５９一１２６７（１９７１）およびＪ．○
ｒｇ．Ｃｈｅｍ３７（１７），２７６５−２７６７（１
９７２）〔ベルギー特許７６５５９６；Ｆａ皿ｄｏｃ６
７５１１Ｓ参照〕および米国特許３５０７８６１、英国
特許１１７４３３５およびカナダ特許８５６７８飴等‘
こ記載されている。セフアレキシンの合成法あるいは精
製法に関しては多数の特許が存在する。Regarding this substance, for example, J. Med. Chem. 12,
310-1313 (1969) J. Crg. Chem3
Mother 9}, 1259-1267 (1971) and J. ○
rg. Chem37(17), 2765-2767(1
972) [Belgium patent 765596; Fa plate doc6
7511S] and U.S. Patent No. 3507861, British Patent No. 1174335 and Canadian Patent No. 85678 Candy etc.'
This is listed. There are numerous patents regarding methods of synthesizing or purifying cephalexin.
例えば米国特許３筋４４１６；同３６磯２０１：同３６
斑２０２；同３６７１４４９（実施例３）；同３６７６
４３４；同３６７６４３７；同３６８９４８３および同
３６９４４３７等である。セフアレキシンの結晶体ある
いは水和物についても多くの記述が存在する。For example, 3 U.S. patents 4416; 36 Iso 201: 36
Spot 202; 3671449 (Example 3); 3676
434; 3676437; 3689483 and 3694437. There are also many descriptions of crystalline forms or hydrates of cephalexin.
例えばＰｆｅｉ船ｒらＪ。ｍＭｌｏｆＰｈａ肌ａｃｅｕ
ｔｊＣａＩＳｃｉｅｎｃｅｓＤ ５９（Ｉ２）１８０９
一 １８１４ （ １９７０ ）， 則ｎｄ らＰｈ
ａｒｍａＣｅｕｔｉＣａＩＪ。川旭１，２１０−２１４
（８月２２日，１９７０）、米国特許３５０２６＄：同
３５３１４８１；同３６５５６５６：同３６９２７８１
ベルギー特許７５３９１０（Ｆｏｒｍｄｏｃ８２１４Ｓ
）、同７７７７８９（Ｆｏｎｎｄｏｃ４８５５６ｒ）お
よびフランス特許２０９６１１７等である。本発明は以
下のＸ線回折データ面間隔ｄ（Ａ） 相対強度１／
１，
１６．０１ ．１９１２．０７
１．００１０．８２
．１３
９．６４ ．０３
８斑 ．０７
８．５３ ．１３
８．１０ ．２６
７．０７ ．０８
６．１０ ．１４
５．６０ ．２２
５．４３ ．６４
４．９８ ．１７
４．７６ ．０９
４．５７ ．１７
４．３９ ．１８
４．２３ ．１８
４．０２ ．３０
３．９４ ．１３
３．８６ ．１９
３７９ ．０４
３．７０ ．０５
３．６１ ．１８
３．４４ ．０８
３．２４ ．１０
３．２０ ．０５
３．１１ ．３１
２．９９ ．０８
２．９１ ．０９
２．８０ ．０７
２．７３ ．０７
２．６７ ．０９
を示す比較的水に溶解しない結晶性セフアレキシン１水
和物の製造方法を与える。For example, Pfei ships r et al. J. mmlofPha skin aceu
tjCaI Sciences D 59 (I2) 1809
1814 (1970), Norind et al. Ph.
armaCeutiCaIJ. Kawaasahi 1, 210-214
(August 22, 1970), US Patent No. 35,026: US Pat. No. 3,531,481; US Pat.
Belgian patent 753910 (Formdoc 8214S
), No. 777789 (Fonndoc No. 48556r), and French Patent No. 2096117. The present invention uses the following X-ray diffraction data surface spacing d(A) relative intensity 1/
1, 16.01. 1912.07
1.0010.82
．． 13 9.64. 03 8 spots. 07 8.53. 13 8.10. 26 7.07. 08 6.10. 14 5.60. 22 5.43. 64 4.98. 17 4.76. 09 4.57. 17 4.39. 18 4.23. 18 4.02. 30 3.94. 13 3.86. 19 379. 04 3.70. 05 3.61. 18 3.44. 08 3.24. 10 3.20. 05 3.11. 31 2.99. 08 2.91. 09 2.80. 07 2.73. 07 2.67. Provided is a method for producing crystalline cephalexin monohydrate which is relatively insoluble in water and exhibits .09.
その方法は以下の操作より成る。すなわち濃厚なセフア
レキシンの酸性水溶液（ｐＨ２．仏〆下、好ましくは１
．７〜２．３または２．３）を調製し、それに十分量の
ｎープタノールを加えて２相の液相を形成（水溶液１容
量に対してｎ−ブタノール０．球容量以上、また好まし
くは上記不溶性のセフアレキシン１水和物の種結晶も添
加する）させ、次いで上記２相系を斑４．０〜５．０（
好ましくはトリェチルアミン、水酸化ナトリウム、水酸
化カリウムあるいは水酸化アンモニウムにより）まで除
々に中和（好ましくは４５℃以下、約２０一２５℃で）
して上記の水不落・性の結晶性セフアレキシン１水和物
を沈でんさせる。低温（２０一２５℃）での操作は高温
操作の際発生する分解反応を抑制するため特に価値があ
る。ｐＨ値は中和過程においては蝿拝されつつある２相
系に、また中和の終期には水相にガラス電極を挿入する
ことにより測定される。好ましい中和剤は水酸化ナトリ
ウム、水酸化カリウム、および水酸化アンモニウムであ
る。The method consists of the following operations. That is, a concentrated acidic aqueous solution of cephalexin (pH 2.0, preferably 1.
．． 7 to 2.3 or 2.3) and add a sufficient amount of n-butanol thereto to form a two-phase liquid phase (at least 0.9 gb volume of n-butanol per 1 volume of aqueous solution, and preferably above) Seed crystals of insoluble cephalexin monohydrate are also added) and the two-phase system is then mixed with a 4.0-5.0 molar mass (
(preferably with triethylamine, sodium hydroxide, potassium hydroxide or ammonium hydroxide) until neutralization (preferably at below 45°C, about 20-25°C)
to precipitate the water-resistant crystalline cephalexin monohydrate. Operation at low temperatures (20-25°C) is of particular value because it suppresses decomposition reactions that occur during high temperature operations. The pH value is measured by inserting a glass electrode into the two-phase system being exposed during the neutralization process and into the aqueous phase at the end of the neutralization. Preferred neutralizing agents are sodium hydroxide, potassium hydroxide, and ammonium hydroxide.
ここに記載した水に水溶性のセフアレキシン１水和物の
大まかな溶解度は１０雌／泌である。この値はかなり大
まかな方法で決定した。すなわち３０の９を１０の‘の
脱イオン水に懸だくさせ５分間振とうしたが懸だく物の
一部は残存した。それに更に１．０被‘の水を加え５分
間振とうしたがやはり全ては溶解しなかった。更に１．
０の‘の水（全部で３．０の‘の日２０）を加えると透
明な溶液が得られた。従って溶解度は１泌あたり１０の
９〜１５の９である。本発明は水に不溶性のセファレキ
シン１水和物の特殊な結晶体およびその精造方法を与え
るものである。この結晶体の用途は前記の科学および薬
学文献に記載されているものと同一である。従って本発
明のセフアレキシン１水刺物の結晶体は人を含む動物に
おける抗生物質として有効であり、かつ良好な安定性を
有し、経口投与において効果的な血中濃度を与える。本
製造においては得られる製品の化学的および物理的性質
の再現性が良好であり、従って本物質の工業的製造およ
び調合に・適していると言えよう。以下実施例によって
本発明を説明するが、本発明はこれらによって限定され
るものではない。The approximate solubility of the water-soluble cephalexin monohydrate described herein is 10 females/secretion. This value was determined using a fairly rough method. That is, 30 parts 9 was suspended in 10 parts deionized water and shaken for 5 minutes, but some of the suspended material remained. An additional 1.0 kg of water was added thereto and shaken for 5 minutes, but still not all of the solution was dissolved. Furthermore 1.
Addition of 0' water (3.0' day 20 total) resulted in a clear solution. Therefore, the solubility is between 9 of 10 and 9 of 15 per secretion. The present invention provides a special water-insoluble crystalline form of cephalexin monohydrate and a method for its purification. The uses of this crystal are the same as those described in the scientific and pharmaceutical literature mentioned above. Therefore, the cephalexin 1 aquarium crystals of the present invention are effective as antibiotics in animals including humans, have good stability, and provide effective blood concentrations upon oral administration. In this production, the reproducibility of the chemical and physical properties of the product obtained is good, and therefore it can be said that it is suitable for industrial production and formulation of this substance. The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.
例１２０−２６０におけるＢＵＯＨ−日２０系からの不
溶性セフアレキシン１水和物２５．０夕の一級セフアレ
キシンを徐々に６０の‘の水に加え、次いで州のＨＣ１
（９．８奴‘）を滴下して最終ｐＨ１．７とした。Example 120-260 insoluble cephalexin monohydrate from the BUOH-day 20 system 25.0 ml of primary cephalexin was gradually added to 60' of water and then the state HC1
(9.8 μg) was added dropwise to adjust the final pH to 1.7.
溶液は若干白濁した。２．５９の脱色用活性炭（‘‘Ｄ
ａｒｋｏＫＢ’）を加えた。The solution became slightly cloudy. 2.59 decolorizing activated carbon (''D
arkoKB') was added.
混合物を１粉ふ間婿拝した後炉過した。２０夕のＮａＯ
Ｈを熔解して１００のとの２０％ＮａＯＨ溶液を調製し
た。The mixture was stirred for one powder and then filtered. 20 evening NaO
A 20% NaOH solution of 100% NaOH was prepared by dissolving H.
活性炭を水で洗浄して最終炉液１１０奴を得た。２０−
２５ｏ０で欄拝しつつ２分間かけて３．５の‘の２０％
ＮａＯＨを加え、最終ｐＨ２．３とした。The activated carbon was washed with water to obtain 110 g of final furnace liquid. 20-
20% of 3.5' in 2 minutes while visiting at 25o0
NaOH was added to give a final pH of 2.3.
。次いで不溶性セフアレキシン１水和物１．０夕を種結
晶として加えた。次いで５０机上のｎ−ブタノールを加
え、さらに２３ｑｏで燈拝しつつ４１／２時間かけて２
０％ＮａＯＨを８．６５机と加えた。ｐ靴ま２．４また
は最終ｐＨ４．５（あるいはそれより若干高い）に維持
し、温度は２０一２５ｏ０に維持した。. Then 1.0 ml of insoluble cephalexin monohydrate was added as seed crystals. Next, add 50 liters of n-butanol and continue to boil for 41/2 hours while heating at 23 qo.
8.65 units of 0% NaOH was added. The final pH was maintained at 2.4 or 4.5 (or slightly higher) and the temperature was maintained at 20-25°C.
分析結果は次のとおりである。Ｋ．Ｆ．日２０＝３．６
％，ＩＰＡ＝０．０８９％，ＢｕＯＨ＝０．７２％，Ｃ
ｈｅｍ．ＰｏｔｅＭｙ８灘ｍｃｇ／地；ＢｉｏＰｏにｎ
ｃｙ＝９２仇ｈｃｇ／奴９０析出した不溶性のセフアレ
キシン１水和物を炉過回収し、次いでｎ−ＢｕＯＨ（５
０の【），水（４０の‘），ｎ−ＢｕＯＨ（５０肌），
ＩＰＡ（１００の‘）で連続的に洗浄し、更に５３一５
ｙｏ（常圧オーブン）で２２時間乾燥した。The analysis results are as follows. K. F. Day 20 = 3.6
%, IPA=0.089%, BuOH=0.72%, C
hem. PoteMy8 Nada mcg/ground; BioPo n
cy=92 hcg/cy
0 [), water (40'), n-BuOH (50 skin),
Wash successively with IPA (100') and further 53-5
It was dried in yo (atmospheric pressure oven) for 22 hours.
医薬グレードの結晶性不溶セフアレキシン１水和物２０
．０夕（乾燥体）を得た。例２ブタノールー水再結晶法
によるセフアレキシン１水和物（不溶体）以下の方法は
目的結晶体と同一の高純度を有する極めて白色の生成物
を与えることが判明している。Pharmaceutical grade crystalline insoluble cephalexin monohydrate 20
．． 0 ml (dry substance) was obtained. Example 2 Cephalexin Monohydrate (Insoluble) by Butanol-Water Recrystallization Method The following method has been found to give a very white product with a high purity identical to that of the desired crystalline form.
プタ／−ル層から残留ジメチルアニリン（ＤＭＡ）およ
び着色体を除き、水層より水溶性不純物を除去するｃ１
１０００夕の−級セフアレキシンを徐々に４０の‘の
６Ｎ ＨＣＩを含有する２４００地の脱イオン水に加え
た。c1: Remove residual dimethylaniline (DMA) and colored bodies from the Pthal/Al layer, and remove water-soluble impurities from the aqueous layer.
1000 g of cephalexin was gradually added to 2400 g of deionized water containing 40 g of 6N HCI.
６Ｎ ＨＣＩを加えることによりｐＨを１．６一１．８
に保持しつつ、添加は約１５分かけて徐々に実施する。Adjust the pH to 1.6-1.8 by adding 6N HCI.
The addition is carried out gradually over a period of about 15 minutes, while maintaining the temperature.
斑は常にチェックし、完全な溶液を得るには統計３９０
〜４００地の鮒ＨＣＩを必要とする。温度は約２０ｑｏ
に維持する。２ １００夕の脱色用活性炭（“Ｄａｒｅ
ｏＫＢ’）を溶液に加え、スラリーを３０分間鷹拝する
。Always check for plaque and use Statistics 390 to get a complete solution.
Requires ~400 pieces of Carp HCI. The temperature is about 20qo
to be maintained. 2 Activated carbon for decolorization (“Dare”)
oKB') is added to the solution and the slurry is incubated for 30 minutes.
スラリーをプレコートしたフィルターで炉適する。３
ケーキを充分な脱イオン水で洗浄し、炉液を４．０リッ
トルにした。A filter pre-coated with slurry is applied to the furnace. 3
The cake was washed with sufficient deionized water to bring the furnace liquor to 4.0 liters.
液量を多くすれば母液中の損失分は増大する。４ 炉液
を約３０一３５机【のトリェチルアミン（ＴＥＡ）を用
いてｐＨ２．１−２．２に調整する。If the amount of liquid is increased, the loss in the mother liquor will increase. 4 Adjust the furnace solution to pH 2.1-2.2 using about 30-35 ml of triethylamine (TEA).
ＰＨ‘まモニターする必要がある。若干にごりが生じる
。５ ２０００地のｎ−ブタノールを上記水溶液に加え
、温度を４０℃にする。PH'ma needs to be monitored. Some cloudiness occurs. 5 Add 2000 ml of n-butanol to the above aqueous solution and bring the temperature to 40°C.
約１００の‘のＴＥＡを加え、そのバッチに種結晶を加
える。この操作により良好な結晶スラリーが得られる。
６ ＴＥＡは５分間かけて（温度を４０３０に保持しつ
つ）一定速度で加え、斑を４．４−４．６とする。Add approximately 100' TEA and seed the batch. A good crystal slurry can be obtained by this operation.
6 TEA is added at a constant rate over 5 minutes (maintaining temperature at 4030) to give a speck of 4.4-4.6.
ＴＥＡの全必要量は３４５〜３５０＊の‘である。７
スラリーをブフナーロートで炉遇し、ケーキを２そのブ
タノールまたは洗浄ブタノールの着色が認められなくな
るまで洗浄する。The total amount of TEA required is 345-350*'. 7
The slurry is heated in a Buchner funnel and the cake is washed until no more color is observed from the butanol or the washed butanol.
＊その濃度をチェックするためにＰＨを４．５にするに
必要なＴＥＡの量は一定量の磯ＨＣＩをＴＥＡであらか
じめ滴定することが必要である。*To check the concentration, it is necessary to titrate a certain amount of Iso HCI with TEA in advance to determine the amount of TEA required to bring the pH to 4.5.
滴定の前にＨＣＩは８倍の脱イオン水で希釈する。この
操作により結晶化の際のＴＥＡの過剰添加を防止し得る
。８ ケーキ一を０一５℃で１５００の‘の脱イオン水
で洗浄する。Before titration, HCI is diluted 8 times with deionized water. This operation can prevent excessive addition of TEA during crystallization. 8. Wash the cake with 1500' deionized water at 0-5°C.
９ ケーキ一を最終的に２０００の‘のィソプロパノー
ルで洗浄する。9. Wash the cake a final time with 2000' of isopropanol.
それを５３−５５ｑｏで１晩（約１６−２岬時間）乾燥
する。原料１０００夕あたり８００一８２０夕の不港性
セフアレキシン１水和物が得られる例３パイロットプラ
ント濃厚水からのＢｕＯＨ−比○システムによる直接結
晶法のセフアレキシン１水和物（不溶体）１０００の‘
のパイロットプラント部分濃縮酸性水溶液（セフアレキ
シンの）を減圧下で約２００の‘まで濃縮した。Dry it overnight (approximately 16-2 hours) at 53-55 qo. Example 3 Direct crystallization of cephalexin monohydrate (insoluble) from pilot plant concentrate water by BuOH-ratio system yields 800-820 m of unportable cephalexin monohydrate per 1000 m of raw material
A pilot plant partially concentrated acidic aqueous solution (of cephalexin) was concentrated to about 200' under reduced pressure.
濃縮物のｐＨは１．１であた。温度は２がｏであった。
１０．０泌のＴＥＡによりｐＨを２．１に調整した。The pH of the concentrate was 1.1. The temperature was 2 o.
The pH was adjusted to 2.1 with 10.0 TEA.
セフアレキシン１水和物（不溶体）１．０夕を種結晶と
して添加し、さらに１５０の‘のｎ−プタ／ールを加え
た。極めて容易に濃厚な結晶が生成した。スラリーをか
くはんしつつ３時間かけてＴＥＡ（８．０の【）を滴下
（１．０の‘）した。スラリーを２０００で１時間蝿拝
し、次いで固体生成物を炉過回収し、フィルターケーキ
を２００叫の含水ブタノール次いで１００の‘の袷（０
−５℃）脱イオン水で洗浄した。ケーキをさらに１００
の上の乾燥ブタノール、次いで１００の‘のィソプロパ
ノールで洗浄した。ケーキを５０００で乾燥した。３０
０夕のセフアレキシン１水和物（不溶体）を得た。1.0 ml of cephalexin monohydrate (insoluble) was added as a seed crystal, and an additional 150' of n-butar was added. Dense crystals formed very easily. While stirring the slurry, TEA (8.0) was added dropwise (1.0') over 3 hours. The slurry was stirred at 2,000 °C for 1 hour, the solid product was then collected by filtration, and the filter cake was washed with 200 °C of aqueous butanol and then 100 °C of water (0.5 °C).
-5°C) and washed with deionized water. 100 more cakes
Washed with 100' of dry butanol and then 100' of isopropanol. The cake was dried at 5000 ml. 30
Cephalexin monohydrate (insoluble form) of 0.0 m was obtained.
種結晶の１．０夕を考慮すれば収量は２９．０夕となる
。分析値 Ｋ．Ｆ．Ｈ２０＝３．９％ｍＡ＝０．１５％
ＢｕＯＨ＝０．５７％Considering 1.0 days of seed crystal, the yield will be 29.0 days. Analysis value K. F. H20=3.9% mA=0.15% BuOH=0.57%
Claims (1)
ン１水和物の製造法においてセフアレキシンの濃厚、酸
性水溶液を調製し、十分量のｎ−ブタノールを加えて２
相の液相を形成させ、次いで上記２相系を徐々に中和し
て上記の水に不溶性の結晶性セフアレキシン１水和物を
析出させることを特徴とする方法。[Claims] 1 X-ray diffraction data Planar spacing d (Å) Relative intensity I/I_1 16.01. 19 12.07 1.00 10.82 . 13 9.64. 03 8.83. 07 8.53. 13 8.10. 26 7.07. 08 6.10. 14 5.60. 22 5.43. 64 4.98. 17 4.76. 09 4.57. 17 4.39. 18 4.23. 18 4.02. 30 3.94. 13 3.86. 19 3.79. 04 3.70. 05 3.61. 18 3.44. 08 3.24. 10 3.20. 05 3.11. 13 2.99. 08 2.91. 09 2.80. 07 2.73. 07 2.67. In the method for producing crystalline cephalexin monohydrate, which has a relatively low water solubility of 0.09, a concentrated, acidic aqueous solution of cephalexin is prepared, and a sufficient amount of n-butanol is added.
A method characterized in that a liquid phase of the phase is formed and then the two-phase system is gradually neutralized to precipitate the water-insoluble crystalline cephalexin monohydrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP48040094A JPS606957B2 (en) | 1973-04-10 | 1973-04-10 | Method for producing antibiotic derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP48040094A JPS606957B2 (en) | 1973-04-10 | 1973-04-10 | Method for producing antibiotic derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS49126811A JPS49126811A (en) | 1974-12-04 |
| JPS606957B2 true JPS606957B2 (en) | 1985-02-21 |
Family
ID=12571278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP48040094A Expired JPS606957B2 (en) | 1973-04-10 | 1973-04-10 | Method for producing antibiotic derivatives |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS606957B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01159523A (en) * | 1987-12-14 | 1989-06-22 | Eiken Kogyo Kk | Combustion device for gas burner |
| JPH01159522A (en) * | 1987-12-14 | 1989-06-22 | Eiken Kogyo Kk | Combustion device for gas burner |
| JP2640950B2 (en) * | 1987-12-14 | 1997-08-13 | エイケン工業株式会社 | Combustion device for gas burner |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5621395B2 (en) * | 1973-07-18 | 1981-05-19 | ||
| EA200400682A1 (en) | 2001-11-16 | 2004-10-28 | Рэнбакси Лабораториз Лимитед | METHOD FOR OBTAINING CRYSTALLINE IMPENEM |
-
1973
- 1973-04-10 JP JP48040094A patent/JPS606957B2/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01159523A (en) * | 1987-12-14 | 1989-06-22 | Eiken Kogyo Kk | Combustion device for gas burner |
| JPH01159522A (en) * | 1987-12-14 | 1989-06-22 | Eiken Kogyo Kk | Combustion device for gas burner |
| JP2640950B2 (en) * | 1987-12-14 | 1997-08-13 | エイケン工業株式会社 | Combustion device for gas burner |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS49126811A (en) | 1974-12-04 |
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