KR940002713B1 - Process for the preparation of photosensitive diazo-type compounds - Google Patents
Process for the preparation of photosensitive diazo-type compounds Download PDFInfo
- Publication number
- KR940002713B1 KR940002713B1 KR1019910022029A KR910022029A KR940002713B1 KR 940002713 B1 KR940002713 B1 KR 940002713B1 KR 1019910022029 A KR1019910022029 A KR 1019910022029A KR 910022029 A KR910022029 A KR 910022029A KR 940002713 B1 KR940002713 B1 KR 940002713B1
- Authority
- KR
- South Korea
- Prior art keywords
- formula
- compound
- reaction
- reacted
- cpd
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/14—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D295/145—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
본 발명은 다음 일반식(Ⅰ)로 표시되는 1-헤테로사이클-2,5-디알콕시-4-아미노벤젠 유도체의 새로운 제조방법에 관한 것이다.The present invention relates to a novel process for preparing 1-heterocycle-2,5-dialkoxy-4-aminobenzene derivatives represented by the following general formula (I).
식중, R1및 R2는 같거나 다르며 각각 탄소수 1-4의 직쇄 또는 측쇄의 알킬 그룹이며, R3는 수소 또는 메틸기이며, Z는 산소 또는 탄소원자이다.Wherein R 1 and R 2 are the same or different and are each a straight or branched alkyl group having 1 to 4 carbon atoms, R 3 is hydrogen or a methyl group, and Z is oxygen or a carbon atom.
상기 일반식(1)의 화합물중 1-모르포리노-2,5-디부톡시-4-아미노벤젠은 공지의 화합물이며, 영국특허 제853020호 및 일본특허공고 소41-18339호에 공개되어 있으며, 디아조타입의 감광제의 원료로서 사용되고 있다.1-morpholino-2,5-dibutoxy-4-aminobenzene in the compound of Formula (1) is a known compound, and is disclosed in British Patent No. 853020 and Japanese Patent Publication No. 41-18339. It is used as a raw material of the diazo type photosensitive agent.
영국특허 제853020호에 의하면 다음의 방법으로 제조하고 있다.According to British Patent No. 853020, it is manufactured by the following method.
그러나 이들 방법은 제조공정이 복잡하며 수율이 나쁜 문제점이 있다.However, these methods have a problem in that the manufacturing process is complicated and the yield is bad.
또한 일본특허공고 소41-18339호에서는 다음의 공정으로 제조하고 있다.In addition, Japanese Patent Publication No. 41-18339 manufactures the following processes.
이 방법의 문제점은 상기 영국특허의 모든 공정을 거치면서 단지 치환반응의 수율을 높이기 위하여 금속 촉매를 사용하는 것이다.The problem with this method is the use of metal catalysts to increase the yield of substitution reactions throughout all the processes of the British patent.
본 발명자들은 상기 일반식(Ⅰ)의 화합물을 더욱 간단한 방법 및 경제적으로 제조하기 위한 연구를 오랜동안 계속한 결과, 다음 일반식(Ⅱ)의 화합물을 직접 암모니아로 처리하면, 상기 공지의 방법중 니트로화 반응 및 환원반응과 같은 복잡한 반응공정을 거치지 않고도 간단히 높은 수율과 순도로 목적화합물을 제조할 수 있는 놀라운 사실을 발견하여 본 발명을 완성하였다.The present inventors have continued for a long time research to prepare the compound of the general formula (I) in a simpler way and economically, and when the compound of the following general formula (II) is directly treated with ammonia, nitro in the known method The present invention has been completed by discovering the surprising fact that a desired compound can be prepared in high yield and purity without undergoing complicated reaction processes such as a reduction reaction and a reduction reaction.
따라서 본 발명의 목적은 더욱 간단하고 낮은 코스트의 원료를 사용하여 높은 수율과 순도로서 일반식(Ⅰ)의 화합물을 제조하는 방법을 제공하는 것이다.It is therefore an object of the present invention to provide a process for the preparation of compounds of general formula (I) in high yield and purity using simpler and lower cost raw materials.
본 발명은 다음 일반식(Ⅳ)의 화합물을 다음 일반식(Ⅲ)의 화합물과 반응시켜서 얻어진 다음 일반식(Ⅱ)의 화합물을 닉켈이나 산화닉켈과 같은 금속 또는 금속산화물 촉매 존재하에 암모니아와 반응시켜서 일반식(Ⅰ)의 화합물을 제조하며, 반응식으로 표시하면 다음의 반응 1과 같다.The present invention is obtained by reacting a compound of formula (IV) with a compound of formula (III) and then reacting a compound of formula (II) with ammonia in the presence of a metal or metal oxide catalyst such as nickel or nickel oxide. The compound of Formula (I) is prepared, and represented by the following reaction scheme.
반응 1:Reaction 1:
식중 R1, R2, R3및 Z는 전술한 바와 같으며, X는 할로겐 원자이다.Wherein R 1 , R 2 , R 3 and Z are as described above and X is a halogen atom.
일반식(Ⅲ)의 화합물은 다음 구조식(Ⅴ)의 화합물을 염기존재하에 일반식 R1X(Ⅵ) 및/또는 R2X(Ⅶ)의 화합물을 반응시켜서 제조하며 반응식으로 나타내면 다음 반응 2와 같다.The compound of formula (III) is prepared by reacting a compound of formula (V) with a compound of the general formula R 1 X (VI) and / or R 2 X (VII) in the presence of a base. same.
반응 2 :Reaction 2:
식중 R1, R2는 전술한 바와 같으며, X는 할로겐원자이다.Wherein R 1 and R 2 are as described above, and X is a halogen atom.
반응 1의 제2공정은 약 150-250도의 온도에서 행한다.The second step of reaction 1 is carried out at a temperature of about 150-250 degrees.
반응시간은 30분 내지 1.5시간동안 행한다.The reaction time is carried out for 30 minutes to 1.5 hours.
반응은 약 10-100Kg/㎠의 압력하에 행함이 바람직하다.The reaction is preferably carried out under a pressure of about 10-100 Kg / cm 2.
촉매는 닉켈이나 또는 산화닉켈과 같은 금속 또는 금속산화물촉매 존재하에 행한다.The catalyst is carried out in the presence of a metal or metal oxide catalyst such as nickel or nickel oxide.
반응은 소량의 물의 존재하에 메탄올 또는 에탄올과 같은 저급알칸올과 같은 용매중에서 반응시킨다.The reaction is reacted in a solvent such as lower alkanol such as methanol or ethanol in the presence of a small amount of water.
사용량은 일반식(Ⅱ)의 화합물 1당량당 촉매 약 0.1당량, 암모니아 약 2.5당량, 물 약 0.3당량 및 저급알칸올 약 100㎖를 사용한다.The used amount is about 0.1 equivalent of catalyst, about 2.5 equivalents of ammonia, about 0.3 equivalents of water, and about 100 ml of lower alkanol per equivalent of Compound (II).
투입은 각각의 성분을 용기에 넣고 암모니아로 가압하에 채우고 밀폐시킨 후 가열하여 반응시키면 약 80%의 수율로 목적화합물이 얻어진다.In the input, each component is placed in a container, filled with ammonia under pressure, sealed, heated and reacted to obtain a target compound in a yield of about 80%.
반응 1의 제1공정은 반응온도 약 150-200도의 온도에서 약 4-8시간 반응시킨다.The first step of the reaction 1 is reacted for about 4-8 hours at the reaction temperature of about 150-200 degrees.
반응은 약 10-50Kg/㎠의 압력에서 행하며 염기촉매 및 황산동의 혼합촉매 존재하에 반응시킨다.The reaction is carried out at a pressure of about 10-50 Kg / cm 2 and reacted in the presence of a mixed catalyst of a base catalyst and copper sulfate.
반응은 모르포린등과 같은 용매중에서 행함이 바람직하다.The reaction is preferably carried out in a solvent such as morpholine.
사용량은 일반식(Ⅲ)의 화합물 1당량당 일반식(Ⅳ)의 화합물 약 2-20당량을 사용하며 약 3-6당량 사용함이 바람직하다.The amount used is about 2-20 equivalents of the compound of formula (IV) per 1 equivalent of the compound of formula (III), and preferably about 3-6 equivalents.
촉매사용량은 염기 약 1당량 및 황산동 약 0.01-0.1당량을 사용한다.The amount of catalyst used is about 1 equivalent of base and about 0.01-0.1 equivalents of copper sulfate.
정제방법은 반응후의 혼합물을 과량의 물로 세척한 후 염화메틸렌을 가하여 추출한 후 염화메틸렌을 증류하여 행한다.The purification method is performed by washing the mixture after the reaction with excess water, extracting by adding methylene chloride and distilling methylene chloride.
약 60-80%의 수율로 목적화합물이 얻어진다.The desired compound is obtained in a yield of about 60-80%.
반응 2의 반응은 약 60-120도의 온도에서 행함이 바람직하다.The reaction of Reaction 2 is preferably carried out at a temperature of about 60-120 degrees.
반응시간은 약 30분 내지 10시간에서 행하며, 약 2-6시간이면 반응이 완결된다.The reaction time is performed in about 30 minutes to 10 hours, and the reaction is completed in about 2-6 hours.
반응시에 촉매로는 수산화 나트륨, 수산화 칼륨, 수산화 리튬, 수산화 칼슘, 수산화 마그네슘등과 같은 알카리 또는 알카리토류 금속의 수산화물, 탄산소다, 탄산칼륨, 탄산칼슘, 탄산마그네슘 등과 같은 알카리 금속 또는 알칼리토류금속의 탄산염, 탄산수소나트륨, 탄산수소칼륨 등과 같은 알칼리금속 또는 알칼리토류 금속의 중탄산염 및 기타 통상의 염기성물질을 사용한다.In the reaction, the catalyst may be an alkali metal or alkaline earth metal such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, or an alkali or alkaline earth metal hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, or the like. Bicarbonates of alkali metals or alkaline earth metals such as carbonates, sodium hydrogen carbonates, potassium hydrogen carbonates and the like, and other conventional basic substances.
또한 트리메틸아민, 트리에틸아민, 피리딘등과 같은 3급아민류등의 존재하에 반응시킬 수도 있다.The reaction may also be carried out in the presence of tertiary amines such as trimethylamine, triethylamine, pyridine and the like.
본 반응은 메틸에틸케톤, 메틸이소부틸케톤 등과 같은 케톤류나 기타 통상의 유기용매중에서 반응시킨다.This reaction is carried out in ketones such as methyl ethyl ketone, methyl isobutyl ketone and the like or other conventional organic solvents.
사용량은 일반식(Ⅴ)의 화합물 1당량당 일반식(Ⅵ)의 화합물 또는 (Ⅶ)의 화합물 1.2-3당량을 사용하며, 염기는 1-3당량 사용함이 바람직하다.The amount used is preferably 1.2-3 equivalents of the compound of formula (VI) or (iii) per 1 equivalent of compound of formula (V), and 1-3 equivalents of base.
정제방법은 용매를 증류한 후 물로 용해하고, 이 용액을 염화메틸렌으로 추출하고 염화메틸렌을 증류시킨다.In the purification method, the solvent is distilled off, dissolved in water, the solution is extracted with methylene chloride, and methylene chloride is distilled off.
다음에 실시예로서 본 발명을 더욱 상세히 설명한다.Next, the present invention will be described in more detail by way of examples.
[실시예 1]Example 1
1) 냉각기, 교반기가 장착된 1L 용량의 4구 플라스크에 메틸에틸케톤 400㎖, 클로로하이드로퀴논 144.56g, 탄산칼륨 276.42g을 넣고 10분간 교반한 후 부틸부로마이드 301.47g을 투입한다.1) Into a 1 L four-necked flask equipped with a cooler and a stirrer, add 400 ml of methyl ethyl ketone, 144.56 g of chlorohydroquinone, and 276.42 g of potassium carbonate, and stir for 10 minutes.
온도를 80도에서 환류시키면서 5시간동안 반응시킨다.The reaction is carried out for 5 hours while refluxing at 80 degrees.
냉각시킨 후 탄산칼륨을 여과하고 메틸에틸케톤을 증류한다.After cooling, potassium carbonate is filtered and methyl ethyl ketone is distilled off.
물 400㎖를 가하여 용해시킨 후 염화메틸렌 400㎖로 추출한다.400 ml of water was added for dissolution and then extracted with 400 ml of methylene chloride.
추출한 염화메틸렌을 증류하면 1-클로로-2,5-디부톡시벤젠 252g이 얻어진다.Distillation of the extracted methylene chloride yields 252 g of 1-chloro-2,5-dibutoxybenzene.
NMR benzene 6.82δ(m)NMR benzene 6.82δ (m)
-OCH2- 4.12δ(t)-OCH 2 - 4.12δ (t)
-CH2CH2- 1.65δ(m) -CH 2 CH 2 - 1.65δ (m )
-CH30.98δ(t)-CH 3 0.98δ (t)
2) 1)에서 얻어진 1-클로로-2,5-디부톡시벤젠 256.78g, 모르포린 435.60g, 가성소다 40.00g, 황산동 1.60g을 1L의 오토클레이브에 넣고 완전히 밀폐한 후 질소가스로 40Kg/㎠까지 압력을 올린 다음 온도를 185도-200도까지 올리고 압력을 45Kg/㎠까지 올린 후 6시간동안 반응시킨다.2) Put 256.78 g of 1-chloro-2,5-dibutoxybenzene, 435.60 g of morpholine, 40.00 g of caustic soda, and 1.60 g of copper sulfate in a 1 L autoclave and completely seal it with nitrogen gas at 40 Kg / ㎠ Raise the pressure to 185 degrees to 200 degrees and raise the pressure to 45Kg / ㎠ and react for 6 hours.
냉각한 후 물 400㎖로 세척한 후 염화메틸렌 400㎖로 추출한다.After cooling, the mixture was washed with 400 ml of water and extracted with 400 ml of methylene chloride.
추출한 염화메틸렌을 증류하여 1-모르포리노-2,5-디부톡시벤젠 230g을 얻는다.The extracted methylene chloride is distilled off to obtain 230 g of 1-morpholino-2,5-dibutoxybenzene.
NMR benzene 6.82δ(m)NMR benzene 6.82δ (m)
-OCH2- 4.12δ(t)-OCH 2 - 4.12δ (t)
-CH2CH2- 1.66δ(m) -CH 2 CH 2 - 1.66δ (m )
-CH30.99δ(t)-CH 3 0.99δ (t)
-OCH2CH2N 2.20δ(m)-OCH 2 CH 2 N 2.20δ (m)
3) 500㎖의 오토클레이브에 1-모르포리노-2,5-디부톡시벤젠 307.42g, 메탄올 100㎖, 물 5.4g을 넣고 산화닉켈 7.47g을 넣고 밀폐한다.3) Add 307.42 g of 1-morpholino-2,5-dibutoxybenzene, 100 ml of methanol, and 5.4 g of water to a 500 ml autoclave, add 7.47 g of nickel oxide, and seal.
밀폐후 암모니아 개스 42.58g을 채우면 압력이 약 10Kg/㎠ 정도로 올라간다.After sealing, filling 42.58 g of ammonia gas increases the pressure to about 10 Kg / cm 2.
승온하여 200도까지 올리면 압력이 80-90Kg/㎠이고 이때부터 1시간 교반한다.When the temperature is raised to 200 degrees, the pressure is 80-90Kg / cm 2 and the mixture is stirred for 1 hour.
냉각후 여과하여 용매를 증류하여 1-모르포리노-2,5-이부톡시아미노 벤젠 257.3g을 얻는다.After cooling, the mixture was filtered to distill the solvent to give 257.3 g of 1-morpholino-2,5-butoxyamino benzene.
NMR benzene 7.37δ(m)NMR benzene 7.37δ (m)
-OCH2- 3.92δ(t)-OCH 2 - 3.92δ (t)
-CH2CH2- 1.61δ(m) -CH 2 CH 2 - 1.61δ (m )
-CH30.94δ(t)-CH 3 0.94δ (t)
OCH2CH2N- 2.10δ(m)OCH 2 CH 2 N- 2.10δ (m)
[실시예 2]Example 2
1) 실시예 1-1)에서 얻어진 1-클로로-2,5-디부톡시벤젠 256.78g, 모르포린 104.54g, 가성소다 40.00g, 황산동 1.60g, 톨루엔 300g을 1L의 오토클레이브에 넣고 완전히 밀폐한 후 질소로 30Kg/㎠까지 압력을 올린 다음 온도를 190도까지 올려 압력이 45Kg/㎠인 것을 확인한 후 6시간동안 반응시킨다.1) 256.78 g of 1-chloro-2,5-dibutoxybenzene, morpholine 104.54 g, caustic soda 40.00 g, copper sulfate 1.60 g and toluene 300 g obtained in Example 1-1) were placed in a 1 L autoclave and completely sealed. After raising the pressure to 30Kg / ㎠ with nitrogen and then the temperature was raised to 190 degrees to confirm that the pressure is 45Kg / ㎠ and reacted for 6 hours.
냉각한 후 물 400㎖로 세척한 후 톨루엔층을 휘발시키면 1-모르포리노-2,5-디부톡시벤젠 230g이 생성된다.After cooling, the mixture was washed with 400 ml of water, followed by volatilization of the toluene layer to produce 230 g of 1-morpholino-2,5-dibutoxybenzene.
2) 500㎖의 오토클레이브에 1-모르포리노-2,5-디부톡시벤젠 307.42g, 아세토니트릴 100㎖, 물 5.4g을 넣고 닉켈 6.00g을 넣고 밀폐한다.2) Into a 500 ml autoclave, add 307.42 g of 1-morpholino-2,5-dibutoxybenzene, 100 ml of acetonitrile, and 5.4 g of water.
밀폐후 암모니아 개스 42.58g을 채우면 압력이 약 10Kg/㎠ 정도로 올라간다.After sealing, filling 42.58 g of ammonia gas increases the pressure to about 10 Kg / cm 2.
승온하여 200도까지 올리면 압력이 85Kg/㎠이고 이때부터 1시간 교반한다.When the temperature is raised to 200 degrees, the pressure is 85Kg / cm 2 and the mixture is stirred for 1 hour.
냉각후 여과하여 용매를 증류하면 1-모르포리노-2,5-디부톡시아미노벤젠 257g을 얻는다.After cooling, the solvent was distilled off by filtration to obtain 257 g of 1-morpholino-2,5-dibutoxyaminobenzene.
본 발명에서 온도는 모두 섭씨온도를 나타낸다.In the present invention, the temperatures all represent degrees Celsius.
Claims (5)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019910022029A KR940002713B1 (en) | 1991-12-03 | 1991-12-03 | Process for the preparation of photosensitive diazo-type compounds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019910022029A KR940002713B1 (en) | 1991-12-03 | 1991-12-03 | Process for the preparation of photosensitive diazo-type compounds |
Publications (2)
Publication Number | Publication Date |
---|---|
KR930012739A KR930012739A (en) | 1993-07-21 |
KR940002713B1 true KR940002713B1 (en) | 1994-03-31 |
Family
ID=19324050
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1019910022029A KR940002713B1 (en) | 1991-12-03 | 1991-12-03 | Process for the preparation of photosensitive diazo-type compounds |
Country Status (1)
Country | Link |
---|---|
KR (1) | KR940002713B1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6835060B2 (en) * | 2018-12-27 | 2021-02-24 | ダイキン工業株式会社 | Cyclobutene manufacturing method |
-
1991
- 1991-12-03 KR KR1019910022029A patent/KR940002713B1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
KR930012739A (en) | 1993-07-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1113100A (en) | Preparation of 1-desoxy-nojirimicin and n-substituted derivatives | |
US5274166A (en) | Dithiocarbamic acid salt, process for production thereof, and process for production of isothiocyanate using said dithiocarbamic acid salt | |
KR940002713B1 (en) | Process for the preparation of photosensitive diazo-type compounds | |
EP0147472B1 (en) | 4-chloro-4-methyl-5-methylene-1,3-dioxolan-2-one | |
Yokoyma et al. | Regiochemical aspects in the reaction of 2, 3, 5-tri-o-benzoyl-d-ribofuranosyl: Acetate with silyl enol ethers catalyzed by stannic chloride | |
AU737994B2 (en) | Process for preparing o-(3-amino-2-hydroxy-propyl)-hydroxymic acid halides | |
KR100369274B1 (en) | Improved process for producing 4-hydroxy-2-pyrrolidone | |
KR930000290B1 (en) | Synthesis of perfluoroalkyl bromides | |
US5756724A (en) | High-yielding ullmann reaction for the preparation of bipyrroles | |
US5399763A (en) | Process for preparing optically active 2-aminopropanal | |
JP3536480B2 (en) | 4,5-Dihalogeno-6-dihalogenomethylpyrimidine and process for producing the same | |
US5089651A (en) | Process for producing 3-iminonitriles | |
JPH04169583A (en) | Phenothiazine derivative and its production | |
HU190224B (en) | Process for producing methyl-2-tetradecyl-glycidate | |
JPH01501002A (en) | Synthesis of N-epoxypropyllactam | |
JPS62249963A (en) | Manufacture of n-(sulfonylmethyl)formaldehydes | |
KR860000624B1 (en) | Process for preparing pirbuterol and analogs | |
US4091033A (en) | Method of making 2-alkoxy-2,3-dihydro-benzofuran-5-ols and their alkyl sulfonic acid esters | |
KR850001473B1 (en) | Process for the preparation of 1-phenyl-8,8-dialkoxy-3,6-diazooctane-4-one derivation | |
KR0127251B1 (en) | Process for preparing of 4,4'-bischloro-methylbiphenyl | |
KR860000623B1 (en) | Process for preparting pirbuterol and analogs | |
KR860000625B1 (en) | Process for preparing pirbuterol and analogs | |
KR100297802B1 (en) | Method for preparing 2- (3-trifluoromethyl) anilinonicotinic acid 2- (N-morpholine) ethyl. | |
JP3515257B2 (en) | Method for producing 2,3,6,7,10,11-hexaacetoxytriphenylene | |
EP3950663A1 (en) | New method for obtaining diester compounds useful for the manufacture of new quaternary ammonium compounds |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
G160 | Decision to publish patent application | ||
E701 | Decision to grant or registration of patent right | ||
GRNT | Written decision to grant | ||
FPAY | Annual fee payment |
Payment date: 19970127 Year of fee payment: 4 |
|
LAPS | Lapse due to unpaid annual fee |