CN1515539A - Preparation method of nitrobenzene chloro-fluoride and its derivative - Google Patents
Preparation method of nitrobenzene chloro-fluoride and its derivative Download PDFInfo
- Publication number
- CN1515539A CN1515539A CNA031506895A CN03150689A CN1515539A CN 1515539 A CN1515539 A CN 1515539A CN A031506895 A CNA031506895 A CN A031506895A CN 03150689 A CN03150689 A CN 03150689A CN 1515539 A CN1515539 A CN 1515539A
- Authority
- CN
- China
- Prior art keywords
- chloro
- dichloronitrobenzene
- fluoroaniline
- fluoronitrobenzene
- derivative
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a preparation method of chlorofluorinated nitrobenzene and its derivative. It includes fluorization reaction step and separation purification step. The described fluorization reaction steps uses the mixture of 3,4-dichloronitrobenzene and 2,3-dichloronitrobenzene as raw material, after the fluorization reaction the described separation and purification step can be made. According to the requirements. It can respectively prepare 3-chloro-2-fluoronitrobenzene, 3-chloro-4-fluoronitrobenzene, 3-chloro-2-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-dichlorofluorobenzene and 2-6-dichlorofluorobenzene. The mixture of 3,4-dichloronitrobenzene and 2,3-dichloronitrobenzene can be nitrated product of ortho-dichlorobenzene, also can be low oil remained after the partial 3,4-dichloronitrobenzene is separated out from the nitrated product.
Description
Technical field
The present invention relates to the preparation method of chloro fluoro nitrobenzene and derivative thereof, be by 3 specifically, 4-dichloronitrobenzene and 2, the miscellany of 3-dichloronitrobenzene prepare 3-chloro-2-fluoronitrobenzene, 3-chloro-4-fluoronitrobenzene and the nitro of the two are replaced the derivative of gained by amino or chlorine method.
Background technology
3-chloro-2-fluoronitrobenzene, 3-chloro-4-fluoronitrobenzene, 3-chloro-2-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4 dichloro fluorobenzene and 2,6-dichlor fluorbenzene are the important intermediate of quinolones such as preparation Ciprofloxacin and Abbott 56619 and agricultural chemicals.
At present, no matter from the angle of production security, the still angle from reducing cost is that to produce the said products all are comparatively rational operational paths to starting raw material with the orthodichlorobenzene.
Chinese patent application 93110558.7 discloses " 2; 4-dichlor fluorbenzene synthesis technique ", it is a starting raw material with orthodichlorobenzene and santochlor mixture, get the nitro dichlorobenzene through nitrated, underpressure distillation, fluoridize and make 3-chloro-4-fluoronitrobenzene and 2-fluoro-5-chloronitrobenzene mixture, make 2,4 dichloro fluorobenzene through chlorination again.
Chinese patent 94120005.1 discloses " 2,4 dichloro fluorobenzene synthetic method ", and it gets mixture with orthodichlorobenzene or santochlor or both and sets out, through nitrated, fractionation by distillation, fluoridize, chlorination gets 2,4 dichloro fluorobenzene.
Chinese patent 92107812.9 discloses " 2,4 dichloro fluorobenzene production technique ", and it is raw material with the orthodichlorobenzene, gets 3 through mixed acid nitrification, fractionation by distillation, the 4-dichloronitrobenzene, again through fluoridize, chlorination gets 2,4 dichloro fluorobenzene.
The somebody is with 2, and the 3-dichloronitrobenzene is a raw material, through fluoridizing, having made 2, the 6-dichlor fluorbenzene after the chlorination.
Chinese patent application 87101430.0 discloses " production method of chloro fluoro nitrobenzene ", and it is raw material with the dichloronitrobenzene, makes chloro fluoro nitrobenzene through fluoridizing.
In the above-mentioned public technology, having with the dichloronitrobenzene is the situation of raw material, but the source of dichloronitrobenzene generally is nitrated by orthodichlorobenzene, thus its still can to belong to the orthodichlorobenzene be the situation of starting raw material.
As from the foregoing, no matter be to be raw material with the orthodichlorobenzene in the prior art, still be starting raw material with orthodichlorobenzene and santochlor mixture, all be to be about to required dichloronitrobenzene separate from the dichloronitrobenzene mixture after nitrated in advance, carries out next step reaction again.Yet, the separation not a duck soup of two kinds of nitration products of orthodichlorobenzene.In the nitration product of orthodichlorobenzene 2, the 3-dichloronitrobenzene generally accounts for 10～20% of nitration product gross weight, 3, the 4-dichloronitrobenzene generally accounts for 80～90%, and the former boiling point is that 257～258 ℃, fusing point are 61～62 ℃, and the latter's boiling point is that 255～256 ℃, fusing point are 41～44 ℃, boiling-point difference of the two and physical properties difference are very little, it separates quite difficulty, and separation costs is very high, thereby directly causes holding at high price of subsequent product.
In addition, with 3, the 4-dichloronitrobenzene is the producer of product, usually adopting orthodichlorobenzene is raw material, after nitrated, carry out Crystallization Separation, its isolating result obtains 3 of purity 〉=99%, the 4-dichloronitrobenzene and be commonly called as " low oil " 2,3-dichloronitrobenzene and 3, the mixture of 4-dichloronitrobenzene, generally the former yield is 60～80%, the latter's yield is 20～40%, in " low oil " 2, the content of 3-dichloronitrobenzene is 20～45% (wt%, down with), 3, the content of 4-dichloronitrobenzene is 55～80%.The purposes of " low oil " is extremely limited, uses mainly as low value solvent based product, is perhaps burned, and has perhaps simply overstock into refuse, even has stealthily been emitted, and has consequently not only wasted resource but also polluted environment, allows rather headache of producer.
Summary of the invention
Technical problem to be solved by this invention be provide at above-mentioned prior art present situation a kind of technology simple, separate easily, production cost significantly reduces and help utilizing the chloro fluoro nitrobenzene of existing waste material and the preparation method of derivative thereof.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the preparation method of this kind chloro fluoro nitrobenzene and derivative thereof, it includes fluorination reaction step and separates purification step, it is characterized in that described fluoridation is with 3,4-dichloronitrobenzene and 2, the miscellany of 3-dichloronitrobenzene is a raw material, carries out described separation purification step after the fluoridation again.
Be about to the gained organic phase after described fluoridation is finished and give the rectifying separation purification, make 3-chloro-2-fluoronitrobenzene and 3-chloro-4-fluoronitrobenzene; Perhaps, be raw material further with 3-chloro-2-fluoronitrobenzene and/or the 3-chloro-4-fluoronitrobenzene that makes, carry out chlorination, the nitro on the substituted benzene ring, make corresponding 2,6-dichlor fluorbenzene and/or 2,4 dichloro fluorobenzene; Perhaps, further 3-chloro-2-fluoronitrobenzene and/or the 3-chloro-4-fluoronitrobenzene with gained reduced, and makes corresponding 3-chloro-2-fluoroaniline and/or 3-chloro-4-fluoroaniline; Perhaps, be raw material further with 3-chloro-2-fluoroaniline and/or the 3-chloro-4-fluoroaniline that makes, carry out diazotization reaction and hydrolysis reaction, make corresponding 2,6-dichlor fluorbenzene and/or 2,4 dichloro fluorobenzene.Reaction formula is as follows:
After described fluoridation is finished, the gained organic phase is reduced, carry out rectifying separation again and purify, made 3-chloro-2-fluoroaniline and 3-chloro-4-fluoroaniline; Perhaps, be raw material further with 3-chloro-2-fluoroaniline and/or the 3-chloro-4-fluoroaniline that makes, carry out diazotization reaction and chlorination reaction, make corresponding 2,6-dichlor fluorbenzene and/or 2,4 dichloro fluorobenzene.Reaction formula is as follows:
Described 3,4-dichloronitrobenzene and 2, the miscellany of 3-dichloronitrobenzene is the nitration product of orthodichlorobenzene, wherein 2, the 3-dichloronitrobenzene accounts for 10～20%, 3 of nitration product gross weight, and the 4-dichloronitrobenzene accounts for 80～90%.
Described 3,4-dichloronitrobenzene and 2, the miscellany of 3-dichloronitrobenzene is that the nitration product of orthodichlorobenzene goes out to account for 3 of nitration product gross weight 60～80% through Crystallization Separation, remaining low oil behind the 4-dichloronitrobenzene, in the low oil 2, the content of 3-dichloronitrobenzene is 20～45% (wt%, down with), 3, the content of 4-dichloronitrobenzene is 55～80%.
Described fluoridation is carried out with having under the phase-transfer catalyst existence condition solvent-free, fluorizating agent is a Potassium monofluoride, and temperature of reaction is 140～190 ℃, and 3,4-dichloronitrobenzene and 2, the miscellany of 3-dichloronitrobenzene and the mol ratio of Potassium monofluoride are 1: 1.05～1.2.
Described phase-transfer catalyst is cetyl trimethylammonium bromide (CTMBC) or tetramethyl ammonium chloride (TMAC).
Compared with prior art, the invention has the advantages that: 1, rectifying separation step of the present invention is after fluorination reaction step, the boiling point of 3-chloro-2-fluoronitrobenzene is 226～228 ℃, the boiling point of 3-chloro-4-fluoronitrobenzene is 240～242 ℃, the boiling-point difference of the two reaches more than 12 ℃, thereby is easy to rectifying separation; Similarly, the boiling point of 3-chloro-2-fluoroaniline and 3-chloro-4-fluoroaniline is respectively 214 ℃ and 227～228 ℃, and boiling-point difference reaches more than 13 ℃, is easy to rectifying separation; Thereby significantly reduced rectifying separation cost in producing.2, for existing " low oil " has found an approach that turns waste into wealth, both make full use of existing resource, reduced environmental pollution again.3, the important intermediate of multiple preparation quinolones of coproduction and agricultural chemicals has easily been enriched the range of product of producer and has been reduced its production cost, makes it have more the market competitiveness, helps the mass production of finished medicines.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment one
Select for use low oil to be starting raw material, in the low oil of present embodiment 2, the weight percentage of 3-dichloronitrobenzene is 30%, 3, and the content of 4-dichloronitrobenzene is 70%.To hang down oil throws to the fluoridation still, add dimethyl formamide (DMF) and KF, three's mol ratio is 1: 2.6: 1.1, stirs and is warming up to about 159 ℃, reacted 8 hours, filter, distillation removes and desolvates, and gets 3-chloro-2-fluoronitrobenzene and 3-chloro-4-fluoronitrobenzene mixture, with aforementioned the two mixture rectification under vacuum, under the 10mmHg condition, in about 90 ℃, get cut 3-chloro-2-fluoronitrobenzene, in about 100 ℃, get 3-chloro-4-fluoronitrobenzene.
Embodiment two
With the 3-chloro-2-fluoronitrobenzene or the pure product of 3-chloro-4-fluoronitrobenzene that make among the embodiment one is raw material, drop in the chlorination tank, feed the chlorine of drying, control still temperature is at 180～210 ℃, adopt the reactive distillation mode, reacted about 10 hours, and collected distillate, be washed to the neutral crude product that gets, underpressure distillation again, promptly make 2 respectively, the pure product of 6-dichlor fluorbenzene or 2,4 dichloro fluorobenzene.
Embodiment three
With the 3-chloro-2-fluoronitrobenzene or the pure product of 3-chloro-4-fluoronitrobenzene that make among the embodiment one is raw material, after reduction, can make 3-chloro-2-fluoroaniline and 3-chloro-4-fluoroaniline respectively.Reduction reaction shortening commonly used or iron powder reducing technology adopt iron powder reducing in the present embodiment.Chloro fluoro nitrobenzene: iron powder: hydrochloric acid: water=1: 1.5: 0.05: 5 (mol ratios), water, hydrochloric acid, iron powder are dropped into reactor, stir, be warming up to 100 ℃, react control dropping chloro fluoro nitrobenzene after 10 minutes, after dripping off, use steam distillation, product is steamed, promptly get 3-chloro-2-fluoroaniline or 3-chloro-4-fluoroaniline after the separation.
Embodiment four
With the organic phase of orthodichlorobenzene through nitrated gained, through depickling, throw to the fluoridation still after removing water treatment, add KF and phase-transfer catalyst tetramethyl ammonium chloride or cetyl trimethylammonium bromide, select the phase-transfer catalyst tetramethyl ammonium chloride in the present embodiment for use, three's mol ratio is 1: 1.1: 0.02, stir and be warming up to about 150 ℃, reacted 6 hours, after filtration, washing, after the drying, get 3-chloro-2-fluoronitrobenzene and 3-chloro-4-fluoronitrobenzene mixture, aforementioned the two mixture directly carried out shortening or with iron powder reducing, get the mixture of 3-chloro-2-fluoroaniline and 3-chloro-4-fluoroaniline, carry out rectification under vacuum then, make 3-chloro-2-fluoroaniline and the pure product of 3-chloro-4-fluoroaniline.
Embodiment five
Restraining the 3-chloro-2-fluoroaniline or the pure product of 3-chloro-4-fluoroaniline that make among embodiment three or the embodiment four with 100 is raw material, in reactor, add 210 gram hydrochloric acid earlier, add 100 gram water again, drip 3-chloro-2-fluoroaniline or 3-chloro-4-fluoroaniline then, and be warming up to fully dissolving, be cooled to 0 ℃, drip then with 50 gram NaNO
2Add the solution that 100 gram water are made, dropwise the back and continue to react 1.5 hours to such an extent that diazonium salt solution is standby, the equal controlled temperature of dropping process and subsequent reactions is below 10 ℃.
30 gram cuprous chlorides are thrown to 125 gram hydrochloric acid, be warming up to and boil, the limit drips above-mentioned diazonium salt solution limit and steams product then, collects overhead product, and layering gets organic phase, and the organic phase drying is handled and promptly got 2, the pure product of 6-dichlor fluorbenzene or 2,4 dichloro fluorobenzene.
In sum, the inventive method can be according to actual needs, after each elementary reaction, selects that one or both carry out the next stage reaction in this stage products obtained therefrom, thus the important intermediate of producing multiple preparation quinolones and agricultural chemicals easily.
Claims (7)
1, the preparation method of a kind of chloro fluoro nitrobenzene and derivative thereof, it includes fluorination reaction step and separates purification step, it is characterized in that described fluoridation is with 3,4-dichloronitrobenzene and 2, the miscellany of 3-dichloronitrobenzene is a raw material, carries out described separation purification step after the fluoridation again.
2, the preparation method of chloro fluoro nitrobenzene according to claim 1 and derivative thereof is characterized in that being about to after described fluoridation is finished the gained organic phase and gives the rectifying separation purification, makes 3-chloro-2-fluoronitrobenzene and 3-chloro-4-fluoronitrobenzene; Perhaps, be raw material further with 3-chloro-2-fluoronitrobenzene and/or the 3-chloro-4-fluoronitrobenzene that makes, carry out chlorination, the nitro on the substituted benzene ring, make corresponding 2,6-dichlor fluorbenzene and/or 2,4 dichloro fluorobenzene; Perhaps, further 3-chloro-2-fluoronitrobenzene and/or the 3-chloro-4-fluoronitrobenzene with gained reduced, and makes corresponding 3-chloro-2-fluoroaniline and/or 3-chloro-4-fluoroaniline; Perhaps, be raw material further with 3-chloro-2-fluoroaniline and/or the 3-chloro-4-fluoroaniline that makes, carry out diazotization reaction and hydrolysis reaction, make corresponding 2,6-dichlor fluorbenzene and/or 2,4 dichloro fluorobenzene.
3, the preparation method of chloro fluoro nitrobenzene according to claim 1 and derivative thereof, it is characterized in that described fluoridation is finished after, the gained organic phase is reduced, carry out rectifying separation again and purify, make 3-chloro-2-fluoroaniline and 3-chloro-4-fluoroaniline; Perhaps, be raw material further with 3-chloro-2-fluoroaniline and/or the 3-chloro-4-fluoroaniline that makes, carry out diazotization reaction and hydrolysis reaction, make corresponding 2,6-dichlor fluorbenzene and/or 2,4 dichloro fluorobenzene.
4, according to the preparation method of claim 1 or 2 or 3 described chloro fluoro nitrobenzenes and derivative thereof, it is characterized in that described 3,4-dichloronitrobenzene and 2, the miscellany of 3-dichloronitrobenzene is the nitration product of orthodichlorobenzene, wherein 2, the 3-dichloronitrobenzene accounts for 10～20%, 3 of nitration product gross weight, and the 4-dichloronitrobenzene accounts for 80～90%.
5, according to the preparation method of claim 1 or 2 or 3 described chloro fluoro nitrobenzenes and derivative thereof, it is characterized in that described 3,4-dichloronitrobenzene and 2, the miscellany of 3-dichloronitrobenzene is that the nitration product of orthodichlorobenzene goes out to account for 3 of nitration product gross weight 60～80% through Crystallization Separation, and remaining low oil behind the 4-dichloronitrobenzene is in the low oil 2, the content of 3-dichloronitrobenzene is 20～45% (wt%, down together), 3, the content of 4-dichloronitrobenzene is 55～80%.
6, according to the preparation method of claim 1 or 2 or 3 described chloro fluoro nitrobenzenes and derivative thereof, it is characterized in that described fluoridation is solvent-free and have under the phase-transfer catalyst existence condition and carry out, fluorizating agent is a Potassium monofluoride, temperature of reaction is 140～190 ℃, and 3,4-dichloronitrobenzene and 2, the miscellany of 3-dichloronitrobenzene and the mol ratio of Potassium monofluoride are 1: 1.05～1.2.
7, the preparation method of chloro fluoro nitrobenzene according to claim 6 and derivative thereof is characterized in that described phase-transfer catalyst is cetyl trimethylammonium bromide (CTMBC) or tetramethyl ammonium chloride (TMAC).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031506895A CN1515539A (en) | 2003-08-28 | 2003-08-28 | Preparation method of nitrobenzene chloro-fluoride and its derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031506895A CN1515539A (en) | 2003-08-28 | 2003-08-28 | Preparation method of nitrobenzene chloro-fluoride and its derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1515539A true CN1515539A (en) | 2004-07-28 |
Family
ID=34240601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA031506895A Pending CN1515539A (en) | 2003-08-28 | 2003-08-28 | Preparation method of nitrobenzene chloro-fluoride and its derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1515539A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796003A (en) * | 2012-07-11 | 2012-11-28 | 常州大学 | Preparation method of 2-fluoro-4,5-dichloronitrobenzene |
| CN103483145A (en) * | 2013-09-09 | 2014-01-01 | 江苏德峰药业有限公司 | Improved synthesis method of dichlorofluorobenzene |
| CN111714921A (en) * | 2020-06-22 | 2020-09-29 | 浙江迪邦化工有限公司 | Solvent crystallization separation system for 3, 4-dichloronitrobenzene and 2, 3-dichloronitrobenzene |
| CN113024372A (en) * | 2021-03-12 | 2021-06-25 | 内蒙古蓝科生物科技有限公司 | Synthetic method of 2-chloro-3-fluoro-4-trifluoromethyl benzoyl chloride |
| CN113024414A (en) * | 2021-03-23 | 2021-06-25 | 江苏合泰新材料科技有限公司 | Method for efficiently synthesizing fluorine-containing compound |
| CN114805080A (en) * | 2022-06-10 | 2022-07-29 | 福建技术师范学院 | Method for continuously separating 3-chloro-4-fluoronitrobenzene |
-
2003
- 2003-08-28 CN CNA031506895A patent/CN1515539A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796003A (en) * | 2012-07-11 | 2012-11-28 | 常州大学 | Preparation method of 2-fluoro-4,5-dichloronitrobenzene |
| CN103483145A (en) * | 2013-09-09 | 2014-01-01 | 江苏德峰药业有限公司 | Improved synthesis method of dichlorofluorobenzene |
| CN111714921A (en) * | 2020-06-22 | 2020-09-29 | 浙江迪邦化工有限公司 | Solvent crystallization separation system for 3, 4-dichloronitrobenzene and 2, 3-dichloronitrobenzene |
| CN111714921B (en) * | 2020-06-22 | 2021-09-07 | 浙江迪邦化工有限公司 | Solvent crystallization separation system for 3, 4-dichloronitrobenzene and 2, 3-dichloronitrobenzene |
| CN113024372A (en) * | 2021-03-12 | 2021-06-25 | 内蒙古蓝科生物科技有限公司 | Synthetic method of 2-chloro-3-fluoro-4-trifluoromethyl benzoyl chloride |
| CN113024414A (en) * | 2021-03-23 | 2021-06-25 | 江苏合泰新材料科技有限公司 | Method for efficiently synthesizing fluorine-containing compound |
| CN114805080A (en) * | 2022-06-10 | 2022-07-29 | 福建技术师范学院 | Method for continuously separating 3-chloro-4-fluoronitrobenzene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102781920B (en) | Process for synthesis of fipronil | |
| CN111925273B (en) | Production method of high-purity cis-1-chloro-3, 3, 3-trifluoropropene | |
| CN112010733B (en) | Preparation method of 3,4, 5-trifluorobromobenzene | |
| CN111995538B (en) | Synthetic method of insecticide fluazuron and intermediate 2, 6-difluorobenzamide thereof | |
| KR20170121159A (en) | Clean process for preparing chloroformyl substituted benzene | |
| CN108047031A (en) | The preparation method of 2,4,6- tri-methyl chlorides and its application for being used to prepare phosphorous photoinitiator | |
| CN1515539A (en) | Preparation method of nitrobenzene chloro-fluoride and its derivative | |
| CN108586251A (en) | A kind of preparation method of benzoyl contraposition fluoroalkyl derivative | |
| JP4367996B2 (en) | Process for producing iodinated aromatic compounds | |
| CN1258519C (en) | Method for coproducing 3-chloro-4-fluoroaniline and 2,6-dichlorofluobenzene | |
| CN112094171B (en) | Method for synthesizing m-chlorotoluene through isomerization reaction | |
| JPH05301833A (en) | Production of 2,4-dichlorofluorobenzene | |
| CN1044899C (en) | Synthetic process of 2,4-fluobenzene dichloride | |
| CN109134204B (en) | Synthesis method of intermediate 2-bromo-4-fluoro-5-chlorophenol | |
| JPS63162634A (en) | Production of substituted 3, 5-dichloro-2, 4-difluorobenzene | |
| CN105348196A (en) | Lorcaserin hydrochloride hemihydrate preparation method | |
| CN101489987A (en) | Isolation of tetracycline derivatives | |
| CN112409169B (en) | Method for preparing polyfluoroaromatic hydrocarbon | |
| AU2003268683B2 (en) | Process for production of an acetylenic compound | |
| CN116283597A (en) | Preparation method of color photographic paper raw material 2,3, 5-trichloro-4-ethylnitrobenzene | |
| CN114163294B (en) | Preparation method of 2-bromo-5-fluorobenzotrifluoride | |
| CN1251363A (en) | Novel process for synthesizing high-purity N-alkyl pyridine salt | |
| CN1033637C (en) | 1.2,4-trichlorobenzene separating and purifying method from mixed trichlorobenzene | |
| CN106631690A (en) | Preparation method of 1-adamantanol | |
| CN112409115B (en) | Preparation method of trifluoromethylthio compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |