DE2626894A1 - PROCESS FOR THE PREPARATION OF 5-ALKYLPICOLIC ACID - Google Patents
PROCESS FOR THE PREPARATION OF 5-ALKYLPICOLIC ACIDInfo
- Publication number
- DE2626894A1 DE2626894A1 DE19762626894 DE2626894A DE2626894A1 DE 2626894 A1 DE2626894 A1 DE 2626894A1 DE 19762626894 DE19762626894 DE 19762626894 DE 2626894 A DE2626894 A DE 2626894A DE 2626894 A1 DE2626894 A1 DE 2626894A1
- Authority
- DE
- Germany
- Prior art keywords
- acid
- preparation
- methylpyridine
- alkyl
- alkylpicolic
- 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
- 239000002253 acid Substances 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title claims description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 150000001204 N-oxides Chemical class 0.000 claims description 5
- GSYSNSTWMPZEQK-UHFFFAOYSA-N 5-butyl-2-methylpyridine Chemical compound CCCCC1=CC=C(C)N=C1 GSYSNSTWMPZEQK-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000008707 rearrangement Effects 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- DGMPVYSXXIOGJY-UHFFFAOYSA-N Fusaric acid Chemical compound CCCCC1=CC=C(C(O)=O)N=C1 DGMPVYSXXIOGJY-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 4
- -1 styryl compound Chemical class 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AJWAAFHFEHFISA-UHFFFAOYSA-N (5-butylpyridin-2-yl)methyl acetate Chemical compound C(C)(=O)OCC1=NC=C(C=C1)CCCC AJWAAFHFEHFISA-UHFFFAOYSA-N 0.000 description 2
- ATMWIQDUDYCXQI-UHFFFAOYSA-N 5-butyl-2-propylpyridine Chemical compound CCCCC1=CC=C(CCC)N=C1 ATMWIQDUDYCXQI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- SHCDHIRSCJOUBW-UHFFFAOYSA-N 5-ethylpyridine-2-carboxylic acid Chemical compound CCC1=CC=C(C(O)=O)N=C1 SHCDHIRSCJOUBW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- AJEJFUHEFJGBBP-UHFFFAOYSA-N C(C1=NC=C(CCC)C=C1)(=O)O.C(CCC)C=1C=CC(=NC1)C(=O)O Chemical compound C(C1=NC=C(CCC)C=C1)(=O)O.C(CCC)C=1C=CC(=NC1)C(=O)O AJEJFUHEFJGBBP-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical compound O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/30—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Description
dr. W. Schalk · dipl.-ing. P. Wirth · dipl.-ing. G. Dannenbergdr. W. Schalk dipl.-ing. P. Wirth dipl.-ing. G. Dannenberg
DR. V. SCHMIED-KOWARZIK · DR. P. WEl N HOLD · DR. D. GUDELDR. V. SCHMIED-KOWARZIK · DR. P. WEl N HOLD · DR. D. GUDEL
6 FRANKFURTAM MAIN CR.ESCHENHEIMER STRASSE S96 FRANKFURTAM MAIN CR.ESCHENHEIMER STRASSE S9
L.P. 1156L.P. 1156
LONZA AG
Gampel/Wallis
(Geschäftsleitung: Basel) SchweizLONZA AG
Gampel / Wallis
(Management: Basel) Switzerland
Verfahren zur Herstellung von 5-Alkylpicolinsäure.Process for the preparation of 5-alkylpicolinic acid.
Die Erfindung betrifft ein Verfahren zur Herstellung von 5-Alkylpicolinsäure aus 5-Alkyl-2-methylpyridin durch Umsetzung derselben mit H2O2 und anschließender Umlagerung des entstandenen N-Oxyds mit Essigsäureanhydrid und nachfolgender Oxydation,The invention relates to a process for the preparation of 5-alkylpicolinic acid from 5-alkyl-2-methylpyridine by reacting the same with H 2 O 2 and subsequent rearrangement of the N-oxide formed with acetic anhydride and subsequent oxidation,
Es sind Synthesemethoden zur Herstellung von 5-Alkylpicolinsäuren, ausgehend von 5-Alkyl-2-methylpyridin, bekannt. Nach Chem. Ber.9]5 (19βθ) S. 1848 wird 5-Butyl-2-methylpyridin mit SeO2 oxydiert. Die Ausbeute liegt bei etwa 50 %. Diese Methode ist für eine technische Durchführung praktisch unmöglich, da bei der Reaktion kolloidales Selen anfällt, das sehr giftig ist und das nur sehr schwer abgetrennt werden kann.Synthesis methods for the preparation of 5-alkylpicolinic acids, starting from 5-alkyl-2-methylpyridine, are known. According to Chem. Ber.9] 5 (19βθ) S. 1848, 5-butyl-2-methylpyridine is oxidized with SeO 2. The yield is around 50 %. This method is practically impossible for an industrial implementation, since colloidal selenium is produced in the reaction, which is very toxic and which can only be separated with great difficulty.
Gemäss HeIv. 40 (1957) S. 1016 wird ausgehend von 5-Butyl-2-propylpyridin entweder durch Kondensation mit Benzaldehyd in Acetanhydrid die Styrylverbindung hergestellt,, die mitAccording to HeIv. 40 (1957) p. 1016, starting from 5-butyl-2-propylpyridine, either by condensation with benzaldehyde in acetic anhydride, the styryl compound is produced, which with
609853/1084609853/1084
Permanganat zum Keton und diese mit Bromlauge zur Fusarinsäure umgesetzt wird oder zunächst das 5-Butyl-2-propylpyridin in das N-Oxyd umgewandelt, welches mit Acetanhydrid in die Acetoxyverbindung übergeführt, diese mit Schwefelsäure in die 2-Propenylverbindung umgewandelt und letztere mit Kaliumpermanganat in Fusarinsäure übergeführt. Diese bekannten Synthesen sind wegen ihrer Umständlichkeit kaum geeignet, technisch angewendet werden zu können.Permanganate to the ketone and this is reacted with bromine to fusaric acid or first of all 5-butyl-2-propylpyridine converted into the N-oxide, which is converted into the acetoxy compound with acetic anhydride, this with sulfuric acid converted into the 2-propenyl compound and the latter converted into fusaric acid with potassium permanganate. These known syntheses are hardly any because of their inconvenience suitable to be used technically.
Es ist auch bekannt, 5-Alkyl-2-methylpyridin mit H2O2/Essigsäureanhydrid in die 2-Acetoxymethylverbindung überzuführen, letztere zur 2-Hydroxymethylverbindung zu hydrousieren und diese durch Oxydation mit KMnO^ in die entsprechende 5-Alkylpicolinsäure überzuführen (jap. Patent 7 420 183). Die Ausbeuten liegen bei nur 34 %.It is also known to convert 5-alkyl-2-methylpyridine with H 2 O 2 / acetic anhydride into the 2-acetoxymethyl compound, to hydrousize the latter to give the 2-hydroxymethyl compound and to convert this into the corresponding 5-alkylpicolinic acid by oxidation with KMnO ^ (jap. Patent 7,420,183). The yields are only 34%.
Ziel der Erfindung ist ein einfaches, technisch durchführbares Verfahren zur Herstellung von 5-Alkylpicolinsäure, insbesondere Fusarinsäure. Das Verfahren der Erfindung ist dadurch gekennzeichnet, dass man das als Zwischenprodukt entstehende 5-Alkyl-2-acetoxymethylpyridin mit konzentrierter Salpetersäure bei Rückfluss-Temperaturen zu der gewünschten Säure umsetzt.The aim of the invention is a simple, technically feasible process for the preparation of 5-alkylpicolinic acid, especially fusaric acid. The method of the invention is characterized in that it is used as an intermediate resulting 5-alkyl-2-acetoxymethylpyridine with concentrated nitric acid at reflux temperatures to the desired Acid converts.
Die Umsetzung des 5-Alkyl-2-methylpyridins mit H2O2 erfolgt nach bekannter Weise, insbesondere durch Behandeln des Ausgangspyridins mit zweckmässig 30 %-iger O-^i in Essigsäure. Das resultierende N-Oxyd wird anschliessend durch Behandeln mit Essigsäureanliydride zwecfcaässig bei Rückfluss-Tempera-The reaction of the 5-alkyl-2-methylpyridine with H2O2 takes place in a known manner, in particular by treating the starting pyridine with advantageously 30% strength O- ^ i in acetic acid. The resulting N-oxide is then removed by treatment with Essigsäureanliydrid e zwecfcaässig at reflux temperature
6 0 9853/10846 0 9853/1084
türen durchgeführt.doors carried out.
Nach dem Verfahren der Erfindung können 5-Alkyl-2-methylpyridin, vorzugsweise solche mit 2 bis 6 C-Atomen im Alkylrest, in die entsprechenden Picolinsäuren übergeführt werden.According to the process of the invention, 5-alkyl-2-methylpyridine, preferably those with 2 to 6 carbon atoms in the alkyl radical, be converted into the corresponding picolinic acids.
Diese Picolinsäuren, insbesondere die 5-Buty!picolinsäure (Fusarinsäure), stellen Welktoxine dar.These picolinic acids, especially 5-butyl picolinic acid (Fusaric acid), represent wilt toxins.
In einen 250 ml Rundkolben, ausgestattet mit Rührer und Rückflusskühler, wurden 48,3 g Essigsäure und 20 g 5-Butyl-2-methylpyridin eingebracht. Zu dieser Lösung wurde 19,7 g Wasserstoffperoxid langsam zugesetzt und die Temperatur während 8 Stunden auf 100 bis 1050C gebracht und diese Temperatur während 8 Stunden gehalten. Danach wurde die Reaktionsmischung auf 400C abgekühlt und 0,24 g MnC>2 zugesetzt. Diese Suspension wurde während einigen Stunden stehengelassen, filtriert und die Essigsäure und das Wasser unter Vakuum mit Hilfe einer Vigreux-Kolonne abdestilliert. Das rohe N-Oxid (etwa 32 g) wurde tropfenweise in vorerwärmtes Essigsäureanhydrid (20,1 ml) während 1'Stunde zudosiert. Die Temperatur wurde während 3 Stunden bei 1400C gehalten, anschliessend der Ueberschuss an Essigsäureanhydrid und Essigsäure unter Vakuum abdestilliert und das rohe 2-Acetoxymethyl-5-butylpyridin fraktioniert destilliert. Die Ausbeute betrug 22,1 g, d.h. 73,5%.48.3 g of acetic acid and 20 g of 5-butyl-2-methylpyridine were placed in a 250 ml round bottom flask equipped with a stirrer and reflux condenser. 19.7 g of hydrogen peroxide were slowly added to this solution and the temperature was brought to 100 to 105 ° C. over 8 hours and this temperature was maintained for 8 hours. Thereafter, the reaction mixture was cooled to 40 0 C and 0.24 g MnC> 2 added. This suspension was left to stand for a few hours, filtered and the acetic acid and the water were distilled off in vacuo with the aid of a Vigreux column. The crude N-oxide (about 32 g) was metered dropwise into preheated acetic anhydride (20.1 ml) over 1 'hour. The temperature was kept at 140 ° C. for 3 hours, then the excess of acetic anhydride and acetic acid was distilled off in vacuo and the crude 2-acetoxymethyl-5-butylpyridine was fractionally distilled. The yield was 22.1 g, ie 73.5%.
609853/1084609853/1084
127 g. einer 74%-igen HNO., wurden in einen 250 ml Rundkolben, ausgestattet mit einem Magnetrührer und einem Rückflusskolben und einem Einlass für Stickstoffperoxyd, eingebracht und auf 115 C erwärmt. Zu dieser Lösung wurden 15 g 2-Acetoxymethyl-5-butylpyridin tropfenweise während 10 Minuten zugesetzt. Während 30 Minuten sank die Temperatur auf 85 C unter starkem Rückfluss und diese Temperatur von 80 bis 85 C wurde 2 1/2 Stunden aufrechterhalten. Anschliessend wurde mit 140 ml destilliertem Wasser verdünnt, diese Lösung bei 60 C unter Vakuum eingeengt (bis auf etwa 50 ml), weiterhin 150 ml Wasser zugesetzt und mit 20%-iger NaOH der pH auf 3,5 eingestellt. Anschliessend wurde zur Trockene verdampft (unter Vakuum), mit 100 ml Methylenchlorid extrahiert. Der Extrakt wurde getrocknet, das Methylenchlorid abdestilliert, weiterhin mit einer Mischung von 64 ml Aethylacetat und 336 ml Petrolaether unter Rückfluss extrahiert, mit Aktivkohle behandelt und filtriert. Die heisse Lösung wurde abgekühlt. Dabei wurde 8,8 g Fusarinsäure mit einem Schmelzpunkt von 101 bis 102 C in einer Reinheit von 99,5 %, entsprechend einer Ausbeute von 71,7 %, erhalten. Der Kristallisationsrückstand enthält noch 1,8 g Fusarinsäure. 127 g. of a 74% HNO., were placed in a 250 ml round bottom flask equipped with a magnetic stirrer and a reflux flask and an inlet for nitrogen peroxide and heated to 115.degree. To this solution, 15 g of 2-acetoxymethyl-5-butylpyridine was added dropwise over 10 minutes. Over 30 minutes the temperature dropped to 85 ° C. under strong reflux and this temperature of 80 to 85 ° C. was maintained for 2 1/2 hours. It was then diluted with 140 ml of distilled water, this solution was concentrated in vacuo at 60 ° C. (down to about 50 ml), further 150 ml of water were added and the pH was adjusted to 3.5 with 20% NaOH. It was then evaporated to dryness (under vacuum) and extracted with 100 ml of methylene chloride. The extract was dried, the methylene chloride was distilled off, further extracted with a mixture of 64 ml of ethyl acetate and 336 ml of petroleum ether under reflux, treated with activated charcoal and filtered. The hot solution was cooled. This gave 8.8 g of fusaric acid with a melting point of 101 to 102 ° C. in a purity of 99.5 %, corresponding to a yield of 71.7 % . The crystallization residue still contains 1.8 g of fusaric acid.
Wie in Beispiel 1 angegeben, wurde 2-Acetoxymethyl-5-aethylpyridin hergestellt, das anschliessend mit Salpetersäure umgesetzt wurde. Es wurde in einer Reinheit von 99,6 % die ent-As indicated in Example 1, 2-acetoxymethyl-5-aethylpyridine was prepared, which was then reacted with nitric acid. It was found in a purity of 99.6 %
6 0 9- 3/10846 0 9-3 / 1084
sprechende 5-Aethylpicolinsäure in einer Ausbeute von 65,4 % isoliert. In der nach der Kristallisation vorhandenen Mutterlauge waren noch etwa 10 % der Picolinsäure vorhanden.Speaking 5-ethylpicolinic acid isolated in a yield of 65.4 % . About 10% of the picolinic acid was still present in the mother liquor present after the crystallization.
609853/ 1 084609853/1 084
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH798475A CH593938A5 (en) | 1975-06-19 | 1975-06-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2626894A1 true DE2626894A1 (en) | 1976-12-30 |
Family
ID=4333371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19762626894 Pending DE2626894A1 (en) | 1975-06-19 | 1976-06-16 | PROCESS FOR THE PREPARATION OF 5-ALKYLPICOLIC ACID |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS523072A (en) |
| CH (1) | CH593938A5 (en) |
| DE (1) | DE2626894A1 (en) |
| FR (1) | FR2316232A1 (en) |
| GB (1) | GB1481159A (en) |
| NL (1) | NL7606631A (en) |
| SE (1) | SE7607026L (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5640674U (en) * | 1979-09-07 | 1981-04-15 | ||
| JPS63172697A (en) * | 1987-01-09 | 1988-07-16 | 松下電送株式会社 | Electrostatic suction board |
| JPS63199491A (en) * | 1987-02-16 | 1988-08-17 | 住友電気工業株式会社 | Manufacturing method of flexible printed wiring board |
| JPS63187053U (en) * | 1987-05-23 | 1988-11-30 |
-
1975
- 1975-06-19 CH CH798475A patent/CH593938A5/xx not_active IP Right Cessation
-
1976
- 1976-06-10 GB GB24060/76A patent/GB1481159A/en not_active Expired
- 1976-06-16 DE DE19762626894 patent/DE2626894A1/en active Pending
- 1976-06-18 JP JP51072699A patent/JPS523072A/en active Pending
- 1976-06-18 FR FR7618724A patent/FR2316232A1/en not_active Withdrawn
- 1976-06-18 SE SE7607026A patent/SE7607026L/en unknown
- 1976-06-18 NL NL7606631A patent/NL7606631A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB1481159A (en) | 1977-07-27 |
| SE7607026L (en) | 1976-12-20 |
| NL7606631A (en) | 1976-12-21 |
| JPS523072A (en) | 1977-01-11 |
| FR2316232A1 (en) | 1977-01-28 |
| CH593938A5 (en) | 1977-12-30 |
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