DK156827B - Process for preparing acylcyanides - Google Patents
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- DK156827B DK156827B DK462184A DK462184A DK156827B DK 156827 B DK156827 B DK 156827B DK 462184 A DK462184 A DK 462184A DK 462184 A DK462184 A DK 462184A DK 156827 B DK156827 B DK 156827B
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DK 156827 BDK 156827 B
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Den foreliggende opfindelse angâr en særlig fremgangsmâde til fremstilling af delvis kendte acylcyanider, der kan anvendes som udgangsstoffer til syntese af her-bicider.The present invention relates to a particular process for the preparation of partially known acyl cyanides which can be used as starting materials for the synthesis of herbicides.
5 Det er allerede kendt, at acylcyanider kan frem- stilles ved omsætning af acylhalogenider med metalcyanider (jfr. Angew. Chem. _68, 425-435 (1956)). Denne fremgangsmâde udviser imidlertid en række ulemper. Sâledes er den f.eks. kostbar og teknisk kun vanskeligt gennemf0rlig, fordi det 10 drejer sig om en tofasereaktion, ved hvilken et fast stof skal omsættes med en væske eller med et i opl0sning foreliggende stof. Desuden giver omsætningen ikke et ensartet reaktionsprodukt, men en vanskeligt adskillelig stofblan-ding, der foruden det pâgældende acylcyanid ogsâ indehol-15 der st0rre mængder af den tilsvarende dimere. Udbytterne af acylcyanid er derfor forholdsvis ringe. En yderligere ulempe ved denne fremgangsmâde bestâr i, at det ved opar-bejdningen dannede spildevand f0r bortledningen skal under-kastes en grundig rensning, fordi det endnu indeholder be-2Q tydelige mængder af meget giftige metalcyanider, der anvendes i overskud ved omsætningen.It is already known that acyl cyanides can be prepared by reacting acyl halides with metal cyanides (cf. Angew. Chem. 68, 425-435 (1956)). However, this approach exhibits a number of disadvantages. Thus, it is e.g. expensive and technically only difficult to do because it is a two-phase reaction in which a solid must be reacted with a liquid or with a substance present in solution. In addition, the reaction does not give a uniform reaction product, but a difficult separable substance mixture which, in addition to the acyl cyanide in question, also contains larger amounts of the corresponding dimer. The yields of acyl cyanide are therefore relatively poor. A further disadvantage of this process is that the wastewater formed before processing must be subjected to a thorough purification because it still contains significant quantities of highly toxic metal cyanides used in the reaction in excess.
Det er endvidere kendt, at aroylcyanider kan fréinstallés ved omsætning af arylcarboxylsyrechlorider med blâ-syre i nærværelse af pyridin som syrebindende middel i ab-25 solut ether (jfr. Angew. Chem., 68, 425-435 (1956)). Ogsâ denne fremgangsmâde er imidlertid forbundet med flere u-lemper. Sâledes er den for det f0rste ikke aiment anven-delig. Herudover er den teknisk ret kostbar, fordi arbej-det med det stærkt toksiske pyridin og med den let antæn-30 delige ether kræver særlig store sikkerhedsforanstaltnin-ger. Desuden er ogsâ her en grundig rensning af det ved oparbejdningen dannede vaskevand uundgâelig pâ grund af deri opl0st pyridin. Uheldigt er det ligeledes, at der un-der reaktionen dannes en betydelig mængde af dimert aroyl-35 cyanid, fordi herved bâde udbyttet af aroylcyanid stærkt nedsættes og dettes isolering vanskeligg0res.Further, it is known that aroyl cyanides can be free-neutralized by reacting aryl carboxylic acid chlorides with cyanide in the presence of pyridine as an acid-binding agent in absolute ether (cf. Angew. Chem., 68, 425-435 (1956)). However, this approach is also associated with several disadvantages. Thus, for the first time, it is not applicable. In addition, it is technically quite costly, because working with the highly toxic pyridine and the easily flammable ether requires particularly large precautions. In addition, thorough cleaning of the wash water formed during the work-up is also unavoidable because of pyridine dissolved therein. It is also unfortunate that during the reaction a considerable amount of dimeric aroylcyanide is formed, as both the yield of aroylcyanide is greatly reduced and its isolation is made difficult.
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Det er desuden kendt at omsætte benzoesyreanhydrid med kaliumcyanid i ækvivalente mængder, hvorved der i rin-ge udbytter (ca. 10% af det teoretiske) fâs benzoylcyanid (Liebigs Annalen der Chemie, 287, side 306 (1895)). Benzoyl-5 cyanidet skal.fjernes fra den som hovedprodukt dannede seje, til harpiks stærkt omdannede m0rkebrune masse med ether.In addition, it is known to react benzoic anhydride with potassium cyanide in equivalent amounts, whereby benzoyl cyanide is obtained in low yields (about 10% of theory) (Liebigs Annalen der Chemie, 287, p. 306 (1895)). The benzoyl-5 cyanide must be removed from the tough formed as the main product, into the resin's highly converted dark brown mass with ether.
Denne fremgangsmâde er teknisk fuldstændig uegnet, fordi .............. ikke kun ekstraktionen med ether f0rer til teknisk uover- vindelige vanskeligheder, men fordi den stærkt harpiksag-1Q tige m0rkebrune masse ikke kan finde yderligere anvendelse.This process is technically completely unsuitable because .............. not only does the extraction with ether lead to technically insurmountable difficulties, but because the highly resin-sawn dark brown mass can find no further use .
Det drejer sig altsâ her kun om en mulig dannelsesmâde for benzoylcyanid.Thus, this is only a possible method of formation of benzoyl cyanide.
Det har nu ved fremgangsmâden if0lge opfindelsen, der er ejendommelig ved det i krav l's kendetegnende del 15 omhandlede, vist sig, at de delvis kendte acylcyanider med formlenIt has now been found by the method according to the invention which is characterized by the characterizing part 15 of claim 1 that the partially known acyl cyanides of the formula
OISLAND
IIII
R-C-CN (I) i hvilken R betyder en alkylgruppe med 1-8 carbonatomer el-2o 1er en eventuelt substitueret arylgruppe, i meget h0je udbytter og i glimrende renhed fâs, nâr carboxylsyreanhydri-der med formlen 0 0 R-C-O-C-R (II) 25 i hvilken R har den ovenfor angivne betydning, eventuelt i nærværelse af et fortyndingsmiddel, ved .temperaturer mel-lem 50 og 250°C omsættes med flydende vandfri blâsyre, hvor-pâ der efter endt omsætning oparbejdes destillativt pâ gængs mâde.RC-CN (I) in which R represents an alkyl group of 1-8 carbon atoms or -2O1 is an optionally substituted aryl group, in very high yields and in excellent purity, when carboxylic anhydrides of formula 0 RCOCR (II) 25 are obtained. which R has the meaning given above, optionally in the presence of a diluent, at temperatures between 50 and 250 ° C is reacted with liquid anhydrous hydrochloric acid, after which, after completion of the reaction, the distillate is worked up in the usual manner.
30 Det mâ betegnes som yderst overraskende, at acyl- cyaniderne med formlen I ved den her omhandlede fremgangsmâde er tilgængelige i h0je udbytter og glimrende renhed, fordi man med henblik pâ den kendte tekniks stade mâtte forvente, at der ved fremgangsmâden enten ville optræde 35 de samme vanskeligheder som ved omsætningen af acylhalogeni-der med alkali- eller tungmetalcyanider i et tofasesystem, 3It should be considered extremely surprising that the acyl cyanides of formula I are available in the present process in high yields and excellent purity because, for the state of the art, one would expect that either of the processes would occur in the process. the same difficulties as in the reaction of acyl halides with alkali or heavy metal cyanides in a two-phase system, 3
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0 eller at det 0nskede acylcyanid kun ville dannes i spor-mængder. Det kunne pâ ingen mâde forudses, at dannelsen af u0nskede dimere acylcyanider eller harpiksagtige pro-dukter fuldstændigt kunne undgâs.0 or that the desired acyl cyanide would only form in trace amounts. In no way could it be foreseen that the formation of unwanted dimeric acyl cyanides or resinous products could be completely avoided.
5 Den her oxnhandlede fremgangsmâde har en række for- dele. Sâledes er den ikke begrænset til fremstillingen af fâ bestemte forbindelser, men kan anvendes i vid udstræk-ning. Desuden giver den her omhandlede fremgangsmâde acyl-cyaniderne i praktisk taget kvantitativt udbytte og til-10 strækkeligt fri for generende og milj0skadelige biproduk- ter.5 The method employed here has a number of advantages. Thus, it is not limited to the preparation of certain compounds, but can be used extensively. In addition, the process of the present invention provides the acyl cyanides in virtually quantitative yield and sufficiently free of bothersome and environmentally harmful by-products.
En yderligere afg0rende fordel ved den her omhandlede fremgangsmâde bestâr i, at oparbejdningen ikke giver nogen problemer. Eftersom der anvendes blâsyre, dannes der 15 som biprodukt f.eks. benzoesyre, der indenfor kemien kan anvendes pâ mange mâder. Den her omhandlede fremgangsmâde udg0r sâledes en værdifuld berigelse af teknikken.A further decisive advantage of the method at issue here is that reprocessing presents no problems. Since formic acid is used, 15 is formed as a by-product e.g. benzoic acid, which can be used in many ways in chemistry. Thus, the method of the present invention constitutes a valuable enrichment of the technique.
Anvender man benzoesyreanhydrid og vandfri blâsyre som udgangsstoffer, kan reaktionsforl0bet gengives ved 20 f0lgende formelskema:If benzoic anhydride and anhydrous hydrochloric acid are used as starting materials, the course of the reaction can be represented by the following formula:
C00C0 COCN COOHC00 CO0 COCN COOH
@( te) +hcn-*@ + (ü/@ (te) + hcn - * @ + (ü /
25 V25 V
De som udgangsstoffer anvendte syreanhydrider er aiment defineret ved formlen II og kan fremstilles pâ kendt mâde. I denne formel betyder R fortrinsvis ligekædet eller 30 forgrenet alkyl med 1-4 carbonatomer. R betyder desuden fortrinsvis eventuelt med alkyl, alkoxy eller carbalkoxy med hver indtil 4 carbonatomer, nitro og/eller halogen, f.eks. fluor, chlor og brom, substitueret aryl, især phenyl eller naphthyl.The acid anhydrides used as starting materials are all defined by formula II and can be prepared in known manner. In this formula, R is preferably straight or branched chain alkyl of 1-4 carbon atoms. R is also preferably optionally substituted with alkyl, alkoxy or carbalkoxy each having up to 4 carbon atoms, nitro and / or halogen, e.g. fluorine, chlorine and bromine, substituted aryl, especially phenyl or naphthyl.
35 Som foretrukne eksempler pâ syreanhydrider med form len II skal i enkeltheder nævnes: eddikesyreanhydrid, pro- 035 As preferred examples of Formula II acid anhydrides are to be mentioned in detail: acetic anhydride,
DK 156827 BDK 156827 B
4 pionsyreanhydrid, pivalinsyreanhydrid, benzoesyreanhydrid, m-chlorbenzoesyreanhydrid, 3,5-dichlorbenzoesyreanhydrid og naphthalen-l-carboxylsyreanhydrid. Som særlig foretrukne anhydrider skal der nævnes aromatiske carboxylsyreanhydri-5 der, især benzoesyreanhydrid.4 pionic anhydride, pivalic anhydride, benzoic anhydride, m-chlorobenzoic anhydride, 3,5-dichlorobenzoic anhydride and naphthalene-1-carboxylic anhydride. As particularly preferred anhydrides, mention should be made of aromatic carboxylic anhydrides, especially benzoic anhydride.
Som fortyndingsmidler, der kan anvendes ved gen-nemf0relsen af den her omhandlede fremgangsmâde, kommer aile indifferente organiske opl0sningsmidler pâ taie, der hverken indgâr i kemisk reaktion med carboxylsyreanhydri-10 derne eller blâsyren. Sâdanne opl0sningsmidler er f.eks. xylen, sâsom o-xylen, chlorbenzen, o-dichlorbenzen, tri-chlorbenzen, nitrobenzen og tetramethylsulfon. Særlig eg-net som fortyndingsmiddel er et overskud af carboxylsyre-anhydrid (II). Det er imidlertid ogsâ principielt muligt 15 at gennemf0re den her omhandlede fremgangsmâde uden fortyndingsmiddel .As diluents which can be used in carrying out the process of this invention, all inert organic solvents are obtained which are neither in chemical reaction with the carboxylic acid anhydrides nor the hydrochloric acid. Such solvents are e.g. xylene, such as o-xylene, chlorobenzene, o-dichlorobenzene, trichlorobenzene, nitrobenzene and tetramethylsulfone. Particularly suitable as a diluent is an excess of carboxylic anhydride (II). However, it is also possible in principle to carry out the process of the present invention without diluent.
Reaktionstemperaturen kan varieres indenfor et st0rre omrâde. Almindeligvis arbejder man ved temperatu-rer mellem 50 og 250°C, fortrinsvis mellem 100 og 230°C.The reaction temperature can be varied within a larger range. Generally, one operates at temperatures between 50 and 250 ° C, preferably between 100 and 230 ° C.
20 Reaktionen gennemf0res almindeligvis ved normalt tryk. Ved anvendelse af lavtkogende, aliphatiske carboxyl-syreanhydrider er imidlertid et let overtryk gunstigt, almindeligvis pâ 1-10, fortrinsvis 1-5 atmosfærers overtryk.The reaction is usually carried out under normal pressure. However, when using low boiling aliphatic carboxylic acid anhydrides, a slight overpressure is favorable, generally of 1-10, preferably 1-5 atmospheres overpressure.
Til afdestillering af de dannede acylcyanider kan det der- 25 . imod. være fordelagti.gt at arbejde ved undertryk i.....omrâdet.To distill off the acyl cyanides formed, it can then be distilled. against. be advantageous to work under vacuum in the ..... area.
fra 750 til 0,05 mm Hg, hvorved det gunstigste tryk fâs ud fra det 0nskede acylcyanid og den anvendte temperatur.from 750 to 0.05 mm Hg, whereby the most favorable pressure is obtained from the desired acyl cyanide and the temperature used.
Ved tilsætning af katalytiske mængder base eller Lewis-syre kan omsætningen fremmes. Egnede baser er f.eks.By the addition of catalytic amounts of base or Lewis acid, the reaction can be promoted. Suitable bases are e.g.
30 tertiære aminer, sâsom dimethylbenzylamin og 1,4-diaza-bicyclo[2,2,2]octan. Egnede Lewis-syrer er f.eks. zink-chlorid, zinkcyanid og kobber-(I)-cyanid.30 tertiary amines, such as dimethylbenzylamine and 1,4-diaza-bicyclo [2,2,2] octane. Suitable Lewis acids are e.g. zinc chloride, zinc cyanide and copper (I) cyanide.
Ved gennemf0relsen af den her omhandlede fremgangsmâde omsætter man almindeligvis st0kiometriske mængder sy-35 reanhydrid med vandfri blâsyre. Syreanhydridet kan imidlertid ogsâ anvendes i overskud, fordelagtigt da endog som opl0sningsmiddel.In carrying out the process of this invention, stoichiometric amounts of acid anhydride are generally reacted with anhydrous hydrochloric acid. However, the acid anhydride can also be used in excess, advantageously then even as a solvent.
55
DK 156827 BDK 156827 B
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Oparbejdningen sker efter en omsætning pâ sædvan-lig mâde ved destination og eventuelt omkrystallisation.The reprocessing takes place after a usual turnover at destination and possibly recrystallization.
De ved den her omhandlede fremgangsmâde fremstille-lige acylcyanider med formlen I er værdifulde udgangsstof-5 fer, f.eks. til syntese af 1,2,4-triazin-5-oner, der har fremragende herbicide egenskaber (jfr. tysk offentligg0rel-sesskrift nr. 2.224.161).The acyl cyanides of formula I prepared by the process of this invention are valuable starting materials, e.g. for the synthesis of 1,2,4-triazine-5-ones having excellent herbicidal properties (cf. German Publication No. 2,224,161).
Sâledes kan f.eks. 3-methyl-4-amino-6-phenyl--l,2,4--triazin-5-onen med formlenThus, e.g. 3-methyl-4-amino-6-phenyl-1,2,4-triazine-5-one of the formula
.10 . . O.10. . ISLAND
15 fremstilles ved, at man i et f0rste trin omsætter benzoyl- cyanid i nærværelse af koncentreret saltsyre med éthanol og bringer den herved dannede phenylglyoxylsyreethylester i et andet trin til omsætning med acetylhydrazin, hvorved der dannes l-phenylglyoxylsyreethylester-2-acetylhydrazon, 2o der i et tredie trin med hydrazinhydrat i nærværelse af pyridin overf0res i det nævnte slutprodukt. Denne fler-trinssyntese forl0ber efter f0lgende formelskema: <1 # trin : 25 <p\-S-CN C2H5°H <Q)-C-Î-OC2H5 (HCl) 2. trin · 30 f/—Λ 0 9 -H?0 O-C-OC-H.15 is prepared by reacting, in a first step, benzoyl cyanide in the presence of concentrated hydrochloric acid with ethanol and bringing the resulting phenylglyoxylic acid ethyl ester in a second step to react with acetylhydrazine to form 1-phenylglyoxylic acid ethyl ester-2-acetylhydrazone a third step of hydrazine hydrate in the presence of pyridine is transferred into said final product. This multi-step synthesis proceeds according to the following formula: <1 # Step: 25 <p \ -S-CN C2H5 ° H <Q) -C-Î-OC2H5 (HCl) Step 2 · 30 f / —Λ 0 9 -H ? 0 OC-OC-H.
// \\_i_c_oc„H, + H_N-NH-C0-CH, ---» ,_ \ W 2 5 2 (CHjOH) _c=n_hh_coc] 3. trin i 0 35 __0=C-0C H // ^A-^N-NH-CO-CHj '—' (Pyridin) CIÎ3 0// \\ _ i_c_oc „H, + H_N-NH-C0-CH, ---», _ \ W 2 5 2 (CH 2 OH) _c = n_hh_coc] 3rd step in 0 35 __0 = C-0C H // ^ A- ^ N-NH-CO-CH2 '-' (Pyridine) CIÎ3 0
DK 156827 BDK 156827 B
66
Fremgangsmâden if01ge opfindelsen skal belyses nær-mere ved hjælp af efterf0lgende fremstillingseksempler.The process according to the invention will be further elucidated by the following manufacturing examples.
Eksempel 1Example 1
5 CO-CNCO-CN
I en med omr0rer, termometer, tilbagesvalingsaf-10 k0ler og drâbetragt forsynet 2 liter firehalset kolbe op-varmes 1130 g benzoesyreanhydrid (5 mol) til 180°C, og i 10bet af 5 timer tildryppes 200 ml vandfri blâsyre (5 mol).In a stirrer, thermometer, reflux cooler and drop-fed 2 liter four-neck flask, 1130 g of benzoic anhydride (5 moles) is heated to 180 ° C and 10 ml of anhydrous formic acid (5 moles) is added dropwise for 10 hours.
Den ikke straks omsatte blâsyre tilbagef0res ved afk0ling igen til reaktionsbeholderen. Efter endt omsætning frak-15 tionsdestilleres der. Udbyttet er 630 g (96% af det teore-tiske) benzoylcyanid med et smeltepunkt pâ 31°C. Den som biprodukt kvantitativt dannede benzoesyre overf0res pâ kendt mâde igen i benzoesyreanhydrid.The non-reacted formic acid is returned to the reaction vessel upon cooling. After completion of the reaction, fractionation is distilled. The yield is 630 g (96% of theory) of benzoyl cyanide having a melting point of 31 ° C. The benzoic acid produced as a by-product in a quantitative manner is transferred in the known way again into benzoic anhydride.
20 Eksempel 2 452 g benzoesyreanhydrid (2 mol) sættes til 160 ml vandfri blâsyre og ledes langsomt gennem et med Raschig--ringe fyldt, til 250°C opvarmet r0r og opfanges i et for-lag. Efter fraktioneret destination, hvorved overskydende 25 blâsyre tilbagevindes, fâr man 236 g benzoylcyanid (90% af det teoretiske) med et smeltepunkt pâ 31°C foruden blâsyre og lidt ikke-omsat benzoesyreanhydrid.Example 2 452 g of benzoic anhydride (2 moles) is added to 160 ml of anhydrous hydrochloric acid and passed slowly through a Raschig-filled tube, heated to 250 ° C and collected in a pre-layer. After fractional distillation, whereby excess cyanide is recovered, 236 g of benzoyl cyanide (90% of theory) is obtained with a melting point of 31 ° C in addition to hydrochloric acid and slightly unreacted benzoic anhydride.
Eksempel 3 30 I en 250 ml trehalset kolbe forsynet med omr0rer, afk0let drâbetragt og tilbagesvalingsk0ler, opvarmes 127 g 4-methyl-benzoesyreanhydrid (0,5 mol) til 185-190°C, og i 10bet af 2 timer tildryppes 20 ml vandfri blâsyre (0,5 mol). Efter afk0ling destilleres reaktionsproduktet. Udbyttet er 35 67,5 g 4-methyl-benzoylcyanid (93% af det teoretiske) medExample 3 In a 250 ml three-necked flask equipped with stirrer, cooled dropping funnel and reflux condenser, 127 g of 4-methyl-benzoic anhydride (0.5 mole) is heated to 185-190 ° C, and in 10bet of 2 hours 20 ml of anhydrous hydrochloric acid are added dropwise. (0.5 mol). After cooling, the reaction product is distilled. The yield is 67.5 g of 4-methyl-benzoyl cyanide (93% of theory) with
7 DK 156827 B7 DK 156827 B
0 et kogepunkt pâ 112-114°C ved 14 mm Hg og et kogepunkt pâ 50-52°C (fra vaskebenzin).0 a boiling point of 112-114 ° C at 14 mm Hg and a boiling point of 50-52 ° C (from washing gasoline).
Eksempel 4 5 I en autoklav opvarmes 102 g eddikesyreanhydrid (1 mol) og 40 ml vandfri blâsyre (1 mol), opl0st i 300 ml eddikesyreethylester, langsomt til 170-180°C.Example 4 In an autoclave, 102 g of acetic anhydride (1 mole) and 40 ml of anhydrous formic acid (1 mole) dissolved in 300 ml of acetic acid ethyl ester are slowly heated to 170-180 ° C.
Efter 3 timers forl0b afk0ler man og fraskiller reak-tionsproduktet ved fraktioneret destination fra opl0s-10 ningsmidlet og fra eddikesyren. üdbyttet er 59,4 g acetylcyanid (86% af det teoretiske), og kogepunktet er 93°C.After 3 hours, the reaction product is cooled and separated at a fractional destination from the solvent and from the acetic acid. The yield is 59.4 g of acetyl cyanide (86% of theory) and the boiling point is 93 ° C.
Eksempel 5 15 930 g Pivalinsyreanhydrid (5 mol) blandes med 240 ml vandfri blâsyre (6 mol), og der opvarmes til 250°C i 3 timer i en autoklav. Den fremkomne reaktions-blanding destilleres fraktioneret. üdbyttet er 490 g (88% af det teoretiske) pivaloylcyanid med kp. 124-126°C.Example 5 930 g of pivalic anhydride (5 moles) are mixed with 240 ml of anhydrous formic acid (6 moles) and heated to 250 ° C for 3 hours in an autoclave. The resulting reaction mixture is fractionally distilled. The yield is 490 g (88% of theory) of pivaloyl cyanide with b.p. 124-126 ° C.
20 25 30 3520 25 30 35
Claims (4)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2614241 | 1976-04-02 | ||
| DE2614241A DE2614241C3 (en) | 1976-04-02 | 1976-04-02 | Process for the production of acyl cyanides |
| DK144277A DK149447C (en) | 1976-04-02 | 1977-04-01 | METHOD OF PREPARING ACYLCYANIDES |
| DK144277 | 1977-04-01 |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| DK462184A DK462184A (en) | 1984-09-27 |
| DK462184D0 DK462184D0 (en) | 1984-09-27 |
| DK156827B true DK156827B (en) | 1989-10-09 |
| DK156827C DK156827C (en) | 1990-02-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK462184A DK156827C (en) | 1976-04-02 | 1984-09-27 | METHOD OF PREPARING ACYLCYANIDES |
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| Country | Link |
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| DK (1) | DK156827C (en) |
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| DK462184A (en) | 1984-09-27 |
| DK156827C (en) | 1990-02-26 |
| DK462184D0 (en) | 1984-09-27 |
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