NO137205B - ANALOGICAL PROCEDURE FOR THE PREPARATION OF PIPERAZINE PYRIMIDINES WITH THERAPEUTIC EFFECT - Google Patents

ANALOGICAL PROCEDURE FOR THE PREPARATION OF PIPERAZINE PYRIMIDINES WITH THERAPEUTIC EFFECT Download PDF

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NO137205B
NO137205B NO3260/73A NO326073A NO137205B NO 137205 B NO137205 B NO 137205B NO 3260/73 A NO3260/73 A NO 3260/73A NO 326073 A NO326073 A NO 326073A NO 137205 B NO137205 B NO 137205B
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methanol
sulfuric acid
trimethylborate
azeotropic mixture
boric acid
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NO137205C (en
NO326073L (en
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Gerard Loiseau
Georges Mattioda
Rene Millischer
Pierre Obellianne
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Ugine Kuhlmann
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
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    • A—HUMAN NECESSITIES
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
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    • A61P25/04—Centrally acting analgesics, e.g. opioids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P25/00—Drugs for disorders of the nervous system
    • A61P25/20—Hypnotics; Sedatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/48—Two nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
    • C07D239/545—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/56—One oxygen atom and one sulfur atom

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Description

Fremgangsmåte til fremstilling av trimethylborat. Process for the production of trimethylborate.

Foreliggende oppfinnelse angår en fremgangsmåte til fremstilling av trimethylborat B(OCH:i).:. The present invention relates to a process for the production of trimethylborate B(OCH:i).:.

Hittil er trimethylborat i alminnelighet fremstillet ved omsetning av borsyre eller borsyreanhydrrd' med methanol. I begge til-felle får man som det første reaksjons-produkt en azeotropisk blanding av trimethylborat og methanol med den omtrent-lige sammensetning B(OCH:i)n.CH:!OH. Der er foreslått og anvendt mange metoder for adskiiielse av denne azeotropiske blanding. Disse metoder er hovedsakelig basert på: 1) - Anvendelse av anorganiske salter som kloridene av lithium, natrium, kalsium, magnesium og aluminium, som er meget oppløselige i methanol og tungt oppløselige i trimethylborat. De frembringer derfor adskillelse av den azeotropiske blanding i to skikt av hvilke det ene består av nesten rent trimethylborat. Dette kan derfor ren-ses ved rektifikasjon. 2) Anvendelse av væsker som ved tilsetning til den azeotropiske blanding med methanol danner en annen azeotropisk blanding hvis- kokepunkt er lavere enn tri-methylfoorait-methanol-Mandingens koke-purøkt. Et typisk eksempel på sådanne' væsker er carbonsulf id som med methanol danner en azeotropisk blanding hvis kokepunkt er 38°C. 3) Anvendelse av væsker som er fullstendig oppløselige i den ene a-v den azeotropiske blandings to bestanddeler, men tungt oppløselige i den annen. Når' sådanne væsker tilsettes til blandingen, forårsaker de utskillelse av to skikt, og fra det ene av disse kan rent trimethylborat lett fåes ved Until now, trimethylborate has generally been prepared by reacting boric acid or boric anhydride with methanol. In both cases, an azeotropic mixture of trimethylborate and methanol with the approximately equal composition B(OCH:i)n.CH:!OH is obtained as the first reaction product. Many methods have been proposed and used for the separation of this azeotropic mixture. These methods are mainly based on: 1) - Use of inorganic salts such as the chlorides of lithium, sodium, calcium, magnesium and aluminium, which are very soluble in methanol and poorly soluble in trimethylborate. They therefore produce separation of the azeotropic mixture into two layers, one of which consists of almost pure trimethylborate. This can therefore be cleared by rectification. 2) Use of liquids which, when added to the azeotropic mixture with methanol, form another azeotropic mixture whose boiling point is lower than tri-methylfoorait-methanol-Mandingen's boiling point. A typical example of such liquids is carbon sulphide, which with methanol forms an azeotropic mixture whose boiling point is 38°C. 3) Use of liquids which are completely soluble in one a-v of the two components of the azeotropic mixture, but poorly soluble in the other. When such liquids are added to the mixture, they cause the separation of two layers, and from one of these pure trimethylborate can be readily obtained by

destillasjon. Blandt slike væsker er vaselin - olje som er fullstendig oppløselig i trimethylborat, men uoppløselig i methanol, samt svovelsyre som' er fullstendig oppløselig i methanol, men tungt oppløselig i trimethylborat. distillation. Among such liquids are petroleum jelly, which is completely soluble in trimethylborate, but insoluble in methanol, and sulfuric acid, which is completely soluble in methanol, but poorly soluble in trimethylborate.

For fremstilling i laboratoriet kan også anorganiske salter- brukes; særlig kalsium-klorid eller lithiumklorid, men ved arbeide i industriell målestokk er anvendelse' av vaselinolje eller svovelsyre' nødvendig. Anvendelse av svovelsyre har imidlertid ikke vært ansett for tilrådelig,, da en betydelig mengde trimethylborat går tapt i svovelsyre-methanol-oppløsningen. For production in the laboratory, inorganic salts can also be used; especially calcium chloride or lithium chloride, but when working on an industrial scale, the use of petroleum jelly or sulfuric acid is necessary. However, the use of sulfuric acid has not been considered advisable, as a significant amount of trimethylborate is lost in the sulfuric acid-methanol solution.

Det er nu funnet at anvendelse av svovelsyre som separasjonsmiddel for azeotropiske blandinger av trimethylborat og methanol'i en overraskende grad er fordelaktig når syren sirkulerer i prosessen under til-bakeføring til en forestringsreaktor. Herved blir det mulig å gjenvinne methanol og trimethylborat som er tilstede i det tilbake-førte materiale. Ved hjelp av fremgangs-måten ifølge oppfinnelsen oppnåes der et praktisk talt kvantitativt utbytte både av borsyre og av methanol. It has now been found that the use of sulfuric acid as a separating agent for azeotropic mixtures of trimethylborate and methanol is advantageous to a surprising extent when the acid circulates in the process during return to an esterification reactor. This makes it possible to recover methanol and trimethylborate which are present in the returned material. By means of the method according to the invention, a practically quantitative yield of both boric acid and methanol is achieved.

I vedføyede tegning vises et prosess-diagram i hvilket 1 betegner en reaktor hvor forestringsreaksjonen mellom borsyre og methanol utføres i nærvær av svovelsyre. Trimethylboratet avdestillerer i form av en azeotropisk blanding med methanol, sammen med overskudd av den methanol som er anvendt for forestringsreaksjonen. In the attached drawing, a process diagram is shown in which 1 denotes a reactor where the esterification reaction between boric acid and methanol is carried out in the presence of sulfuric acid. The trimethyl borate distills off in the form of an azeotropic mixture with methanol, together with an excess of the methanol used for the esterification reaction.

Apparaturen er fortrinsvis av bly eller annet materiale som er motstandsdyktig mot ca. 40%'s svovelsyre ved temperaturer fra 130 til 150°C. The equipment is preferably made of lead or other material that is resistant to approx. 40% sulfuric acid at temperatures from 130 to 150°C.

Gjennom ledningen 5 tilføres reaktoren 1 en blanding av methanol og svovelsyre som inneholder litt trimethylborat og som er erholdt ved å blande tilbakeført materiale fra ledningene 7 og 12 med ren methanol. Gjennom ledningen 6 tilføres borsyre 1 fast form og som er erholdt ved tilsetning av ren borsyre til tilbakeført borsyreholdig materiale fra ledningen 15. Forestringen foregår ved oppvarmning av blandingen i reaktoren 1 til kokning, og altså under av-destiilasjon av trimethylborat i form av en azeotropisk blanding med methanol. Derpå avdestillereres overskudd av methanol som føres tilbake til reaktoren gjennom ledningen 7. Through line 5, reactor 1 is supplied with a mixture of methanol and sulfuric acid which contains a little trimethylborate and which is obtained by mixing recycled material from lines 7 and 12 with pure methanol. Through line 6, boric acid 1 is supplied in solid form and which is obtained by adding pure boric acid to returned boric acid-containing material from line 15. The esterification takes place by heating the mixture in reactor 1 to boiling, and thus during de-distillation of trimethylborate in the form of an azeotropic mixture with methanol. Excess methanol is then distilled off and returned to the reactor through line 7.

Det syreholdige residuum med høy temperatur tas ut fra reaktoren gjennom ledningen 9, avkjøles, hvorved mesteparten av ikke reagert borsyre utfelles og ledes til filteret 4 ved romtemperatur. Her gjenvinnes borsyre og føres tilbake gjennom ledningen 15. The high-temperature acidic residue is taken out of the reactor through the line 9, cooled, whereby most of the unreacted boric acid is precipitated and led to the filter 4 at room temperature. Boric acid is recovered here and fed back through line 15.

Filtratet fra filtratet 4 består av svovelsyre fortynnet med vannet fra forestringen samt en meget liten mengde methanol og borsyre og ledes bort fra prosessen. The filtrate from filtrate 4 consists of sulfuric acid diluted with the water from the esterification as well as a very small amount of methanol and boric acid and is led away from the process.

Den azeotropiske blanding av trimethylborat og methanol som er avdestillert fra forestringsreaktoren blandes med til-' bakeført azeotropisk blanding fra ledningen 10 og går derfra til en vaske-separator 2 sammen med en viss mengde konsentrert svovelsyre som tilføres gjennom ledningen 11. The azeotropic mixture of trimethylborate and methanol which is distilled from the esterification reactor is mixed with the returned azeotropic mixture from line 10 and goes from there to a washing separator 2 together with a certain amount of concentrated sulfuric acid which is supplied through line 11.

Ved å utføre f.eks. tre vaskninger med forskjellige mengder svovelsyre får man på den ene side nesten rent trimethylborat og pa den annen side en blanding av svovelsyre, methanol og trimethylborat som føres tilbake til forestringsreaktoren. By performing e.g. three washings with different amounts of sulfuric acid give, on the one hand, almost pure trimethylborate and, on the other hand, a mixture of sulfuric acid, methanol and trimethylborate which is returned to the esterification reactor.

Det erholdte trimethylborat ledes etter vaskningen med konsentrert svovelsyre inn i et destillasjonsapparat 3 fra hvilket man får den azeotropiske blanding som føres tilbake gjennom ledningen 10, samt rent trimethylborat som tas ut gjennom ledningen 14. The obtained trimethylborate is led after washing with concentrated sulfuric acid into a distillation apparatus 3 from which the azeotropic mixture is obtained which is fed back through the line 10, as well as pure trimethylborate which is taken out through the line 14.

Graden av overføring av borsyre til trimethylborat i forestringstrinnet er hovedsakelig avhengig av mengdeforholdet methanol: borsyre, samt av den tilstedevær-ende mengde svovelsyre. The degree of transfer of boric acid to trimethylborate in the esterification step is mainly dependent on the quantity ratio of methanol: boric acid, as well as on the amount of sulfuric acid present.

Det foretrekkes å anvende et molart forhold CH3 " OH =2,5 ganger det teore-H:s BOb It is preferred to use a molar ratio CH3 " OH =2.5 times the theoretical H's BOb

H-SO-i tiske, samt et vektsforhold — — = 0,6. H-SO-i tical, as well as a weight ratio — — = 0.6.

Hs BOa Hs BOa

Imidlertid er det mulig å bruke andre mengdeforhold hvorved graden av omdannelse av borsyre varierer litt. However, it is possible to use other ratios whereby the degree of conversion of boric acid varies slightly.

En annen faktor som kan innvirke på omdannelsen er destillasjonens varighet. Når dannelsen av trimethylborat blir lang-som, foretrekkes det å avbryte destillasjo-nen av den azeotropiske blanding og lede til gjenvinning methanolen som så anvendes påny i den samme reaktor. Another factor that can affect the conversion is the duration of the distillation. When the formation of trimethylborate becomes slow, it is preferred to interrupt the distillation of the azeotropic mixture and recycle the methanol, which is then used again in the same reactor.

Når man anvender et molforhold på f. CH3OH When using a molar ratio of e.g. CH3OH

eks. = 2,3, og et vektsforhold e.g. = 2.3, and a weight ratio

H3BO3H3BO3

H2SO4 H2SO4

—= 0,6 samt en destillasjonstid på HhBO», —= 0.6 and a distillation time of HhBO",

8-10 timer, kan der oppnåes en omdannelse av borsyre på 89%. 8-10 hours, a conversion of boric acid of 89% can be achieved.

De ovenfor angitte data referer seg til anvendelsen av ren methanol og 98-100%'s svovelsyre. Ved anvendelse av f.eks. 96%'s methanol og 94%'s svovelsyre avtar omdannelsen av borsyre ganske lite. Den erholdte azeotropiske blanding har i alminnelighet et innhold av trimethylborat på ca. 70-72 %. Dette er litt lavere enn det teoretiske som er 74,5%. Det foretrekkes å vaske slike azeotropiske blandinger mere enn én gang med konsentrert svovelsyre, f.eks. tre ganger. The above data refer to the use of pure methanol and 98-100% sulfuric acid. When using e.g. 96% methanol and 94% sulfuric acid decrease the conversion of boric acid quite a bit. The resulting azeotropic mixture generally has a trimethylborate content of approx. 70-72%. This is slightly lower than the theoretical figure of 74.5%. It is preferred to wash such azeotropic mixtures more than once with concentrated sulfuric acid, e.g. three times.

Som et eksempel beskrives i det føl-gende en vaskeprosess bestående av tre trinn: I en skilletrakt anbringes 1000 deler av en blanding som består av 70% trimethylborat og 30% methanol. Blandingen tilsettes 170 deler 100%'s svovelsyre og blandes i nogen tid hvorpå man lar den stå. Der skiller seg ut to skikt med følgende sammensetning. As an example, a washing process consisting of three steps is described below: In a separating funnel, 1000 parts of a mixture consisting of 70% trimethylborate and 30% methanol are placed. The mixture is added to 170 parts of 100% sulfuric acid and mixed for some time, after which it is left to stand. There are two layers with the following composition.

Operasjonen gjentas ved å tilsette 35 deler 100%'s svovelsyre til skikt 2. Der danner seg påny to skikt med følgende sammensetning: The operation is repeated by adding 35 parts of 100% sulfuric acid to layer 2. There, two layers form again with the following composition:

Den samme operasjon gjentas så for The same operation is then repeated for

tredje gang ved å tilsette skikt 2 23 deler the third time by adding layer 2 23 parts

100%'s svovelsyre. Der danner seg to skikt 100% sulfuric acid. Two layers form there

med følgende sammensetning: with the following composition:

Skikt 1: 46 deler Av de 700 deler trimethylborat som opp-rinnelig var tilstede i den azeotropiske blanding, utvinnes ved slutten av den tre-trins operasjon 609 deler med 99,5%'s ren-609 het. Dette tilsvarer et utbytte på x 100 = 87% trimethylborat med 99,5%'s renhet, men som ved ytterligere rensning kan brin-ges på en renhet av 100%. Det totale utbytte er således praktisk talt kvantitativt både beregnet på den anvendte borsyre og på den anvendte methanol. Ved å gå frem som ovenfor angitt varierer nemlig utbyttet beregnet på borsyre fra 96 til 98%, mens utbyttet beregnet på methanol varierer fra 94 til 96%. Layer 1: 46 parts Of the 700 parts of trimethylborate originally present in the azeotropic mixture, at the end of the three-stage operation 609 parts with 99.5% purity are recovered. This corresponds to a yield of x 100 = 87% trimethylborate with 99.5% purity, but which can be brought to a purity of 100% by further purification. The total yield is thus practically quantitatively calculated both on the boric acid used and on the methanol used. By proceeding as indicated above, the yield calculated for boric acid varies from 96 to 98%, while the yield calculated for methanol varies from 94 to 96%.

Claims (4)

1. Fremgangsmåte til fremstilling av trimethylborat ved forestring av borsyre ned et overskudd av methanol i nærvær iv svovelsyre og derpå følgende adskillelse iv trimethylboratet fra den erholdte azeo-;ropiske blanding av methanol-trimethyl-Dorat ved behandling av denne med konsentrert svovelsyre, karakterisert/ed at hele mengden av den svovelsyre iom anvendes til adskillelsen av den azeo- .ropiske blanding føres tilbake til forest- •ingsreaktoren, hvorved methanol og tri-nethylborat som er tilstede i svovelsyren gjenvinnes.1. Method for the production of trimethylborate by esterification of boric acid down an excess of methanol in the presence of sulfuric acid and then the following separation of the trimethylborate from the obtained azeotropic mixture of methanol-trimethylborate by treating this with concentrated sulfuric acid, characterized in that the entire amount of the sulfuric acid is used for the separation of the azeotropic mixture is returned to the esterification reactor, whereby methanol and tri-nethylborate present in the sulfuric acid are recovered. 2. Fremgangsmåte ifølge påstand 1, karakterisert ved at man anvender methanolen og borsyren i et molart for-aold CH.sOH : HnBOa på mellom 1 og 5 -anger det teoretiske, fortrinsvis 2,5 ganger let teoretiske.2. Method according to claim 1, characterized in that the methanol and boric acid are used in a molar ratio of CH.sOH : HnBOa of between 1 and 5 times the theoretical, preferably 2.5 times the theoretical. 3. Fremgangsmåte ifølge påstand 1 eller l, karakterisert ved at man anven-ier svovelsyren og borsyren i et vektsforhold HjSOi : H3BO3 i forestringstrinnet på nellom 0,2 og 1,5, fortrinnsvis 0,6.3. Process according to claim 1 or 1, characterized in that the sulfuric acid and boric acid are used in a weight ratio HjSOi : H3BO3 in the esterification step of between 0.2 and 1.5, preferably 0.6. 4. Fremgangsmåte ifølge hvilkensom-lelst av de foregående påstander, k a r a k - erisert ved at man til adskillelse av len azeotropiske blanding anvender svovelsyre med en konsentrasjon mellom 98 og 100%.4. Method according to any one of the preceding claims, characterized in that sulfuric acid with a concentration between 98 and 100% is used for the separation of an azeotropic mixture.
NO3260/73A 1973-07-06 1973-08-16 ANALOGICAL PROCEDURE FOR THE PREPARATION OF PIPERAZINE PYRIMIDINES WITH THERAPEUTIC EFFECT. NO137205C (en)

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FR7324874A FR2257294B1 (en) 1973-07-06 1973-07-06

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NO326073L NO326073L (en) 1975-02-03
NO137205B true NO137205B (en) 1977-10-10
NO137205C NO137205C (en) 1978-01-18

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JP (1) JPS5849548B2 (en)
BE (1) BE803803A (en)
CH (1) CH582171A5 (en)
DE (1) DE2342880A1 (en)
ES (1) ES418113A1 (en)
FR (1) FR2257294B1 (en)
GB (1) GB1434544A (en)
LU (1) LU68263A1 (en)
MX (1) MX2978E (en)
NO (1) NO137205C (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH602663A5 (en) * 1975-05-23 1978-07-31 Mar Pha Etu Expl Marques
FR2417507A2 (en) * 1977-07-28 1979-09-14 Ugine Kuhlmann DIAMINO-2,4 (OR -4,6) METHYLTHIO-5 PYRIMIDINES HERBICIDES
JPS54159877A (en) * 1978-06-07 1979-12-18 Matsushita Electronics Corp Detection method for semiconductor substrate position and break
FR2503162A1 (en) * 1981-04-07 1982-10-08 Pharmindustrie NOVEL PIPERAZINO-2 PYRIMIDINE DERIVATIVES, PROCESSES FOR THEIR PREPARATION AND THEIR USE AS MEDICAMENTS OR AS INTERMEDIATES FOR THE PRODUCTION OF MEDICAMENTS
JPS6177335A (en) * 1984-09-25 1986-04-19 Kazumichi Kimura Defective mark detector for semiconductor pellet
IT1191845B (en) * 1986-01-20 1988-03-23 Dompe Farmaceutici Spa PHARMACOLOGICALLY ACTIVE ALCHYLOLS
JPH02114936U (en) * 1989-03-03 1990-09-14

Also Published As

Publication number Publication date
CH582171A5 (en) 1976-11-30
DE2342880A1 (en) 1975-01-30
FR2257294B1 (en) 1977-07-01
MX2978E (en) 1980-01-17
LU68263A1 (en) 1973-10-24
JPS5025578A (en) 1975-03-18
JPS5849548B2 (en) 1983-11-05
BE803803A (en) 1974-02-20
NO137205C (en) 1978-01-18
ES418113A1 (en) 1976-03-16
GB1434544A (en) 1976-05-05
NO326073L (en) 1975-02-03
FR2257294A1 (en) 1975-08-08

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