NO150668B - PROCEDURE FOR THE PREPARATION OF A MONOLITIC MACHINE PART WITH PARTS OF DIFFERENT ALLOY COMPOSITION BY POWDER METAL SURGERY - Google Patents
PROCEDURE FOR THE PREPARATION OF A MONOLITIC MACHINE PART WITH PARTS OF DIFFERENT ALLOY COMPOSITION BY POWDER METAL SURGERY Download PDFInfo
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- NO150668B NO150668B NO812680A NO812680A NO150668B NO 150668 B NO150668 B NO 150668B NO 812680 A NO812680 A NO 812680A NO 812680 A NO812680 A NO 812680A NO 150668 B NO150668 B NO 150668B
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- 238000000034 method Methods 0.000 title claims description 16
- 239000000203 mixture Substances 0.000 title description 12
- 238000002360 preparation method Methods 0.000 title description 3
- 239000000956 alloy Substances 0.000 title 1
- 229910045601 alloy Inorganic materials 0.000 title 1
- 239000002184 metal Substances 0.000 title 1
- 239000000843 powder Substances 0.000 title 1
- 238000001356 surgical procedure Methods 0.000 title 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 claims description 23
- 150000003951 lactams Chemical class 0.000 claims description 16
- VQTGUFBGYOIUFS-UHFFFAOYSA-N nitrosylsulfuric acid Chemical compound OS(=O)(=O)ON=O VQTGUFBGYOIUFS-UHFFFAOYSA-N 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 6
- 150000002923 oximes Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000007789 gas Substances 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- -1 cycloalkane carboxylic acids Chemical class 0.000 description 4
- JQYWAZNRRQRPNN-UHFFFAOYSA-N cyclododecylmethanol Chemical compound OCC1CCCCCCCCCCC1 JQYWAZNRRQRPNN-UHFFFAOYSA-N 0.000 description 4
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 4
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 description 4
- ZHPBLHYKDKSZCQ-UHFFFAOYSA-N cyclooctylmethanol Chemical compound OCC1CCCCCCC1 ZHPBLHYKDKSZCQ-UHFFFAOYSA-N 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YDLSUFFXJYEVHW-UHFFFAOYSA-N azonan-2-one Chemical compound O=C1CCCCCCCN1 YDLSUFFXJYEVHW-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000007034 nitrosation reaction Methods 0.000 description 3
- 229960001730 nitrous oxide Drugs 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940093499 ethyl acetate Drugs 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 230000009935 nitrosation Effects 0.000 description 2
- 239000001272 nitrous oxide Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002026 chloroform extract Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- SFVWPXMPRCIVOK-UHFFFAOYSA-N cyclododecanol Chemical compound OC1CCCCCCCCCCC1 SFVWPXMPRCIVOK-UHFFFAOYSA-N 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
Description
Foreliggende oppfinnelse angår en fremgangsmåte for fremstilling The present invention relates to a method for production
av usubstituerte GO-laktamer med 6-12 karbonatomer i ringen fra cykloalifatiske hydroksymetylforbindelser med 6-12 karbonatomer i ringen, og det særegne ved fremgangsmåten i henhold til oppfinnelsen er at de cykloalifatiske hydroksymetylforbindelser forst behandles med of unsubstituted GO-lactams with 6-12 carbon atoms in the ring from cycloaliphatic hydroxymethyl compounds with 6-12 carbon atoms in the ring, and the peculiarity of the method according to the invention is that the cycloaliphatic hydroxymethyl compounds are first treated with
a) dinitrogentrioksyd i nærvær av svovelsyre ella? a) dinitrogen trioxide in the presence of sulfuric acid or?
b) nitrosylsvovelsyre b) nitrosylsulphuric acid
hvoretter de dannede oksimer ved behandling med oleum omleires i after which the oximes formed by treatment with oleum are rearranged in
Fremgangsmåte for fremstilling av usubstituerte Process for the preparation of unsubstituted
U-<»->laktamer med 6-12 karbonatomer i ringen. U-<»->lactams with 6-12 carbon atoms in the ring.
reaksjonsblandingen til de tilsvarende laktamer. the reaction mixture of the corresponding lactams.
Det er kjent at det dannes karboksylgrupper når nitrogenoksyder, spesielt dinitrogenoksyd, påvirker primære, alkoholiske hydroksylgrupper i passende opplosningsmidler. Denne oksydasjons-reaksjon kan også utfores når det karbonatom som bærer den primære alkoholiske hydroksylgruppe er bundet til et tertiært karbonatom, for eksempel ved de cykloalifatiske hydroksymetylforbindelser av typen hydroksymetylcykloheksan og dets ring-homologer. It is known that carboxyl groups are formed when nitrogen oxides, especially nitrous oxide, affect primary alcoholic hydroxyl groups in suitable solvents. This oxidation reaction can also be carried out when the carbon atom carrying the primary alcoholic hydroxyl group is bound to a tertiary carbon atom, for example with the cycloaliphatic hydroxymethyl compounds of the hydroxymethylcyclohexane type and its ring homologues.
Det er videre fra australsk patentskrift 239*7^6 kjent å fremstille kaprolaktam ved at heksahydrobenzosyre eller et funksjonelt derivat derav behandles med et nitrosylerende middel i nærvær av svovelsyre. Dette patentskrift omhandler en metode hvor heksahydrobenzosyren nitroseres i en opplosning av nitrosylsvovelsyre i konsentrert svovelsyre. ;Nevnes skal også at det fra australsk patentskrift 2<>>+7.258, se særlig eksempel 1, er kjent å fremstille laktamer - uten isolering av cykloalkankarboksylsyrer - fra heksahydrotoluen, cykloheksyl-karbinoler e.l. forbindelser som utgangsforbindelser ved behandling med nitroserende midler i surt miljo. Her tilsettes reagensene i vilkårlig rekkefolge, men uten noen utsatt tilsetning av oleum etter at dannelsen av oksimer i reaksjonsblandingen har funnet sted. Det er i forbindelse med de senere anforte utforelseseksempler (se disse) inntatt et sammenligningseksempel hvorav fremgår at de utbytter som kan oppnås ikke kan sammenlignes med de utbytter som kan oppnås ved fremgangsmåten ifolge den foreliggende oppfinnelse. ;Ved fremgangsmåten ifolge det australske patentskrift 2^-7.258 ;hvor oleum tilsettes med en gang, inntreffer det gjerne dannelse av det tilsvarende sulfat, hvorved det dannede hydroksymetylcykloalkan unndras fra den aktuelle reaksjon. Ved omsetningen i henhold til foreliggende oppfinnelse gjennomfares oksydasjons- ;og nitroseringsreaksjonen for omleiringsreaksjonen, hvorved den utsatte tilsetning av oleum har til formål at alkoholen primært overfores i cykloalkankarboksylsyre som nitroseres, og forst ;deretter omleires det erholdte produkt ved tilsetning av oleum. Den foreliggende prosess er en såkalt direkte prosess for fremstilling av laktamer fra lett tilgjengelige hydroksymetylcykloalkaner, idet de som mellomprodukt dannede oksimer uten isolering omleires i de tilsvarende laktamer. Fremgangsmåten utfores således i en eneste, av to trinn bestående arbeidsgang ut fra angjeldende hydroksymetylforbindelse. ;Som nitroserende og samtidig oksyderende middel anvendes ;a) dinitrogentrioksyd i nærvær av konsentrert svovelsyre, eller ;b) nitrosylsvovelsyre. ;De oksimer som dannes fra de cykloalifatiske hydroksymetyl-f orbindelser ved behandling med disse midler iscfleres ikke, men omleires i reaksjonsblandingen med oleum uten noen reaksjonsavbrytelse til laktamet av den aminokarbonsyre som har et karbonatom mindre enn utgangsforbindelsen. ;Denne omsetning og de utbytter av laktamer som kan oppnås ved hjelp av den er desto mer bemerkelsesverdige når det tas hensyn til hvor mange enkelt-reaksjoner som finner sted etter hverandre i reaksjonsblandingen. ;For å utfore fremgangsmåten kreves det intet spesielt utstyr. Reaksjonen kan, som nevnt(utfores på to måter. Ved anvendelse av dinitrogentrioksyd som oksyderende og nitroserende agens foregår omsetningen i et trangt, hoyt reaksjonskar som er forsynt med et termometer, rorer, samt en fritte henhv. et gassinnledningsror ved den nedre ende. Hydroksymetylcyklohydrokarbonet oppvarmes til ca. 50°C. Ved langsom tilsetning av konsentrert svovelsyre fra en dråpetrakt under samtidig innblåsing av tort dinitrogentrioksyd blir reaksjonen satt i gang. En ytterligere ekstra oppvarming av reaksjonsblandingen trenges ikke mer, da omsetningen forloper sterkt eksotermisk. Tilsetning av svovelsyren og dinitrogentrioksydet foregår på den måten at det stadig foreligger omtrent ekvimolære mengder i blandingen. ;Reaksjonen kan reguleres ved. hjexp av tiisetningshastigheten, spesielt av dinitrogentrioksydet og ved passende dimensjonering av reaksjonskaret på den måte at det dels nettopp blåses inn så meget dinitrogenoksyd (1\|0/NU2~gassblanding ) at reaks jonsblandin-gen holdes på den onskede temperatur og dels ved at dinitrogentrioksydet absorberes helt. Reaksjonstiden utgjor ved mengder på 0,1 tix 2,5 moi av de forskjellige oksymetylcykloaikaner med 6-12 ringkarbonatomer 3-12 timer. ;Da det under oksydenngsfasen av reaksjonen dannes den mengde vann som tilsvarer den oksyderte alkoholmengde og som delvis fordampes ved reaksjonstemperaturen, er det tilrådelig å fjerne vannet så meget som mulig ved å anordne en passende utskiller. I mange tilfeller har reaksjonsblandingen lett for a danne skadelig skum. Ved tilsetning av små mengder av en handexsvanlig silikonolje kan dette fenomen hindres. Moi-forholdet mellom de reaksjonskomponen-ter som tilfores , hydroksymetylcykloalkan: dinitrogentrioksyd: konsentrert svovelsyre utgjor i: (2-5) : (1-3 )j fortrinnsvis 1:2,5:2,5. Omsetningen foregår normalt uten forhoyet trykk ved en temperatur pa 40 - 90°C, fortrinnsvis 7o - bO°C. ;Hvis det for oksyderingen og nitroseringen av hydroksymetylcykloal-kanet brukes nitrosylsvovelsyre foregår omsetningen av reaksjons-deltakerne også i et rorformet reaksjonskar som er forsynt mea termometer og rorer. Reaksjonstemperaturen hoides på 30 - 60°C, fortrinnsvis ved 45 - 55°C. Omsetningen er sterkt eksotermisk. Reaksjonstiden er 3 - 12 timer, i alminnelighet dog 5-8 timer ;ait etter arten av den omsatte hydroksymetylforbindelse. Mol-forhoidet hydroksymetyxcykxoalkan til nitrosylsvovelsyre er i:(1,5 - 3)j fortrinnsvis dog l:(l,7 - 2), ;Etter avsluttet oksydering og samtidig nitrosering som gjennomfares diskontinuerlig eller, ved passende reaksjonskar, også kontinuerlig ved hjelp av dinitrogentrioksya i nærvær av svovelsyre eller ved hjelp av bare nitrosylsvovelsyre blir det til reaksjonsproduktet tilsatt oieum i egnet konsentrasjon (10 - 60$), hvorved det ved samtidig oppvarming av reaksjonsblandingen til 9u - 130 °C, fortrinnsvis dog 100 - 110 oC oppnås omiagring av de dannede oksimer ;til de tilsvarende laktamer. ;Fremstillingen av laktamene fra den samlede reaksjonsblanding foregår ved å helle den avkjolte blanding under samtidig god omroring ut i en ca. 10$ natriumhydroksyd - eller ca. 10$ ammoniakk ;-opplosning, idet svovelsyren og også de karboksylsyrer som dannes under reaksjonen nøytraliseres og saltene skiller seg ut i en form som er tungt- eller uopploselig i vann, idet de er flokket og nærmest farvelose, og kan isoleres ved filtrering. Ved ;oppløselige laktamer kan opparbeidelsen lettes ved ekstra ekstraksjon av den vandigalkaliske opplosning med et inert opplosningsmiddel, f.eks. kloroform, karbontetraklorid eller også eter. ;Ved flere gangers ansyring av den vandige laktammoderlut og ekstrahering med ett av de nevnte inerte opplosningsmidler, kan den cykloalifatiske karbonsyre som dannes ved oksyderingen og ikke omsettes videre, isoleres. ;Da hydroksymetylcykloalkaner med like C-tall i ringen lett kan fremsbiiles i teknisk målestokk ved hydroformyleringen over de cykliske olefiner, som på sin side kan fremstilles fra butadien, etylen eller acetylen, er fremgangsmåten i henhold til oppfinnelsen av spesiell interesse da de laktamer som oppnås som sluttprodukter er utmerkede og foretrukkede utgangsmaterialer for, fremstilling av de meget viktige polyamider. ;Sammenligningseksempel vedr. omsetning av hydroksy-cyklododekan med nitrosylsvovelsyre tilsvarende fremgangsmåten i henhold til eks. 1 i australsk patentskrift 247.254. ;108 g hydroksymetylcyklododekan blandes forsiktig med 102 ml 100$ svovelsyre og 106 g nitrosylsvovelsyre, idet det påsees at temperaturen ikke overstiger 45°C. Til denne blanding tilsettes deretter ytterligere 53 g nitrosylsvovelsyre såvel som 53 g oleum (60$). Under tilsetningen opptrer sterk gassutvikling og mork-farving av reaksjonsproduktet. Etter avsluttet sammenblanding oppvarmes reaksjonsproduktet ved 65°C i en time. Deretter helles blandingen ut på is slik at svovelsyrekonsentrasjonen utgjor ca. 25$. Det bunnfall som danner seg ekstraheres med kloroform og ;kloroformlbsningen utrystes deretter med fortynnet natronlut. KLoroformekstrakten inndampes og den fettaktige rest omkrystalli-seres fra di-isopropyleter. Det erholdes 23,2 g dodekalaktam tilsvarende 2i,5$ av teoretisk utbytte, regnet pa hydroksymetyl-cykiododekan. Smeltepunkt 1m-6°C mot kontroli-smeltepunkt 152-153°C ;Dette utbytte kan ikke sammenliknes med det utbytte som oppnås i henhold tii det etterfølgende eks. 1 hvor det gås fram etter fremgangsmåten i henhold til oppfinnelsen. ;Ytterxigere oppnås ved fremgangsmåten tilsvarende eks. 2 i det samme patentskrift, ved anvendelse av dicykloheksylkarbmol et kaproiaktamutbytte pa bare 15$. Ved anvendelse av hydroksymetyx-cykloheksan og nitrosylsvovelsyre ligger utbyttet ennå lavere. ;Eksempel 1 ;I et rbrformet reaksjonskar som er åpent oventil og nedentil er forsynt med et gassinniopsror, i midten med termometer, oventil med en dråpetrakt og dessuten med en rorer bie 2o g (0,11 mol) hydroksymetyicyklododekan (92,6$) oppvarmet tii 45°C. Etter at denne temperatur var oppnådd bie det fra en ampuxle over et t<*>6rre-tårn blåst inn en moderat strom rent dinitrogentrioksyd (NO og N02It is further known from Australian patent document 239*7^6 to produce caprolactam by treating hexahydrobenzoic acid or a functional derivative thereof with a nitrosylating agent in the presence of sulfuric acid. This patent document deals with a method where the hexahydrobenzoic acid is nitrosated in a solution of nitrosylsulphuric acid in concentrated sulfuric acid. It should also be mentioned that from Australian patent document 2<>>+7,258, see especially example 1, it is known to prepare lactams - without isolation of cycloalkane carboxylic acids - from hexahydrotoluene, cyclohexyl carbinols, etc. compounds as starting compounds when treated with nitrosating agents in an acidic environment. Here, the reagents are added in arbitrary order, but without any deferred addition of oleum after the formation of oxime in the reaction mixture has taken place. In connection with the later cited examples of embodiment (see these), a comparison example has been included from which it is clear that the yields that can be obtained cannot be compared with the yields that can be obtained by the method according to the present invention. In the method according to the Australian patent document 2^-7,258, where oleum is added at once, the formation of the corresponding sulfate often occurs, whereby the formed hydroxymethylcycloalkane is removed from the reaction in question. In the reaction according to the present invention, the oxidation and nitrosation reaction is carried out for the rearrangement reaction, whereby the delayed addition of oleum has the purpose that the alcohol is primarily converted into cycloalkanecarboxylic acid which is nitrosated, and first, then the product obtained is rearranged by the addition of oleum. The present process is a so-called direct process for the production of lactams from readily available hydroxymethylcycloalkanes, whereby the oximes formed as an intermediate product are rearranged in the corresponding lactams without isolation. The method is thus carried out in a single, two-step procedure based on the hydroxymethyl compound in question. ;A) nitrous oxide in the presence of concentrated sulfuric acid, or ;b) nitrosylsulphuric acid is used as a nitrosating and simultaneously oxidizing agent. The oximes formed from the cycloaliphatic hydroxymethyl compounds by treatment with these agents are not crystallized, but are rearranged in the reaction mixture with oleum without any interruption of the reaction to the lactam of the aminocarboxylic acid which has one carbon atom less than the starting compound. ;This turnover and the yields of lactams that can be obtained by means of it are all the more remarkable when one takes into account how many individual reactions take place one after the other in the reaction mixture. No special equipment is required to carry out the procedure. The reaction can, as mentioned, be carried out in two ways. When using dinitrogen trioxide as an oxidizing and nitrosating agent, the reaction takes place in a narrow, tall reaction vessel which is equipped with a thermometer, stirrers, as well as a frit or a gas introduction stirrer at the lower end. The hydroxymethylcyclohydrocarbon is heated to approximately 50°C. By slowly adding concentrated sulfuric acid from a dropping funnel while simultaneously blowing in dry dinitrogen trioxide, the reaction is started. A further additional heating of the reaction mixture is no longer needed, as the reaction proceeds strongly exothermicly. Addition of the sulfuric acid and dinitrogen trioxide takes place in such a way that there are always approximately equimolar amounts in the mixture. The reaction can be regulated by increasing the deposition rate, especially of the dinitrogen trioxide and by suitably dimensioning the reaction vessel in such a way that just as much dinitrogen oxide (1\|0 /NU2~gas mixture ) to react ion mixture n is kept at the desired temperature and partly by the dinitrogen trioxide being completely absorbed. For amounts of 0.1 x 2.5 moi of the various oxymethylcycloalkanes with 6-12 ring carbon atoms, the reaction time is 3-12 hours. As during the oxidation phase of the reaction the amount of water corresponding to the oxidized amount of alcohol is formed and partially evaporates at the reaction temperature, it is advisable to remove the water as much as possible by arranging a suitable separator. In many cases, the reaction mixture tends to form harmful foam. This phenomenon can be prevented by adding small amounts of a handex-ordinary silicone oil. The Moi ratio between the reaction components which are supplied, hydroxymethylcycloalkane: dinitrogen trioxide: concentrated sulfuric acid is i: (2-5) : (1-3) j preferably 1:2.5:2.5. The reaction normally takes place without increased pressure at a temperature of 40 - 90°C, preferably 7o - bO°C. If nitrosylsulphuric acid is used for the oxidation and nitrosation of the hydroxymethylcycloalkane, the reaction of the reaction participants also takes place in a tube-shaped reaction vessel which is equipped with a thermometer and stirrups. The reaction temperature is maintained at 30 - 60°C, preferably at 45 - 55°C. The turnover is highly exothermic. The reaction time is 3 - 12 hours, but generally 5-8 hours, depending on the nature of the reacted hydroxymethyl compound. The molar ratio of hydroxymethoxycycloxoalkane to nitrosylsulphuric acid is i:(1.5 - 3)j, however, preferably l:(1.7 - 2), ;After completion of oxidation and simultaneous nitrosation, which is carried out discontinuously or, in suitable reaction vessels, also continuously with the help of dinitrogentrioxy in the presence of sulfuric acid or with the help of only nitrosylsulphuric acid, oil is added to the reaction product in a suitable concentration (10 - 60$), whereby, by simultaneously heating the reaction mixture to 9u - 130 °C, preferably 100 - 110 oC, the omiagration of the formed oximes to the corresponding lactams. The production of the lactams from the overall reaction mixture takes place by pouring the cooled mixture while simultaneously stirring well into an approx. 10$ sodium hydroxide - or approx. 10$ ammonia solution, as the sulfuric acid and also the carboxylic acids formed during the reaction are neutralized and the salts separate in a form that is difficult or insoluble in water, as they are flocculent and almost colourless, and can be isolated by filtration. In the case of soluble lactams, the preparation can be facilitated by additional extraction of the water-alkaline solution with an inert solvent, e.g. chloroform, carbon tetrachloride or ether. By acidifying the aqueous lactam mother liquor several times and extracting with one of the aforementioned inert solvents, the cycloaliphatic carbonic acid which is formed during the oxidation and is not reacted further, can be isolated. As hydroxymethylcycloalkanes with the same C number in the ring can easily be produced on a technical scale by hydroformylation over the cyclic olefins, which in turn can be produced from butadiene, ethylene or acetylene, the method according to the invention is of particular interest as the lactams obtained as end products are excellent and preferred starting materials for the manufacture of the very important polyamides. ;Comparative example regarding reaction of hydroxy-cyclododecane with nitrosylsulphuric acid corresponding to the method according to ex. 1 in Australian patent document 247,254. ;108 g of hydroxymethylcyclododecane are carefully mixed with 102 ml of 100% sulfuric acid and 106 g of nitrosylsulphuric acid, ensuring that the temperature does not exceed 45°C. A further 53 g of nitrosylsulphuric acid as well as 53 g of oleum ($60) are then added to this mixture. During the addition, there is strong gas evolution and dark coloration of the reaction product. After complete mixing, the reaction product is heated at 65°C for one hour. The mixture is then poured onto ice so that the sulfuric acid concentration is approx. 25$. The precipitate that forms is extracted with chloroform and the chloroform solution is then shaken with dilute caustic soda. The chloroform extract is evaporated and the fatty residue is recrystallized from diisopropyl ether. 23.2 g of dodecalactam are obtained, corresponding to 21.5% of the theoretical yield, calculated on hydroxymethyl-cyclododecane. Melting point 1m-6°C versus control melting point 152-153°C; This yield cannot be compared with the yield obtained according to the following example. 1 where the procedure according to the invention is carried out. ;Further is achieved by the method corresponding to e.g. 2 in the same patent document, using dicyclohexylcarbmol a caproiactam yield of only 15$. When using hydroxymethylcyclohexane and nitrosylsulphuric acid, the yield is even lower. ;Example 1 ;In a tubular reaction vessel which is open at the top and bottom is provided with a gas inlet tube, in the middle with a thermometer, at the top with a dropping funnel and also with a stirrer bee 2o g (0.11 mol) of hydroxymethylcyclododecane (92.6$) heated to 45°C. After this temperature had been reached, a moderate stream of pure dinitrogen trioxide (NO and N02
i forholdet 1:1) gjennom gassinnledningsroret og samtidig begynte den dråpevise tilsetning av 96 - 100$ svovelsyre. Etter ca. lOmin. kom reaksjonen i gang og kunne erkjennes ved den jevne1 tempera-turstigning i reaksjonsblandingen. Etter at reaksjonen var kommet i gang,lot det seg også merke en gassutvikling som ofte steg til kraftig skum men som dog kunne holdes sterkt tilbake ved tilsetning av spor av en vanlig silikonolje. Tilsetningen av nitrose gasser samt svovelsyren ble foretatt slik at reaksjonstemperaturen inn-stilte seg på 75 - 80°C og ingen nitrose gasser forlot reaksjons-kare.t. Etter 3 timer var 22,6 g dinitrogentrioksyd (0,3 mol) samt 25 g svovelsyre (2,5 mol) omsatt og tilsetningen ble avbrutt, og i lopet av 15 min. dråpevis. ble det så tilsatt 20 g oleum (60$). Under tilsetningen av oleum kunne det igjen merkes en kraftig gassutvikling. Etter avsluttet oleum-tilsetning ble blandingen in the ratio 1:1) through the gas introduction pipe and at the same time the dropwise addition of 96 - 100% sulfuric acid began. After approx. lOmin. the reaction started and could be recognized by the steady temperature rise in the reaction mixture. After the reaction had started, gas development was also noticeable, which often rose to strong foam, but which could however be strongly contained by adding traces of a normal silicone oil. The addition of nitrous gases and the sulfuric acid was carried out so that the reaction temperature settled at 75 - 80°C and no nitrous gases left the reaction vessel. After 3 hours, 22.6 g of dinitrogen trioxide (0.3 mol) and 25 g of sulfuric acid (2.5 mol) had reacted and the addition was interrupted, and in the course of 15 min. drop by drop. 20 g of oleum ($60) was then added. During the addition of oleum, a strong gas development could again be felt. After finishing the oleum addition, the mixture became
oppvarmet til 110°C og holdt i 45 min. ved denne temperatur. heated to 110°C and held for 45 min. at this temperature.
Ved deretter å helle blandingen, som i mellomtiden var blitt avkjolet, under samtidig meget god omroring og ytre kjoling ut i kold 10$ natronlut eller ammoniakkvann kunne den fri syre nøytra-liseres og det rå laktam skilles ut i form av et gulaktig til nesten farvelost bunnfall i finkrystallinsk form. By then pouring the mixture, which had been cooled in the meantime, while at the same time very good stirring and external dressing into cold 10% caustic soda or ammonia water, the free acid could be neutralized and the crude lactam separated in the form of a yellowish to almost colorless precipitate in fine crystalline form.
Utbytte: 10,1 g, d.v.s. 54,6$ regnet på det hydroksymetylcyklododekan som var benyttet. Yield: 10.1 g, i.e. 54.6$ calculated on the hydroxymethylcyclododecane that was used.
For oppnåelse av farvelose produkter ble det ved en krystallise-ring fra etylacetat oppnådd meget rent dodeka„laktam i farvelose nåler med et smeltepunkt på 151 - 153°C. Hvis rålaktamet ikke var farv>elost,ble det opplost i 80$ vandig metanol, eventuelt gjort lysere med aktivt kull, noytralisert om igjen med natronlut henholdsvis med ammoniakk og denne opplosning ble langsomt helt ut i et stort overskudd av kokende vann. To obtain colorless products, very pure dodeca-lactam was obtained in colorless needles with a melting point of 151 - 153°C by crystallization from ethyl acetate. If the crude lactam was not colourless, it was dissolved in 80% aqueous methanol, optionally brightened with activated charcoal, neutralized again with caustic soda or ammonia and this solution was slowly poured into a large excess of boiling water.
Herunder ble det rensede laktam skilt ut i form av små, farvelose krystallnåler som etter torring og omkrystallisering fra etylace - tat ga meget rent dodeka^laktam. Below this, the purified lactam was separated in the form of small, colorless crystal needles which, after drying and recrystallization from ethylacetate, gave very pure dodeca-lactam.
EksempejL 2 Example 2
I den apparatur som er beskrevet i eksempel 1 ble innfort 10,8$ In the apparatus described in example 1, $10.8 was introduced
(0,1 mol) hydroksymetylcykloheksan og det ble under omroring oppvarmet til 60°C. I lopet av 3 timer ble så 29,6 g (0,3 mol) 100$ svovelsyre dryppe(t inn og 22,8 g (0,3 mol) dinitrogentrioksyd blåst inn. Ved hjelp av den reaksjonsvarme, som ble frigjort holdt temperaturen seg på 70 - 80°C. Deretter fikk blandingen reagere i ennå en time ved romtemperatur og til slutt ble 22 g 23$ oleum tilsatt i små porsjoner hvorunder blandingen igjen ble sterkt oppvarmet. Ved ekstra oppvarming ble produktet oppvarmet til 100 - 110°C hvorunder det ble en moderat gassutvikling. Når de,t ikke ble frigjort mere gass, d.v.s. etter ca. en time, ble den morkebrune tyktflytende masse som da var avkjolet _,under kraftig omroring fort inn i så meget 10$ natronlut at den opplosning som ble oppnådd .reagerte svakt alkalisk. Ved ekstrahering av den (0.1 mol) of hydroxymethylcyclohexane and it was heated to 60°C with stirring. Over the course of 3 hours, 29.6 g (0.3 mol) of 100% sulfuric acid were dripped in and 22.8 g (0.3 mol) of dinitrogen trioxide was blown in. With the help of the heat of reaction, which was released, the temperature was maintained itself at 70 - 80°C. The mixture was then allowed to react for another hour at room temperature and finally 22 g of 23$ oleum was added in small portions during which the mixture was again strongly heated. With additional heating the product was heated to 100 - 110°C during which there was a moderate evolution of gas. When no more gas was liberated, i.e. after about an hour, the dark brown viscous mass which had then cooled _,under vigorous stirring, quickly entered so much 10% caustic soda that the solution which was obtained .reacted slightly alkaline On extracting it
opplosning, som på forhånd var avfarget med litt aktiv kull, solution, which was previously decolorized with a little activated charcoal,
ved hjelp av kloroform ble det endelig oppnådd 5,6 g epsilon-kaprolaktam, d.v.s. 49,6$ av den teoretiske mengde regnet på det oksymetylcykloheksan som var brukt. Frysepunkt: 68 - 69°C. with the aid of chloroform, 5.6 g of epsilon-caprolactam were finally obtained, i.e. 49.6$ of the theoretical amount calculated on the oxymethylcyclohexane that had been used. Freezing point: 68 - 69°C.
Eksempel 3 Example 3
14,2 g (0,1 mol) hydroksymetylcyklooktan, 29,6 g 100$ svovelsyre samt 22,6 g dinitrogentrioksyd ble, som beskrevet i eksemplene 1 og 2, omsatt i lopet av 3^- time ved 70 - 80°C. Etter ytterligere 2 timer ved romtemperatur foretas tilsetningen av 22 g oleum (23$ S0^) samt en times oppvarming av blandingen til 100°C. 1 14.2 g (0.1 mol) of hydroxymethylcyclooctane, 29.6 g of 100% sulfuric acid and 22.6 g of dinitrogen trioxide were, as described in examples 1 and 2, reacted over the course of 3 hours at 70 - 80°C. After a further 2 hours at room temperature, 22 g of oleum (23$ SO^) are added and the mixture is heated to 100°C for one hour. 1
Etter foretatt opparbeidelse på den måten som er beskrevet i eksempel 2 ble det oppnådd 4,05 g kapryllaktam (smeltepunkt for det omkrystalliserte produkt: 73 -75°C) d.v.s. et utbytte på 28,7$ av den teoretiske mengde regnet på det hydroksymetylcyklooktan som var brukt. After working up in the manner described in example 2, 4.05 g of capryllactam was obtained (melting point for the recrystallized product: 73-75°C), i.e. a yield of 28.7$ of the theoretical amount calculated on the hydroxymethylcyclooctane used.
Eksempel 4 Example 4
14,2 g (0,1 mol) hydroksymetylcyklooktan omsettes i et rorformet reaksjonskar med rorer i lopet av 6 timer med tilsammen 21,2 g (0,17 mol) nitrosylsvovelsyre. Reaksjonstemperaturen var 45 - 50°C, hoyst 55°C, tilsetningen av nitrosylsvovelsyre foregikk i små porsjoner i lopet av hele reaksjonstiden. Etter hver tilsetning lot det seg merke en sterkt reaksjon og den varme som ble frigjort måtte eventuelt fores bort ved ytre kjoling. Etter avslutning av omsetningen med nitrosylsvovelsyre ble det tilsatt 22 g oleum (24$ So^) og blandingen ble oppvarmet i 30 min. til 95°C. 14.2 g (0.1 mol) of hydroxymethylcyclooctane are reacted in a tube-shaped reaction vessel with stirrups over the course of 6 hours with a total of 21.2 g (0.17 mol) of nitrosylsulphuric acid. The reaction temperature was 45 - 50°C, at most 55°C, the addition of nitrosylsulphuric acid took place in small portions during the entire reaction time. After each addition, a strong reaction was noticeable and the heat that was released had to be removed by external dressing. After completion of the reaction with nitrosylsulphuric acid, 22 g of oleum (24% SO^) were added and the mixture was heated for 30 min. to 95°C.
Opparbeidelsen foregikk slik som beskrevet i eksempel 2. Det ble oppnådd 11,25 g rått kapryllaktam hvorav det ved destillering under nedsatt trykk kunne isoleres 6,31 g rent kapryllaktam. Utbyttet 44,4$ regnet på det hydroksymetylcyklooktan som var brukt. KpQ}If: 113 - 115°C. The processing took place as described in example 2. 11.25 g of crude capryllactam were obtained, from which 6.31 g of pure capryllactam could be isolated by distillation under reduced pressure. Yield 44.4$ calculated on the hydroxymethylcyclooctane used. KpQ}If: 113 - 115°C.
Claims (1)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO812680A NO150668C (en) | 1981-08-07 | 1981-08-07 | PROCEDURE FOR THE PREPARATION OF A MONOLITIC MACHINE PART WITH PARTS OF DIFFERENT ALLOY COMPOSITION BY POWDER METAL SURGERY |
| EP82304080A EP0072175B1 (en) | 1981-08-07 | 1982-08-02 | Method of producing a monolithic alloy component preform |
| DE8282304080T DE3268398D1 (en) | 1981-08-07 | 1982-08-02 | Method of producing a monolithic alloy component preform |
| JP57136796A JPS5842703A (en) | 1981-08-07 | 1982-08-05 | Manufacture of preform of one body powder alloy part from more than two kinds of powder alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO812680A NO150668C (en) | 1981-08-07 | 1981-08-07 | PROCEDURE FOR THE PREPARATION OF A MONOLITIC MACHINE PART WITH PARTS OF DIFFERENT ALLOY COMPOSITION BY POWDER METAL SURGERY |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO812680L NO812680L (en) | 1983-02-08 |
| NO150668B true NO150668B (en) | 1984-08-20 |
| NO150668C NO150668C (en) | 1984-11-28 |
Family
ID=19886182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO812680A NO150668C (en) | 1981-08-07 | 1981-08-07 | PROCEDURE FOR THE PREPARATION OF A MONOLITIC MACHINE PART WITH PARTS OF DIFFERENT ALLOY COMPOSITION BY POWDER METAL SURGERY |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0072175B1 (en) |
| JP (1) | JPS5842703A (en) |
| DE (1) | DE3268398D1 (en) |
| NO (1) | NO150668C (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4602952A (en) * | 1985-04-23 | 1986-07-29 | Cameron Iron Works, Inc. | Process for making a composite powder metallurgical billet |
| US4721598A (en) * | 1987-02-06 | 1988-01-26 | The Timken Company | Powder metal composite and method of its manufacture |
| GB2233000A (en) * | 1989-05-25 | 1991-01-02 | Gkn Technology Ltd | Connecting rod |
| SE503422C2 (en) * | 1994-01-19 | 1996-06-10 | Soederfors Powder Ab | Process when making a composite product of stainless steel |
| US5762843A (en) * | 1994-12-23 | 1998-06-09 | Kennametal Inc. | Method of making composite cermet articles |
| US5541006A (en) * | 1994-12-23 | 1996-07-30 | Kennametal Inc. | Method of making composite cermet articles and the articles |
| US6183687B1 (en) | 1995-08-11 | 2001-02-06 | Kennametal Inc. | Hard composite and method of making the same |
| US5623723A (en) * | 1995-08-11 | 1997-04-22 | Greenfield; Mark S. | Hard composite and method of making the same |
| JP2000080407A (en) * | 1998-09-03 | 2000-03-21 | Ykk Corp | Manufacture of formed part |
| US6908688B1 (en) | 2000-08-04 | 2005-06-21 | Kennametal Inc. | Graded composite hardmetals |
| US7967924B2 (en) * | 2005-05-17 | 2011-06-28 | General Electric Company | Method for making a compositionally graded gas turbine disk |
| GB0920697D0 (en) * | 2009-11-26 | 2010-01-13 | Rolls Royce Plc | Method of manufacturing a multiple composition component |
| US9475118B2 (en) * | 2012-05-01 | 2016-10-25 | United Technologies Corporation | Metal powder casting |
| GB2523583C (en) * | 2014-02-28 | 2019-12-25 | Castings Tech International Limited | Forming a composite component |
| DE102014006371A1 (en) * | 2014-05-05 | 2015-11-05 | Gkn Sinter Metals Engineering Gmbh | Hydrogen storage manufacturing apparatus and method and hydrogen storage |
| CN115070043A (en) * | 2021-03-10 | 2022-09-20 | 中国航发商用航空发动机有限责任公司 | GH4065A and GH4169 same-material and different-material multistage rotor assembly and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB530639A (en) * | 1938-06-16 | 1940-12-17 | Meutsch Voigtlaender & Co | Process for the production of articles provided with coatings or insets of hard metal |
| GB1149769A (en) * | 1966-01-03 | 1969-04-23 | Eugen Durrwachter | Process and apparatus for the manufacture of multilayer blocks |
| US3862286A (en) * | 1972-10-10 | 1975-01-21 | Aluminum Co Of America | Method of fabricating compacted powdered metal extrusion billets |
-
1981
- 1981-08-07 NO NO812680A patent/NO150668C/en unknown
-
1982
- 1982-08-02 DE DE8282304080T patent/DE3268398D1/en not_active Expired
- 1982-08-02 EP EP82304080A patent/EP0072175B1/en not_active Expired
- 1982-08-05 JP JP57136796A patent/JPS5842703A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0072175B1 (en) | 1986-01-08 |
| EP0072175A1 (en) | 1983-02-16 |
| JPS5842703A (en) | 1983-03-12 |
| NO150668C (en) | 1984-11-28 |
| NO812680L (en) | 1983-02-08 |
| DE3268398D1 (en) | 1986-02-20 |
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