NO134669B - - Google Patents
Download PDFInfo
- Publication number
- NO134669B NO134669B NO3681/72A NO368172A NO134669B NO 134669 B NO134669 B NO 134669B NO 3681/72 A NO3681/72 A NO 3681/72A NO 368172 A NO368172 A NO 368172A NO 134669 B NO134669 B NO 134669B
- Authority
- NO
- Norway
- Prior art keywords
- methionine
- ammonia
- nitrile
- reaction
- mixture
- Prior art date
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 47
- 229930182817 methionine Natural products 0.000 claims description 33
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 229910021529 ammonia Inorganic materials 0.000 claims description 18
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 12
- -1 methionine nitrile Chemical class 0.000 claims description 11
- 150000002825 nitriles Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- CLUWOWRTHNNBBU-UHFFFAOYSA-N 3-methylthiopropanal Chemical compound CSCCC=O CLUWOWRTHNNBBU-UHFFFAOYSA-N 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005219 aminonitrile group Chemical group 0.000 description 1
- ICAIHGOJRDCMHE-UHFFFAOYSA-O ammonium cyanide Chemical compound [NH4+].N#[C-] ICAIHGOJRDCMHE-UHFFFAOYSA-O 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical compound CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16K—VALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
- F16K1/00—Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces
- F16K1/16—Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces with pivoted closure-members
- F16K1/18—Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces with pivoted closure-members with pivoted discs or flaps
- F16K1/22—Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces with pivoted closure-members with pivoted discs or flaps with axis of rotation crossing the valve member, e.g. butterfly valves
- F16K1/226—Shaping or arrangements of the sealing
- F16K1/2263—Shaping or arrangements of the sealing the sealing being arranged on the valve seat
Landscapes
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Control Of Throttle Valves Provided In The Intake System Or In The Exhaust System (AREA)
- Fluid-Driven Valves (AREA)
- Control Of The Air-Fuel Ratio Of Carburetors (AREA)
- Lift Valve (AREA)
Abstract
Spjeld-ventil.Throttle valve.
Description
Fremgangsmåte til fremstilling av methionin. Process for the production of methionine.
Foreliggende oppfinnelse angår en fremgangsmåte til fremstilling av methionin [ (a-amino-y-methylmercaptosmøre-syre)], hvorved man får et meget rent produkt under anvendelse av et enklere ar-beidskretsløp og oppnåelse av høyere utbytter enn i de hittil kjente fremgangsmåter. The present invention relates to a method for the production of methionine [(α-amino-y-methylmercaptobutyric acid)], whereby a very pure product is obtained using a simpler work cycle and achieving higher yields than in the hitherto known methods.
Der er kjent fremgangsmåter til fremstilling av methionin under anvendelse av p-methylmercaptopropionaldehyd som ut-gangsmateriale. I disse fremgangsmåter overføres denne forbindelse til cyanhydrin, There are known methods for producing methionine using p-methylmercaptopropionaldehyde as starting material. In these methods, this compound is transferred to cyanohydrin,
og en hydroxylgruppe i dette erstattes ved innvirkning av ammoniakk med en amino- and a hydroxyl group in this is replaced by the action of ammonia with an amino-
gruppe. Ved hjelp av to trinn fåes methionin-nitril som forsåpes så at der dannes methionin (fremgangsmåter av type 1). group. Using two steps, methionine-nitrile is obtained which is saponified so that methionine is formed (methods of type 1).
Der er også kjent andre fremgangsmåter hvorved methionin-nitril fremstilles i én operasjon og i et enkelt trinn, idet man omsetter (3-methylmercaptopropionaldehyd oppløst i vandig alkohol med natriumcyanid, et ammoniumsalt og overskudd av ammoniakk. Også i disse fremgangsmåter fåes methionin ved forsåpning av det erholdte methionin-nitril (fremgangsmåter av type 2). Other methods are also known by which methionine-nitrile is produced in one operation and in a single step, reacting (3-methylmercaptopropionaldehyde dissolved in aqueous alcohol with sodium cyanide, an ammonium salt and excess ammonia. In these methods, too, methionine is obtained by saponification of the obtained methionine nitrile (methods of type 2).
De reaksjoner som fremgangsmåtene The reactions that the procedures
av den første type er basert på er følgende: of the first type is based on is the following:
Ifølge US patenter nr. 2 485 236 (1949), According to US Patent No. 2,485,236 (1949),
2 542 768 (1951) og 2 564 105 (1951) får man cyanhydrin ved å tilsette hydrogencyanidsyre til p-methylmercaptopropionaldehyd i nærvær av et svakt alkalisk stoff som pyri-din. I det annet trin av disse fremgangsmåter bruker man ammoniakk i et mengdeforhold på 10—30 mol pr. mol cyanhydrin, ved en temperatur fra 80 til 90° C og under 2 542 768 (1951) and 2 564 105 (1951) cyanohydrin is obtained by adding hydrocyanic acid to p-methylmercaptopropionaldehyde in the presence of a weakly alkaline substance such as pyridine. In the second step of these methods, ammonia is used in a quantity ratio of 10-30 mol per mole of cyanohydrin, at a temperature from 80 to 90° C and below
et trykk på 40—50 atmosfærer. Under disse betingelser finner reaksjonen sted i løpet av 15 minutter, mens den ved romtemperatur ville kreve 12—15 timer. a pressure of 40-50 atmospheres. Under these conditions, the reaction takes place within 15 minutes, while at room temperature it would require 12-15 hours.
Ved forsåpning i et surt medium får By saponification in an acidic medium,
man methionin med utbytter på ca. 75 pst. man methionine with yields of approx. 75 percent
I fremgangsmåtene av type 2 fremstil- In the methods of type 2 manufacturing
les aminonitril i et enkelt arbeidstrin i overensstemmelse med følgende reaksjon: read aminonitrile in a single working step according to the following reaction:
D. O. Holland beskriver i J. Chem. Soc. (1952), sider 3403—3409 en fremgangsmåte til fremstilling av methionin-nitril som består i å oppløse natriumcyanid og ammoniumklorid i ekvimolekylære mengdeforhold i vandig alkohol mettet med ammoniakk og derpå gradvis tilsette aldehyd mens temperaturen holdes på 15—20° C. I den vandige alkohol er der tilstede 13 —14 mol NH, pr. mol aldehyd. Blandingen omrøres derpå, og man lar den reagere i mere enn 12 timer. D. O. Holland describes in J. Chem. Soc. (1952), pages 3403-3409 a method for the production of methionine-nitrile which consists in dissolving sodium cyanide and ammonium chloride in equimolecular quantities in aqueous alcohol saturated with ammonia and then gradually adding aldehyde while the temperature is kept at 15-20° C. In the aqueous alcohol is present there 13 -14 mol NH, per moles of aldehyde. The mixture is then stirred and allowed to react for more than 12 hours.
I US patent nr. 2 732 400 (1956) beskrives en fremgangsmåte som består i at man omsetter |3-methylmercaptopropionaldehyd med et alkalimetallcyanid (NaCN) og med et ammoniumsalt som ammoniumklorid i vandig alkohol som er mettet med ammoniakk. Ammoniakken brukes i stort overskudd, nemlig fra 3 til 15 mol pr. mol aldehyd. Reaksjonen finner sted ved romtemperatur i løpet av noen timer. Når reaksjonen er fullført, destilleres reaksjonsblandingen i vakuum ved en temperatur som ikke overstiger 35° C for å fjerne al-koholen. I reaksjonskaret får man da to skikt, et øvre oljeaktig skikt som inneholder methionin-nitril, og et nedre vandig skikt som inneholder salter. Methionin-nitrilet skilles derpå fra den vandige saltoppløs-ning ved ekstraksjon med ether eller kloroform og påfølgende avdestillasjon av oppløsningsmidlet. Det erholdte methionin-nitril underkastes forsåpning med en oppløsning av natrium- eller kalium-hydroxyd i vandig alkohol. Ef ter nøytrali-sasjon med eddiksyre utfelles methionin i et utbytte på 63 pst. beregnet på den anvendte mengde (3-methylmercaptopropionaldehyd. In US patent no. 2 732 400 (1956) a method is described which consists in reacting |3-methylmercaptopropionaldehyde with an alkali metal cyanide (NaCN) and with an ammonium salt such as ammonium chloride in aqueous alcohol which is saturated with ammonia. The ammonia is used in large excess, namely from 3 to 15 mol per moles of aldehyde. The reaction takes place at room temperature within a few hours. When the reaction is complete, the reaction mixture is distilled in vacuum at a temperature not exceeding 35° C to remove the alcohol. Two layers are then obtained in the reaction vessel, an upper oily layer containing methionine-nitrile, and a lower aqueous layer containing salts. The methionine nitrile is then separated from the aqueous salt solution by extraction with ether or chloroform and subsequent distillation of the solvent. The methionine nitrile obtained is subjected to saponification with a solution of sodium or potassium hydroxide in aqueous alcohol. After neutralization with acetic acid, methionine is precipitated in a yield of 63 per cent calculated on the amount used (3-methylmercaptopropionaldehyde.
Ifølge dette US patent er det også mulig å utføre forsåpningen av nitrilet direkte ved å tilsette natriumhydroxyd, vann og methanol til reaksjonsblandingen. Opera-sjonen krever 19 minutter ved koketempe-ratur og påfølges av nøytralisasjon med eddiksyre. Herved utskilles methionin med utbytte på 48 pst. beregnet på den anvendte mengde p-methyl-mercaptopropionsyre-aldehyd. According to this US patent, it is also possible to carry out the saponification of the nitrile directly by adding sodium hydroxide, water and methanol to the reaction mixture. The operation requires 19 minutes at boiling temperature and is followed by neutralization with acetic acid. Hereby, methionine is secreted with a yield of 48 percent calculated on the amount of p-methyl-mercaptopropionic acid aldehyde used.
Det er nu funnet at man kan oppnå betydelige fordeler fremfor de foran be-skrevne fremgangsmåter til fremstilling av methionin og methionin-nitril ved å an-vende vannfri flytende ammoniakk som reaksjonskomponent og reaksjonsmedium under omsetningen mellom methylmercaptopropionaldehyd og hydrogencyanidsyre, eller oppløselige cyanider sammen med ammoniumsalter. Herved muliggjøres dannelse av methionin-nitril med høye utbytter i et enkelt trin på relativt kort tid. It has now been found that significant advantages can be achieved over the previously described methods for producing methionine and methionine nitrile by using anhydrous liquid ammonia as reaction component and reaction medium during the reaction between methylmercaptopropionaldehyde and hydrocyanic acid, or soluble cyanides together with ammonium salts . This enables the formation of methionine-nitrile with high yields in a single step in a relatively short time.
I fremgangsmåten ifølge oppfinnelsen går man frem på følgende måte: (1) man omsetter i en enkelt operasjon i nærvær av overskudd av ammoniakk, methyl-mercap-topropionaldehyd og hydrogencyanidsyre, eller med oppløselige cyanider sammen med ammoniumsalter, hvorved der dannes methionin-nitril som man (2) hydrolyserer i et surt medium med påføl-gende nøytralisasjon av det hydrolyserte produkt med ammoniakk og (3) renser det herved erholdte urene methionin ved omkrystallisasjon fra vann og behandling med avfarvende kull, og det karakteristiske trekk ved oppfinnelsen er at man i trin (1) anvender flytende, vannfri ammoniakk som reaksjonsmedium. In the method according to the invention, one proceeds in the following way: (1) one reacts in a single operation in the presence of an excess of ammonia, methyl mercaptopropionaldehyde and hydrocyanic acid, or with soluble cyanides together with ammonium salts, whereby methionine nitrile is formed which one (2) hydrolyzes in an acidic medium with subsequent neutralization of the hydrolysed product with ammonia and (3) purifies the resulting impure methionine by recrystallization from water and treatment with decolorizing charcoal, and the characteristic feature of the invention is that in step (1) uses liquid, anhydrous ammonia as reaction medium.
Fortrinnsvis utfører man reaksjonen ved temperaturer mellom -=-10°C og 50°C, fordelaktig mellom 10 og 25°C. The reaction is preferably carried out at temperatures between -=-10°C and 50°C, advantageously between 10 and 25°C.
Når reaksjonen er fullført, fordampes overskuddet av ammoniakk. Når fremgangsmåten er utført under anvendelse av ammoniumcyanid (av HCN + NHS), får man nitril og vann som residuum efter inndampningen. Når man imidlertid bruker cyanider av alkalimetaller eller jord-alkalimetaller sammen med ammoniumsalter, består residuet av nitril og anorga-niske salter oppløst i vann. I begge tilfelle får man methionin-nitril med nesten kvantitativt utbytte. When the reaction is complete, the excess ammonia evaporates. When the method is carried out using ammonium cyanide (of HCN + NHS), nitrile and water are obtained as a residue after evaporation. However, when cyanides of alkali metals or alkaline earth metals are used together with ammonium salts, the residue consists of nitrile and inorganic salts dissolved in water. In both cases methionine-nitrile is obtained with almost quantitative yield.
Ved hjelp av denne fremgangsmåte er det mulig å unngå både fremstillingen av cyanhydrin i et adskilt arbeidstrin og de vanskeligheter som er forbundet med ad-skillelse av nitrilet fra overskuddet av ammoniakk oppløst i vandig alkohol. Den flytende ammoniakk som brukes i fremgangsmåten ifølge oppfinnelsen, kan av-destilleres ved romtemperatur. Methionin-nitril overføres til methionin ved hydrolyse i surt medium, påfølgende nøytralisasjon med ammoniakk og rensning av methi-oninråproduktet ved hjelp av konvensjo-nelle metoder. By means of this method, it is possible to avoid both the production of cyanohydrin in a separate work step and the difficulties associated with separating the nitrile from the excess of ammonia dissolved in aqueous alcohol. The liquid ammonia used in the method according to the invention can be distilled off at room temperature. Methionine-nitrile is transferred to methionine by hydrolysis in an acidic medium, subsequent neutralization with ammonia and purification of the methionine raw product using conventional methods.
De fordeler fremfor kjente metoder som oppnåes ved fremgangsmåten ifølge oppfinnelsen er følgende: særlig høye utbytter, nemlig 80—90 pst. beregnet på den anvendte mengde p-methylmercaptopropionaldehyd, et meget rent sluttprodukt (methionininnhold fra 99 til 99,2 pst.), og en stor forenkling av arbeidskretsløpet samt gunstige mengdeforhold mellom de anvendte utgangsmaterialer. De høye utbytter og sluttproduktets høye renhet an-tas å skyldes den kjennsgjerning at man ved å bruke flytende ammoniakk som opp-løsningsmiddel oppnår en rask dannelse av nitril ved lave temperaturer, ved ammo-niakkf ordampningen. The advantages over known methods achieved by the method according to the invention are the following: particularly high yields, namely 80-90 per cent calculated on the amount of p-methylmercaptopropionaldehyde used, a very pure end product (methionine content from 99 to 99.2 per cent), and a great simplification of the work cycle as well as favorable quantity ratios between the starting materials used. The high yields and the high purity of the end product are believed to be due to the fact that by using liquid ammonia as a solvent, a rapid formation of nitrile is achieved at low temperatures, during the ammonia evaporation.
I motsetning hertil når i de kjente fremgangsmåter nitrilet bemerkelsesverdig høyere temperaturer under arbeidskrets-løpet som temperaturer nær opp til romtemperatur, i lengre tidsrom. In contrast, in the known methods, the nitrile reaches remarkably higher temperatures during the working cycle, such as temperatures close to room temperature, for a longer period of time.
Dette forårsaker forandringer i dette mellomprodukt hvorved utbyttet av methionin påvirkes ugunstig. This causes changes in this intermediate product whereby the yield of methionine is adversely affected.
I det følgende beskrives som eksempler noen utførelsesformer for oppfinnelsen. In the following, some embodiments of the invention are described as examples.
Eksempel 1. Example 1.
I en autoklav ble der ført inn 0,85 liter flytende vannfri ammoniakk, 1,1 mol natriumcyanid og 1,2 mol ammoniumklorid. Blandingen ble omrørt og tilsatt 1 mol methylmercaptopropionaldehyd. 0.85 liters of liquid anhydrous ammonia, 1.1 mol of sodium cyanide and 1.2 mol of ammonium chloride were introduced into an autoclave. The mixture was stirred and 1 mol of methylmercaptopropionaldehyde was added.
Autoklaven ble lukket og holdt på romtemperatur i 90 minutter, hvorpå ammoniakken ble blåst ut, fremdeles ved romtemperatur. Man fikk et residuum bestående av methionin-nitril og en mettet saltopp-løsning. Methionin-nitrilet ble skilt fra saltene ved filtrering. The autoclave was closed and kept at room temperature for 90 minutes, after which the ammonia was blown out, still at room temperature. A residue consisting of methionine-nitrile and a saturated salt solution was obtained. The methionine nitrile was separated from the salts by filtration.
Eksempel 2. Example 2.
1,8 mol HCN og 2 liter flytende ammoniakk ble ført inn i en autoklav. Under omrøring av denne blanding ble den tilsatt 1,5 mol p-methylmercaptopropionaldehyd. 1.8 moles of HCN and 2 liters of liquid ammonia were introduced into an autoclave. While stirring this mixture, 1.5 mol of p-methylmercaptopropionaldehyde was added to it.
Autoklaven ble derpå lukket, holdt på romtemperatur i 90 minutter og ammoniakken blåst av, fremdeles ved romtemperatur. Man fikk methionin-nitril med nesten kvantitativt utbytte som et residuum sammen med reaksjonsvannet. The autoclave was then closed, kept at room temperature for 90 minutes and the ammonia blown off, still at room temperature. Methionine nitrile was obtained with almost quantitative yield as a residue together with the reaction water.
Eksempel 3. Example 3.
0,85 liter vannfri flytende ammoniakk, 1,1 mol natriumcyanid og 1,2 mol ammoniumklorid ble ført inn i en autoklav. Blan- 0.85 liters of anhydrous liquid ammonia, 1.1 moles of sodium cyanide and 1.2 moles of ammonium chloride were introduced into an autoclave. Blan-
dingen ble omrørt, hvorpå den ble tilsatt 1 mol p-methylmercaptopropionaldehyd. the mixture was stirred, whereupon 1 mol of p-methylmercaptopropionaldehyde was added.
Autoklaven ble lukket, holdt på romtemperatur i iy2 time, hvorpå ammoniakken ble avblåst. The autoclave was closed, kept at room temperature for iy2 hours, after which the ammonia was blown off.
Man fikk methionin-nitril med nesten kvantitativt utbytte som et residuum sammen med vann og de salter som var dan-net ved reaksjonen. Methionin-nitrilet ble skilt fra reaksjonsblandingen ved filtrering. Det filtrerte produkt ble dråpevis under kraftig omrøring og mens temperaturen ble holdt på 25°C ved kjøling tilsatt til en oppløsning av 196 g konsentrert svovelsyre og 180 g vann. Blandingen ble derpå kokt i i<y>2 time. Methionine-nitrile was obtained with almost quantitative yield as a residue together with water and the salts formed by the reaction. The methionine nitrile was separated from the reaction mixture by filtration. The filtered product was added dropwise under vigorous stirring and while the temperature was kept at 25°C by cooling to a solution of 196 g of concentrated sulfuric acid and 180 g of water. The mixture was then boiled for i<y>2 hours.
Ef ter avkjøling ble blandingen tilsatt 15 pst.'s vandig ammoniakk og nøytrali-sert til en pH-verdi på 6. Herved utfeltes farveløst methionin sammen med ammo-niumsulfat i omtrentlig like mengder. Produktet ble frafiltrert og vasket på filteret med moderlut fra en foregående krystallisasjon av et teknisk rent methionin. Man fikk 130 g teknisk rent methionin. Dette ble oppløst i 1—1,2 liter kokende moderlut fra den foregående krystallisasjon. After cooling, the mixture was added with 15 percent aqueous ammonia and neutralized to a pH value of 6. This precipitated colorless methionine together with ammonium sulfate in approximately equal amounts. The product was filtered off and washed on the filter with mother liquor from a previous crystallization of a technically pure methionine. 130 g of technically pure methionine was obtained. This was dissolved in 1-1.2 liters of boiling mother liquor from the previous crystallization.
Blandingen ble tilsatt aktivert kull og kokt i 15 minutter. Den ble derpå filtrert og hensatt til krystallisasjon ved romtemperatur. Activated charcoal was added to the mixture and boiled for 15 minutes. It was then filtered and allowed to crystallize at room temperature.
Man fikk 128,5 g produkt som inne-holdt 99,2 pst. methionin med et utbytte beregnet på p-methylmercaptopropionaldehyd tilsvarende 85 pst. av det teoretiske. 128.5 g of product was obtained which contained 99.2 per cent methionine with a yield calculated for p-methylmercaptopropionaldehyde corresponding to 85 per cent of the theoretical.
Eksempel 4. Example 4.
1,8 mol hydrogencyanidsyre og 2 liter flytende ammoniakk ble ført inn i en autoklav. Blandingen ble omrørt og tilsatt 1,5 mol p-methylmercaptopropionaldehyd. Autoklaven ble derpå lukket og holdt på romtemperatur i iy2 time hvorpå ammoniakken ble avblåst. 1.8 moles of hydrocyanic acid and 2 liters of liquid ammonia were introduced into an autoclave. The mixture was stirred and 1.5 mol of p-methylmercaptopropionaldehyde was added. The autoclave was then closed and kept at room temperature for iy2 hours, after which the ammonia was blown off.
Man fikk methionin-nitril nesten med kvantitativt utbytte som et residuum sammen med reaksjonsvannet. En blanding av 294 g svovelsyre og 270 g vann ble under kraftig omrøring og mens temperaturen ble holdt på 25°C ved kjøling tildryppet dette methionin-nitril. Den erholdte blanding ble kokt i iy2 time. Methionine-nitrile was obtained in almost quantitative yield as a residue together with the water of reaction. A mixture of 294 g of sulfuric acid and 270 g of water was added dropwise to methionine-nitrile under vigorous stirring and while the temperature was kept at 25°C by cooling. The resulting mixture was boiled for iy2 hours.
Den ble derpå avkjølt og tilsatt 15 pst.'s vandig ammoniakk inntil blandingens pH-verdi var 6. Herved ble der utfelt nesten farveløst methionin sammen med ammo-niumsulfat i omtrentlig like deler. Produktet ble frafiltrert og vasket på filtret med en moderlut fra en forutgående krystallisasjon av teknisk rent methionin. Man fikk 195 g teknisk rent methionin som ble oppløst i 1,5—1,7 liter kokende moderlut fra foregående krystallisasjoner. Blandingen ble tilsatt aktivert kull og kokt i 15 minutter. Den ble derpå filtrert og hensatt til krystallisasjon ved romtemperatur. It was then cooled and 15% aqueous ammonia was added until the mixture's pH value was 6. This precipitated almost colorless methionine together with ammonium sulphate in approximately equal parts. The product was filtered off and washed on the filter with a mother liquor from a previous crystallization of technically pure methionine. 195 g of technically pure methionine was obtained, which was dissolved in 1.5-1.7 liters of boiling mother liquor from previous crystallizations. Activated charcoal was added to the mixture and boiled for 15 minutes. It was then filtered and allowed to crystallize at room temperature.
Man fikk 193 g methionin med renhet 99,2 pst. Dette tilsvarer et utbytte på 85 pst. av det teoretiske beregnet på det anvendte p-methylmercaptopropionaldehyd. 193 g of methionine with a purity of 99.2% was obtained. This corresponds to a yield of 85% of the theoretical amount calculated for the p-methylmercaptopropionaldehyde used.
Litteratur: E. Cohn — A. 240,279 (1887) J. Herb A. 288, 10 (1890) L. Chardonnes, W. Schlapback, Heiv. Chem. Literature: E. Cohn — A. 240,279 (1887) J. Herb A. 288, 10 (1890) L. Chardonnes, W. Schlapback, Heiv. Chem.
A. 29, 1413 (1946) R. Adams, A. Thai, Org. Synth. Coll. Vol. A. 29, 1413 (1946) R. Adams, A. Thai, Org. Synth. Coll. Vol.
I, 427 (1952) I, 427 (1952)
Houben Weyl — Methoden der organischen Chemie, Vol. VIII, side 431—432. Houben Weyl — Methoden der organischen Chemie, Vol. VIII, pages 431-432.
Claims (1)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8122171A JPS4846919A (en) | 1971-10-14 | 1971-10-14 | |
JP1578772A JPS4884921A (en) | 1972-02-14 | 1972-02-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
NO134669B true NO134669B (en) | 1976-08-16 |
NO134669C NO134669C (en) | 1976-11-24 |
Family
ID=26351993
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO368172A NO134669C (en) | 1971-10-14 | 1972-10-13 |
Country Status (6)
Country | Link |
---|---|
DE (1) | DE2251134A1 (en) |
FR (1) | FR2152268A5 (en) |
GB (1) | GB1404167A (en) |
IT (1) | IT962127B (en) |
NL (1) | NL7211253A (en) |
NO (1) | NO134669C (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53133226U (en) * | 1977-03-30 | 1978-10-21 | ||
AT379001B (en) * | 1978-03-10 | 1985-11-11 | Adams Gmbh & Co Kg Geb | FLAP VALVE |
DE3150999C2 (en) * | 1981-12-23 | 1985-06-20 | Klöckner-Humboldt-Deutz AG, 5000 Köln | Wet setting machine for processing coal or other minerals |
-
1972
- 1972-08-16 IT IT5221172A patent/IT962127B/en active
- 1972-08-17 NL NL7211253A patent/NL7211253A/xx not_active Application Discontinuation
- 1972-09-12 FR FR7232322A patent/FR2152268A5/fr not_active Expired
- 1972-10-13 NO NO368172A patent/NO134669C/no unknown
- 1972-10-13 GB GB4748472A patent/GB1404167A/en not_active Expired
- 1972-10-16 DE DE19722251134 patent/DE2251134A1/en active Pending
Also Published As
Publication number | Publication date |
---|---|
DE2251134A1 (en) | 1973-04-19 |
GB1404167A (en) | 1975-08-28 |
IT962127B (en) | 1973-12-20 |
FR2152268A5 (en) | 1973-04-20 |
NL7211253A (en) | 1973-04-17 |
NO134669C (en) | 1976-11-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2557913A (en) | Production of methionine | |
US2405966A (en) | Synthesis of nitriles | |
US2654779A (en) | Method of preparation of guanidino fatty acids | |
NO134669B (en) | ||
US3131210A (en) | Process for methionine nitrile synthesis | |
US2564647A (en) | Hydantoin manufacture | |
US2665313A (en) | Production of 1, 6-naphthalenediol | |
US2335997A (en) | Production of beta-alanine and beta-alanates from acrylonitrile | |
US2603651A (en) | Process for preparing lysine | |
US2688023A (en) | 5-(3-cyanopropyl) hydantoin and its preparation and use to prepare 5-(4-aminobutyl) hydantoin | |
US3864378A (en) | Process for preparing 2-hydroxyethyliminodiacetonitrile | |
US2336067A (en) | Preparation of beta-alanine | |
US3980653A (en) | Process for the production of 3,6-bis-(2-methylmercaptoethyl)-2,5-piperazinedione | |
US2011589A (en) | Process of producing pentaerythrite | |
CN109836344B (en) | Method for producing glycine by organic solvent | |
US2377401A (en) | Preparation of beta-alanine | |
US2553055A (en) | Synthesis of 5-(sec.-butyl) hydantion | |
US4052451A (en) | Preparation of calcium pantothenate | |
US3122583A (en) | Preparation of diaminopimelic acid | |
US2938029A (en) | Alpha-oximino-epsilon caprolactam | |
US1611941A (en) | Method of preparing substituted cyanamides | |
US2481597A (en) | Substituted propionic acids and processes of preparing the same | |
US3980698A (en) | Resolution of amines | |
US2846470A (en) | Process for producing glutamine | |
JP3623809B2 (en) | Process for producing β-alanine-N, N-diacetic acid and its salt |