NO129517B - - Google Patents
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- NO129517B NO129517B NO00645/70A NO64570A NO129517B NO 129517 B NO129517 B NO 129517B NO 00645/70 A NO00645/70 A NO 00645/70A NO 64570 A NO64570 A NO 64570A NO 129517 B NO129517 B NO 129517B
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- Prior art keywords
- semicarbazone
- hydantoin
- ester
- condensation
- aminohydantoin
- Prior art date
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- 238000000034 method Methods 0.000 claims description 11
- KVYKDNGUEZRPGJ-UHFFFAOYSA-N 1-Aminohydantoin Chemical compound NN1CC(=O)NC1=O KVYKDNGUEZRPGJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 229940091173 hydantoin Drugs 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- -1 amino compound Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007859 condensation product Substances 0.000 claims description 5
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 claims description 5
- 150000007659 semicarbazones Chemical class 0.000 claims description 5
- AKGUXECGGCUDCV-UXBLZVDNSA-N [(e)-benzylideneamino]urea Chemical compound NC(=O)N\N=C\C1=CC=CC=C1 AKGUXECGGCUDCV-UXBLZVDNSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000001469 hydantoins Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 229940053195 antiepileptics hydantoin derivative Drugs 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 230000003385 bacteriostatic effect Effects 0.000 claims 1
- 235000019439 ethyl acetate Nutrition 0.000 claims 1
- 239000000543 intermediate Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- 150000001299 aldehydes Chemical class 0.000 description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HQDAJGNZGNZGCO-UHFFFAOYSA-N (propan-2-ylideneamino)urea Chemical compound CC(C)=NNC(N)=O HQDAJGNZGNZGCO-UHFFFAOYSA-N 0.000 description 3
- PEVLAELZNUZRPV-UHFFFAOYSA-N 1-(benzylideneamino)imidazolidine-2,4-dione Chemical compound O=C1NC(=O)CN1N=CC1=CC=CC=C1 PEVLAELZNUZRPV-UHFFFAOYSA-N 0.000 description 3
- LHRHWUPORFCSKI-UHFFFAOYSA-N 1-aminoimidazolidine-2,4-dione;sulfuric acid Chemical compound OS(O)(=O)=O.NN1CC(=O)NC1=O LHRHWUPORFCSKI-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 2
- 150000002168 ethanoic acid esters Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003385 sodium Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WHNSJMMQNFSFBX-UHFFFAOYSA-N 2-[amino(carbamoyl)amino]acetic acid Chemical compound NC(=O)N(N)CC(O)=O WHNSJMMQNFSFBX-UHFFFAOYSA-N 0.000 description 1
- SXINBFXPADXIEY-UHFFFAOYSA-N 5-Nitrofurfural Chemical compound [O-][N+](=O)C1=CC=C(C=O)O1 SXINBFXPADXIEY-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- GKKCIDNWFBPDBW-UHFFFAOYSA-M potassium cyanate Chemical compound [K]OC#N GKKCIDNWFBPDBW-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B22/00—Buoys
- B63B22/18—Buoys having means to control attitude or position, e.g. reaction surfaces or tether
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- Ocean & Marine Engineering (AREA)
- Bridges Or Land Bridges (AREA)
- Other Liquid Machine Or Engine Such As Wave Power Use (AREA)
- Plural Heterocyclic Compounds (AREA)
- Testing Or Calibration Of Command Recording Devices (AREA)
Description
Fremgangsmåte for fremstilling av hydantoinderivater. Process for the production of hydantoin derivatives.
Nærværende oppfinnelse vedrører en fremgangsmåte for fremstilling av hydantoinderivater og har til gjenstand å fremskaffe 1 -amino-hydantoinderivateir som finner anvendelse for fremstillingen av det verdifulle antibakterielle stoff 1-(5'-nitro-2'-furfuiylidenamino)-hydantoin. The present invention relates to a method for the production of hydantoin derivatives and aims to provide 1-amino-hydantoin derivatives which find use for the production of the valuable antibacterial substance 1-(5'-nitro-2'-furfurylideneamino)-hydantoin.
Det er kjent å fremstille l-(5'-nitro-2'-furfurylidenamino)-hydantoin ved å kondensere 5-nitro-2-fura'ldehyd eller dets diacetat med 1-aminohydantoinsulfat eller hydrokloridet eller annet oppløselig salt av 1-aminohydantoin i vandig alkoholisk opp-løsning, vanligvis i nærvær av mineralsyre. 1-aminohydanitoinsaltene ble fremstilt enten etter Traube og Hoffa's metode (Ber. 31, 167) eller fra 2-semikarbazid-eddiksyre (britisk patent nr. 757 822). Ved disse syn-teser fremstilles hydrazln-eddiksyre eller dens ester fra monokloreddiksyre eller dens ester ved reaksjon med hydrazin. Hydrazin-forbindelsen omdannes til den tilsvarende E-semikarbazid-eddiksyre eller ester ved It is known to prepare 1-(5'-nitro-2'-furfurylideneamino)-hydantoin by condensing 5-nitro-2-fura'aldehyde or its diacetate with 1-aminohydantoin sulfate or the hydrochloride or other soluble salt of 1-aminohydantoin in aqueous alcoholic solution, usually in the presence of mineral acid. The 1-aminohydanitoin salts were prepared either by the method of Traube and Hoffa (Ber. 31, 167) or from 2-semicarbazide-acetic acid (British Patent No. 757,822). In these syntheses, hydrazlnacetic acid or its ester is produced from monochloroacetic acid or its ester by reaction with hydrazine. The hydrazine compound is converted to the corresponding E-semicarbazide-acetic acid or ester by
«cyanering» med natrium- eller kaliumcya-nat i svakt sur eller alkalisk oppløsning. Semikarbazid-eddiksyren eller esteren omdannes til et 1-amino-hydantoinsaJlt ved "cyanation" with sodium or potassium cyanate in weakly acidic or alkaline solution. The semicarbazide-acetic acid or ester is converted into a 1-amino-hydantoinsaJlt by
behandling med mineralsyre. Utbyttet opp-nådd ved denne kjente fremgangsmåte er ca. 4|0 % av det teoretiske, når basert på monokloreddiksyre eller dens ester og min-dre enn 40 % når basert på hydrazin et som utgangsmateriale. treatment with mineral acid. The yield achieved by this known method is approx. 4|0% of the theoretical, when based on monochloroacetic acid or its ester and less than 40% when based on hydrazine as starting material.
Ifølge nærværende oppfinnelse er der fremskaffet en fremgangsmåte for fremstilling av derivater av hydantoin med den generelle formel According to the present invention, a method for the production of derivatives of hydantoin with the general formula has been provided
hvor R tilsvarer enten to hydrogenatomer eller en toverdig organisk rest med forme- i hvilken Rx og R.2 kan være et alifatisk, aromatisk eller heterocyklisk radikal, og en av de to kan være hydrogen, og karakteristisk er at man kondenserer et semikarbazon med den generelle formel: where R corresponds to either two hydrogen atoms or a divalent organic residue of the form in which Rx and R.2 can be an aliphatic, aromatic or heterocyclic radical, and one of the two can be hydrogen, and a characteristic is that a semicarbazone is condensed with the general formula:
hvor Rx og R2where Rx and R2
har ovennevnte betydning, med en mono-halogeneddiksyre-ester i et praktisk talt vannfritt oppløsningsmiddel som innehol-der et alkalisk kondensasjonsmiddel, og enten isolerer kondensasjonsproduktet av 1-aminohydantoin fra dette, eller eventuelt ved hydrolyse overfører til den frie aminoforbindelse henholdsvis dennes salter. Det alkaliske kondensasjonsmiddel er for- has the above-mentioned meaning, with a mono-haloacetic acid ester in a practically anhydrous solvent containing an alkaline condensation agent, and either isolates the condensation product of 1-aminohydantoin from this, or possibly by hydrolysis transfers to the free amino compound or its salts. The alkaline condensing agent is for-
trinnsvis et alkalimetall-alkoksyd som natriummetoksyd eller natriumetoksyd og reaksjonen utføres fortrinnsvis i i det vesentlige vannfri etanol eller metanol. step by step an alkali metal alkoxide such as sodium methoxide or sodium ethoxide and the reaction is preferably carried out in essentially anhydrous ethanol or methanol.
Fremgangsmåten etter oppfinnelsen resulterer i fremstillingen av aldehyd- eller ketonkondensasjonsprodukter av 1-aminohydantoin, hvilke stoffer ved hydrolyse på i og for seg kjent måte kan overføres til 1-aminohydantoinet som sådant og dets sure salter, hvilke forbindelser har evne til å kondensere med andre aldehyder eller ketoner og gir et gjennomsnittlig høyt utbytte. The process according to the invention results in the production of aldehyde or ketone condensation products of 1-aminohydantoin, which substances can be transferred by hydrolysis in a manner known per se to the 1-aminohydantoin as such and its acidic salts, which compounds have the ability to condense with other aldehydes or ketones and gives an average high yield.
Oppfinnelsen inkluderer derfor hydro-lysen av kondensasjonsproduktet av semi-karbazonet med halogen-substituert eddiksyreester ved innvirkning av en mineralsyre for å gi et salt av 1-aminohydantoih. Som foran nevnt kan 1-aminohydantoin eller dets salt omsettes imed 5-initro-2-fur-furaldehyd eller diacetatet av dette hvor-ved erholdes 1-(5'-nitro-2'-f urfury liden-amino)-hydantoin. Kondensasjonsproduktet kan også omsettes direkte med et annet aldehyd eller keton som erstatter det opprinnelige aldehyd eller keton. The invention therefore includes the hydrolysis of the condensation product of the semi-carbazone with halogen-substituted acetic acid ester by the action of a mineral acid to give a salt of 1-aminohydantoih. As mentioned above, 1-aminohydantoin or its salt can be reacted with 5-initro-2-furfuraldehyde or its diacetate, whereby 1-(5'-nitro-2'-furfurylidene-amino)-hydantoin is obtained. The condensation product can also be reacted directly with another aldehyde or ketone that replaces the original aldehyde or ketone.
Aceton-semikarbazon eller benzaldehyd-semikarbazon er egnede semikarbazo-ner og etyl-monokloracetat er en egnet substituert eddiksyreester. Forskjellige derivater av 1-aminohydantoin kan på egnet måte isoleres fra reaksjonsblandingen av-hengig av utgangsmaterialene. Ved å gå ut fra benzaldehydsemikarbazon, er sluttproduktet for reaksjonen natriumderivatet av l-(benzylidenamino)-hydantoin, og fritt 1-(benzyliden-amino) -hydantoin oppnåes ved å surgjøre reaksjonsblandingen. Med aceton-semikarbazon som utgangsprodukt er sluttproduktet natriuimderivatet av 1-(isopropylidenamino) -hydantoin. 1- (iso-propylldenamino)-hydantoin isoleres ikke lett ved surgjøring, men 1-aminohydantoinsulfat kan isoleres fra reaksjonsblandingen imed svovelsyre, og andre salter kan isoleres på liknende måte. Ved tilsetning av et egnet aldehyd eller keton til den sur-gjorte reaksjonsblanding erholdes det tilsvarende derivat av det anvendte aldehyd eller keton. Således fås ved tilsetning av 5-nitro-2-furaldehyd eller dets diacetat 1-(5'-nitro-2'-furfurylidenamino)-hydantoin. Acetone semicarbazone or benzaldehyde semicarbazone are suitable semicarbazones and ethyl monochloroacetate is a suitable substituted acetic acid ester. Various derivatives of 1-aminohydantoin can be suitably isolated from the reaction mixture depending on the starting materials. Starting from benzaldehyde semicarbazone, the end product of the reaction is the sodium derivative of 1-(benzylideneamino)-hydantoin, and free 1-(benzylidene-amino)-hydantoin is obtained by acidifying the reaction mixture. With acetone-semicarbazone as starting product, the end product is the sodium derivative of 1-(isopropylideneamino)-hydantoin. 1-(iso-propylldenamino)-hydantoin is not easily isolated by acidification, but 1-aminohydantoin sulfate can be isolated from the reaction mixture with sulfuric acid, and other salts can be isolated in a similar way. By adding a suitable aldehyde or ketone to the acidified reaction mixture, the corresponding derivative of the aldehyde or ketone used is obtained. Thus 1-(5'-nitro-2'-furfurylideneamino)-hydantoin is obtained by adding 5-nitro-2-furaldehyde or its diacetate.
De følgende eksempler gis for å illu-strere på hvilken måte oppfinnelsen kan utføres i praksis. The following examples are given to illustrate the way in which the invention can be carried out in practice.
Eksempel 1 : Example 1 :
16,3 g benzaldehyd-semikarbazon ble oppløst i en oppløsning av 2,3 g natrium 1 50 ml absolutt etanol under oppvarmning. 16.3 g of benzaldehyde-semicarbazone were dissolved in a solution of 2.3 g sodium 1 50 ml absolute ethanol under heating.
Til denne blanding ble tilsatt 6,125 g etyl-monokloracetat dråpevis under omrøring og med tilstrekkelig hastighet til å opprett-holde tilbakeløp uten ytre oppvarmning. Blandingen ble tilbakeløpsbehandlet i 10 minutter. 1,15 g natrium oppløst i 25 ml absolutt etanol ble derpå tilsatt, fulgt av 3,1 g kloreddiksyreester som tidligere. Blandingen ble igjen tilbakeløpsbehandlet i 10 minutter. Ytterligere 1,15 g natrium opp-løst i 25 ml absolutt etanol og 3,1 g kior-eddiksyreester tole tilsatt i den nevnte rek-kefølge i alternerende små ekvivalente mengder og med kort tilbakeløp etter hver estertilsetning. Blandingen ble til slutt til-bakeløpsbehandlet i 30 minutter. Mestepar-ten av alkoholen ble fjernet ved destillasjon og ble samlet opp under tørre betingelser slik at den kan brukes igjen. Til residuet ble tilsatt fortynnet saltsyre inntil blandingen ble sur overfor Kongorødt. Det hvite, faste stoff ble filtrert, vasket godt med vann og derpå tørket ved 100°—110° C. Utbytte 18,5 g, s.p. 228°—240° C. Dette ma-teriale ble krystallisert fra vandig etanol og gir 13,8 g l-(benzylidenamino)-hydantoin, s.p. 253—254° C. To this mixture was added 6.125 g of ethyl monochloroacetate dropwise with stirring and at a sufficient rate to maintain reflux without external heating. The mixture was refluxed for 10 minutes. 1.15 g of sodium dissolved in 25 ml of absolute ethanol was then added, followed by 3.1 g of chloroacetic acid ester as before. The mixture was again refluxed for 10 minutes. A further 1.15 g of sodium dissolved in 25 ml of absolute ethanol and 3.1 g of chloroacetic acid ester were added in the aforementioned order in alternating small equivalent amounts and with short reflux after each ester addition. The mixture was finally refluxed for 30 minutes. Most of the alcohol was removed by distillation and was collected under dry conditions so that it can be used again. Dilute hydrochloric acid was added to the residue until the mixture became acidic to Congo red. The white solid was filtered, washed well with water and then dried at 100°-110° C. Yield 18.5 g, m.p. 228°-240° C. This material was crystallized from aqueous ethanol to give 13.8 g of 1-(benzylideneamino)-hydantoin, m.p. 253—254° C.
Eksempel 2: Example 2:
Forsøket beskrevet i eksempel 1 ble gjentatt til trinnet for fjerning av etano-len. Til residuet ble tilsatt 200 ml av en 2 vektprosent vandig oppløsning av na-triumhydroksyd og blandingen ble omrørt og derpå filtrert. Filtratet ble surgjort til Kongorød-reaksjon med saltsyre og det bunnf elte 1- (benzylidenamino) -hydantoin filtrert fra, vasket med vann og tørket. Utbytte 15 g. s.p. 245°—250° C. The experiment described in Example 1 was repeated to the step of removing the ethanol. To the residue was added 200 ml of a 2% by weight aqueous solution of sodium hydroxide and the mixture was stirred and then filtered. The filtrate was acidified to Congo red reaction with hydrochloric acid and the precipitated 1-(benzylideneamino)-hydantoin was filtered off, washed with water and dried. Yield 15 g. s.p. 245°—250° C.
Eksempel 3: Example 3:
10,8 g natriummetoksyd ble oppløst i 90 ml absolutt tørr industriell metylert mineralolje under oppvarmning og i denne oppløsning ble oppløst 23 g aceton-semikarbazon. Blandingen ble tilsatt langsomt under omrøring til 12,25 g etylmonokloracetat, blandet med 30 ml absolutt tørr industriell metylert mineralolje, og temperaturen tole holdt ved ca. 55°—60° C. Blandingen ble omrørt ved 55°—60° C i 30 minutter. Ytterligere 10,8 g natriummetoksyd oppløst i 100 ml absolutt tørr industriell metylert mineralolje ble tilsatt, fulgt av 12,35 g etyl-monokloracetat, og reaksjonstemperaturen ble holdt ved ca, 55°—60° C. Omrøringen ble fortsatt under disse tilsetninger. Blandingen ble derpå omrørt ved ca. 60° C i 30 minutter. Reaksjonsblandingen ble avkjølt 10.8 g of sodium methoxide were dissolved in 90 ml of absolutely dry industrial methylated mineral oil while heating and in this solution 23 g of acetone-semicarbazone were dissolved. The mixture was added slowly with stirring to 12.25 g of ethyl monochloroacetate, mixed with 30 ml of absolute dry industrial methylated mineral oil, and the temperature tole maintained at approx. 55°-60° C. The mixture was stirred at 55°-60° C. for 30 minutes. A further 10.8 g of sodium methoxide dissolved in 100 ml of absolute dry industrial methylated mineral oil was added, followed by 12.35 g of ethyl monochloroacetate, and the reaction temperature was maintained at about 55°-60° C. Stirring was continued during these additions. The mixture was then stirred at approx. 60° C for 30 minutes. The reaction mixture was cooled
og en blanding av 100 ml vann og 22 g kon-sentrert svovelsyre ble tilsatt under vold-som omrøring. Reaksjonsblandingen ble and a mixture of 100 ml of water and 22 g of concentrated sulfuric acid was added with vigorous stirring. The reaction mixture was
oppvarmet til ca. 78° C i 5 minutter for å heated to approx. 78° C for 5 minutes to
oppnå en i det vesentlige klar oppløsning achieve a substantially clear resolution
og ble derpå kjølt og omrørt ved ca. 15° C and was then cooled and stirred at approx. 15° C
i 1 time. Det hvite krystallinske faste stoff for 1 hour. The white crystalline solid
ble filtrert fra og vasket med vandig alko-hol og derpå tørket. Utbytte 48,7 g innehol-dende ca. 44 % 1-aminohydantoinsulfat og was filtered off and washed with aqueous alcohol and then dried. Yield 48.7 g containing approx. 44% 1-aminohydantoin sulfate and
resten er hovedsakelig natriumsulf at. the rest is mainly sodium sulfate.
Claims (5)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1936558A DE1936558C3 (en) | 1969-07-18 | 1969-07-18 | Anchored buoy with a stabilizing part to reduce vertical and rolling movements |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO129517B true NO129517B (en) | 1974-04-22 |
Family
ID=5740183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO00645/70A NO129517B (en) | 1969-07-18 | 1970-02-23 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3727248A (en) |
| DE (1) | DE1936558C3 (en) |
| FR (1) | FR2037546A5 (en) |
| GB (1) | GB1310256A (en) |
| NL (1) | NL146443B (en) |
| NO (1) | NO129517B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2218239B1 (en) * | 1973-02-16 | 1975-10-31 | Inst Francais Du Petrole | |
| JPS57190822A (en) * | 1981-05-19 | 1982-11-24 | Ishikawajima Harima Heavy Ind Co Ltd | Floating structure |
| US20080223278A1 (en) * | 2007-03-12 | 2008-09-18 | Universidad Catolica De La Santisima Concepcion | Autonomous, multipurpose floating platform for environmental and oceanographic monitoring |
| DE102008044633A1 (en) * | 2008-08-27 | 2010-03-04 | Clement, Jürgen | Damping system for a buoyant structure |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3082608A (en) * | 1960-05-30 | 1963-03-26 | Intercontinental Marine Dev Lt | Marine platform |
| US3159130A (en) * | 1962-02-26 | 1964-12-01 | Shell Oil Co | Floating storage tank |
| US3191202A (en) * | 1963-07-31 | 1965-06-29 | Eugene H Handler | Minimum motion moored buoy system |
| US3369516A (en) * | 1966-03-17 | 1968-02-20 | Roger J. Pierce | Stable oceanic station |
-
1969
- 1969-07-18 DE DE1936558A patent/DE1936558C3/en not_active Expired
-
1970
- 1970-02-18 NL NL707002241A patent/NL146443B/en unknown
- 1970-02-23 NO NO00645/70A patent/NO129517B/no unknown
- 1970-03-03 FR FR7007564A patent/FR2037546A5/fr not_active Expired
- 1970-07-07 US US00052844A patent/US3727248A/en not_active Expired - Lifetime
- 1970-07-09 GB GB3332070A patent/GB1310256A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| NL7002241A (en) | 1971-01-20 |
| US3727248A (en) | 1973-04-17 |
| DE1936558C3 (en) | 1974-05-30 |
| NL146443B (en) | 1975-07-15 |
| GB1310256A (en) | 1973-03-14 |
| DE1936558A1 (en) | 1971-02-11 |
| DE1936558B2 (en) | 1973-10-25 |
| FR2037546A5 (en) | 1970-12-31 |
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