NO142647B - PROCEDURE FOR THE PREPARATION OF LUBRICABLE WATER-IN-OIL EMULSES WITH LOW FAT CONTENT - Google Patents
PROCEDURE FOR THE PREPARATION OF LUBRICABLE WATER-IN-OIL EMULSES WITH LOW FAT CONTENT Download PDFInfo
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- NO142647B NO142647B NO763783A NO763783A NO142647B NO 142647 B NO142647 B NO 142647B NO 763783 A NO763783 A NO 763783A NO 763783 A NO763783 A NO 763783A NO 142647 B NO142647 B NO 142647B
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- acetonyl
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- 238000000034 method Methods 0.000 title claims description 6
- 235000004213 low-fat Nutrition 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 27
- -1 2-(4-pyridyl)ethyl group Chemical group 0.000 claims description 22
- SXINBFXPADXIEY-UHFFFAOYSA-N 5-Nitrofurfural Chemical compound [O-][N+](=O)C1=CC=C(C=O)O1 SXINBFXPADXIEY-UHFFFAOYSA-N 0.000 claims description 8
- 125000001539 acetonyl group Chemical group [H]C([H])([H])C(=O)C([H])([H])* 0.000 claims description 8
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical group O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 238000003776 cleavage reaction Methods 0.000 claims description 4
- 230000007017 scission Effects 0.000 claims description 4
- 230000000845 anti-microbial effect Effects 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229940091173 hydantoin Drugs 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001469 hydantoins Chemical class 0.000 description 4
- 241000287828 Gallus gallus Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000013330 chicken meat Nutrition 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 208000015181 infectious disease Diseases 0.000 description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- PEVLAELZNUZRPV-IZZDOVSWSA-N 1-[(e)-benzylideneamino]imidazolidine-2,4-dione Chemical compound O=C1NC(=O)CN1\N=C\C1=CC=CC=C1 PEVLAELZNUZRPV-IZZDOVSWSA-N 0.000 description 2
- VIRWKAJWTKAIMA-UHFFFAOYSA-N 2-chloroethyl acetate Chemical compound CC(=O)OCCCl VIRWKAJWTKAIMA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 208000003495 Coccidiosis Diseases 0.000 description 2
- 241000223932 Eimeria tenella Species 0.000 description 2
- 206010023076 Isosporiasis Diseases 0.000 description 2
- 241000699670 Mus sp. Species 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229940095076 benzaldehyde Drugs 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- NXFQHRVNIOXGAQ-YCRREMRBSA-N nitrofurantoin Chemical compound O1C([N+](=O)[O-])=CC=C1\C=N\N1C(=O)NC(=O)C1 NXFQHRVNIOXGAQ-YCRREMRBSA-N 0.000 description 2
- 229960000564 nitrofurantoin Drugs 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009885 systemic effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- TWLHXPNXGVFASI-UHFFFAOYSA-N 3-(2-hydroxyethyl)-1-[(5-nitrofuran-2-yl)methylideneamino]imidazolidine-2,4-dione Chemical compound OCCN1C(N(CC1=O)N=CC1=CC=C(O1)[N+](=O)[O-])=O TWLHXPNXGVFASI-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- LPYIXHHGKPBPCF-UHFFFAOYSA-N acetic acid;5-nitrofuran-2-carbaldehyde Chemical compound CC(O)=O.CC(O)=O.[O-][N+](=O)C1=CC=C(C=O)O1 LPYIXHHGKPBPCF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- BULLHNJGPPOUOX-UHFFFAOYSA-N chloroacetone Chemical compound CC(=O)CCl BULLHNJGPPOUOX-UHFFFAOYSA-N 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- AFDJQFFKYDCYIG-JSGFVSQVSA-M sodium;3-[(e)-(5-nitrofuran-2-yl)methylideneamino]-5-oxo-4h-imidazol-2-olate Chemical compound [Na+].[O-]C1=NC(=O)CN1\N=C\C1=CC=C([N+]([O-])=O)O1 AFDJQFFKYDCYIG-JSGFVSQVSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
- A23D7/015—Reducing calorie content; Reducing fat content, e.g. "halvarines"
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
- A23D7/01—Other fatty acid esters, e.g. phosphatides
- A23D7/013—Spread compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Edible Oils And Fats (AREA)
- Colloid Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Fats And Perfumes (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Fremgangsmåte for fremstilling av nye, i hydantoinkjernens 3-stilling substituerte l-(5-nitro-furfurylidenamino)-hydantoiner med antimikrobiell virkning. Process for the production of new 1-(5-nitro-furfurylideneamino)-hydantoins substituted in the 3-position of the hydantoin nucleus with antimicrobial action.
Foreliggende oppfinnelse går ut på The present invention is based on
fremstillingen av nye i hydantoinkjernens the production of new ones in the hydantoin nucleus
3-stilling substituerte l-(5-nitro-furfuryl-idenamino)-hydantoiner med antimikrobiell virkning og av formel I: 3-position substituted l-(5-nitro-furfuryl-idenamino)-hydantoins with antimicrobial action and of formula I:
i hvilken R betegner en acetonyl-, hydroxyethyl- eller 2-(4-pyridyl)-ethylgruppe. in which R denotes an acetonyl, hydroxyethyl or 2-(4-pyridyl)ethyl group.
Disse hydantoiner utgjør i høy grad These hydantoins make up to a high degree
effektive, relativt ugiftige systemiske anti-mikrobielle midler. De innvirker på systemiske infeksjoner hos dyr, infeksjoner som effective, relatively non-toxic systemic anti-microbial agents. They affect systemic infections in animals, infections such as
forårsakes av mikroorganismer som f. eks. are caused by microorganisms such as
Staphylococcus aureus og Eimeria tenella. Staphylococcus aureus and Eimeria tenella.
Mus, som er blitt dødelig infisert med Mice, which have been fatally infected with
Staphylococcus aureus, kan beskyttes ved Staphylococcus aureus, can be protected by
peroral administrasjon av en eneste dose oral administration of a single dose
av 105—210 mg/kg av disse forbindelser, of 105-210 mg/kg of these compounds,
hvilken dose inngis efter infeksjonen som which dose is given after the infection which
en suspensjon i carboxymethyl-cellulose. a suspension in carboxymethyl cellulose.
Kyllinger som er infisert med Eimeria tenella, og har fått en sykdom som kalles Chickens that are infected with Eimeria tenella, and have contracted a disease called
kockidios, kan beskyttes mot sykdommen, coccidiosis, can protect against the disease,
og hindres fra å dø ved administrasjon av and prevented from dying by administration of
forbindelsene i kyllingforet med et innhold the compounds in the chicken feed with a content
av 0,022 vektprosent. of 0.022 weight percent.
Den dose av disse forbindelser som kre-ves for å tilveiebringe en terapeutisk virkning, er betydelig mindre enn den som fremkaller en ikke-ønsket giftvirkning. Doser som mus tåler av disse forbindelser ligger mellom 770 og 2200 mg/kg. Hos kyllinger viser det seg ingen tegn på toksisk bivirkning ved det innhold, som anvendes for å bekjempe kockidios. The dose of these compounds required to provide a therapeutic effect is considerably less than that which induces an unwanted toxic effect. Doses that mice can tolerate of these compounds are between 770 and 2200 mg/kg. In chickens, there are no signs of toxic side effects from the content, which is used to combat coccidiosis.
Det er blitt funnet at de nye forbindelser av formel I kan fremstilles fra utgangs-materialer som er lett tilgjengelige. Frem-gangsmåten ifølge foreliggende oppfinnelse består i at hvis R betyr en acetonyl- eller hydroxyethylgruppe, omsettes en forbindelse av formelen II: It has been found that the new compounds of formula I can be prepared from readily available starting materials. The method according to the present invention consists in that if R means an acetonyl or hydroxyethyl group, a compound of the formula II is reacted:
hvor A betegner resten av et aldehyd, f. eks. benzaldehyd, i form av et salt, med en forbindelse av formelen RjX, hvor R, betyr en acetonylgruppe eller en acetyloxyethylgruppe og X betyr et halogenatom, eller hvis R betyr en 2-(4-pyridyl)-ethylgruppe omsettes en forbindelse av formelen II med 4-vinylpyridin, at den erholdte forbindelse underkastes hydrolyse før avspalting av aldehydet, og hvis R, betyr en acetyloxyethylgruppe, avspalting av acetylgruppen, til dannelse av en forbindelse av formelen III hvor R har samme betydning som ovenfor, og at den erholdte forbindelse av formelen III samtidig eller i et senere trinn omsettes med 5-nitro-2-furaldehyd eller et reaktivt derivat derav, eller at hvis R betegner en acetonyl- eller hydroxyethylgruppe, omsettes en forbindelse av formelen IV where A denotes the residue of an aldehyde, e.g. benzaldehyde, in the form of a salt, with a compound of the formula RjX, where R means an acetonyl group or an acetyloxyethyl group and X means a halogen atom, or if R means a 2-(4-pyridyl)-ethyl group, a compound of the formula II is reacted with 4-vinylpyridine, that the compound obtained is subjected to hydrolysis before cleavage of the aldehyde, and if R, means an acetyloxyethyl group, cleavage of the acetyl group, to form a compound of the formula III where R has the same meaning as above, and that the compound obtained of the formula III is simultaneously or in a later step reacted with 5-nitro-2-furaldehyde or a reactive derivative thereof, or that if R denotes an acetonyl or hydroxyethyl group, a compound of the formula IV is reacted
i saltform med en forbindelse av formelen R,X, hvor Rt og X hver har samme betydning som ovenfor, og, hvis R, betyr en acetyloxyethylgruppe, hydrolyseres den erholdte forbindelse for avspaltning av acetylgruppen, eller hvis R betyr en 2-(4-pyridyl)-ethylgruppe, omsettes forbindelsen av formelen IV med 4-vinyl-pyridin. in salt form with a compound of the formula R,X, where Rt and X each have the same meaning as above, and, if R represents an acetyloxyethyl group, the resulting compound is hydrolyzed to remove the acetyl group, or if R represents a 2-(4- pyridyl)-ethyl group, the compound of formula IV is reacted with 4-vinyl-pyridine.
Den fremgangsmåte som kommer til anvendelse ifølge oppfinnelsen beror på hvilken funksjonell enhet det er som inn-går i midlet for å innføre R-substituenten i 3-stillingen. Hvis forbindelsen av formelen R,X utgjøres av klorethylacetat, som omsettes med natriumsaltet av l-(benzyl-idenamino)-hydantoin, hvilken reaksjon hensiktsmessig skjer i et inert reaksjons-medium inneholdende et organisk oppløs-ningsmiddel, f. eks. pyridin eller dimethyl-formamid, kan reaksjonen illustreres på følgende måte: The method used according to the invention depends on which functional unit is included in the agent for introducing the R-substituent in the 3-position. If the compound of the formula R,X consists of chloroethyl acetate, which reacts with the sodium salt of l-(benzylideneamino)-hydantoin, which reaction conveniently takes place in an inert reaction medium containing an organic solvent, e.g. pyridine or dimethylformamide, the reaction can be illustrated as follows:
Hvis forbindelsen av formel II omsettes med 4-vinylpyridin, er det ikke nødvendig å anvende saltformen av l-(alkyliden-amino)hydantoinet, idet reaksjonen går raskt og med godt utbytte i nærvær av et oppløsningsmiddel under innvirkningen av varme. Reaksjonen kan illustreres på føl-gende måte: If the compound of formula II is reacted with 4-vinylpyridine, it is not necessary to use the salt form of the l-(alkylideneamino)hydantoin, the reaction proceeding rapidly and with good yield in the presence of a solvent under the influence of heat. The reaction can be illustrated as follows:
For å overføre de i ovenstående formler (I og II) viste i 3-stillingen substituerte 1-(alkylidenamino)hydantoiner til den øns-kede 5-nitro-2-furfurylidenforbindelse, er det funnet å være fordelaktig å behandle dem i surt vandig medium, f. eks. vandig mineralsyre, under innvirkning av varme, og å tilsette 5-nitro-furaldehydet eller reaktivt derivat derav f. eks. 5-nitrofuralde-hyddiacetat, som lett hydrolyseres under reaksjonsbetingelsene, til reaksjonsblandingen. Hvis alkylidenkomponenten er flyk-tig, kan den flyktige forbindelse fjernes fra reaksjonsblandingen ved dampdestillasjon i nærvær av syre og hydrolysen oppnåes samtidig. In order to transfer the 1-(alkylideneamino)hydantoins substituted in the 3-position shown in the above formulas (I and II) to the desired 5-nitro-2-furfurylidene compound, it has been found to be advantageous to treat them in an acidic aqueous medium , e.g. aqueous mineral acid, under the influence of heat, and adding the 5-nitro-furaldehyde or reactive derivative thereof, e.g. 5-nitrofuralde-hyddioacetate, which is readily hydrolyzed under the reaction conditions, to the reaction mixture. If the alkylidene component is volatile, the volatile compound can be removed from the reaction mixture by steam distillation in the presence of acid and the hydrolysis achieved simultaneously.
De i 3-stillingen substituerte l-(5-nitrof ur f urylidenamino) hydantoiner som fremstilles ifølge oppfinnelsen, er lette å overføre i en form som er hensiktsmessig for dosering efter de anvendte metoder. Tabletter, suspensjoner, elixirer og lignende kan fremstilles under anvendelse av fyll-stoffer og tilsetningsmidler som bærere for den aktive komponent. The 1-(5-nitrofurfurylideneamino)hydantoins substituted in the 3-position which are produced according to the invention are easy to transfer in a form which is suitable for dosing according to the methods used. Tablets, suspensions, elixirs and the like can be prepared using fillers and additives as carriers for the active component.
Eksempel 1. 3- 12-( 4- pyridyl) ethyl]- l-( 5-nitrofurf urylidenamino) hydantoin. Example 1. 3-12-(4-pyridyl)ethyl]-1-(5-nitrofurfurylideneamino)hydantoin.
En blanding av 157 g (0.77 mol) 1-benzylidenaminohydantoin, 500 ml pyridin og 90 g (0.86 mol) 4-vinylpyridin kokes under tilbakeløp i 30 timer og helles derefter i 3,5 liter vann. Den dannede faste substans frafiltreres, vaskes med vann og tørkes ved 110° C. Man får 203 g (85 pst.) av mellom-produktet. Dette produkt dampdestilleres med en blanding av 300 ml vann og 80 ml svovelsyre, i det øyemed å fjerne benzalde-hydet. Oppløsningen filtreres gjennom leirjord for klaring og behandles derefter med alkoholisk oppløsning av 100 g (0,7 mol) 5-nitro-2-furaldehyd. En mindre mengde nitrofurantoin, som dannes, fjernes ved filtrering, og filtratet ekstraheres med ether for å fjerne eventuelt overskudd av 5-nitro-2-furaldehyd. Det oppnådde raffi-nat gjøres basisk med ammoniakk for utfelling av det rå l-(5-nitrofurfuryliden-amino) -3- [2- (4-pyridyl) -ethyl]hydantoin. Efter filtrering, vasking med vann, alkohol og ether, og lufttørking, veier denne substans 158 g (70 pst.). Den renses ved å opp-løse igjen i fortynnet saltsyre, behandling med kull og utfelling påny. Man får et utbytte av 87,5 pst. Ved omkrystallisering fra en blanding av nitromethan og methanol 1 : 1 (10 ml/l g) under anvendelse av aktivt kull fåes rent 3-[2-(4-pyridyl)ethyl]-l-(5-nitrofurfurylidenamino)'hydantoin, som smelter ved 210—212° C. A mixture of 157 g (0.77 mol) 1-benzylideneaminohydantoin, 500 ml pyridine and 90 g (0.86 mol) 4-vinylpyridine is refluxed for 30 hours and then poured into 3.5 liters of water. The solid substance formed is filtered off, washed with water and dried at 110° C. 203 g (85 per cent) of the intermediate product are obtained. This product is steam distilled with a mixture of 300 ml of water and 80 ml of sulfuric acid, in order to remove the benzalde hyde. The solution is filtered through clay for clarification and then treated with an alcoholic solution of 100 g (0.7 mol) of 5-nitro-2-furaldehyde. A small amount of nitrofurantoin, which is formed, is removed by filtration, and the filtrate is extracted with ether to remove any excess of 5-nitro-2-furaldehyde. The obtained raffinate is made basic with ammonia to precipitate the crude 1-(5-nitrofurfurylidene-amino)-3-[2-(4-pyridyl)-ethyl]hydantoin. After filtration, washing with water, alcohol and ether, and air drying, this substance weighs 158 g (70 per cent). It is purified by dissolving again in dilute hydrochloric acid, treatment with charcoal and precipitation again. A yield of 87.5% is obtained. By recrystallization from a mixture of nitromethane and methanol 1:1 (10 ml/l g) using activated carbon, pure 3-[2-(4-pyridyl)ethyl]-l- (5-nitrofurfurylideneamino)'hydantoin, which melts at 210-212° C.
I stedet for 5-nitro-2-furaldehyd er det mulig å anvende 5-nitro-2-furaldehyddi-acetat, hvorunder det foretas oppvarmning for hydrolysering av dette. Instead of 5-nitro-2-furaldehyde, it is possible to use 5-nitro-2-furaldehyde diacetate, during which heating is carried out to hydrolyze this.
Eksempel 2. Example 2.
3-( 2- hydroxyethyl )- l-( 5-nitrofurf urylidenamino ) hydantoin. 3-(2-hydroxyethyl)-1-(5-nitrofurfurylideneamino)hydantoin.
Til en oppløsning av 10,2 g (0,05 mol) 1-benzylidenaminohydantoin i 250 ml di-methylformamid tilsettes 2,2 g 55-prosents natriumhydrid i mineralolje. Når natrium-hydridet er oppløst, tilsettes 6,2 g (0.0506 mol) klorethylacetat (JACS 46 : 766/1924/). Blandingen opphetes ved 110—120° C nat-ten over og kjøles derefter. Efter frafiltrer-ing av saltet, fjernes dimethylformamidet under forminsket trykk. Resten omdestille-res i nærvær av fortynnet svovelsyre, til fastsubstansen er oppløst. Den vandige oppløsning behandles med aktivt kull, filtreres og bringes til å reagere med 7 g 5-nitro-2-furaldehyd i alkohol. Efter kjøling filtreres den gule utfelling, vaskes med vann, alkohol og ether og tørkes ved 110° C. Man får 11,5 g (81,5 pst.) av 3-(2-hydroxyethyl) -1- (5-nitrofurf urylidenamino) - hydantoin, som spaltes ved ca. 233° C. Ved omkrystallisering fra nitromethan under anvendelse av aktivt kull, øker spaltnings-punktet til 236—380° C. To a solution of 10.2 g (0.05 mol) 1-benzylideneaminohydantoin in 250 ml of dimethylformamide, 2.2 g of 55 percent sodium hydride in mineral oil is added. When the sodium hydride has dissolved, 6.2 g (0.0506 mol) of chloroethyl acetate (JACS 46: 766/1924/) are added. The mixture is heated at 110-120° C overnight and then cooled. After filtering off the salt, the dimethylformamide is removed under reduced pressure. The residue is redistilled in the presence of dilute sulfuric acid, until the solid is dissolved. The aqueous solution is treated with activated carbon, filtered and reacted with 7 g of 5-nitro-2-furaldehyde in alcohol. After cooling, the yellow precipitate is filtered, washed with water, alcohol and ether and dried at 110° C. 11.5 g (81.5 percent) of 3-(2-hydroxyethyl)-1-(5-nitrofurfur urylideneamino ) - hydantoin, which breaks down at approx. 233° C. On recrystallization from nitromethane using activated carbon, the decomposition point increases to 236-380° C.
I stedet for 5-nitro-2-furaldehyd kan man anvende diacetatet av dette. Instead of 5-nitro-2-furaldehyde, the diacetate of this can be used.
Eksempel 3. Example 3.
3- acetonyl- l-( 5-nitrofurf urylidenamino) hydantoin. 3-acetonyl-1-(5-nitrofurfurylideneamino)hydantoin.
En blanding av 40 g (0.15 mol) av natrium-nitrofurantoin, som kan fremstilles ved at man behandler en suspensjon av nitrofurantoin i vannfri alkohol med natrium-methoxyd, 500 ml dimethylform-amid og 15 ml kloraceton oppvarmes på dampbad i 2y4 time, hvorefter dimethylformamidet avdestilleres under forminsket trykk. Resten tritureres med vann, filtreres, vaskes med vann, alkohol og ether og tør-kes. Man får 35,5 g (81 pst. råprodukt) 3-acetonyl-l- (5-nitrofurf urylidenamino) - hydantoin. Ved omkrystallisering fra 175 ml nitromethan under anvendelse av aktivt kull, får man 29,4 g (83 pst. utbytte) rent produkt med smeltepunkt 230—233° C. A mixture of 40 g (0.15 mol) of sodium nitrofurantoin, which can be prepared by treating a suspension of nitrofurantoin in anhydrous alcohol with sodium methoxide, 500 ml of dimethylformamide and 15 ml of chloroacetone is heated on a steam bath for 2y4 hours, after which the dimethylformamide is distilled off under reduced pressure. The residue is triturated with water, filtered, washed with water, alcohol and ether and dried. 35.5 g (81% crude product) of 3-acetonyl-1-(5-nitrofurfurylideneamino)-hydantoin are obtained. By recrystallization from 175 ml of nitromethane using activated carbon, 29.4 g (83% yield) of pure product with a melting point of 230-233° C is obtained.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB46217/75A GB1564801A (en) | 1975-11-07 | 1975-11-07 | Phase inverting low fat spreads |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO763783L NO763783L (en) | 1977-05-10 |
| NO142647B true NO142647B (en) | 1980-06-16 |
| NO142647C NO142647C (en) | 1980-09-24 |
Family
ID=10440342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO763783A NO142647C (en) | 1975-11-07 | 1976-11-08 | PROCEDURE FOR THE PREPARATION OF LUBRICABLE WATER-IN-OIL EMULSES WITH LOW FAT CONTENT |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS6033533B2 (en) |
| AT (1) | AT351914B (en) |
| AU (1) | AU503491B2 (en) |
| BE (1) | BE848068A (en) |
| CH (1) | CH629973A5 (en) |
| DE (1) | DE2650957C2 (en) |
| FR (1) | FR2330326A1 (en) |
| GB (1) | GB1564801A (en) |
| IE (1) | IE43810B1 (en) |
| IT (1) | IT1106503B (en) |
| LU (1) | LU76140A1 (en) |
| NL (1) | NL7612399A (en) |
| NO (1) | NO142647C (en) |
| SE (1) | SE424500B (en) |
| ZA (1) | ZA766636B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3370124D1 (en) * | 1982-07-08 | 1987-04-16 | Unilever Nv | Process for the production of a reduced fat spread |
| ZA834973B (en) * | 1982-07-08 | 1985-02-27 | Unilever Plc | A process for producing a reduced fat spread |
| GB2158452B (en) * | 1984-05-11 | 1988-01-27 | Unilever Plc | Fat-continuous emulsions and spreads |
| GB2160215B (en) * | 1984-06-11 | 1988-08-03 | Unilever Plc | Fat spreads containing emulsion disruptors |
| US4632841A (en) * | 1984-06-11 | 1986-12-30 | Lever Brothers Company | Low fat spreads containing emulsion disruptors |
| GB8620897D0 (en) * | 1986-08-29 | 1986-10-08 | Unilever Plc | Emulsions with reduced fat content |
| IE65808B1 (en) * | 1988-10-19 | 1995-11-15 | Waterford Coop Dairy | A Low Fat Spread |
| GB8826994D0 (en) * | 1988-11-18 | 1988-12-21 | Unilever Plc | Low fat spread |
| JP3662445B2 (en) * | 1999-06-30 | 2005-06-22 | 花王株式会社 | Water-in-oil emulsified fat composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3360377A (en) * | 1964-04-10 | 1967-12-26 | Spitzer Joseph George | Method for production of low-calorie margarine substitute products |
| GB1129923A (en) * | 1965-04-01 | 1968-10-09 | Unilever Ltd | Spread |
| US3457086A (en) * | 1967-03-27 | 1969-07-22 | Corn Products Co | Low-fat table spread compositions |
| BE786588A (en) * | 1971-07-20 | 1973-01-22 | Unilever Nv | FOOD COMPOSITIONS |
| LU66093A1 (en) * | 1972-09-15 | 1974-03-25 | ||
| GB1450269A (en) * | 1974-02-26 | 1976-09-22 | Unilever Ltd | Low fat spread |
-
1975
- 1975-11-07 GB GB46217/75A patent/GB1564801A/en not_active Expired
-
1976
- 1976-11-05 BE BE172146A patent/BE848068A/en not_active IP Right Cessation
- 1976-11-05 LU LU76140A patent/LU76140A1/xx unknown
- 1976-11-05 FR FR7633459A patent/FR2330326A1/en active Granted
- 1976-11-05 SE SE7612405A patent/SE424500B/en unknown
- 1976-11-05 ZA ZA00766636A patent/ZA766636B/en unknown
- 1976-11-08 NO NO763783A patent/NO142647C/en unknown
- 1976-11-08 IT IT69668/76A patent/IT1106503B/en active
- 1976-11-08 AU AU19418/76A patent/AU503491B2/en not_active Expired
- 1976-11-08 NL NL7612399A patent/NL7612399A/en active Search and Examination
- 1976-11-08 JP JP51134025A patent/JPS6033533B2/en not_active Expired
- 1976-11-08 IE IE2473/76A patent/IE43810B1/en unknown
- 1976-11-08 AT AT828776A patent/AT351914B/en not_active IP Right Cessation
- 1976-11-08 DE DE2650957A patent/DE2650957C2/en not_active Expired
- 1976-11-08 CH CH1404976A patent/CH629973A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| AT351914B (en) | 1979-08-27 |
| NO763783L (en) | 1977-05-10 |
| SE7612405L (en) | 1977-05-08 |
| ZA766636B (en) | 1978-06-28 |
| JPS5284181A (en) | 1977-07-13 |
| GB1564801A (en) | 1980-04-16 |
| IT1106503B (en) | 1985-11-11 |
| DE2650957C2 (en) | 1985-09-05 |
| ATA828776A (en) | 1979-01-15 |
| AU503491B2 (en) | 1979-09-06 |
| IE43810L (en) | 1977-05-07 |
| NL7612399A (en) | 1977-05-10 |
| SE424500B (en) | 1982-07-26 |
| AU1941876A (en) | 1978-05-18 |
| JPS6033533B2 (en) | 1985-08-03 |
| LU76140A1 (en) | 1977-06-02 |
| NO142647C (en) | 1980-09-24 |
| IE43810B1 (en) | 1981-06-03 |
| FR2330326B1 (en) | 1982-05-28 |
| BE848068A (en) | 1977-05-05 |
| FR2330326A1 (en) | 1977-06-03 |
| CH629973A5 (en) | 1982-05-28 |
| DE2650957A1 (en) | 1977-05-12 |
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