NO151306B - DEVICE FOR TREASURY SIGNS - Google Patents
DEVICE FOR TREASURY SIGNS Download PDFInfo
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- NO151306B NO151306B NO812694A NO812694A NO151306B NO 151306 B NO151306 B NO 151306B NO 812694 A NO812694 A NO 812694A NO 812694 A NO812694 A NO 812694A NO 151306 B NO151306 B NO 151306B
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- acetamide
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- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000000543 intermediate Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 229940027988 antiseptic and disinfectant nitrofuran derivative Drugs 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- IAIWVQXQOWNYOU-FPYGCLRLSA-N nitrofural Chemical class NC(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 IAIWVQXQOWNYOU-FPYGCLRLSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 20
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- SXINBFXPADXIEY-UHFFFAOYSA-N 5-Nitrofurfural Chemical compound [O-][N+](=O)C1=CC=C(C=O)O1 SXINBFXPADXIEY-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- -1 dimethyl sulphoxy- Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- ICJCTFXJEJPHOD-UHFFFAOYSA-N acetic acid;methylhydrazine;hydrochloride Chemical compound Cl.CNN.CC(O)=O ICJCTFXJEJPHOD-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- TUFSAOUTLIMEDI-UHFFFAOYSA-M C(C)(=O)[O-].[Na+].NN Chemical compound C(C)(=O)[O-].[Na+].NN TUFSAOUTLIMEDI-UHFFFAOYSA-M 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 2
- 229940080818 propionamide Drugs 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- DXWCZMGIIFEEPU-OWOJBTEDSA-N (e)-3-(5-nitrofuran-2-yl)prop-2-enal Chemical compound [O-][N+](=O)C1=CC=C(\C=C\C=O)O1 DXWCZMGIIFEEPU-OWOJBTEDSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QOZOTTGEJMSPOM-UHFFFAOYSA-N C(C)(=O)N.NN Chemical compound C(C)(=O)N.NN QOZOTTGEJMSPOM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- YIUZDGLJEZOSGS-UHFFFAOYSA-N bis(3-methyl-5-nitrofuran-2-yl)methanone Chemical compound CC1=C(OC(=C1)[N+](=O)[O-])C(=O)C=1OC(=CC=1C)[N+](=O)[O-] YIUZDGLJEZOSGS-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- LIAWOTKNAVAKCX-UHFFFAOYSA-N hydrazine;dihydrochloride Chemical compound Cl.Cl.NN LIAWOTKNAVAKCX-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G23/00—Forestry
- A01G23/02—Transplanting, uprooting, felling or delimbing trees
- A01G23/099—Auxiliary devices, e.g. felling wedges
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Ecology (AREA)
- Forests & Forestry (AREA)
- Environmental Sciences (AREA)
- Supports For Plants (AREA)
- Protection Of Plants (AREA)
- Sawing (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Joining Of Building Structures In Genera (AREA)
- Dowels (AREA)
Description
Fremgangsmåte for fremstilling av nye mellomprodukter, egnet for fremstilling av nitrofuranderivater. Process for the production of new intermediates, suitable for the production of nitrofuran derivatives.
Oppfinnelsen vedrører fremstilling av forbindelser med formelen The invention relates to the preparation of compounds with the formula
hvor n betegner 0 eller 1, R betegner et hydrogenatom eller en metylgruppe, A betegner en lavere alkylengruppe, og X betegner en amino-, lavere monoalkyl-amino- eller hydroksylgruppe. Fremgangsmåten ifølge oppfinnelsen er karakterisert ved at en forbindelse med formelen hvor n og R hver har den ovenfor angitte betydning, omsettes med en forbindelse av formelen where n represents 0 or 1, R represents a hydrogen atom or a methyl group, A represents a lower alkylene group, and X represents an amino, lower monoalkylamino or hydroxyl group. The method according to the invention is characterized in that a compound of the formula where n and R each have the above meaning is reacted with a compound of the formula
der A og X hver har den ovenfor angitte where A and X each have the above stated
betydning. importance.
Reaksjonskomponentene sammenføres The reaction components are combined
hensiktsmessig i nærvær av et inert opp-løsningsmiddel som reaksjonsmedium. Hensiktsmessig lett tilgjengelige inerte oppløs-løsningsmidler er alkanoler, dimetylsulfok- suitably in the presence of an inert solvent as reaction medium. Suitable readily available inert dissolve-solvents are alkanols, dimethyl sulphoxy-
syd, dimetylformamid, dioksan, estre av alifatiske syrer og nitrometan. Reaksjons-produktene utvinnes ved filtrering og omkrystalliseres eventuelt. Reaksjonen kan utføres ved værelsestemperatur eller ved forhøyet temperatur for at hastigheten skal være større. Det er ønskelig å utføre reaksjonen ved en svakt sur pH-verdi på ca. 5—7. Denne kan innstilles ved tilsetning av en syre, f. eks. eddiksyre til reaksjonsblan-dingen. Eventuelt kan et surere medium til-veiebringes ved tilsetning av en syre, f. eks. saltsyre, for at reaksjonen skal ledes til av-slutning og derved oppnås bedre utbytter av sluttproduktet. syd, dimethylformamide, dioxane, esters of aliphatic acids and nitromethane. The reaction products are recovered by filtration and possibly recrystallized. The reaction can be carried out at room temperature or at an elevated temperature in order for the rate to be greater. It is desirable to carry out the reaction at a slightly acidic pH value of approx. 5-7. This can be adjusted by adding an acid, e.g. acetic acid to the reaction mixture. Optionally, a more acidic medium can be provided by adding an acid, e.g. hydrochloric acid, in order for the reaction to be carried to completion and thereby achieve better yields of the final product.
Disse mellomprodukter kan anvendes på flere forskjellige måter for fremstilling av andre forbindelser i denne serie. Den metode som skal anvendes for fremstilling av en spesiell forbindelse avhenger i høy grad av valg og muligheter. These intermediates can be used in several different ways for the production of other compounds in this series. The method to be used for the production of a particular compound depends to a large extent on choice and possibilities.
Hvis i mellomproduktet av den oven-nevnte formel X betegner en amino- eller lavere monoalkylaminogruppe, kan den omsettes med et acylhalogenid, syreanhyd-rid eller et alkylhalogenformiat, hvorved det fremkommer antimikrobielt virkende forbindelser. If in the intermediate product of the above-mentioned formula X denotes an amino or lower monoalkylamino group, it can be reacted with an acyl halide, acid anhydride or an alkyl halide formate, whereby antimicrobially active compounds are produced.
Hvis i mellomproduktet av den oven-nevnte formel X betegner en hydroksylgruppe, kan denne omsettes med halogener-ingsmidler og amin, hvorved det også opp-står antimikrobielt virkende forbindelser. If in the intermediate product of the above-mentioned formula X denotes a hydroxyl group, this can be reacted with halogenating agents and amine, whereby antimicrobially active compounds also arise.
Eksempel 1. Example 1.
2 - (5-nitro-2 -f urf urylidenhydrazin) - acetamid 2-(5-nitro-2-furylidenehydrazine)-acetamide
1020 g (7,25 mol) metyl-hydrazinacetat-hydroklorid oppløses i 10.200 ml kon-centrert ammoniumhydroksydoppløsning, og oppløsningen hensettes ved værelsetemperatur i en lukket beholder i 35 min. Luft føres gjennom oppløsningen i 3y2 time for å fjerne ammoniakkoverskudd. Oppløsnin-gen surgjøres deretter til en pH verdi på ca. 5 (hydrion-papir) med 7200 ml eddiksyre. Den viskose oppløsning fortynnes med 10.000 ml vann og behandles deretter med en med kull klaret oppløsning av 920 g (6,25 mol) 5-nitro-2-furaldehyd oppløst i 6000 ml metanol, ved oppløsningen tilsettes som en tynn stråle i løpet av 40 min. Det dannede gule faste stoff omrøres i ca. 25 minutter etter at tilsetningen er avslut-tet og hensettes natten over ved værelsetemperatur. Det faste stoff oppsamles på filter. Det vaskes ved omrøring i 30 min. med 20 liter vann. Den vaskes ytterligere med 14 liter 50 pst.-ig metanol. Filterkaken skylles med 2500 ml eter. Den tørkes i en på 60° C innstillet ovn med kraftig trekk. Utbytte av 2-(5-nitro-2-furfurylidenhyd-razin)acetamid er 1152 g (75 pst. av det teoretiske), smeltepunkt 202,5—204,5° C. 1020 g (7.25 mol) of methyl hydrazine acetate hydrochloride are dissolved in 10,200 ml of concentrated ammonium hydroxide solution, and the solution is allowed to stand at room temperature in a closed container for 35 minutes. Air is passed through the solution for 3y2 hours to remove excess ammonia. The solution is then acidified to a pH value of approx. 5 (hydrion paper) with 7200 ml of acetic acid. The viscous solution is diluted with 10,000 ml of water and then treated with a charcoal-clarified solution of 920 g (6.25 mol) of 5-nitro-2-furaldehyde dissolved in 6000 ml of methanol, to the solution is added as a thin jet over 40 my. The yellow solid formed is stirred for approx. 25 minutes after the addition has been completed and left overnight at room temperature. The solid material is collected on a filter. It is washed by stirring for 30 min. with 20 liters of water. It is further washed with 14 liters of 50% methanol. The filter cake is rinsed with 2500 ml of ether. It is dried in an oven set at 60°C with a strong draft. Yield of 2-(5-nitro-2-furfurylidenehydrazine)acetamide is 1152 g (75 percent of the theoretical), melting point 202.5-204.5° C.
Eksempel 2. Example 2.
N-etyl-2-(5-nitrofurfurylidenhydrazin) acetamid. N-ethyl-2-(5-nitrofurfurylidenehydrazine) acetamide.
Metyl-hydrazinacetat-hydroklorid (70 g, 0,5 mol) ble satt til en oppløsning av 300 ml 70-prosentig etylamin og 300 ml vann, og den dannede oppløsning bringes til å reagere ved værelsetemperatur i 5 timer. pH verdien innstilles på 5—6 ved tlisetning av eddiksyre under avkjøling, hvoretter en oppløsning av 70 g (0,5 mol) 5-nitrofurfural i 250 ml alkohol tilsettes. Etter omrøring i noen minutter avkjøles blandingen, det faste stoff filtreres og vaskes med en 50 : 50 blanding av isopropanol og eter. Etter omkrystallisering fra 800 ml isopropanol i nærvær av karbon fås 70 g (58 pst.), N-etyl-2- (5-nitrof urfurylidenhydrazin) - acetamid, med smeltepunkt 145—148° C. Methyl hydrazine acetate hydrochloride (70 g, 0.5 mol) was added to a solution of 300 ml of 70 percent ethylamine and 300 ml of water, and the resulting solution was reacted at room temperature for 5 hours. The pH value is adjusted to 5-6 by adding acetic acid while cooling, after which a solution of 70 g (0.5 mol) 5-nitrofurfural in 250 ml of alcohol is added. After stirring for a few minutes, the mixture is cooled, the solid is filtered and washed with a 50:50 mixture of isopropanol and ether. After recrystallization from 800 ml of isopropanol in the presence of carbon, 70 g (58 per cent) of N-ethyl-2-(5-nitrofurylidenehydrazine)-acetamide are obtained, with a melting point of 145-148°C.
Eksempel 3. Example 3.
(5-nitrofurfurylidenhydrazin) eddiksyre. (5-nitrofurfurylidenehydrazine) acetic acid.
Til en oppløsning av 4,02 1 (4120 g) 85-prosentig hydrazin-hydrat og 826 g natri-umhydroksyd i en 12 1 kolbe, idet oppløs-ningen er blitt oppvarmet til 90° C, tilsettes en oppløsning av 945 g (10 mol) klor-eddiksyre i 1,5 1 vann i løpet av 2 timer, idet temperaturen holdes ved 100—105° C. Oppløsningen kokes deretter under tilba-keløp i 1 time og destilleres i vakuum til 3,5—4 1 destillat er blitt oppsamlet. Resi-duet behandles med 675 g polyglykol 400 og destillasjonen bringes til å fortsette til det ikke lenger oppsamles noe destillat. Blandingen filtreres varm, og det faste stoff skylles flere ganger med metanol og tørres i en damoppvarmet ovn. A solution of 945 g (10 mol) of chloroacetic acid in 1.5 1 water over the course of 2 hours, the temperature being kept at 100-105° C. The solution is then boiled under reflux for 1 hour and distilled in vacuum until 3.5-4 1 distillate is been collected. The residue is treated with 675 g of polyglycol 400 and the distillation is allowed to continue until no more distillate is collected. The mixture is filtered hot, and the solid is rinsed several times with methanol and dried in a steam-heated oven.
Utbyttet med natriumhydrazinacetat er The yield with sodium hydrazine acetate is
1530 g. 1530 g.
En med kull klaret oppløsning av 500 g (4,46 mol) natriumhydrazinacetat i 1,8 1 vann innstilles på pH = 6 med iseddik under avkjøling og behandles med en oppløs-ning av 375 g (2,66 mol) 5-nitrofurfural i 2,8 1 alkohol. Etter flere timers omrøring faller det ut en orangefarvet utfelling. Blandingen avkjøles og det faste stoff filtreres fra og vaskes med isopropanol. Utbytte natrium- (5-nitrofurfurylidenhydrazin) eddiksyre er 304 g (29 pst.), smeltepunkt 165—175° C. A charcoal-clarified solution of 500 g (4.46 mol) sodium hydrazine acetate in 1.8 1 water is adjusted to pH = 6 with glacial acetic acid while cooling and treated with a solution of 375 g (2.66 mol) 5-nitrofurfural in 2.8 1 alcohol. After several hours of stirring, an orange precipitate falls out. The mixture is cooled and the solid is filtered off and washed with isopropanol. Yield of sodium (5-nitrofurfurylidenehydrazine) acetic acid is 304 g (29 per cent), melting point 165-175° C.
En med kull klaret oppløsning av 87 g av natriumsaltet i 1,6 1 vann surgjøres med 10 prosentig saltsyre. Det gule faste stoff filtreres fra og vaskes med vann. Utbytte (5-nitrofurfurylidenhydrazin) eddiksyre er 63,8 g smeltepunkt 132—135° C. A charcoal-clarified solution of 87 g of the sodium salt in 1.6 1 water is acidified with 10 percent hydrochloric acid. The yellow solid is filtered off and washed with water. Yield (5-nitrofurfurylidenehydrazine) acetic acid is 63.8 g melting point 132-135° C.
Eksempel 4. Example 4.
2-[3-(5-nitro-2-furyl)allylidenhydra-zin] acetamid. 2-[3-(5-nitro-2-furyl)allylidenehydrazine]acetamide.
En oppløsning av 281 g (2 mol) metyl-hydrazinacetat-hydroklorid i 2800 ml 68-prosentig ammoniumhydroksyd hensettes ved værelsetemperatur i 35 min, behandles med kull, hvoretter overskudd av ammoniakk fjernes ved gjennombobling av luft. pH innstilles på 6 ved tilsetning av eddiksyre under avkjøling, hvoretter den ene halvdel av oppløsningen settes til en varm alkoholisk oppløsning av 167 g (1 mol) 3-(5-nitro-2-furyl)-akrolein i 4 1 alkohol. Etter avkjøling f raf Utreres det røde faste stoff og vaskes med alkohol, vann og deretter med alkohol, hvorved det fås 100 g (42 pst.), 2-[3-(5-nitro-2-furyl)allyliden-hydrazin] acetamid, med smeltepunkt 190 —194° C. A solution of 281 g (2 mol) methyl hydrazine acetate hydrochloride in 2800 ml of 68-percent ammonium hydroxide is left at room temperature for 35 minutes, treated with charcoal, after which excess ammonia is removed by bubbling air through. The pH is adjusted to 6 by adding acetic acid while cooling, after which one half of the solution is added to a hot alcoholic solution of 167 g (1 mol) 3-(5-nitro-2-furyl)-acrolein in 4 1 alcohol. After cooling from raf, the red solid is filtered off and washed with alcohol, water and then with alcohol, thereby obtaining 100 g (42 per cent), 2-[3-(5-nitro-2-furyl)allylidene-hydrazine] acetamide , with a melting point of 190 -194° C.
Eksempel 5. Example 5.
2-(a-metyl-5-nitrofurfurylidenhydrazin) acetamid. 2-(α-methyl-5-nitrofurfurylidenehydrazine) acetamide.
Til en oppløsning av 155 g (1 mol) metyl-5-nitro-2-furylketon i 2,5 1 varm alkohol tilsettes en oppløsning av 1 mol hydra-zinacetamid (se eksempel 4). Et orangefarget fast stoff faller ut ved avkjøling og filtreres fra samt omkrystalliseres fra 3,2 1 alkohol. Utbytte 2-(a-metyl-5-nitrofurfurylidenhydrazin) acetamid er 114 g (48 pst.), med smeltepunkt 167—170° C. To a solution of 155 g (1 mol) of methyl-5-nitro-2-furyl ketone in 2.5 1 of hot alcohol is added a solution of 1 mol of hydrazine acetamide (see example 4). An orange colored solid precipitates on cooling and is filtered off and recrystallized from 3.2 1 alcohol. The yield of 2-(α-methyl-5-nitrofurfurylidenehydrazine) acetamide is 114 g (48 per cent), with a melting point of 167-170° C.
Eksempel 6. Example 6.
N-metyl-2-(5-nitrofurfurylidenhydrazin) acetamid. N-methyl-2-(5-nitrofurfurylidenehydrazine) acetamide.
En oppløsning av 70 g (0,5 mol) metyl-hydrazinacetathydroklorid i 500 ml 40-prosentig metylamin hensettes ved værelsetemperatur i 4 timer og innstilles deretter på pH 5—6 med eddiksyre under avkjøling. Oppløsningen settes til 70 g (0,5 mol) 5-nitrofurfural i 250 ml alkohol for dannelse av et orangefarget fast stoff. Det faste stoff filtreres fra, vaskes med isopropanol, vann og isopropanol samt tørkes. Utbytte N-metyl-2-(5-nitrofurfurylidenhydrazin-acetamid) er 99 g (88 pst.), smeltepunkt 155—163° C. Ved omkrystallisering av 40 g av det faste stoff fra 750 ml alkohol fås 36 g (80 pst.), smeltepunkt 162—164° C. A solution of 70 g (0.5 mol) methyl hydrazine acetate hydrochloride in 500 ml of 40 percent methylamine is left at room temperature for 4 hours and then adjusted to pH 5-6 with acetic acid while cooling. The solution is added to 70 g (0.5 mol) of 5-nitrofurfural in 250 ml of alcohol to form an orange colored solid. The solid is filtered off, washed with isopropanol, water and isopropanol and dried. Yield N-methyl-2-(5-nitrofurfurylidenehydrazine-acetamide) is 99 g (88 percent), melting point 155-163° C. By recrystallization of 40 g of the solid from 750 ml of alcohol, 36 g (80 percent ), melting point 162-164° C.
Eksempel 7." 2-(5-nitrofurfurylidenhydrazin) pro-pionamid. Example 7." 2-(5-Nitrofurfurylidenehydrazine) propionamide.
Til en oppløsning av 210 g (4,2 mol) 100-prosentig hydrazinhydrat i 300 ml alkohol tilsettes en oppløsning av 150 g (1,38 mol) ct-klorpropionsyre i 300 ml alkohol i en time. Emulsjonen oppvarmes under til-bakeløp i 45 min. omrøres i 15 min. og met-tes med tørr HCl-gass. Blandingen oppvarmes under tilbakeløp i en time og filtreres. Hydrazinindihydrokloridet vaskes med alkohol pg eter. De forenede filtrater avkjø-les i løpet av natten, idet det dannes et hvitt fast stoff som vaskes med eter. Utbytte etyl-a-hydrazinpropionat er 115 g (49,5 pst.), med smeltepunkt 90—100° C. De forenede filtrater avkjøles ytterligere for dannelse av 27 g (11,6 pst.), smeltepunkt - 103—106° C. To a solution of 210 g (4.2 mol) of 100 percent hydrazine hydrate in 300 ml of alcohol, a solution of 150 g (1.38 mol) of ct-chloropropionic acid in 300 ml of alcohol is added for one hour. The emulsion is heated under reflux for 45 min. stir for 15 min. and saturated with dry HCl gas. The mixture is heated under reflux for one hour and filtered. The hydrazine dihydrochloride is washed with alcohol and ether. The combined filtrates are cooled overnight, forming a white solid which is washed with ether. The yield of ethyl-α-hydrazine propionate is 115 g (49.5 percent), with a melting point of 90—100° C. The combined filtrates are further cooled to form 27 g (11.6 percent), melting point - 103—106° C .
En oppløsning av 12 g etyl-a-hydrazinpropionat i 120 ml ammoniakk hensettes ved værelsestempertaur natten over. Etter filtrering fjernes overskuddet av ammoniakk ved gjennombobling av luft og oppløs-ningen innstilles under avkjøling på pH 6—7 med eddiksyre. Til denne oppløsning settes 10,1 g 5-nitrofurfural i 480 ml alkohol. Det orangefargede faste stoff filtreres, A solution of 12 g of ethyl-α-hydrazine propionate in 120 ml of ammonia is left at room temperature overnight. After filtration, the excess ammonia is removed by bubbling air through and the solution is adjusted while cooling to pH 6-7 with acetic acid. 10.1 g of 5-nitrofurfural in 480 ml of alcohol are added to this solution. The orange colored solid is filtered,
vaskes med isopropanol, vann og isopropanol samt tørkes for dannelse av 9,4 g washed with isopropanol, water and isopropanol and dried to form 9.4 g
(59 pst.) 2-(5-nitrofurfurylidenhydrazin) - (59 percent) 2-(5-nitrofurfurylidenehydrazine) -
propionamid, med smeltepunkt 178—180° C. propionamide, with melting point 178-180° C.
Ved omkrystallisering av 5,0 av det faste By recrystallization of 5.0 of the solid
stoff fra 1300 ml acetonitril fås 4,0 g (46,5 substance from 1300 ml of acetonitrile, 4.0 g (46.5
pst.) med smeltepunkt 181,5—184° C. wt.) with a melting point of 181.5-184° C.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE8005636A SE443278B (en) | 1980-08-08 | 1980-08-08 | Apparatus for tree felling wedges |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO812694L NO812694L (en) | 1982-02-09 |
| NO151306B true NO151306B (en) | 1984-12-10 |
| NO151306C NO151306C (en) | 1985-03-20 |
Family
ID=20341528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO812694A NO151306C (en) | 1980-08-08 | 1981-08-07 | DEVICE FOR TREASURY SIGNS |
Country Status (4)
| Country | Link |
|---|---|
| CA (1) | CA1177475A (en) |
| FI (1) | FI68340C (en) |
| NO (1) | NO151306C (en) |
| SE (1) | SE443278B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2846514B1 (en) * | 2002-10-31 | 2005-01-14 | Joseph Clochard | MANEUVER DEVICE FOR TILTING CONTROL OF A TRUNK PORTION DEBITED |
| SE543990C2 (en) * | 2020-08-17 | 2021-10-19 | Husqvarna Ab | Tree felling wedge |
-
1980
- 1980-08-08 SE SE8005636A patent/SE443278B/en not_active IP Right Cessation
-
1981
- 1981-08-07 NO NO812694A patent/NO151306C/en unknown
- 1981-08-07 CA CA000383476A patent/CA1177475A/en not_active Expired
- 1981-08-07 FI FI812447A patent/FI68340C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| SE443278B (en) | 1986-02-24 |
| CA1177475A (en) | 1984-11-06 |
| FI68340C (en) | 1985-09-10 |
| FI812447L (en) | 1982-02-09 |
| SE8005636L (en) | 1982-02-09 |
| NO151306C (en) | 1985-03-20 |
| NO812694L (en) | 1982-02-09 |
| FI68340B (en) | 1985-05-31 |
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