DK156607B - Fremgangsmaade til fremkaldelse af hankoenssterilitet i en cerealiekornplante - Google Patents
Fremgangsmaade til fremkaldelse af hankoenssterilitet i en cerealiekornplante Download PDFInfo
- Publication number
- DK156607B DK156607B DK106078AA DK106078A DK156607B DK 156607 B DK156607 B DK 156607B DK 106078A A DK106078A A DK 106078AA DK 106078 A DK106078 A DK 106078A DK 156607 B DK156607 B DK 156607B
- Authority
- DK
- Denmark
- Prior art keywords
- oxo
- carboxylic acid
- compounds
- dihydro
- cereal
- Prior art date
Links
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- 230000036512 infertility Effects 0.000 title description 7
- 150000001875 compounds Chemical class 0.000 claims description 49
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 206010021929 Infertility male Diseases 0.000 claims description 9
- 208000007466 Male Infertility Diseases 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 7
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01H—NEW PLANTS OR NON-TRANSGENIC PROCESSES FOR OBTAINING THEM; PLANT REPRODUCTION BY TISSUE CULTURE TECHNIQUES
- A01H1/00—Processes for modifying genotypes ; Plants characterised by associated natural traits
- A01H1/02—Methods or apparatus for hybridisation; Artificial pollination ; Fertility
- A01H1/026—Methods or apparatus for hybridisation; Artificial pollination ; Fertility by treatment with chemicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/22—O-Aryl or S-Aryl esters thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
- C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D237/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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Description
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Den foreliggende opfindelse angâr en frerogangsmâde til frem-kaldelse af selektiv hankonsteri1itet i en cerealiekornplante.
Kerner af cerealier, sâsom majs, hvede, rug, byg, hirse, durra 5 og teff (Epagrostis abyssinica) er blandt de storste fodevare-afgroder over hele verden. Denne betydningsfuldhed har fort til udstrakt efterforskning med henblik pâ forbedring af pro-duktiviteten og næringsværdien af disse afgroder. En af de mest betydningsfulde tilnærmelser i retning af forbedring af 10 kvaliteten og udbyttet af cerealiekernerne har været hybridi-seri ngen.
Mens hybridisering har været en effektiv teknik for nogen afgroder, i særdeleshed majs, har der været talrige problemer 15 med de nuværende teknikker. F.eks. kræver hybridisering af majs en tidsforbrugende fjernelse af hanblomster med hândkraft eller en ineffektiv mekanisk fjernelse af hanblomster, som mu-ligvis skader majsplanten. Hybridisering af majs, byg og hvede ved hjælp af cytoplasmisk hankonssterile varieteter kan kun 20 foretages med en begrænset genetisk basis, som kræver en bêva-ringslinie og en genopbygningslinie. Desuden nedvendiggor cytoplasmisk hankonssterile teknikker med byg og hvede en yderst forfinet fremgangsmâde for at klare disse afgreders genetiske kompleksiteter, og hidtil har man ikke opnâet storre succès 25 ved udvikling af en passende fremgangsmâde. Da fremkaldelse af selektiv hankenssteri1itet ved hjælp af kemiske midler ville bevirker, at mange af de problemer, man stâr overfor ved de nuværende hybridiseringsteknikker, ville undgâs, ville nye forbindelser, som frembringer den onskede sterilitet, være 30 yderst onskelige ved pâlideligt og pà okonmisk mâde at tilve-jebringe de hankonssterile planter, som er nodvendige til hybridisering. 1 overensstemmelse med den foreliggende opfindelse tilveje-35 bringes der en fremgangsmâde til fremkaldelse af hankonssteri-litet i cerealiekornplanter, hvilken fremgangsmâde er ejendom-melig ved, at den omfatter, at planten forud for meiose be-handles med en mængde, som er virksom til at fremkalde han-
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2 kenssteri1itet i planten, af mindst én forbindelse med formlen (I):
O
R4 1 rI
5 Y| R2 10 hvori Rl betegner en carboxygruppe, eller et agronomisk accep-tabelt sait deraf, eller alkoxycarbonyl med op til 12 carbonatomer i alkoxydelen, R2 betegner phenyl, der eventuelt er substitueret med op 15 til tre substituenter med ialt 0 til 6 carbonatomer, idet substituenten eller substituenterne er udvalgt blandt (1) alkyl, (2) C4H4 til dannelse af en naph-thylgruppe, (3) alkoxy, (4) halogen, (5) nitro, (6) trif1uormethyl, (7) alkanoyloxy og (8) alkylthio, 20 R3 betegner (Cj-^J-alkyl, og r4 betegner hydrogen, (Cj_4)-alkyl eller halogen.
I en foretrukket udforelsesform betegner R1 en carboxygruppe eller et alkalimetalsalt deraf, R3 en methylgruppe, R4 et hy-25 drogenatom og R2 en 4-chlorsubstitueret phenylgruppe.
Nâr Rl betegner et sait af en carboxygruppe, kan et alkalime-tal, jordalkalimetal eller overgangsmetal levere kationen. Kationen kan ogsâ være en ammonium- eller substitueret ammoni-30 umgruppe. Repræsentative metalsaltkationer indbefatter alkali-metalkationer, som er foretrukne, sâsom natrium, kalium og lithium; jordalkalimetalkationer, sâsom calcium, magnésium, barium og strontium, eller tungmetalkationer, sâsom zink, man-gan, cupri, cupro, ferri, ferro, titan og aluminium. Til ammo-35 niumsaltene herer salte, hvori ammoniumkationen har formlen NZlz2Z3Z4, hvori Z1, Z2, Z3 og Z4 (som kan være ens eller for-skellige) betegner hydrogen, hydroxy, (Ci_4)-alkoxy, (0^-20)-alkyl, (C3_8)-alkenyl, (C3_8)-alkynyl, (C2-8)-hydroxyalkyl,
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3 alkoxyalkyl med fra 2 til 8 carbonatomer, (C2-6)-a«ninoalky1, (C2-6)_ha1ogenalkyl, substitueret eller usubstitueret phenyl, substitueret eller usubstitueret phenylalkyl med op til 4 carbonatomer i alkyldelen, amino eller alkyl-substitueret amino.
5 Alternativt kan to vilkârlige af Z1, Z2, Z3 og Z4 være forbun-det til sammen med nitrogenatomet at danne en 5- eller 6-led-det heterocykl isk ring, soin eventuelt indeholder indtil ét yderligere heterooxygen-, nitrogen- eller svovlatom i ringen, og som fortrinsvis er mættet som i en piperidin-, morpholin-, 10 pyrrolidin eller piperazinring. Et andet alternativ er, at tre vilkârlige af zl, Z2, Z3 og Z* kan være forbundet til sammen med nitrogenatomet at danne en 5- eller 6-leddet aromatisk he-terocyklisk ring, sàsom en pyrrol- eller pyridinring. Nâr am-moniumgruppen indeholder en substitueret alkyl-, substitueret 15 phenyl- eller substitueret phenylalkylgruppe, vil substituen-terne sædvanligvis være udvalgt blandt halogen, (Ci_8)-a1kyl# (Ci_4)-alkoxy, hydroxy, nitro, trifluormethyl, cyano, amino og (Cx_4)alkylthio. Sâdanne substituerede phenylgrupper har fortrinsvis op til to sâdanne substituenter. Repræsentative ammo-20 niumkationer indbefatter ammonium, dimethylammonium, 2-ethyl-hexylammonium, bis(2-hydroxyethylJammonium, tris(2-hydroxy-ethylJammonium, dicyklohexylammonium, jt-octylammonium, 2-hy-droxyethylammonium, morpholinium, piperidinium, 2-phenethylam-monium, 2-methylbenzylammonium, n-hexylammonium, triethylammo-25 nium, trimethy 1 ammonium, tri (n.-butyl Jammonium, methoxyethylam-monium, diisopropylammonium, pyridinium, diallylammonium, pry-azolium, propargylammonium, dimethylhydrazinium, hydroxyammo-nium, methoxyammonium, dodècylammonium, octadecylammonium, 4-dichlorpheny1 ammonium, 4-nitrobenzylammonium, benzyltrimethyl-30 ammonium, 2-hydroxyethyldimethyloctadecylammonium, 2-hydroxy-ethyldiethyloctylammonium, decyltrimethylammonium, hexyltri-ethylammonium og 4-methylbenzyltrimethylammonium.
Repræsentative udformninger af R2 indbefatter en phenylgruppe 35 substitueret med (1) alkyl, fortrinsvis med op til 4 carbonatomer, (2) C4H4 til dannelse af en naphthylgruppe, (3) alkoxy, fortrinsvis med op til 4 carbonatomer, (4) halogen, sàsom fluor, chlor, brom og iod, (5) nitro, (6) trifluormethyl, (7)
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4 alkanoyloxy, fortrinsvis med op til 4 carbonatoraer og (8) al-kyTthio, fortrinsvis med op til 4 carbonatomer. Phenylgruppen kan ogsâ være substitueret sâledes, at der dannes en kondense-ret ring. De mest foretrukne substituenter pâ phenylgruppen er 5 1 eller 2 halogenatomer, en (Ci_4)-alkyl-, fortrinsvis methyl- gruppe, en (Ci_4)-alkoxy-, fortrinsvis methoxygruppe eller en tri f1uormethylgruppe.
Typiske forbindelser inden for opfindelsens rammer indbefat-10 ter: 1-phenyl-1,4-dihydro-4-oxo-6-methylpyridazi n-3-carboxylsyre, 1-(4-chlorphenyl)-1,4-di hydro-4-oxo-6-methylpyridazin-3-carbo-xylsyre, 15 1-(4-f1uorphenyl)-1,4-dihydro-4-oxo-6-methylpyridazin-3-carbo- xylsyre, 1-(4-bromphenyl}-1,4-di hydro-4-oxo-6-methylpyridazin-3-carbo-xylsyre, 1-(4-iodphenyl)-1,4-di hydro-4-oxo-6-methylpyridazin-3-carbo-20 xylsyre, l-(3-fluorphenyl)-l,4-di hydro-4-oxo-6-methylpyridazin-3-carbo-xylsyre, 1-(3-chlorpheny1)-1,4-di hydro-4-oxo-6-methylpyridazin-3-carbo-xylsyre, 25 1-(3-bromphenyl)-l,4-dihydro-4-oxo-5-methylpyridazin-3-carbo- xylsyre, l-(3,4-dichlorphenyl)-l,4-dihydro-4-oxo-6-methylpyridazin-3-carboxylsyre, l-(2-fluorphenyl)-l,4-di hydro-4-oxo-6-methylpyri dazin-3-carbo-30 xylsyre, 1-(2-chlorphenyl)-1,4-dihydro-4-oxo-6-methy1pyridazin-3-carbo-xylsyre, l-(4-trifluormethylphenyl)-l,4-di hydro-4-oxo-6-methy1-pyri sa-zi n-3-carboxylsyre, 35 1-(3-trifluormethylphenyl)-l,4-dihydro-4-oxo-6-methylpyrisa- zi n-3-carboxylsyre, 1-pheny1-1,4-di hydro-4-oxo-6-ethylpyridazi n-3-carboxylsyre, 1-(4-chlorphenyl)-1,4-di hydro-4-oxo-6-ethylpyri dazi n-3-carbo- 5 xylsyre, l-(4-fluorpheny1)-1,4-di hydro-4-oxo-6-ethylpyri dazin-3-carbo-xylsyre, 1-(3,4-dichlorphenyl)-1,4-di hydro-4-oxo-6-ethylpyridazi n-3-5 carboxylsyre, 1-phenyl-l,4-di hydro-4-oxo-6-propylpyridazi n-3-carboxylsyre, 1-pheny1-1,4-di hydro-4-oxo-5,6-dimethylpyri daz i n-3-carboxylsyre, l-{4-chlorphenyl)-l,4-dihydro-4-oxo-5,6-dimethylpyridazin-3-10 carboxylsyre, 1-phenyl-l,4-dihydro-4-oxo-5-ethyl-6-methylpyridazin-3-carbo-xylsyre, 1-phenyl-l,4-dihydro-4-oxo-5,6-diethy1pyridazin-3-carboxy1syre, 15 l-(4-methylphenyl)-l,4-dihydro-4-oxo-6-methylpyridazin-3-car-boxylsyre, l-(2-chlor-4-methylphenyl)-1,4-dihydro-4-oxo-6-methylpyrisa-z i n-3-carboxylsyre, l-(2,4,6-trichlorphenyl)-l,4-dihydro-4-oxo-6-methyl-pyridazin-20 3-carboxylsyre, 1-(3-ethoxyphenyl)-1,4-di hydro-4-oxo-6-ethylpyridazi n-3-car-boxylsyre, 1-(4-methylthiophenyl)-l,4-dihydro-4-oxo-6-methylpyridazin-3-carboxylsyre, 2 5 1-phenyl-5-brom-l,4-dihydro-4-oxo-6-methylpyridazi n-3-carbo-xylsyre, 1-(3-chlorphenyl)-5-chlor-l,4-dihydro-4-oxo-6-methylpyridazin- 3- carboxylsyre, l-(4-chlorphenyl)-5-brom-l,4-dihydro-4-oxo-6-ethy1pyridazi n-30 3-carboxylsyre, samt saltene og esterne af ovenstâende syrer.
Forbindelserne kan fremstilles ved for analoge forbindelser i og for sig kendte fremgangsmâder eller andre fremgangsmâder 35 udtænkt til formâlet. Ved en bekvem fremgangsmâde omsættes en 4- hydroxy-2-pyron med formlen:
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6 <x | (II) r3/\°A0 5 hvori R6 betegner et hydr'ôgenatom eller en alkylgruppe, og R3 har den ovenfor defïnerede betydning, eller et sait af en py-ron med formlen (II) (fremstillet ved behandling af pyronen med et ækvivalent af en passende vandig base, sâsom kalium-10 eller natriumhydroxid, -acetat eller -carbonat), sædvanligvis ved en temperatur fra -10 til 50°C, i et polært oplesningsmid-del, sâsom vand, methanol, éthanol, glyme eller dimethylform-amid, med et diazoniumsalt, sâsom diazoniumchlorid, fremstillet ved konventionel diazoteringsteknik ud fra en amin med 15 formlen R2 - NH2 (III) hvori R2 har den ovenfor definerede betydning. Den opnâede hy-20 drazon, som har formlen: | (IV) 25 hvori R2, R3 og R*> har den ovenfor definerede betydning, be-handles dernæst med enten en vandig syre, sâsom saltsyre, tri-f1uoreddikesyre, svovlsyre, methansulfonsyre eller salpetersy-30 re, eller en vandig base, sâsom natriumcarbonat eller natriumhydroxid, sædvanligvis ved en temperatur fra 20 til 150eC, og fortrinsvis 40 til l00eC, til frembringelse (ved en omlejring) af en pyridazin med formlen: 35
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7 VST* 5 R2 hvor r2, r3 0g r6 har den ovenfor definerede betydning.
Estere af pyridazinen med formel (V) fremstilles ved esterifi-10 cering med en passende alkohol, fortrinsvis en (Cj_4)-alkanol.
En bekvem teknik er en Fischer-esterificering under anvendelse af vandfri saltsyre eller svovlsyre som katalysator og alkoho-len som oplosningsmiddel. Denne esterificering gennemfmres sædvanligvis ved en temperatur fra 35 til 150°C, eventuelt unis der anvendelse af et inert co-oplosningsmiddel, sâsom methy-lenchlorid, ethylenchlorid, diethylether, toluen eller xylen.
Salte af pyridazinerne med formel (V) og deres 5-halogenanalo-ge forbindelser kan fremstilles ved konventionelle teknikker, sâsom ved neutralisation med en passende uorganisk eller orga-20 nisk base i et oplosningsmiddeT, sâsom vand eller methanol.
Forbindelserne, hvori R4 betegner et halogenatom, kan frem-stilles ved omsætning af de tilsvar.ende pyridaziner, hvori R4 betegner et hydrogenatom, med et ækvivalent af et halogene-25 ringsmiddel, sâsom brom, chlor, suifurylbromid eller sulfuryl-chlorid eller lignende, i et passende inert oplesningsmiddel, sâsom hexan, benzen, ethylendichlorid eller methanol, sædvanligvis ved en temperatur fra 0 til 50°C, og fortrinsvis ved stuetemperatur.
30 I den efterfolgende tabel I er anfart typiske forbindelser til anvendelse ved fremgangsmâden ifolge opfindelsen, deres smel-tepunkter og grundstofanalyse. De efter tabel I folgende ud-forelseseksempler viser syntesen af forbindelserne 10, 12, 14 35 og 16 i tabel I, og i disse eksempler er aile temperaturer i °C og dele og procenter pâ vægtbasis, medmindre andet er an-fert.
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8
TABEL I
1-Aryl-l/4-dihydro-4-oxo-pyridaziner 5
N
CH3^^ à
X
. r Forbind- , n „ 15 else nr. R_ X Smp.°C %C *H %N %Ha3- 1 H 3-F 213-5 Beregnet 58,06 3,65 11,29 7,65
Fundet 58,07 3,60 11,33 7,68 2 H 4-CH,,3-Cl 202-3 56,22 3,63 10,09 12,77 3 55,92 3,84 10,90 13,36 3 H 4-1 241-2 40,47 2,55 7,87 35,64 20 41,20 2,46 8,05 35,67 4 H 4-Br 243 46,62 2,93 9,06 25,85 47,45 3,14 9,26 25,64 5 h 4-CF, 234-5 52,35 3,04 9,40 19,11 3 51,99 2,97 9,13 18,94 6 H 4-NO- 244-5 52,37 3,30 15,27 ----- 25 3 52,76 3,33 15,69 ----- . 0 Beregnet 63,92 4,95 11,47 ----- 7 H 4-CH3 162-3 pundet 63,66 4,89 11,52 ----- 8 H 2,3-benzo- 218-20 61,06 3,52 8,90 11,27 4_C1 61,07 3,42 8,86 11,00 9 H 4-OCHo 169-70 59,94 4,64 10,77 ----- 30 3 60,14 4,62 10,82 ----- ]_q h 4-F 185-7 58,06 3,65 11,29 7,65 58,73 3,64 11,74 7,47 11 H 3,4-diCl 220-2 48,18 2,69 9,37 23,71 48,03 2,73 9,21 23,96 12 H 4-C1 229-30 54,45 3,43 10,59 13,39 35 54,49 3,44 10,44 13,59 13 H 3-Cl 192-3 ~
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9 TABEL I (fortsat) 5 -
Forbind- .
else nr. χ X Smp. C %C %H %N %Hal
14 . H H 173 "III
10 15 Br 4-CH-, 241 48,31 3,43 8,67 24,73 iD ür 3 49,37 3,59 9,25 23,65^ ig Br 4-F 219-20 44,06 2,46 8,57 24,43 44,50 2,52 9,00 24,26 77 Br 4-Br >?ςπ 37'14 2'08 7'22 41,19 17 Br B 250 36,73 1,93 7,35 40,33 15 19 t»T. H ion 46,62 2,93 9,06 25,85 15 18 46,63 2,33 9,25 25,62 ia Cl 4—Br 255—9 41,95 2,3o 8,16 23,26 19 ci 4 Br . 3 4lf6S 2,31 7,74 23,17 * % Br; % P: beregnet 5,81; fundet 5,83 20 #* % Br; % F; beregnet 10,37; fundet 9,91 25 30 35
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10
Eksempel 1 (Forbindelse 10/ Tabel I)
Fremstilling af l-(4-fluorphenyl)-l,4-dihydro-4-oxo-6-methylpvr idaz in- 3 -carboxylsyre____ 4-Hydroxy-6-methyl-2-pyron (7/88 g) suspenderes i 250 ml vand, ®· og 6/63 g vandfri .natriumcarbonat sættes til suspensionen til udvirk-ning af opl0sning af pyronen.
I en separat kolbe blandes 7/22 g 4-fluoranilin med 25 ml kon-cantreret saltsyre og 31 ml vand. Den resultarende opl0sning holdes ved ca. 5 til 10°, og en opl0sning af 4/75 g natriumnitrit i 16 ml 10 vand tilsættes. Den opnâede opl0sning af 4-fluorphenyldiazoniumchlorid sættes drâbevis til den omr0rte pyron-opl0sning, idet temperaturen holdes ved ca. 5 til 10°, og pH-værdien pâ ca. 8 til 9 ved tilsætning af smâ mængder vandig natriumhydroxid.
Den opnâede hydrazon tilbagesvales i ca. 2 timer med 500 ml kon-centrerat saltsyre. K0ling og filtrering giver 10/2 g l-(4-fluor-phenyl)-1,4-dihydro-4-oxo-6-methylpyridazin-3-carboxylsyre, som om-krystalliseres fra chloroform/ether (smp. 185-187°C).
Eksemoel 2 (Forbindelse 12, Tabel I) 20 --
Fremstilling af 1-(4-chlorphenyl)-l,4-dihydro-4-oxo-6-methylpyridazin-carboxylsyre og dets natriumsalt_ p-Chloranilin (12,75 g) opl0ses i 40 ml koncentreret saltsyre og afk0les til 0°, og til den sâledes opnâede opl0sning sættes en 25 opl0sning af 7,6 g natriumnitrit med temperatur mellem 0 og 5°. Den diazoterede anilin sættes under isafk0ling til en pâ forhând frem-stillet opl0sning af 12,6 g 4-hydroxy-6-methyl-2-pyron og 55 g na-triumcarbonat i 500 ml vand.
Den resulterende opslæmning opvarmes under tilbagesvaling natten 30 over. Nâr fuldstændig omsætning ikke iagttages, indstilles pH-værdien til 12, og tilbagesvalingen fortsættes. Den m0rke opl0sning neutra-liseres til en pH-værdi pâ 6 - 7 med eddikesyre og behandles med ak-tiveret trækul. Filtratet g0res surt til en pH-værdi pâ 2 med koncentreret saltsyre under isafk0ling til udfældning af produktet. Syren 3 5 omkrystalliseres fra acetone/’nexan, hvilket giver 10,5 g (39%) 1-(4-chlorphenyl)-1,4-dihydro-4-oxo-6-methylpyridazin-3-carboxylsyre (smp. 229-230°C).
Syren (5,0 g) omdannes til natriumsaltet ved behandling med
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11 0,7β g natriumhydroxid i 200 ml vandfri methanol. Opl0sningsmidlet fjernes, og det faste stof vaskes med ether og t0rres i vakuum ved 90°C.
Analyse for ci2^c^N2OWa’^ H20: 5 Beregnet: C, 48,75; H, 3,07; N, 9,48; Cl, 11,99; Na, 7,78.
Fundet: C, 48,11; H, 2,80; N, 9,24; Cl, 12,37; Na, 7,62.
Eksempel 3 (Forbindelse 14, Tabel I)
Fremstilling af l-phenyl-l,4-dihydro-4-oxo-6-methylpyridazin-3-1Q carboxylsyre_ _ I 375 ml vand suspenderes 11,8 g 4-hydroxy-6-methyl-2-pyron, og 9,95 g vandfri natriumcarbonat tilsættes til udvirkning af opl0s-ning af pyronen.
I en separat kolbe blandes 9,08 g anilin med 37,5 ml koncentre-15 saltsyre og 47 ml vand. Den resulterende opl0sning holdes ved ca. 5 til 10°, og en opl0sning af 7,13 g natriumnitrit i 24 ml vand tilsættes. Den resulterende opl0sning af phenyldiazoniumchlorid sæt-tes drâbevis til den omr0rte pyron-opl0sning, idet temperaturen holdes pâ ca. 5 til 10°. pH-vsrdien holdes pâ ca. 8 til 9 ved tilsæt-20 ning af smâ mængder natriumhydroxid-opl0sning.
Efter at tilsætningen er afsluttet, isoleras den opnâede hydra-zon (18 g) ved filtrering og resuspenderes i 500 ml koncentreret saltsyre. Blandingen tilbagesvales i 2½ time og k0les sâ. l-Phenyl-1,4-dihydro-4-oxo-6-methylpyridazin-3-carboxylsyren fælder ud som brun-25 lige krystaller, som omkrystalliseres fra vand. Udbytte 7,0 g; smp. 173°.
Eksempel 4 (Forbindelse 16, Tabel I)
Fremstilling af 1-(4-fluorphenyl)-5-brom-l,4-dihydro-4-oxo-30 methylpyridazin-3-carboxylsyre._ 1- ( 4-Fluorphenyl) -1,4-dihydro-4-oxo-6-methylpyridazin-3-carboxyl- syre (1,5 g) suspenderes i 100 ml t0r methanol, og 0,242 g natrium- hydroxid tilsættes. Til oplpsningen sættes drâbevis 1,038 g brom opl0st i 50 ml methanol. Opl0sningsmidlet fjernes, hvorved der efter-3 5 lades et hvidt fast stof, som tages op i fortyndet base, og opl0s-ningen g0res sur med saltsyre. Det resulterende bundfald filtreras og omkrystalliseres fra cnloroform/ether til frembringelse af 1;4 g 1- (4-fluorphenyl) -5-brom-l,4-dihydro-4-oxo-6-methylpvridazin-3-carbox-ylsyra. (Smp. 219-220°).
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12
Forbindelserne er særlig nyttige som kemiske hybridiseringsmidler ved cereal-afgroder, sâsom hvede, byg, majs, ris, dur-ra, hirse, havre og rug. Nâr forbindelserne anvendes soin kemiske hybridiseringsmidler, fremkalder de effektivt en hoj grad 5 af selektiv hankonssteri1itet og det uden ogsà at fremkalde hunkenssteri1itet af betydning i de behandlede planter og uden hos de behandlede planter at fremkalde vækstinhibering af betydning. Som betegnelsen hankenssteri1itet anvendes heri, orn-fatter den bâde egentlig hankenssteri1itet, som viser sig ved 10 mangel pâ hanblomstdele eller ved stérile pollen, og funktio-nel hankenssterilitet, ved hvilken hanblomsten er ude af stand til at fremkalde bestevning. Forbindelserne fremkalder ogsà andre plantevækstregulerende reaktioner, sàsom f.eks. kontrol af blomstring, kontrol af frugtsætning og inhibering af fre-15 dannelse ved ikke-cereal iearter og andre beslægtede vækstregu-lerende reaktioner.
Anvendt som hybridiseringsmidler tilferes forbindelserne i en hvilken som helst mængde, som vil være tilstrækkelig til at 20 fremkalde den enskede plantereaktion uden at fremkalde nogen uensket eller phytotoksisk reaktion. Forbindelserne tilferes sædvanligvis afgroderne, som skal behandles, i en mængde pâ 0,035 til 22,42 kg pr. hektar, og fortrinsvis 0,14 til 11,21 kg pr. hektar. Tilferselsmængden vil variere i afhængighed af 25 afgreden, som behandles, forbindelsen, som anvendes til be-handlingen, og tilsvarnde faktorer.
For at opnâ hybridfre anvendes folgende fremgangsmâde sædvanligvis. De to stamvækster, som skaï krydses, plantes i skif-30 tende rækker. Hunkonsstamvæksten behandles med en forbindelse til anvendelse ved fremgangsmâden ifelge opfindelsen. Den sâ-ledes frembragte hankenssterile hunkonsstamvækst vil blive be-stovet med pollen fra den anden hankensfertile hankensstem-vækst, og freiene, som produceres af hunkensstemvæksten vil 35 være hybridfre, som dernæst kan hostes pâ konventionel mâde.
En foretrukket fremgangsmâde til tilfersel af en af de omhand-lede forbindelser som kemisk hybridiseringsmiddel er ved blad-
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13 vækstti1fersel . Nâr denne fremgangsmàde anvendes, fremkaldes selektiv hankenssteri1itet mest effektivt, nâr forbindelsen tilferes mellem blomst-initiering og roeiose. Forbindelserne kan ogsâ tilferes son) en frebehandling ved udbledning af fre-5 ene i et flydende præparat indeholdende den aktive komponent eller ved overtrækning af freene med forbindelsen. Ved frebehandl ingsti lfersler tilferes forbindelserne sædvanligvis i en mængde pâ ca. 1/4 ti1 10 kg pr. 100 kg fre. Forbindelserne er ogsâ virksomme, nâr de tilferes jorden eller vandoverf1aden 10 ved risafgreder.
Forbindelserne kan anvendes som hybridiseringsmidler sammen, f.eks. i blanding, med andre plantevækstregulatorer, sâsom au-xiner, gibberelliner, ethylen-afgivende midler, sâsom ethe-15 phon, pyridoner, cytokininer, maleinsyrehydrazid, ravsyre 2,2-dimethylhydrazid, cholin og salte deraf, (2-chlorethyl)trime-thylammoniumchlorid, triiodbenzoesyre, tributyl-2,4-dichlor-benzylphosphoniumchlorid, polymère N-vinyl-2-oxazolidioner, tri(dimethylamoniethylJphosphat og salte deraf, og N-dimethyl-20 amino-l,2,3,6-tetrahydrophthalamsyre og salte deraf. Under visse betingelser kan forbindelserne med fordel anvendes i forbindelse med jordbrugspesticider, sâsom herbicider, fungi- cider, insekticider og plantebaktericider.
25 En eller flere af forbindelserne kan tilferes dyrkningsmediet eller planterne, som skal behandles, enten alene, eller som det sædvanligvis sker, som en komponent i et væsktregulerings-præparat eller -sammensætning, som ogsâ omfatter en agronomisk acceptabel bærer, sâsom f.eks. en bærer, som er agronomisk ac-30 ceptabel, men farmaceutisk uacceptabel. Med "agronomisk acceptabel bærer" menes et hvilket som helst materiale, som kan anvendes t i1 at oplese, dispergere eller fordele en forbindelse i præparatet uden ugunstigt at pâvirke effektiviteten af forbindelsen, og som i sig selv ikke har nogen skadelig virkning 35 af betydning pâ jorden, apparaturet, afgroderne eller det agronomiske mil je. De vækstregulerende præparater kan være af enten fast eller flydende sammensætning eller kan være oples-ninger. F.eks. kan forbindelserne udformes som befugtelige
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14 pulvere, emulgerbare koncentrater, puddere, granulater, aero-soler eTler letflydende emulsionskoncentrater. I sâdanne præ-parater strækkes forbindelserne med en flydende eller fast bæ-rer, og om onsket inkorporeres passende overfladeaktivt mid-5 1er.
Det er sædvanligvis onskværdigt, specielt ved bladvækstti1-fersel at indbefatte hjælpestoffer, sàsom befugtningsmidler, spredningsmidler, dispergeringsmidler, vedhæftningsmidler, 10 klæbemidler og lignende i overensstemmelse med jordbrugsprak- sis. Eksempler pâ hjælpestoffer, som er almindeligt anvendt inden for omrâdet, kan findes i publikationen John W. McCut-cheon. Inc. "Détergents and Emulsifiers Annual".
15 Forbindelserne kan oploses i et hvilket som helst passende op-lesningsmiddel. Eksempler pà oplosningsmidler, som er nyttige ved udovelse af opfindelsen, indbefatter vand, alkoholer, ke-toner, aromatiske carbonhydrider, halogenerede carbonhydrider, dimethylformamid, dioxan og dimethylsulfoxid. Ogsâ blandinger 20 af disse oplosningsmiddel kan anvendes. Oplosningens koncen-tration kan variere fra ca. 2 til ca. 98 v«gt% med et fore-trukket interval mellem ca. 20% og ca. 75%.
Til fremstilling af emulgerbare koncentrater kan forbindelsen 25 opleses i organiske oplesningsmidler, sâsom benzen, toluen, xylen, methyleret naphthalen, majsolie, fyrrenàlsolie, o-di-chlorbenzen, isophoron, cyklohexanon eller methyloleat, eller i blandinger af disse oplesningsmidler, sammen med et emulge-ringsmiddel eller overfladeaktivt middel, som muligger disper-30 gering i vand. Egnede emulgatorer omfatter f.eks. ethylenoxid-derivaterne af alkylphenoler eller langkædede alkoholer, mer-captaner, carboxylsyrer samt reaktive aminer og delvist este-rificerede polyhydroxyalkoholer. I oplesningsmiddel opleselige sulfater eller sulfonater, sâsom jordalkalisaltene eller amin-35 saltene af alkylbenzensulfonater og fedtalkoholnatriumsulfa-terne med overfladeaktive egenskaber kan anvendes som emulgatorer enten alene eller i forbindelse med et ethylenoxid-om-sætningsprodukt. Letflydende emulsionskoncentrater sammensæt-
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15 tes pâ lignende mâde som de emulgerbare koncentrater og indbe-fatter ud over ovenstâende komponenter vand og et stabilise-ringsmiddel,sâsom et vand-opleseligt cellulosederivat eller et vand-opleseligt sait af en polyacrylsyre. («Concentrât ionen af 5 den aktive komponent i emulgerbare koncentrater er sædvanlig-vis ca. 10 til 60 vægt%, og i letflydende emulsionskoncentra-ter er den sædvanligvis ca. 10 til 60 vægt% eller endog sé hej som 75 vægt%.
10 Befugtelige pulvere, som er egnede til spr0jtning, kan frem- stilles ved blanding af den aktive forbindelse med et findelt faststof, sâsom lerarter, uorganiske silikater og carbonater og silicium-oxider og tilsætning af befugtningsmidler, vedhæftningsmidler og/elle: dispergeringsmidler til sâdanne blandinger, Koncentrationen af aktive 15 komponenter i sâdanne befugtelige pulvere er sædvanligvis i inter-vallet fra ca. 20 til 98 vægt%, fortrinsvis ca. 40 til 75 vægt%.
Et dispergeringsmiddel kan sædvanligvis udg0re ca. 0,5 til ca. 3 vægt' af det befugtelige pulver, og et befugtningsmiddel kan sædvanligvis udg0re fra ca. 0,1 til ca. 5 vægt% af præparatet.
20 Puddere kan fremstilles ved blanding af de aktive forbindelser med findelte inerte faststoffer, som kan være af organisk eller uorganisk art. Materialer, som er egnede til dette formai, omfatter f.eks. botaniske meltyper, siliciumoxider,, silikater, carbonater og lerarter. En bekvem mâde til fremstilling af et pudder er at fortynde 25 et befugteligt pulver med en findelt bærer. Pudderkoncentrater inde-holdende ca. 20 til 80% af den aktive komponent fremstilles hyppigt, og de fortyndes derefter til en brugskoncentration pâ ca. 1 til 10 vægt%.
Præparater pâ granulatform kan fremstilles ved imprægnering af 30 et faststof sâsom granuleret valkejord, vermikulit, formalede majs-kolber, fr0skaller, inklusive klid eller andre kornskaller eller lignende materiale. En opl0sning af en eller flere af forbindelserne i ët flygtigt organisk opl0sningsmiddel kan spr0jtes over eller blandes med det granulatforméde faststof, og opl0sningsmidlet kan 35 dernæst fjernes ved fordampning. Det granulatformede materiale kan hâve en hvilken som helst passende st0rrelse med et foretrukket st0r-relsesinterval fra 16 til 60 mesh (USA-standard sigteserie). Den aktive forbindelse vil sædvanligvis udg0re ca. 2 til 15 vægt% af det granulerede præparat.
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16
Salte af forbindelserne kan udformes og tilfares som vandige oplasninger. Saltene vil typisk udgare ca. 0,05 til ca. 50 vægt%, fortrinsvis ca. 0,1 til ca. 10 vægt% af oplasningen. Disse præparater kan ogsâ fortyndes yderligere med vand, far 5 de pâfares, hvis dette anskes. Ved visse anvendelser kan akti-viteten af disse præparater forages ved i dem at inkorporere et hjælpemiddel, sâsom glycerin, methylethylcellulose, hydro-xyethylcellulose, polyoxyethylensorbitan-monooleat, polypro-pylenglycol, polyacrylsyre, polyethylennatriummalat og poly-10 ethylenoxid. Hjælpestoffet vil sædvanligvis udgare ca. 0,1 til ca. 5 vægt%, fortrinsvis ca. 0,5 til ca. 2 vægt% af præpara-tet. Sâdanne præparater kan ogsâ om ansket indeholde et agro-nomisk acceptabelt overfladeaktivt middel.
15 Forbindelserne kan tilfares som sprajtemidler ved de sædvanligvis anvendte metoder, sâsom konventionelle hydrauliske sprajtemidler, forstavede sprajtemidler og puddere. Til lavvo-lumentilfarsel anvendes sædvanligvis en oplasning af forbin-delsen. Fortyndingen og det tilfarte volumen vil sædvanligvis 20 afhænge af sâdanne faktorer som typen af det anvendte udstyr, tilfarselsmetoden, arealet, som skal behandles, og typen og udviklingsstadiet af afgraden, som behandles.
Det efterfalgende eksempel, hvormed det ikke er hensigten pâ 25 nogen mâde at begrænse opfindelsen, illustreres den vækstregu-lerende aktivitet af forbindelserne.
Anvendelseseksempel 1 30 Kemisk hvbridiserinqsaktivitet
De efterfalgende fremgangsmâder anvendes til vurdering af ak-tiviteten af forbindelserne til fremkaldelse af hankanssteri-litet hos cerealier.
35 En stakket varietet (Fielder) og en staklas varietet (Mayo-64) af vàrhvede anbringes i en mængde pâ 6 til 8 korn per 15,25 cm potte indeholdende et sterilt medium af 3 vægtdele jord og 1 vægtdel humus. Planterne dyrkes under kort-dags (9 timer) be-
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17 tingelser de forste 4 uger for at opnà god vegetativ vækst for blomst-initiering. Planterne overflyttes sâ til lang-dags (16 timer) betingelser, som tiIvejebringes med hojintensitetslys i væksthuset. Planterne godes 2, 4 og 8 uger efter plantm'ngen 5 med et vand-oplosel igt godningsmiddel (nitrogen-phosphor-kali-um = 16%-25%-16%) i en mængde pâ 1,3 ml per liter vand og sprojtes hyppigt med et passende insekticid, sâsom det, der forhandles under varemærket "Isotox", "til bekæmpelse af blad-lus og pudres med svovl til bekæmpelse af skimmel.
10
Forsogsforbindelser tilfores bladvæksten af de avnede hunkonsplanter, nàr disse planter nâr flagbladfremkomststadiet (trin 8 pâ Feekes' skala). Aile forbindelser tilfores i et bærervolumen pâ 468 liter per hektar, indeholdende et overfla-15 deaktivt middel sâsom det, der forhandles under varemærket "Triton X-100", i en mængde pâ 0,3 g per liter.
Efter aksfremkomsten for anthesis lukkes 4 til 6 aks per potte inde i en pose for at forhindre udkrydsning. Ved de forste 20 tegn pâ blomsterâbning krydsbestoves to aks per potte med den staklose hankonsstamvækst under anvendelse af ti1nærmelsesme-toden. Sâsnart froene bliver klart synlige, mâles akslængden, og antallet af fro per smàaks tælles i bàde indelukkede og krydsede aks. Hankonssteri1iteten kan sâ beregnes som procent 25 inhibering af frosætning i indelukkede aks pâ behandlede planter, og hunkonsferti1iteten i krydsede aks kan beregnes som procent af kontrolfrosætning. Efter modning udsâs froene fra krydsede aks til bestemmelse af hybridi seri ngsprocent. Den ovenfor anforte "ti1nærmelsesmetode" indebærer, at aksene, som 30 skal krydsbestoves, bringes tæt pâ hinanden eller i kontakt.
Procent sterilitet, procent fertilitet og procent akslængdein-hibering beregnes ud fra folgende formler: 35
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18 s - st a) % sterilitet = —-- X 100
Sc
Sc = fr0/smâaks i indelukkede aks pâ kontrolplanter S= fr0/smâaks i indelukkede aks pâ behandlede planter *5 ^ b) % fertilitet = Ffc X 100
TT
Ft = fr0/smâaks i tilnærmelseskrydsede aks pâ behandlede planter F = fr0/smâaks i ikke-indelukkede aks pâ kontrolplanter lu c
c) % aks-inhibering = ——-- X
Hc
Hc = akslængde pâ kontrolplanter Ht = akslængde pâ behandlede planter.
15 I tabel II er summeret typiske resltater opnâet ved underse-gelse af forbindelser til anvendelse ved fremgangsmâden ifelge opfindelsen. En tankestreg viser, at der ikke blev foretaget nogen bestemmelse.
20
TABEL II
Gametocid aktivitet
i T
CH3 30
X
35 19 % Sterilitet (ved kg/ha) X_ R 8,96 4,48 2,24 1,12 0,56 0,28 3F HH --- 100 94 72 46+ 7+ 5 74 83 3F H Na — 100 100 100 100 81 4-CH3,3-Cl HH 16 3 10 14 10 --- 4-CH3,3-Cl H Na 0 14 2 13 6 --- 4-1 H H --- 100 100 100 99 10 4-1 H Na 100 100 100 100 100 97+ 82 4-Br H H ---- 100 100 100 100 --- 4-Br H Na 100 100 100 100 100+ 98+ 86 73 4-CF3 H H --- 100 97 100 96 15 4-CF3 H Na 100 100 100 100 97+ 99+ 90 80 4-N02 HH 9 18 --- --- --- --- 4-N02 H Na 9 16 8 16 8 4-CH3 H H 73 41 20 4-CHH Na 100 98+ 92+ 38 12 --- 100 100 4-C1 HH 33 15 --- --- --- --- (naphthyl) 4-C1 H Na 0 5 4 4 9 --- (naphthyl) 25 4-OCH3 H H 100 94 --- --- --- --- 4-0CH-, H Na 100 100+ 99+ 83+ 43+ --- J 100 98 100 100 4-F H H 100 —- --- -— --- --- 4-F H Na 100 100 100 100 95 66+ 88 30 3,4-diCl H H 100 --- --- --- --- --- 3,4-diCl H Na 100 98 92 16 --- --- 4-C1 H H 100 100 96 --- --- --- 4-C1 H Na 100 100 100+ 100+ 100+ 100+ 45 34 90 72 35 3-Cl H Na 86 --- --- --- --- --- 3-C1 H Na 100 100 74 64+ 94 --- 73 DK 156607 B ' 20 TABEL II (fortsat) 5 % Sterilitet (ved kg/ha) x_ R 8,96 4/48 2/24 1/12 0/56 0/28 H H H 75 --- --- --- --- --- in H H Na 100 100 100 100 97+ 40+ 10 90 97 4-CH3 Br H --- 6 2 10 7 --- 4-CH3 Br Na 9 3 --- 8 7 --- 4-F Br H --- --- --- --- --- --- 4-F Br Na 100 100 100 100+ 84+ 15 15 65 73 4-Br Br H --- --- --- 82 48 32 ± 4-Br Br Na --- --- --- --- --- --- H Br H --- --- --- --- --- --- H Br Na --- --- --- 100 88 18 ii 20 4-Br Cl Na --- 100 100 92 55 --- 4-Cl H CH3 ++ 100 ++ --- 100 ---*** 4-C1 H C2H5 100 --- 100 --- 100 ---**** + multiple resultater, sâledes at multiple adskilte fors0g gennemf0rtes.
25 i 35 ved 0/14 kg/ha fcfe 0 ved 0/14 kg/ha 96 ved 0,14 kg/ha 99 ved 0,14 kg/ha ++ aksfremkomst inhiberet ved 2,24 og 8,96 kg/ha.
30 35 DK 156607 B'
Tabel III
21
Tabel III nedenfor viser yderligere f-orbindelser, som er ble-vet fremstillet.
VV* (i) A"
R I
10
Qr x 15 Eksempel_Rf_R^_X_R*_ A H CH3 4-Br C02-n-C4H9 B H CH3 4-1 C02CH3 C H CH3 4-1 C02-n-C4Hg D H CH3 4-€1 C02-(1/2CU++) 20 E H CH3 4-CH3S C02CH3 F H CH3 4~CH3C02 C02Na 6 H CH3 4~CH3S C02Na H n-C3H7 CH3 4-C1 C02CH3 I H n-C4Hg 4-C1 C02CH3 25 J H CH3 4~C1 C02CH3 K H CH3 4-C1 C02-n-C6H13 L H CH3 4-C1 C02CH2C6H13 M H CH3 4-Cl C02CH3 N H CH3 4-Cl C02CH3 30 0 H CH3 4-C1 C02C2H5 P H C2H5 4—C1 C02CH3 Q H C2H5 4-C1 C02Na R CH3 C2H5 4-C1 C02Na 35
Tabel IV
Tabel IV nedenfor giver fysiske karakteristika og/eller grund- stofanalyse for forbindelserne vist i tabel III.
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22 5
Eksempel Smeltepunkt _(°C)_%C %H %H %Hal A 85,5-88 Beregnet: 52,61 4,69 7,67
Fundet : 52,25 4,70 7,90 10 B 186-189 42,18 3,00 7,57 41,95 2,91 7,16 C 134-137 46,61 4,16 6,80 46,84 4,26 6,95 D 263-265 41,24 4,04 8,02 10,15e) 39,55 3,40 7,62 9,35 15 E 157-159 57,91 4,86 9,65 57,98 4,88 9,66 F 300 51,22 3,99 8,54&) 51,32 3,73 8,68 20 G 310 .......... .....
H Halvfast 59,90 5,34 8,74 60,13 5,45 8,57 I Olie 59,90 5,34 8,74 25 59,85 5,61 9,11 J 183-193 49,54 3,84 8,89e) 50,12 3,69 9,29 K 62,33 5,52 8,08 62,45 5,75 8,45 30 L 125-127 63,24 5,87 7,77 63.44 5,97 7,48 H 154-156 52,97 3,76 9,51e*) 52.45 3,89 9,48 N 200-202 56,02 3,98 10,05 12,72 56,15 4,06 10,10 12,71 3 5 0 143 57,44 4,48 9,57 12,11e) 57,37 4,51 9,56 12,06 P 110-114 57,44 4,48 9,57 57,20 4,34 9,60
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23 Q 48,93 3,80 8,79f) 48,22 3,56 9,22 R 165 50,53 4,24 8,429) 5 50,39 3,86 8,41 a) % Cl; Cu: beregnet: 9,09 fundet : 10,60 % H2O: beregnet: 15,47 10 fundet : 15,96 b) % Na·. beregnet: 7,01 fundet : 8,19 15 c) Analyse for hydrochloridsalt d) %S·. beregnet: 10,88 fundet : 12,25 20 e) % Cl : f) % Na: beregnet: 7,22 fundt : 7,40 % H2O beregnet: 5,65 25 fundet : 4,74 (monohydraf) g) % Na beregnet: 6,91 fundet : 6,1 % H2O beregnet: 5,42 30 fundet : 4,31 (monohydrat)
Tabel V nedenfor viser hankonssteri1itetsdata for forbindel-serne i tabel III, som blev opnâet ved fremgangsmâden, der blev anvendt til at fà de i tabel II anforte resultater.
35
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24
Tabel V
% Hankenssteri1itet (ved kg/ha) 5 Eks. 8,96 4,48 2,24 1,12 0,56 0,28 0,14 0,07 A --- --- --- --- 100 100 90 90 B --- ...... --- 100 100 98 97 C ......... --- 100 100 100 94 D --- --- 100+++ 100+++ 91+++ 63+++ --- --- 10 E 100 --- 96 --- 56 --- 16 --- F --- 4 3 --- 0 ... ......
G --- --- ---19 8 7 55 H --- 100 100 100 89 72 I --- --- --- 49 7 0 0 15 J ++ --- ++ --- 100 --- 96 --- K --- --- --- 31 12 2 0 L --- --- --- 63 9 1 0 M 100 --- 99 --- 67 --- 9 N ......... 100 100 100 98 20 0 100 --- 100 --- 100 --- 99 --- P ......... 100 100 100 98 Q 100 --- 100 100 100 98 95 --- R 100 --- 100 88 37 2 0 --- 25 ++ Aksemergens înhiberet ved 2,24 og 8,96 kg/ha +++ Jordgennemblodningsprove, ikke bladpàsprojtning
Blandt forbindelserne kan specielt nævnes en hidtil ukendt klasse af forbindelser, nemlig forbindelserne med den tidlige-30 re anferte formel (I), hvori R4 er forskellig fra hydrogen, f.eks. halogen.
Opfindelsen er af særlig betydning derved, at den tilvejebrin-ger en fremgangsmâde til ved hybridisering at forbedre den 35 kommercielle værdi af fre til fremstilling af cerealiekorn, soin indbefatter (1) at et mekanisk spredningsaggregat fedes med et hybridiseringspræparat indeholdende en forbindelse med formel (I) og en agronomisk acceptabel bærer derfor, (2) at
Claims (3)
10 Patentkrav.
1. Fremgangsmàde til fremkaldelse af hankonssteri1itet i en cerealiekornplante, kendetegnet ved, at den omfat- 15 ter, at planten forud for meiose behandles med en mængde, som er virksom til at frembringe hankonssteri1itet i planten, af mindst én forbindelse med formlen: O 20 ll/^1 11 (I) , yv. .n k1 hvori r! betegner en carboxygruppe, eller et agronomisk accep-tabelt sait deraf, eller alkoxycarbonyl med op til 12 carbonatomer i alkoxydelen, R1 betegner phenyl, der eventuelt er substitueret med op 30 til tre substituenter med ialt 0 til 6 carbonatomer, idet substituenten eller substituenterne er udvalgt blandt (1) alkyl, (2) C4H4 til dannelse af en naph-thylgruppe, (3) alkoxy, (4) halogen, (5) nitro, (6) trif1uormethyl, (7) alkanoyloxy og (8) alkylthio,
35 R2 betegner (Ci_4)-alkyl, og R* betegner hydrogen, (Ci_4)-alkyl eller halogen. Fremgangsmàde ifolge krav 1, kendetegnet ved, 2 at RI ha tonoor an rarhnyunriinna aller et alliai imetalealt rlar — DK 156607 B af, R2 betegner 4-chlorphenyl, R3 betegner methyl og R4 betegner hydrogen. 5 10 15 20 25 30 35
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US77639477A | 1977-03-10 | 1977-03-10 | |
| US77639477 | 1977-03-10 |
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| DK106078A DK106078A (da) | 1978-09-11 |
| DK156607B true DK156607B (da) | 1989-09-18 |
| DK156607C DK156607C (da) | 1990-02-05 |
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| DK106078A DK156607C (da) | 1977-03-10 | 1978-03-09 | Fremgangsmaade til fremkaldelse af hankoenssterilitet i en cerealiekornplante |
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| NZ (1) | NZ186596A (da) |
| PL (2) | PL115813B1 (da) |
| PT (1) | PT67747A (da) |
| SE (2) | SE446812B (da) |
| TR (1) | TR20326A (da) |
| ZA (1) | ZA781424B (da) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1132566A (en) * | 1979-07-30 | 1982-09-28 | Glenn R. Carlson | Process for the preparation of 1-aryl-1, 4-dihydro-4-oxopyridazine-3-carboxylic acid esters |
| CA1138872A (en) * | 1979-07-30 | 1983-01-04 | Rohm And Haas Company | Process for the preparation of 1-aryl-1,4- dihydro-4-oxopyridazine-3-carboxamides |
| EP0037133A1 (en) * | 1980-03-26 | 1981-10-07 | Shell Internationale Researchmaatschappij B.V. | Pyridazinone compounds, process for their preparation, compositions containing them and a method of regulating the growth of plants, increasing the yield of soya bean plants and sterilizing the male anthers of plants, including small grain cereal plants, using them as well as a method of producing F1 hybrid seed |
| US4707181A (en) * | 1980-10-03 | 1987-11-17 | Rohm And Haas Company | 1-aryl-1,4-dihydro-4-oxo-3,5-dicarboxypyridazine derivatives and their use as plant growth regulators and hybridizing agents |
| US5062880A (en) * | 1980-10-03 | 1991-11-05 | Monsanto Company | 1-aryl-1,4-dihydro-4-oxo-5-carboxypyridazine derivatives and their use as plant growth regulators and hybridizing agents |
| AR230050A1 (es) * | 1980-10-03 | 1984-02-29 | Rohm & Haas | Compuesto derivado de 1-fenil-1,4-dihidro-4-oxo-3,5-dicarboxipirazina,composicion que lo comprende y procedimientos para repararlo |
| US4732603A (en) * | 1980-10-03 | 1988-03-22 | Rohm And Haas Company | 1-aryl-1,4-dihydro-4-oxo-5-carboxypyridazine derivatives and their use as plant growth regulators and hybridizing agents |
| GR75799B (da) * | 1980-10-03 | 1984-08-02 | Ici Plc | |
| CA1166646A (en) * | 1981-02-20 | 1984-05-01 | Thomas R. Opie | Process for the preparation of 4-hydroxy-6-methyl-2- pyrone |
| DK154836C (da) * | 1982-03-04 | 1989-05-16 | Ici Plc | Substituerede pyridaziner, deres anvendelse som plantevaekstreguleringsmidler og plantevaekstreguleringsmidler, der indeholder dem |
| US4623378A (en) * | 1983-08-10 | 1986-11-18 | Ciba-Geigy Corporation | Gametocidal pyridazinylcarboxylic acid derivatives |
| US5169429A (en) * | 1988-10-14 | 1992-12-08 | Monsanto Company | Hybridization of sunflowers and safflowers |
| FR2648135B1 (fr) * | 1989-06-07 | 1991-09-27 | Pf Medicament | Derives de phenyl-1-dihydro-1,4 amino-3 oxo-4 pyridazines, leur preparation et leur application en therapeutique |
| AU6057590A (en) * | 1989-07-07 | 1991-02-06 | Moskovsky Gosudarstvenny Universitet Imeni M.V.Lomonosova | Method for sterilization of plant anthers |
| FR2676733B1 (fr) * | 1991-05-22 | 1993-10-01 | Fabre Medicament Pierre | Derives de phenyl-1 dihydro-1,4 hydroxy-3 oxo-4 pyridazines, leur preparation et leur application en therapeutique. |
| EP1149108A1 (en) | 1999-02-02 | 2001-10-31 | Monsanto Co. | Production of phosphonopyrazoles |
| WO2025244119A1 (ja) * | 2024-05-24 | 2025-11-27 | 住友化学株式会社 | ピリダジン誘導体及びそれを含有する組成物 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2454742A (en) * | 1948-11-23 | Pyridazone derivatives and method | ||
| US2835671A (en) * | 1958-05-20 | Pyridazine derivatives |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE954332C (de) * | 1953-05-12 | 1956-12-13 | Ciba Geigy | Verfahren zur Herstellung neuer Ester |
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1977
- 1977-03-10 PL PL1977205233A patent/PL115813B1/pl unknown
-
1978
- 1978-02-03 SE SE7801307A patent/SE446812B/sv not_active IP Right Cessation
- 1978-02-23 IL IL54122A patent/IL54122A/xx unknown
- 1978-02-27 GB GB7638/78A patent/GB1596611A/en not_active Expired
- 1978-02-27 CA CA297,781A patent/CA1103477A/en not_active Expired
- 1978-02-27 AR AR271235A patent/AR219522A1/es active
- 1978-02-28 TR TR20326A patent/TR20326A/xx unknown
- 1978-03-01 NZ NZ186596A patent/NZ186596A/xx unknown
- 1978-03-01 DE DE19782808795 patent/DE2808795A1/de active Granted
- 1978-03-01 DE DE2858755A patent/DE2858755C2/de not_active Expired - Lifetime
- 1978-03-03 ES ES467543A patent/ES467543A1/es not_active Expired
- 1978-03-04 GR GR55611A patent/GR64069B/el unknown
- 1978-03-06 CS CS781414A patent/CS199719B2/cs unknown
- 1978-03-07 PT PT67747A patent/PT67747A/pt unknown
- 1978-03-07 DD DD78204010A patent/DD140410A5/de unknown
- 1978-03-07 EG EG150/78A patent/EG13401A/xx active
- 1978-03-07 BR BR7801362A patent/BR7801362A/pt unknown
- 1978-03-07 FR FR7806494A patent/FR2383605A1/fr active Granted
- 1978-03-08 AU AU33980/78A patent/AU524926B2/en not_active Expired
- 1978-03-08 CH CH251278A patent/CH629077A5/fr not_active IP Right Cessation
- 1978-03-09 BE BE185777A patent/BE864704A/xx not_active IP Right Cessation
- 1978-03-09 JP JP2714478A patent/JPS53133633A/ja active Granted
- 1978-03-09 IT IT67511/78A patent/IT1111613B/it active
- 1978-03-09 BG BG038956A patent/BG34901A3/xx unknown
- 1978-03-09 HU HU78RO969A patent/HU182990B/hu unknown
- 1978-03-09 DK DK106078A patent/DK156607C/da not_active IP Right Cessation
- 1978-03-10 PL PL20523378A patent/PL205233A1/xx unknown
- 1978-03-10 NL NLAANVRAGE7802656,A patent/NL171118C/xx not_active IP Right Cessation
- 1978-03-10 ZA ZA00781424A patent/ZA781424B/xx unknown
- 1978-07-24 FR FR7821842A patent/FR2392980A1/fr active Granted
-
1985
- 1985-07-05 SE SE8503365A patent/SE469585B/sv not_active IP Right Cessation
-
1987
- 1987-03-09 JP JP62053913A patent/JPS62265204A/ja active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2454742A (en) * | 1948-11-23 | Pyridazone derivatives and method | ||
| US2835671A (en) * | 1958-05-20 | Pyridazine derivatives |
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| PUP | Patent expired |