NO142122B - NEW RELATIONS WITH PLANT GROWTH REGULATORY EFFECT - Google Patents
NEW RELATIONS WITH PLANT GROWTH REGULATORY EFFECT Download PDFInfo
- Publication number
- NO142122B NO142122B NO75753857A NO753857A NO142122B NO 142122 B NO142122 B NO 142122B NO 75753857 A NO75753857 A NO 75753857A NO 753857 A NO753857 A NO 753857A NO 142122 B NO142122 B NO 142122B
- Authority
- NO
- Norway
- Prior art keywords
- keto
- isopropylidene
- gulonate
- growth
- compounds
- Prior art date
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- 230000008635 plant growth Effects 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 78
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
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Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Oppfinnelsen vedrører nye forbindelser med plantevekstregulerende virkning med den generelle formel The invention relates to new compounds with plant growth-regulating action with the general formula
hvor n betyr tallet 1 eller 2, og X er 0 til 1, where n means the number 1 or 2, and X is 0 to 1,
når n er tallet 1, when n is the number 1,
betyr R<1> natrium; kalium; ammonium; ammonium substituert med ett eller flere lavere alkyl, lavere alkenyl eller hydroksy-lavere alkyl; rettkjedet eller forgrenet alkyl, alkenyl eller alkynyl med opp til 20 karbonatomer; eller halogen-lavere alkyl; means R<1> sodium; potassium; ammonium; ammonium substituted with one or more lower alkyl, lower alkenyl or hydroxy-lower alkyl; straight or branched chain alkyl, alkenyl or alkynyl of up to 20 carbon atoms; or halo-lower alkyl;
og når n er tallet 2, betyr R' kalsium; magnesium eller lavere alkylen, and when n is the number 2, R' means calcium; magnesium or lower alkylene,
R'l' R<l>2' R*3 og R,4 ketvr lavere alkyl, samt enantiomerer og racemiske blandinger av forbindelsen med formel II, med det forbehold at når R' betyr metyl, etyl, allyl, natrium eller kalium, betyr R'-^<R>'2» <R*>30<j R<*>4 lavere alkyl med mer enn 1 karbonatom. R'l' R<l>2' R*3 and R,4 are lower alkyl, as well as enantiomers and racemic mixtures of the compound of formula II, with the proviso that when R' means methyl, ethyl, allyl, sodium or potassium, means R'-^<R>'2» <R*>30<j R<*>4 lower alkyl with more than 1 carbon atom.
ringsmidler før og etter spiring og som herbicid middel. ring agents before and after germination and as a herbicide.
En foretrukket gruppe av forbindelser er de med den generelle formel A preferred group of compounds are those of the general formula
hvor n og X har de i formel II angitte betydninger, når n er 1 betyr R^ ammonium, substituert ammonium, rettkjedet eller forgrenet alkyl med 3-20 karbonatomer, alkenyl med 2 eller 4-20 karbonatomer, eller alkynyl med opp til 20 karbonatomer, eller halogen-lavere alkyl og, når n er 2, betyr R^ kalsium, magnesium eller lavere alkylen, enantiomerer og racemiske where n and X have the meanings given in formula II, when n is 1 R^ means ammonium, substituted ammonium, straight-chain or branched alkyl with 3-20 carbon atoms, alkenyl with 2 or 4-20 carbon atoms, or alkynyl with up to 20 carbon atoms , or halo-lower alkyl and, when n is 2, R^ means calcium, magnesium or lower alkylene, enantiomers and racemic
blandinger, og særlig ved den generelle formel mixtures, and especially by the general formula
hvor Re betyr alkyl med 3-12 karbonatomer. where Re means alkyl with 3-12 carbon atoms.
De forannevnte forbindelsene har alle L-konfigurasjon da de er avledet av den i naturen forekommende ketoheksosen, L-sorbose. L-sorbosen er den eneste kjente i naturen forekommende form av sorbose. Imidlertid kan den tilsvarende enantiomeren til L-sorbosen, nemlig D-sorbose, fremstilles syntetisk. Man skal s<p>e-sielt nevne at forbindelsene som tilsvarer L-sorbosen kan fremstilles på analog måte med D-konfigurasjon samt racemiske blandinger av disse forbindelser, ved at man i stedet for L-sorbosen benytter D-sorbosen som utgangsmateriale, eller at man som ut-__,, gangsmateriale benytter en blanding av D- og L-sorbose-når man ønsker den tilsvarende racemiske blanding....De "preparative met-odene er nøyaktig de samme, uavhengig om man som utgangsmateriale anvender en forbindelse.av L-formen, D-formen eller den tilsvarende racemiske blanding. På samme måte er alle strukturformlene, slik som angis i det forangående eller den etterfølgende beskrivelse, ikke å oppfatte som strukturformler som skal beskrive en bestemt eller en absolutt konfigurasjon, men disse strukturformler skal omfatte alle mulige konfigurasjoner, dvs. de omfatter spesielt enantiomerer og de racemiske blandingene. Eksemplene og den øvrige beskrivelse vedrører, når ikke noe annet uttrykkelig sies, de racemiske forbindelsene. The aforementioned compounds all have L-configuration as they are derived from the naturally occurring ketohexose, L-sorbose. L-sorbose is the only known naturally occurring form of sorbose. However, the corresponding enantiomer of L-sorbose, namely D-sorbose, can be prepared synthetically. In particular, it should be mentioned that the compounds corresponding to L-sorbose can be prepared in an analogous way with D-configuration as well as racemic mixtures of these compounds, by using D-sorbose as starting material instead of L-sorbose, or that one uses a mixture of D- and L-sorbose as starting material when the corresponding racemic mixture is desired....The "preparative methods are exactly the same, regardless of whether one uses a compound as starting material .of the L-form, the D-form or the corresponding racemic mixture. In the same way, all the structural formulas, as indicated in the preceding or the following description, are not to be understood as structural formulas which should describe a particular or an absolute configuration, but these structural formulas shall include all possible configurations, i.e. they include in particular enantiomers and the racemic mixtures.The examples and the rest of the description relate, when nothing else is expressly stated, to the racemic compounds the parts.
De forbindelser som omfattes av formelen n oppviser plantevekst-, regulerende aktivitet og herbicid aktivitet etter og/eller før spiring. Den vekstregulerende virkningen etter spiring overvei-er imidlertid da de flesté forbindelser har denne virkning, og da denne aktivitet egner seg for kontroll av vekst av ugress som opptrer i gressplenen. The compounds covered by the formula n exhibit plant growth, regulatory activity and herbicidal activity after and/or before germination. However, the growth-regulating effect after germination is considered because most compounds have this effect, and because this activity is suitable for controlling the growth of weeds that appear in the lawn.
Uttrykket "plantevekstreguleringsmiddel", som benyttes her, betegner f.eks. en forbindelse som enten sinker eller stimilerer veksten av hoved- eller bi-grener, hhv. planteskudd. En slik forbindelse er i stand å påvirke (sinke eller stimulere) blomst-utviklingen, påbegynnelsen av blomstring, skudd- eller gren-dannelse, parthenocarpi, frukt og/eller blad-avfall samt frukt og/eller blad-modning. Videre har man effekter og påvirkninger av stofftransporter inne i planten, f.eks. stimulering av latex-strømning og/eller metabolismen eller f.eks. en økning i sukker-innholdet i planten osv. Dessuten har forbindelsene en herbicid Ivirkning. Når det gjelder gressplener bevirker f.eks. disse reguleringsmidlene en forsinkelse av gressplenveksten, og kan ytterligere bevirke en videre rotskudd-dannelse. Når det gjel- The term "plant growth regulator", which is used here, denotes e.g. a compound which either slows down or stimulates the growth of main or secondary branches, resp. plant shoots. Such a compound is capable of influencing (retarding or stimulating) flower development, initiation of flowering, shoot or branch formation, parthenocarpy, fruit and/or leaf drop as well as fruit and/or leaf ripening. Furthermore, there are effects and influences of substance transport inside the plant, e.g. stimulation of latex flow and/or metabolism or e.g. an increase in the sugar content of the plant, etc. In addition, the compounds have a herbicidal effect. When it comes to lawns, e.g. these regulatory agents delay lawn growth, and can further cause further root shoot formation. When it comes to
der buskplanter bevirker disse reguleringsaktiviteter en forsinkelse av veksten i høyden under samtidig stimulering av veksten til siden. where shrub plants these regulatory activities cause a delay in growth in height while simultaneously stimulating growth to the side.
Uttrykket "lavere alkyl" i kombinasjoner som f.eks. halogen-lavere alkyl henfører seg til rettkjedete eller forgrenete hydro-karboner, som har opp til 7 karbonatomer, som f.eks. metyl, etyl, propyl, isopropyl, butyl, tert.-butyl, pentyl osv.. Betegnelsen "halogen-lavere alkyl" omfatter rettkjedete eller forgrenete alkylgrupper med opp til 7 karbonatomer, hvor 1 eller flere hy-drogenatomer er erstattet med halogenatomer, som f.eks. 2,2,2-tri-kloretyl, 2,2-dikloretyl, 2-kloretyl, 4-klorbutyl, 2,2,2,-trifluor-etyl, 2-fluoretyl, 2-brom-l,l,2,2-tetrafluoretyl, 2,2,3,3,4,4,4-heptafluorbutyl, osv.. Betegnelsen ammonium angir de tilsvarende salter av 2-keto-gulonsyrederivater med formel I eller II, Betegnelsen "substituert ammonium" betyr ammoniumrester, hvor ett eller to av hydrogenatomene er erstattet med en lavere alkyl, lavere alkenyl eller hydroksyalkylsubstituent. The term "lower alkyl" in combinations such as Halogen-lower alkyl refers to straight-chain or branched hydrocarbons, which have up to 7 carbon atoms, such as e.g. methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, etc. The term "halogen-lower alkyl" includes straight-chain or branched alkyl groups with up to 7 carbon atoms, where 1 or more hydrogen atoms are replaced by halogen atoms, which e.g. 2,2,2-tri-chloroethyl, 2,2-dichloroethyl, 2-chloroethyl, 4-chlorobutyl, 2,2,2,-trifluoroethyl, 2-fluoroethyl, 2-bromo-1,1,2,2 -tetrafluoroethyl, 2,2,3,3,4,4,4-heptafluorobutyl, etc. The term ammonium indicates the corresponding salts of 2-keto-gulonic acid derivatives of formula I or II. The term "substituted ammonium" means ammonium residues, where one or two of the hydrogen atoms are replaced by a lower alkyl, lower alkenyl or hydroxyalkyl substituent.
Eksempler på representanter som kan henføres til formel II og Examples of representatives that can be attributed to formula II and
som har virkning som plantevekstreguleringsmiddel og/eller som har en herbicid virkning er: Ammonium-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; Kalsium-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; Dimetylaro onium-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; N-etanolai;mionium2, 3:4, 6-di-0-isopropyliden-2-keto-L-gulonat; n-butyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 3-klorpropyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; n-heksyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; n-heptyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; n-oktyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; n-nonyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; n-undesyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 2,2,2-trikloretyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; n-dodecyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; n-propyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; which have an effect as a plant growth regulator and/or which have a herbicidal effect are: Ammonium 2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; Calcium 2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; Dimethylaronium 2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; N-ethanolamine 2, 3:4, 6-di-O-isopropylidene-2-keto-L-gulonate; n-butyl 2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 3-Chloropropyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; n-hexyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; n-heptyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; n-octyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; n-nonyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; n-undecyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 2,2,2-trichloroethyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; n-dodecyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; n-propyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate;
1- propyl-2,3:4,6-di-O-isopropyliden-2-keto-L-gulonat; n-desyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 2- brometyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 2-butyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 1- amyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; bis-2,3:4,6-di-0-isopropyliden-2-keto-gulonat-etylenglykolester; t-butyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 2- pentinyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 1- heksin-3-yl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 3- metyl-l-butyn-3-yl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 5-heksenyl-2,3:4,6-di-O-isopropyliden-2-keto-L-gulonat; 3- <p>ent<y>l-2,3.:A-,.6-di-0-isopropyliden-2-keto-K-gulonat; Diklormetyl-2,3:4,6-di-0-isbpropylidéh-2-keto-L-gulonat; 2,2-dikloretyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 2- kloretyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 4- klorbutyl-2,3:4,6-di-O-isopropyliden-2-keto-L-gulonat; 2,2,2-trifluoretyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 2-fluoretyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 2-brom-l,1,2,2-tetrafluoretyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 1-propyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; n-decyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 2-bromomethyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 2-Butyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 1-amyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; bis-2,3:4,6-di-O-isopropylidene-2-keto-gulonate-ethylene glycol ester; t-butyl 2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 2-pentynyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 1-hexin-3-yl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 3-methyl-1-butyn-3-yl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 5-hexenyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 3- <p>ent<y>l-2,3.:A-,.6-di-O-isopropylidene-2-keto-K-gulonate; Dichloromethyl 2,3:4,6-di-O-isopropylideh-2-keto-L-gulonate; 2,2-dichloroethyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 2-chloroethyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 4-chlorobutyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 2,2,2-trifluoroethyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 2-Fluoroethyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 2-bromo-1,1,2,2-tetrafluoroethyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate;
2,2,3,3,4,4,4-heptafluorbutyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 2,2,3,3,4,4,4-heptafluorobutyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate;
2,2,3,3,4,4,5,5-oktafluorpentyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat. 2,2,3,3,4,4,5,5-octafluoropentyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate.
Spesielt foretrukne forbindelser er: 2-propynyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; n-pentyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat. Particularly preferred compounds are: 2-propynyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; n-Pentyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate.
De aktive forbindelsene er spesielt anvendbare i midler for regulering av planteveksten, og da spesielt veksten av gress og ugress, såvel som andre uønskede planter, hvilke vekster, tilfeldigvis blander seg inn i i de bevisst plantede planter. Forbindelsene oppviser riktignok plantevekstregulerende virkning før spiring, men de er imidlertid spesielt anvendbare når de anvendes som plantevekstreguleringsmidler etter spiring og som induserende middel ved frukt-løsning. Virkningen etter spiring av den aktive forbindelsen blir innenfor rammen av nærværende oppfinnelse bekreftet ved kontroll av veksten av uønskete planter. Således var det f.eks. hittil ikke mulig å gjennomføre en etterspylingskontroll av Digitaria sanguinalis med et etterspirings-herbicid. Dette lykkes imidlertid med de aktive forbindelsene ifølge nærværende oppfinnelse, da forbindelsene forsinker veksten og modningen av dette gresset sterkt, hvorved forfrøing og utbredelse av dette gress forhindres. The active compounds are particularly useful in agents for regulating plant growth, and especially the growth of grass and weeds, as well as other unwanted plants, which growths happen to interfere with the deliberately planted plants. The compounds do indeed exhibit a plant growth-regulating effect before germination, but they are, however, particularly useful when they are used as plant growth-regulating agents after germination and as an inducing agent for fruit release. The effect after germination of the active compound is confirmed within the scope of the present invention by controlling the growth of unwanted plants. Thus it was e.g. until now, it has not been possible to carry out a post-irrigation control of Digitaria sanguinalis with a post-emergence herbicide. However, this is successful with the active compounds according to the present invention, as the compounds greatly delay the growth and maturation of this grass, whereby pre-seeding and propagation of this grass is prevented.
Ved kontrollen av gressplener, og da spesielt villagressplener og industri-gressplener (f.eks. golfplasser) har det vist seg at man bør etterstrebe en maksimal forsinkelse, som viser seg ved en reduksjon av gresshøyden sammenlignet med en ubehandlet kon-trollprøve, på ca. 40 - 60 %, hvorved en forsinkelse av gress-veksten på 50% er å foretrekke. En forsinkelse av mindre enn 40% må allerede betegnes som uvirksom da den nødvendige estetiske effekt ikke visuelt kommer frem, og på grunn av at det nødvendige vedlikehold av gressplenen ikke minskes. På den annen side er en forsinkelse av veksten på mer enn 60% heller ikke ønsket da gressplenen vil gjøre et karrig inntrykk og hurtig bli bevokst med ugress og andre uønskede planter. In the control of grass lawns, and especially wild grass lawns and industrial lawns (e.g. golf courses), it has been shown that you should strive for a maximum delay, which is shown by a reduction in the height of the grass compared to an untreated control sample, of approx. . 40 - 60%, whereby a delay of grass growth of 50% is preferable. A delay of less than 40% must already be described as ineffective as the necessary aesthetic effect does not appear visually, and because the necessary maintenance of the lawn is not reduced. On the other hand, a delay in growth of more than 60% is also not desired as the lawn will make a barren impression and quickly become overgrown with weeds and other unwanted plants.
De aktive forbindelsene viser herbicid virksomhet spesielt overfor kornblomstugress, som f.eks. Matricaria Species og annet ugress, såsom Papaver rhoeas, Stellaria media og Capsella bursa pastoris. The active compounds show herbicidal activity especially against cornflower weeds, such as e.g. Matricaria Species and other weeds, such as Papaver rhoeas, Stellaria media and Capsella bursa pastoris.
Forbindelsene er spesielt aktive i og mot følgende planter: The compounds are particularly active in and against the following plants:
a) Gressarter, såsom Agropyron repens, Bromus inermis, Bromus erectus, Deschampsia flexuosa, Alopecurus pratensis, Arrhena-therum elatius, Dactylis glomerata, Festuca pratensis, Trisetum flavescens, Holcus lanatus, Lolium perenne, Poa annua, Poa neu-moralis, Festuca ovina, Festuca rubra, Festuca nigrescens, Cyno-surus cristatus, Agrostic schraderiana, Agrostis stolonifera, Phleum pratense, Phleum nodosum, Cynodon dactylon, Stenotaphrum secundatum, Paspalum notatum, Ermochloa olphiuroides og andre gress-sorter for gressplen eller ugress-sorter, sukker-rør og kornarter, såsom ris, hvete, rug, bygg, havre osv.; b) trær og busker, som f.eks. frukt-trær, såsom eple-, pære-, fersken-, kirsebær- og sitrus- såvel som kakao-, te-, kaffe-, banan-, gummi-, oliven og nøtte-trær; c) prydplanter, såsom liguster, hvitbøk, hvit seder, enebær-busker, roser, asalea, krysantemum, poinsettia, alpefioler, pyracanta, forsythia, magnolia, petunia og bromeliaceae; d) jordbrukspalnter, som f.eks. bomull, soyabønner, jord-nøtter, tobakk, lin, sukker-roer og ananas; ... — •• - --e) grønnsaksorter, såso.m-salanac"eae, (f.eks. tomater), belg-frukter, gresskar, meloner osv.; f) bær, såsom jordbær, bringebær, blåbær, bjørnebær og rips. a) Grass species, such as Agropyron repens, Bromus inermis, Bromus erectus, Deschampsia flexuosa, Alopecurus pratensis, Arrhena-therum elatius, Dactylis glomerata, Festuca pratensis, Trisetum flavescens, Holcus lanatus, Lolium perenne, Poa annua, Poa neu-moralis, Festuca ovina . and cereals, such as rice, wheat, rye, barley, oats, etc.; b) trees and shrubs, such as fruit trees, such as apple, pear, peach, cherry and citrus as well as cocoa, tea, coffee, banana, rubber, olive and nut trees; c) ornamental plants, such as privet, white beech, white cedar, juniper bushes, roses, azalea, chrysanthemum, poinsettia, alpine violets, pyracanta, forsythia, magnolia, petunia and bromeliaceae; d) agricultural plants, such as cotton, soybeans, peanuts, tobacco, flax, sugar beet and pineapple; . blackberries and currants.
Videre er disse forbindelser nyttige da de reduserer skjæringen Furthermore, these compounds are useful as they reduce shear
av vinrankene. of the vines.
For å oppnå en jevn fordeling av de aktive'forbindelser i de vekstregulerende midler ifølge oppfinnelsen, blir forbindelsen eller forbindelsene blandet med konvensjonelle, for herbicide vanlige hjelpestoffer, modifiseringsmidler, fortynningsmidler eller kondisjoneringsmidler, hvorved disse videre blir formulert til løsninger, emulsjoner, emulgerbare konsentrater, dispersjo-ner, støv, granulater eller fuktbart pudder. In order to achieve an even distribution of the active compounds in the growth-regulating agents according to the invention, the compound or compounds are mixed with conventional auxiliaries, modifiers, diluents or conditioning agents, common for herbicides, whereby these are further formulated into solutions, emulsions, emulsifiable concentrates, dispersions, dust, granules or wettable powder.
Flytende formuleringer av aktivstoffet eller aktivstoffene for direkte besprøytning kan f.eks. fremstilles som vandige løsnin-ger eller muligens som løsninger i løsningsmiddelblandinger som inneholder f.eks. aceton, metanol, dimetylformamid i forholdet 90:8:2 (Volum)volum). Liquid formulations of the active substance or active substances for direct spraying can e.g. are prepared as aqueous solutions or possibly as solutions in solvent mixtures containing e.g. acetone, methanol, dimethylformamide in the ratio 90:8:2 (Volume)volume).
Emulgerbare konsentrater, som inneholder 25 - 50% eller mer av virkestoff, avhengig av dets løselighet, kan fremstilles i egne-de løsningsmidler, f.eks. N-metylpyrrolidin, dimetylformamid osv.. Overflateaktive stoffer, som f.eks. fuktemidler, disper-geringsmidler, emulgeringsmidler osv., blir tilsatt i tilstrekkelig mengde for å oppnå en formulering med de tilsiktede karakte- Emulsifiable concentrates, which contain 25 - 50% or more of active ingredient, depending on its solubility, can be prepared in suitable solvents, e.g. N-methylpyrrolidine, dimethylformamide, etc.. Surfactants, such as e.g. wetting agents, dispersing agents, emulsifying agents, etc., are added in sufficient quantity to achieve a formulation with the intended character-
ristika. ristics.
Forskjellige anvendelsesformål av de aktive forbindelsene kan gjøres bedre for de forskjellige anvendelsesområder når man tilsetter forbindelser som forbedrer dispersjonen , adhesjonen, motstand mot regn og inntrengningén, såsom fettsyrer, voks, harpikser, fuktemidler, emulgeringsmidler, mineral- eller plan-teoljer, bindemidler osv.. På samme måte kan man utvide det bio-logiske spektrum til disse forbindelsene hhv. midlene sterkt ved tilsetning av stoffer som har baktericide, herbicide og fun-gicide egenskaper, eller,ved at man tilsetter gjødningsmidler, chelatdannende midler og andre plantevekstregulerende midler. Different applications of the active compounds can be made better for the different areas of application when adding compounds that improve dispersion, adhesion, resistance to rain and penetration, such as fatty acids, waxes, resins, wetting agents, emulsifiers, mineral or vegetable oils, binders, etc. In the same way, the biological spectrum can be extended to these compounds or the agents strongly by adding substances that have bactericidal, herbicidal and fungicidal properties, or by adding fertilisers, chelating agents and other plant growth regulating agents.
De angitte anvendelsesmengdene baserer seg på de her viste resultater og omfatter ikke så brede marginer at alle mulige tilfeller er dekket, da tallrike faktorer vil påvirke anvendelsesmengden. Eksempelvis vil mengden ikke bare variere for de forskjellige plantearter men også innenfor en bestemt art, f.eks. avhengig av faktorer, såsom plantens størrelse og alder, den spesielt anvendte forbindelse, årstiden, jordsmonnet og klimatiske betingelser ved tidspunktet for anvendelsen, såsom luft-temperatur, lysintensitet, regn og vind, Når forbindelsene eller midlene videre anvendes ved gjennombløting av marken er det nød-vendig med høyere konsentrasjoner, da plantene ved denne be-handlingsmåte indirekte behandles i motsetning til en direkte behandling eller påføring av midlet eller forbindelsen skjer på blader og stammer, f.eks. ved å besprute planten. The indicated application amounts are based on the results shown here and do not include such wide margins that all possible cases are covered, as numerous factors will affect the application amount. For example, the amount will not only vary for the different plant species but also within a specific species, e.g. depending on factors, such as the size and age of the plant, the particular compound used, the season, the soil and climatic conditions at the time of application, such as air temperature, light intensity, rain and wind. When the compounds or agents are further applied by soaking the field, it is necessary - suitable with higher concentrations, as the plants are indirectly treated with this method of treatment in contrast to a direct treatment or application of the agent or compound to leaves and stems, e.g. by spraying the plant.
Mengden av aktivstoff i plantevekstregulerende midler varierer følgelig avhengig av planten som skal kontrolleres, den nødven-dige anvendelsesmengde, anvendelsesmåte, det anvendte aktivstoffet og hvor langt kontrollen av planteveksten ønskes gjen-nomført. I alminnelighet inneholder midlene i den sprøytefer-dige formen mindre enn 50% aktivstoff. The amount of active substance in plant growth regulators therefore varies depending on the plant to be controlled, the necessary amount of application, method of application, the active substance used and how far the control of plant growth is desired. In general, the agents in the ready-to-spray form contain less than 50% active substance.
Prinsipielt er aktivstoffmengden som kommer til anvendelse slik valgt at en virkningsfull kontroll av planteveksten oppnåes. Som det f.eks. i det foregående er forklart blir ved kontrollen av gressplenen en slik mengde aktivstoff anvendt, slik at man får en forsinkelse av den normale veksthastigheten på 40 - 60%. På tilsvarende måte er valget av den minste anvendelsesmengde bestemt av den minste mengde av aktivstoff som er i stand til å bevirke en vekstforsinkelse som overensstemmer med den nedre ønskede grense. Valget av den maksimale anvendelsesmengden be-stemmes tilsvarende av den mengde aktivstoff som avstedkommer en vekstforsinkelse som overensstemmer med den ønskede øvre grense, dvs. når det gjelder gress, som anvendes som prydplen, den mengde som forhindrer at prydplénen får et karrig utseende, men som på den annen side forhindrer en for hurtig gressgroing, og slik at en uønsket klorosis (dvs. at gressplenen blir gul) ikke fåes. Når det gjelder tomatplanter er kriteriene for en virkningsfull vekstforsinkelse anderledes då en dverglignende plante, som ikke betyr tap av fruktkvalitet eller frukt-kvanti-tet, er spesielt ønsket. Parametrene for en virkningsfull vekstregulerende aktivitet for slike planter er en forsinket lengdevekst, og en forsterket eller ikke forsinket vekst til siden som minimumseffekt og forsinket lengde- og side-vekst som maksimal-effekt. Mengden av aktivstoff, som overensstemmer med disse kriterier hhv. bevirker disse kriterier, blir f.eks. når det gjelder tomatplanter bestemt under hensyn til de nevnte synspunkter. For å oppnå størst mulig virkning for vekstreguleringen etter spiring anvendes mengder på 0,5 kg til 20 kg eller mer pr. hektar. Disse mengder baserer seg på vekten av den aktive forbindelsen. På lignende måte vil den største vekstregulerende aktivitet etter spiring vanligvis være mengder som ligger mellom 1 - 15 kg eller mer aktivstoff pr. hektar. En foretrukket doseringsmengde for sprøyteløsninger ligger mellom 10 til 100.000 ppm. avhengig av plantearten som skal behandles og den forbindelse som anvendes. En spesielt foretrukket doseringsmengde ligger vanligvis mellom 100 og 20.000 ppm. In principle, the amount of active substance used is chosen in such a way that effective control of plant growth is achieved. As it e.g. as explained above, when controlling the lawn, such an amount of active substance is used, so that the normal growth rate is delayed by 40 - 60%. In a similar way, the choice of the smallest amount of use is determined by the smallest amount of active substance which is able to cause a growth delay which corresponds to the lower desired limit. The choice of the maximum amount of use is correspondingly determined by the amount of active substance that causes a growth delay that corresponds to the desired upper limit, i.e. in the case of grass, which is used as an ornamental lawn, the amount that prevents the ornamental lawn from getting a barren appearance, but which on the other hand, it prevents too rapid grass growth, and so that an unwanted chlorosis (ie the lawn turns yellow) does not occur. When it comes to tomato plants, the criteria for an effective growth delay are different as a dwarf-like plant, which does not mean a loss of fruit quality or fruit quantity, is particularly desired. The parameters for an effective growth-regulating activity for such plants are a delayed longitudinal growth, and an enhanced or not delayed lateral growth as a minimum effect and delayed longitudinal and lateral growth as a maximum effect. The amount of active substance, which complies with these criteria or causes these criteria, e.g. in the case of tomato plants determined taking into account the aforementioned views. To achieve the greatest possible effect for growth regulation after germination, quantities of 0.5 kg to 20 kg or more are used per hectares. These amounts are based on the weight of the active compound. In a similar way, the greatest growth-regulating activity after germination will usually be amounts between 1 - 15 kg or more of active substance per hectares. A preferred dosage amount for spray solutions lies between 10 to 100,000 ppm. depending on the plant species to be treated and the compound used. A particularly preferred dosage amount is usually between 100 and 20,000 ppm.
En ytterligere fordel ved anvendelsen av aktivstoffet ifølge A further advantage of the use of the active substance according to
oppfinnelsen er fravær av enhver varig effekt på plantene eller en regulerende virkning som forblir i jorden. Disse forbindelser nedbrytes langsomt og man får således en reduksjon av aktiviteten. Denne effekt har fordeler på grunn av: the invention is the absence of any lasting effect on the plants or a regulatory effect that remains in the soil. These compounds break down slowly and you thus get a reduction in activity. This effect has advantages due to:
a) at man oppnår en korttidseffekt som lar seg forlenge ved etterfølgende ytterligere behandling: b) at de normale vekstfohold til planten kommer tilbake i den utstrekning som aktiviteten avtar; og c) det blir ingen skadelige rester tilbake hverken på plante eller i jorden. a) that a short-term effect is achieved which can be extended by subsequent further treatment: b) that the normal growth conditions of the plant return to the extent that the activity decreases; and c) no harmful residues remain either on the plant or in the soil.
Varigheten av forsinkelseseffekten varierer avhengig av den anvendte forbindelse og andre faktorer, såsom den behandlede plan-teart, klimatiske betingelser osv.. The duration of the delay effect varies depending on the compound used and other factors, such as the treated plant species, climatic conditions, etc.
Selv om forbindelsene ifølge oppfinnelsen har en plantevekstregulerende og herbicid aktivitet, så er de praktisk talt ugiftige for dyr. Spaltningsproduktene, som til å begynne med er 2-keto-L-gulonsyre og til slutt karbohydrater er likeledes ugiftige. Although the compounds according to the invention have a plant growth regulating and herbicidal activity, they are practically non-toxic to animals. The cleavage products, which are initially 2-keto-L-gulonic acid and finally carbohydrates are likewise non-toxic.
Det er innlysende at ikke alle forbindelser, som omfattes av formelen II er aktive mot alle planter. Hver av de aktive forbindelsene oppviser imidlertid innenfor rammen av nærværende oppfinnelse aktivitet overfor en spesiell plante eller spesielle planter, og denne aktivitet er en funksjon av forbindelsen. Som det i det etterfølgende nærmere skal beskrives, er det en spesiell fordel med nærværende oppfinnelse at de vekstregulerende midlene ved anvendelse for behandling av forskjellige planter før og etter spiring oppviser vekstregulerende aktivitet og herbicid aktivitet. Herved er spektret av de aktuelle plantene meget bredt. Den vekstregulerende aktiviteten til de virksomme forbindelsene blir ytterligere bekreftet ved de etterfølgende mikrofor-søk for aktivitets bestemmelse etter spiring. It is obvious that not all compounds covered by formula II are active against all plants. However, within the scope of the present invention, each of the active compounds exhibits activity towards a particular plant or particular plants, and this activity is a function of the compound. As will be described in more detail below, it is a particular advantage of the present invention that the growth-regulating agents, when used for the treatment of various plants before and after germination, exhibit growth-regulating activity and herbicidal activity. This means that the spectrum of the relevant plants is very broad. The growth-regulating activity of the active compounds is further confirmed by the subsequent microexperiments for activity determination after germination.
A. Forsøk med 2, 3:4, 6- di- 0- isopropyliden- 2- keto- L- gulonsyre A. Experiments with 2, 3:4, 6-di-O-isopropylidene-2-keto-L-gulonic acid
såvel som salter og estere av denne forbindelse. as well as salts and esters of this compound.
Den vekstforsinkede virkning av foretrukne forbindelser i forbindelse med gress vises i det følgende ved drivhusforsøk, og spesielt virkningen etter spring for Digitaria sanguinalis og Poa pratensis. The growth-delayed effect of preferred compounds in connection with grass is shown below in greenhouse experiments, and in particular the effect after emergence for Digitaria sanguinalis and Poa pratensis.
Forbindelsen som skal undersøkes, oppløses i en løsningsmiddel-blanding som består av 90 volumdeler aceton, 8 volumdeler metanol og 2 volumdeler dimetylformamid. The compound to be examined is dissolved in a solvent mixture consisting of 90 parts by volume of acetone, 8 parts by volume of methanol and 2 parts by volume of dimethylformamide.
Gresset (Digitaria sanguinalis) er 10 dager gammelt og noe mindre enn 2,5 cm høyt. Også Poa pratensis ble klippet til en høyde på ca. 2,5 cm før de aktuelle forbindelsene kom til anvendelse. The grass (Digitaria sanguinalis) is 10 days old and slightly less than 2.5 cm high. Poa pratensis was also cut to a height of approx. 2.5 cm before the compounds in question were applied.
Forbindelsene ble sprøytet på gresset i en mengde på 0,5 til 8 kg/hektar. Virkningen, dvs. vekstforsinkelsen, blir bestemt ved måling av gresshøyden og gressvekten av klippet gress etter 11 til 26 dager. The compounds were sprayed onto the grass at a rate of 0.5 to 8 kg/hectare. The effect, i.e. the growth delay, is determined by measuring the grass height and grass weight of the cut grass after 11 to 26 days.
I forsøkene ble 3 standardforbindelser tatt med. som"saffBr>enlig-ningsforsøk. Maleinsyrehydrazid (6-hydroksy-3-(2H)-pyrridazinon) ble anvendt i vandig løsning, dvs. som vannløselig konsentrat (300 g/l). Dessuten anvendte man n-butyl-9-hydroksyfluoren-(9)-karboksylat, i det etterfølgende betegnet IT-3233, og metyl-2-klor-9-hydroksyfluren-(9)-karboksylat, i det følgende betegnet IT-3456, i den oven beskrevne løsningsmiddelblanding. In the experiments, 3 standard compounds were included. as a "saffron" test. Maleic hydrazide (6-hydroxy-3-(2H)-pyrridazinone) was used in aqueous solution, i.e. as a water-soluble concentrate (300 g/l). In addition, n-butyl-9-hydroxyfluorene was used -(9)-carboxylate, hereinafter designated IT-3233, and methyl 2-chloro-9-hydroxyflurene-(9)-carboxylate, hereinafter designated IT-3456, in the solvent mixture described above.
Ytterligere referanseforbindelser som kan anvendes er CCC (2-klor etyltrimetyl-ammoniumklorid), Alar (N-dimetylaminoravsyre), 2,4-D (2,4-diklorfenoksy-eddiksyre), MCPA 82-metyl-4-klorfen-oksyeddiksyre), CMPP (2-metyl-4-klorfenoksypropionsyre), ioxy-nil (3,5-dijod-4-hydroksy-benzonitril) og ethrel (2-kloretyl-fosfor-syre). Additional reference compounds that can be used are CCC (2-chloroethyltrimethylammonium chloride), Alar (N-dimethylaminosuccinic acid), 2,4-D (2,4-dichlorophenoxyacetic acid), MCPA 82-methyl-4-chlorophenoxyacetic acid), CMPP (2-methyl-4-chlorophenoxypropionic acid), ioxy-nil (3,5-diiodo-4-hydroxy-benzonitrile) and ethrel (2-chloroethyl-phosphoric acid).
Forsøksresultatene er sammenfattet i de etterfølgende tabeller The test results are summarized in the following tables
I og II. I and II.
Da løsninger i vanlige løsningsmidler ikke er spesielt egnet for praktisk anvendelse, så ble DAG og tilsvarende derivater prøvet i emulgerbare formuleringer. (25% aktivstoff, 41% xylen, 2% Atlox 3404, 2% Atlox 3403). Flere estere ble undersøkt i den nevnte løsningsmiddelblanding. Dessuten ble vandige løsninger av DAG, som innehold 1% Tween 20 (polyoksysorbitanmonostearat) As solutions in common solvents are not particularly suitable for practical use, DAG and corresponding derivatives were tested in emulsifiable formulations. (25% active substance, 41% xylene, 2% Atlox 3404, 2% Atlox 3403). Several esters were investigated in the aforementioned solvent mixture. In addition, aqueous solutions of DAG, containing 1% Tween 20 (polyoxysorbitan monostearate) were
og da enten ubuffret eller buffret ved pH 5-7, fremstilt, Vandige løsninger av salter av DAG, som likeledes inneholder Twenn 20, ble tatt med i undersøkelsen. and when either unbuffered or buffered at pH 5-7, prepared, Aqueous solutions of salts of DAG, which likewise contain Twenn 20, were included in the investigation.
Undersøkelser med hensyn til vekstforsinkelse ble utført på et plantespektrum som består av f.eks. Digitaria sanguinalis, soya-bønner og tomater, og hvorved plantene ble behandlet da de var ca. 2 uker gamle. Ved behandlingen av Digitaria sanguinalis ca. 2 cm høy, soyabønneplan.tene, ca... 5-6 cm høye med de første blader, og tomatene var 3-4 cm. høye. og med 3-4 ekte-blader. Man sprøytet enten med vandige løsninger, løsningsmiddelblandiriger-_eller emulgerbare konsentrater av aktivstoffet. Investigations with regard to growth delay were carried out on a plant spectrum consisting of e.g. Digitaria sanguinalis, soya beans and tomatoes, and with which the plants were treated when they were approx. 2 weeks old. When treating Digitaria sanguinalis approx. 2 cm high, soybean plants, about... 5-6 cm high with the first leaves, and the tomatoes were 3-4 cm. high. and with 3-4 true leaves. One sprayed either with aqueous solutions, solvent mixers or emulsifiable concentrates of the active ingredient.
Resultatene av denne undersøkelse med saltene og estrene av DAG The results of this investigation with the salts and esters of DAG
i forskjellige formuleringer er angitt i tabell III, hvor forsinkelseseffekten er angitt med tall. Bedømmelsesskalaen defineres som følger: in different formulations are indicated in table III, where the delay effect is indicated by numbers. The rating scale is defined as follows:
0 ingen synlig vekstforsinkelse 0 no visible growth retardation
1, 2, 3 - liten forsinkelse, paltene oppviser liten eller over-" - 1, 2, 3 - slight delay, the palts exhibit little or over-" -
hode ingen reduksjon av veksten av de synlige plante-delene ; head no reduction of the growth of the visible plant parts;
4, 5, 6 - Moderat vekstforsinkelse, plantene oppviser redusert 4, 5, 6 - Moderate growth delay, the plants show reduced
vekst av synbare plantedeler; growth of visible plant parts;
7, 8, 9 - kraftig forsinkelse, plantene oppviser liten eller 7, 8, 9 - strong delay, the plants show little or
eller overhode ingen vekst; or no growth at all;
10 - ingen vekst. 10 - no growth.
Forsøksdata viser at saltene og estrene av DAG er mer aktive enn maleinsyrehydrazid og referanseforbindelsen IT 3456, og da som veksthemmer etter spiring for Digitaria sanguinalis, og bare lit-mindre aktiv enn en soyabønneveksthemmer etter spiring. Experimental data show that the salts and esters of DAG are more active than maleic hydrazide and the reference compound IT 3456, and then as a post-germination growth inhibitor for Digitaria sanguinalis, and only slightly less active than a soybean growth inhibitor after germination.
Følgende tabell IV inneholder forsøksdata med hensyn til 12 forskjellige nytteplanter og ugress, hvorved plantene ble sprøy-tet da de var ca. 2 uker gamle. Fire representative estere av DAG (2,3:4,6-di-0-isopropyliden-2-keto-L-gulonsyre) ble sammenlignet med standardprøven, dvs. maleinsyrehydrazid. Man anvendte den samme bedømmelsesskalaen som i tabell III. The following table IV contains experimental data with regard to 12 different useful plants and weeds, whereby the plants were sprayed when they were approx. 2 weeks old. Four representative esters of DAG (2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid) were compared with the standard sample, i.e., maleic hydrazide. The same rating scale as in Table III was used.
Når det gjelder tomatplanter blir lengdeveksten sterkt forsinket. I stedet for dette kan man iaktta en stimulering av utvikling av sideskudd, slik at man totalt får en forgrenet, busket plante. Det er bemerkelsesverdig at hverken mengden eller kvaliteten av fruktene forandres. I tabellene III til IV tok man ved doseringen av saltene, esterne og andre analoge forbindelser samt DAG ikke hensyn til syreekvivalenten. In the case of tomato plants, length growth is greatly delayed. Instead of this, you can observe a stimulation of the development of side shoots, so that in total you get a branched, bushy plant. It is remarkable that neither the quantity nor the quality of the fruits changes. In tables III to IV, when dosing the salts, esters and other analogous compounds as well as DAG, no account was taken of the acid equivalent.
Selv om hovedanvendelsesområdet av forbindelsene ifølge oppfinnelsen er i et vekstreguleringsmiddel som anvendes etter spiring, så lar den aktive forbindelsen med formel I seg også anvende som vekstreguleringsmiddel før spiring. F. eks. blir den herbicide aktiviteten før spiring av DAG-forbindelser vist ved hjelp av n-propylesteren til DAG. Doseringen sprøytes i en doseringsmengde på 8 kg/hektar. Meget kraftiq vekstforsinkelse, (dvs. liten eller overhodet ingen vekst) for Sorghum halepense, Amaranthus sp. og Digitaria sanguinalis viser seg etter 20 og Although the main area of application of the compounds according to the invention is in a growth regulator that is used after germination, the active compound of formula I can also be used as a growth regulator before germination. For example the pre-germination herbicidal activity of DAG compounds is shown using the n-propyl ester of DAG. The dosage is sprayed in a dosage quantity of 8 kg/hectare. Very strong growth retardation, (ie little or no growth) for Sorghum halepense, Amaranthus sp. and Digitaria sanguinalis appears after 20 and
27 dager. 27 days.
Ytterligere undersøkelser av DAG og dennes salter ble utført med forskjellige gress-sorter, kornsorter, prydplanter, perennerende planter og grønnsaker. Further investigations of DAG and its salts were carried out with different grasses, cereals, ornamentals, perennials and vegetables.
Ammoniumsaltet til DAG og n-butylesteren til DAG ble undersøkt som vekstforsinkende middel på brasiliansk pepper (Schinus terebinthifolius Raddi) og sumak (Rhus spp.). Plantebladene ble sprøytet så lenge at man fikk et sammenhengende sprøytebe-legg. Som referanseforbindelse anvendte man "Maintain CF 125" The ammonium salt of DAG and the n-butyl ester of DAG were investigated as growth retarders on Brazilian pepper (Schinus terebinthifolius Raddi) and sumac (Rhus spp.). The plant leaves were sprayed for such a long time that a continuous spray coating was obtained. "Maintain CF 125" was used as a reference compound
(en blanding av metyl-2-klor-9-hydroksyfluoren-9-karboksylat, metyl-9-hydroksyfluoren-9-karboksylat og metyl-2,7-diklor-9-hyd-roksyfluoren-9-karboksylat). 4 3 dager etter sprøytingen ble minskningen hhv. uteblivelsen av lengdegroingen, bladavfall og bladenes deformasjon undersøkt. I tabell XII er resultatene angitt i tall. Bedømmelsesskalaen er følgende: (a mixture of methyl 2-chloro-9-hydroxyfluorene-9-carboxylate, methyl 9-hydroxyfluorene-9-carboxylate and methyl 2,7-dichloro-9-hydroxyfluorene-9-carboxylate). 4 3 days after spraying, the reduction was the absence of longitudinal growth, leaf waste and the deformation of the leaves investigated. In Table XII, the results are given in numbers. The rating scale is as follows:
0 - ingen effekt 0 - no effect
1 - forsinket lengdevekst 1 - delayed length growth
2 - lengdeveksten stanset 2 - length growth stopped
3 - lengdeveksten stanset og deformerte blader 3 - longitudinal growth stopped and deformed leaves
4 - fullstendig blad-avfall, nye blader er små oq deformerte. 4 - complete leaf waste, new leaves are small or deformed.
(r) (r) (s) (s)
"Trinton ^-'B-1956 er et vanndispergerbart, overf lateaktivt middel på kunstharpiksbasis, fremstilt av Rohm & Haas. "Maintain CF-125" er en blanding av metyl-2-klor-9-hydroksyfluoren-9-karboksylat, metyl-9-hydroksyfluoren-9-karboksylat og metyl-2,7-diklor-9-hydroksyfluoren-9-karboksylat. "Trinton ^-'B-1956 is a water-dispersible, resin-based surfactant manufactured by Rohm & Haas. "Maintain CF-125" is a mixture of methyl 2-chloro-9-hydroxyfluorene-9-carboxylate, methyl- 9-hydroxyfluorene-9-carboxylate and methyl 2,7-dichloro-9-hydroxyfluorene-9-carboxylate.
01je-hjelpestoffet, som kommer til anvendelse i den forannevnte formulering, er standard-petroleum som vanligvis anvendes i herbicidformuleringer, og da spesielt når herbicidet skal anvendes for behandling av trelignende planter. Denne olje under-støtter såvel inntrengningen som også hefte-evnen til aktivstoff et. "Sun Oil 11E", som er et emulgerbart og ikke fyto-toksisk s<p>ray-olje, ble anvendt i formuleringene ifølge tabell The 01je auxiliary substance, which is used in the aforementioned formulation, is standard petroleum which is usually used in herbicide formulations, and especially when the herbicide is to be used for the treatment of tree-like plants. This oil supports the penetration as well as the binding ability of the active substance. "Sun Oil 11E", which is an emulsifiable and non-phyto-toxic s<p>ray oil, was used in the formulations according to table
XII. XII.
Foretrukkede vekstregulerende, herbicide forbindelser ifølge oppfinnelsen er således det tilsvarende natrium-, kalium-, ammonium-, kalsium- og dimetylammoniumsaltet av 2,3:4,6-di-0-isopropyliden-2-keto-L-gulonsyre (DAG), såvel som de lavere alkyl- og lavere alkynylestere av DAG, og da spesielt propar-gylesteren. Preferred growth-regulating, herbicidal compounds according to the invention are thus the corresponding sodium, potassium, ammonium, calcium and dimethylammonium salt of 2,3:4,6-di-0-isopropylidene-2-keto-L-gulonic acid (DAG), as well as the lower alkyl and lower alkynyl esters of DAG, and especially the propargyl ester.
Det ble videre funnet at et vekstregulerende middel, som inneholder en av forbindelsene med den generelle formel II ved sprøyting på fruktbærende trær i betydelig grad reduserer den kraften som må anvendes for å skille frukten fra stilken. Dette viser seg ved sammenligning med ubehandlede trær. Man kunne videre slå fast at frukt, som ble høstet og som var behandlet med vekstreguleringsmidlene ifølge oppfinnelsen, var forholds-vis frie for skader og forråtnelse. It was further found that a growth regulator containing one of the compounds of the general formula II when sprayed on fruit-bearing trees significantly reduces the force that must be used to separate the fruit from the stem. This is shown by comparison with untreated trees. It could further be established that fruit, which was harvested and which had been treated with the growth regulators according to the invention, were relatively free from damage and decay.
Midlene kan påføres de fruktbærende trær i flytende eller faste-formuleringer. Påføringen kan skje over røtter, stammer, grener, blad eller frukter. F.eks. kan fruktavskillings-midler ifølge nærværende oppfinnelse påsprøytes eller påstøves trærne, eller midlene kan anbringes på jorden under trærne, slik at midlene kan absorberes av røttene. En foretrukket anvendelses-metode, som også er den mest virksomme, består i å påføre midlene i form av en vandig sprayløsning. Hvis ønsket, kan man anvende en formulering som er basert på et egnet organisk løsnings-middel som f.eks. en oljelignende sprayløsning. The agents can be applied to the fruit-bearing trees in liquid or solid formulations. The application can take place over roots, trunks, branches, leaves or fruits. E.g. fruit stripping agents according to the present invention can be sprayed or dusted on the trees, or the agents can be placed on the soil under the trees, so that the agents can be absorbed by the roots. A preferred application method, which is also the most effective, consists in applying the agents in the form of an aqueous spray solution. If desired, one can use a formulation which is based on a suitable organic solvent such as e.g. an oil-like spray solution.
For å oppnå den største virkning ved anvendelse av de normale fruktavskillingsmidler ifølge nærværende oppfinnelse, blir midlet fortrinnsvis anvendt en til to uker (avhengig av tempera-turen) før frukten høstes. I områder hvor man må kalkulere med regn, og da i tidsintervaller mellom anvendelsen av midlet og innhøstingen, blir hensiktsmessig et vanlig adhesjonsmiddel tilsatt formuleringen. Eksempler på slike adhesjonsmidler omfatter f.eks. lim, kasein, salter til alginsyre, cellulosegummi oq tilsvarende derivater, oolyvinylpyrrolidon, invertsirup,.korn-sirup osv. In order to achieve the greatest effect when using the normal fruit separation agents according to the present invention, the agent is preferably used one to two weeks (depending on the temperature) before the fruit is harvested. In areas where one has to calculate with rain, and then in time intervals between the application of the agent and the harvest, a common adhesion agent is appropriately added to the formulation. Examples of such adhesion agents include e.g. glue, casein, salts of alginic acid, cellulose gum and similar derivatives, oolyvinylpyrrolidone, invert syrup, corn syrup, etc.
Fruktavskillingsmidler inneholder som aktivstoff forbindelser med formel II. Hvis ønsket kan konvensjonelle, inerte material-er, og da slike som benyttes i jordbruket spesielt når de aktuelle midlene tjener til å behandle trær eller når de anvendes i forbindelse med aktivstoffer i kjente fruktavskillingsmidler, tilsettes. Slike hjelpestoffer omfatter f.eks. også overflateaktive forbindelser, bærestoffer, adhesjonsmidler, stabiliser-ingsmidler osv. Fruit separating agents contain compounds of formula II as active ingredients. If desired, conventional, inert materials, such as are used in agriculture in particular when the agents in question serve to treat trees or when they are used in conjunction with active substances in known fruit separation agents, can be added. Such excipients include e.g. also surface-active compounds, carriers, adhesion agents, stabilizers, etc.
Konsentrasjonen av aktivstoff med den generelle formel II i de nye fruktavskillingsmidlene varierer, men for å oppnå en optimal virkning er det nødvendig at en tilstrekkelig mengde kommer til anvendelse. Således inneholder en vandig sprøyteløsning fra ca. 0,05 vekts-% til ca. 1,5 vekts-% aktivstoff. Konsentrasjonen varierer naturligvis avhengig av fruktsorten og treets eller buskens størrelse. Doseringsmengden er den som virkelig letter høstingen. Når det gjelder sprøyteløsninger blir den vandige løsningen, som inneholder fruktavskillingsmidlet, sprøytet på en slik måte at treet blir belagt med et heldekkende sprøytebelegg. Dette betinger anvendelsen av ca. 3000 til ca. 9000 liter av en fortynnet løsning (ca. 0,1-1 vekts-% aktivstoff) pr. hektar, The concentration of active substance with the general formula II in the new fruit separation agents varies, but in order to achieve an optimal effect, it is necessary that a sufficient amount is used. Thus, an aqueous spray solution contains from approx. 0.05% by weight to approx. 1.5% by weight of active substance. The concentration naturally varies depending on the type of fruit and the size of the tree or bush. The dosing amount is what really facilitates harvesting. In the case of spray solutions, the aqueous solution, which contains the fruit separating agent, is sprayed in such a way that the tree is coated with a full coverage spray coating. This requires the use of approx. 3000 to approx. 9,000 liters of a diluted solution (approx. 0.1-1% by weight of active substance) per hectares,
og da avhengig av antallet og størrelsen av trærne som skal behandles . and then depending on the number and size of the trees to be treated.
For fremstilling av en foretrukket sprøyte-formulering som inneholder fruktavskillingsmidler blir aktivstoffet eller et salt derav dispergert eller løst i et bærestoff, såsom vann. Den flytende sprøyteløsningen kan tilsettes 0,1 til ca. 0,5 vekts-% overflateaktivt stoff beregnet på bærematerialets vekt. Typiske overf lateaktive stoffer er "Triton^5t-B. 1956" , dvs. et vanndispergerbart og på harpiksbasis oppbygget overflateaktivt middel, og som er fremstilt av Rohm & Haas. Videre kan "X-77 (Chevron-Ortho)", et ikke-ionisk overflateaktivt middel som inneholder For the preparation of a preferred spray formulation containing fruit release agents, the active substance or a salt thereof is dispersed or dissolved in a carrier, such as water. The liquid spray solution can be added 0.1 to approx. 0.5% by weight surfactant calculated on the weight of the carrier material. Typical surface-active substances are "Triton^5t-B. 1956", i.e. a water-dispersible and resin-based surface-active agent, which is produced by Rohm & Haas. Furthermore, "X-77 (Chevron-Ortho)", a non-ionic surfactant containing
som grunnsubstans alkylaryl-polyoksyetylenglykoler, frie fett- - syrer og isopropanol, fremstilles. as basic substances alkylaryl polyoxyethylene glycols, free fatty acids and isopropanol are produced.
Frukt-avskillingsmidlene bevirker avskilling av fruktene fra et utall av frukt-trær. Typiske frukter av denne art er f.eks. appelsiner, grapefrukt, oliven, epler, kirsebær osv. De virker også på andre nytteplanter som f.eks. bomull og soyabønner (her får man bladavfall). The fruit-separating agents effect the separation of the fruits from a multitude of fruit trees. Typical fruits of this species are e.g. oranges, grapefruit, olives, apples, cherries, etc. They also work on other useful plants such as e.g. cotton and soybeans (you get leaf waste here).
Som allerede nevnt sprøyter man fruktavskillingsmidlet på trærne i form av vandige løsninger. 1 dette henseende omfatter også oppfinnelsen på tilsvarende måte ekvivalente mengder av vannløselige salter av forbindelser med formel II. Slike salter omfatter f.eks. ammoniumsaltet osv. I de tilfeller hvor de anvendte forbindelsene er vannuløselige blir emulgerbare kons-entrater eller fuktbare pulverformuleringer av aktivstoffet fremstilt, hvilke kan dispergeres i vann og således danne sprøyteløsning. As already mentioned, the fruit separation agent is sprayed on the trees in the form of aqueous solutions. 1 in this respect, the invention also covers equivalent amounts of water-soluble salts of compounds of formula II in a similar manner. Such salts include e.g. the ammonium salt, etc. In cases where the compounds used are water-insoluble, emulsifiable concentrates or wettable powder formulations of the active substance are prepared, which can be dispersed in water and thus form a spray solution.
Fuktbart pulver fremstilles ved at man anvender et inert fortynningsmiddel, f.eks. kaolin. En typisk sprøyteløsning som er formulert med et fuktbart pulver inneholder f.eks. aktivstoffet, ca. 1 - 5% inert fortynningsmiddel, mindre mengder dispergerinqs-middel, fuktemiddel og antiskummiddel og den tilsvarende og nød-vendige mengde vann. Wettable powder is produced by using an inert diluent, e.g. kaolin. A typical spray solution that is formulated with a wettable powder contains e.g. the active substance, approx. 1 - 5% inert diluent, smaller amounts of dispersing agent, wetting agent and antifoam agent and the corresponding and necessary amount of water.
Da appelsiner kan betraktes som typiske frukter som blir lettere å høste ved behandling med. kjemiske fruktavskillingsmidler, så blir virkningen av de nye fruktavskillingsmidlene illustrert ved hjelp av appelsintrær. As oranges can be considered typical fruits that are easier to harvest when treated with chemical fruit peelers, then the effect of the new fruit peelers is illustrated using orange trees.
Natriumsaltet av 2 ,3 :.4 , 5-di-0-isopropyliden-2-keto-L-gulonsyre undersøkes som fruktavskillingsmiddel på sitrusfrukter, f.eks.. appelsiner. Vandige løsninger som inneholder-0,05> vekts-% 0,1, 0,25, 0,5 og 1,0 vekts-% av dette natriumsalt og 0,5% "Triton B-1956" fremstilles. Disse løsninger s<p>røytes på Valencia-appelsiner, kjerneløse sumpgra<p>efrukt- og røde grapefrukt- trær. En uke etter sprøytingen er den eneste iakttag-bare effekt et lett bladavfall hos de trær som ble behandlet med en høyere dosemengde. To uker etter sprøytingen er de fleste appelsin- og grapefrukt-frukter falt av hos de trær som ble behandlet med en dosemengde på minst 1%. Trær som ble behandlet med en dose på 0,5% hadde kvittet seg med ca. halvdelen av fruktene, og de gjenværende fruktene hang meget løst. The sodium salt of 2,3:.4,5-di-0-isopropylidene-2-keto-L-gulonic acid is being investigated as a fruit peeling agent on citrus fruits, e.g. oranges. Aqueous solutions containing -0.05% by weight 0.1, 0.25, 0.5 and 1.0% by weight of this sodium salt and 0.5% "Triton B-1956" are prepared. These solutions are applied to Valencia oranges, seedless swamp grapefruit and red grapefruit trees. One week after spraying, the only observable effect is a slight leaf drop in the trees treated with a higher dose. Two weeks after spraying, most orange and grapefruit fruits have fallen off in the trees that were treated with a dosage of at least 1%. Trees treated with a dose of 0.5% had got rid of approx. half of the fruits, and the remaining fruits hung very loosely.
I tillegg til fruktavskillingseffekten viste fruktene også en tydelig forsterkning av fargen, f.eks. en betydelig dypere og mørkere farge enn de ubehandlede fruktene. In addition to the fruit separation effect, the fruits also showed a clear strengthening of the colour, e.g. a significantly deeper and darker color than the untreated fruits.
Sukkerinnholdet og det totale faststoffinnholdet i de behandlede fruktene hadde sammenlignet med de ubehandlede fruktene likeledes økt. The sugar content and the total solids content of the treated fruits had also increased compared to the untreated fruits.
Lignende resultater ble oppnådd ved sprøyting av f.eks. ammoniumsaltet eller dietylammoniumsaltet eller n-butylesteren av 2,3:4,6-di-0-isopropyliden-2-keto-L-gulonsyre. Similar results were obtained by spraying e.g. the ammonium salt or the diethylammonium salt or the n-butyl ester of 2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid.
Anvendt som fruktavskillingsmiddel eller som herbicid etter eller før spiring, dvs. så snart forbindelsene anvendes som plantevekstreguleringsmidler, så kan forbindelsene med formel II fremstilles og formuleres slik som det er beskrevet i det foranstående og i det etterfølgende. Used as a fruit separating agent or as a herbicide after or before germination, i.e. as soon as the compounds are used as plant growth regulators, the compounds of formula II can be prepared and formulated as described above and below.
2,3:4,6-di-0-isopropyliden-2-keto-L-gulonsyre-monohydrat er et kjent handelspreparat og er et mellomprodukt ved fremstil-lingen av L-askorbinsyre (Chemical Abstracts Al_ (1953) 10643 e) . Den blir fremstilt ved oksydasjon av diaceton-L-sorbofuranose i alkalisk eller nøytralt medium. Diaceton-L-sorbofuranose fremstilles ved omsetning av L-sorbose med aceton i nærvær av en sterk syre. 2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid monohydrate is a known commercial preparation and is an intermediate product in the production of L-ascorbic acid (Chemical Abstracts Al_ (1953) 10643 e). It is produced by oxidation of diacetone-L-sorbofuranose in an alkaline or neutral medium. Diacetone-L-sorbofuranose is produced by reacting L-sorbose with acetone in the presence of a strong acid.
De nye forbindelsene kan fremstilles ved at man The new compounds can be produced by
a) i nærvær av en base omsetter en syre med den generelle formel a) in the presence of a base reacts an acid with the general formula
hvor R^, R'2, R' og R'4 har den i formel I angitte where R^, R'2, R' and R'4 have that in formula I indicated
betydning, importance,
med en forbindelse med den generelle formel with a compound of the general formula
hvor X betyr klor, brom eller p-toluensulfonsyreester og hvor where X means chlorine, bromine or p-toluenesulfonic acid ester and where
R5 betyr rettkjedet eller forgrenet alkyl, alkenyl eller alkynyl med opptil 20 karbonatomer eller halogen-lavere alkyl, R5 means straight-chain or branched alkyl, alkenyl or alkynyl with up to 20 carbon atoms or halogen-lower alkyl,
eller or
b) i det tilfelle hvor en forbindelse med formel II tilsiktes hvor n betyr tallet 2, omsetter man i nærvær av en base en b) in the case where a compound of formula II is intended where n means the number 2, one reacts in the presence of a base a
syre med formel V med en forbindelse med den generelle formel acid of formula V with a compound of the general formula
hvor X.^ og X betyr klor, brom eller jod og R,, lavere alkvlen, where X.^ and X mean chlorine, bromine or iodine and R,, lower alkvlen,
eller or
c) i det tilfelle hvor en forbindelse med formel II tilsiktes, og hvor n betyr tallet 2, omsetter et med formel V tilsvarende c) in the case where a compound of formula II is intended, and where n means the number 2, one of formula V reacts correspondingly
syrehalogenid med en diol med den generelle formel acid halide with a diol of the general formula
hvor Rg har den i formelen VII angitte betydning, where Rg has the meaning given in formula VII,
eller or
d) i det tilfelle hvor et salt med formel II tilsiktes, og hvor n betyr tallet 1 og R' ammonium; ammonium substituert med d) in the case where a salt of formula II is intended, and where n means the number 1 and R' ammonium; ammonium substituted with
ett eller flere lavere alkyl, lavere alkenyl eller hydroksy-lavere alkyl, bringer en syre med den generelle formel V i kontakt med en forbindelse med den generelle formel one or more lower alkyl, lower alkenyl or hydroxy-lower alkyl brings an acid of the general formula V into contact with a compound of the general formula
hvor i Rg og Rg betyr hydrogen, lavere alkyl, where in Rg and Rg means hydrogen, lower alkyl,
lavere alkenyl eller hydroksy-lavere alkyl, lower alkenyl or hydroxy-lower alkyl,
eller når n betyr 2, med kalsiumhydroksyd eller magnesium-hydroksyd. or when n means 2, with calcium hydroxide or magnesium hydroxide.
Saltene av DAG fremstilles på vanlig måte. For dette formål blir DAG under kraftig omrøring tilsatt til en vandig oppløs-ning av en base ved romtemperatur. Ved denne arbeidsprosess holdes løsningen ved en pH-verdi over 7. Etter endt reaksjon blir overskudd av vann fjernet i høyvakuum. Vannfritt aceton (ca. 10 volumdeler) blir deretter tilsatt til den erholdte sirup og omrørt over natten. Det hvite krystallinske bunn-fallet, som danner seg, filtreres, vaskes med aceton og tørkes. I tilfelle av ikke flyktige baser tilsettes ekvivalente mengder syrer. Hvis flyktige baser anvendes, som f.eks. ammoniumhydrok-syd eller dimetylamin, så anvendes et overskudd av base og det benyttede overskuddet dampes deretter bort i vakuum. Da DAG under de vanlige forestringsbetingelser, som f.eks. ved for-estring ifølge Fischer, ikke er stabil, så fremstiller man de nye estere av DAG ved omsetning av f.eks. de tilsvarende lavere alkyl-, lavere alkenyl- eller lavere alkinylhalogenider under basiske betingelser ved romtemperatur, og ved at man anvender inerte organiske løsningsmidler, såsom dimetylformamid (Df'?F) . Esterne er uløselige i vann men løseliae i metanol, aceton, etanol, kloroform, pentan, benzen, eter osv. The salts of DAG are prepared in the usual way. For this purpose, DAG is added under vigorous stirring to an aqueous solution of a base at room temperature. In this work process, the solution is kept at a pH value above 7. After the reaction is finished, excess water is removed in a high vacuum. Anhydrous acetone (about 10 parts by volume) is then added to the syrup obtained and stirred overnight. The white crystalline precipitate that forms is filtered, washed with acetone and dried. In the case of non-volatile bases, equivalent amounts of acids are added. If volatile bases are used, such as ammonium hydroxide or dimethylamine, then an excess of base is used and the used excess is then evaporated away in a vacuum. Then DAG under the usual esterification conditions, such as e.g. in the case of esterification according to Fischer, is not stable, then the new esters of DAG are produced by reacting e.g. the corresponding lower alkyl, lower alkenyl or lower alkynyl halides under basic conditions at room temperature, and by using inert organic solvents, such as dimethylformamide (Df'?F). The esters are insoluble in water but soluble in methanol, acetone, ethanol, chloroform, pentane, benzene, ether, etc.
Videre kan man bringe en syre med formel V til reaksjon med Furthermore, an acid of formula V can be brought into reaction with
en alkohol med formel IX ved at man bringer disse reaktantene til reaksjon i nærvær av en ekvimolar mengde dicykloheksylkar-bodiimid i et inert organisk løsningemiddel. Foretrukkede løsningsmidler er metylenklorid, dimetylformamid, eter, tetra-hydrofuran eller etylacetat (sml. også Tetrahedron 21, 3531 an alcohol of formula IX by reacting these reactants in the presence of an equimolar amount of dicyclohexylcarbodiimide in an inert organic solvent. Preferred solvents are methylene chloride, dimethylformamide, ether, tetrahydrofuran or ethyl acetate (see also Tetrahedron 21, 3531
(1965)). (1965)).
Løsninger som består av et løsningsmiddel og en forbindelse ifølge oppfinnelsen er riktignok egnet for drivhusforsøk, men er imidlertid ikke egnet for feltforsøk. Fuktbart pulver er likeledes ikke generelt anvendbart da DAG-derivatene må opp-løses for at de skal kunne utfolde den nødvendige aktivitet. Solutions consisting of a solvent and a compound according to the invention are indeed suitable for greenhouse experiments, but are not, however, suitable for field experiments. Wettable powders are likewise not generally applicable as the DAG derivatives must be dissolved in order for them to be able to display the necessary activity.
Saltene er vannløselige og behøver ingen spesiell formulerina. The salts are water-soluble and do not require a special formulation.
DAG-esteren formuleres som emulgerbart konsentrat nå xylen-basis, som deretter blandes med vann. Av disse konsentrater kan man fremstille emulsjoner som inneholder 25 til 50 vekts-%. Typiske emulgerbare, konsentrater er for DAG-esteren angitt i det følgende. The DAG ester is formulated as an emulsifiable concentrate on a xylene base, which is then mixed with water. Emulsions containing 25 to 50% by weight can be prepared from these concentrates. Typical emulsifiable concentrates for the DAG ester are given below.
"Atlox 3403" er en blanding av polyoksyetylenetere, polyoksy-etylenglycerol og alkylarylsulfonat. "Atlox 3403" is a mixture of polyoxyethylene ethers, polyoxyethylene glycerol and alkylaryl sulfonate.
"Atlox 3404" er en blanding av polyoksyetylen-alkylaryleter og et alkylarylsulfonat. "Atlox 3404" is a mixture of polyoxyethylene alkyl aryl ether and an alkyl aryl sulfonate.
"Emulphor EL 620" er en polyetylisert nlanteolje. "Emulphor EL 620" is a polyethylated oil.
"Drewmulse GMC-8 er monoglyceridet til en laveremolekylær, mettet kokosnøttfettsyre. "Drewmulse GMC-8 is the monoglyceride of a lower molecular weight saturated coconut fatty acid.
I en ytterligere form tilsettes til en vandig løsning av 2,3:4,6-di-O-isopropyliden-2-keto-L-gulonsyre under omrøring en ekvimolar mengde dietanolamin. Man erholder en klar løsning, hvor pH innstilles på 8 ved at man tilsetter dråpevis dietanolamin. In a further form, an equimolar amount of diethanolamine is added to an aqueous solution of 2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid with stirring. A clear solution is obtained, the pH of which is set to 8 by adding diethanolamine drop by drop.
I en ytterligere form tilsettes under omrøring til en vandig løs-ning av 2,3:4,6-di-O-isopropyliden-2-keto-L-gulonsyre ammoniakk (25% ekvimolekylær mengde). Man erholder en klar løsning hvis pH innstilles på 8 ved at man tilsetter dråpevis ammoniakk (25%). In a further form, ammonia (25% equimolecular amount) is added while stirring to an aqueous solution of 2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid. A clear solution is obtained if the pH is set to 8 by adding ammonia (25%) drop by drop.
Forbindelsene med formel II, hvor R'^, R'2/ R'3 og R'^ har en annen betydning enn metyl, viser likeledes vekstregulerende virkning før og etter spiring. F.eks. forhindrer 2,3:4,6-di-0-butyliden-2-keto-L-gulonsyre i en doseringsmenqde på 8 kg/ hektar som vekstregulerende middel før spiring veksten av Amaranthus sp. fullstendig etter 2 0 dager, og som vekstregulerende middel etter spiring bevirker den nevnte syre en sterk reduksjon i veksten av røde bønner. 2,3:4,6-di-O-(3-pentyliden)-2-keto-L-qulonsyre avstedkommer i en doseringsmenqde oå 8 kg/ hektar som vekst-reguleringsmiddel etter spiring krafiq vekstforsinkelse for Amaranthus sp., Brassita kaber, Ipomoea sp. The compounds of formula II, where R'^, R'2/R'3 and R'^ have a meaning other than methyl, likewise show growth-regulating action before and after germination. E.g. prevents 2,3:4,6-di-0-butylidene-2-keto-L-gulonic acid in a dosage amount of 8 kg/hectare as a growth regulator before germination the growth of Amaranthus sp. completely after 20 days, and as a growth regulator after germination, the aforementioned acid causes a strong reduction in the growth of red beans. 2,3:4,6-di-O-(3-pentylidene)-2-keto-L-quolic acid is produced in a dosage amount of up to 8 kg/hectare as a growth regulator after germination due to growth delay for Amaranthus sp., Brassita kaber, Ipomoea sp.
og røde bønner. and red beans.
Forbindelser hvor 4,6-0-isopropylidengruppen er erstattet med Compounds where the 4,6-0-isopropylidene group is replaced by
en annen gruppe fremstilles ved hjelp av den såkalte "ketal-utvekslings-reaksjon". For dette formål oppløses DAG i ønsket keton, aldehyd, ketal og acetal og en syrekatalysator tilsettes. Disse forbindelser lar seg også fremstilles ved at man anvender en lignende ketal-utvekslings-reaksjon, hvorved man som utqanqs-materiale anvender 2,3:4,6-di-O-isopropyliden-a-L-sorbofuranose og ved at man oksyderer det erholdte produkt. another group is produced using the so-called "ketal exchange reaction". For this purpose, DAG is dissolved in the desired ketone, aldehyde, ketal and acetal and an acid catalyst is added. These compounds can also be prepared by using a similar ketal exchange reaction, whereby 2,3:4,6-di-O-isopropylidene-α-L-sorbofuranose is used as starting material and by oxidizing the product obtained .
Eksempler på ketoner og aldehyder som kan anvendes ved den preparative fremgangsmåten er de med den generelle formel R^g- C<*-> R-]^' hvor R^Q f.eks. betyr metyl eller etyl, og R.... betyr metyl eller etyl. Typiske forbindelser av denne type er f.eks. dietylketon eller metyletylketon. Ketoner hvor begae restene R^q oq R^ er like store viser seg som ikke særlig qun-stige da disse restene er sterisk hemmet ved reaksjonen. Ved å anvende et usymmetrisk aldehyd eller keton vil etter reaksjons-forløpet den voluminøse resten befinne seg i "Exo"-stilling (R'^ i formel II), og er ansvarlig for et nytt asymmetrisentrum. Examples of ketones and aldehydes that can be used in the preparative method are those with the general formula R^g-C<*-> R-]^' where R^Q e.g. means methyl or ethyl, and R.... means methyl or ethyl. Typical compounds of this type are e.g. diethyl ketone or methyl ethyl ketone. Ketones where the two residues R^q and R^ are of equal size do not appear to be particularly qun-rising as these residues are sterically inhibited during the reaction. By using an unsymmetrical aldehyde or ketone, after the course of the reaction the bulky residue will be in the "Exo" position (R'^ in formula II), and is responsible for a new center of asymmetry.
Enhver sterk syre kan anvendes som katalysator. En foretrukket katalysator er perklorsyre. Ytterligere eksempler på slike syrer er svovelsyre, klorhydrogensyre, p<->toluensulfonsyre, metan- Any strong acid can be used as a catalyst. A preferred catalyst is perchloric acid. Further examples of such acids are sulfuric acid, hydrochloric acid, p<->toluenesulfonic acid, methane-
sulfonsyre og trifluormetansulfonsyre. sulfonic acid and trifluoromethanesulfonic acid.
Et foretrukket temperaturområde for, denne reaksjon ligger mellom ca. -20° og ca. 50°, hvorved området mellom 20° og 30° (romtemperatur) er spesielt foretrukket. Spaltningspunktet for DAG er samtidig den øvre grense hvortil reaksjonsblandingen kan oppvarmes. Av denne grunn blir reaks jonsblandingen:.-ikke opp-varmet over 100°C. A preferred temperature range for this reaction is between approx. -20° and approx. 50°, whereby the range between 20° and 30° (room temperature) is particularly preferred. The cleavage point for DAG is also the upper limit to which the reaction mixture can be heated. For this reason, the reaction mixture is not heated above 100°C.
Forbindelser i hvilke begge isopronylidengrunnene er erstattet " med andre grupper fremstilles ved å utgå fra sorbose ved at man følger de av Reichstein og Griissner, Heiv. Chim.Acta, 17, 311 Compounds in which both isopronylidene bases are replaced by other groups are prepared starting from sorbose by following those of Reichstein and Griissner, Heiv. Chim. Acta, 17, 311
(1934) angitte betingelser. Ved denne metode omsettes, et eanet keton eller et egnet aldehyd med L-sorbose i nærvær av en sterk"""" ~-syre som katalysator, f.eks. svovelsyre, ved romtemperatur eller under romtemperatur. Deretter blir det således erholdte mellom-produktet oksydert i alkalisk eller nøytralt reaksjonsmiljø. (1934) specified conditions. In this method, an ene ketone or a suitable aldehyde is reacted with L-sorbose in the presence of a strong """" ~-acid as a catalyst, e.g. sulfuric acid, at or below room temperature. The intermediate product thus obtained is then oxidized in an alkaline or neutral reaction environment.
Ved fremstilling av di-O-alkyliden-sorbofuranose anvendes fortrinnsvis som sur katalysator perklorsyre, klorhydrogensyre, p-toluensulfonsyre osv., hvorved svovelsyre er spesielt foretrukket. In the production of di-O-alkylidene sorbofuranose, perchloric acid, hydrochloric acid, p-toluenesulfonic acid etc. are preferably used as acid catalysts, whereby sulfuric acid is particularly preferred.
Da reaksjonen forløper eksotermt arbeides det ved romtemperatur eller under romtemperatur,, hvorved et spesielt foretrukket temperaturområde ligger mellom ca. 0° og ca. -20°. As the reaction proceeds exothermically, work is carried out at room temperature or below room temperature, whereby a particularly preferred temperature range is between approx. 0° and approx. -20°.
Ved den etterfølgende fremstilling av syren av sorbofuranose-mellomproduktet utføres oksydasjonen i nøytralt eller alkalisk miljø og herved anvendes oksydasjonsmidler, såsom natrium-permanganat, kaliumbikromat, kaliumpermanganat/kaliumhydroksyd og natriumhypokloritt/Ni<++>. De to sistnevnte oksydasjonsmidlene foretrekkes. Oksydasjonen kan også utføres katalytisk ved at man anvender palladium eller platina og oksygen. In the subsequent preparation of the acid from the sorbofuranose intermediate, the oxidation is carried out in a neutral or alkaline environment and thereby oxidizing agents are used, such as sodium permanganate, potassium bichromate, potassium permanganate/potassium hydroxide and sodium hypochlorite/Ni<++>. The two latter oxidizing agents are preferred. The oxidation can also be carried out catalytically by using palladium or platinum and oxygen.
Et egnet temperaturområde ligger mellom romtemperatur oa 100°, hvorved området mellom ca. 50° og ca. 60° er foretrukket. A suitable temperature range is between room temperature and 100°, whereby the range between approx. 50° and approx. 60° is preferred.
Etterfølgende eksempler skal anskueliggjøre oppfinnelsen. The following examples shall illustrate the invention.
EKSEMPEL 1 EXAMPLE 1
Etyl- 2, 3:4, 6- di- Q- isopropvliden- 2- keto- L- gulonat. Ethyl- 2, 3:4, 6- di- Q- isopropvlidene- 2- keto- L- gulonate.
Til en oppløsning av 100 g vannfritt kaliumkarbonat i 946 ml dimetylformamid tilsettes under omrøring ved romtemperatur 292,2 g 2,3:4,6-di-0-isopropyliden-2-keto-L-gulonsyre-monohydrat (DAG-monohydrat) og deretter 205 g etyljodid. Omrør-ingen fortsettes 2 4 timer ved romtemperatur. Blandingen filtreres så for å fjerne uorganiske salter og dimetylformamidet fjernes ved destillasjon i vakuum (ca. 60°C og ca. 10 mmHg). Det tilsettes 200 ml aceton for å oppløse den tilbakeblivende eteren. Uoppløste uorganiske salter filtreres fra. Filterkaken vaskes ut med 100 ml aceton. Filtratet tilsettes løs-ningen som inneholder esteren og råproduktet isoleres ved vakuumdestillasjon av løsningsmidlet inntil en mengde på ca. 500 ml og etterfølgende avkjøling av denne løsningen til 5°. Råproduktet omkrystalliseres i metanol eller metanol/aceton To a solution of 100 g of anhydrous potassium carbonate in 946 ml of dimethylformamide, 292.2 g of 2,3:4,6-di-0-isopropylidene-2-keto-L-gulonic acid monohydrate (DAG monohydrate) and then 205 g of ethyl iodide. Stirring is continued for 2 4 hours at room temperature. The mixture is then filtered to remove inorganic salts and the dimethylformamide is removed by distillation in vacuum (approx. 60°C and approx. 10 mmHg). 200 ml of acetone are added to dissolve the remaining ether. Undissolved inorganic salts are filtered off. The filter cake is washed out with 100 ml of acetone. The filtrate is added to the solution containing the ester and the crude product is isolated by vacuum distillation of the solvent up to an amount of approx. 500 ml and subsequent cooling of this solution to 5°. The crude product is recrystallized in methanol or methanol/acetone
og man erholder 284 g etyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, flytetemperatur: 99 - 100,5°C. and 284 g of ethyl 2,3:4,6-di-0-isopropylidene-2-keto-L-gulonate are obtained, pour temperature: 99 - 100.5°C.
Ifølge denne vanligvis anvendbare forskrift blir, According to this generally applicable regulation,
ved å gå ut fra 2,3:4,6-di-0-isopropyliden-2-keto-L-gulonsyre og 1,2-dibrometan i et molforhold på 2:1 av bis-esteren: bis-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat-etylenglykol-esteren fremstilt. starting from 2,3:4,6-di-0-isopropylidene-2-keto-L-gulonic acid and 1,2-dibromoethane in a molar ratio of 2:1 of the bis-ester: bis-2,3: The 4,6-di-O-isopropylidene-2-keto-L-gulonate ethylene glycol ester prepd.
EKSEMPEL 2 EXAMPLE 2
n- butyl- 2, 3:4, 6- di- 0- isopropyliden- 2- keto- L- gulonat Under omrøring blir en suspensjon av 100 g vannfritt kaliumkarbonat i 946 ml dimetylformamid tilsatt 2,3:4,6-di-0-isopropyliden-2-keto-L-gulonsyre-monohydrat (292,2 g) og deretter 197 g n-butyljodid. Blandingen røres 48 timer ved romtemperatur, filtreres deretter fra og etterfølgende fjerning av de uorganiske saltene. Dimetylformamidet fjernes ved vakuumdestillasjon. Til resten tilsettes 200 ml aceton og fremdeles tilstedeværende uorganiske salter filtreres fra. Filterkaken vaskes med 100 ml aceton. Filtratet forenes med esterløsningen og konsentreres i vakuum. Omkrystallisasjon av resten i metanol-aceton gir 172 g fargeløse krystaller av n-butyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, med et smeltepunkt på 53,9 - 56,8°C. n- butyl- 2, 3:4, 6- di- 0- isopropylidene- 2- keto- L-gulonate While stirring, a suspension of 100 g of anhydrous potassium carbonate in 946 ml of dimethylformamide is added to 2,3:4,6-di- O-isopropylidene-2-keto-L-gulonic acid monohydrate (292.2 g) and then 197 g of n-butyl iodide. The mixture is stirred for 48 hours at room temperature, then filtered and subsequent removal of the inorganic salts. The dimethylformamide is removed by vacuum distillation. 200 ml of acetone is added to the residue and any inorganic salts still present are filtered off. The filter cake is washed with 100 ml of acetone. The filtrate is combined with the ester solution and concentrated in vacuo. Recrystallization of the residue in methanol-acetone gives 172 g of colorless crystals of n-butyl-2,3:4,6-di-0-isopropylidene-2-keto-L-gulonate, with a melting point of 53.9 - 56.8 °C.
EKSEMPEL 3 EXAMPLE 3
n- propyl- 2, 3:4, 6- di- 0- isopropyliden- 2- keto- L- gulonat n-propyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat fremstilles analogt arbeidsforskriftene i eksemplene 1 og 2, hvorved man anvender 200 g 1-brompropan som halogenid. Utbytte 150,6 g, smeltepunkt 80 - 81°C. n- propyl- 2, 3:4, 6- di- 0- isopropylidene- 2- keto- L-gulonate n- propyl-2,3:4,6-di- 0-isopropylidene-2-keto-L-gulonate is prepared analogously to the work regulations in examples 1 and 2, whereby 200 g of 1-bromopropane is used as halide. Yield 150.6 g, melting point 80 - 81°C.
EKSEMPEL 4 EXAMPLE 4
n- pentyl- 2, 3:4, 6- di- 0- isopropyliden- 2- keto- L- gulonat n-pentyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulGnat fremstilles analogt arbeidsforskriftene i eksemplene 1 og 2, hvorved man anvender 300 g 1-brompentan som halogenid. n-pentyl-2,3:4,6-di-0-isopropylidene-2-keto-L-gulonate n-pentyl-2,3:4,6-di-0-isopropylidene-2-keto-L-gulGnate is prepared analogously to the work regulations in examples 1 and 2, whereby 300 g of 1-bromopentane is used as halide.
Utbytte 503 g; kokepunkt 195°C/0,5 mmHg. Yield 503 g; boiling point 195°C/0.5 mmHg.
EKSEMPEL 5 EXAMPLE 5
n- dodecyl- 2, 3:4, 6- di- 0- isopropyliden- 2- keto- L- gulonat N-dodecyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat fremstilles analogt arbeidsforskriftene i eksemplene 1 og 2, utbytte 75 g, etter to omkrystallisasjoner i etanol; smp. 10,5°C. n-dodecyl-2,3:4,6-di-0-isopropylidene-2-keto-L-gulonate N-dodecyl-2,3:4,6-di-0-isopropylidene-2-keto-L-gulonate prepared analogously to the work regulations in examples 1 and 2, yield 75 g, after two recrystallizations in ethanol; m.p. 10.5°C.
EKSEMPEL 6 EXAMPLE 6
Isopropyl- 2 , 3:4, 6- di- O— isopropyliden- 2- keto- L-. gulonat Isopropyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat fremstilles analogt arbeidsforskriftene i eksemplene 1 og 2, hvorved man anvender 250 g 2-brompropan. Utbytte 116,8 g, smp. 107,5 - 109°C. Isopropyl- 2 , 3:4, 6- di- O— isopropylidene- 2- keto- L-. gulonate Isopropyl-2,3:4,6-di-0-isopropylidene-2-keto-L-gulonate is prepared analogously to the working instructions in examples 1 and 2, whereby 250 g of 2-bromopropane is used. Yield 116.8 g, m.p. 107.5 - 109°C.
På lignende måte kan videre rettkjedete og forgrenete, ali-fatiske hydrokarbyl og halogen-lavere alkyl-estere fremstilles. In a similar manner, further straight-chain and branched, aliphatic hydrocarbyl and halogen-lower alkyl esters can be prepared.
EKSEMPEL 7 EXAMPLE 7
Natrium- 2, 3- 0- isopropyliden- 4, 6- 0- etyliden- 2- keto- L- gulonat Sodium- 2, 3- 0- isopropylidene- 4, 6- 0- ethylidene- 2- keto- L-gulonate
48 g 2,3:4,6-di-0-isopropyliden-2-keto-L-gulonsyre (DAG) opp-løses i 250 g paraldehyd. Fem dråper 70%'ig perklorsyre tilsettes og deretter lar man reaksjonen pågå 12 dager ved romtemperatur under stadig kontroll ved hjelp av tynnsjiktskromato-grafi eller gass-væske kromatografi til den er avsluttet. Opp-løsningen tilsettes deretter under heftiq omrøring til 16,8 g natriumbikarbonat, som var oppslemmet i 100 ml vann. Overskyt- 48 g of 2,3:4,6-di-0-isopropylidene-2-keto-L-gulonic acid (DAG) are dissolved in 250 g of paraldehyde. Five drops of 70% perchloric acid are added and then the reaction is allowed to continue for 12 days at room temperature under constant control using thin-layer chromatography or gas-liquid chromatography until it is finished. The solution is then added with vigorous stirring to 16.8 g of sodium bicarbonate, which was suspended in 100 ml of water. Surplus-
ende paraldehyd og overskytende vann destiller fra i vakuum. Resten krystalliseres i alkohol/vann og man erholder 50,4 g natrium-2,3-0-isopropyliden-4,6-0-etyliden-2-keto-L-gulonat. Fysikalsk-kjemiske data (kjerneresonans-spektrum, masse-spektrum, infrarødt spektrum) o<p>pviser følgende struktur: end paraldehyde and excess water distill from in vacuo. The residue is crystallized in alcohol/water and 50.4 g of sodium 2,3-0-isopropylidene-4,6-0-ethylidene-2-keto-L-gulonate is obtained. Physico-chemical data (nuclear resonance spectrum, mass spectrum, infrared spectrum) show the following structure:
På samme måte som foran beskrevet kan andre 2,3-0-isopropyliden-4,6-0-(R1~R2)-2-keto-L-gulonsyre (struktur II), hvor R'^ og R'2~ substituentene betyr rettkjedet eller forgrenet, alifatisk lavere hydrokarbyl eller halogen-lavere alkyl. In the same way as described above, other 2,3-0-isopropylidene-4,6-0-(R1~R2)-2-keto-L-gulonic acid (structure II), where the R'^ and R'2~ substituents means straight chain or branched, aliphatic lower hydrocarbyl or halogen-lower alkyl.
EKSEMPEL 8 EXAMPLE 8
2- kloretyl- 2, 3:4, 6- di- 0- isopropyliden- 2- keto- L- gulonat 6 g 2,3:4,6-di-0-isopropyliden-2-keto-L-gulonsyre (vannfri) opp-løses i 14 ml pyridin og 3,2 ml metylenklorid og tilsettes dråpevis under omrøring og iskjøling med 3,2 ml tionylklorid. Etter 3 timer ved romtemperatur tilsettes reaksjonsløsningen med 5,9 ml 2-kloretanol og røres deretter ytterligere 3 timer. Deretter opptas reaksjonsløsningen i metylenklorid og vaskes i rekkefølge med iskald 2-n saltsyre, 2-n natronlut og vann, den organiske fasen tørkes over natriumsulfat og inndampes. Resten renses på en silikagelsøyle og destilleres deretter. Man erholder 5 g av et oljeaktig produkt, kg.: 88°C/0,01 mmHa. 2- chloroethyl- 2, 3:4, 6- di- 0- isopropylidene- 2- keto- L-gulonate 6 g 2,3:4,6-di- 0-isopropylidene-2-keto-L-gulonic acid (anhydrous ) is dissolved in 14 ml of pyridine and 3.2 ml of methylene chloride and added dropwise with stirring and ice-cooling with 3.2 ml of thionyl chloride. After 3 hours at room temperature, the reaction solution with 5.9 ml of 2-chloroethanol is added and then stirred for a further 3 hours. The reaction solution is then taken up in methylene chloride and washed in sequence with ice-cold 2-n hydrochloric acid, 2-n caustic soda and water, the organic phase is dried over sodium sulphate and evaporated. The residue is purified on a silica gel column and then distilled. 5 g of an oily product is obtained, kg.: 88°C/0.01 mmHa.
Analogt de forangående eksempler, spesielt eksemplene 1, 2 og 8 fremstilles etterfølgende forbindelser: ammonium-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, flyte-temperatur: 177,5 - 178,5°C; kalsium-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, flyte-temperatur: 265 - 267°C; dimetylammonium-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, flytetemperatur: 155 - 165°C. N-etanolammonium-2,3:4,5-di-0-isopropyliden-2-keto-L-gulonat, flytetemperatur: 208 - 209°C; n-butyl-2,3:4,6-di-O-isopropyliden-2-keto-L-gulonat, flyte-temperatur: 54 - 57°C; 3-klorpropyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, kokepunkt: 130°C/0,005 mmHg; 25 n-heksyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, nD :1,4544; n-heptyl-2,3:4,6-di-O-isopropyliden-2-keto-L-gulonat> kp.: 102 - 103°C/0,01 mmHg; n-oktyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, n 25: 1,4538; n-nonyl-2,3:4,6-di-0-isonropvliden-2-keto-L-gulonat, n 25: 1,4548: 25 n-undecyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, wn • : 1,4555; Analogous to the previous examples, especially examples 1, 2 and 8, the following compounds are prepared: ammonium 2,3:4,6-di-0-isopropylidene-2-keto-L-gulonate, pour temperature: 177.5 - 178, 5°C; calcium 2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate, pour point: 265 - 267°C; Dimethylammonium 2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate, pour point: 155 - 165°C. N-ethanolammonium 2,3:4,5-di-O-isopropylidene-2-keto-L-gulonate, pour point: 208 - 209°C; n-butyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate, pour point: 54 - 57°C; 3-Chloropropyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate, boiling point: 130°C/0.005 mmHg; 25 n-hexyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate, nD : 1.4544; n-heptyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate > bp: 102 - 103°C/0.01 mmHg; n-octyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate, n 25: 1.4538; n-nonyl-2,3:4,6-di-0-isonropvlidene-2-keto-L-gulonate, n 25: 1.4548: 25 n-undecyl-2,3:4,6-di-0- isopropylidene-2-keto-L-gulonate, wn • : 1.4555;
2,2,2-trikloretyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, flytetemperatur: 65 - 66°C; 2,2,2-trichloroethyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate, pour point: 65 - 66°C;
n-dodecyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, flyte-temperatur: 10,5°C; n-dodecyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate, pour point: 10.5°C;
n-propyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, flyte-temperatur: 80 - 81°C; n-propyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate, pour point: 80 - 81°C;
1- propyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, flyte-temperatur: 107,5 - 109°C; 1-propyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate, pour temperature: 107.5 - 109°C;
n-decyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, kp.: 193°C/0,5 mmHg; n-decyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate, bp: 193°C/0.5 mmHg;
2- brometyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, kp.: 2-bromomethyl-2,3:4,6-di-0-isopropylidene-2-keto-L-gulonate, bp.:
ca. 157°C/0,1 torr; 2-butyl-2,3:4,6-di-0-isopropyliden-2-keto-L-aulonat, flytetemperatur: 95,5 - 96,5°C; 1- amyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, kp.: ca. 135°C/0,1 mmHg; bis-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat-etylenglykol-ester, flyte-temperatur: 150 - 151°C; t.-butyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 2- pentinyl-2,3:4,6:di-0-isopropyliden-2-keto-L-gulonat; l-heksin-3-yl-2,3:4,6-di-0-isopropyliden<l->2-keto-L-gulonat; 3- metyl-l-butin-3-yl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; about. 157°C/0.1 torr; 2-Butyl-2,3:4,6-di-O-isopropylidene-2-keto-L-aulonate, pour point: 95.5 - 96.5°C; 1- amyl-2,3:4,6-di-0-isopropylidene-2-keto-L-gulonate, bp.: approx. 135°C/0.1mmHg; bis-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate-ethylene glycol ester, pour point: 150 - 151°C; t-butyl 2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 2-pentynyl-2,3:4,6:di-O-isopropylidene-2-keto-L-gulonate; 1-hexin-3-yl-2,3:4,6-di-O-isopropylidene<1>2-keto-L-gulonate; 3-methyl-1-butyn-3-yl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate;
5-heksenyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 5-hexenyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate;
3- pentyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; diklormetyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 2,2-dikloretyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 2-kloretyl-2,3:4,6-di-0-iso<p>ropyliden-2-keto-L-gulonat; 4- klorbutyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 2,2,2-trifluoretyl-2,3:4,6-di-O-isopropyliden-2-keto-L-gulonat; 2-fluoretyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 2-brom-l,1,2,2-tetrafluoretyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 3-pentyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; dichloromethyl 2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 2,2-dichloroethyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 2-Chloroethyl-2,3:4,6-di-O-iso<p>ropylidene-2-keto-L-gulonate; 4-chlorobutyl 2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 2,2,2-trifluoroethyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 2-Fluoroethyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate; 2-bromo-1,1,2,2-tetrafluoroethyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate;
2,2,3,3,4,4,4-heptafluorbutyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 2,2,3,3,4,4,4-heptafluorobutyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate;
2,2,3,3,4,4,5,5-oktafluorpentyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat; 2,2,3,3,4,4,5,5-octafluoropentyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate;
2-propinyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, flyte-temperatur: 91,5 - 92,5°C; 2-propynyl-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonate, pour point: 91.5 - 92.5°C;
n-pentyl-2,3:4,6-di-0-isopropyliden-2-keto-L-gulonat, kp.: ca. 195°C/0,1 mmHg; n-pentyl-2,3:4,6-di-0-isopropylidene-2-keto-L-gulonate, bp.: approx. 195°C/0.1mmHg;
Claims (7)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NO753857A NO142122C (en) | 1972-08-03 | 1975-11-17 | NEW RELATIONS WITH PLANT GROWTH REGULATORY EFFECT |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US27753872A | 1972-08-03 | 1972-08-03 | |
US33560773A | 1973-02-26 | 1973-02-26 | |
US34703573A | 1973-04-02 | 1973-04-02 | |
NO3109/73A NO142060C (en) | 1972-08-03 | 1973-08-02 | PLANT GROWTH REGULATOR. |
NO753857A NO142122C (en) | 1972-08-03 | 1975-11-17 | NEW RELATIONS WITH PLANT GROWTH REGULATORY EFFECT |
Publications (3)
Publication Number | Publication Date |
---|---|
NO753857L NO753857L (en) | 1974-02-05 |
NO142122B true NO142122B (en) | 1980-03-24 |
NO142122C NO142122C (en) | 1980-07-02 |
Family
ID=27532549
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO753857A NO142122C (en) | 1972-08-03 | 1975-11-17 | NEW RELATIONS WITH PLANT GROWTH REGULATORY EFFECT |
Country Status (1)
Country | Link |
---|---|
NO (1) | NO142122C (en) |
-
1975
- 1975-11-17 NO NO753857A patent/NO142122C/en unknown
Also Published As
Publication number | Publication date |
---|---|
NO753857L (en) | 1974-02-05 |
NO142122C (en) | 1980-07-02 |
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