NO833295L - BRASSINOSTEROID DERIVATIVES AND AGENTS FOR PLANT REGULATORY EFFECT ON PLANTS CONTAINING THESE COMPOUNDS - Google Patents
BRASSINOSTEROID DERIVATIVES AND AGENTS FOR PLANT REGULATORY EFFECT ON PLANTS CONTAINING THESE COMPOUNDSInfo
- Publication number
- NO833295L NO833295L NO833295A NO833295A NO833295L NO 833295 L NO833295 L NO 833295L NO 833295 A NO833295 A NO 833295A NO 833295 A NO833295 A NO 833295A NO 833295 L NO833295 L NO 833295L
- Authority
- NO
- Norway
- Prior art keywords
- oxa
- homo
- cholestan
- ethyl
- cholest
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims description 29
- 150000001647 brassinosteroids Chemical class 0.000 title claims description 7
- 230000001105 regulatory effect Effects 0.000 title description 2
- -1 2-methyl-heptan-6-yl Chemical group 0.000 claims description 44
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 23
- 241000196324 Embryophyta Species 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 230000012010 growth Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 5
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 4
- 229940071536 silver acetate Drugs 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 3
- 230000033444 hydroxylation Effects 0.000 claims description 3
- 238000005805 hydroxylation reaction Methods 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 150000004965 peroxy acids Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 235000021374 legumes Nutrition 0.000 claims description 2
- 244000068988 Glycine max Species 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 229960000583 acetic acid Drugs 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- KDCIHNCMPUBDKT-UHFFFAOYSA-N hexane;propan-2-one Chemical compound CC(C)=O.CCCCCC KDCIHNCMPUBDKT-UHFFFAOYSA-N 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 8
- 239000005457 ice water Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 6
- 239000013543 active substance Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 244000045561 useful plants Species 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
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- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
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- 239000002253 acid Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000004009 herbicide Substances 0.000 description 4
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000006220 Baeyer-Villiger oxidation reaction Methods 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
- 239000010695 polyglycol Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000010626 work up procedure Methods 0.000 description 3
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- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- OILXMJHPFNGGTO-UHFFFAOYSA-N (22E)-(24xi)-24-methylcholesta-5,22-dien-3beta-ol Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)C=CC(C)C(C)C)C1(C)CC2 OILXMJHPFNGGTO-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- OILXMJHPFNGGTO-MPVBJYOVSA-N Brassicasterin Natural products CC(C)[C@@H](C)C=C[C@H](C)[C@H]1CC[C@H]2[C@@H]3CC=C4C[C@@H](O)CC[C@]4(C)[C@@H]3CC[C@@]12C OILXMJHPFNGGTO-MPVBJYOVSA-N 0.000 description 2
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 241001300479 Macroptilium Species 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
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- UWYPWKXXZPDDSN-GAOTXHHCSA-N [(2R,3S,5S,8S,9S,10R,13R,14S,17R)-2-acetyloxy-10,13-dimethyl-17-[(2R)-6-methylheptan-2-yl]-6-oxo-1,2,3,4,5,7,8,9,11,12,14,15,16,17-tetradecahydrocyclopenta[a]phenanthren-3-yl] acetate Chemical compound C(C)(=O)O[C@H]1[C@H](C[C@@H]2C(C[C@H]3[C@@H]4CC[C@H]([C@@H](CCCC(C)C)C)[C@]4(CC[C@@H]3[C@]2(C1)C)C)=O)OC(C)=O UWYPWKXXZPDDSN-GAOTXHHCSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
- OILXMJHPFNGGTO-ZAUYPBDWSA-N brassicasterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)/C=C/[C@H](C)C(C)C)[C@@]1(C)CC2 OILXMJHPFNGGTO-ZAUYPBDWSA-N 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
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- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
- HCWYXKWQOMTBKY-UHFFFAOYSA-N calcium;dodecyl benzenesulfonate Chemical compound [Ca].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 HCWYXKWQOMTBKY-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- QSKWJTXWJJOJFP-UHFFFAOYSA-N chloroform;ethoxyethane Chemical compound ClC(Cl)Cl.CCOCC QSKWJTXWJJOJFP-UHFFFAOYSA-N 0.000 description 1
- OAIVIYSBZFEOIU-UHFFFAOYSA-N chloroform;propan-2-one Chemical compound CC(C)=O.ClC(Cl)Cl OAIVIYSBZFEOIU-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000035613 defoliation Effects 0.000 description 1
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ZKQFHRVKCYFVCN-UHFFFAOYSA-N ethoxyethane;hexane Chemical compound CCOCC.CCCCCC ZKQFHRVKCYFVCN-UHFFFAOYSA-N 0.000 description 1
- DLLJVQNYBYOKGS-UHFFFAOYSA-N ethoxyethane;pentane Chemical compound CCCCC.CCOCC DLLJVQNYBYOKGS-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 230000005089 fruit drop Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 231100000001 growth retardation Toxicity 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000007273 lactonization reaction Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- FDJABJJEKWDNQO-UHFFFAOYSA-N pentane;propan-2-one Chemical compound CC(C)=O.CCCCC FDJABJJEKWDNQO-UHFFFAOYSA-N 0.000 description 1
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000885 phytotoxic effect Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 230000002786 root growth Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007226 seed germination Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- HCXVJBMSMIARIN-PHZDYDNGSA-N stigmasterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)/C=C/[C@@H](CC)C(C)C)[C@@]1(C)CC2 HCXVJBMSMIARIN-PHZDYDNGSA-N 0.000 description 1
- BFDNMXAIBMJLBB-UHFFFAOYSA-N stigmasterol Natural products CCC(C=CC(C)C1CCCC2C3CC=C4CC(O)CCC4(C)C3CCC12C)C(C)C BFDNMXAIBMJLBB-UHFFFAOYSA-N 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 238000001665 trituration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J3/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by one carbon atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N49/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds containing the group, wherein m+n>=1, both X together may also mean —Y— or a direct carbon-to-carbon bond, and the carbon atoms marked with an asterisk are not part of any ring system other than that which may be formed by the atoms X, the carbon atoms in square brackets being part of any acyclic or cyclic structure, or the group, wherein A means a carbon atom or Y, n>=0, and not more than one of these carbon atoms being a member of the same ring system, e.g. juvenile insect hormones or mimics thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J73/00—Steroids in which the cyclopenta[a]hydrophenanthrene skeleton has been modified by substitution of one or two carbon atoms by hetero atoms
- C07J73/001—Steroids in which the cyclopenta[a]hydrophenanthrene skeleton has been modified by substitution of one or two carbon atoms by hetero atoms by one hetero atom
- C07J73/003—Steroids in which the cyclopenta[a]hydrophenanthrene skeleton has been modified by substitution of one or two carbon atoms by hetero atoms by one hetero atom by oxygen as hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Insects & Arthropods (AREA)
- Agronomy & Crop Science (AREA)
- Steroid Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
Foreliggende oppfinnelse angår nye brassino-steroidderivater, fremgangsmåte for. fremstilling av disse forbindelser såvel som midler med vekstregulerende virkning for planter inneholdende disse forbindelser. The present invention relates to new brassino-steroid derivatives, method for. production of these compounds as well as agents with growth-regulating action for plants containing these compounds.
Fra pollen fra raps ble et plantevekstfremmende steroid - brassinolid - isolert og strukturen ble klarlagt (s. M.D. Grove et al., Nature Vol. 281, 216 (1979)). Den vekstregulerende virkning av denne forbindelse er imidlertid ikke tilfredsstillende. From rapeseed pollen, a plant growth-promoting steroid - brassinolide - was isolated and its structure elucidated (p. M.D. Grove et al., Nature Vol. 281, 216 (1979)). However, the growth-regulating effect of this compound is not satisfactory.
Målet med foreliggende oppfinnelse er å tilveie-bringe nye brassinosteroidderivater som sammenlignet med det kjente konstitusjonsanaloge brassinolid utviser overlegne vekstregulerende egenskaper for planter. The aim of the present invention is to provide new brassinosteroid derivatives which, compared to the known constitutional analogue brassinolide, exhibit superior growth-regulating properties for plants.
Dette mål løses ifølge oppfinnelsen med et middel som er kjennetegnet ved at det inneholder minst én forbindelse av generell formel According to the invention, this objective is solved with an agent which is characterized by the fact that it contains at least one compound of the general formula
hvori R^~ j betegner en Cg-C-^<-a>lkylrest eller en Cg-<C>1Q<->alkenylrest og in which R^~j denotes a Cg-C-^<-a>alkyl radical or a Cg-<C>1Q<->alkenyl radical and
Z betegner gruppen - C - 0 - CH9 - eller - 0 - C - CH9 -,Z denotes the group - C - 0 - CH9 - or - 0 - C - CH9 -,
ii ^ ii z 0 0 ii ^ ii z 0 0
1*2 og R^er enten forskjellig og betegner hydrogen eller en acylrest, eller betegner sammen gruppen 1*2 and R^ are either different and denote hydrogen or an acyl residue, or together denote the group
eller or
hvori X betegner vannstoff, where X denotes hydrogen,
C^-C^-alkyl eller Cj^-C^-alkoxy og Y betegner vannstoff, C^-C^-alkyl, C^-C-j-alkoxy eller aryl. C₁-C₁-alkyl or C₁-C₁- alkoxy and Y denotes hydrogen, C₁-C₁-alkyl, C₁-C₁-j- alkoxy or aryl.
De nye forbindelser opptrer som geometriske isomerer, hvoved -0R2 og -OR^er cis 2a,3a eller cis 23,33-orientert. De enkelte isomerer og deres blandinger faller innen oppfinnelsens ramme. The new compounds act as geometric isomers, whereby -OR2 and -OR2 are cis 2a,3a or cis 23,33-oriented. The individual isomers and their mixtures fall within the scope of the invention.
De nye forbindelser egneri.seg fremragende til regulering av plantevekst av forskjellige nytteplanter og overgår i deres virkningsspekter såvel som i deres forenlig-het på en overraskende måte det tidligere angitte produkt med samme virkningsretning. The new compounds are excellently suitable for regulating plant growth of various useful plants and surpass in their spectrum of action as well as in their compatibility in a surprising way the previously indicated product with the same direction of action.
De nye forbindelser øker den vegetative vekst av nytteplanter, men kan i visse konsentrasjonsområder også hemme denne.Envidere er det mulig å oppnå en viss tilvekst på grunn av innvirkning på den generative fase. The new compounds increase the vegetative growth of useful plants, but in certain concentration ranges can also inhibit this. Furthermore, it is possible to achieve a certain increase due to an impact on the generative phase.
Generelt virker substansene på membransysternet i nytteplanter og endrer dets permeabilitet for forskjellige stoffer. In general, the substances act on the membrane system in useful plants and change its permeability to different substances.
Under bestemte betingelser kan de også gi en anti-strekkvirkning. Under certain conditions, they can also provide an anti-stretch effect.
Da de nye forbindelser såvel kvalitativt som kvantitativt forårsaker endringer på plantene samt også forandringer i plantenes metabolisme, hører de inn under klassen av plantevekstregulatorer som utviser.følgende anvendelsesmuligheter. As the new compounds both qualitatively and quantitatively cause changes in the plants as well as changes in the plants' metabolism, they belong to the class of plant growth regulators which exhibit the following application possibilities.
Hemning av den vegative vekst av treaktige planter og ugress eksempelvis ved veikanter, skinneanlegg og lig-nende, for å unngå en for kraftig vekst. Veksthemning av korn for å unngå legde, og av bomull for å øke utbyttet. Inhibition of the vegetative growth of woody plants and weeds, for example at roadsides, rail installations and the like, to avoid excessive growth. Growth retardation of cereals to avoid late blight, and of cotton to increase yield.
Innvirkning på forgreningen av vegativ.e og generative organer i pryd-^og nytteplanter for å øke blomsterpro-duksjon eller i tobakk og.tomater for å hemme sideskudd. Effect on the branching of vegetative and generative organs in ornamental and useful plants to increase flower production or in tobacco and tomatoes to inhibit side shoots.
Forbedring av fruktkvaliteten, for eksempel en økning i sukkerinnholdet i sukkerrør, sukkerroer eller ved frukt og oppnå en samtidig modning av avlingen som fører til et høyere utbytte. Improving the quality of the fruit, for example an increase in the sugar content of sugar cane, sugar beet or fruit and achieving a simultaneous ripening of the crop leading to a higher yield.
Økning av motstandskraften overfor stress, slik som f.eks. overfor klimåtiske påvirkninger slik som kulde og tørke, men også overfor fytotoksiske påvirkninger av kjemikalier. Increasing resistance to stress, such as e.g. to climatic influences such as cold and drought, but also to phytotoxic effects of chemicals.
Påvirkning av latexstrømmen i gummiplanter. Influence of latex flow in rubber plants.
Dannelse av parthenokarpe frukter, pollensterilitet og arvelighetspåvirkning er andre anvendelsesmuligheter. Formation of parthenocarpic fruits, pollen sterility and influence of heredity are other application possibilities.
Kontroll av spiring av frø eller dannelse av knop-per. Control of seed germination or bud formation.
Avløving eller bivirkning på fruktfall for åDefoliation or adverse effect on fruit drop to
lette innhøstningen.ease the harvest.
De nye forbindelser egner seg særlig til å påvirke den vegetative og generative vekst av enkelte belgfrukter slik som f.eks. soya. The new compounds are particularly suitable for influencing the vegetative and generative growth of certain legumes such as e.g. soy.
Anvendelsesmengdene utgjør alt etter anvendelsesmålet generelt 0,001 til 1 kg virkestoff/ha, men eventuelt kan også større mengder anvendes. Depending on the application target, the application amounts generally amount to 0.001 to 1 kg of active substance/ha, but possibly larger amounts can also be used.
Anvendelsestiden retter seg etter anvendelsesmålet og de klimatiske betingelser. The period of use depends on the purpose of use and the climatic conditions.
Blant de nye forbindelser som utmerkear.' seg ved den beskrevne virkning er særlig slike av generell formel I hvori R,., betegner 2-methyl-heptan-6-yl, 2^methyl-3-ethyl-hept-4-en-6-yl, 2,3-dimethyl-hept-4-en-6-yl, 2-methyl-3-ethyl-heptan-6-yl eller 2,3-dimethyl-heptan-6-yl og Among the new connections that stand out.' themselves by the described effect are particularly those of general formula I in which R,., denotes 2-methyl-heptan-6-yl, 2-methyl-3-ethyl-hept-4-en-6-yl, 2,3- dimethyl-hept-4-en-6-yl, 2-methyl-3-ethyl-heptan-6-yl or 2,3-dimethyl-heptan-6-yl and
Z betegner gruppen Z denotes the group
eller R2og R^er enten forskjellig og betegner hydrogen eller en formylrest, en C2-C7-alkyl-CO-rest, en C-j-C-^-alkoxy-C-^-C-j-alkyl-CO-rest eller en aryl-CO-rest eller betegner sammen gruppen eller or R 2 and R 3 are either different and denote hydrogen or a formyl residue, a C 2 -C 7 -alkyl-CO residue, a C 1 -C 4 -alkyl-CO residue or an aryl CO residue or collectively denotes the group or
hvori X betegner hydrogen, C-^-C^-alkyl eller C-^-C^-alkoxy og Y betegner hydrogen, Ci~C4-alkyl, C-^-C-j-alkoxy eller aryl. in which X denotes hydrogen, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy and Y denotes hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkyl or aryl.
Som Cg-C^Q-alkyl- og alkenylrester kan eksempelvis nevnes 2-methyl-heptan-6-yl, 2-methyl-3-ethyl-hept-4-en-6-yl, 2,3-dimethyl-hept-4-en-6-yl, 2-methyl-3-ethyl-heptan-6-yl og 2,3-dimethyl-heptan-6-yl; arylrester kan bety formylrest, Examples of Cg-C^Q-alkyl and alkenyl residues that can be mentioned are 2-methyl-heptan-6-yl, 2-methyl-3-ethyl-hept-4-en-6-yl, 2,3-dimethyl-hept- 4-en-6-yl, 2-methyl-3-ethyl-heptan-6-yl and 2,3-dimethyl-heptan-6-yl; aryl residues can mean formyl residues,
en<C>2<-C>7-alkyl-CG—rest, en C2-C7-alkoxy-C1-C3-alkyl-CO-rest og en aryl-CO-rest, slik som f.eks. acétoxy, methoxyacetoxy, ethoxyacetoxy, propionyloxy, butyryloxy, valeryloxy, pentanoyl-oxy, hexanoyloxy, heptanoyloxy, dimethylacetoxy, diethyl-acetoxy, benzoyloxy og fenylacetoxy. a<C>2<-C>7-alkyl-CG—residue, a C2-C7-alkoxy-C1-C3-alkyl-CO-residue and an aryl-CO-residue, such as e.g. acetoxy, methoxyacetoxy, ethoxyacetoxy, propionyloxy, butyryloxy, valeryloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, dimethylacetoxy, diethylacetoxy, benzoyloxy and phenylacetoxy.
Som C^-C^-alkylrester kan eksempelvis nevnesFor example, C1-C3-alkyl radicals can be mentioned
methyl, ethyl, propyl, isopropyl, butyl, sek.butyl, tert.-butyl og klormethyl; Ci-C^-alkoxyrester er eksempelvis methoxy, ethoxy og propoxy; og som arylrester kan endelig nevnes nafthyl, fenyl, 2-klorfenyl, 3-klorfenyl, 4-klorfenyl, 2,6-diklorfenyl, 2,4-diklorfenyl, 3,4-diklorfenyl, 2,4,6-tri-klorfenyl, 4-bromfenyl-2,4-dibromfenyl, 2,6-dibromfenyl, 2,4,6-tribromfenyl,.2-fluorfenyl, 3-fluorfenyl, 4-fluorfenyl, 2,4-difluorfenyl, 2-methylfenyl, 3-methylfenyl, 4-methylfenyl, 3,4-dimethylfenyl, 2-methoxyfenyl, 3-methoxyfenyl, 4-methoxyfenyl, 3,4-dioxymethylenfenyl, 2-fenoxyfenyl, 3-fenoxyfenyl, 2-nitrofenyl og 3-nitrofenyl. methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl and chloromethyl; C 1 -C 4 -Alkoxy residues are, for example, methoxy, ethoxy and propoxy; and finally naphthyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,6-dichlorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,4,6-tri-chlorophenyl, 4-bromophenyl-2,4-dibromophenyl, 2,6-dibromophenyl, 2,4,6-tribromophenyl,.2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 2-methylphenyl, 3-methylphenyl , 4-methylphenyl, 3,4-dimethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 3,4-dioxymethylenephenyl, 2-phenoxyphenyl, 3-phenoxyphenyl, 2-nitrophenyl and 3-nitrophenyl.
De nye forbindelser kan enten anvendes alene, i blanding med hverandre eller med andre virkestoffer. Eventuelt kan bladfjernende midler, bladbeskyttelsesmidler eller pesticider tilsettes alt etter det ønskede formål. The new compounds can either be used alone, in a mixture with each other or with other active substances. Optionally, defoliating agents, leaf protection agents or pesticides can be added depending on the desired purpose.
Såfremt en utvidelse av virkningsspekteret.taes i betraktning kan også andre biocider tilsettes. Som herbicid virksomme'blandingspartnere egner seg eksempelvis de virkestoffer som er angitt i Weed Abstracts, Vol. 31, 1981, If an extension of the spectrum of action is taken into account, other biocides can also be added. Suitable as herbicidally active 'mixing partners' are, for example, the active substances indicated in Weed Abstracts, Vol. 31, 1981,
under titelen "List of common names and Abbreviations employed for currently used herbicides and plant growth regulators in weed abstracts". I tillegg kan også ikke fytotoksiske midler anvendes som med herbicidene og/eller vekstregulatorene kan gi en synergistisk virkningsøkning, under the title "List of common names and Abbreviations employed for currently used herbicides and plant growth regulators in weed abstracts". In addition, phytotoxic agents cannot be used which with the herbicides and/or growth regulators can give a synergistic increase in effectiveness,
slik som blant annet fuktemidler, emulgatorer, løsningsmid-ler og oljeaktige tilsetningsstoffer. such as, among other things, wetting agents, emulsifiers, solvents and oily additives.
Hensiktsmessig anvendes de nye virkestoffer eller deres blandinger i form.av tilberedelser slik som pulvere, strømidler, granulater, løsninger, emulsjoner eller suspen-sjoner, under tilsetning av flytende og/eller faste bærer-stoffer, henholdsvis fortynningsmidler, og eventuelt under tilsetning av fuktemidler, bindemidler, emulgeringsmidler og/eller dispergeringshjelpemidler. Appropriately, the new active substances or their mixtures are used in the form of preparations such as powders, flow agents, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers, respectively diluents, and possibly with the addition of wetting agents , binders, emulsifiers and/or dispersing aids.
Egnede flytende bærere er f.eks. vann, alifatiskeSuitable liquid carriers are e.g. water, aliphatic
og aromatiske hydrocarboner slik som benzen, toluen, xylen, cyclohexanon, isoforon, dimethylsulfoxyd, dimethylformamid og mineraloljefraksjoner. and aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethylsulfoxide, dimethylformamide and mineral oil fractions.
Som faste bærestoffer egner seg mineraljord slik som f.eks. leirearter, silicagel, talkum, kaolin, attapulkus-leire, kalkstein, kieselsyre og planteprodukter, slik som f.eks. mel. Mineral soil such as e.g. clay species, silica gel, talc, kaolin, attapulkus clay, limestone, silicic acid and plant products, such as e.g. flour.
Som overflateaktive stoffer kan eksempelvis nevnes calciumligninsulfonat, polyoxyethylen-alkylfenolether, nafthalinsulfonsyrer og deres salter, fenolsulfonsyrer og deres salter, formaldehydkondensater, fettalkoholsulfater såvel som substituerte benzensulfonsyrer og deres salter. Examples of surfactants include calcium lignin sulfonate, polyoxyethylene alkyl phenol ether, naphthalene sulfonic acids and their salts, phenol sulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates as well as substituted benzene sulfonic acids and their salts.
Andelen av virkestoffet i de forskjellige tilberedelser kan varierer innen vide grenser. Eksempelvis inneholder midlet 10 til 80 vekt% virkestoff, 90 til 20 vekt% flytende eller faste bærestoffer såvel som opp til 20 vekt% overflateaktive stoffer. The proportion of the active substance in the different preparations can vary within wide limits. For example, the agent contains 10 to 80% by weight of active ingredient, 90 to 20% by weight of liquid or solid carriers as well as up to 20% by weight of surfactants.
Utbringelse av midlet kan skje på vanlig måte, eksempelvis med vann som bærer i sprøytemengder på fra 100 til 1000 liter/ha. En anvendelse av midlet i den såkalte low-volume eller ultra-low-volume-metoden er også mulig såvel som anvendelse i form av såkalte mikrogranulater. Application of the agent can be carried out in the usual way, for example with water carrying spray quantities of from 100 to 1000 litres/ha. Application of the agent in the so-called low-volume or ultra-low-volume method is also possible, as well as application in the form of so-called microgranules.
For fremstilling av tilberedelsene kan eksempelvis følgende bestanddeler anvendes: For the preparation of the preparations, for example, the following ingredients can be used:
A.<g>prøytepulver A.<g>spraying powder
a) 80 vekt% virkestoffa) 80% by weight active substance
15 vekt% kaolin15% by weight kaolin
5 vekt% overflateaktivt stoff på basis av natrium-saltet av N-methyl-N-oleyl-taurin og calciumsaltet av ligninsulfonsyre. 5% by weight surfactant based on the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of ligninsulfonic acid.
b) 50 vekt% virkestoffb) 50% by weight active ingredient
40 vekt% leiremineraler40 wt% clay minerals
5 vekt% cellebek5% by weight cell pitch
.5 vekt% overflateaktivt stoff på basis av fen blanding . av_calciumsalter av ligninsulfonsyre med alkylfenol-polyglykolether. .5% by weight surface-active substance on the basis of fen mixture. of_calcium salts of ligninsulfonic acid with alkylphenol-polyglycol ether.
c) 2 0 vekt% virkestoffc) 20% by weight active ingredient
70 vekt% leiremineraler70% by weight clay minerals
5 vekt% cellebek5% by weight cell pitch
5 vekt% overflateaktivt stoff på basis av en blanding av calciumsalter av ligninsulfonsyre med alkyl-fenolpolyglycolether. 5% by weight surfactant on the basis of a mixture of calcium salts of ligninsulfonic acid with alkyl-phenol polyglycol ether.
d) 5 vekt% virkestoffd) 5% by weight active ingredient
80 vekt% leirearter80% by weight clay species
10 vekt% cellebek10% by weight cell pitch
5 vekt% overflateaktivt stoff på basis av et fett-syrekondensasjonsprodukt. 5% by weight surfactant based on a fatty acid condensation product.
B. EmulsjonskonsentratB. Emulsion concentrate
20 vekt% virkestoff20% by weight active ingredient
4 0 vekt% xylen40% by weight xylene
35 vekt% dimethylsulfoxyd.-35% by weight dimethylsulfoxyd.-
5 vekt% av en blanding av nonylfenylpolyethylen eller calciumdodecylbenzensulfonat. 5% by weight of a mixture of nonylphenyl polyethylene or calcium dodecylbenzene sulphonate.
C. PastaC. Pasta
45 vekt% virkestoff45% by weight active ingredient
5 vekt% natriumaluminiumsilicat5% by weight sodium aluminum silicate
15 vekt% cetylpolyglycolether med 8 mol ethylenoxyd 15% by weight of cetyl polyglycol ether with 8 mol of ethylene oxide
2 vekt% spindelolje2% by weight spindle oil
10 vekt% polyethylenglycol10 wt% polyethylene glycol
23 deler vann.23 parts water.
De nye forbindelser kan eksempelvis fremstilles ved at forbindelser av generell formel The new compounds can, for example, be prepared by compounds of the general formula
omsettes ved osmiumtetroxyd-katalysert hydroxylering med t-butylhydroperoxyd eller med N-methyl-morfolin-N-oxyd til forbindelser av generell formel eller innvirkes av sølvacetat og jod i vandig eddiksyre under dannelse av forbindelser av generell formel reacted by osmium tetroxide-catalyzed hydroxylation with t-butyl hydroperoxide or with N-methyl-morpholine-N-oxide to compounds of general formula or acted upon by silver acetate and iodine in aqueous acetic acid to form compounds of general formula
som behandles med persyrer under dannelse av de ønskede fremgangsmåteprodukter hvori R, -, og R2har de ovenfor angitte betydninger. which is treated with peracids to form the desired process products in which R, -, and R2 have the meanings indicated above.
For fremstilling av forbindelsene av formel I utgår man fra steriner slik som cholesterin, stigmasterin, brassicasterin eller p-sitosterin, og omsetter disse på i og for seg kjent måte til A 2-6-ketosteroider av formel II For the preparation of the compounds of formula I, one starts from sterols such as cholesterin, stigmasterin, brassicasterin or p-sitosterin, and converts these in a manner known per se to A 2-6-ketosteroids of formula II
(In Heiv. 49, 1581 (1966)). (In Heiv. 49, 1581 (1966)).
Den videre omsetning til 2a,3a-cis-glycoler av formel III skjer etter kjente metoder, nemlig osmiumtetroxyd-katalysert hydroxylering med 80 %-ig t-butylhydroperoxyd (K.B. Sharpless JACS 98, 1986 (1976)) eller med N-methyl-morfolin-N-oxyd (V.van Rheen, Tetrahedron Lett. 1976, 1973). The further reaction to 2a,3a-cis-glycols of formula III takes place according to known methods, namely osmium tetroxide-catalyzed hydroxylation with 80% t-butyl hydroperoxide (K.B. Sharpless JACS 98, 1986 (1976)) or with N-methyl-morpholine -N-oxide (V. van Rheen, Tetrahedron Lett. 1976, 1973).
Til 23,3&-cis-glycolene eller deres derivater av formel IV kommer man via Prevost-reaksjonen med sølvacetat og jod i vandig eddiksyre (49, 1581 (1966)). The 23,3&-cis-glycols or their derivatives of formula IV are obtained via the Prevost reaction with silver acetate and iodine in aqueous acetic acid (49, 1581 (1966)).
Fremstilling av B-ringlactonet av formel I skjer ved Baeyer-Villiger-oxydasjon med persyrer slik som trifluor- pereddiksyre, permaursyre, permaleinsyre, etc. av 6-keto-steroidet av formel III og IV. Med forbindelser med en C22~C23~dobbeltbinding i sidekjeden må denne dobbeltbinding beskyttes ved bromering før lactoniseringen. Production of the B-ring lactone of formula I takes place by Baeyer-Villiger oxidation with peracids such as trifluoroperacetic acid, permauric acid, permaleic acid, etc. of the 6-keto steroid of formulas III and IV. With compounds with a C22~C23~ double bond in the side chain, this double bond must be protected by bromination before lactonization.
Etter Baeyer-Villiger-oxydasjonen kan dobbeltbindingen regenereres med sink i eddiksyre. After the Baeyer-Villiger oxidation, the double bond can be regenerated with zinc in acetic acid.
De etterfølgende eksempler illustrerer fremstil-lingen av de nye forbindelser. The following examples illustrate the preparation of the new compounds.
Eksempel 1Example 1
a) 3,56 g 24 S ethyl-5a-cholesta-2,22-dien-6-on ble løst i 6 0 ml t-butanol, 4 ml 20 %-ig tetraethylammoniumhydroxyd-løsning ble tilsatt, blandingen ble avkjølt til 0° C og ble tilsatt 12 ml 80 %-ig t-butylhydroperoxyd og 6 ml a) 3.56 g of 24 S ethyl-5a-cholesta-2,22-dien-6-one was dissolved in 60 ml of t-butanol, 4 ml of 20% tetraethylammonium hydroxide solution was added, the mixture was cooled to 0 ° C and 12 ml of 80% t-butyl hydroperoxide and 6 ml were added
av en osraiumtetroxydløsning (fremstilt fra 250 mg OsO^, 49,75 ml t-butanol og 0,25 ml 80. %-ig t-butylhydroperoxyd) . Reaksjonsløsningen ble omrørt i 6 timer ved romtemperatur, ble helt over i 5 %-ig natriumhydrogensulfitt-løsning og ble ekstrahert med eddikester. Ekstraktet ble vasket med vann, tørket over natriumsulfat og ble inndampet. Etter omkrystallisering fra methylenklorid-methanol ble det erholdt 2,3 g 2a,3a-dihydroxy-24-S-ethyl-5a-cholest-22-en-6-on. of an osraium tetroxide solution (prepared from 250 mg of OsO^, 49.75 ml of t-butanol and 0.25 ml of 80% t-butyl hydroperoxide). The reaction solution was stirred for 6 hours at room temperature, poured into 5% sodium hydrogen sulphite solution and extracted with ethyl acetate. The extract was washed with water, dried over sodium sulfate and evaporated. After recrystallization from methylene chloride-methanol, 2.3 g of 2α,3α-dihydroxy-24-S-ethyl-5α-cholest-22-en-6-one was obtained.
Sm.p. 234,5 - 235,5° C. Sm.p. 234.5 - 235.5° C.
b) 2,2 g 2a,3a-dihydroxy-24-S-ethyl-5a-cholest-22-en-6-on ble løst i 15 ml- pyridin, ble tilsatt 8 ml acetanhydrid b) 2.2 g of 2a,3a-dihydroxy-24-S-ethyl-5a-cholest-22-en-6-one was dissolved in 15 ml of pyridine, 8 ml of acetic anhydride was added
og 22 0 mg 4-dimethylaminopyridin og fikk stå i 17 timer ved 20° C. Deretter ble produktet utfelt i isvann, ble and 220 mg of 4-dimethylaminopyridine and allowed to stand for 17 hours at 20° C. The product was then precipitated in ice water,
fraskilt, vasket.og tørket.separated, washed.and dried.
c) 2,6 g urent diacetat ble i 30 ml ether. og 30 ml iseddik tilsatt 0,28 ml brom og ble omrørt i 10 minutter ved c) 2.6 g of impure diacetate was dissolved in 30 ml of ether. and 30 ml of glacial acetic acid added with 0.28 ml of bromine and was stirred for 10 minutes at
romtemperatur. For opparbeidelsen ble blandingen fortynnet med ether, vasket nøytral med vann og ble inndampet i vakuum. Det ble erholdt 3,2 g urent 2a,3a-diacetoxy-22,2 3-dibrom-24-ethyl-5a-cholestan-6-on. room temperature. For the work-up, the mixture was diluted with ether, washed neutral with water and evaporated in vacuo. 3.2 g of impure 2a,3a-diacetoxy-22,2-3-dibromo-24-ethyl-5a-cholestan-6-one were obtained.
d) 4,5 ml 30 %-ig hydrogenperoxyd ble suspendert i 28 ml methylenklorid, ble avkjølt til -10° C og ble langsomt d) 4.5 ml of 30% hydrogen peroxide was suspended in 28 ml of methylene chloride, was cooled to -10° C and slowly
dråpevis tilsatt 27,7 ml trifluoreddiksyreanhydrid slik at temperaturen ikke oversteg +10° C. Deretter ble 27.7 ml of trifluoroacetic anhydride were added dropwise so that the temperature did not exceed +10° C. Then
3,2 g 2a,3a-diacetoxy-22,23-dibrom-24-ethyl-5a-cholestan-6-on løst i 25 ml methylenklorid tilsatt, og blandingen ble omrørt i 40 minutter ved romtemperatur. Reaksjonsblandingen ble deretter fortynnet med methylenklorid og vasket med vann, 5 %-ig natriumcarbonatløsning og med vann, ble tørket og inndampet i vakuum. Residuet ble i 100 ml eddiksyre oppvarmet med 5 g sinks.tøv i 1 time på dampbad. Sink/ble frafiltrert og blandingen ble fortynnet med methylenklori.d og vasket nøytral med vann og inndampet. Etter kromatografi.på silicagel (gradient-elueringrtoluen-eddikester) og krystallisering fra aceton-hexan ble det erholdt 1,5 g 2a,3a-diacetoxy-24-ethyl-7-oxa-B-horao-5a-cholest-22-6-on, sm.p. 221 - 223°C og 310 mg ,2a,3a-diacetoxy-24-ethyl-6-oxa-B-homo-5a-cholest-22-en-7-on, sm.p. 202 - 204° C. 3.2 g of 2a,3a-diacetoxy-22,23-dibromo-24-ethyl-5a-cholestan-6-one dissolved in 25 ml of methylene chloride was added, and the mixture was stirred for 40 minutes at room temperature. The reaction mixture was then diluted with methylene chloride and washed with water, 5% sodium carbonate solution and with water, was dried and evaporated in vacuo. The residue was heated in 100 ml of acetic acid with 5 g of zinc dust for 1 hour on a steam bath. Zinc was filtered off and the mixture was diluted with methylene chloride and washed neutral with water and evaporated. After chromatography on silica gel (gradient-elution-toluene-acetic ester) and crystallization from acetone-hexane, 1.5 g of 2a,3a-diacetoxy-24-ethyl-7-oxa-B-horao-5a-cholest-22-6 was obtained -on, sm.p. 221 - 223°C and 310 mg of ,2a,3a-diacetoxy-24-ethyl-6-oxa-B-homo-5a-cholest-22-en-7-one, m.p. 202 - 204°C.
Eksempel 2Example 2
a) Til en løsning av 2 g 24-ethyl-5a-cholesta-2,22-dien-6-on i 270 ml iseddik og 3,7 ml vann ble tilsatt 3,2 g a) To a solution of 2 g of 24-ethyl-5a-cholesta-2,22-dien-6-one in 270 ml of glacial acetic acid and 3.7 ml of water was added 3.2 g
sølvacetat og 1,9 g jod, og blandingen ble oppvarmet til 4 5° C under omrøring i 3 timer. Etter avfiltrering av silver acetate and 1.9 g of iodine, and the mixture was heated to 45°C with stirring for 3 hours. After filtering off
sølvsaltet, vasking med kloroform ble filtratet fortynnet med kloroform og ble vasket med vann, natriumthiosulfat og vann, ble tørket og inndampet. Etter krystallisering fra aceton-hexan ble det erholdt.1,2 g 23-acetoxy-33-hydroxy-2 4-ethyl-5a-cholest-22-en-6-on. the silver salt, washing with chloroform, the filtrate was diluted with chloroform and was washed with water, sodium thiosulfate and water, was dried and evaporated. After crystallization from acetone-hexane, 1.2 g of 23-acetoxy-33-hydroxy-2 4-ethyl-5a-cholest-22-en-6-one was obtained.
Sm.p. 192 - 194° C. Sm.p. 192 - 194° C.
b) Etter bromering av A 22-dobbeltbindingen, Baeyer-Villiger-oxydasjon og sinkreduksjon slik som beskrevet i Eksempel b) After bromination of the A 22 double bond, Baeyer-Villiger oxidation and zinc reduction as described in Example
lc) og ld) ble råproduktet kromatografert på silicagel. lc) and ld) the crude product was chromatographed on silica gel.
Ved hjelp av gradienteluering med kloroform-aceton ble det etter omkrystallisering fra hexan-ether erholdt.i 75 %-ig utbytte 23-acetoxy-33-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-on, sm.p. 151 - 153° C og i 10 %-ig utbytte 23-acetoxy-33_hydroxy-24-ethyl-6-oxa-B-homo-5a-cholest-22-en-7-on, sm.p. 175 - 176° C. Using gradient elution with chloroform-acetone, after recrystallization from hexane-ether, 23-acetoxy-33-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22- en-6-one, m.p. 151 - 153° C and in 10% yield 23-acetoxy-33_hydroxy-24-ethyl-6-oxa-B-homo-5a-cholest-22-en-7-one, m.p. 175 - 176° C.
Eksempel 3Example 3
a) 2,2 g 23-acetoxy-33-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-on ble i 50 ml methanol tilsatt en løs- ning av 500 mg kaliumhydroxyd i 10 ml methanol, og blandingen ble omrørt i 30 minutter ved romtemperatur. Blandingen ble surgjort med eddiksyre, produktet ble utfelt i isvann, fraskilt, vasket og tørket. Etter krystallisering fra kloroform-ether ble det erholdt 1,7 g 23,33-dihydroxy-2 4-ethyl-7-oxa-B-homo-5a-cholest-22-en-6 -on. a) 2.2 g of 23-acetoxy-33-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one was added to 50 ml of methanol to a solution of 500 mg potassium hydroxide in 10 ml of methanol, and the mixture was stirred for 30 minutes at room temperature. The mixture was acidified with acetic acid, the product was precipitated in ice water, separated, washed and dried. After crystallization from chloroform-ether, 1.7 g of 23,33-dihydroxy-2 4-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one was obtained.
Sm.p. 211 - 213° C. Sm.p. 211 - 213° C.
b) 500 mg .23/33-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22- en-6-on ble i 4 ml pyridin avkjølt til -10° C tilsatt b) 500 mg of .23/33-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one was added in 4 ml of pyridine cooled to -10° C
0,5 ml acetanhydrid og blandingen ble omrørt i 3,5 time ved -5 til fl°.C. Etter utfelling med isvann, separering av produktet, vasking og tørking ble dette omkrystallisert fra aceton-hexan. Det ble erholdt. 410. mg 33acetoxy-23- hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-on. 0.5 ml of acetic anhydride and the mixture was stirred for 3.5 hours at -5 to fl°. After precipitation with ice water, separation of the product, washing and drying, this was recrystallized from acetone-hexane. It was obtained. 410. mg 33-acetoxy-23-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one.
Sm.p. 182 - 184° C. Sm.p. 182 - 184° C.
Eksempel 4Example 4
1 g 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-on ble løst i 10 ml pyridin, ble avkjølt til 0° C og ble tilsatt 1 ml acetanhydrid. Blandingen ble omrørt i 5 timer ved 0 - 5° C, ble helt over i isvann, produktet ble fraskilt, vasket og tørket. Etter omkrystallisering fra pentan ble det erholdt 950 mg 2a-acetoxy-3a-hydroxy-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 165,5 - 167° C. 1 g of 2α,3α-dihydroxy-7-oxa-B-homo-5α-cholestan-6-one was dissolved in 10 ml of pyridine, cooled to 0° C. and 1 ml of acetic anhydride was added. The mixture was stirred for 5 hours at 0 - 5° C, poured into ice water, the product was separated, washed and dried. After recrystallization from pentane, 950 mg of 2α-acetoxy-3α-hydroxy-7-oxa-B-homo-5α-cholestan-6-one, m.p. 165.5 - 167° C.
Fremstilling av utgangsmaterialer:Preparation of starting materials:
a) 25 g 5a-cholest-2-en-6-on ble løst i 140 ml tetrahydrofuran, ble tilsatt 14 g N-methylmorfolin-N-oxyd, 25 ml a) 25 g of 5α-cholest-2-en-6-one was dissolved in 140 ml of tetrahydrofuran, 14 g of N-methylmorpholine-N-oxide, 25 ml
vann og 50 ml t-butanol og under omrøring en løsning avwater and 50 ml of t-butanol and, while stirring, a solution of
250 mg.osmiumtetroxyd i 50 ml tetrahydrofuran. Reaksjons-løsningen ble omrørt i 17 timer ved romtemperatur under ute-lukkelse av lys. Deretter ble produktet utfelt i 7 liter isvann som var blitt- tilsatt 50 ml 2N svovelsyre og 1 g natriumsulfid, produktet ble fraskilt, vasket med vann, ble oppløst i kloroform og løsningen ble inndampet i vakuum. Råproduktet (30 g). ble løst i 140 ml pyridin, og etter tilsetning av 70 ml acetanhydrid og 3 g 4-dimethylaminopyridin fikk blandingen stå i 16 timer ved romtemperatur. Etter vannutfelling, separering av produktet, vasking med vann og 250 mg osmium tetroxyd in 50 ml tetrahydrofuran. The reaction solution was stirred for 17 hours at room temperature under exclusion of light. The product was then precipitated in 7 liters of ice water to which 50 ml of 2N sulfuric acid and 1 g of sodium sulphide had been added, the product was separated, washed with water, dissolved in chloroform and the solution evaporated in vacuo. The raw product (30 g). was dissolved in 140 ml of pyridine, and after adding 70 ml of acetic anhydride and 3 g of 4-dimethylaminopyridine, the mixture was allowed to stand for 16 hours at room temperature. After water precipitation, separation of the product, washing with water and
tørking ble dette kromatografert på silicagel. Etter omkrystallisering fra ethanol ble det i 75 %-ig utbytte erholdt 2a,3a-diacetoxy-5a-cholestan-6-on, sm.p. 150,0 - drying, this was chromatographed on silica gel. After recrystallization from ethanol, 2a,3a-diacetoxy-5a-cholestan-6-one was obtained in 75% yield, m.p. 150.0 -
151,5° C og i 15 % utbytte 23,3&-diacetoxy-5a-cholestan-6-on, sm.p. 183,5 - 185° C. b) 26 ml 30 %-ig hydrogenperoxyd ble. suspendert i methylenklorid, ble avkjølt til -10° C hvorpå 161 ml trifluoreddiksyreanhydrid langsomt ble dråpevis tilsatt .slik at temperaturen ikke oversteg +10° C. • Deretter ble 2 7,2 g 2a,3a-diacetoxy-5a-cholestan-6-on i 160 ml methylenklorid tilsatt og blandingen ble omrørt i 40 minutter ved romtemperatur. For opparbeidelse ble reaksjonsblandingen fortynnet med methylenklorid og vasket med vann, 5 %-ig natriumcarbo-natløsning og med vann og ble inndampet i vakuum. Etter kromatografi på silicagel og omkrystallisering fra aceton-hexan ble det i 81 % utbytte erholdt 2a,3a-diacetoxy-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 183 - 184° C og i 6,2 % utbytte 2a,3a-diacetoxy-6-oxa-B-homp-5a-cholestan-7-on, 151.5° C and in 15% yield 23,3β-diacetoxy-5α-cholestan-6-one, m.p. 183.5 - 185° C. b) 26 ml of 30% hydrogen peroxide was. suspended in methylene chloride, was cooled to -10° C, whereupon 161 ml of trifluoroacetic anhydride was slowly added dropwise, so that the temperature did not exceed +10° C. • Then 2 7.2 g of 2a,3a-diacetoxy-5a-cholestane-6- on in 160 ml of methylene chloride added and the mixture was stirred for 40 minutes at room temperature. For work-up, the reaction mixture was diluted with methylene chloride and washed with water, 5% sodium carbonate solution and with water and was evaporated in vacuo. After chromatography on silica gel and recrystallization from acetone-hexane, 2a,3a-diacetoxy-7-oxa-B-homo-5a-cholestan-6-one was obtained in 81% yield, m.p. 183 - 184° C and in 6.2% yield 2a,3a-diacetoxy-6-oxa-B-homp-5a-cholestan-7-one,
sm.p. 245 - 247° C. sm.p. 245 - 247° C.
c) 28,3 g 2a,3a-diacetoxy-7-oxa-B-homo-5a-cholestan-6-on ble løst i 500 ml methanol og etter tilsetning av en c) 28.3 g of 2a,3a-diacetoxy-7-oxa-B-homo-5a-cholestan-6-one was dissolved in 500 ml of methanol and after the addition of a
løsning av 14 g kaliumhydroxyd i 150 ml methanol ble blandingen omrørt i 30 minutter ved romtemperatur. Reaksjons-løsningen ble deretter surgjort med eddiksyre, ble utfelt med isvann, produktet ble fraskilt, vasket med vann og tørket. Etter omkrystallisering fra aceton-pentan ble det erholdt 22,4 g (95 %) 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 138 - 140° C. solution of 14 g of potassium hydroxide in 150 ml of methanol, the mixture was stirred for 30 minutes at room temperature. The reaction solution was then acidified with acetic acid, precipitated with ice water, the product was separated, washed with water and dried. After recrystallization from acetone-pentane, 22.4 g (95%) of 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-one were obtained, m.p. 138 - 140° C.
Eksempel 5Example 5
a) 1,1 g 2a,3a-diacetoxy-6-oxa-B-homo-5a-cholestan-7-oh ble som beskrevet i Eksempel 4c) forsåpet. Det ble a) 1.1 g of 2a,3a-diacetoxy-6-oxa-B-homo-5a-cholestan-7-oh was saponified as described in Example 4c). It was
erholdt 785 mg 2a,3a-dihydroxy-6-oxa-B-homo-5a-chole-stan-7-on med sm.p. 216,5 - 218° C. obtained 785 mg of 2a,3a-dihydroxy-6-oxa-B-homo-5a-chole-stan-7-one with m.p. 216.5 - 218° C.
b) 25 0 mg 2a,3a-dihydroxy-6-oxa-B-homo-5a-cholestan-7-orT ble løst i 2 ml pyridin, ble avkjølt til -10° C, ble b) 250 mg of 2a,3a-dihydroxy-6-oxa-B-homo-5a-cholestan-7-orT was dissolved in 2 ml of pyridine, was cooled to -10° C, was
tilsatt 0,24 ml acetanhydrid og ble omrøtt i 4 timer ved added 0.24 ml of acetic anhydride and was stirred for 4 hours at
-5 til 0° C. Etter utfelling med isvann, separering av produktet, vasking og tørking ble dette omkrystallisert -5 to 0° C. After precipitation with ice water, separation of the product, washing and drying, this was recrystallized
fra aceton-hexan. Det ble erholdt 210 mg 2a-acetoxy-3a-hydroxy-6-oxa-B-homo-'5a-cholestan-7-on, sm.p. 199 - from acetone-hexane. 210 mg of 2a-acetoxy-3a-hydroxy-6-oxa-B-homo-'5a-cholestan-7-one were obtained, m.p. 199 -
201° C. 201°C.
Eksempel 6Example 6
600 mg 2a,3a-dihydroxy-24-methyl-6-oxa-B-homo-5a-cholest-22-en-7-on ble acetylert som beskrevet i Eksempel 5 b). Det ble erholdt 515 mg 2a-acetoxy-3a-hydroxy-24-methyl-6-oxa-B-homo-5a-cholest-22-en-7-on, sm.p. 173 - 174°C. Fremstilling av utgangsmaterialer: Fra brassicasterin ble etter kjente metoder 24-methyl-5a-cholesta-2/22^.dien-6-on fremstilt, og dette ble omsatt som beskrevet i Eksempel 1. 600 mg of 2a,3a-dihydroxy-24-methyl-6-oxa-B-homo-5a-cholest-22-en-7-one was acetylated as described in Example 5 b). 515 mg of 2α-acetoxy-3α-hydroxy-24-methyl-6-oxa-B-homo-5α-cholest-22-en-7-one were obtained, m.p. 173 - 174°C. Preparation of starting materials: 24-methyl-5a-cholesta-2/22^.dien-6-one was prepared from brassicasterin according to known methods, and this was reacted as described in Example 1.
Eksempel 7Example 7
1 g 2(3,3f}-dihydroxy-7-oxa-B-homo-5a-cholestan-6-on ble løst i 100 ml aceton og 100 ml tetrahydrofuran, ble avkjølt til 0° C, ble tilsatt 0,5 ml bortrifluorid-etherat og ble omrørt i 30.minutter ved 0 til 5° C. Etter tilsetning av 1 ml pyridin ble blandingen inndampet i. vakuum og produktet ble omkrystallisert fra methylenklorid-isopropylether. 1 g of 2(3,3f}-dihydroxy-7-oxa-B-homo-5a-cholestan-6-one was dissolved in 100 ml of acetone and 100 ml of tetrahydrofuran, was cooled to 0° C, was added 0.5 ml boron trifluoride etherate and was stirred for 30 minutes at 0 to 5° C. After addition of 1 ml of pyridine, the mixture was evaporated in vacuo and the product was recrystallized from methylene chloride-isopropyl ether.
Det ble erholdt 731 mg 23,33-isopropylidendioxy-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 216 - 217° C. 731 mg of 23,33-isopropylidenedioxy-7-oxa-B-homo-5a-cholestan-6-one were obtained, m.p. 216 - 217° C.
På analog måte.ble fremstilt: In an analogous way.was produced:
2a,3a-isopropylidendioxy-7-oxa-B-homo-5a-cholestan-6-on,2a,3a-isopropylidenedioxy-7-oxa-B-homo-5a-cholestan-6-one,
sm.p. 216 - 217° C. sm.p. 216 - 217° C.
2a,3a-isopropylidendioxy-2 4-ethyl-7-oxa-B-homo-5a-cholestan-22-en-6-on, sm.p. 157 - 158° C. 2α,3α-isopropylidenedioxy-2 4-ethyl-7-oxa-B-homo-5α-cholestan-22-en-6-one, m.p. 157 - 158° C.
Eksempel 8Example 8
900 mg 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-on ble løst i 10 ml pyridin, ble avkjølt til 0° C, ble tilsatt 1,8 ml valeriansyreanhydrid og ble omrørt i 10 timer ved 0 til 5° C. Etter opparbeidelse som teskrevet i Eksempel 4 ble det erholdt 950 mg 2a-valeryloxy-3a-hydroxy-7-oxa-B-homo-5a-cholestan-6-on,sm.p. 92 - 94° C. 900 mg of 2α,3α-dihydroxy-7-oxa-B-homo-5α-cholestan-6-one was dissolved in 10 ml of pyridine, cooled to 0° C, 1.8 ml of valeric anhydride was added and stirred for 10 hours at 0 to 5° C. After work-up as described in Example 4, 950 mg of 2a-valeryloxy-3a-hydroxy-7-oxa-B-homo-5a-cholestan-6-one, m.p. 92 - 94° C.
Eksempel 9Example 9
2a,3a-diacetoxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-on ble forsåpet som beskrevet i Eksempel 3 og ble partielt acetylert. Det ble i 70 %-ig utbytte erholdt 2a-acetoxy-3a-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-on, sm.p. 158 - 160° C. 2α,3α-diacetoxy-24-ethyl-7-oxa-B-homo-5α-cholest-22-en-6-one was saponified as described in Example 3 and was partially acetylated. 2α-acetoxy-3α-hydroxy-24-ethyl-7-oxa-B-homo-5α-cholest-22-en-6-one was obtained in 70% yield, m.p. 158 - 160° C.
Eksempel 10Example 10
900 mg 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-on ble løst i 10 ml pyridin, ble avkjølt til 0° C, ble tilsatt 1 ml ethoxyeddiksyreanhydrid og ble omrørt i 5 timer ved 0 — 5° C. Etter opparbeidelse som beskrevet i Eksempel 4 ble" det etter omkrystallisering. fra aceton-hexan erholdt 720 mg 2a-e±hoxyacetoxy-3a-hydroxy-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 172 - 173° C. 900 mg of 2α,3α-dihydroxy-7-oxa-B-homo-5α-cholestan-6-one was dissolved in 10 ml of pyridine, cooled to 0° C, 1 ml of ethoxyacetic anhydride was added and stirred for 5 hours at 0 — 5° C. After working up as described in Example 4, after recrystallization from acetone-hexane, 720 mg of 2a-e±hoxyacetoxy-3a-hydroxy-7-oxa-B-homo-5a-cholestan-6-one were obtained , mp 172 - 173° C.
Eksempel 11Example 11
300 mg 2a,3a-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-on ble i 3 ml pyridin omrørt med 780 mg fenyleddiksyreanhydrid i 10 timer ved 0 - 5° C. Etter opparbeidelse og omkrystallisering fra aceton-hexan.ble det erholdt 210 mg 2a-fenylacetoxy-3a-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-ren-6-on, sm.p- 185 - 186° C. 300 mg of 2a,3a-dihydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one was stirred in 3 ml of pyridine with 780 mg of phenylacetic anhydride for 10 hours at 0 - 5°C After working up and recrystallization from acetone-hexane, 210 mg of 2a-phenylacetoxy-3a-hydroxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-ren-6-one were obtained, m.p. - 185 - 186° C.
Eksempel 12Example 12
500 mg 2a, 3a-dihydroxy-7-oxa-B-homio-5a-cholestan-6-on ble i 50 ml benzen tilsatt 0,75 ml triethylorthoeddiksyre-ester og 5 mg p-toluensulfonsyre. Løsningen ble omrørt i 20 minutter ved romtemperatur, ble tilsatt 3 dråper pyridin og ble inndampet i vakuum. Residuet ble løst i methylenklorid, ble vasket med vann, tørket over natriumsulfat og inndampet. Det ble erholdt 605 mg 2a,3a-(1-ethoxy-ethylendioxy)-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 150 - 154° C. 500 mg of 2a, 3a-dihydroxy-7-oxa-B-homio-5a-cholestan-6-one was added to 50 ml of benzene, 0.75 ml of triethyl orthoacetic acid ester and 5 mg of p-toluenesulfonic acid. The solution was stirred for 20 minutes at room temperature, 3 drops of pyridine were added and evaporated in vacuo. The residue was dissolved in methylene chloride, washed with water, dried over sodium sulfate and evaporated. 605 mg of 2a,3a-(1-ethoxy-ethylenedioxy)-7-oxa-B-homo-5a-cholestan-6-one were obtained, m.p. 150 - 154° C.
På analog måte ble fremstilt: 2a,3a-(1-ethoxy-ethylendioxy)-6-oxa-B-homo-5a-cholestan-7-on In an analogous manner was prepared: 2a,3a-(1-ethoxy-ethylenedioxy)-6-oxa-B-homo-5a-cholestan-7-one
sm.p. 122 - 124° C, sm.p. 122 - 124° C,
2a,3a-(1-ethoxy-propylidendioxy)-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 115 - 118° C, 22,3a- (1-methoxy-methylendioxy)-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-on, sm.p. 123 - 125° C. 2α,3α-(1-ethoxy-propylidenedioxy)-7-oxa-B-homo-5α-cholestan-6-one, m.p. 115 - 118° C, 22,3a-(1-methoxy-methylenedioxy)-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one, m.p. 123 - 125° C.
Eksempel 13Example 13
500 mg 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-on ble i 5 ml tetrahydrofuran tilsatt 1,5 ml acetofenon og 0,1 ml bortrifluorid-etherat og ble oppvarmet i 3 timer til tilbakeløpskokning. Deretter ble løsningen inndampet i vakuum, 1 ml pyridin ble tilsatt, og løsningen ble inndampet i høyvakuum. Etter triturering med hexan ble det erholdt 500 mg of 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-one was added to 5 ml of tetrahydrofuran, 1.5 ml of acetophenone and 0.1 ml of boron trifluoride etherate and heated for 3 hours to reflux . Then the solution was evaporated in vacuo, 1 ml of pyridine was added, and the solution was evaporated in high vacuum. After trituration with hexane, it was obtained
465 mg amorft 2a,3a-(1-methyl-l-fenyl-methylendioxy)-7-oxa-B-homo-5a-cholestan-6-on som diastereoraer blanding med smeltepunkt 130,5 - 132° C. 465 mg of amorphous 2a,3a-(1-methyl-1-phenyl-methylenedioxy)-7-oxa-B-homo-5a-cholestan-6-one as diastereomeric mixture with melting point 130.5 - 132° C.
Eksempel 14Example 14
500 mg 2a,3a-dihydroxy-7-oxa-B-horao-5a-cholestan-6-on ble løst i 15 ml diethylcarbonat, ble oppvarmet til kokning og etter avdestillering av 2 ml diethylcarbonat ble 30 mg natriummethylat tilsatt. Fra reaksjonsløsningen ble noen ml avdestillert i løpet av 3 minutter. Etter avkjøling ble reaksjonsløsningen tilsatt 0,15 ml iseddik og ble inndampet i vakuum. Residuet ble omkrystallisert fra aceton-hexan. Det ble erholdt 450 mg 2a,3a-carbonyldioxy-7-oxa-B-homo-5a-cholestan-6-on, sm.p. 203,5 - 205° C. 500 mg of 2a,3a-dihydroxy-7-oxa-B-horao-5a-cholestan-6-one was dissolved in 15 ml of diethyl carbonate, heated to boiling and after distilling off 2 ml of diethyl carbonate, 30 mg of sodium methylate was added. A few ml were distilled from the reaction solution within 3 minutes. After cooling, 0.15 ml of glacial acetic acid was added to the reaction solution and evaporated in vacuo. The residue was recrystallized from acetone-hexane. 450 mg of 2a,3a-carbonyldioxy-7-oxa-B-homo-5a-cholestan-6-one were obtained, m.p. 203.5 - 205° C.
På analog måte ble fremstilt: 2a,3a-carbonyldioxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-on, sm.p. 193 - 195° C In an analogous manner was prepared: 2a,3a-carbonyldioxy-24-ethyl-7-oxa-B-homo-5a-cholest-22-en-6-one, m.p. 193 - 195° C
23,33-carbonyldioxy-7-oxa-B-homo-5a-cholestan-6-on,23,33-carbonyldioxy-7-oxa-B-homo-5a-cholestan-6-one,
sm.p. 212 - 214° C sm.p. 212 - 214° C
Eksempel 15Example 15
300 mg 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-on ble løst i 2 ml benzaldehyd, 0,02 ml 70 %-ig perklor-syre ble tilsatt og blandingen ble omrørt i 2 timer ved romtemperatur. Deretter ble løsningen nøytralisert med pyridin, ble fortynnet med hexan og kromatografert over silicagel. Med hexan-eddikester (6:4) ble det eluert 258 mg 2a, 3a-benzylidendioxy-7-oxa-B-homo-5a-cholestan-6-on som ble omkrystallisert fra ether-pentan. Sm.p. 137 - 139° C. 300 mg of 2a,3a-dihydroxy-7-oxa-B-homo-5a-cholestan-6-one was dissolved in 2 ml of benzaldehyde, 0.02 ml of 70% perchloric acid was added and the mixture was stirred for 2 hours at room temperature. The solution was then neutralized with pyridine, diluted with hexane and chromatographed over silica gel. With hexane-acetic ester (6:4) 258 mg of 2a,3a-benzylidenedioxy-7-oxa-B-homo-5a-cholestan-6-one were eluted, which was recrystallized from ether-pentane. Sm.p. 137 - 139° C.
På analog måte ble fremstilt: In an analogous way, the following was produced:
2a,3a-benzylidendioxy-6-oxa-B-homo-5a-cholestan-7-on,2a,3a-benzylidenedioxy-6-oxa-B-homo-5a-cholestan-7-one,
sm.p. 179 - 180° C, sm.p. 179 - 180° C,
23/33-benzylidendioxy-6-oxa-B-homo-5a-cholestan-7-on, 23/33-benzylidenedioxy-6-oxa-B-homo-5a-cholestan-7-one,
sm.p. 129 - 131° C sm.p. 129 - 131° C
23,33-benzylidendioxy-7-oxa-B-homo-5a-cholestan-6-on-23,33-benzylidenedioxy-7-oxa-B-homo-5a-cholestan-6-one-
sm.p. 153 - 155° C sm.p. 153 - 155° C
De nye forbindelser utgjør krystallinske farve- og luktløse substanser som er tungt løselige i vann, betinget løselige i alifatiske hydrocarboner slik som petrolether, hexan, pentan og cyclohexan, godt løselige i halogenerte hydrocarboner slik som kloroform, methylenklorid, tetra-klorcarbon, aromatiske hydrocarboner slik som benzen, toluen og xylen, ethere slik som diethylether, tetrahydrofuran og dioxan, carboxylsyrenitriler slik som acetonitril,. ketoner slik som aceton, alkoholer slik som methanol og ethanol, carboxylsyreamider slik som dimethylformamid og sulfoxyder slik som dimethylsulfoxyd. The new compounds are crystalline, colorless and odorless substances that are poorly soluble in water, conditionally soluble in aliphatic hydrocarbons such as petroleum ether, hexane, pentane and cyclohexane, well soluble in halogenated hydrocarbons such as chloroform, methylene chloride, tetrachlorocarbon, aromatic hydrocarbons such as such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane, carboxylic acid nitriles such as acetonitrile,. ketones such as acetone, alcohols such as methanol and ethanol, carboxylic acid amides such as dimethylformamide and sulfoxides such as dimethylsulfoxyd.
De etterfølgende eksempler illustrerer anvendelses-mulighetene for de nye forbindelser, i form av de tidligere angitte tilberedelser. The following examples illustrate the application possibilities for the new compounds, in the form of the previously indicated preparations.
Eksempel 16Example 16
Vekstøkning av buskbønner.Growth of bush beans.
Buskbønner av sorten "Pinto" ble dyrket i klima-kammer ved 25° C og 90 % luftfuktighet under innvirkning av lys med en høy andel av intensitet i. området.660 nm og en meget lav andel i området 730 nm. Bush beans of the variety "Pinto" were grown in climate chambers at 25° C and 90% humidity under the influence of light with a high proportion of intensity in the range of 660 nm and a very low proportion in the range of 730 nm.
Etter 6 dagers dyrkning ble 10 og 20 mikrogram av de forbindelser som skulle prøves, oppløst i løsningsmidlet, og påført på det utviklende andre internodium. 3 dager etter påføring ble økningen av internodiene målt og den prosentuelle forlengelse bestemt i sammenligning med kontrollen. After 6 days of cultivation, 10 and 20 micrograms of the compounds to be tested were dissolved in the solvent and applied to the developing second internode. 3 days after application, the increase of the internodes was measured and the percentage elongation determined in comparison with the control.
Tabellen inneholder resultatene av disse forsøk. The table contains the results of these experiments.
Resultatene viser at de nye forbindelser under de angitte prøvebetingelser"utviser en mer intensiv strekning enn sammenligningsmidlet og kontrollen. The results show that the new compounds under the specified test conditions exhibit a more intensive stretch than the comparator and the control.
Sammenligningsmidlet forårsaker ennvidere bare en mer eller mindre sterk økning av tykkelsesveksten, hvilket til og med delvis fører til en sammenpresning av internodiene. The comparator further only causes a more or less strong increase in thickness growth, which even partially leads to a compression of the internodes.
Eksempel 17Example 17
Stimulering av rotvekst ved mungbønner.Stimulation of root growth in mung beans.
Mungbønner ble under veksthusbetingelser bragt til spiring i vandige emulsjoner av de forbindelser som skulle prøves i en konsentrasjon på 0,01 vekt%. Under greenhouse conditions, mung beans were germinated in aqueous emulsions of the compounds to be tested in a concentration of 0.01% by weight.
Etter 6 dager ble rotlengden av de spirede planter bestemt. After 6 days, the root length of the germinated plants was determined.
Tabellen inneholder resultatene av disse forsøk i form av prosentangivelser. The table contains the results of these trials in the form of percentages.
Eksempel 18 Example 18
Økning av motstandskraften i nytteplanter.Increasing the resilience of useful plants.
De i tabellen angitte nytteplanter ble ved pre-emergensmetoden behandlet med vandige emulsjoner av de forbindelser som skulle prøves eller deres blandinger. En uke etter behandlingen ble behandlingsresultatet vurdert etter et skjema.fra 0 til 10, hvori 0 = 100 %-ig tilintetgjørelse og 10 = ingen beskadigelse. The useful plants indicated in the table were treated by the pre-emergence method with aqueous emulsions of the compounds to be tested or their mixtures. One week after the treatment, the treatment result was assessed according to a form from 0 to 10, where 0 = 100% destruction and 10 = no damage.
Det fremgår at de nye forbindelser gir plantene en høyere motstandskraft enn det kjente herbicid. It appears that the new compounds give the plants a higher resistance than the known herbicide.
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DD (1) | DD213347A5 (en) |
DE (1) | DE3234605A1 (en) |
DK (1) | DK417783A (en) |
ES (1) | ES8404696A1 (en) |
FI (1) | FI833252A (en) |
FR (1) | FR2532941A1 (en) |
GB (1) | GB2127021A (en) |
GR (1) | GR78759B (en) |
IL (1) | IL69701A0 (en) |
IT (1) | IT1194398B (en) |
LU (1) | LU85002A1 (en) |
NL (1) | NL8302425A (en) |
NO (1) | NO833295L (en) |
PL (1) | PL243719A1 (en) |
PT (1) | PT77257B (en) |
SE (1) | SE8304841L (en) |
ZA (1) | ZA836872B (en) |
ZW (1) | ZW19683A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4886544A (en) * | 1987-03-17 | 1989-12-12 | Hayashi Sei Ichi | 23-phenylbrassinosteroids |
CN116636533B (en) * | 2023-07-27 | 2023-10-20 | 海南大学三亚南繁研究院 | Method for improving cold resistance of rubber sapling |
-
1982
- 1982-09-15 DE DE19823234605 patent/DE3234605A1/en not_active Withdrawn
-
1983
- 1983-07-07 NL NL8302425A patent/NL8302425A/en not_active Application Discontinuation
- 1983-07-19 JP JP58130371A patent/JPS5955887A/en active Pending
- 1983-08-19 ES ES525035A patent/ES8404696A1/en not_active Expired
- 1983-08-23 BR BR8304545A patent/BR8304545A/en unknown
- 1983-08-26 PT PT77257A patent/PT77257B/en unknown
- 1983-09-01 AU AU18612/83A patent/AU1861283A/en not_active Abandoned
- 1983-09-09 SE SE8304841A patent/SE8304841L/en not_active Application Discontinuation
- 1983-09-12 GB GB08324347A patent/GB2127021A/en not_active Withdrawn
- 1983-09-12 PL PL24371983A patent/PL243719A1/en unknown
- 1983-09-12 IL IL69701A patent/IL69701A0/en unknown
- 1983-09-12 FI FI833252A patent/FI833252A/en not_active Application Discontinuation
- 1983-09-13 DD DD83254773A patent/DD213347A5/en unknown
- 1983-09-13 GR GR72433A patent/GR78759B/el unknown
- 1983-09-13 IT IT22861/83A patent/IT1194398B/en active
- 1983-09-14 LU LU85002A patent/LU85002A1/en unknown
- 1983-09-14 BE BE0/211536A patent/BE897758A/en not_active IP Right Cessation
- 1983-09-14 KR KR1019830004315A patent/KR840005736A/en not_active Application Discontinuation
- 1983-09-14 NO NO833295A patent/NO833295L/en unknown
- 1983-09-14 DK DK417783A patent/DK417783A/en not_active Application Discontinuation
- 1983-09-15 FR FR8314671A patent/FR2532941A1/en not_active Withdrawn
- 1983-09-15 ZA ZA836872A patent/ZA836872B/en unknown
- 1983-09-15 ZW ZW196/83A patent/ZW19683A1/en unknown
Also Published As
Publication number | Publication date |
---|---|
IT1194398B (en) | 1988-09-22 |
ES525035A0 (en) | 1984-05-16 |
JPS5955887A (en) | 1984-03-31 |
IT8322861A1 (en) | 1985-03-13 |
FI833252A0 (en) | 1983-09-12 |
ES8404696A1 (en) | 1984-05-16 |
DD213347A5 (en) | 1984-09-12 |
BE897758A (en) | 1984-03-14 |
ZA836872B (en) | 1984-05-30 |
DK417783D0 (en) | 1983-09-14 |
FR2532941A1 (en) | 1984-03-16 |
AU1861283A (en) | 1984-03-22 |
IL69701A0 (en) | 1983-12-30 |
BR8304545A (en) | 1984-04-24 |
PT77257A (en) | 1983-09-01 |
GR78759B (en) | 1984-10-02 |
DE3234605A1 (en) | 1984-03-22 |
GB2127021A (en) | 1984-04-04 |
PL243719A1 (en) | 1984-07-30 |
ZW19683A1 (en) | 1983-12-21 |
PT77257B (en) | 1986-02-04 |
DK417783A (en) | 1984-03-16 |
FI833252A (en) | 1984-03-16 |
SE8304841D0 (en) | 1983-09-09 |
LU85002A1 (en) | 1984-03-16 |
NL8302425A (en) | 1984-04-02 |
GB8324347D0 (en) | 1983-10-12 |
IT8322861A0 (en) | 1983-09-13 |
KR840005736A (en) | 1984-11-16 |
SE8304841L (en) | 1984-03-16 |
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