GB2023582A - 1,4-oxaza-spirohydrocarbon derivatives, their preparation and plant protecting compositions containing them - Google Patents
1,4-oxaza-spirohydrocarbon derivatives, their preparation and plant protecting compositions containing them Download PDFInfo
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- GB2023582A GB2023582A GB7918949A GB7918949A GB2023582A GB 2023582 A GB2023582 A GB 2023582A GB 7918949 A GB7918949 A GB 7918949A GB 7918949 A GB7918949 A GB 7918949A GB 2023582 A GB2023582 A GB 2023582A
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- compound
- oxaza
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- herbicide
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- 230000002633 protecting effect Effects 0.000 title abstract description 8
- 239000000203 mixture Substances 0.000 title description 24
- 238000002360 preparation method Methods 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- 239000004009 herbicide Substances 0.000 description 23
- 241000196324 Embryophyta Species 0.000 description 21
- 239000000729 antidote Substances 0.000 description 15
- 230000002363 herbicidal effect Effects 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000004480 active ingredient Substances 0.000 description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- 229940075522 antidotes Drugs 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002689 soil Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- JJMWKUJHFDFXAQ-UHFFFAOYSA-N CCCC1=C[S+](CC)C(NC([O-])=O)=C1CCC Chemical compound CCCC1=C[S+](CC)C(NC([O-])=O)=C1CCC JJMWKUJHFDFXAQ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- FBCCMZVIWNDFMO-UHFFFAOYSA-N dichloroacetyl chloride Chemical compound ClC(Cl)C(Cl)=O FBCCMZVIWNDFMO-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- POSWICCRDBKBMH-UHFFFAOYSA-N 3,3,5-trimethylcyclohexan-1-one Chemical compound CC1CC(=O)CC(C)(C)C1 POSWICCRDBKBMH-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
- YRMLFORXOOIJDR-UHFFFAOYSA-N Dichlormid Chemical compound ClC(Cl)C(=O)N(CC=C)CC=C YRMLFORXOOIJDR-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- -1 alkaline earth metal salts Chemical class 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical class OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
- PJXIBUIXCXSNCM-UHFFFAOYSA-N 2,2,4-trimethylcyclopentan-1-one Chemical compound CC1CC(=O)C(C)(C)C1 PJXIBUIXCXSNCM-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 244000075850 Avena orientalis Species 0.000 description 1
- 235000007319 Avena orientalis Nutrition 0.000 description 1
- 235000006463 Brassica alba Nutrition 0.000 description 1
- 244000140786 Brassica hirta Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241001465363 Panicum capillare Species 0.000 description 1
- 244000088461 Panicum crus-galli Species 0.000 description 1
- 235000011999 Panicum crusgalli Nutrition 0.000 description 1
- 235000011096 Papaver Nutrition 0.000 description 1
- 240000001090 Papaver somniferum Species 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 240000003461 Setaria viridis Species 0.000 description 1
- 235000002248 Setaria viridis Nutrition 0.000 description 1
- 240000002913 Trifolium pratense Species 0.000 description 1
- 235000015724 Trifolium pratense Nutrition 0.000 description 1
- 235000007244 Zea mays Nutrition 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 244000038559 crop plants Species 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 231100000208 phytotoxic Toxicity 0.000 description 1
- 230000000885 phytotoxic effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 235000013526 red clover Nutrition 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
Landscapes
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
1,4-Oxaza-spirohydrocarbon derivatives of the <IMAGE> wherein R1, R2 and R3 independently represent hydrogen or lower alkyl; with the proviso that at least one of them is alkyl; and n is 0 or 1, exhibit plant protecting properties. The novel compounds may be made by dichloroacetylation of the corresponding N-unsubstituted bases.
Description
SPECIFICATION 1,4-Oxaza-spirohydrocarbon derivatives, their preparation and plant protecting compositions containing them
This invention relates to a plant protecting composition. More particularly, this invention relates to a plant protecting composition which comprises as an antidote a new 1 ,4-oxaza-spirohydrocarbon derivative of the general formula I
wherein R1, R2and R3 independently represent hydrogen or lower alkyl, with the proviso that at least one of them is alkyl; and n is O or 1, and optionally one or more herbicides, in admixture with an agriculturally acceptable carrier and/or adjuvant. As carrier there may be used solid and/or liquid carriers, and the adjuvant preferably comprises one or more surface active agents.The term 'plant protecting' refers herein to the protection of desirable crop or ornamental species as opposed to undesirable weed species.
The above-defined derivatives of the general formula I and a process for the preparation thereof are also within the scope of the invention.
It is well known that certain herbicides, in addition to their weed-killing effect, adversely affect the growth of cultivated plants and may cause serious damage. Some herbicides for example inhibit the growth of cultivated plants, cause growth anomalies or decrease the crop. Selectivity of the herbicides, i.e. tolerance by the cultivated plants is generally increased by using herbicide compositions containing two or more active ingredients or by using so-called antidotes in or simultaneously with the herbicide compositions. Useful antidotes are described for example in the published German patent application (DOS) No. 2,218,097.
It has now surprisingly been found that new derivatives of the general formula I, wherein R,. R2, R3 and n have the meanings defined above, considerably decrease or even eliminate the undesired damage of cultivated plants caused by herbicides. Said antidotes are especially effective in combination with herbicides of the thiolcarbamate type, thereby increasing their selectivity.
The new derivatives of the general formula I, wherein R1, R2, R3and n are as defined above, can be prepared bydichloroacetylating a compound of the general formula II
wherein R1, R2, R3 and n have the meanings defined above, e.g. with dichloroacetyl chloride in the presence of an acid binding agent, preferably triethylamine.
Compounds of the general formula II can be obtained by reacting a cycloalkanone of the general formula Ill
wherein1, R2, R3 and n are as given above, with ethanolamine [J.A.C.S. 75, 358 (1953)].
The plant protecting compositions according to the invention can be applied to the soil or admixed into the soil in a manner known per Se. A direct treatment of the plants or steeping of the seeds is also possible. The antidotes of the general formula I are either formulated together with the herbicide(s) or are employed in the form of separate formulations before, after or simultaneously with the treatment with the herbicide(s).
As it has already been stated, the antidotes according to the invention are preferably used to decrease the undesired effect of herbicidal thiolcarbamate derivatives. In this way also those thiolcarbamate-type herbicides can be safely used for which the effective and phytotoxic doses are very near or even overlapping. It must, however, not be left out of consideration that the activity of herbicides is strongly influenced by factors like soil composition, weather conditions etc.
The antidotes according to the invention can be used in the form of compositions containing two or more herbicide active ingredients. One of said herbicides is preferably a thiolcarbamate derivative.
If the antidote is used in combination with one or more herbicides, it is preferably applied in the same way as known for herbicides alone in the form of suitable ready to use formulations.
The quantity of the antidote may be varied within a wide range depending on the weeds to be controlled, the cultivated plants, the herbicide(s) used and the desired effect. It is generally used in a quantity of 0.001 to 50 parts by weight, preferably 0.1 to 10 parts by weight, related to 100 parts by weight of the herbicide.
If compounds of the general formula I are used in plant protecting compositions, in combination with herbicide active ingredients, the total active ingredient concentration is between 0.1 and 95%.
If compounds of the general formula I are used as separate compositions, said compositions generally contain 0.1 to 95% by weight, preferably 0.5 to 70% by weight of antidote.
A preferred representative of the compounds of the general formula I is the N-(dichloroacetyl) 6,6,8-trimethyl-1 ,4-oxaza-spiro[4,4jnonane.
The compositions according to the invention contain, in addition to the active ingredients, one or more conventional solid or liquid carriers, or diluents, and optionally surface active agents, such as dispersing or emulsifying agents.
As solid carrier or diluent for example talc, silica gel, aluminium silicates, tricalcium phosphate, kaolin and bentonite can be used.
Typical representatives of liquid carriers or diluents are hydrocarbons and derivatives thereof, such as toluene, xylene, acetophenone, polar solvents, and mineral, vegetable or animal oils.
The surface active agents can have an ionic or anionic character. As surface active agent for example the condensation products of ethylene oxide with nonyl- or octylphenone, alkali metal or alkaline earth metal salts of sulphonic esters and sulphonic acid derivatives, and salts of lignin sulphonic acid can be used.
Application of the compositions according to the invention can be effected by spraying, sprinkling, dusting etc. in the form of suitable formulations, such as tank mixtures, solutions, suspensions, emulsions, wettable powders, dusts, powders, granules. It is preferred to start from concentrated solutions, which can be diluted in the place of application to the desired concentration or can be admixed with separate formulations of the herbicides.
Further details of the invention are illustrated by the following Example and biological test, which are not intended to limit the scope of the invention in any way.
Example 1.
N-dichloroacetyl-6,6,8-trimethyl- 1 ,4-oxaza-spiro[4,4]nonane.
To a mixture of 80 ml. of benzene and 12.61 g. (0.1 moles) of 2,2,4-trimethyl-cyclopentanone 6.21 g. (0.1 moles) of ethanolamine are added and the reaction mixture is boiled for 3.5 hours while water formed is continuously eliminated. To a benzene solution of 6,6,8-trimethyl-1 ,4-oxaza- spiro[4,4]nonaneobtained 10.12 g. (0.1 moles) of triethylamine are added ata temperature not exceeding 1 50 C. followed by the portionwise addition of 14.74 g. (0.1 moles) of dichloroacetyl chloride with stirring, at a temperature of OOC to 159C. The reaction is strongly exothermic therefore effective cooling is required to keep the temperature in the desired range.The reaction mixture is then stirred at room temperature for 0.5 hour, whereupon the salt precipitated is dissolved by adding water. The benzene phase is separated, washed with an aqueous sodium hydrogen carbonate solution and subsequently with water, then is dried over anhydrous sodium sulphate. The benzene solution is filtered and washed with a small portion of benzene. By distilling off the solvent 20.4 g. (72.9%) of the title compound are obtained as a yellow liquid; n20 = 1.4892.
Biological tests
Pots of 30 x 40 x 10 cm. are filled with quartz sand free of organic materials. The surface of the soil is sprayed with a herbicidal composition containing 3-ethyl-dipropyl-thiocarbamate in an amount of 10 kg. of active ingredient/ha, and simultaneously with an antidote composition containing N dichloroacetyl-6,6,8-trimethyl-1 ,4-oxaza-spiro[4,4]nonane in amounts of 0.1, 1,2, 5 and 10 kg. of active ingredient/ha, respectively. The soil is then thoroughly mixed and the cultivated plants and weeds to be tested are sown into the soil treated as described above.
For comparison purposes untreated control plants and plants treated with 10 kg./ha of the herbicide S-ethyl-dipropyl-thiolcarbamate alone and in admixture with 1 kg./ha of N,N-diallyldichloroacetamide (known antidote), are used.
The pots are kept in a greenhouse, at 21 C to 32 OC and watered as necessary.
Results were evaluated 3 to 6 weeks following the treatment, with respect to selectivity and phytotoxicity.
The following plants were tested: Zea mays, Avena sativa, Papaver somnfferum, Trifolium pratense, Sinapis alba, Panicum capillare, Setaria viridis, Echinochloa crus-galli.
The results obtained are shown in the following table.
From the data it can be clearly seen that N-dichloroacety 6,6,8-trimethyl-1 ,4-oxazaspiro[4,4]nonane has a satisfactory antidote effect even in a dose of 0.1 kg./ha., i.e. in an amount of 1% related to the weight of the herbicide; in other words, in this dose it protects the crop plants without decreasing the herbicidal effect of the active ingredient. The same effect is achieved only with a 1 kg./ha. dose of the known antidote tested, i.e. with an amount of 10% related to the herbicide used in the combination.
In the following table:
A = a 10:1 mixture of S-ethyl-dipropyl-thiolcarbamate and N,N-diallyl-dichloroacetamide;
B = S-ethyl-dipropyl-thiolcarbamate;
C = N-dichloroacetyl-6,6,8-trimethyl-1 ,4-oxaza-spiro[4,4] nonane.
Example 2.
N-(dichloroacetyl)-7,7,9-trimethyl- 1 ,4-oxaza-spiro[4,5]decane
To a mixture of 80 ml. of benzene and 14.10 g. (0.1 mole) of 3,3,5-trimethyl-cyclohexanone 6.21 g. (0.1 mole) of ethanolamine are added and the reaction mixture is boiled for 4.5 hours, while water formed is continuously eliminated.To the benzene solution of 7,7,9-trimethyl-1 ,4-oxazaspiro[4,5]decaneobtained 10.12 g. (0.1 mole) of triethylamine are added ata temperature not exceeding 1 50C, followed by the portionwise addition of 14.74 g. (0.1 mole) of dichloroacetyl chloride with stirring, at a temperature of 0 C to 1 50C. The reaction mixture is then stirred at room temperature for 0.5 hour, whereupon the salt precipitated is dissolved by adding water. The benzene phase is separated, washed with an aqueous sodium hydrogen carbonate solution, then dried over anhydrous sodium sulphate. The benzene solution is filtered. By distilling off the solvent and cooling the solution 22.4 g. (76.2%) of the title compound are obtained. M.p. 121-1230C.
The biological tests were carried out as described in Example 1.
The results obtained are shown in the table.
In the table:
D = N-(dichloroacetyl)-7 ,7,9-trimethyl- 1 ,4-oxaza-spiro[4,5]decane.
TABLE
Green
Undamaged welght of Number
Active Dose Dose plants malze/pot of plants Weight ingredient (kg./ha.) Antidote (kg./ha.) (g.) (g.) (pieces) Maize/g. (pieces) (g.)
Untreated control - - - 100 114 93 1.14 80 97
A 10 - - 97 100 88 1.03 80 86
B 10 - - 94 103 84 1.09 80 94
B 10 C 0.1 100 111 91 1.11 80 97
B 10 C 1 80 97 69 1.21 80 88
B 10 C 2 92 100 89 1.06 80 88
B 10 C 5 73 98 91 1.34 80 86
B 10 C 10 84 86 89 1.02 80 75
B 10 D 1 98 105 92 1.20 80 95
B 10 D 2 100 102 90 1.16 80 90
B 10 D 5 95 98 90 1.15 80 88
B 10 D 10 93 93 86 1.08 80 82
Claims (16)
- CLAIMS 1. 1 ,4-Oxaza-spirohydrocarbon derivatives of the general formula Iwherein R1, R2 and R3 independently represent hydrogen or lower alkyl; with the proviso that at least one of them is alkyl; and n is O or 1.
- 2. N-(Dichloroacetyl)-6,6,8-trimethyl-1,4-oxaza-spiro[4,4]nonane.
- 3. N-(Dichloroacetyl)-7,7,9-trimethyl-1,4-oxazo-spiro[4,5]decane.
- 4. Compounds of claim 1,-substantially as described herein.
- 5. A process for preparing a compound of claim 1 which comprises dichloroacetylating a compound of the general formula IIwherein R1, R2, R3 and n have the meanings defined in claim 1.
- 6. A process according to claim 5 wherein said compound of general formula (Il) is reacted with dichloroacetyl chloride in the presence of an acid-binding agent.
- 7. A process according to claim 5, substantially as illustrated in Examples 1 and 2.
- 8. A process for increasing the crop safety of herbicidal compositions containing as active ingredients thiolcarbamate derivatives, which comprises applying to the soil or the plants before, after or simultaneously with said herbicidal compositions a crop plant-protecting amount of a compound of any of claims 1-4.
- 9. A process according to claim 8, substantially as hereinbefore described with reference to the Biological Tests.
- 10. A plant protecting composition comprising a compound of claim 1 or 4 in admixture with an agriculturally acceptable carrier and/or adjuvant.
- 11. A composition according to claim 10 comprising the compound of claim 2.
- 12. A composition according to claim 10 comprising the compound of claim 3.
- 13. A composition according to any of claims 10-1 2 including at least one herbicide.
- 14. A composition according to claim 13 wherein said herbicide is a thiolcarbamate.
- 15. A composition according to claim 13 or 14 comprising 0.1 to 10 parts by weight of said compound and 100 parts by weight of said herbicide.
- 16. A composition according to claim 10, substantially as described herein with reference to the Examples.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU78NO228A HU178064B (en) | 1978-05-31 | 1978-05-31 | Antidote composition containing n-/trimethyl-cyclopentillidene /-ethanol-amine-dichloracetate and process for preparing the active material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2023582A true GB2023582A (en) | 1980-01-03 |
| GB2023582B GB2023582B (en) | 1982-11-03 |
Family
ID=11000049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7918949A Expired GB2023582B (en) | 1978-05-31 | 1979-05-31 | 1,4-oxaza-spirohydrocarbon derivatives their preparation and plant protecting compositions containing them |
Country Status (19)
| Country | Link |
|---|---|
| BE (1) | BE876570A (en) |
| BG (1) | BG30315A3 (en) |
| CS (1) | CS220787B2 (en) |
| DD (2) | DD143999A5 (en) |
| DE (1) | DE2922270A1 (en) |
| DK (1) | DK225679A (en) |
| ES (1) | ES481057A1 (en) |
| FR (1) | FR2427332A1 (en) |
| GB (1) | GB2023582B (en) |
| GR (1) | GR68367B (en) |
| HU (1) | HU178064B (en) |
| IE (1) | IE48779B1 (en) |
| IT (1) | IT1121547B (en) |
| LU (1) | LU81341A1 (en) |
| NL (1) | NL7904295A (en) |
| PL (1) | PL115639B1 (en) |
| PT (1) | PT69694B (en) |
| RO (1) | RO77441A (en) |
| TR (1) | TR20608A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6078952A (en) * | 1983-10-07 | 1985-05-04 | Daicel Chem Ind Ltd | 3,3,5-trimethylcyclohexane derivative |
| US4938796A (en) * | 1987-07-06 | 1990-07-03 | Ici Americas Inc. | Herbicidal compositions of acylated 1,3-dicarbonyl herbicides and antidotes therefor |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU80912A1 (en) * | 1978-02-06 | 1979-06-07 | Nitrokemia Ipartelepek | WEED KILLERS |
| HUT49981A (en) * | 1988-05-31 | 1989-12-28 | Eszakmagyar Vegyimuevek | Antidotal herbicide comprising chloroacetanilide derivative as active ingredient |
-
1978
- 1978-05-31 HU HU78NO228A patent/HU178064B/en unknown
-
1979
- 1979-05-20 GR GR59220A patent/GR68367B/el unknown
- 1979-05-28 BE BE1/9407A patent/BE876570A/en not_active IP Right Cessation
- 1979-05-28 CS CS793670A patent/CS220787B2/en unknown
- 1979-05-28 FR FR7913430A patent/FR2427332A1/en active Granted
- 1979-05-29 PT PT69694A patent/PT69694B/en unknown
- 1979-05-30 PL PL1979215973A patent/PL115639B1/en unknown
- 1979-05-30 DD DD79213266A patent/DD143999A5/en unknown
- 1979-05-30 BG BG043787A patent/BG30315A3/en unknown
- 1979-05-30 ES ES481057A patent/ES481057A1/en not_active Expired
- 1979-05-30 DD DD79216689A patent/DD147108A5/en unknown
- 1979-05-30 DK DK225679A patent/DK225679A/en unknown
- 1979-05-31 IT IT23181/79A patent/IT1121547B/en active
- 1979-05-31 TR TR20608A patent/TR20608A/en unknown
- 1979-05-31 LU LU81341A patent/LU81341A1/en unknown
- 1979-05-31 GB GB7918949A patent/GB2023582B/en not_active Expired
- 1979-05-31 NL NL7904295A patent/NL7904295A/en not_active Application Discontinuation
- 1979-05-31 DE DE19792922270 patent/DE2922270A1/en not_active Withdrawn
- 1979-05-31 RO RO7997691A patent/RO77441A/en unknown
- 1979-08-08 IE IE1332/79A patent/IE48779B1/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6078952A (en) * | 1983-10-07 | 1985-05-04 | Daicel Chem Ind Ltd | 3,3,5-trimethylcyclohexane derivative |
| US4938796A (en) * | 1987-07-06 | 1990-07-03 | Ici Americas Inc. | Herbicidal compositions of acylated 1,3-dicarbonyl herbicides and antidotes therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2023582B (en) | 1982-11-03 |
| IE791332L (en) | 1979-11-30 |
| FR2427332B1 (en) | 1983-07-18 |
| TR20608A (en) | 1982-01-01 |
| PL215973A1 (en) | 1980-02-11 |
| RO77441A (en) | 1981-11-04 |
| NL7904295A (en) | 1979-12-04 |
| DE2922270A1 (en) | 1979-12-06 |
| IE48779B1 (en) | 1985-05-15 |
| DK225679A (en) | 1979-12-01 |
| IT7923181A0 (en) | 1979-05-31 |
| BG30315A3 (en) | 1981-05-15 |
| ES481057A1 (en) | 1980-08-16 |
| DD143999A5 (en) | 1980-09-24 |
| HU178064B (en) | 1982-02-28 |
| PL115639B1 (en) | 1981-04-30 |
| LU81341A1 (en) | 1979-09-11 |
| PT69694B (en) | 1982-01-07 |
| GR68367B (en) | 1981-12-23 |
| BE876570A (en) | 1979-11-28 |
| IT1121547B (en) | 1986-04-02 |
| FR2427332A1 (en) | 1979-12-28 |
| DD147108A5 (en) | 1981-03-18 |
| PT69694A (en) | 1979-06-01 |
| CS220787B2 (en) | 1983-04-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 746 | Register noted 'licences of right' (sect. 46/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |