USE OF ACYLCYANAMIDES OR SALTS THEREOF FOR REGULATING PLANT GROWTH

Abstract

The present invention relates to the use of acyl cyanamides or salts thereof as an active ingredient of plant growth regulators, in particular for breaking the dormancy of fruit trees.

Claims

1. Use of at least one compound from the group of acylcyanamides or a salt thereof according to formula (I) or formula (II) for regulating the generative growth of plants or for breaking the dormancy of fruit trees, wherein the following applies to formula (I) and formula (II) ##STR00013## wherein radicals R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and cations M.sup.1, M.sup.2 independently of one another mean: R.sup.1=hydrogen, C.sub.1 to C.sub.20 alkyl, C.sub.3 to C.sub.12 cycloalkyl, C.sub.2 to C.sub.20 alkenyl, C.sub.1 to C.sub.20 alkoxy, aryl, alkylaryl or arylalkyl, or a radical Q, wherein Q is: Q=C.sub.1 to C.sub.20 alkyl, C.sub.3 to C.sub.12 cycloalkyl, C.sub.2 to C.sub.20 alkenyl, C.sub.1 to C.sub.20 alkoxy, aryl, alkylaryl or arylalkyl, each substituted by a radical of formula (III) or formula (IV) ##STR00014## M.sup.1, M.sup.2 independently of one another Li, Na, K, ½Ca, ½Mg, or NR.sup.2R.sup.3R.sup.4R.sup.5, R.sup.2, R.sup.3, R.sup.4, R.sup.5=independently of one another hydrogen or C.sub.1 to C.sub.20 alkyl.

2. The use according to claim 1, characterized in that at least one compound from the group of acylcyanamides or a salt thereof according to formula (I) or formula (II) is used, wherein radicals R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and cations M.sup.1, M.sup.2 independently of one another mean: R.sup.1=hydrogen, C.sub.1 to C.sub.20 alkyl, C.sub.3 to C.sub.12 cycloalkyl, C.sub.2 to C.sub.20 alkenyl, C.sub.1 to C.sub.20 alkoxy or a radical Q, wherein Q is: Q=C.sub.1 to C.sub.20 alkyl, C.sub.3 to C.sub.12 cycloalkyl, C.sub.2 to C.sub.20 alkenyl, C.sub.1 to C.sub.20 alkoxy, each substituted by a radical of formula (III) or formula (IV), M.sup.1, M.sup.2 independently of one another Li, Na, K, ½Ca, ½Mg, or NR.sup.2R.sup.3R.sup.4R.sup.5, R.sup.2, R.sup.3, R.sup.4, R.sup.5=independently of one another hydrogen or C.sub.1 to C.sub.20 alkyl.

3. The use according to claim 1, characterized in that at least one compound from the group of acylcyanamides or a salt thereof according to formula (I) or formula (II) is used, wherein radicals R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and cations M.sup.1, M.sup.2 independently of one another mean: R.sup.1=aryl, alkylaryl or arylalkyl, or a radical Q, wherein Q is: Q=aryl, alkylaryl or arylalkyl, each substituted by a radical of formula (III) or formula (IV), M.sup.1, M.sup.2 independently of one another Li, Na, K, ½Ca, ½Mg, or NR.sup.2R.sup.3R.sup.4R.sup.5, R.sup.2, R.sup.3, R.sup.4, R.sup.5=independently of one another hydrogen or C.sub.1 to C.sub.20 alkyl.

4. The use according to claim 1, characterized in that at least one compound from the group of acylcyanamides or a salt thereof according to formula (I) or formula (II) is used, wherein radical R.sup.1 and cations M.sup.1, M.sup.2 independently of one another mean: R.sup.1=hydrogen, methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, n-pentyl, n-hexyl, n-heptyl, n-octyl or a radical Q, wherein Q is: Q=methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, each substituted by a radical of formula (III) or formula (IV), M.sup.1, M.sup.2=independently of one another Na or K.

5. The use according to claim 1, characterized in that at least one compound selected from the group consisting of sodium formylcyanamide, sodium acetylcyanamide, sodium propionylcyanamide, sodium n-butyrylcyanamide, sodium isobutyrylcyanamide, sodium methoxycarbonylcyanamide, sodiumethoxycarbonylcyanamide, potassium formyl cyanamide, potassium acetyl cyanamide, potassium propionylcyanamide, potassium n-butyryl cyanamide, potassium isobutyrylcyanamide, potassium methoxycarbonylcyanamide or potassiumethoxycarbonylcyanamide is used.

6. The use according to claim 1, characterized in that as plants, as crops and cultivated plants or as fruit trees, plants selected from the group consisting of grape (Vitis vinifera), kiwi (Actinidia deliciosa, Actinidia chinensis, or Actinidia arguta), blueberry (Vaccinium myrtillus, Vaccinium corymbosum, Vaccinium virgatum, Vaccinium angustifolium or Vaccinium myrtilloides), cherry (Prunus avium or Prunus cerasus), plum or damson (Prunus domestica), apple (Malta domestica or Malta orientalis), pear (Pyrus communis, Pyrus pyraster or Pyrus pyrifolia), quince (Cydonia oblonga), peach (Prunus persica), apricot (Prunus armeniaca), raspberry (Rubus idaeus), persimmon (Diospyrus kaki), fig (Ficus carica) or their cross products or cultivars are treated.

7. A plant growth regulator concentrate for regulating the generative growth of plants or for breaking the dormancy of fruit trees comprising a) at least one active ingredient from the group of acylcyanamides or a salt thereof according to formula (I) or formula (II), wherein the following applies to formula (I) and formula (II): ##STR00015## wherein radicals R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and cations M.sup.1, M.sup.2 independently of one another mean: R.sup.1=hydrogen, C.sub.1 to C.sub.20 alkyl, C.sub.3 to C.sub.12 cycloalkyl, C.sub.2 to C.sub.20 alkenyl, C.sub.1 to C.sub.20 alkoxy, aryl, alkylaryl or arylalkyl, or a radical Q, wherein Q is: Q=C.sub.1 to C.sub.20 alkyl, C.sub.3 to C.sub.12 cycloalkyl, C.sub.2 to C.sub.20 alkenyl, C.sub.1 to C.sub.20 alkoxy, aryl, alkylaryl or arylalkyl, each substituted by a radical of formula (III) or formula (IV) ##STR00016## M.sup.1, M.sup.2 independently of one another Li, Na, K, ½Ca, ½Mg, or NR.sup.2R.sup.3R.sup.4R.sup.5, R.sup.2, R.sup.3, R.sup.4, R.sup.5=independently of one another hydrogen or C.sub.1 to C.sub.20 alkyl, b) at least one additive from the group of solvents, oils, surfactants or emulsifiers that is safe or approved for agricultural purposes, wherein the concentrate having a concentration of active ingredient in the range of 100 to 600 g/l.

8. The plant growth regulator concentrate according to claim 7, characterized in that the concentrate a) comprises at least one active ingredient selected from the group consisting of acylcyanamides or a salt thereof according to formula (I) or formula (II), wherein radicals R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and cations M.sup.1, M.sup.2 independently of one another mean: R.sup.1=hydrogen, C.sub.1 to C.sub.20 alkyl, C.sub.3 to C.sub.12 cycloalkyl, C.sub.2 to C.sub.20 alkenyl, C.sub.1 to C.sub.20 alkoxy or a radical Q, wherein Q is: Q=C.sub.1 to C.sub.20 alkyl, C.sub.3 to C.sub.12 cycloalkyl, C.sub.2 to C.sub.20 alkenyl, C.sub.1 to C.sub.20 alkoxy, each substituted by a radical of formula (III) or formula (IV), M.sup.1, M.sup.2 independently of one another Li, Na, K, ½Ca, ½Mg, or NR.sup.2R.sup.3R.sup.4R.sup.5, R.sup.2, R.sup.3, R.sup.4, R.sup.5=independently of one another hydrogen or C.sub.1 to C.sub.20 alkyl.

9. The plant growth regulator concentrate according to claim 7, characterized in that the concentrate is a solution, an emulsion or an emulsifiable solution comprising as solvent a solvent selected from the group consisting of water, ethanol, isopropanol, glycol, polyglycol, glycerol or mixtures of these solvents.

10. The plant growth regulator concentrate according to claim 7, characterized in that the concentrate is a solution, an emulsion or an emulsifiable solution comprising as oil an oil from the group of plant oils.

11. The plant growth regulator concentrate according to claim 7, characterized in that the concentrate is a solution, an emulsion or an emulsifiable solution comprising as surfactant a surfactant selected from the group consisting of nonionic surfactants.

12. The plant growth regulator concentrate according to claim 7, characterized in that the concentrate comprises as surfactant a surfactant containing one or more compounds selected from the group consisting of ethoxylates according to formula (VII), fatty alcohol glucosides according to formula (VIII), or mixtures thereof, wherein the following applies to formula (VII) and formula (VIII), ##STR00017## wherein radicals R.sup.11, R.sup.12 and indices n, m simultaneously or independently mean: R.sup.11=a linear or branched alkyl or alkenyl group having 6 to 24 carbon atoms, a partially or fully fluorinated alkyl group having 6 to 18 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, a mono- or polyfunctional siloxane group, R.sup.12=a linear or branched alkyl or alkenyl group containing 6 to 24 carbon atoms, n=a number from 2 to 20, m=a number from 1 to 5.

13. The plant growth regulator concentrate according to claim 7, characterized in that the concentrate is a solution, an emulsion or an emulsifiable solution comprising as emulsifier an emulsifier selected from the group consisting of nonionic oil-in-water emulsifiers.

14. The plant growth regulator concentrate according to claim 7, characterized in that the concentrate further comprises at least one formulation adjuvant approved for agricultural use selected from the group consisting of pH regulators, colorants, thickeners, dispersants, solubilizers, viscosity modifiers, labeling agents and bittering agents.

15. The plant growth regulator concentrate according to claim 7, characterized in that the concentrate comprises: a) at least one active ingredient from the group consisting of sodium formylcyanamide, sodium acetylcyanamide, sodium propionylcyanamide, sodium n-butyrylcyanamide, sodium isobutyrylcyanamide, sodium methoxycarbonylcyanamide, sodium ethoxycarbonylcyanamide, potassium formylcyanamide, potassium acetylcyanamide, potassium propionylcyanamide, potassium n-butyrylcyanamide, potassium isobutyrylcyanamide, potassium methoxycarbonylcyanamide or potassium ethoxycarbonylcyanamide, b) at least one additive from the group of solvents that is safe or approved for agricultural purposes, and c) at least one additive from the group of oils, surfactants or emulsifiers that is safe or approved for agricultural purposes, wherein the concentrate having a concentration of active ingredient in the range of 100 to 600 g/l.

16. A method for regulating the generative growth of plants or for breaking the dormancy of fruit trees comprising application by dipping, brushing or spraying of the branches, sprouts or buds of the plants with an aqueous solution comprising at least one active ingredient from the group of acylcyanamides or a salt thereof according to formula (I) or formula (II), during dormancy of the plants, wherein the following applies to formula (I) and formula (II) ##STR00018## wherein radicals R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and cations M.sup.1, M.sup.2 independently of one another mean: R.sup.1=hydrogen, C.sub.1 to C.sub.20 alkyl, C.sub.3 to C.sub.12 cycloalkyl, C.sub.2 to C.sub.20 alkenyl, C.sub.1 to C.sub.20 alkoxy, aryl, alkylaryl or arylalkyl, or a radical Q, wherein Q is: Q=C.sub.1 to C.sub.20 alkyl, C.sub.3 to C.sub.12 cycloalkyl, C.sub.2 to C.sub.20 alkenyl, C.sub.1 to C.sub.20 alkoxy, aryl, alkylaryl or arylalkyl, each substituted by a radical of formula (III) or formula (IV) ##STR00019## M.sup.1, M.sup.2=independently of one another Li, Na, K, ½Ca, ½Mg, or NR.sup.2R.sup.3R.sup.4R.sup.5, R.sup.2, R.sup.3, R.sup.4, R.sup.5=independently of one another hydrogen or C.sub.1 to C.sub.20 alkyl.

Description

EXAMPLES

Synthesis Examples

Example A-1

[0210] Synthesis of Sodium Acetylcyanamide (CAS 84946-07-6) from Solid Cyanamide

[0211] 180.1 g (1.0 mol) of a 30% solution of sodium methylate was introduced. Under good cooling, a total of 42.25 g (1.005 mol) of solid cyanamide was introduced in portions at a maximum of 25° C. Then 134.83 g (1.82 mol) of methyl acetate was added and the suspension was heated to reflux (about 64° C.) for 10 hours. The reaction mixture was cooled to 10° C., the precipitated sodium acetylcyanamide fraction 1 was filtered off and dried at 60° C. The obtained mother liquor was evaporated to half the volume, cooled to 10° C. and the precipitated fraction 2 was filtered off and dried. In total, the following were obtained:

[0212] Fraction 1: 75 g (71% yield) with 99.4% content, melting point 239° C.

[0213] Fraction 2: 19 g (18% yield) with 99.0% content, melting point 238° C.

[0214] .sup.1H-NMR in DMSO 1.70 ppm (s), .sup.13C-NMR 180.75, 122.60, 25.26 ppm

Example A-1a

[0215] Synthesis of Sodium Acetylcyanamide (CAS 84946-07-6) from Sodium Hydrogencyanamide

[0216] 120 g methanol and 88.8 g (1.20 mol) methyl acetate were introduced. 64.04 g (1.0 mol) sodium hydrogencyanamide was suspended in it. The reaction mixture was heated to 70° C. for 10 hours. Then, it was completely evaporated to dryness and the solid obtained was post-dried at 60° C. in vacuo. 106 g (100% yield) of sodium acetylcyanamide with a content of 98.9% was obtained.

Example A-1 b

Synthesis of Acetylcyanamide (CAS 5634-51-5) as Free NH Acid

[0217] 120 g methanol and 88.8 g (1.20 mol) methyl acetate were introduced. 64.04 g (1.0 mol) sodium hydrogencyanamide was suspended in it. The reaction mixture was heated to 70° C. for 10 hours. Then it was cooled and another 500 g of methanol was added. At 10 to 20° C., 49.0 g (0.5 mol) of concentrated sulfuric acid was added, precipitating sodium sulfate. The suspension was filtered, rewashed with methanol, and the combined filtrates were largely completely evaporated. 84 g of an oil with density 1.100 g/cm.sup.3 and refractive index no 1.425, each measured at 20° C., were obtained. The yield was quantitative.

Example A-1c

Synthesis of Potassium Acetylcyanamide (CAS 1146597-19-4)

[0218] 280.4 g (1.0 mol) of a 25% solution of potassium methylate was introduced. Under good cooling, a total of 42.25 g (1.005 mol) of solid cyanamide was introduced in portions at a maximum of 25° C. Then 134.83 g (1.82 mol) of methyl acetate was added and the suspension was heated to reflux (about 64° C.) for 10 hours. The reaction mixture was evaporated to about half the volume and cooled to 10° C. The precipitated solid was filtered off and dried at 60° C. 94 g of a white solid with an N content of 23.0% was obtained. The yield was 77%.

Example A-2

Synthesis of Sodium Formylcyanamide (CAS 71675-63-3)

[0219] 909.5 g (5.0 mol) of a 29.7% sodium methylate solution was introduced. Under good cooling at 10 to 20° C., a total of 211.05 g (5.0 mol) of 99.6% solid cyanamide was introduced in portions. Then 250 ml of methanol was added to ensure good stirring ability. Then, 309.55 g (5.0 mol) of a 97.0% formic acid methyl ester was added under cooling. The reaction mixture was heated to about 38° C. (strong reflux) for a total of 18 hours. It was then cooled to 10° C. and the precipitated product fraction 1 was filtered off and dried at 60° C. The filtrate was evaporated to dryness and post-dried (fraction 2). In total, the following were obtained:

[0220] Fraction 1: 343.9 g (75% yield) with 30.22% N content, melting point 256° C.

[0221] Fraction 2: 16.9 g (25% yield) with 30.34% N content, melting point 255° C.

[0222] .sup.1H-NMR in DMSO: 8.43 ppm, .sup.13C-NMR 171.88, 122.5 ppm

Examples A-3 to A-15

Synthesis of Further Sodium Acylcyanamides

[0223] The further syntheses were carried out analogously to Example A-1a from sodium hydrogencyanamide. According to the target compound desired in each case, 1.2 mol of a carboxylic acid methyl ester was introduced into 120 methanol, 64.04 g (1.0 mol) of sodium hydrogencyanamide was suspended therein and the reaction mixture was heated to reflux (about 65° C.) for mostly 10 hours. The obtained reaction mixtures were partially evaporated, mixed with 100 g of t-butyl methyl ether and the obtained suspensions were filtered off at 10° C. The respective products were washed with t-butyl methyl ether and dried at 60° C.

[0224] In the following tables 1 and 2, the respective substances, deviations from the above standard specification, if applicable, yields as well as the characterization of the obtained products have been summarized.

TABLE-US-00001 TABLE 1 Characteristic data of inventive acylcyanamides and their preparation Input Example (carboxylic acid Process details and no. Product name ester) yield Analytical data A-3 Sodium methoxy Dimethyl complete Content > 98%, carbonyl cyanamide carbonate evaporation of the melting point CAS 51234-98-1 reaction suspension; 242.5° C. yield 99% A-4 Sodium benzoyl Benzoate acid Yield 76% Content 100 %, cyanamide methyl ester melting point CAS 67998-88-3 295.6° C. A-5 Sodium propionyl Propionic acid Yield 41% Content > 98%, cyanamide methyl ester melting point 143° C. CAS 84945-99-3 under decomposition A-6 Sodium butyryl Butyric acid Yield 44% Content > 98%, cyanamide methyl ester melting point 176-181° C. A-7 Sodium isobutyryl Isobutyric acid Yield 57% Content > 96 %, cyanamide methyl ester contained approx. 4 % methanol, melting point 127-133° C. A-8 Sodium pivaloyl 2,2-dimethyl 72 h reaction time Content > 98%, cyanamide acetic acid required; melting point methyl ester yield 70% 295-300° C. A-9 Sodium hexanoyl Hexanoate acid Yield 55% Content > 98%, cyanamide methyl ester melting point 170-174° C. A-10 Sodium dodecanoyl Dodecanoic acid Yield 82% Content > 98%, cyanamide methyl ester melting point CAS 93238-02-9 155-160° C. A-11 Sodium oleyl Oleate acid 72 hr reaction time Content approx. 85% cyanamide methyl ester required, the product was obtained by evaporation as oil; yield quantitative A-12 Sodium phenylacetyl Phenylacetate Yield 60% Content 96%, cyanamide acid methyl ester hygroscopic, CAS 103818-57-1 contained 4% water, melting point 183-187° C. A-13 Sodium-4-methyl- 4-Methylbenzoic Yield 73% Content > 98%, benzoyl-cyanamide acid methyl ester melting point 340° C. CAS 67998-89-4 under decomposition A-14 Disodium-(3-(cyano- Succinic acid Input 0.5 mol Content 92%, amidocarbonyl)- dimethyl ester succinic acid contained 8% propionyl- dimethyl ester, 240 sodium-3- cyanamide) ml methanol; (methoxycarbonyl)- CAS 88245-65-2 yield 48% propionyl- cyanamide, no melting point, decomposition starting at 300° C. A-15 Disodium-(5-(cyano- Adipic acid Input 0.5 mol Content 96%, amidocarbonyl)- dimethyl ester dimethyl adipate, contained 4% pentanoyl- 240 ml methanol; sodium-5- cyanamide) yield 36% (methoxycarbonyl)- CAS 88245-91-2 pentanoyl- cyanamide, melting point 272-278° C. under decomposition

TABLE-US-00002 TABLE 2 NMR data of inventive acylcyanamides, each dissolved in de DSMO .sup.1H—NMR (ppm) .sup.13C—NMR (ppm) A-3 3.40 163.39, 122.26, 51.55 A-4 7.90 (m, 2 H), 7.36 (m, 1 H), 7.28 (m, 2 H) 174.77, 138.48, 129.89, 128.14 (2 C). 127.44 (2 C), 122.86 A-5 1.94 (q), 0.89 (t) 183.59, 122.70, 31.01, 10.84 A-6 1.92 (t), 1.42 (m), 0.80 (t) 182.79, 122.70, 40.09, 19.39, 14.06 A-7 2.16 (sept), 0.92 (d) 186.96, 123.04, 36.12, 20.42 (2 C) A-8 0.97 (s) 188.22, 123.49, 38.85, 28.64 (3 C) A-9 1.91 (t, 2 H), 1.40 (m, 2 H), 1.24-1.17 (m, 4H), 182.80, 122.68, 38.03, 31.32, 25.81, 0.83 (t, 3H) 22.09, 13.98 A-10 1.90 (t, 2 H), 1.39 (m, 2 H), 1.24-1.19 (m, 182.63, 122.66, 38.08, 31.32, 29.10-29.06 16 H), 0.84 (t, 3 H) (5 C), 28.74, 26.14, 22.11, 13.95 A-11 5.30 (m, 2 H), 1.97 (m, 4 H), 1.89 (t, 2 H), 1.38 182.49, 129.74, 129.60, 122.63, 31.30, (m, 2 H), 1.29-1.22 (m, 20 H), 0.83 (t, 3 H) 30.91,29.18-28.60 (8 C), 26.68, 26.61, 26.14, 22.10, 13.93 A-12 7.24-7.20(m, 4 H), 7.14 (m, 1 H), 3.25 (s, 2 H) 180.57, 138.49, 129.19 (2 C), 127.82 (2 C), 125.61, 122.39, 45.30 A-13 7.79 (d, 2 H), 7.09 (d, 2 H), 2.28 (s, 3 H) 174.85, 139.38, 135.81, 128.23 (2 C), 128.04 (2 C), 123.00, 20.97 A-14 2.10 (t, 4 H) 182.91 (2 C), 122.61 (2 C), 34.92 (2 C) A-15 1.89 (m, 4 H), 1.35 (m, 4 H) 182.85 (2 C), 122.68 (2 C), 38.07 (2 C), 26.16 (2 C)

Examples Concentrate Production

Example B-1

[0225] Sodium Acetylcyanamide as Aqueous Solution with Surfactant

[0226] 250 g sodium acetylcyanamide from Example A-1 was dissolved in 600 g water, to which 2.4 g of the nonionic surfactant BreakThru® OE-446 (manufacturer Evonik) was added and the mixture was filled up to a total of 1000 g with water. A clear solution was obtained.

Example B-1a

Sodium Acetylcyanamide as Emulsifiable Solution in Ethanol/Water/Biodiesel/Surfactant

[0227] 200 g sodium acetylcyanamide from Example A-1 were dissolved in 600 g of a mixture of 80 wt. % ethanol and 20 wt. % water. 50 g of rapeseed oil methyl ester, 2.4 g of the nonionic surfactant BreakThru® S-240 (manufacturer Evonik) and 20 mg of the dye Iragon Blue ABL9-L (manufacturer BASF) were added. The mixture was filled up to 1000 g with ethanol/water. A slightly blue colored, clear solution was obtained, which was easily emulsifiable in water.

Example B-1b

Potassium Acetylcyanamide as a Solid

[0228] 100 g potassium acetylcyanamide from Example A-1c was finely ground with 1 g sodium dodecyl sulfate and 100 g anhydrous sodium sulfate. A white solid was obtained which was readily soluble in water, with slight foaming.

Example B-2

[0229] Sodium Formylcyanamide as Aqueous Solution with Surfactant

[0230] 250 g sodium formylcyanamide from Example A-2 was dissolved in 500 g water, to which 2.4 g of the nonionic surfactant BreakThru® OE-446 and 20 mg of the dye Iragon Blue ABL9-L were added and filled up to 1000 g with water. A clear, blue colored concentrate solution was obtained.

Example B-3

[0231] Sodium Propionylcyanamide as Aqueous Solution with Surfactant

[0232] 250 g sodium propionylcyanamide from Example A-2 was dissolved in 500 g water, to which 2.4 g of the nonionic surfactant BreakThru® OE-446 and 20 mg of the dye Iragon Blue ABL9-L were added and filled up to 1000 g with water. A clear, blue colored concentrate solution was obtained.

Reference Example B-16

Preparation of a Concentrate Containing Cyanamide

[0233] 400 g pure cyanamide was dissolved in 600 g water. The pH value was adjusted to 4.2 with about 0.1 g phosphoric acid. 10 g BreakThru® OE446 and 20 mg Iragon Blue ABL9-L were added. A blue colored concentrate solution B-16 was obtained.

Storage Stability of Concentrate Solutions B-1, B-2 and B-3 in Comparison with B-16 (Reference)

[0234] The concentrate solutions from B-1, B-2, B-3 and the cyanamide-containing reference solution B-16 were set up at 60° C. and samples were taken after different periods of time in each case. These were analyzed immediately by ion chromatography for their content of acylcyanamides and cyanamide, respectively. The respective starting solution stored at −18° C. served as a reference. In each case, the content was assigned to 100%, and the decrease in concentration was determined in relation to this.

TABLE-US-00003 TABLE 3 Storage stability Concentrate B-1 B-2 B-3 B-16 freshly prepared  100%  100%  100%  100% after 1 day at 99.9% 81.6% 99.5% 98.6% 60° C. after 2 days at 99.5% 66.8% 99.3% 97.4% 60° C. after 4 days at 99.3% 41.7% 98.1% 90.0% 60° C. after 7 days at 98.3%  <30%  97.5% 46.4% 60° C. after 14 days at 95.0%  <30%  96.6% <30% 60° C.

[0235] The result shows that the solutions of sodium acetylcyanamide (B-1) and sodium propionylcyanamide (B-3) have a much better shelf life and thus a better storability than the concentrate solution of cyanamide (B-16) corresponding to the prior art. This is of decisive advantage for handling in agriculture.

Examples Greenhouse Tests

[0236] Greenhouse tests were conducted using cut fruit tree branches placed in water jars and maintained under controlled conditions with temperature regulation at approximately 22° C. and natural lighting.

[0237] Branches of the following species fruit trees were used:

C1: Table Apple, Type Boiken Apple

[0238] Table apple: Malus domestica type Boiken first described in 1828 in Bremen after Deichvogt Boiken. Apple type for rough locations and for almost every soil suitable scattered fruit type, whereby heavy soils and not too warm locations are required. Tree growth initially strong, later medium. Older crowns become broadly spherical and are loosely branched. Flowering starting medium-late and long lasting, petals large with little pink. Yield starting late (October) and irregular; with long shelf life and pressure resistance. The type shows low respiration in storage and gains quality as it matures.

C2: Table Apple, Type Zabergäu-Renette

[0239] Table apple: Malus domestica type Zabergäu-Renette first developed in 1885 as a chance seedling in Hausen a.d. Zaber/Baden-Württemberg and initially grown as ‘Hausener Graue Renettte’. No defined storage type; requires heavy soils (loam). Tree growth initially strong with oblique upright leading branches, later medium with flat branches. Crown broad and flat-spherical with flat fruiting wood. Leaves large, broad oval and with clearly separated tip. Triploid type with late and long-lasting flowering. Yield starting early, medium high and somewhat alternate.

C3: Table Cherry, Type Burlat

[0240] Table cherry: Prunus avium type Bigarreau Burlat or Hativ Burlat is a strong-growing somewhat sparse growing sweet cherry tree with horizontal side sprouts. The type has been known since 1930 and is one of the most important types in commercial cultivation. Flowering is early, followed by an early ripening week (end of May 2nd cherry type) and yield starting late. Medium but regular yields identify the type as a secondary type for early and dry areas.

C4: Grape, Type Pinot Noir

[0241] Grape: Vitis vinifera subsp. vinifera type Pinot Noir is an important and high quality red wine type that has existed for possibly 2000 years. It is cultivated all over the world because the type produces high quality red wines and has sufficient winter frost resistance. The type requires early and good areas with deep, warm, medium-heavy and fertile soils with good water supply. Pinot Noir produces regular, medium-high to high yields. However, there are a large number of clones that differ in yield, berry size and looseness.

[0242] Branches or sprouts were pruned in November, approximately 1 week after the last leaf fall but before the first night frost. Branch cuttings were brought to equal length, divided into groups of 5 branches each, so that a uniform number of buds and sprout shape per group was achieved.

[0243] The test solutions were prepared directly, i.e. without intermediate preparation of a concentrate. For each of the test substances A-1 to A-13, an aqueous solution of 0.15 mol of the test substance and 0.15 g BreakThru® OE-446 was prepared and filled up to a total of 500 g with water. Of bis-cyanamides A-14 and A-15, 0.075 mol each was filled up to 500 g in an analogous manner. These test solutions (in combination with the above 4 species/types Cx) were given the test numbers Cx-A1 to Cx-A15.

[0244] Reference solutions for negative and positive control, respectively, were: [0245] Cx-0: 500 g pure water (negative control) [0246] Cx-0a: 0.15 g BreakThru® OE-446, filled up to 500 g with pure water (negative control) [0247] Cx-16: 0.15 mol (6.30 g) pure cyanamide and 0.15 g BreakThru® OE-446 filled up to 500 g with water (positive control)

[0248] The test solutions (15 test solutions) were each placed in a photo dish, the 5 each branches were dipped in the solution, additionally wetted with a brush as necessary, so that the entire surface was wetted. The branches were placed on filter paper so that excess liquid could drip off and allowed to dry for 20 minutes. Then, the 5 respectively uniformly treated branches were placed in a jar of pure water and set up in the greenhouse as described above.

[0249] After specified evaluation times T1 to T6 (after 14, 16, 21, 27, 36 and 56 days, respectively, each determined after application of the test solution “day 0”), the bud development of each test group was evaluated. This was done with the following evaluation scale: [0250] Stage 0: Buds unchanged [0251] Stage 1: Buds slightly swollen, first green tips visible [0252] Stage 2: strongly swollen, green buds [0253] Stage 3: Buds before breaking open, leaf or flower root already visible [0254] Stage 4: Flower buds fully developed, but still closed, white petals already visible. In the case of the grapevine, stage 4 was the unfolding of the first leaves [0255] Stage 5: Flowers fully open or, in the case of grapevine, unfolding of the flower roots (“Gescheine”) on the fully leafed sprouts.

Evaluation of the Tests

[0256] A dormancy-breaking effect is present if, depending on the species under investigation (fruit tree), evaluation stage 4 is reached or exceeded after a number of n days (depending on the species (fruit tree)) in comparison with the negative control (water or water with surfactant). The greater the difference in time and/or the evaluation stage compared to the negative control, the better the dormancy-breaking effect is to be classified.

n (for C1, C2, C4): 36 days
n (for C3): 27 days

[0257] A good dormancy-breaking effect exists if, depending on the species under investigation (fruit tree), evaluation stage 4 is reached or exceeded after a number of n days (depending on the species (fruit tree)) in comparison with the negative control (water or water with surfactant). The greater the difference in time and/or the evaluation stage compared to the negative control, the better the dormancy-breaking effect is to be classified.

n (for C1, C2, C4): 27 days
n (for C3): 21 days

TABLE-US-00004 TABLE 3 Results of apple branches C1 at evaluation times T1 to T6: T1/(14 T2/(16 T3/(21 T4/(27 T5/(36 T6/(56 d) d) d) d) d) d) C1-0 0 0 0 1 1 1 C1-0a 0 0 0 1 1 1 C1-A1 0 0 2 3 5 5 C1-A2 0 0 4 5 5 5 C1-A3 1 1 2 3 4 5 C1-A4 1 1 1 2 3 4 C1-A5 2 2 4 5 5 5 C1-A6 2 3 4 5 5 5 C1-A7 2 3 4 5 5 5 C1-A8 0 0 2 4 4 4 C1-A9 0 1 1 2 2 3 C1-A10 1 2 4 5 5 5 C1-A11 0 1 2 3 5 5 C1-A12 0 1 2 2 5 5 C1-A13 0 0 0 1 4 4 C1-A14 1 1 2 3 5 5 C1-A15 0 0 1 2 3 4 C1-16 3 4 5 5 5 5

[0258] The test results show that 12 (80%) of the investigated substances have a dormancy-breaking effect according to the definition given above (cf. A1, A2, A3, A5, A6, A7, A8, A10, A11, A12, A13, A14). 6 (40%) of the investigated substances even show a good to very good dormancy-breaking effect on the investigated species (cf. A2, A5, A6, A7, A8, A10).

TABLE-US-00005 TABLE 4 Results of apple branches C2 at evaluation times T1 to T6 T1/(14 T2/(16 T3/(21 T4/(27 T5/(36 T6/(56 d) d) d) d) d) d) C2-0 0 0 0 0 0 0 C2-0a 0 0 0 1 2 3 C2-A1 0 0 1 3 5 5 C2-A2 0 0 1 3 5 5 C2-A3 0 0 0 2 4 4 C2-A4 0 0 0 1 2 2 C2-A5 0 0 0 1 3 4 C2-A6 0 0 1 2 5 5 C2-A7 0 0 1 1 5 5 C2-A8 0 0 0 1 2 4 C2-A9 0 1 4 5 5 5 C2-A10 0 0 0 1 2 4 C2-A11 0 0 3 3 4 5 C2-A12 0 0 3 3 4 5 C2-A13 0 0 1 3 3 5 C2-A14 0 0 0 1 3 4 C2-A15 0 0 1 5 5 5 C2-16 0 0 3 4 5 5

[0259] The test results show that 9 (60%) of the investigated substances have a dormancy-breaking effect according to the definition given above (cf. A1, A2, A3, A6, A7, A9, A11, A12, A15). 2 (13%) of the investigated substances even show a good to very good dormancy-breaking effect on the investigated species (cf. A9, A15).

Overall Result Apple (C1, C2)

[0260] Depending on the apple type tested, 14 of the 15 substances tested showed a dormancy-breaking effect in at least one apple type. Particularly emphasized are substances A6, A7, A9 and A15, which showed a similar or equally good effect compared to the positive control.

TABLE-US-00006 TABLE 5 Results of cherry branches C3 at evaluation times T1 to T6 T1/(14 T2/(16 T3/(21 T4/(27 T5/(36 T6/(56 d) d) d) d) d) d) C3-0 0 0 0 0 1 5 C3-0a 0 0 0 0 0 3 C3-A1 1 2 5 5 5 5 C3-A2 1 2 5 5 5 5 C3-A3 0 0 0 1 3 5 C3-A4 1 2 4 4 5 5 C3-A5 1 2 4 4 4 5 C3-A6 1 1 3 5 5 5 C3-A7 0 0 1 2 4 5 C3-A8 0 0 1 2 4 5 C3-A9 0 1 2 3 5 5 C3-A10 1 2 4 4 4 5 C3-A11 2 3 5 5 5 5 C3-A12 0 1 2 5 5 5 C3-A13 0 0 0 1 2 5 C3-A14 0 1 4 5 5 5 C3-A15 0 1 1 1 2 4 C3-16 2 4 5 5 5 5

[0261] The test results show that 9 (60%) of the investigated substances have a dormancy-breaking effect according to the definition given above (cf. A1, A2, A4, A5, A6, A10, A11, A12, A14). 7 (47%) of the investigated substances even show a good to very good dormancy-breaking effect on the investigated species cherry (cf. A1, A2, A4, A5, A10, A11, A14). In contrast to the apple species (C1, C2), substance A4 has a good dormancy-breaking effect on the cherry species. It should also be emphasized in this regard that substance A11 exhibits an equal effect with that of cyanamide.

TABLE-US-00007 TABLE 6 Results of wine sprouts C4 at evaluation times T1 to T6 T1/(14 T2/(16 T3/(21 T4/(27 T5/(36 T6/(56 d) d) d) d) d) d) C4-0 0 0 0 0 2 5 C4-0a 0 0 0 0 1 5 C4-A1 0 0 0 1 4 5 C4-A2 0 1 3 5 5 5 C4-A3 0 0 0 1 5 5 C4-A4 0 0 0 3 5 5 C4-A5 0 0 0 1 3 5 C4-A6 0 0 0 1 2 5 C4-A7 0 0 0 2 5 5 C4-A8 0 0 0 1 4 5 C4-A9 0 0 0 2 5 5 C4-A10 0 0 0 1 2 4 C4-A11 0 0 1 3 4 5 C4-A12 0 0 1 3 4 4 C4-A13 0 0 0 1 3 5 C4-A14 0 0 0 2 4 4 C4-A15 0 0 0 1 4 5 C4-16 0 0 2 5 5 5

[0262] The test results show that 11 (73%) of the investigated substances have a dormancy-breaking effect according to the definition given above (cf. A1, A2, A3, A4, A7, A8, A9, A11, A12, A14, A15). 1 (7%) of the investigated substances even show a good to very good dormancy-breaking effect on the investigated species wine (cf. A2). It should be emphasized in this regard that substance A2 exhibits an equal effect with cyanamide.

Overall Result

[0263] A compilation of the results on the four fruit tree species C1 to C4 shows that sodium acylcyanamides A1 to A15 according to the invention all exhibit a more or less strong dormancy-breaking effect compared with the water reference (negative control). The effect is similar, but in some cases somewhat weaker or slightly delayed compared with the positive reference cyanamide (=standard agent according to prior art), the efficiency of which is achieved in some cases depending on the species.

Examples for the Production of Spray Mixtures from Concentrates

Example D-1

Preparation of a Spray Mixture Containing Sodium Acetylcyanamide

[0264] 10 parts of the concentrate solution from Example B-1 were diluted with 90 parts of water. A water-clear solution was obtained, which was used as a spray mixture. The spray mixture contained about 0.24 mol of the active ingredient acetylcyanamide per liter.

Example D-1a

Preparation of a Spray Mixture-Emulsion Containing Sodium Acetylcyanamide

[0265] 8 parts of the concentrate solution from Example B-1a were added to 92 parts of water. The two components mixed to form a bluish colored, slightly turbid emulsion. The spray mixture contained about 0.15 mol acetylcyanamide per liter.

Reference Example D-18

Preparation of a Spray Mixture Containing Cyanamide

[0266] 2.5 parts of the concentrate solution from Example B-18 were mixed with 97.5 parts of water to obtain the reference spray mixture D-18. The spray mixture contained about 0.24 mol of the active ingredient cyanamide per liter.

Field Tests

Example E1

Table Grapes USA

[0267] Three sections of a commercial table grape plantation near Madera State of California were treated with the following spray mixtures during the dormancy phase 45 days prior to natural bud burst (February 11):

E1-0: 600 liters per hectare of water with an addition of 0.1% Break-Thru® OE-446
E1-1: 600 liters per hectare of the spray mixture from example D-1
E1-18: 600 liters per hectare of the spray mixture from example D-18

[0268] As a result, the grapevine sprouts were evenly wetted.

[0269] Bud burst was recorded numerically on the 30th and 41st day after application.

[0270] Budding means number of buds that have developed at least one leaf after n days, based on the total number of buds on the sprouts at time n=0 days (day of application of spray mixture).

TABLE-US-00008 TABLE 7 Results table grapes USA 30 days 41 days E1-0 (zero reference) 42.5% budding 76.3% budding E1-1 (invention) 50.5% budding 74.0% budding E1-18 (comparison) 55.8% budding 77.5% budding

[0271] After 30 days, budding was significantly premature due to the treatment, wherein the E1-1 treatment according to the invention was not quite as effective as the prior art with cyanamide (E1-18). Due to the specific weather conditions, after 41 days, the advantage provided by both active ingredient treatments had been eroded.

Example E2

Table Grapes Spain

[0272] Three sections of a table grape plantation in southern Spain (type Red Globe) were treated with the following spray mixtures during the dormancy phase 45 days before natural bud burst (February 5):

E2-0: 600 liters per hectare of water with an addition of 0.1% Break-Thru® OE-446
E2-1: 600 liters per hectare of the spray mixture from example D-1
E2-18: 600 liters per hectare of the spray mixture from example D-18

[0273] As a result, the grapevine sprouts were evenly wetted.

[0274] On April 3, bud burst was recorded numerically.

[0275] Budding means number of buds that have developed at least one leaf after n days, based on the total number of buds on the sprouts at time n=0 days (day of application of spray mixture).

TABLE-US-00009 TABLE 8 Results table grapes Spain E2-0 (zero reference) 73.8% budding E2-1 (invention) 86.7% budding E2-18 (comparison) 86.0% budding

[0276] Thus, the treatment with sodium acetylcyanamide according to the invention is as effective as the prior art treatment with cyanamide.

Example E3

Table Grapes India

[0277] Three sections of a table grape plantation in India with types Bordon AR and Hammar AR were treated with the following spray mixtures during the dormancy phase:

E3-0: 600 liters per hectare of water with an addition of 0.1% Break-Thru® OE-446
E3-1: 600 liters per hectare of the spray mixture from example D-1
E3-18: 600 liters per hectare of the spray mixture from example D-18

[0278] As a result, the grapevine sprouts were evenly wetted.

[0279] After 30 and 45 days, respectively, bud burst was recorded numerically.

[0280] Budding means number of buds that have developed at least one leaf after n days, based on the total number of buds on the sprouts at time n=0 days (day of application of spray mixture).

TABLE-US-00010 TABLE 9 Results table grapes India Type Bordon AR Type HammarAR Evaluation time 30 days 45 days 30 days 45 days E3-0 (zero 33.1% 58.6% 10.0% 71.2% reference) budding budding budding budding E3-1 (invention) 36.6% 66.8% 18.0% 81.3% budding budding budding budding E3-18 36.1% 68.1% 15.3% 81.0% (comparison) budding budding budding budding

[0281] Thus, the treatment with sodium acetylcyanamide according to the invention is at least as effective as the prior art treatment with cyanamide.