US0093.07765B2

(12) Patent (10) Patent No.: US 9,307,765 B2 Shroffet al. (45) Date of Patent: Apr. 12, 2016

(54) SELECTIVE WEED CONTROL USING (58) Field of Classification Search D-NAPROPAMIDE None See application file for complete search history. (71) Applicant: UPL Limited, Mumbai (IN) (72) Inventors: Jaidev Rajnikant Shroff, Mumbai (IN); (56) References Cited Vikram Rajnikant Shroff, Mumbai U.S. PATENT DOCUMENTS (IN); Jean-Jacques Heller, Courbevoie M (FR) 3,718,455. A 2, 1973 Baker et al. 5,583,090 A 12/1996 Stern et al. (73) Assignee: UPL Limited, Mumbai, Maharashtra 5,783,520 A 7/1998 Anderson et al. (IN) 6,677.276 B1* 1/2004 Hacker et al...... 504,127 RE38,675 E 12/2004 Lee et al. (*) Notice: Subject to any disclaimer, the term of this 8,309,765 B2 * 1 1/2012 Shroffet al...... 564,140 patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days. FOREIGN PATENT DOCUMENTS WO WO 2009/004642 A2 1/2009 (21) Appl. No.: 13/839,979 WO WO 2009004642 * 1, 2009 (22) Filed Mar 15, 2013 WO WO 2011/121407 A1 10, 2011 1C ar, 15, * cited by examiner (65) Prior Publication Data US 2014/0274717 A1 Sep. 18, 2014 Primary Examiner — Alton Pryor (74) Attorney, Agent, or Firm — Wiley Rein LLP (51) Int. Cl. AOIN 43/60 (2006.01) (57) ABSTRACT AOIN37/18 (2006.01) AOIN 43/80 (2006.01) The present invention provides a novel use of D-Napropam AOIN39/02 (2006.01) ide and a method comprising the use of D-Napropamide and (52) U.S. Cl. combinations comprising the same. CPC ...... A0IN 43/80 (2013.01); A0IN39/02 (2013.01) 14 Claims, No Drawings US 9,307,765 B2 1. 2 SELECTIVE WEED CONTROL USING Napropramide is a selective systemic herbicide absorbed D-NAPROPAMIDE by roots and translocated acripetally. It inhibits root develop ment and growth. FIELD OF INVENTION Unsolved problems in this area include widely differing sensitivities of crop against herbicidal chemicals as The present invention relates to the use of Napropamide-M well as the fact that repression of one weed species may cause for selective control of dicotyledonous weeds. increased growth of another competing weed species, and BACKGROUND AND PRIOR ARTS that some weeds tend to become resistant against previously Many herbicides are reported in the prior art. However, the effective herbicides. herbicidal effectiveness of a given compound cannot be pre 10 U.S. Pat. No. 3,718,455 discloses new organic compounds dicted from an examination of the Substituent groups of the of formula I used as herbicides. compound and often quite closely related compounds, which will have quite different weed control abilities. Various her bicides or the isomers of the same herbicide may have over lapping or complementary areas of activity or selectivity, and 15 can thus be useful to control a variety of weeds upon appli cation of a composition. Furthermore, the various known herbicides are not completely effective. An ideal herbicide should give selective weed control, over the full growing season, with a single administration. It should be able to control all common weeds by controlling their growth and reproduction as the seed, the germinating seed, the seedling, This structure includes the compound Napropamide and the growing . (Compound No. 54 and Compound No. 55). The herbicidal Although the enantiomers of chiral substances have the activity of compounds 1 to 22 is reported on crabgrass, annual same physicochemical properties, their biochemical activi 25 bluegrass, watergrass and foxtail. This patent discloses that ties can be quite different because biochemical processes Compound No. 54 and Compound No. 55 possess good her usually show high stereo- or enantioselectivity. bicidal activity and can be used as pre-emergent and post The “active' enantiomer of a chiral chemical may have the emergent herbicides (Table III). This patent disclosure did not desired effect on a target species, whereas the other enanti investigate and does not indicate any differential selectivity of omer may not. It is advisable to use only the biologically 30 D-Napropamide towards different weed classes or types. active enantiomers, thereby reducing the total amount of WO2009004642 discloses a process for manufacture of chemical pollutants released into the environment. high purity D-(-)-N,N-diethyl-2-(C.-naphthoxy)propiona Many agrochemicals have chiral structures. For example, mide from L-2-Halopropionic Acid or (S)-(–)-2-Halopropi about 30% of currently registered pesticide active ingredients onic Acid and composition comprising high purity D-(-)-N. contain one or more chiral centers. Herbicides are used to 35 N-diethyl-2-(C.-naphthoxy)propionamide. Again, this patent control the growth of undesired vegetation, and they account disclosure did not investigate and does not indicate any dif for most of the agrochemicals in use today. Some chiral ferential selectivity of D-Napropamide towards different herbicides are sold as purified, optically active isomers, but weed classes or types. for economic reasons, many others are still used as racemates. There is a need in the art for enhanced uses of D-Napropa Different enantiomers of chiral herbicides can have different 40 mide and for improved methods of herbicidal control by using enantioselective activities on target weeds and different toxic D-Napropamide. effects on non-target organisms because of their enantiose lective interactions with enzymes and biological receptors in SUMMARY OF THE INVENTION organisms but the herbicidal selectivity of a specific isomer is not predictable. 45 In one aspect, the present invention provides the use of N,N-diethyl-2-(C.-naphthoxy)propionamide is known as D-Napropamide for selective control of dicotyledonous napropamide, and its racemic mixture is generally marketed weeds at a locus. under trade name as “Devrinol'. It is used for pre-emergence In another aspect, the present invention provides a method control of annual grasses and broad-leaved weeds in many of selectively controlling dicotyledonous weeds infestation at crops and plantations. 50 a locus by treating said locus with a herbicidally effective The second carbon atom at the propionamide group in amount of D Napropamide. napropamide has a hydrogen atom, a methyl group, a naph In yet another aspect, the present invention provides a thoxy moiety and a carboxamide group thereby forming a herbicidal composition for selectively controlling the dicoty chiral center. Hence the molecule FIG. I can exist in two ledonous weeds infestation at a locus, said composition com chiral stereoisomers: Dor (R) and L or (S)-isomers. 55 prising D Napropamide.

DETAILED DESCRIPTION OF THE INVENTION In this specification, the terms Napropamide-M and 60 D-Napropamide are used interchangeably. Racemic Napropamide has a satisfactorily good herbicidal activity. D-Napropamide possesses improved activity than L-Napropamide. A comparatively similar distribution of her bicidal activity enhancement by use of D-Napropamide (over 65 racemic Napropamide) for monocotyledonous weeds as well as dicotyledonous weeds was expected. It was surprisingly found that D-Napropamide demonstrates a selectively US 9,307,765 B2 3 4 enhanced control in the growth of dicotyledonous weeds in Aeschynomene virginica, Agalinis purpurea, Agalinis Seta agronomic crops vis-a-vis the control in monocotyledonous cea, Agalinis tenuifolia, Agastache nepetoides, Agastache weeds. Scrophulariifolia, Ageratina altissima, Ageratina aromatica, Therefore, in an embodiment, the present invention pro Agrimonia parviflora, Agrimonia pubescens, Agrimonia ros vides use of D-Napropamide for the control of a dicotyledon 5 tellata, Alnus serrulata, Amaranthus cannabinus, Amaran ous weed at a locus. Typically, the D-Napropamide is used for thus hybridus, Amaranthus spinosus, Ambrosia artemisiifo selective control of said dicotyledonous weed. lia, Ambrosia trifida, Amelanchier arborea, Amelanchier The term locus as used herein shall denote the vicinity of a Canadensis, Amelanchier laevis, Amelanchier obovalis, desired crop in which weed control, typically selective weed Amelanchier stolonifera, Amorpha fruticosa, Amphicarpaea control, of dicotyledonous weeds is desired. The locus 10 bracteata, Anaphalis margaritacea, Anemone quinquefolia, includes the vicinity of desired crop plants wherein the weed Anemone virginiana, Angelica venenosa, Antennaria plan infestation has either emerged or is yet to emerge. The term taginifolia, Apocynum androsaemifolium, Apocynum can crop shall include a multitude of desired crop plants or an nabinum, Aquilegia Canadensis, Arabis lyrata, Aralia nudi individual crop plant growing at a locus. caulis, Aralia racemosa, Aralia spinosa, Argemone The term control indicates eradication of the investigated 15 Mexicana, Aristolochia serpentaria, Arnoglossum atriplici weed(s). A 100% control signifies total eradication of the folium, Arnoglossum reniforme, Artemisia campestris, Arte weed(s) under investigation. misia ludoviciana, Asarum Canadense, Asclepias amplexi In another embodiment, the present invention provides a caulis, Asclepias incarnate, Asclepias purpurascens, method of controlling dicotyledonous weeds infestation at a Asclepias quadrifolia, Asclepias rubra, Asclepias Syriaca, locus by treating said locus with a herbicidally effective 20 Asclepias tuberose, Asclepias variegate, Asclepias verticil amount of D-Napropamide. lata, Aureolaria pedicularia, Aureolaria virginica, Baccharis Preferably, treating the locus with D-Napropamide com halimifolia, Baptisia tinctoria, Bartonia paniculata, Barto prises administering to the Soil in which the desired crop is to nia virginica, Betula nigra, Betula populifolia, Bidens aris be planted, an effective amount of D-Napropamide. The tosa, Bidens bidentoides, Bidens bipinnata, Bidens Cernua, administration is preferably by application either before seed 25 Bidens coronate, Bidens discoidea, Bidens frondosa, Bidens ing, during seeding, or, as in most applications, after seeding laevis, Bidens tripartite, Boehmeria cylindrical, Brasenia and before the crop emerges, so as to prevent the emergence Schreiberi, Brickellia eupatorioides, Cakile edentula, Cal of any weeds. litriche heterophylla, Callitriche terrestris, Caltha palustris, In an embodiment, D-Napropamide is administered prior Calystegia Spithamaea, Campanula aparinoides, Campsis to the emergence of any weed. 30 radicans, Cardamine bulbosa, Cardamine concatenate, Car Among the crops which show pre-emergence tolerance to damine parviflora, Cardamine pensylvanica, Carya alba, D-Napropamide and in which this compound can be used as Carya glabra, Carya ovate, Carva pallid, Castanea dentate, a herbicide are winter oilseed rape, strawberries, blackcur Castanea punila, Castilleja coccinea, Catalpa bignonioides, rants, gooseberries, raspberries, field trees, shrubs, broccoli, Ceanothus americanus, Celastrus scandens, Celtis Occiden cabbage, calabrese, cauliflower, kale and Brussels sprouts. 35 talis, Celtis tenuifolia, Cephalanthus Occidentalis, Cerastium The method of the present invention is particularly useful in nutans, Ceratophyllum demersum, Cercis Canadensis, controlling the growth of dicotyledonous weeds in these Chaerophyllum procumbens, Chamaecrista fasciculate, crops. Chamaecrista nictitans, Chamaedaphne calyculata, In an embodiment, the dicotyledonous weeds which were Chamaesyce maculate, Chamaesyce nutans, Chamaesyce found Surprisingly susceptible to D-Napropamide are 40 polygonifolia, Chamerion angustifolium, Chelone glabra, selected from the group comprising chickweed, speedwell, Chenopodium pratericola, Chenopodium rubrum, Chenopo poppy, field bindweed, hairy fleabane, nettleleaf goosefoot, dium simplex, Chimaphila maculate, Chimaphila umbellate, common groundsel, horseweed, common lambsqaurters, Chionanthus virginicus, Chrysopsis mariana, Chrysosple little mallow, burning nettle, Sowthistles, carpetweed, fathen, nium americanum, Cicuta bulbifera, Cicuta maculate, blackberry nightshade, small flowered mallow, nettles, dead 45 Hybanthus concolor; Hydrastis Canadensis, Hydrocotyle nettle, knotweed, common Sowthistle and amaranthus. Americana, Hydrocotyle umbellate, Hydrocotyle verticillata, However, it should be understood that the use of boreale, , Hypericum crux D-Napropamide and a method of the present invention is not andreae, , , limited to the control of these weeds alone but is applicable to Hypericum ellipticum, , Hypericum any dicotyledonous weed. 50 hypericoides, , , The herbicide of the invention can be applied to the soil or , Ilex glabra, Ilex laevigata, Ilex to crops in any amount which will give the required control of mucronata, Ilex opaca, Ilex verticillata, Impatiens capensis, weeds. A preferred rate of application is from about 0.5 to Ionactis linariifolius, Ipomoea pandurata, Itea virginica, about 20 L/Ha of D Napropamide, and most preferably from Juglans cinerea, Juglans migra, Kalmia angustifolia, Kalmia about 1 to about 8 L/Ha. 55 latifolia, Kosteletzkya virginica, Krigia biflora, Krigia vir In an embodiment, Napropamide-M may be preferably ginica, Lactuca biennis, Lactuca Canadensis, Lactuca hir used for control of dicotyledonous weeds in oil-seed rape at a sute, Laportea Canadensis, Lathyrus palustris, Lathyrus dose of 500-1500 g/Ha, preferably 750-850 g/Ha. venosus, Lechea minor; Lechea mucronata, Lechea racemu In another embodiment, Napropamide-M may be prefer losa, Leiophyllum buxifolium, Lepidium densiflorum, Lepi ably used in field crops in the range of 450-600 g/Ha. 60 dium virginicum, Lespedeza angustifolia, Lespedeza capi In another embodiment, Napropamide-M may be used in tata, Lespedeza frutescens, Lespedeza hirta, Lespedeza perennial crops at a dosage of 2000-3000 g/Ha. repens, Lespedeza Stuevei, Lespedeza violacea, Lespedeza In an embodiment, the dicotyledonous weeds especially virginica, Liatris pilosa, Liatris Spicata, Limosella australis, susceptible to D-Napropamide may be selected from the Lindera benzoin, Lindernia dubia, Linum intercursum, group consisting of Acalypha gracilens, Acalypha Ostrvifolia, 65 Linum striatum, Linum virginianum, Liquidambar styraci Acalypha rhomboidea, Acalypha virginica, Acer rubrum, flua, Liriodendron tulipifera, Lobelia Canbyi, Lobelia cardi Acer saccharinum, Actaea pachypoda, Actaea racemosa, nalis, Lobelia inflate, Lobelia nuttallii, Lobelia spicata, Lud US 9,307,765 B2 5 6 wigia alternifolia, Ludwigia hirtella, Ludwigia palustris, Pseudognaphalium obtusifolium, Ptilimnium capillaceum, Ludwigia Sphaerocarpa, Lupinus perennis, Lycopus ameri Pycnanthemum clinopodioides, Pycnanthemum incanum, canus, Lycopus amplectens, Lycopus rubellus, Lycopus uni Pycnanthemum muticum, Pycnanthemum tenuifolium, Pyc florus, Lycopus virginicus, Lyonia ligustrina, Lyonia mari nanthemum verticillatum, Pycnanthemum virginianum, ana, Lysimachia ciliate, Lysimachia hybrid, Lysimachia Pyrola Americana, Pyrola chlorantha, Pyrola elliptica, Pyxi quadrifolia, Lysimachia terrestris, Lysimachia thyrsiflora, danthera barbulata, Quercus alba, Quercus coccinea, Ouer Magnolia tripetala, Magnolia virginiana, Melampyrum lin cus ilicifolia, Quercus marilandica, Quercus michauxii, eare, Menispermum canadense, Mentha A piperita, Mentha Quercus palustris, Quercus phellos, Quercus prinoides, arvensis, Menyanthes trifoliate, Micranthemum micran Quercus prinus, Quercus rubra, Quercus stellata, Ranuncu thenoides, Mikania Scandens, Mimulus alatus, Mimulus rin 10 lus ambigens, Ranunculus hispidus, Ranunculus longirostris, gens, Minuartia caroliniana, Mirabilis nyctaginea, Mitchella Ranunculuspensylvanicus, Ranunculus pusillus, Ranunculus repens, Moehringia lateriflora, Mollugo verticillata, recurvatus, Ranunculus Sceleratus, Ranunculus trichophyl Monarda punctata, Monotropa hypopithys, Monotropa uni lus, Rhexia mariana, Rhexia virginica, Rhododendron maxi flora, Morella caroliniensis, Morella cerifera, Morella pen mum, Rhododendron periclymenoides, Rhododendron prino sylvanica, Morus rubra, Myosotis laxa, Myosotis verna, 15 phyllum, Rhododendron viscosum, Rhus copallinum, Rhus Myrica gale, Myriophyllum humile, Myriophyllum pinnatum, glabra, Rhus typhina, Ribes americanum, Robinia pseudoa Myriophyllum tenellum, Nelumbo lutea, Nuphar lutea, Nut cacia, Robinia viscose, Rorippa palustris, Rosa Carolina, tallanthus Canadensis, Nymphaea odorata, Nyssa sylvatica, Rotala ramosior; Rubus Canadensis, Rubus cuneifolius, Obolaria virginica, Oclemena memoralis, Oenothera biennis, Rubus flagellaris, Rubus hispidus, Rubus Occidentalis, Rud Oenothera fruticosa, Oenothera laciniata, Oenothera peren beckia hirta, Rudbeckia laciniata, Rumex altissimus, Rumex nis, Oldenlandia un Wora, Oligoneuron rigidium, Onosmo orbiculatus, Sabatia angularis, Sabatia diformis, Sagina dium virginianum, Opuntia humifitsa, Orthilia Secunda, decumbens, Salix bebbiana, Salix discolor, Salix erio Osmorhiza claytonia, Osmorhiza longistylis, Oxalis dillenii, cephala, Salix humilis, Salix interior, Salix nigra, Salix peti Oxalis stricta, Oxypolis rigidior, Packera aurea, Packera Olaris, Salix sericea, Salvia lyrata, Sanguinaria Canadensis, Obovata, Packera paupercula, Panax trifolius, Paronychia 25 Sanguisorba Canadensis, Sanicula Canadensis, Sanicula Canadensis, Paronychia fastigiata, Parthenocissus quinque marilandica, Sarracenia purpurea, Saururus Cernutus, Saxi folia, Pedicularis Canadensis, Pedicularis lanceolata, Pen fraga pensylvanica, Saxifraga virginiensis, Schwalbea stemon hirsutus, Penstemon laevigatus, Penthorum sedoides, Americana, Scrophularia lanceolata, Scrophularia marilan Phlox divaricata, Phlox maculate, Phlox pilosa, Phlox subu dica, Scutellaria elliptica, Scutellaria galericulata, Scutel lata, Phoradendron leucarpum, Photinia floribunda, Pho 30 laria integrifolia, Scutellaria lateriflora, Senna hebecarpa, tinia melanocarpa, Photinia pyrifolia, Phryma leptostachya, Sericocarpus asteroids, Sericocarpus linifolius, Sicyos angu Physalis heterophylla, Physalis longifolia, Physalis pubes latus, Sida spinosa, Silene antirrhina, Silene stellata, Sium cens, Physocarpus opulifolius, Phytolacca Americana, Pilea suave, Solanum carolinense, Solanum ptycanthum, Solanum Fontana, Pilea punila, Plantago aristata, Plantago pusilla, rostratum, Solidago bicolor; Solidago caesia, Solidago Plantago virginica, Platanus Occidentalis, Pluchea foetida, 35 erecta, Solidago fistulosa, Solidago flexicaulis, Solidago Podophyllum peltatum, Polemonium reptans, Polygala brevi gigantean, Solidago juncea, Solidago latissimifolia, Sol folia, Polygala cruciata, Polygala incarnate, Polygala lutea, idago memoralis, Solidago Odora, Solidagopatula, Solidago Polygala mariana, Polygala nuttalii, Polygala polygama, puberula, Solidago rugosa, Solidago Sempervirens, Solidago Polygala sanguine, Polygala Senega, Polygala verticillata, stricta, Solidago uliginosa, Solidago ulmifolia, Spergularia Polygonella articulate, Polygonum amphibium, Polygonum 40 salina, Spiraea alba, Stachys hyssopifolia, Stachys palustris, arifolium, Polygonum careyi, Polygonum erectum, Stachys tenuifolia, Staphylea trifolia, longifolia, Stellaria Polygonum hydropiperoides, Polygonum lapathifolium, pubera, Strophostyles helvola, Strophostyles unbellate, Sty Polygonum pensylvanicum, Polygonum punctatum, losanthes biflora, Symphyotrichum cordifolium, Symphyotri Polygonum robustius, Polygonum Sagittatum, Polygonum chum dumosum, Symphyotrichum ericoides, Symphyotri tenue, Populus grandidentata, Populus tremuloides, Poten 45 chum leave, Symphyotrichum lanceolatum, Symphyotrichum tilla arguta, Potentilla Canadensis, Potentilla norvegica, lateriflorum, Symphyotrichum movi-belgii, Symphyotrichum Potentilla simplex, Prenanthes altissima, Prenanthes autum patens, Symphyotrichum pilosum, Symphyotrichum nalis, Prenanthes serpentaria, Prenanthes trifoliolata, Pros puniceum, Symphyotrichum subulatum, Symphyotrichum erpinaca intermedia, Proserpinaca palustris, Proserpinaca undulatum, Teucrium Canadense, Thalictrum pubescens, pectinata, Prunella vulgaris, Prunus Americana, Prunus 50 Thalictrum revolutum, Thalictrum thalictroides, Thaspium angustifolia, Prunus maritime, Prunus pumila, Prunus sero barbinode, Thaspium trifoliatum, Tilia Americana, Toxico tina, Pseudognaphalium helleri, Pseudognaphalium obtusi dendron pubescens, Toxicodendron radicans, Toxicodendron folium, Ptilimnium capillaceum, Pycnanthemum clinopodio vernix, Triadenum virginicum, Trichosterna brachiatum, Tri ides, Pycnanthemum incanum, Pycnanthemum multicum, chosterna dichotomum, Trichosterna Setaceum, Trientalis Pycnanthemum tenuifolium, Pycnanthemum verticillatum, 55 borealis, Triodanis perfoliata, Ulmus Americana, Ulmus Pycnanthemum virginianum, Pyrola Americana, Pyrola rubra, Utricularia geminiscapa, Utricularia gibba, Utricu chlorantha, Pyrola elliptica, Pyxidanthera barbulata, Ouer laria intermedia, Utricularia juncea, Utricularia mac cus alba, Quercus coccinea, Polygonum pensylvanicum, rorhiza, Utricularia purpurea, Utricularia radiate, Utricu Polygonum punctatum, Polygonum robustius, Polygonum laria striata, Utricularia subulata, Vaccinium angustifolium, Sagittatum, Polygonum tenue, Populus grandidentata, Popu 60 Vaccinium corymbosum, Vaccinium fiscatum, Vaccinium lus tremuloides, Potentilla arguta, Potentilla Canadensis, macrocarpon, Vaccinium stamineum, Valerianella umbili Potentilla norvegica, Potentilla simplex, Prenanthes cata, Verbena hastate, Verbena simplex, Verbena urticifolia, altissima, Prenanthes autumnalis, Prenanthes serpentaria, Verbesina alternifolia, Veronica anagallis-aquatica, Prenanthes trifoliolata, Proserpinaca intermedia, Proserpi Veronica peregrine, Veronica scutellata, Veronicastrum vir naca palustris, Proserpinaca pectinata, Prunella vulgaris, 65 ginicum, Viburnum acerifolium, Viburnum dentatum, Vibur Prunus Americana, Prunus angustifolia, Prunus maritime, num nudum, Viburnum prunifolium, Viola A palmate, Viola Prunus punila, Prunus serotina, Pseudognaphalium helleri, affinis, Viola bicolor, Viola blanda, Viola brittoniana, Viola US 9,307,765 B2 7 8 cucullata, Viola hirsutula, Viola labradorica, Viola lan cides, oxadiazolone herbicides; phenylurea herbicides, sulfo ceolata, Viola macloskeyi, Viola pedata, Viola pubescens, nanilide herbicides; triazolopyrimidine herbicides, amide Viola sagittata, Viola triloba, Vitis aestivalis, Vitis labrusca, herbicides, pyridazine herbicides, dinitroaniline herbicides Vitis riparia, Vitis vulpine, Xanthium strumarium, and Zizia or combinations thereof. aptera. In another preferred embodiment the present invention In another embodiment, the use and method of the present provides a herbicidal combination which comprises: invention is effective against dicotyledonous weeds selected (a) D-Napropamide; and from Cirsium arvense, Taraxacum officinale, Ranunculus (b) clomazone. repens, Senecio vulgaris, Papaver rohoeas, Veronica persica, In another preferred embodiment the present invention Matricaria sp., Fallopia Convolvulus, Veronica arvensis, 10 Veronica hederofolia, Stellaria media and Polygonum con provides a herbicidal combination which comprises: volvulus. (a) D-Napropamide; and In another embodiment, the present invention provides a (b) Benfluralin. herbicidal composition comprising D Napropamide and In yet another embodiment the present invention provides agronomically acceptable excipients. These compositions 15 use of combination comprising combination of D-Napropa were found useful in the practice of the enhanced use and mide and a second herbicide for the control of weeds at a improved method of the present invention. The agronomi locus. cally acceptable excipients may be selected from carriers, In another preferred embodiment the present invention inert materials, organic or inorganic solvents, minerals, provides a method of controlling the weed infestation at a mixed solvents, wetting agents and/or emulsifying agents, locus by treating with a combination comprising combination adhesive agents, anti-caking agents, deflocculating agents, of D-Napropamide and a second herbicide. and the like. The herbicidal composition may be formulated In another preferred embodiment the present invention in the form of solid and liquid formulations. provides a herbicidal combination which comprises: In another aspect, the present invention provides a combi (a) D-Napropamide; and nation comprising Napropamide-Malong with a second her 25 (b) Clomazone. bicide selective for monocotyledonous weeds. It was surpris In a preferred embodiment, clomazone is combined with ingly found that a broad-spectrum herbicide effect was Napropamide-M as an encapsulated Suspension. In achieved with a reduced overall amount of active ingredient one embodiment, the capsule Suspension formulation of clo when Napropamide-M was combined with a second herbi mazone is as described in U.S. Reissue Pat. No. RE38675, cide. 30 The present invention therefore also provides a herbicide U.S. Pat. No. 5,583,090, U.S. Pat. No. 5,783,520 or PCT combination which comprises: Publication No. WO/2011/121407, all of which are incorpo (a) D-Napropamide; and rated herein by reference. (b) a second herbicide which is active against monocotyle In another embodiment, the present invention provides a donous weeds. 35 herbicidal combination comprising (a) Napropamide-M; (b) In an embodiment, the second herbicide selected is such an urea herbicide selected from benzthiazuron, cumyluron, that not only it is active against monocotyledonous weeds but cycluron, dichloralurea, diflufenZopyr, isonoruron, isouron, is, preferably, relatively more active against monocotyledon methabenzthiaZuron, monisouron, noruron, anisuron, butu ous weeds than dicotyledonous weeds. ron, chlorbromuron, chloreturon, chlorotoluron, chloroXu Further, following the finding of the present invention that 40 ron, daimuron, difenoXuron, dimefuron, diuron, fenuron, flu D-Napropamide has enhanced activity specifically against ometuron, fluothiuron, isoproturon, linuron, methiuron, dicotyledonous weeds, it is possible to formulate the herbi methyldymron, metobenzuron, metobromuron, metoXuron, cide such that it is active in controlling dicotyledonous weeds, monolinuron, monuron, neburon, parafluron, phenobenzu yet is less active (preferably Substantially inactive) against ron, Siduron, tetrafluron, thidiaZuron, amidosulfuron, azim monocotyledonous plant species. Accordingly, the present 45 Sulfuron, benSulfuron, chlorimuron, cyclosulfamuron, ethox invention also provides the use of D-Napropamide for the ysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, control of a dicotyledonous weed at a locus, wherein the foramsulfuron, halosulfuron, imaZoSulfuron, mesosulfuron, D-Napropamide is applied in an amount Such that it is effec metazosulfuron, methiopyrisulfuron, monosulfuron, nicosul tive in controlling said dicotyledonous weed, yet is less active furon, orthosulfamuron, oxasulfuron, primisulfuron, propy (preferably substantially inactive) against monocotyledonous 50 risulfuron, pyrazosulfuron, rimsulfuron, Sulfometuron, Sulfo plant species. Sulfuron, trifloxysulfuron, Zuomihuanglong, chlorSulfuron, Typically, said monocotyledonous plant species may be a cinosulfuron, ethametSulfuron, iodosulfuron, iofensulfuron, crop plant. metsulfuron, prosulfiron, thifensulfuron, triasulfuron, tribe In this embodiment, the activity of the D-Napropamide nuron, triflusulfuron, tritosulfuron, buthiuron, ethidimuron, against the monocotyledonous plant species is typically Such 55 tebuthiuron, thiazafluron and thidiaZuron; and (c) an agricul that the mean final foliar fresh weight of the monocotyledon turally acceptable carrier or diluent. ous plant species 21 days after application of the D-Napropa In an embodiment, the present invention provides a com mide is 70% or more, more typically 80% or more, preferably bination comprising (a) Napropamide-M; and (b) dimefuron. 90% or more, than the weight obtained with untreated plants. In an embodiment, Napropamide-M is combined with a In an embodiment, the second herbicide is selected from 60 triazine herbicide selected from the group consisting of dipro but not limited to, clomaZone, a urea herbicide, a triazine petryn, fucaojing, trihydroxytriazine, atrazine, chlorazine, herbicide, a hydroxybenzonitrile herbicide, a thiocarbamate cyanazine, cyprazine, eglinazine, ipazine, mesoprazine, pro herbicide, a pyridazine herbicide, chloroacetanilide herbi cyazine, proglinazine, propazine, Sebuthylazine, simazine, cides; benzothiazole herbicides; carbanilate herbicides, terbuthylazine, trietazine, indaziflam, triaziflam, atraton, cyclohexene oxime herbicides; picolinic acid herbicides: 65 methometon, prometon, secbumeton, simeton, terbumeton, pyridine herbicides; quinolinecarboxylic acid herbicides: ametryn, aZiprotryne, cyanatryn, desmetryn, dimethametryn, chlorotriazine herbicides, aryloxyphenoxypropionic herbi methoprotryne, prometryn, simetryn and terbutryn. US 9,307,765 B2 10 In another embodiment, Napropamide-M may be com mide, flucarbazone, flupoxam, fomesafen, halosafen, huang bined with a nitrile herbicide selected from bromobonil, bro caoling, isocarbamid, isoxaben, naptalam, pethoxamid, pro moxynil, chloroxynil, dichlobenil, iodobonil, ioxynil and pyZamide, quinonamid, saflufenacil, tebutam and tiafenacil. pyraclonil. In another embodiment, Napropamide-M may be com In an embodiment, Napropamide-M may be combined bined with a pyridazine herbicide selected from credazine, with a thiocarbamate herbicide selected from dazomet and cyclopyrimorate, pyridafol and pyridate. metam. In an embodiment, Napropamide-M may be combined In another embodiment, Napropamide-M may be com with glufosinate. An additional advantage demonstrated by bined with a pyridazine herbicide selected from credazine, this combination was that Napropamide-M acted pre-emer cyclopyrimorate, pyridafoland pyridate. 10 gence while any weeds emerged was quickly killed by the In another embodiment, Napropamide-M may be com glufosinate component thereby rendering the pre-emergent bined with a chloroacetanilide herbicide selected from herbicide Napropamide-M active yet again. Therefore, the acetochlor, alachlor, butachlor, butenachlor, delachlor, combination of Napropamide-M with glufosinate was found diethatyl, dimethachlor, ethachlor, ethaprochlor, metaza to be surprisingly efficacious as a pre-emergent and broad chlor, metolachlor, S-metolachlor, pretilachlor, propachlor, 15 spectrum post-emergent herbicide. propisochlor, prynachlor, terbuchlor, thenylchlor and In yet another embodiment, Napropamide-M may be com xylachlor. bined with a dinitroaniline herbicide selected from benflura In another embodiment, Napropamide-M may be com lin, butralin, chlorinidine, dinitramine, dipropalin, ethalflura bined with a benzothiazole herbicide selected from benazo lin, fluchloralin, isopropalin, methalpropalin, nitralin, lin, benzthiazuron, fenthiaprop, mefenacet and methabenz oryzalin, pendimethalin, prodiamine, profluralin and triflura thiaZuron. lin. In another embodiment, Napropamide-M may be com In another embodiment, Napropamide-M may be com bined with a carbanilate herbicide selected from a carbanilate bined with a third herbicide. The third herbicide may be herbicide selected from barban, BCPC, carbasulam, carbeta selected from the herbicides listed above in any of the mide, CEPC, chlorbufam, chlorpropham, CPPC, desme 25 embodiments although the second and third herbicides may dipham, phenisopham, phenmedipham, phenmedipham not be the same. ethyl, propham and Swep. In yet another preferred embodiment the present invention In another embodiment, Napropamide-M may be com further comprises third herbicide selected from clomazone, bined with a cyclohexene oxime herbicide selected from chloroacetanilide herbicides; pyrazole herbicides; quinolin alloxydim, butroxydim, clethodim, cloproxydim, cycloxy 30 ecarboxylic acid herbicides and amide herbicides. dim, profoxydim, Sethoxydim, tepraloxydim and tralkoxy In this embodiment, the chloroacetanilide herbicide, pyra dim. Zole herbicides, quinoline carboxylic acid herbicide and In another embodiment, Napropamide-M may be com amide herbicide may be selected from the list of compounds bined with a picolinic acid herbicide selected from aminopy defined in the embodiments described above for these classes ralid, clopyralid, halauxifen and picloram. 35 of compounds. In an embodiment, Napropamide-M may be combined In another embodiment the present invention also provides with a pyridine herbicide selected from aminopyralid, cliodi a herbicide combination which comprises: nate, clopyralid, diflufenican, dithiopyr, flufenican, fluroxy (c) D-Napropamide: pyr, halauXifen, haloxydine, picloram, picolinafen, pyriclor, (d) a second herbicide; and pyroxSulam, thiazopyr and triclopyr. 40 (e) a third herbicide. In an embodiment, Napropamide-M may be combined In yet another embodiment the present invention provides with a quinoline carboxylic acid herbicide selected from a ternary herbicidal combination which comprises quinclorac and quinmerac. D-Napropamide; benfluralin; and clomazone. In another embodiment, Napropamide-M may be com In yet another embodiment the present invention provides bined with an aryloxyphenoxypropionic acid herbicide 45 a ternary herbicidal combination which comprises selected from cloprop, 4-CPP dichlorprop, dichlorprop-P, D-Napropamide; dimethachlor; and clomaZone. 3,4-DP, fenoprop, mecoprop, mecoprop-P, chlorazifop, clod In another embodiment, the present invention provides a inafop, clofop, cyhalofop, diclofop, fenoxaprop, fenoxaprop combination comprising: P. fenthiaprop, fluazifop, fluazifop-P, haloxyfop, haloxyfop (a) Napropamide-M; and P. isoxapyrifop, kuicaoxi, metamifop, propaquizafop, 50 (b) a second herbicide component selected from any one quizalofop, quizalofop-P and trifop. of: In another embodiment, Napropamide-M may be com (i) S-Metolachlor; bined with a oxadiazolone herbicide selected from dimefu (ii) ClomaZone; ron, methazole, oxadiargyl and oxadiaZon. (iii) Flufenacet: In another embodiment, Napropamide-M may be com 55 (iv) Diflufenican; bined with a sulfoanilide herbicide selected from benzofluor, (v) Flufenacet+diflufenacet: cloranSulam, dicloSulam, florasulam, flumetSulam, metosu (vi) Benfluraline; lam, perfluidone, profluaZol and pyrimisulfan. (vii) Quinmerac: In another embodiment, Napropamide-M may be com (viii) Metazachlor; bined with a triazolopyrimidine herbicide selected from clo 60 (ix) Quinmerac+Metazachlor; ranSulam, diclosulam, floraSulam, flumetSulam, metoSulam, (x) Glufosinate; penoXSulam and pyroxSulam. (xi) Metribuzin; In another embodiment, Napropamide-M may be com (xii) Clomazone--S-Metolachlor; bined with amide herbicides selected from allidochlor, ami (xiii) Dimethachlor; carbazone, beflubutamid, benzadox, benzipram, bro 65 (xiv) Benazolin; mobutide, cafenstrole, CDEA, cyprazole, dimethenamid, (XV) Carbetamide: dimethenamid-P, diphenamid, epronaz, etnipromid, fentraza (xvi) Clethodim; US 9,307,765 B2 11 12 (xvii) Cycloxydim; Example 1 (xviii) Sethoxydim; (xix) Clopyralid: Controlled Trial: Comparative Effect of D-Isomer of (XX) Cyanazine; Napropamide and Napropamide for Controlling (XXi) Simazine; Stellaria media (Dicot Weed) and Poa annua (xxii) Diclofop: (Monocot Weed) (xxiii) Fenoxaprop-P: A study was carried out to determine the relative biological (xxiv) Fluazifop-P: activity of the D and L isomers of Napropamide when applied (XXV) Haloxyfop-P: pre-emergence to one monocotyledon and one dicotyledon (XXvi) Propaquizafop; 10 species. Napropamide, containing 450 grammes active Sub (xxvii) Quizalafop; stance per liter (ga.S./L) formulated as a suspension concen (xxviii) Dimefuron; trate and the D-isomer of Napropamide (1000 ga.s./L) were (xxix) Flumetsulam: applied at a range of concentrations from 0.1575 to 1.26 (XXX) PropyZamide: kilograms of active Substance per hectare (kga.S/Ha). (xxxi) Pyridate; 15 ECso values in kg a.s./Ha were calculated from the dose (xxxii) Trifluralin; and response data using final foliar fresh weight data for each (xxxiii) Clomazone--Metazachlor. species and was used to determine the relative biological The compound Napropamide-M is known in the art and activity of the D and L isomers of Napropamide. The meth can be prepared by any of the known methods such as the one odology was based on the OECD guideline 2008, according disclosed in WO2009004642, which is incorporated herein to the revision of July 2006 for seedling emergence and by reference in its entirety. growth. The study was conducted to GLP standards. The invention will now be explained in more detail in the Seeds were Sown directly into non-porous plastic pots con following examples that illustrate, but are not intended to taining the following mix of soil: 10 L of sterile loam-4 L of limit, the invention. coarse grit (washed quartztite, nominal 4 mm)+10 L of sand. 25 This soil mix was characterized as a sandy loam with an EXAMPLES organic carbon content of 1.5% and pH of 7.2. Details of the plant species, number of seeds perpot and pot size are shown Field trials were conducted on various moncotyledonous below. All seeds were sown 1-2 cm deep. weeds and dicotyledonous weeds and the effect of D-isomer Details of Plant Species

Variety Weed type Species Common name (Source) Seedspot Pot size Monocotyledon Poa annua Meadow grass Herbiseed 4 7 x 7 x 8 cm Dicotyledon Steliaria media Chickweed Herbiseed 6 7 x 7 x 8 cm of Napropamide was studied to understand the selective and The highest concentration of Napropamide was prepared effective control of dicotyledonous weeds over monocotyle by measuring a calculated Volume by weight and diluting donous weeds. The effect of D-isomer of Napropamide in 40 with tap water to the full required volume. Lower concentra comparison to racemic napropramide and untreated was stud tions were prepared by serial dilution with water. D-Napropa ied, which is concluded hereinbelow: mide was prepared by dissolving the calculated weight in acetone and adding water to give the full required Volume in Statistical Analysis Model: 50:50 acetone--water. Lower concentrations were prepared Several small plot replicated trials were carried out to 45 by serial dilution with 50:50 acetone--water. D-Napropamide evaluate and/or compare the efficacy of D-Napropamide dissolved completely. against a range of indicated annual broadleaved and grass Preparation of the Highest Rate Spray Solutions for Poa weed species in the indicated crops. No problems were CF2C encountered during mixing or application of any of the prod uct formulations or tank mixtures under test. 50 Active Application Amount Volume In each of the reported data, the homogeneity of variance Test item Ingredient Rate volume weighed prepared was tested by Bartlett's test. Wherever this test indicated no Napropamide 450 1.26 193.12 LHa 6.321 g 400 mL. homogeneity of variance, the transformed values were used (water) gas/L kg as L. for analysis of variance. Assessment data was then analyzed 55 D 1OOO 1.26 193.12 LHa 2.611 g 400 mL. using a two-way analysis of variance (ANOVA) on untrans Napropamide gas/kg kgas/L (acetone + formed and transformed data. The probability of no signifi water) cant differences occurring between treatment means was cal culated as the F probability value (p(F)). A mean comparison Preparation of Highest Rate Spray Solutions for Stellaria test was only performed and reported when the treatment of F 60 media that was calculated during analysis of variance was signifi cant at the observed significance level specified for the mean comparison test. Where the data was transformed, treatment Active Application Amount Volume means in the reports were presented in their detransformed Test item ingredient Rate volume weighed prepared state, with the appropriate letter test and mean descriptions 65 Napropamide 450 1.26 196.17 L/Ha 6.223 g 400 mL. (LSD and standard deviation) derived from the transformed gas/L kg as L. (water) ANOVA US 9,307,765 B2 14 -continued ECso Values in kg as?ha Based on the Final Fresh Weights

Active Application Amount Volume Test item ingredient Rate volume weighed prepared Type of weed Species Common name ECso (kg/Ha) D 1OOO 1.26 196.17 L/Ha 2.569g 400 mL. Monocot Poa annia Meadow grass d- 0.44 Napropamide gas/kg kg as L. (acetone + Napropamide 126 water) 1 Napropamide Napropamide 0.72 Dicot Steiliaria media Chickweed d- O.OS4 The sprayer was calibrated within 24 hours prior to appli 10 Napropamide cation by weight of 15 applications of water to six 86 mm ID L- 1.26 petri dishes. The total weight of water over a known area Napropamide enabled a simple calculation giving the Volume rate to be Napropamide O.22 made. The Volume rate achieved was within the range speci fied in the study plan (200 L/Hat 10%). 15 Conclusion: D-Napropamide demonstrates distribution of Replication was 5 pots per treatment for each plant species. enhanced activity towards control of dicot weed vis-a-vis After application, pots were placed on the bench in glass only a moderate selectivity towards monocot weed in com house in randomized blocks. Plants were assessed for emer parison with Napropamide. D-Napropamide was found about gence, mortality and visual injury (expressed as a percentage 1.63 times more active than racemic Napropamide and 2.86 of the untreated control: 0% no injury, 1-39% slight injury, more active than L-Napropamide in monocotyledonous 40-69%-moderate injury, 70-99%-severe injury and weeds. Surprisingly, D-Napropamide was found to be about 100% all plants dead) at 14 and 21 days after 50% emergence 4.07 times more active than racemic Napropamide and 23.33 in the untreated controls. Fresh weights (biomass above soil times more active than L-Napropamide in dicotyledonous level) were also recorded 21 days after 50% emergence in the weeds. The degree of enhancement in efficacy seen over untreated controls. Plants were fully turgid at the time of 25 racemic Napropamide and L-Napropamide towards the con harvest. trol of dicotyledonous weeds was surprising. Equally Surpris 1. Mean Final Foliar Fresh Weights (g) ing was a clear trend of differentiated selectivity of D-Napropamide towards the control of dicotyledonous weeds vis-a-vis the control of monocotyledonous weeds. Pog Steiaria 30 Treatment Rate (kg/Ha) (iiii media Example 2 Untreated Acetone + Water O.90 1.44 D-Napropamide 0.1575 O.93 O.498 D-Napropamide O.315 O.64 O.198 Selectivity of D-Napropamide for Controlling D-Napropamide O.63 O.45 O.17 35 Ranunculus repens, Senecio Vulgaris and Papaver Napropamide O.315 0.57 O.3 Napropamide O.63 O.98 O.328 rhoeas (Dicotyledonous Weed) in Strawberry Farm Trial was carried out on strawberries to evaluate the effi D-Napropamide demonstrates distribution of enhanced cacy and selectivity of D-Napropamide and equivalent rate of activity towards control of dicot weed vis-a-vis only a mod 40 DeVrinol (Napropramide) applied pre-emergence. Efficacy erate selectivity towards monocot weed in comparison with was assessed visually after the emergence of significantly Napropamide. new growth in untreated plot. The percentage control of 2. Mean Final Foliar Fresh Weights Expressed as Percentage D-isomer of Napropamide and DeVrinol was assessed incom of Untreated Controls: parison to the untreated after 224 days after application. 45 TABLE 2 Treatment Rate (kg/Ha) Poaannia Steiaria media Mean Percentage Control of Ranunculus repens (dicotyledonous weed Untreated Acetone + Water 1OO 100 Percentage Percentage d-Napropamide 0.1575 1OO 35 50 d-Napropamide O.315 71 14 Control at Control at d-Napropamide O.630 50 12 S No. Treatment 224 DAA Treatment 224 DAA Napropamide 0.1575 1OO 70 Napropamide 1.26 23 16 1 Untreated O.OO 1 Napropamide 33.3 D-Napropamide 66.7 5 LHa 3.0 L Ha 55 3 Napropamide 66.7 D-Napropamide 100 D-Napropamide demonstrates distribution of enhanced 7 LHa 4.2 LHa activity towards control of dicot weed vis-a-vis only a mod 4 Napropamide 83.3 D-Napropamide 100 erate selectivity towards monocot weed in comparison with 14 Li Ha 8.5 L Hal LSD (P = 0.5) 4.640 Napropamide. SD 3.179 Assessment data was recorded on pro-forma sheets and 60 entered into Gylling ARM7 software. ECs values were cal culated using audited means data from the final assessments The tested formulations contained 450 g/L of Napropam (21 day). Gylling ARM 7.0 software used a simple probit— ide and Napropamide-M respectively. maximum likelihood estimation method with 99% confi Conclusion: D-Napropamide demonstrated Surprising effi dence level. The ECso values generated were then visually 65 cacy in the control of Ranunculus repens vis-a-vis the checked against the means data table to Verify they appeared control achieved by Napropamide at an equivalent dos COrrect. age. US 9,307,765 B2 15 16 TABLE 3 Conclusion: D-Napropamide demonstrates poor efficacy in the control of Aperaspica-venti, a monocot weed, Mean Percentage Control of Senecio vulgaris: vis-a-vis the control achieved by Napropamide at an Percentage Percentage equivalent dosage. Control at 70 Control at 70 5 S No. Treatment DAA Treatment DAA TABLE 6 1 Untreated O.OO 1 Napropamide 5 37.5 D-Napropamide 75.0 Mean Percentage Control of Peronica persica (dicot weed LHa 3.0 L Ha Percentage Percentage 3 Napropamide 7 2SO D-Napropamide SO.O 10 Control at Control at LHa 4.2 LiHa 4 Napropamide 14 12.5 D-Napropamide 75.0 S No. Treatment 63 DAA Treatment 63 DAA LHa 8.5 L Hal 1 Untreated O.OO 2 D Napropamide 100.00 Napropamide 75.00 The tested formulations contained 450 g/L of Napropam 450 g/L (a) 1.4 1.6 L Ha ide and Napropamide-M respectively. 15 LHa Conclusion: D-Napropamide demonstrated Surprising effi 3 D Napropamide 100.00 Napropamide 75.00 cacy in the control of Senecio vulgaris, a dicotyledonous 450 g/L (a) 1.6 2.8 L Hal weed, vis-a-vis the control achieved by Napropamide at LHa an equivalent dosage. LSD (P = 0.5) 10.367 TABLE 4 The tested formulations contained 450 g/L of Napropam Mean Percentage Control of Papaverrhoeas: ide and Napropamide-M respectively. Percentage Percentage Conclusion: D-Napropamide demonstrates superior effi Control at 70 Control at 70 25 cacy in the control of Veronica persica, a dicot weed, S No. Treatment DAA Treatment DAA vis-a-vis the control achieved by Napropamide at an 1 Untreated O.OO equivalent dosage. 1 Napropamide 5 62.5 D-Napropamide 71.7 LHa 3.0 L Ha 3 Napropamide 7 81.7 D-Napropamide 95.0 TABLE 7 LHa 4.2 LiHa 30 4 Napropamide 14 82.5 D-Napropamide 97.5 Mean Percentage Control of Triticum aestivum (monocot weed). LiHa 8.5 L Hal Percentage Percentage Control at Control at The tested formulations contained 450 g/L of Napropam Sir No. Treatment 51DAA Treatment 72DAA 35 ide and Napropamide-M respectively. 1 Untreated O.OO Conclusion: D-Napropamide demonstrated Surprising effi 2 D Napropamide O.OO D Napropamide O.OO cacy in the control of Papaverrhoeas vis-a-vis the con 450 g/L (a) 1.4 450 g/L (a) 1.4 trol achieved by Napropamide at an equivalent dosage. LHa LHa 3 D Napropamide O.OO D Napropamide O.OO Example 3 450 g/L (a) 1.6 450 g/L (a) 1.6 40 LHa LHa Selectivity of D-Isomer of Napropamide for 4 D-Napropamide O.OO D-Napropamide O.OO Controlling Annual Broadleaved and Grass Weed 450 g/L (a) 1.8 450 g/L (a) 1.8 Species in Winter Oilseed Rape LHa LHa 5 D-Napropamide O.OO D-Napropamide O.OO 450 g/L (a) 2.0 450 g/L (a) 2.0 Trials were conducted to evaluate the selectivity and effi LHa LHa cacy of D-isomer of Napropamide when applied pre-emer LSD (P = 0.5) O.OOO gence to oilseed rape crop. The % control of weed was SD O.OOO assessed at regular intervals. TABLE 5 Conclusion: D-Napropamide demonstrates negligible con 50 trol of Triticum aestivum, a monocot weed. Mean Percentage Control of Aperaspica-venti (Monocot Weed Percentage Percentage TABLE 8 Control at Control at S No. Treatment 63 DAA Treatment 63 DAA Mean Percentage Control of Cirsium arverse. 55 1 Untreated O.OO Percentage 1 D Napropamide 35.00 Napropamide 40.00 Control at 51 450 g/L (a) 1.4 1.6 L Ha S No. Treatment DAA LHa 3 D Napropamide 52.50 Napropamide 76.25 1 Untreated O.OO 2 D Napropamide 100.00 Napropamide 450 2O.OO 450 g/L (a) 1.6 2.8 L Hal 60 LHa 450 g/L (a) 1.6 g/L (a) 2.8 L Ha 4 D-Napropamide 58.75 Napropamide 67.50 LHa 450 g/L (a) 1.6 2.8 L Hal LHa LSD (P = 0.5) 10.367 Conclusion: D-Napropamide demonstrates Superior con 65 trol of Cirsium arvense, a dicot weed vis-a-vis a negli The tested formulations contained 450 g/L of Napropam gible control of the same weed with an equivalent dos ide and Napropamide-M respectively. age of Napropamide. US 9,307,765 B2 17 18 TABLE 9 Napropamide formulations containing 450 g/L active ingre dient and the activity was noted after 60 days of application. Mean Percentage Control of Senecio Pulgaris: Percentage Percentage TABLE 12 Control at Control at 5 S No. Treatment 214 DAA Treatment 63 DAA Mean Percentage Control of Digitaria sanguinalis:

1 Untreated O.OO S No. Treatment % Control % Control 2 D Napropamide 94.72 Napropamide 36.96 450 g/L (a) 1.6 450 g/L (a) Treatment evaluation 16 DAA 33 DAA LHa 1.6 L Ha 10 interval 3 D Napropamide 82.15 Napropamide 4.65 BBCH Weed 12 21 450 g/L (a) 1.6 450 g/L (a) Groundcover (%) weed 4.75 7.00 LHa 2.8 L Hal 1 D Napropamide 3 L/Ha 7.50 8.75 SP (P = 0.5) E. 2 D Napropamide 4.5 L/Ha 1O.OO 10.00 3 D Napropamide 6 L/Ha 1O.OO 12.SO 15 4 D Napropamide 7.5 L/Ha 1O.OO 11.25 Conclusion: D-Napropamide demonstrates superior effi- 5 DNapropamide 9 LHa 1O.OO 18.75 6 Napropamide 9 LiHa 12.SO 1S.OO cacy in the control of Senecio vulgaris, a dicot weed, LSD (P = 0.05) 4.675 4.682 vis-a-vis the control achieved by Napropamide at an sid. Dev. 3.162 3.07 equivalent dosage. 20 CV 31.62 24.45

TABLE 10 Conclusion: D-Napropamide is only as efficacious or less Mean Percentage Control of Matricaria sp. in comparison to Napropamide in the control of mono Percentage Percentage 25 cotyledonous weeds. Control at ground S No. Treatment 49 DAA Treatment cover 90 Example 5 1 Untreated O.OO Untreated 4...SO (0.0%) 2 PNippa's 97.00 PN's 3.%) 30 Broad Spectrum Effect of D-Napropramid and LHa LHa Clomazone on Dicot and Monocot Weeds 3 Napropamide 61.25 Napropamide 2.13 450 g/L (a) 450 g/L (a) (52.8%) 2.8 L Hal 2.8 L. Ha The effect of combination of D-napropramide and Cloma LSD (P = 0.5) 24,514 1.1.89 Zone was tested in the field, post sowing of the seeds. The SD 16.862 O.818 combination of D-napropramide and ClomaZone was tested at different amounts on monocot and dicot weeds. The field Conclusion: D-Napropamide demonstrates superior effi- was observed after 50 days, results of which are reproduced cacy in the control of Matricaria sp., a dicot weed, herein below: vis-a-vis the control achieved by Napropamide at an 40 equivalent dosage. D-Napropramide D-Napropramide TABLE 11 (450 g/L SC (a) (91 g/L MEC (a) 1.7l) + Clomazone 8.41 l) + Mean Percentage Control of Fallopia convolvulus (a dicot weed): (3 g s (a) s 45 0. Percentage Percentage (% control) control) Control at 63 control at 63 ALOMY Alopecurus OO 100 S No. Treatment DAA Treatment DAA (19/mi)) myosuroides Huds 1 Untreated O.OO Untreated O.OO (monocot); 2 D Napropamide 100.00 Napropamide 450 30.00 so to M, feltterm OO 100 450 ? 2.O g/L (c) 1.6 LiHa PAPRH Papaverrhoeas L OO 100 2 3 D Napropamide 100.00 Napropamide 450 O.OO CSC, Centatinea Cvantis L. OO 100 450 g/L (a) 1.6 g/L (a) 2.8 L Ha (104/m) (dicot) cy LHa GERPU Geranium pusillum OO 100 55 (156/m) L. (dicot) Conclusion: D-Napropamide demonstrates superior effi- slip, gis dissectin OO 98.3 cacy in the control of Fallopia convolvulus., a dicot TRZAW Wheat (monocot) OO 98.3 weed, vis-a-vis the control achieved by Napropamide at (88/m) al equivalent dosage. HORVW Hordein irregulare OO 100 60 (89/mi) Aberg & Wiebe (monocot) Example 4 BARVU Barbarea vulgaris OO 100 (78/mi) Ait. f. (dicot) Effect of D-Isomer of Napropamide for Controlling Digitaria sanguinalis (Monocot Weed) 65 It was concluded that the combination of D-Napropramide A plot with 20% density of Digitaria sanguinalis (monocot and Clomazone was very effective in controlling both the weed) was treated with D-Napropamide and Racemic dicot weeds and monocot weeds. US 9,307,765 B2 19 20 Example 6 groundsel, horseweed, common lambsquarters, little mallow, burning nettle, sowthistles, carpetweed, fathen, blackberry Broad Spectrum Effect of D-Napropramid and nightshade, Small flowered mallow, nettles, deadnettle, knot Combination of Dimetachlor--Clomazone weed, common sowthistle, and amaranthus. 6. The method of claim 1, wherein the weed is selected The field infected with TRZAW (wheat-monocot) 20/m from the group consisting of Cirsium arvense, Taraxacum was treated with D-napropramid (1.2 l/ha) and in combina officinale, Ranunculus repens, Senecio vulgaris, Papaver tion with dimethachlor--Clomazone (1.5 l/ha). The result is rohoeas, Veronica persica, Matricaria spp., Fallopia Convol tabulated herein below: vulus, Veronica arvensis, Veronica hederofolia, Stellaria 10 media, and Polygonum convolvulus. 7. The method of claim 1, wherein the weed is chickweed Column (Stellaria media). 8. The method of claim 1, wherein the treating comprises D-Napropramide (450 93 treating the soil in which a desired crop is to be planted. g/L SC (a) 1.2 l) + 15 9. The method of claim 8, wherein the treating is before dimethachlor + Seeding, during seeding, or after seeding before the crop Clomazone (500 g/L dimethachlor + 360 g/L emerges. clomazone (a) 1.5 l) 10. The method of claim 8, wherein the treating is prior to D-Napropamide (450 g/L 90 the emergence of any weed. SC (a) 1.2 l) + dimetachlor + Clomazone 11. The method of claim 8, wherein said crop is selected (500 g/L dimethachlor + from the group consisting of winter oilseed rape, strawber 360 g/L clomazone (a) ries, blackcurrants, gooseberries, raspberries, field trees, 1.5 l) shrubs, broccoli, cabbage, calabrese, cauliflower, kale, and Brussel's sprouts. From the above table it is evident that 90 to 93% of mono 25 12. An herbicide formulation consisting essentially of an cot weed control was observed after the application of herbicidally effective amount of: D-napropramide and combination of dimetachlor+Cloma D-Napropamide; Zone (1.5 l/ha). a combination of chloroacetanilide herbicide and quinoline We claim: carboxylic acid herbicide, 1. A method of controlling a weed infestation at a locus, 30 wherein the chloroacetanilide is selected from the group comprising the step of treating said locus with an herbicidally consisting of acetochlor, alachlor, butachlor, buten effective amount an herbicide formulation consisting essen achlor, delachlor, diethatyl, dimethachlor, ethachlor, tially of: ethaprochlor, metazachlor, metolachlor, S-meto at least one agronomically acceptable excipient; and lachlor, pretilachlor, propachlor, propisochlor, an herbicide combination consisting of D-Napropamide 35 prynachlor, terbuchlor, thenylchlor, and xylachlor; and a combination of chloroacetanilide herbicide and and the quinoline carboxylic acid herbicide is selected quinoline carboxylic acid herbicide, wherein from the group consisting of quinclorac and quin the chloroacetanilide herbicide is selected from the merac; and group consisting of acetochlor, alachlor, butachlor, agronomically acceptable excipients, butenachlor, delachlor, diethatyl, dimethachlor, eth 40 wherein said formulation exhibits superior herbicidal achlor, ethaprochlor, metazachlor, metolachlor, activity efficacy compared with an equivalent formula S-metolachlor, pretilachlor, propachlor, propisochlor, tion that uses Napropamide instead of D-Napropamide. prynachlor, terbuchlor, thenylchlor, and xylachlor 13. The herbicide formulation of claim 12, wherein the and combinations thereof, and chloroacetanilide herbicide is metazachlor, and the quinoline the quinoline carboxylic acid herbicide is selected from 45 carboxylic acid herbicide is quinmerac. the group consisting of quinclorac and quinmerac and 14. An herbicidal formulation consisting essentially of: combinations thereof; and at least one agronomically acceptable excipient; and optionally, an herbicide selected from the group consisting an herbicide composition consisting of D-Napropamide of clomaZone, a pyrazole herbicide, and an amide her and a combination of chloroacetanilide herbicide and bicide different from D-Napropamide: 50 quinoline carboxylic acid herbicide, wherein wherein said formulation exhibits superior herbicidal activity the chloroacetanilide herbicide is selected from the group efficacy compared with an equivalent formulation that uses consisting of acetochlor, alachlor, butachlor, buten Napropamide instead of D-Napropamide. achlor, delachlor, diethatyl, dimethachlor, ethachlor, 2. The method of claim 1, wherein the locus is the vicinity ethaprochlor, metazachlor, metolachlor, S-metolachlor, of a desired crop. 55 pretilachlor, propachlor, propisochlor, prynachlor, ter 3. The method of claim 2, wherein said crop is selected buchlor, thenylchlor, and xylachlor, and the quinoline from the group consisting of winter oilseed rape, strawber carboxylic acid herbicide is selected from the group ries, blackcurrants, gooseberries, raspberries, field trees, consisting of quinclorac and quinmerac; and shrubs, broccoli, cabbage, calabrese, cauliflower, kale, and optionally, an herbicide selected from the group consisting Brussel's sprouts. 60 of clomazone, a pyrazole herbicide, and an amide her 4. The method of claim 1, wherein the treating is before or bicide different from D-Napropamide: after emergence of the weed. wherein said formulation exhibits superior herbicidal 5. The method of claim 1, wherein the weed is selected activity efficacy compared with an equivalent formula from the group consisting of chickweed, speedwell, poppy, tion that uses Napropamide instead of D-Napropamide. field bindweed, hairy fleabane, nettleleaf goosefoot, common ck k k k k