Synthesis methods, complexes and delivery methods for the safe and convenient storage, transport and application of compounds for inhibiting the ethylene response in plants

Abstract

The present invention generally relates to the regulation of plant physiology, in particular to methods for inhibiting the ethylene response in plants or plant products, and has three embodiments. The first embodiment relates to methods of minimizing impurities capable of reversibly binding to plant ethylene receptor sites during the synthesis of cyclopropene and its derivatives such as methylcyclopropene, thereby avoiding the negative effects these impurities have on plants treated with cyclopropene and its derivatives. The second embodiment relates to complexes formed from molecular encapsulation agents such as cyclodextrin, and cyclopropene and its derivatives such as methylcyclopropene, in addition to cyclopentadiene and diazocyclopentadiene and their derivatives, thereby providing a convenient means for storing and transporting these compounds capable of inhibiting the ethylene response in plants, which are reactive gases and highly unstable because of oxidation and other potential reactions. The third embodiment relates to convenient methods of delivering to plants these compounds capable of inhibiting the ethylene response in the plants in order to extend their shelf life.

What is claimed is:  
     
         1 . A method of minimizing impurities capable of reversibly binding to plant ethylene receptor sites comprising the steps of reacting, in an inert environment, a metal amide salt and a halogenated carbene, optionally in the presence of a non-reactive solvent, to form a compound having the following structure  
       
         
           
           
               
               
           
         
       
       wherein n is a number from 1 to 10 and R is selected from the group consisting of hydrogen, saturated or unsaturated C1 to C10 alkyl, hydroxy, halogen, C1 to C10 alkoxy, amino and carboxy.  
     
     
         2 . The method of  claim 1  wherein the metal amide salt is selected from the group consisting of sodium amide, lithium arnide, potassium amide, lithium diisopropylamide and sodium diisopropylamide.  
     
     
         3 . The method of  claim 1  wherein the halogenated carbene is selected from the group consisting of 3-chloro-3-methyl-2-methylpropene, 3-bromo-3-methyl-2-methylpropene, 3-chloro-2-methylpropene and 3-bromo-2-methylpropene.  
     
     
         4 . The method of  claim 2  wherein the halogenated carbene is selected from the group consisting of 3-chloro-3-methyl-2-methylpropene, 3-bromo-3-methyl-2-methylpropene, 3-chloro-2-methylpropene and 3-bromo-2-methylpropene.  
     
     
         5 . A method of minimizing impurities capable of reversibly binding to plant ethylene receptor sites comprising the steps of reacting, in an inert environment, a metal amide salt and a halogenated methyl propene, optionally in the presence of a nonreactive solvent, to form methylcyclopropene.  
     
     
         6 . The method of  claim 5  wherein the metal amide salt is selected from the group consisting of sodium amide, lithium amide, potassium amide, lithium diiscpropylamide and sodium diisopropylamide.  
     
     
         7 . The method of  claim 5  wherein the halogenated methyl propene is 3-chloro-2-methylpropene.  
     
     
         8 . The method of  claim 6  wherein the halogenated methyl propene is 3-chloro-2-methylpropene.  
     
     
         9 . A complex formed from a molecular encapsulation agent and a compound having the following structure  
       
         
           
           
               
               
           
         
       
       wherein n is a number from 1 to 10 and R is selected from the group consisting of hydrogen, saturated or unsaturated C1 to C10 alkyl, hydroxy, halogen, C1 to C10 alkoxy, amino and carboxy.  
     
     
         10 . The complex of  claim 9  wherein the molecular encapsulation agent is selected from the group consisting of a cyclodextrin, a crown ether, a polyoxyalkylene, a prophorine, a polysiloxane, a phophazene and a zeolite.  
     
     
         11 . The complex of  claim 9  wherein the molecular encapsulation agent is cyclodextrin.  
     
     
         12 . The complex of  claim 11  wherein the cyclodextrin is alpha-cyclodextrin.  
     
     
         13 . A complex formed from a molecular encapsulation agent and a compound having the following structure  
       
         
           
           
               
               
           
         
       
       wherein n is a number from 1 to 10 and R is selected from the group consisting of hydrogen, saturated or unsaturated C1 to C10 alkyl, hydroxy, halogen, C1 to C10 alkoxy, amino and carboxy.  
     
     
         14 . The complex of  claim 13  wherein the molecular encapsulation agent is selected from the group consisting of a cyclodextrin, a crown ether, a polyoxyalkylene, a prophorine, a polysiloxane, a phophazene and a zeolite.  
     
     
         15 . The complex of  claim 13  wherein the molecular encapsulation agent is cyclodextrin.  
     
     
         16 . The complex of  claim 15  wherein the cyclodextrin is alpha-cyclodextrin.  
     
     
         17 . A method of delivering a compound to a plant to inhibit an ethylene response in the plant, the method comprising the step of contacting a complex formed from a molecular encapsulation agent and a compound having the following structure  
       
         
           
           
               
               
           
         
       
       wherein n is a number from 1 to 10 and R is selected from the group consisting of hydrogen, saturated or unsaturated C1 to C10 alkyl, hydroxy, halogen, C1 to C10 alkoxy, amino and carboxy, with a solvent capable of dissolving the molecular encapsulation agent, and thereby liberating the compound from the molecular encapsulation agent so that it can contact the plant.  
     
     
         18 . The method of  claim 17  wherein the molecular encapsulation agent is selected from the group consisting of a cyclodextrin, a crown ether, a polyoxyalkylene, a prophorine, a polysiloxane, a phophazene and a zeolite.  
     
     
         19 . The method of  claim 17  wherein the molecular encapsulation agent is cyclodextrin.  
     
     
         20 . The method of  claim 19  wherein the cyclodextrin is alpha-cyclodextrin.  
     
     
         21 . The method of  claim 17  wherein the solvent comprises water.  
     
     
         22 . The method of  claim 21  wherein the water additionally comprises an acidic or alkaline agent.  
     
     
         23 . The method of  claim 17  further comprising bubbling a gas through the solvent while it is in contact with the complex.  
     
     
         24 . The method of  claim 17  further comprising applying heat to the solvent either before it contacts the complex or during that contact.  
     
     
         25 . A method of delivering a compound to a plant to inhibit an ethylene response in the plant, the method comprising the step of contacting a complex formed from a molecular encapsulation agent and a compound having the following structure  
       
         
           
           
               
               
           
         
       
       wherein n is a number from 1 to 10 and R is selected from the group consisting of hydrogen, saturated or unsaturated C1 to C10 alkyl, hydroxy, halogen, C1 to C10 alkoxy, amino and carboxy, with a solvent capable of dissolving the molecular encapsulation agent, and thereby liberating the compound from the molecular encapsulation agent so that it can contact the plant.  
     
     
         26 . The method of  claim 25  wherein the molecular encapsulation agent is selected from the group consisting of a cyclodextrin, a crown ether, a polyoxyalkylene, a prophorine, a polysiloxane, a phophazene and a zeolite.  
     
     
         27 . The method of  claim 25  wherein the molecular encapsulation agent is cyclodextrin.  
     
     
         28 . The method of  claim 27  wherein the cyclodextrin is alpha-cyclodextrin.  
     
     
         29 . The method of  claim 25  wherein the solvent comprises water.  
     
     
         30 . The method of  claim 29  wherein the water additionally comprises an acidic or alkaline agent.  
     
     
         31 . The method of  claim 25  further comprising bubbling a gas through the solvent while it is in contact with the complex.  
     
     
         32 . The method of  claim 25  further comprising applying heat to the solvent either before it contacts the complex or during the contact.