Nitrogen atom transfer

Abstract

Process and apparatus for addition of nitrogen to an organic molecule under electrochemical conditions. Processes include aziridination of olefins and imination of sulfoxides to form sulfoximines. Nitrene generation in the presence of a carboxylate is described

1 . An electrochemical process for the formation of a compound having formula I,  
       
         
           
           
               
               
           
         
       
       the process comprising step of: 
 contacting a compound having formula II and a compound having formula III,  
                     
 with each other in an electrolytic cell under conditions of electrolysis sufficient to form the compound of formula I, wherein: 
 (A) A is selected from the group consisting of C, N and O, and 
 (i) when A is a carbon atom, each of R 1 , R 2 , R 3 , and R 4  is hydrogen or an organic group;  
 (ii) when A is a nitrogen atom, each of R 1 , R 2 , and R 3 , is hydrogen or an organic group, and R 4  is an electron pair;  
 (iii) when A is an oxygen atom, each of R 1  and R 2  is hydrogen or an organic group, and each of R 3  and R 4  is an electron pair; and  
 (iv) R 5  is NR 6 R 7  and each of R 6  and R 7  is an organic group.  
 
 
 
     
     
         2 . The process of  claim 1 , wherein A is a carbon atom.  
     
     
         3 . The process of  claim 1 , wherein A is a nitrogen atom.  
     
     
         4 . The process of  claim 1 , wherein A is an oxygen atom.  
     
     
         5 . The process of  claim 2 ,  3 , or  4 , wherein the group of organic groups from which each of R 1 , R 2 , R 3 , and R 4  may be selected is the group consisting of alkyl, alkenyl, alkynyl, aryl, and substituted alkyl, alkenyl, alkynyl, aryl, wherein the substituents are selected from the group of alkyl, alkenyl, alkynyl, aryl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino, secondary amino, tertiary amino, amide, nitrile, nitro, epoxide, imine, aziridine, sulfone, phosphone, and silane.  
     
     
         6 . The process of  claim 5 , wherein said group from which each of R 1 , R 2 , R 3 , and R 4  may be selected is the group consisting of alkyl, alkenyl, alkynyl, aryl, and substituted alkyl, alkenyl, alkynyl, aryl, wherein the substituents are selected from the group of alkyl, aryl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino, secondary amino, tertiary amino, amide, nitro, epoxide, aziridine, sulfone, phosphone, and silane.  
     
     
         7 . The process of  claim 6 , wherein said group from which each of R 1 , R 2 , R 3 , and R 4  may be selected is the group consisting of alkyl and aryl, and substituted alkyl and aryl, wherein the substituents are selected from the group of alkyl, aryl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino, secondary amino, tertiary amino, amide, nitro, epoxide, aziridine, sulfone, phosphone, and silane, and preferably wherein each of R 1 , R 2 , R 3 , and R 4  includes up to 20 carbon atoms, more preferably up to 18 carbon atoms, more preferably up to 16 carbon atoms, more preferably up to 14 carbon atoms, or up to 12 carbon atoms, or up to 10 carbon atoms, or up to 8 carbon atoms, or up to 6 carbon atoms.  
     
     
         8 . The process of  claim 5 ,  6  or  7 , wherein the substituents are selected from the group of halide, ketone, alcohol and ester.  
     
     
         9 . The process of any of  claims 2  to  8  wherein, when A is a carbon atom, (i) if R 3  and P4 are each hydrogen, then each of R 1  and R 2  is not hydrogen, or the double bond shown in formula II is conjugated with another olefinic double bond, (ii) if a first carbon atom of the double bond shown in formula II is in an α-position with respect to a carbonyl group of R 1 , then the second carbon atom of the double bond is not in an α-position with respect to a carbonyl group of R 3 , and (iii) if a first carbon atom of the double bond shown in formula II is in an α-position with respect to a carbonyl group of R 2 , then the second carbon atom of the double bond is not in an α-position with respect to carbonyl group of R 4 .  
     
     
         10 . The process of any of  claims 1  to  9 , wherein compound II is selected from the group consisting of cyclohexene, cyclohex-2-enone, 2-methyl-pent-2-ene, 3-bromo-2-methyl-propene, trans-3-phenyl-acrylic acid methyl ester, cyclooctene, 2-methyl-buta-1,3-diene, trans-1,3-diphenylpropenone, trans-hex-4-en-3-one, trans-but-2-enedioic acid dimethyl ester, trans-3-phenyl-prop-2-en-1-ol, trans-4-phenyl-but-3-enoic acid methyl ester, 2-(acetoxy-phenyl-methyl)-acrylic acid methyl ester, 2-(hydroxy-phenyl-methyl)-acrylic acid methyl ester, trans-1,4-dichlorobutene, cis-1,4-dichlorobutene, 2-(phenyl p-toluenesulfonamidomethyl)acrylic acid methyl ester and any derivative thereof obtained by substitution of a hydrogen of a C—H bond with an alkyl, phenyl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino, secondary amino, tertiary amino, amide, nitro, epoxide, aziridine, sulfone, phosphone, and silane, wherein any said group can itself be substituted with a said group.  
     
     
         11 . The process of  claim 10 , wherein compound II is selected from the group consisting of cyclohexene, cyclohex-2-enone, 2-methyl-pent-2-ene, 3-bromo-2-methyl-propene, trans-3-phenyl-acrylic acid methyl ester, cyclooctene, 2-methyl-buta-1,3-diene, trans-1,3-diphenylpropenone, trans-hex-4-en-3-one, trans-but-2-enedioic acid dimethyl ester, trans-3-phenyl-prop-2-en-1-ol, trans-4-phenyl-but-3-enoic acid methyl ester, 2-(acetoxy-phenyl-methyl)-acrylic acid methyl ester, 2-(hydroxy-phenyl-methyl)-acrylic acid methyl ester, trans-1,4-dichlorobutene, cis-1,4-dichlorobutene, and 2-(phenyl p-toluenesulfonamidomethyl)acrylic acid methyl ester.  
     
     
         12 . The process of any of  claims 1  to  11 , wherein R 5  is selected from the group consisting of:  
       
         
           
           
               
               
           
         
       
       wherein each of R 8 , R 9 , R 10 , R 11 , R 12  and R 13  is an organic group.  
     
     
         13 . The process of  claim 12 , wherein each of R 8 , R 9 , R 10 , R 11 , R 12  and R 13  is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, and substituted alkyl, alkenyl, alkynyl, aryl, wherein the substituents are selected from the group of alkyl, alkenyl, alkynyl, aryl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino, secondary amino, tertiary amino, amide, nitrile, nitro, epoxide, imine, aziridine, sulfone, phosphone, and silane.  
     
     
         14 . The process of  claim 12 , wherein each of R 8 , R 9 , R 10 , R 11 , R 12  and R 13  is selected from the group consisting of alkyl, aryl, phenyl and substituted alkyl, aryl and phenyl, wherein the substituents are selected from the group of alkyl, aryl, phenyl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino, secondary amino, tertiary amino, amide, nitro, epoxide, aziridine, sulfone, phosphone, and silane.  
     
     
         15 . The process of  claim 14 , wherein each of R 8 , R 9 , R 10 , R 11 , R 12  and R 13  includes up to 20 carbon atoms, more preferably up to 18 carbon atoms, more preferably up to 16 carbon atoms, more preferably up to 14 carbon atoms, or up to 12 carbon atoms, or up to 10 carbon atoms, or up to 8 carbon atoms, or up to 6 carbon atoms.  
     
     
         16 . The process of  claim 13 ,  14 , or  15 , wherein each of the substituents of said substituted alkyl and aryl groups from which R 8 , R 9 , R 10 , R 11 , R 12  and R 13  can be selected is selected from the group consisting of halide, ketone, alcohol and ester.  
     
     
         17 . The process of any of  claims 1  to  16 , wherein the compound having formula III is N-aminophthalmide.  
     
     
         18 . The process of any of  claims 1  to  17 , wherein the compound having formula III has a lower oxidation potential than that of a compound having formula II.  
     
     
         19 . The process of any of  claims 1  to  17  wherein the compound having formula III is oxidized at a faster rate than a compound having formula II under said conditions of electrolysis.  
     
     
         20 . The process of any preceding claim, wherein the solvent of the electrolytic cell is a polar non-protic solvent, and particularly wherein the solvent is selected from the group consisting of dichloromethane, acetonitrile, N,N-dimethylformamide, tetrahydrofuran, nitromethane, chloroform, propylene carbonate, and mixtures thereof.  
     
     
         21 . An electrochemical process for the formation of a compound having formula IV,  
       
         
           
           
               
               
           
         
       
       the process comprising step of: 
 contacting a compound having formula V and a compound having formula III,  
                     
 with each other in an electrolytic cell under conditions of electrolysis sufficient to form the compound of formula IV, wherein: 
 (i) B is selected from the group consisting of P, S, Se and Te;  
 (ii) each of R 14  and R 15  is hydrogen or an organic group; and  
 (iii) R 5  is NR 6 R 7  and each of R 6  and R 7  is an organic group.  
 
 
     
     
         22 . The process of  claim 21 , wherein B is a phosphorus atom.  
     
     
         23 . The process of  claim 21 , wherein B is a sulfur atom.  
     
     
         24 . The process of  claim 21 , wherein B is an selenium atom.  
     
     
         25 . The process of  claim 21 , wherein B is an tellurium atom.  
     
     
         26 . The process of  claim 22 ,  23 ,  24  or  25  wherein each of R 14 , and R 15  may be selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, and substituted alkyl, alkenyl, alkynyl, aryl, wherein the substituents are selected from the group of alkyl, alkenyl, alkynyl, aryl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino, secondary amino, tertiary amino, amide, nitrile, nitro, epoxide, imine, aziridine, sulfone, phosphone, and silane.  
     
     
         27 . The process of  claim 26 , wherein each of R 14 , and R 15  maybe selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, and substituted alkyl, alkenyl, alkynyl, aryl, wherein the substituents are selected from the group of alkyl, aryl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino, secondary amino, tertiary amino, amide, nitro, epoxide, aziridine, sulfone, phosphone, and silane and preferably wherein each of R 14  and R 15  includes up to 20 carbon atoms, more preferably up to 18 carbon atoms, more preferably up to 16 carbon atoms, more preferably up to 14 carbon atoms, or up to 12 carbon atoms, or up to 10 carbon atoms, or up to 8 carbon atoms, or up to 6 carbon atoms.  
     
     
         28 . The process of  claim 27 , wherein each of R 14 , and R 15  may be selected from the group consisting of alkyl and aryl, and substituted alkyl and aryl, wherein the substituents are selected from the group of alkyl, aryl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino, secondary amino, tertiary amino, amide, nitro, epoxide, aziridine, sulfone, phosphone, and silane.  
     
     
         29 . The process of  claim 26 ,  27  or  28 , wherein the substituents are selected from the group of halide, ketone, alcohol and ester.  
     
     
         30 . The process of any of  claims 21  to  29 , wherein compound V is selected from the group consisting of compounds VIII to XV,  
       
         
           
           
               
               
           
         
       
       and any derivative of any of compounds VIII to XV obtained by substitution of a hydrogen of a C—H bond with an alkyl, phenyl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino, secondary amino, tertiary amino, amide, nitro, epoxide, aziridine, sulfone, phosphone, and silane, wherein any said group can itself include such a substituent.  
     
     
         31 . The process of  claim 30 , wherein compound V is selected from the group consisting of compounds VIII to XV.  
     
     
         32 . The process of any of  claims 21  to  31 , wherein R 5  is selected from the group consisting of:  
       
         
           
           
               
               
           
         
       
       wherein each of R 8 , R 9 , R 10 , R 11 , R 12  and R 13  is an organic group.  
     
     
         33 . The process of  claim 32 , wherein each of R 8 , R 9 , R 10 , R 1 , R 12  and R 13  is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, and substituted alkyl, alkenyl, alkynyl, aryl, wherein the substituents are selected from the group of alkyl, alkenyl, alkynyl, aryl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino, secondary amino, tertiary amino, amide, nitrile, nitro, epoxide, imine, aziridine, sulfone, phosphone, and silane.  
     
     
         34 . The process of  claim 32 , wherein each of R 8 , R 9 , R 10 , R 11 , R 12  and R 13  is selected from the group consisting of alkyl, aryl, phenyl and substituted alkyl, aryl and phenyl, wherein the substituents are selected from the group of alkyl, aryl, phenyl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino, secondary amino, tertiary amino, amide, nitro, epoxide, aziridine, sulfone, phosphone, and silane.  
     
     
         35 . The process of  claim 34 , wherein each of R 8 , R 9 , R 10 , R 11 , R 12  and R 13  includes up to includes up to 20 carbon atoms, more preferably up to 18 carbon atoms, more preferably up to 16 carbon atoms, more preferably up to 14 carbon atoms, or up to 12 carbon atoms, or up to 10 carbon atoms, or up to 8 carbon atoms, or up to 6 carbon atoms.  
     
     
         36 . The process of  claim 33 ,  34 , or  35 , wherein each of the substituents of said substituted alkyl and aryl groups from which R 8 , R 9 , R 10 , R 1 , R 12  and R 13  can be selected is selected from the group consisting of halide, ketone, alcohol and ester.  
     
     
         37 . The process of any of  claims 21  to  36 , wherein the compound having formula III is N-aminophthalimide.  
     
     
         38 . The process of any of  claims 21  to  37 , wherein the compound having formula III has a lower oxidation potential than that of a compound having formula II.  
     
     
         39 . The process of any of  claims 21  to  37  wherein the compound having formula III is oxidized at a faster rate than a compound having formula II under said conditions, of electrolysis.  
     
     
         40 . The process of any of  claims 21  to  39 , wherein the solvent of the electrolytic cell is a polar non-protic solvent, and particularly wherein the solvent is selected from the group consisting of dichloromethane, acetonitrile, N,N-dimethylformamide, tetrahydrofuran, nitromethane, chloroform, propylene carbonate, and mixtures thereof.  
     
     
         41 . An electrochemical process for the formation of a compound having formula VI,  
       
         
           
           
               
               
           
         
       
       the process comprising step of: 
 contacting a compound having formula VII and a compound having formula III,  
                     
 with each other in an electrolytic cell under conditions of electrolysis sufficient to form the compound of formula VI, wherein: 
 (i) when D is a carbon atom, each of R 16  and R 17  is hydrogen or an organic group; and  
 (ii) when D is a nitrogen atom, R 16  is hydrogen or an organic group, and R 17  is an electron pair.  
 
 
     
     
         42 . The process of  claim 41 , wherein D is a carbon atom.  
     
     
         43 . The process of  claim 41 , wherein D is a nitrogen atom.  
     
     
         44 . The process of  claim 42  or  45  wherein each of R 16 , and R 17  may be selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, and substituted alkyl, alkenyl, alkynyl, aryl, wherein the substituents are selected from the group of alkyl, alkenyl, alkynyl, aryl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino, secondary amino, tertiary amino, amide, nitrile, nitro, epoxide, imine, aziridine, sulfone, phosphone, and silane, and preferably wherein each of R 16  and R 17  includes up to 20 carbon atoms, more preferably up to 18 carbon atoms, more preferably up to 16 carbon atoms, more preferably up to 14 carbon atoms, or up to 12 carbon atoms, or up to 10 carbon atoms, or up to 8 carbon atoms, or up to 6 carbon atoms.  
     
     
         45 . The process of  claim 44 , wherein each of R 16 , and R 17  maybe selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, and substituted alkyl, alkenyl, alkynyl, aryl, wherein the substituents are selected from the group of alkyl, aryl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino, secondary amino, tertiary amino, amide, nitro, epoxide, aziridine, sulfone, phosphone, and silane.  
     
     
         46 . The process of  claim 45 , wherein each of R 16 , and R 17  may be selected from the group consisting of alkyl and aryl, and substituted alkyl and aryl, wherein the substituents are selected from the group of alkyl, aryl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino, secondary amino, tertiary amino, amide, nitro, epoxide, aziridine, sulfone, phosphone, and silane.  
     
     
         47 . The process of  claim 44 ,  45  or  46 , wherein the substituents are selected from the group of halide, ketone, alcohol and ester.  
     
     
         48 . The process of any of  claims 41  to  47 , wherein R 5  is selected from the group consisting of:  
       
         
           
           
               
               
           
         
       
       wherein each of R 8 , R 9 , R 10 , R 11 , R 12  and R 13  is an organic group.  
     
     
         49 . The process of  claim 48 , wherein each of R 8 , R 9 , R 10 , R 11 , R 12  and R 13  is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, and substituted alkyl, alkenyl, alkynyl, aryl, wherein the substituents are selected from the group of alkyl, alkenyl, alkynyl, aryl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino, secondary amino, tertiary amino, amide, nitrile, nitro, epoxide, imine, aziridine, sulfone, phosphone, and silane.  
     
     
         50 . The process of  claim 48 , wherein each of R 8 , R 9 , R 10 , R 11 , R 12  and R 13  is selected from the group consisting of alkyl, aryl, phenyl and substituted alkyl, aryl and phenyl, wherein the substituents are selected from the group of alkyl, aryl, phenyl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino, secondary amino, tertiary amino, amide, nitro, epoxide, aziridine, sulfone, phosphone, and silane.  
     
     
         51 . The process of  claim 50 , wherein each of R 8 , R 9 , R 10 , R 11 , R 12  and R 13  includes up to includes up to 20 carbon atoms, more preferably up to 18 carbon atoms, more preferably up to 16 carbon atoms, more preferably up to 14 carbon atoms, or up to 12 carbon atoms, or up to 10 carbon atoms, or up to 8 carbon atoms, or up to 6 carbon atoms.  
     
     
         52 . The process of  claim 49 ,  50 , or  51 , wherein each of the substituents of said substituted alkyl and aryl groups from which R 8 , R 9 , R 10 , R 11 , R 12  and R 13  can be selected is selected from the group consisting of halide, ketone, alcohol and ester.  
     
     
         53 . The process of any of  claims 41  to  52 , wherein the compound having formula II is N-aminophthalimide.  
     
     
         54 . The process of any of  claims 41  to  53 , wherein the compound having formula III has a lower oxidation potential than that of a compound having formula II.  
     
     
         55 . The process of any of  claims 41  to  53  wherein the compound having formula III is oxidized at a faster rate than a compound having formula II under said conditions of electrolysis.  
     
     
         56 . The process of any of  claims 41  to  55 , wherein the solvent of the electrolytic cell is a polar non-protic solvent, and particularly wherein the solven is selected from the group consisting of dichloromethane, acetonitrile, N,N-dimethylformamide, tetrahydrofuran, nitromethane, chloroform, propylene carbonate, and mixtures thereof.  
     
     
         57 . An electrochemical process of any preceding claim wherein said contacting step includes contacting said compounds with each other in an anode compartment of said electrolytic cell in an anolyte which comprises a carboxylate ion.  
     
     
         58 . The process of  claim 57 , wherein the anolyte solution is substantially free of a metal catalyst.  
     
     
         59 . The process of  claim 58 , wherein said metal is selected from the group of lead cadmium, cerium, cobalt, chromium, copper, ion, mercury, iridium, manganese, molybdenum, nickel, osmium, palladium, rhenium, rhodium, ruthenium, antimony, thallium, tin and vanadium.  
     
     
         60 . The process of any of  claims 57  to  59 , wherein said anode a platinum electrode.  
     
     
         61 . The process of any of  claims 57  to  60 , wherein an acid form of said carboxylate has a first pK a , and said anolyte solution further comprises an acid having a second pK a  wherein said second pK a  exceeds the first pK a .  
     
     
         62 . The process of  claim 61  wherein the carboxylate and the acid having the second pK a  are solubilized in the solution and the carboxylate is provided in solution in a stoichiometric amount equal to at least half that of the hydrazine derivative.  
     
     
         63 . The process of  claim 62  wherein the acid form of said carboxylate has the formula RCO 2 H wherein R is an organic group.  
     
     
         64 . The process of  claim 62  wherein the acid for of said carboxylate has the formula RCO 2 H wherein R is an alkyl group or a haloalkyl group.  
     
     
         65 . The process of any of  claims 61  to  64  wherein the first pK a  is in the range of about −2 to about +7.  
     
     
         66 . The process of  claim 65  wherein the first pK a  is in the range of about −1 to about +6.  
     
     
         67 . The process of  claim 66  wherein the first pK a  is in the range of about 0 to about +5.  
     
     
         68 . The process of  claim 67  wherein the first pK a  is about 0.3.  
     
     
         69 . The process of  claim 67  wherein the first pK a  is about 2.8.  
     
     
         70 . The process of  claim 67  wherein the first pK a  is about 4.8.  
     
     
         71 . The process of any of  claims 57  to  65 , wherein said carboxylate is selected from the group acetate, trifluoroacetate, and monochloroacetate.  
     
     
         72 . The process of any of  claims 61  to  71 , wherein said acid is an ammonium acid and said second pK a  exceeds the first pK a  by at least 2.  
     
     
         73 . The process of  claim 72 , wherein said ammonium acid has the formula R 1 R 2 R 3 NH +  wherein each of R 1 , R 2  and R 3  is an organic group or hydrogen.  
     
     
         74 . The process of  claim 73 , wherein each of R 1 , R 2  and R 3  of the ammonium acid is an alkyl group or hydrogen.  
     
     
         75 . The process of any of  claims 61  to  63 , wherein said acid having the second pK a  is triethylammonium.  
     
     
         76 . The process of any of  claims 57  to  75 , wherein the carboxylate is provided in solution in a stoichiometric amount about equal to that of the hydrazine derivative.  
     
     
         77 . The process of any of  claims 57  to  76 , wherein the anolyte solution further comprises a counterion to the carboxylate, the counterion having the formula R 1 R 2 R 3  R 4  N +  wherein each of R 1 , R 2 , R 3 , and R 4  is an organic group.  
     
     
         78 . The process of  claim 77 , wherein each said organic group of the counterion is an alkyl group or a haloalkyl group.  
     
     
         79 . The process of  claim 78 , wherein each said organic group of the counterion is an alkyl group.  
     
     
         80 . The process of  claim 79 , wherein each said organic group of the counterion is an alkyl group selected from the group of methyl, ethyl, propyl, butyl and pentyl.  
     
     
         81 . The process of any preceding claim, wherein said contacting step is carried out in an anodic half cell divided from and operatively linked to a cathodic half cell.  
     
     
         82 . The process of  claim 81 , wherein said half cells are linked by an ion permselective diaphragm.  
     
     
         83 . The process of  claim 82  wherein said diaphragm comprises a synthetic polymer having anions affixed thereto.  
     
     
         84 . The process apparatus of  claim 83 , wherein said anions include perfluorosulfonate groups.  
     
     
         85 . The process of  claim 84 , wherein said diaphragm comprises a Nafion membrane.  
     
     
         86 . The process of any preceding claim, wherein compound II, V, or VII, as the case may be, has a more positive potential than the voltage at which the contacting step is conducted.  
     
     
         87 . The process of  claim 86  wherein compound III has first and second peak potentials, each of which potentials is between about 0 and 3 volts against Ag/AgCl, more preferably between about 1 and 2 volts.  
     
     
         88 . The process of any preceding claim wherein the mole ratio of the compound having formula Im to the compound having formula II, V, or VU, as the case may be, is from about 1:1 to about 1000:1; more preferably between 500:1 and 1:1; more preferably between about 100: and 1:1; more preferably between about 25:1 and 1:1; more preferably between about 10:1 and 1:1; more preferably between about 5:1 and 1:1, more preferably between about 2:1 and 1:1.  
     
     
         89 . The process of any preceding claim wherein the electric potential applied during the contacting step is applied for a period between about 1 minute and 10 hours.  
     
     
         90 . In a process of addition of a nitrogen across a multiple bond of an organic molecule wherein a first atom of the multiple bond is a carbon atom, and the second atom is selected from the group of carbon, oxygen and nitrogen, the improvement comprising electrochemically generating the nitrogen for the addition from a primary hydrazine derivative in the presence of a carboxylate anion.  
     
     
         91 . The process of  claim 90 , wherein the nitrogen is generated from a compound having the structure indicated by formula III, as defined in any of claims  1  and  12  to  17 .  
     
     
         92 . The process of  claim 91 , wherein the organic molecule has the structure indicated by formula I as defined in any of  claims 1  to  11 , or formula VII as defined in any of  claims 41  to  47 .  
     
     
         93 . In a process of addition of a nitrogen to a heteroatom of an organic molecule wherein the heteroatom forms a double bond with an oxygen atom and is a P, S, Se or Te atom, the improvement comprising electrochemically generating the nitrogen for the addition from a primary hydrazine derivative in the presence of a carboxylate anion.  
     
     
         94 . The process of  claim 93 , wherein the nitrogen is generated from a compound having the structure indicated by formula HI, as defined in any of claims  1  and  12  to  17 .  
     
     
         95 . The process of  claim 94 , wherein the organic molecule has the structure indicated by formula V as defined in any of  claims 21  to  29 .  
     
     
         96 . A product when obtained by a process defined by any preceding claim.  
     
     
         97 . A process for electrochemically generating a nitrene, the process comprising the step of: 
 exposing a hydrazine derivative contained in an anolyte solution of an electroytic cell to the anode of the cell in the presence of a carboxylate ion, wherein one of the nitrogens of the hydrazine group is a primary amino group.    
     
     
         98 . The process of  claim 97 , wherein the anolyte solution is substantially free of a metal catalyst.  
     
     
         99 . The process of  claim 98 , wherein said metal is selected from the group of lead cadmium, cerium, cobalt, chromium, copper, ion, mercury, iridium, manganese, molybdenum, nickel, osmium, palladium, rhenium, rhodium, ruthenium, antimony, thallium, tin and vanadium.  
     
     
         100 . The process of any of  claims 97  to  99 , wherein said anode a platinum electrode.  
     
     
         101 . The process of any of  claims 97  to  100 , wherein an acid form of said carboxylate has a first pK a , and said anolyte solution further comprises an acid having a second pK a  wherein said second pK a  exceeds the first pK a .  
     
     
         102 . The process of  claim 101  wherein the carboxylate and the acid having the second pK a  are solubilized in the solution and the carboxylate is provided in solution in a stoichiometric amount equal to at least half that of the hydrazine derivative.  
     
     
         103 . The process of  claim 102  wherein the acid form of said carboxylate has the formula RCO 2 H wherein R is an organic group.  
     
     
         104 . The process of  claim 102  wherein the acid for of said carboxylate has the formula RCO 2 H wherein R is an alkyl group or a haloalkyl group.  
     
     
         105 . The process of any of  claims 101  to  104  wherein the first pK a  is in the range of about −2 to about +7.  
     
     
         106 . The process of  claim 105  wherein the first pK a  is in the range of about −1 to about +6.  
     
     
         107 . The process of  claim 106  wherein the first pK a  is in the range of about 0 to about +5.  
     
     
         108 . The process of  claim 107  wherein the first pK a  is about 0.3.  
     
     
         109 . The process of  claim 107  wherein the first pK a  is about 2.8.  
     
     
         110 . The process of  claim 107  wherein the first pK a  is about 4.8.  
     
     
         111 . The process of any of  claims 97  to  105 , wherein said carboxylate is selected from the group acetate, trifluoroacetate, and monochloroacetate.  
     
     
         112 . The process of any of  claims 101  to  111 , wherein said acid is an ammonium acid and said second pK a  exceeds the first pK a  by at least 2.  
     
     
         113 . The process of  claim 112 , wherein said ammonium acid has the formula R 1 R 2 R 3 NH +  wherein each of R 1 , R 2  and R 3  is an organic group or hydrogen.  
     
     
         114 . The process of  claim 113 , wherein each of R 1 , R 2  and R 3  of the ammonium acid is an alkyl group or hydrogen.  
     
     
         115 . The process of any of  claims 101  to  103 , wherein said acid having the second pK a  is triethylammonium.  
     
     
         116 . The process of any of  claims 97  to  115 , wherein the carboxylate is provided in solution in a stoichiometric amount about equal to that of the hydrazine derivative.  
     
     
         117 . The process of any of  claims 97  to  116 , wherein the anolyte solution further comprises a counterion to the carboxylate, the counterion having the formula R 1 R 2 R 3  R 4  N +  wherein each of R 1 , R 2 , R 3 , and R 4  is an organic group.  
     
     
         118 . The process of  claim 117 , wherein each said organic group of the counterion is an alkyl group or a haloalkyl group.  
     
     
         119 . The process of  claim 118 , wherein each said organic group of the counterion is an alkyl group.  
     
     
         120 . The process of  claim 119 , wherein each said organic group of the counterion is an alkyl group selected from the group of methyl, ethyl, propyl, butyl and pentyl.  
     
     
         121 . The process of any of  claims 97  to  120  wherein said hydrazine derivative comprises a molecule having the structure indicated as formula Im as defined in any of claims  1  and  12  to  17 .  
     
     
         122 . The process of any of  claims 97  to  121 , wherein the anolyte solution comprises a solvent as defined in  claim 20 .  
     
     
         123 . An apparatus for electrochemical generation of a nitrene, the apparatus comprising: 
 an anodic half cell operatively linked to a cathodic half cell; and    an anolyte solution comprising a carboxylate anion and a primary hydrazine derivative.    
     
     
         124 . The apparatus of  claim 123 , wherein said half cells are linked by an ion permselective diaphragm.  
     
     
         125 . The apparatus of  claim 124 , wherein said diaphragm comprises a synthetic polymer having anions affixed thereto.  
     
     
         126 . The apparatus of  claim 125 , wherein said anions include perfluorosulfonate groups.  
     
     
         127 . The apparatus of  claim 126 , wherein said diaphragm comprises a Nafion membrane.  
     
     
         128 . The apparatus of any of  claims 123  to  127 , wherein the hydrazine has a formula im as defined in any of claims  1  and  5  to  17 .  
     
     
         129 . The apparatus of any of  claims 123  to  128 , wherein the anolyte solution is substantially free of a metal catalyst.  
     
     
         130 . The apparatus of  claim 129 , wherein said metal is selected from the group of lead cadmium, cerium, cobalt, chromium, copper, ion, mercury, iridium, manganese, molybdenum, nickel, osmium, palladium, rhenium, rhodium, ruthenium, antimony, thallium, tin and vanadium.  
     
     
         131 . The apparatus of any of  claims 123  to  130 , wherein said anode a platinum electrode.  
     
     
         132 . The apparatus of any of  claims 123  to  131 , wherein an acid form of said carboxylate has a first pK a , and said anolyte solution further comprises an acid having a second pK a  wherein said second pK a  exceeds the first pK a .  
     
     
         133 . The apparatus of  claim 132  wherein the carboxylate and the acid having the second pK a  are solubilized in the solution and the carboxylate is provided in solution in a stoichiometric amount equal to at least half that of the hydrazine derivative.  
     
     
         134 . The apparatus of  claim 133  wherein the acid form of said carboxylate has the formula RCO 2 H wherein R is an organic group.  
     
     
         135 . The apparatus of  claim 133  wherein the acid for of said carboxylate has the formula RCO 2 H wherein R is an alkyl group or a haloalkyl group.  
     
     
         136 . The apparatus of any of  claims 132  to  135  wherein the first pK a  is in the range of about −2 to about +7.  
     
     
         137 . The apparatus of  claim 136  wherein the first pK a  is in the range of about −1 to about +6.  
     
     
         138 . The apparatus of  claim 137  wherein the first pK a  is in the range of about 0 to about +5.  
     
     
         139 . The apparatus of  claim 138  wherein the first pK a  is about 0.3.  
     
     
         140 . The apparatus of  claim 138  wherein the first pK a  is about 2.8.  
     
     
         141 . The apparatus of  claim 138  wherein the first pK a  is about 4.8.  
     
     
         142 . The apparatus of any of  claims 123  to  136 , wherein said carboxylate is selected from the group acetate, trifluoroacetate, and monochloroacetate.  
     
     
         143 . The apparatus of any of  claims 132  to  142 , wherein said acid is an ammonium acid and said second pK a  exceeds the first pK a  by at least 2.  
     
     
         144 . The apparatus of  claim 143 , wherein said ammonium acid has the formula R 1 R 2 R 3 NH +  wherein each of R 1 , R 2  and R 3  is an organic group or hydrogen.  
     
     
         145 . The apparatus of  claim 144 , wherein each of R 1 , R 2  and R 3  of the ammonium acid is an alkyl group or hydrogen.  
     
     
         146 . The apparatus of any of  claims 132  to  134 , wherein said acid having the second pK a  is triethylammonium.  
     
     
         147 . The apparatus of any of  claims 123  to  146 , wherein the carboxylate is provided in solution in a stoichiometric amount about equal to that of the hydrazine derivative.  
     
     
         148 . The apparatus of any of  claims 123  to  147 , wherein the anolyte solution further comprises a counterion to the carboxylate, the counterion having the formula R 1 R 2 R 3  R 4  N +  wherein each of R 1 , R 2 , R 3 , and R is an organic group.  
     
     
         149 . The apparatus of  claim 148 , wherein each said organic group of the counterion is an alkyl group or a haloalkyl group.  
     
     
         150 . The apparatus of  claim 149 , wherein each said organic group of the counterion is an alkyl group.  
     
     
         151 . The apparatus of  claim 149 , wherein each said organic group of the counterion is an alkyl group selected from the group of methyl, ethyl, propyl, butyl and pentyl.  
     
     
         152 . A process for screening an olefin for electrochemical aziridination of an olefin with a hydrazine derivative, the process comprising the steps of: 
 providing the olefin;    determining the redox potential of the olefin at a predetermined voltage at which the aziridine derivative is oxidized, wherein a said olefin determined to have a less positive potential than the predetermined voltage is eliminated as a candidate for electrochemical aziridination by said hydrazine derivative.    
     
     
         153 . A process for screening an olefin for electrochemical aziridination of an olefin with a hydrazine derivative, the process comprising the steps of: 
 providing the olefin;    determining the redox potential of the olefin at a predetermined voltage at which the aziridine derivative is oxidized, wherein a said olefin determined to have a more positive potential than the predetermined voltage is selected as a candidate for electrochemical aziridination by said hydrazine derivative.    
     
     
         154 . The process of  claim 152  or  153 , wherein said hydrazine derivative has first and second peak potentials, each of which potentials is between about 0 and 3 volts against Ag/AgCl.  
     
     
         155 . The process of  claim 154 , wherein said hydrazine derivative has first and second peak potentials, each of which potentials is between about 0 and 3 volts against Ag/AgCl.