Stable Ethylene Inhibiting Compounds and Methods for Their Preparation

1 . A method of using, as a plant ethylene response antagonist, any one of a compound comprising a structure selected from the group consisting of:

wherein:

a) each R1, R2, R3, and R4 is independently a group of the formula:

-(L) n -Z

i) p is an integer from 3 to 10;

q is an integer from 4 to 11;

n is an integer from 0 to 12;

ii) each L is independently selected from a member of the group D, E, or J

D is of the formula:

E is of the formula:

 and

J is of the formula:

A) each X and Y is independently a group of the formula:

-(L) m -Z;

 and

B) m is an integer from 0 to 8; and

C) no more than two E groups are adjacent to each other and no J groups are adjacent to each other;

iii) each Z is independently selected from:

A) hydrogen, halo, cyano, nitro, nitroso, azido, chlorate, bromate, iodate, isocyanato, isocyanido, isothiocyanato, pentafluorothio, or

B) a group G, wherein G is an unsubstituted or substituted; unsaturated, partially saturated, or saturated; monocyclic, bicyclic, tricyclic, or fused; carbocyclic or heterocyclic ring system wherein;

1) when the ring system contains a 3 or 4 membered heterocyclic ring, the heterocyclic ring contains 1 heteroatom;

2) when the ring system contains a 5, or more, membered heterocyclic ring or a polycyclic heterocyclic ring, the heterocyclic or polycyclic heterocyclic ring contains from 1 to 4 heteroatoms;

3) each heteroatom is independently selected from N, O, and S;

4) the number of substituents is from 0 to 5 and each substituent is independently selected from X;

b) W1 and W2 are selected from F, Cl, Br, I, alkoxy, acyloxy, alkoxycarbonyloxy, aminocarbonyloxy, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkylsulfonyloxy, and arylsulfonyloxy;

c) provided that at least one of W1 and W2 is Br or I; and

d) the total number of non-hydrogen atoms is 50 or less;

by contacting the plant with the compound.

2 . The method of claim 1 wherein each of W1 and W2 are I.

3 . The method of claim 1 wherein the compound is 1,2-diiodo-1-methylcyclopropane.

4 . A method to inhibit the ethylene response in plants comprising the steps of:

A) contacting a compound of structure V, VI, VII, or VIII:

wherein:

a) each R1, R2, R3, and R4 is independently a group of the formula:

-(L) n -Z

i) p is an integer from 3 to 10;

q is an integer from 4 to 11;

n is an integer from 0 to 12;

ii) each L is independently selected from a member of the group D, E, or J

D is of the formula:

E is of the formula:

 and

J is of the formula:

 A) each X and Y is independently a group of the formula:

-(L) m -Z;

 and

 B) m is an integer from 0 to 8; and

 C) no more than two E groups are adjacent to each other and no J groups are adjacent to each other;

iii) each Z is independently selected from:

A) hydrogen, halo, cyano, nitro, nitroso, azido, chlorate, bromate, iodate, isocyanato, isocyanido, isothiocyanato, pentafluorothio, or

B) a group G, wherein G is an unsubstituted or substituted; unsaturated, partially saturated, or saturated; monocyclic, bicyclic, tricyclic, or fused; carbocyclic or heterocyclic ring system wherein;

 1) when the ring system contains a 3 or 4 membered heterocyclic ring, the heterocyclic ring contains 1 heteroatom;

 2) when the ring system contains a 5, or more, membered heterocyclic ring or a polycyclic heterocyclic ring, the heterocyclic or polycyclic heterocyclic ring contains from 1 to 4 heteroatoms;

 3) each heteroatom is independently selected from N, O, and S;

 4) the number of substituents is from 0 to 5 and each substituent is independently selected from X;

b) W1 and W2 are selected from F, Cl, Br, I, alkoxy, acyloxy, alkoxycarbonyloxy, aminocarbonyloxy, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkylsulfonyloxy, and arylsulfonyloxy;

c) provided that at least one of W1 and W2 is Br or I; and

d) the total number of non-hydrogen atoms is 50 or less;

with a reducing or nucleophilic agent to convert the compound of structure V, VI, VII, or VIII into its respective analogous compound of structure I, II, III, or IV:

and

B) contacting the plant with the compound of structure I, II, III, or IV.

5 . The method of claim 4 wherein the reducing agent is selected from the group consisting of metals, organometallic reagents and low valent metal ions.

6 . The method of claim 4 wherein the nucleophilic agent is selected from the group consisting of mercaptans, selenides, phosphines, phosphites, Na2S, Na2Te, Na2S2O4, diethylphosphite sodium salt, KSCN, NaSeCN, thiourea, diphenyltelurium and NaI.

7 . The method of claim 4 wherein each of W1 and W2 are I.

8 . The method of claim 4 wherein the compound of structure V, VI, VII, or VIII is 1,2-diiodo-1-methylcyclopropane.