Methods of producing sulfilimine compounds

Patent metadata

Field	Value
Publication number	US-9227936-B2
Application number	US-201313768543-A
Country	US
Kind code	B2
Filing date	Feb 15, 2013
Priority date	Feb 16, 2012
Publication date	Jan 5, 2016
Grant date	Jan 5, 2016

Abstract

Methods of producing a sulfilimine compound, such as N-cyano-S-methyl-S-[1-(6-trifluoromethyl-3-pyridinyl)ethyl]sulfilimine or other substituted sulfilimine compound. The method includes combining a sulfide compound, cyanamide, a hypochlorite compound, and a base, and oxidizing the sulfide compound to form the sulfilimine compound. The sulfide compound may include a 2-trifluoromethyl-5-(1-substituted)alkyl-thiopyridine compound. The base may include sodium hydroxide. A buffer, such as a phosphate buffer, may, optionally, be used in the reaction.

First claim

What is claimed is:

1. A method of producing a sulfilimine compound, comprising:
reacting 2-trifluoromethyl-5-(1-substituted)alkylthiopyridine compound with cyanamide, hypochlorite compound, and base to form a sulfilimine compound,
wherein the base is selected from the group consisting of alkali metal hydroxide, alkali metal carbonate, and combinations thereof,
wherein the 2-trifluoromethyl-5-(1-substituted)alkylthiopyridine compound has the following formula:

wherein
each of R 7 and R 8 is independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl; or R 7 taken together with R 8 is a 3- to 6-membered saturated ring; or R 7 taken together with R 8 is a 4- to 6-membered saturated ring containing at least one of O or N atom, and
R 9 is a C 1 -C 4 alkyl; or R 9 taken together with either of R 7 or R 8 is a 4- to 6-membered saturated ring.

2. The method of claim 1 , wherein reacting 2-trifluoromethyl-5-(1-substituted)alkylthiopyridine compound with cyanamide, hypochlorite compound, and base comprises oxidizing the 2-trifluoromethyl-5-(1-substituted)alkylthiopyridine compound with a hypochlorite compound solution comprising from 2% by weight to 20% by weight of a metallic salt of hypochlorous acid, in the presence of the cyanamide and the base.

3. The method of claim 1 , wherein reacting 2-trifluoromethyl-5-(1-substituted)alkylthiopyridine compound with cyanamide, hypochlorite compound, and base comprises combining the 2-trifluoromethyl-5-(1-substituted)alkylthiopyridine compound with the cyanamide and the alkaline metal hydroxide to provide a mixture, and then adding the hypochlorite compound to the mixture.

4. The method of claim 1 , wherein reacting a reacting 2-trifluoromethyl-5-(1-substituted)alkylthiopyridine compound with cyanimide, hypochlorite compound, and base comprises reacting the 2-trifluoromethyl-5-(1-substituted)alkylthiopyridine compound with the cyanamide, the hypochlorite compound, and sodium hydroxide.

5. The method of claim 1 , wherein reacting 2-trifluoromethyl-5-(1-substituted)alkylthiopyridine compound with cyanamide, hypochlorite compound, and base comprises reacting 5-[1-(methylthio)ethyl]-2-trifluoromethylpyridine with the cyanamide, sodium hypochlorite, and sodium hydroxide to form the sulfilimine compound.

6. The method of claim 3 , further comprising adding a phosphate buffer to the mixture.

7. A method of producing N-cyano-S-methyl-S-[1-(6-trifluoromethyl-3-pyridinypethyl] sulfilimine, comprising:
combining 5-[1-(methylthio)ethyl]-2-trifluoromethylpyridine with cyanamide and sodium hydroxide to provide a mixture; and
adding sodium hypochlorite to the mixture to oxidize the 5-[1-(methylthio)ethyl]-2-trifluoromethylpyridine to N-cyano-S-methyl-S- [1 -(6-trifluoromethyl-3 -pyridinyl)ethyl]sulfilimine.

8. The method of claim 7 , wherein the 5-[1-(methylthio)ethyl]-2-trifluoromethylpyridine comprises from 1×10 −5 moles of acidic impurities to 1×10 −4 moles of acidic impurities per gram of the mixture.

9. The method of claim 7 , wherein adding sodium hypochlorite to the mixture comprises adding an aqueous sodium hypochlorite solution comprising from 12.5% by weight to 17% by weight of sodium hypochlorite to the mixture.

10. The method of claim 7 , wherein adding sodium hypochlorite to the mixture comprises adding an aqueous sodium hypochlorite solution comprising from 12.5% by weight to 20% by weight of sodium hypochlorite to the mixture.

11. The method of claim 7 , wherein
combining 5- [1-(methylthio)ethyl]-2-trifluoromethylpyridine with cyanamide and sodium hydroxide to provide a mixture comprises combining the 5-[1-(methylthio)ethyl]-2-trifluoromethylpyridine with from 1.0 molar equivalents to 1.6 molar equivalents of the cyanamide relative to the 5[1-(methylthio)ethyl]-2-trifluoromethylpyridine, and the sodium hydroxide to provide the mixture; and
adding sodium hypochlorite to the mixture comprises adding from 1.0 to 1.2 molar equivalents of the sodium hypochlorite relative to the 5-[1-(methylthio)ethyl]-2-trifluoromethylpyridine to the mixture.

12. The method of claim 11 , wherein molar ratio of cyanamide to sodium hypochlorite is 1.2.

13. A method of producing a sulfilimine compound, comprising oxidizing 2-trifluoromethyl-5-(1-substituted)alkylthiopyridine compound with sodium hypochlorite compound in the presence of sodium hydroxide (NaOH) base and cyanamide at a temperature from -40° C. to 30° C. to form a sulfilimine compound, wherein the 2-trifluoromethyl-5-(1-substituted)alkylthiopyridine compound has the following formula:

wherein
X is a moiety selected from the group consisting of a halogen, a C 1 -C 4 alkyl, a C 1 -C 4 haloalkyl, a C 2 -C 4 alkenyl, a C 2 -C 4 alkynyl, a C 2 -C 4 haloalkenyl, a C 1 -C 4 alkoxy, a C 1 -C 4 haloalkoxy, CN, NO 2 , SO m R 6 where m is an integer from 0-2, COOR 4 , and CONR 4 R 5 ;
Y is a moiety selected from the group consisting of hydrogen, a halogen, a C 1 -C 4 alkyl, a C 1 -C 4 haloalkyl, a C 2 -C 4 alkenyl, a C 2 -C 4 alkynyl, a C 2 -C 4 haloalkenyl, a C 1 -C 4 alkoxy, a C 1 -C 4 haloalkoxy, CN, NO 2 , SO m R 1 where m is an integer from 0-2, COOR 4 , CONR 4 R5, aryl. and heteroaryl;
n is an integer from 0-3;
L is either a single bond; —CH(CH 2 ) p — where R 1 , S, and L taken together are a 4-, 5-, or 6-membered ring and p is an integer from 1-3; —CH(CH 2 OCH 2 )— where R 1 , S, and L taken together are a 6-membered ring; or —CH— where L, R 2 , and the common carbon to which they connect taken together are a 5-membered or 6-membered ring with up to, but no more than, 1 heteroatom;
R 1 is a moiety selected from the group consisting of a C 1 -C 4 alkyl, a C 1 -C 4 haloalkyl, a C 3 -C 6 alkenyl, a C 3 -C 6 alkynyl, a C 3 -C 6 haloalkenyl, an arylalkyl, a heteroarylalkyl, or —CH 2 — in cases where R 1 , S, and L taken together are a 4-, 5-, or 6-membered ring;
each of R 2 and R 3 is independently selected from the group consisting of hydrogen, halogen, C 1 -C 4 alkyl, a C 1 -C 4 haloalkyl, a C 2 -C 4 alkenyl, a C 2 -C 4 alkynyl, a C 2 -C 4 haloalkenyl, a C 1 -C 4 alkoxy, a C 1 -C 4 haloalkoxy, CN, SO m R 6 where m is an integer from 0-2, COOR 4 , CONR 4 R 5 , an arylalkyl, a heteroarylalkyl, or R 2 and R 3 and the common carbon to which they attach form a 3-6 membered ring;
each of R 4 and R 5 is independently selected from the group consisting of hydrogen, a C 1 -C 4 alkyl, a C 1 -C 4 haloalkyl, a C 3 -C 6 alkenyl, a C 3 -C 6 alkynyl, a C 3 -C 6 haloalkenyl, an aryl, a heteroaryl, an arylalkyl, or a heteroarylalkyl; and
R 6 is a moiety selected from the group consisting of a C 1 -C 4 alkyl, a C 1 -C 4 haloalkyl, a C 3 -C 6 alkenyl, a C 3 -C 6 alkynyl, a C 3 -C 6 haloalkenyl, an arylalkyl, and a heteroarylalkyl.

Assignees

• Dow Agrosciences Llc

Inventors

• Adaway Timothy J

Classifications

• C07D275/02

  not condensed with other rings · CPC title

• C07D277/20

  having two or three double bonds between ring members or between ring members and non-ring members · CPC title

• C07D237/06

  having three double bonds between ring members or between ring members and non-ring members · CPC title

• C07D241/10

  having three double bonds between ring members or between ring members and non-ring members · CPC title

• C07D249/08

  1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles · CPC title