Process for preparing phosphorothioates and phenylphosphonothioates

• US 4,092,312 A
• Filed: 01/21/1977
• Issued: 05/30/1978
• Est. Priority Date: 07/31/1975
• Status: Expired due to Term

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Yoshimine, Masao, Kroposki, Lorraine M.
• Primary Examiner(s): Tovar, Jose
• Application Number:
  US05/761,186
• Time in Patent Office: 494 Days
• Field of Search: 260/251 P, 260/250 BP, 260/929, 260/964, 260/973
• US Class Current: 544/243
• CPC Class Codes: B01J 31/0237 Amines
• CPC Class Codes: B01J 31/0239 Quaternary ammonium compounds
• CPC Class Codes: C07F 9/18 with hydroxyaryl compounds
• CPC Class Codes: C07F 9/4084 Esters with hydroxyaryl compounds
• CPC Class Codes: C07F 9/58 Pyridine rings
• CPC Class Codes: C07F 9/650952 having the nitrogen atoms in the positions 1 and 4

Abstract

Mixtures of (1) a quaternary ammonium salt(s) and (2) 1,4-diazabicyclo[2.2.2]octane are novel catalysts in the process of reacting an alkali metal phenate, pyridinate or pyrimidinate with an O,O-dialkyl phosphorochloridothioate or O-alkyl phenylphosphonochloridothioate to produce the corresponding phosphorothioates and phenylphosphonothioates. The process is conducted under alkaline conditions in a liquid reaction medium. As an example, O,O-diethyl O-(3,5,6-trichloro-2-pyridyl)phosphorothioate is prepared in excellent yields and purity by reacting sodium 3,5,6-trichloropyridinate with O,O-diethyl phosphorochloridothioate in a stirred methylene chloride-water reaction medium in the presence of a catalytic amount of benzyltriethylammonium chloride and 1,4-diazabicyclo[2.2.2]octane.

Claims

1. In the process of preparing a compound corresponding to the formula ##STR35## wherein:

R₁ and R₂ are each independently lower alkyl; and

R is ##STR36## wherein;

n is 0, 1, 2 or 3; and

X is nitro, cyano, halo, lower alkyl, lower alkoxy, lower alkylthio or lower alkylsulfinyl, with the proviso that R does not bear more than one nitro group, lower alkylthio group or lower alkyl-sulfinyl group;

by reacting in an inert liquid reaction medium under neutral or alkaline conditions (a) a compound corresponding to the formula

space="preserve" listing-type="equation">R--O.sup.⊖

M.sup.⊕

or M.sup.⊕

.spsp.⊖

O--C.sub.6 H.sub.4 --S--C.sub.6 H.sub.4 --O.sup.⊖

M.sup.⊕

with (b) a compound corresponding to the formula ##STR37## wherein M is an alkali metal and R, R₁ and R₂ have the aforesaid meaning;

the improvement consisting of conducting the process in the presence of a small but catalytic amount of (1) a quaternary ammonium salt having a minimum solubility of at least 1 weight percent in the liquid reaction medium at 25°

C and (2) 1,4-diazabicyclo[2.2.2]octane.

2. The process defined in claim 1 wherein (1) is a quaternary ammonium salt of the formula R₁ '"'"'R₂ '"'"'R₃ '"'"'R₄ '"'"'N.sup.⊕

A.sup.⊖

, wherein R₁ '"'"'-R₄ '"'"' are each independently hydrocarbyl groups of from 1 to about 12 carbon atoms, or R₁ '"'"' is joined with R₂ '"'"' to form a 5- or 6-membered heterocyclic ring wherein one member of said heterocyclic ring is a quaternized nitrogen atom, a second member of said heterocyclic ring is an atom or carbon or a non-adjacent atom of nitrogen, oxygen or sulfur, and the remaining members of said heterocyclic ring are carbon atoms; and

A.sup.⊖

is a neutralizing anion;

said quaternary ammonium salt having a maximum carbon content of about 31 carbon atoms.

3. The process defined in claim 2 wherein (1) is benzyltrimethylammonium chloride or bromide, or benzyltriethylammonium chloride or bromide.

4. The process defined in claim 3 wherein (1) is benzyltriethylammonium chloride.

5. The process defined in claim 1 wherein the mole ratio of (1) to (2) is from about 1:

20 to about 20;

1.

6. The process defined in claim 5 wherein said ratio is from about 1:

2 to about 2;

1.

7. The process defined in claim 1 wherein the combined amount of (1) and (2) is from about 0.25 to about 20 mole percent, based on the combined moles of (a) and (b).

8. The process defined in claim 7 wherein the combined amount of (1) and (2) is from about 0.5 to about 2 mole percent.

9. The process defined in claim 1 wherein said process is conducted in an agitated two-phase solvent system consisting of an inert water-immiscible organic liquid and water.

10. The process defined in claim 1 wherein R is ##STR38##

11. The process defined in claim 10 wherein R₁ and R₂ are methyl or ethyl.

12. The process defined by claim 10 wherein (1) is benzyltrimethylammonium chloride or bromide or benzyltriethylammonium chloride or bromide.

13. The process defined in claim 12 wherein (2) is benzyltriethylammonium chloride.

14. The process defined in claim 13 wherein said process is conducted in an agitated two-phase solvent system consisting of an inert water-immiscible organic liquid and water.

15. The process defined in claim 14 wherein M is sodium or potassium;

(b) is O,O-diethyl phosphorochloridothioate;

said two-phase solvent system is a mixture of methylene chloride and water; and

the reaction temperature is from about 40°

to about 60°

C.