CA1099278A - Manufacture of substituted phenyl phosphates involving use of phase transfer catalysts - Google Patents

Abstract

MANUFACTURE OF SUBSTITUTED PHENYL PHOSPHATES
INVOLVING USE OF PHASE TRANSFER CATALYSTS

Abstract of the Disclosure Substituted phenyl phosphates, phosphonates, phosphinates, and thiono and thiolo derivatives thereof having the formula in which R is a member selected from the group con-sisting of alkyl and alkoxy, R1 is a member selected from the group con-sisting of alkyl, alkoxy, aryl, aralkyl, amino, and alkyl-substituted amino;
X is oxygen or sulfur;
Z is oxygen or sulfur;
W is a member selected from the group con-sisting of alkyl, alkoxy, alkylthio, nitro, halogen, and alkanoyl; and n is an integer from 0 to 3;
are manufactured by a process which comprises reacting a phosphoryl halide of the formula in which Y is chlorine or bromine; with an alkali metal or alkaline earth metal salt of a compound having the formula in the presence of a catalytic amount of a phase transfer catalyst selected from the group consisting of macrocyclic polyethers and quaternary salts having the formula (R2R3R4R5M)+Q-in which R2, R3, R4 3 and R5 taken individually are independently selected from the group consisting of alkyl, alkenyl, aryl, alkaryl, aralkyl, and cycloalkyl;
or any two are joined to constitute a hexagonal or pentagonal heterocyclic moiety containing the M atom plus at most one non-adjacent nitrogen, oxygen, or sulfur atom;
M is a member selected from the group con-sisting of nitrogen, phosphorus, and arsenic; and Q is an anion selected from the group con-sisting of halide, hydroxyl, bisulfate, perchlorate, nitrate, acetate, tosylate, benzoate, and carbonate ions.

Description

3gZ'7~3 ' Back~ound_o the Invention Subs~ituted phenyl phospha~es, phosphonates, phosphinates, and thiono and thiolo deriva~ives thereof, are known for their usefulness as insecticides, acaricides, and nematocides~ as well as their usefulness as intermediates in the manuacture of additional compounds, which are in turn known to be use~ul as insecticides~ an~mal parasiticides, herbicides, and foliage fungi pro~ectants Typical Qf the latter is a disclosure in U.S. Patent .3,733,375 of oxime carbamate phosphates, phosphonates, phosphinates, and phosphoramidates. Typical of the substitu~ed phenyl compounds are those disclosed in U.S. Patent 2,988~474.

The method o manufac~ure disclosed in U.S. Patent

2,988,474 involves the reaction of a phosphoryl halide with thio-phenol or an alkyl substituted thiophenol, in the presence of an alkali in an organic solvent. Similarly, U.S. Pa~en~ 3,~44,586 discloses the reaction of a phosphoryl halide with an alkali me~al or tertiary amine salt.of a halopyridinol.

Subs2quent ~o ~hese paten~s, ~he discovery was made in U.S. Patent 3,907,815 that the yieldand purity of the products of this reaction can be substantially improved by the use o~ a ca~alyst mixture comprising a quaternary ammoni~m salt and 1,4-diazabicyclo[2.2.2]-octane. It has now been discovered ~hat highly e~fective catalysis can occur with the use of a single phase transfer catalyst, and without ~he need o u~ilizing a combination of the above two catalysts.

--2~

Phase transfer catalyscs are known for their ability to promote reactions bet~Jeen reactan~s residing in separate but contiguous liquid phases by transerring one reac~ant across the interface. The use of quaternary salts as phase transfer catalysts in allcyl l~alide displacemen~ reactionsg dichlorocyclopropanation of a~kenes, oxidation of alkenes, and other reactions is taught in C M. Starks, J~ Am. Chem. Soc. 93 (1), 195-199 (1971~. Other uses are disclosed in W.P Weber, G W. Gol-el~ and I.K. Ugi, Chem Internat Edit. 11 (6), 530-531 (1972); H.E. Hennis, L.E.
Thompson, and J.P~ Long, I & EC Prod Res. and Dev. 7 (2), 96-101 (1968); British Patent 1,227,144; E.V. Dahmlow, An~ew. Chem.
Inte~nat._Edit. 13 (3), 170-179 (197~); and J. Dockx,~ S~n~hesis Reviews, 441-456 (1973).

The use of macrocyclic polyethers or crown ethers as phase transfer ca~alysts is disclosed for a number o different reactions, including halide subs~:itutiQn reac~ions~ dichloro-carbene insertions, reaction of 1,2-glycols wi~h dichlorocarbene, synthesis of isoni~riles, carboxyclic acids, alkyla~îons~
~drolysis reactions, and other~, in Fendler and Fendler, ~ ~ , Academic Press 9 New York (1975).

9~
This invention rela~es to a novel method of` preparing substituted phenyl phosphates, phosphonates, phosphinates, and thiono and thiolo derivatives thereo. The compounds which can be manuf~ctured by the process of this inven~ion have ~he formula 27~

R~ X
~P~Z OE. wn (I) in which R is a member selected from the group consisting o~
alkyl having 1 to 6 carbon atoms and alkoxy having 1 ~o 6 carbon atoms, preerably al~oxy having 1 to 6 carbon atoms, more preferably alkoxy ha~ing 1 to 4 carbon atoms, and rnost preferably alkoxy having 1 to 2 carbon atoms, Rl is a member selected rom the group cunsis~ing of ;~
alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, alkylthio having 1 to 6 carbon atoms, aryl~ alkar~l in which the alkyl group has 1 to 6 carbon atoms, amîno,and alkyl-substituted amino having 1 ~o 6 carbon atoms, preferably alkoxy havin~ 1 to 6 carbon atoms; more preferab~y lS alkoxy having 1 to 4 carbon atoms; most preferably alkoxy having 1 to 2 carbon atom~;
X is a member selec~ed from the group consisting o oxygen and sulfur;
Z is a member sele~ed ~rom the group consisting of ox~gen and ~ulfur~
W is a member selected from ~he group consisting o al~yl having 1 ~o 6 carbon atoms, preferably 1 to 4 carbon atoms, most pre~erably 1 to 2 carbon a~oms;
alk4xy having 1 to 6 carbo~ atom~, preferably 1 to 4 carbon atoms, most preferably 1 to 2 carbon atoms, alkylthio having 1 to 6 carbon atone, preferably 1 to 4 carbon atomsg most preferably 1 to 2 carbon atoms; nitro; halogen; and alkanoyl having 1 to 6 carbon atoms, preferably 1 to 4 car`bon atoms, most preferably 1 ~o 2 ca~bon atoms;
and S n is an integPr from 0 to 3, inclusive.
All o ~he carbon atom ranges quoted in this speci~ica~ion and subseq~ent claims are intended ~o be inclusive o~ both upper and lower l~li~s~ When n is a number greater than 1, ~he W groups can be the same or different.

The inven~ion comprises reacting a phosphoryl halide o the formula R~ X
(II) R/
in which R, Rl and X are as defined abova; and Y is a halogen selected ~xom the group consis~ing of chlorine and bromine, preferably chlorineg with an alkali metal or alkaline earth metal salt, preerably a sodium~ potassium or barium salt5 most preferably a sodium salt, of a compound of the formula HZ~ (II r) in which Z, W, and n are as de~ined above; in the presence of a catalytic amount of a phase transfer catalyst selected from the group consis~ing of macrocyclic polyethers and quaternary salts having the formula (~2~3R4R5M~ Q (IV) in which R2, R3, R~ and R5 ~aken individually are independen~ly 1G3C~9127B

selected from the group consisting of alkyl having 1 to 25 carbon a~oms3 alkenyl having 2 to 25 carbon atoms, aryl, alkaryl, aralkyl~ and cycloalkyl having 4 to 8 carbon atoms; or any two of the groups R2, R3, R4 and R5 are joined to constitute a hexagonal or pentagonal heterocyclic moiety containing the quaternized M atom plus a maximum of one non-adjacent nitrogen9 oxygen or sulfur atom;
M is a member selec~ed from the group consisting of nitrogen, phosphorus, and arsenic; pre~erably nitrogen and phosphorus; most preferably nitrogen;
and Q is an anion selected from the group consisting of halide, hydroxyl, bisulfate, perchlorate, nitrate, acetate, tosylate, benzoa~e, and carbonate ions;
preferably halide, hydroxy~ and bisulfa~e; and most preferably chloride, bromide, and h~droxyl.

The preferred embodiments of onm~tla IV are those in whi~h R29 R33 R4 and R5 are members selected rom the group con~
sisting of alkyl having 1 to 25 caxbon atoms, alkenyl having 2 ~o 25 carbon atoms, cycloalkyl ha~ing 4 to 8 carbon atoms, aryl9 alkaryl, and aralkyl. Most preferably, the to~al number o~ carbon a~oms present in all four groups is, ~n order of increa~ing preerance, 10 to 70~ lo to 40~ and 10 to 30.

As used in this specification:

~he term "alkyl" refer~ to a monovalent straight or branched chain saturated alipha~ic hydrocarbon group of the specified number of carbon a~oms, e.g., methyl3 ethyl, propyl, i-propylg and the like;
the ter~ "alkenyl" refers to a monovalent straight or branched chain aliphatic hydrocarbon group o the speci~ied number oE carbon ~oms, and containing at leas~ one double bond, e.g.g allyl, butenyl~ butadienyl, and ~he like;
the term "alkoxy" refers to a monovalent straight or ; branched chain saturated aliphatic hydrocarbonoxy group of ~he specified ~lumber o~ carbon atoms, e.g., me~hoxy~ ethoxy, and the Like;
the term "alkylthio" refers to an alkoxy group as defined above, in which the oxygen atom is replaced by a sulfur a~om, e.g., methylthio, ethylthio, and the like;
~he term "aryl" refers to a monovalent, monocyclic or bicyclic aromatic hydrocarbon group, i.e., phenyl and naphthyl;
the ~erm "alkaryl" reers to an aryl group as defined above5 in which a~ least one hydrogen atom is substituted by an alkyl group as defined above, e.g., p~tolyl, 2,4 dimethylphe7lyl, and the like;
~he term "aralkyl" refers ~o an alkyl group as defined above, in which a hydrogen atom is substituted by an aryl g*oup as defined above, e.g., benzyl, phenethyl, naphthylmethyl, and the like;
the term "cycloalkyl" refers to a monovalent cyelical saturated hydrocarbon group of ~he speciied number of carbon atom~
e.g., cyclobutyl, cyclohexyl, and the like;
the t~rms "halogen" and "halide" refer to fluorine, chlorîne, bromine, and iodine;

~he ~erm "alkanoyl" refers to a carbonyl group with an allcyl group as defined above conn~c~ed to one of the bonds o the carbonyl carbon.

The terms "alkali metal" and "alkaline earth metal"
refe~ to elemen~s in Groups IA and ILA, respectivel~, of the Periodic Chaxt of the Elements (Lan~e's Handbo k of ChemistrY, Revised Tenth Edition, McGraw-Hill, 1967). The alkali metals are preferred over the alkaline earth me~als, and sodium and po~assium, particularly sodium, are the most preferred among the alk2li metals.

The term "phase transfer catalyst" refers to any catalyst which facilitates the transfer o a chemical species from one liquid phase to another across the phase interface.

The quaternary salts of Formula IV can exist as shown or in varied forms, e.g., where the cation contains two or more quaternized M atoms. In the latter case, multicharged anions or combinations of anions will be used to balance the charge.
Mixtures of quaternary salts can likewise be utilized in the practice of the invention. Double or multiunctionaL quaternary salts in which the general formula (R2R3R4R5M3~ is repea~ed a plur~lity o~ times with the same ~r diferent substituent com binations, can also be utilized effectively.

The mos~ preferred quaternary salts are tetra-n-butyl-phosphonium chlorideg hexadec~tributylphosphonium bromide, benzyl-triethylammonium chloride, benzyltxiethylammonium bromide, ~IL0~27~3 tetra-n-butylammonium bisulfate, tricapryl~ethylammonium chloride, and dimethyldicocoarnmonium chloride. The latter two catalysts are manufactured by General Mills Co., Chemical Division, Kankakee, Illinois, and are also designated by ~he narnes 'lALiquat 33 ~" and "~liquat 221~", respectively.

The term "macrocyclic polyethers" is used herein to denote heterocyclic ring compounds comprising oxygen and carbon a~oms connected in a ring such that each oxygen atom is separated by at least two carbon atoms. The compounds are also known as "crown ethers" and are either symme~rical or asymmetricalg generally comprising a central or main heterocyclic ring of carbon and oxygen atoms as described above in which the oxygen atoms together form a single plane which is displaced frorn the carbon atoms. Saturated or aromatic side rings are often attached to the carbon atoms in the central ring. Examples of such polyethers are dibenzo-14-crown-4, benzo-15-crown-5, 18crown-6y perhydro-dibenzo-18-crown-6, dibenzo 18~crown-6, and tetrabenzo-24-crown-8.

According to the process o the invention~ a phosphoryl halide o formula II above is reacted with an al~ali metal or alkaline earth metal salt of Compound III a~ove to produce Compound I above, în the presence of a ca~alytic amount of a phase transfer catalyst. The alkali metal or alkaline earth metal salt can be manufactured extrinsic to the system, or can be generated in situ by reaction of compound III with a caustic agent.
The term "caustic agent" is used to refer to alkali metal and alkaline earth metal hydroxides and carbonates, for example, sodium hydroxide, potassium hydroxide, barium hydro~ide 7 sodium carbonate, and potassium carbonate. The preferred caustic agents are sodium hydroxide and sodium carbonate.

The reaction system comprises two liquid phases, the lowe~ aqueous phase containing the Compound III salt, the caustic agen~, and the phenol or thîophenol when used, and the upper organic phase containing the phosphoryl halide. Tn general, the phase transfer catalyst will distribute itself batween both phases.
It has been discovered, however, that ~he most effective phase transer catalysts avor the organic phase. The catalytic mechanism generally operates to transport the phenate or ~hio-phenate anion from the aqueous phase across t~e interface into the organic phase where it reacts with the phosphoryl halide.

The order of addition of the reactants is not essential to the practice o the invention In general, however~ it will be most convenient to form the Compound III salt irst, by adding the phenol or thiophenol to the caustic solution. The phase transfer catalyst and the phosphoryl halide can then be added directly to the same vessel.

In oxder to prevent liberation of the phenol or thio-phenol rom the metal salt9 i~ is necessary to mainta;n a basic solution. Reasonable reaction rates are attained at pH above about 8.4. A solution of excessively high pH could hydroxlyze the phosphoryl halide. Under preferable operating corldi~ions, ~he pH
is maintained between about 9.0 and about 12.0, most preferably between about 10.0 and about 12Ø The appropriate pH of the $27~3 solution is governed by the particular reactants used. For example, as the acidity o~ the ph~nol or thiophenol increases 3 ~he more acceptable lower pH values become. In order to maintain the desired pH, it may b2 necessary to add additionaL caustic solution as the reaction proceeds.

Ei~her the phosphoryl halide or the Compound III salt can be used in excess) depending on the economics of the process.
Maximum conversior. of either will be attained when the o~her is used in excess. High excesses of the sal~ are to be avoided, however, since nucleophilic attack of the product may result.
An excess o up to about 10% of the salt with respect to the phosphoryl halide on a molar basis will be most coovenient.

Control of ~he reac~ion can be enhanced by the use of an inert solvent. Hydrocarbon and c~lorina~ed hydrocarbon solvents are useful for th~s purpose. Examples of such solvents are met~ylene chlorîde~ chlorobenzene, carbon tetr~chloride, toluene, benzene, cyclohexane, and heptane.

The reaction tempera~ure is not an essential characteristic of the process of the invention, and is limited only by consider-ations o~ having the reactlon proceed at a reasonable rate, avoiding decomposition of the system components, and maintaining ~he reaction mixture in the liquid phase. Normally, the reaction can proceed at any temperature ranging from room ~emperalure up to the boiling point o the solvent or any of the reactants used. T~e preferred temperature range is from about 60C to about 120C, with about 80C to about 100C most pre~erred.

The term "catalytic amoun~" is used herein to represent any amount of phase trans~er catalyst which will facilitate the trans~er of a chemical species from one liquid phase to ano~her~
and thus enhance the progress of the reaction. The amo~nt oi S catalyst normally will range from about 0.2 to about 10 mole percent with xespect to the phenol or mercaptide salt, preferably rom 0.5 to about 4.0 mole pQrcent.

At the completion of the reaction, the product will reside in the organic phase, which can be separa~ed rom the ~0 aqueous phase by dccanta~ion or any other conventional technique.
If an excess o~ phenol or thiophenol was used, it can be remo~ed fronl the solution by a caustic wash. Excess phosphoryl halide can be removed by a water wash. The produc t can then be isola~ed ~rom th~ solvent by evaporation or any other conventional recovery lS technique. While the phase transfer catalyst is generally in small enough quan~ity that its removal from the produc t is unnecessaryg~ it can be removed by distillation ox crystallization techniques Compounds produced by the process o~ the invention are 2C known to exhibit ac~ivity as insecticides, acaricides and nematocides. In~addition, Compound I can be ~urther con~erted to add~tionaL compounds, for examplP, oxime carbamate phosphates, phosphonates 7 phosphinates, and phosphoramidates To accomp1ish this, Compound I wherein W is an alkanoyl group can be reacted 25 with hydroxylamine hydrochloride in a condensation reac~ion, and the resulting product further reacted with a substituted isocyanateg acid chloride, chloroformate, chlorothi.olformate 9 s~llonyl chloride, 71~

carbamyl chloride, phosphoryl chloride, thionophosphoryl chloride, trichloroace~aldehyde, etc. The resulting compounds are known to be use~ul as insecticides, animal parasiticides, and foliage fungi protectants.

S The following are examples of the utility o the process of the invention, and are o~fered merely as illus~rat~ons thereof.
They are not intended to impose any limitations on the scope of the inven t ion .

EXAMPLE I
O,O-Diethyl-O phenYl Phosphorothioate A ~Lask eq~lipped with heating mantle, stîrrerg and L0 water-cooled reflux condenser was charged with the following, in the order lis~ed:
20i g (2.20 mole) phenol 800 ml toluene 2.1 g ALiqua~ 33 ~
lS 400 g (2.00 moie) 20% aqueous NaOH
The resulting two-liquid-phase system was heated to 80C. Diethyl phosphorochloridothionate (337 g, 2.00 mole) was ~hen added drop~
wise as the reaction mixture was vigorously agi~ated The reaction m~ure was then hea~ed at reflux (91C) for four ~ours while small qua~tities of 50~/O NaOH were added to keep the pH between 11 and 12.
The mixture was then allowed to cool to room temperature and 200 ml of water was added The phases were separated and the organic layer was washed with 10% NaOH. The solven~ was then evaporated at 70C under vacuum to yield ~40 g of ~he title compound (89%
technical yield), identity confirmed by chromatographic assay.

EXA~PLE II
4-~0-(O~O-Diethy~hosphor~thioyl~-acetophenoneoximino-N'-methyl-carb This example illus~rate~ the combina~ion of the process of ~he invention with additional reactions performed subsequent thereto to produce an oxime carbamate thionophosphina~e.

A reaction flask equipped with agitator~ condenser, and heating mantle was charged with 200 g (L.0 mole) of 20% NaOH and heated to 80C. The ~ollowing were then addPd, in the order listed:
136 g (1.0 mole) p-hydroxyacetophenone 400 ml ~oluene 6.8 g benzyltriethylammonium chloride 198 g (1-05 rllole) (C2H5O32PSCl The reaction mixture was heated a~ reflux (90C) with agitation until monitoring by gas-liquid chromatography showed no remaining (C2H5~)2PSCl. During the reaction, the pH was maintained between 10 and 11 by adding small amounts of 50% caustic The system was phase separa~ed and ~he organic phase was washed, to yield a toL~ene solution of O,O-diethyl-O-(p-acetylphenyl) phosphorothioateg isolated yield 99% based on p~hydroxyacetophenone, with a purity o 98 area %. A similar run withou~ the u~e ~ the phase ~ransfer catalyst produced a ~ield of 87% and ~equired 8 hours.

To the toluene solution were added the following in the order listed:
450 ml methanol 91 g (0.51 mole) (NH2OH)2 H2SO4 50 ml H2O

;14-7~

The mixture was heated to refl~Y (63C) and 80 g (1.0 mole) of 53% caustic was added dropwise at a ra~e such ~hat ~he pH
remained between 1.0 and 3.5. A~ the completion of the reaction, as determined by gas-liquid chromatography3 the solution was washed and phase separated. The organic phase was dried, yielding a solution of 4-0,0-diethylthiophosphoroacetophenone oxime, isolated cr~de yield 97.5% based on the phosphorothioate.

Finally, 10 ml of ~riethylamine was added ~o ~he organic solution, ollowed by 60 g (1.05 mole) o methylisocyanate in dropwise manner. The temperature was allowed to rise to 60C
and held at this level for two hours. The solution was then washed with water and the title compound was recovered from the solvent by evaporation. The isolated crude weight yield was 99~/O~
based on the oxime, with melting point 51-54Cg and purity 97.9%
by weight, determined by gas-liquid chromatography.

EXAMPLE III

This example is similar to Example I with the exception that the phase transfer catalyst used herein is benzyltriethyl-ammonium chlorideg rather than Aliquat 336~.

A flask equipped with heating man~le, stirrer, and water-cooled re~lux condenser was charged with the following, in the order listed:
104 g (1.10 mole) phenol 200 ml benzene .

4 g benzyltriethylammonium chloride 200 g 25% aqueous NaOH
189 g (1.0 mole) diethylphosphorochloridothioate The resulting two-liquid-phase system was heated at xefl~x for 82 minutes. Analysis by gas-liquid chromatography indicated 99.9%
(area) of product, and 0.1% (area) of the chloxidate. The reaction mixture was cooled to room temperature and 100 ml of water was added. The phases were separated and the organic phase was washed with 12G/o NaOH. The solvent was then evaporated to yield 213 g of the title compound (86% technical yield~, with 99% purity by w~ight, identity confirmed by chroma~ographie assay.

A similar run usi~g the same reagents with no catalys~
gave a product of 97.3% purity by we~gh~, af~er a re1~ perio~ o 275 minutes.

EXAMPLE IV
O-Ethyl-S-phenyl ethylphos~honod~thioate A reaction ~ask was charged with the following:
30 ml (0.55 mole) 20~/o aqueous NaOH
66 ml water 49 ml (0.5~5 mole) thiophenol A mixture of the following was pr~ ared sepaxately:
75 ml (8625g, 0.~ mole) C2H5PSCl(OC2H
250 ml tolu~ne 0.5 g Aliqua~ 33 ~
The latter mix~ure was added to the former over a period of 4 minutes at 60C. Ten minutes later, the syste~ was phase separa~ed and the title compound was recovered from the organic phase by evaporation of the solvent under high vacuum The resîdue was -16;-filtered and purified to yield 119.6 g of the ~itle compound, identified by gas-liquid chromatography, and analyzed as 98.4 weight % pure~

~17-

Claims (25)

WHAT IS CLAIMED IS:

1. A process for the manufacture of a compound having the formula (I) in which R is a member selected from the group consisting of alkyl and alkoxy and contains 1 to 6 carbon atoms;
R1 is a member selected from the group consisting of alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, alkylthio having 1 to 6 carbon atoms, aryl, alkaryl in which the alkyl group has 1 to 6 carbon atoms 3 amino, and alkyl-substituted amino having 1 to 6 carbon atoms;
X is a member selected from the group consisting of oxygen and sulfur;
Z is a member selected from the group consisting of oxygen and sulfur;
W is a member selected from the group consisting of alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, alkylthio having 1 to 6 carbon atoms, alkanoyl having 1 to 6 carbon atoms, nitro, and halogen; and n is an integer from 0 to 3, inclusive;
which comprises reacting a phosphoryl halide of the formula (II) in which R, R1 and X are as defined above, and Y is a halogen selected from the group consisting of chlorine and bromine, with an alkali metal or alkaline earth metal salt of a compound of the formula (III) in which Z, W and n are as defined above, in a two-phase reaction system comprising an alkaline aqueous phase and a hydrocarbon or chlorinated hydrocarbon phase, at a pH of between 8.4 and 12.0, and in the presence of a catalytic amount of a phase transfer catalyst selected from the group consisting of macrocyclic poly-ethers and quaternary salts having the formula (R2R3R4R5M)+Q- (IV) in which R2, R3, R4 and R5 taken individually are independently selected from the group consisting of alkyl having 1 to 25 carbon atoms, alkenyl having 2 to 25 carbon atoms, aryl, alkaryl, aralkyl, and cycloalkyl having 4 to 8 carbon atoms, or any two of the groups R2, R3, R4, and R5 are joined to constitute a hexagonal or pentagonal heterocyclic moiety con-taining the quaternized M atom plus a maximum of one non-adjacent nitrogen, oxygen, or sulfur atom;
M is a member selected from the group consisting of nitrogen, phosphorus and arsenic; and Q is an anion selected from the group consisting of halide, hydroxyl, bisulfate, perchlorate, nitrate, acetate, tosylate, benzoate, and carbonate ions.

2. The process of Claim 1 in which the alkali metal or alkaline earth metal salt is generated in situ by reaction of Compound III with a caustic agent at a pH above about 8.4.

3. The process of Claim 1 in which the pH is between about 9,0 and about 12Ø

4. The process of Claim 1 in which the pH is between about 10.0 and about 12Ø

5. The process of Claim 1 in which the reaction occurs at a temperature between about 60°C and about 120°C.

6. The process of Claim 1 in which the reaction occurs at a temperature between about 80°C and about 100°C.

7. The process of Claim 1 in which the amount of catalyst present ranges from about 0.2 to about 10 mole percent with respect to Compound III.

8. The process of Claim 1 in which the amount of catalyst present ranges from about 0.5 to about 4 mole percent with respect to Compound III.

9. The process of Claim 1 in which the reaction occurs in the presence of an inert hydrocarbon or chlorinated hydro-carbon solvent.

10. The process of Claim 1 in which Compound III is at up to about 10% molar excess with respect to Compound II.

11. The process of Claim 1 in which the phase transfer catalyst is a quaternary salt having the formula (R2R3R4R5M)+Q-in which R2, R3, R4, and R5 taken individually are independently selected from the group consisting of alkyl having 1 to 25 carbon atoms, alkenyl having 2 to 25 carbon atoms, aryl, alkaryl, aralkyl, and cycloalkyl having 4 to 8 carbon atoms, or any two of the groups R2, R3, R4, and R5 are joined to constitute a hexagonal or pentagonal heterocyclic moiety con-taining the quaternized M atom plus a maximum of one non-adjacent nitrogen, oxygen, or sulfur atom;
M is a member selected from the group consisting of nitrogen, phosphorus and arsenic; and Q is an anion selected from the group consisting of halide, hydroxyl, bisulfate, perchlorate, nitrate, acetate, tosylate, benzoate, and carbonate ions.

12. The process of Claim 11 in which R2, R3, R4, and R5 are independently selected from the group consisting of alkyl having 1 to 25 carbon atoms, alkenyl having from 2 to 25 carbon atoms, aryl, alkaryl, aralkyl, and cycloalkyl having from 4 to 8 carbon atoms.

13. The process of Claim 12 in which R2, R3, R4, and R5 together have a total of 10 to 70 carbon atoms.

14. The process of Claim 12 in which R2, R3, R4, and R5 together have a total of 10 to 40 carbon atoms

15. The process of Claim 12 in which R2, R3, R4, and R5 together have a total of 10 to 30 carbon atoms.

16. The process of Claim 12 in which M is a member selected from the group consisting of nitrogen and phosphorus.

17. The process of Claim 12 in which M is nitrogen.

18. The process of Claim 12 in which Q is an anion selected from the group consisting of halide, hydroxyl, and bisulfate.

19. The process of Claim 12 in which Q- is an anion selected from the group consisting of chloride, bromide, and hydroxyl.

20. The process of Claim 11 in which the phase transfer catalyst is selected from the group consisting of tetra-n-butyl-phosphonium chloride, hexadecyltributylphosphonium bromide, benzyltriethylammonium bromide, tetra-n-butylammonium bisulfate, tricaprylylmethylammonium chloride, and dimethyldicocoammonium chloride.

21. The process of Claim 1 in which R is alkoxy having 1 to 6 carbon atoms, R1 is alkoxy having 1 to 6 carbon atoms, and Z is oxygen.

22. The process of Claim 21 in which R is ethoxy, R1 is ethoxy, X is sulfur, and n is zero.

23. The process of Claim 21 in which R is ethoxy is ethoxy, X is sulfur, n is 1, and W is 4-acetyl,

24. The process of Claim 1 in which R is alkoxy having 1 to 6 carbon atoms, R1 is alkoxy having 1 to 6 carbon atoms, and Z is sulfur.

25. The process of Claim 22 in which R is ethoxy, is ethyl, X is sulfur, and n is zero.