# US 4,396,556 A · Process of preparing organophosphorus compounds by phase transfer catalysis

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 4,396,556 A
- Document ID: US4396556A
- Status: Granted
- Kind: A
- Application number: 06/239,731
- Filed: 1981-03-02
- Granted: 1983-08-02
- Earliest claimed: 1981-03-02
- Assignees: Occidental Research Corporation
- Inventors: Kenneth M. Kem
- Web page: https://patentgrep.com/patent/US4396556A

## CPC

- C22B 3/3844: {Phosphonic acid, e.g. H2P(O)(OH)2}
- C01G 56/001: {Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange}
- C07F 9/3211: {Esters of acyclic saturated acids which can have further substituents on alkyl}
- C07F 9/4006: {Esters of acyclic acids which can have further substituents on alkyl}
- C07F 9/5304: {Acyclic saturated phosphine oxides or thioxides}
- C22B 3/382: {Phosphine chalcogenides, e.g. compounds of the formula R3P=X with X = O, S, Se or Te}
- Y02P 10/20: Recycling
- C22B: PRODUCTION AND REFINING OF METALS (electrolytic C25); PRETREATMENT OF RAW MATERIALS
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Novel organic tertiary phoshine oxides and organic phoshonic acid esters, for example, bidentate organophosphorus actinide extractants, such as the carbamoylmethylphosphonates (CMP's) can be prepared (for example, in 90% or better yield and purity) by a process involving phase transfer catalysis, under conditions where degradive hydrolysis of the products or reactants is substantially avoided. For example, carbamoylmethylphosphonates can be prepared by reaction of the corresponding secondary phosphites with 2-substituted acetamides (wherever the substituent is a good leaving group, e.g. chlorine) in a two-phase system containing a high concentration of an aqueous base (preferably sodium hydroxide) and a suitable phase transfer catalyst, e.g., tetralkylammonium chlorides. Similarly, secondary phosphine oxides can be converted to novel tertiary carbamoylmethylphoshine oxides which are useful as extractants for transplutonium elements.

## Claims

### Claim 1

Process for preparing an organophosphorus compound of the formula (I): ##STR22## wherein R.sup.1 and R.sup.2 can be different or the same and are selected from the group consisting of alkoxyl containing at least 3 carbon atoms, alkyl, aryl, and aryloxyl groups, and wherein R.sup.1 and R.sup.2 can be in connection forming a heterocyclic ring structure of about 5 to about 7 members including the phosphorus atom; R.sup.3, R.sup.4, R.sup.5 and R.sup.6 can be different or the same and are selected from the group consisting of hydrogen, alkyl, or aryl groups and where R.sup.5 and R.sup.6 can be in connection forming a heterocyclic ring structure of about 3 to about 7 members including the amide nitrogen atom, said process comprising
(a) reacting an organophosphorus compound of the formula (II), wherein R.sup.1 and R.sup.2 are as defined in formula (I): ##STR23## with a 2-substituted alkanoic amide of the formula (III): ##STR24## where X is a good leaving group, and R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are as defined as in formula (I); and
(b) conducting said reacting in a liquid-liquid, two-phase system comprising an aqueous phase containing a high concentration of an aqueous base and an organic phase containing a phase transfer catalyst and under reaction conditions such that degradative hydrolysis of the products or reactants is substantially avoided and such that said organophosphorus compound of formula (I) is a product of said reaction.

### Claim 2

Process for preparing carbamoylmethylphosphonates comprising:
(a) reacting (i) a secondary phosphite ester of the formula ##STR25## wherein R.sup.1 and R.sup.2 can be different or the same and are selected from the group consisting of alkoxyl containing at least 3 carbon atoms, or aryloxyl groups, and wherein R.sup.1 and R.sup.2 can be in connection forming a heterocyclic ring structure of about 5 to about 7 members including the phosphorus atom,
with (ii) a 2-substituted alkanoic amide of the formula ##STR26## wherein X is good leaving group, and R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are the same or different and are selected from the group consisting of hydrogen, alkyl, aryl, and where R.sup.5 and R.sup.6 can be in connection forming a heterocyclic ring structure of about 3 to about 7 members including the amide nitrogen atom;
(b) conducting said reacting in a liquid-liquid two-phase system comprising an aqueous phase containing a high concentration of (iii) an aqueous base, and an organic phase containing (iv) a phase transfer catalyst under reaction conditions wherein degradative hydrolysis of the product and reactants is substantially avoided and where the carbamoylmethylphosphonate is produced; and
(c) recovering said carbamoylmethylphosphonate.

### Claim 3 (depends on 2)

The process of claim 2 wherein said reaction conditions include agitation of said two-phase system at a controlled rate such that the rate of the desired reaction is high relative to the rate of said degradative hydrolysis.

### Claim 4 (depends on 2)

The process of claim 2 wherein said reaction conditions include conducting said reacting within a temperature range such that the desired reaction proceeds at a rate which produces said carbamoylmethylphosphonate and substantially avoiding degradative hydrolysis of the products and reactants.

### Claim 5 (depends on 2)

The process of claim 2 wherein the aqueous phase of said two-phase system has a sufficiently high ionic strength so that distribution of the carbomoylmethylphosphonate, phosphite ester and 2-substituted alkanoic amide to the aqueous phase is not significant, thus preventing appreciable degradative hydrolysis of the organic species.

### Claim 6 (depends on 4)

The process of claim 4 wherein said temperature range is between about -20.degree. C. to about 50.degree. C.

### Claim 7 (depends on 5)

The process of claim 5 wherein said ionic strength is at least as great as that of a 25% by weight solution of sodium hydroxide in water.

### Claim 8 (depends on 2)

The process of claim 2 wherein X is chlorine.

### Claim 9 (depends on 2)

The process of claim 2 wherein said phase transfer catalyst is selected from quaternary ammonium compounds and quaternary phosphonium compounds.

### Claim 10 (depends on 9)

The process of claim 9 wherein said catalyst has the formula (Z).sub.4 NX' or (Z).sub.4 PX' wherein Z can be the same or different and is selected from alkyl groups containing 1-18 carbon atoms and wherein X' is selected from chloride, perchlorate, hydrogen sulfate, bromide, alkyl sulfate, and alkyl sulfonate, wherein the alkyl group has no more than about 4 carbon atoms.

### Claim 11 (depends on 9)

Th process of claim 9 wherein said catalyst has the structure (Z).sub.4 NX' or (Z).sub.4 PX' wherein no more than one Z group is an alkyl group containing less than 4 carbon atoms and the other three Z groups are alkyl groups, which can be the same or different, containing at least 4 carbon atoms.

### Claim 12 (depends on 10)

The process of claim 10 wherein said catalyst is selected from methyltricaprylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrahexylammonium chloride, and tetrabutylphosphonium chloride.

### Claim 13 (depends on 2)

The process of claim 2 wherein the 2-substituted alkanoic amide comprises an N,N-dialkylchloroacetamide of the formula: ##STR27## wherein R.sup.5 and R.sup.6 are the same or different and are alkyl groups of about 1 to about 8 carbon atoms, or can form a heterocyclic ring containing about 5 to about 7 members including the amide nitrogen atom.

### Claim 14 (depends on 2)

The process of claim 2 wherein R.sup.1 and R.sup.2 are selected from the group consisting of primary branched or linear alkoxyl groups of about 4 to 10 carbon atoms, primary linear or branched alkyl groups of from about 1 to about 12 carbon atoms; aryloxy groups which do not impart excessive water solubility to compounds of formula II; and aryl groups that do not impart excessive water solubility to compounds of formula II.

### Claim 15 (depends on 14)

The process of claim 14 wherein one of R.sup.1 and R.sup.2 is aryl and the other is not aryl.

### Claim 16 (depends on 2)

The process of claim 2 wherein at least one of R.sup.3 and R.sup.4 is hydrogen.

### Claim 17 (depends on 16)

The process of claim 16 wherein one of R.sup.3 and R.sup.4 is selected from the group consisting of alkyl groups of about 1 to about 18 carbon atoms.

### Claim 18 (depends on 2)

The process of claim 2 wherein one of R.sup.5 and R.sup.6 is hydrogen and the other is aryl.

### Claim 19 (depends on 2)

The process of claim 2 wherein one of R.sup.5 and R.sup.6 is hydrogen and the other is a linear or branched primary alkyl group containing about 4 to about 18 carbon atoms.

### Claim 20 (depends on 2)

The process of claim 2 wherein one or both of R.sup.5 and R.sup.6 is selected from branched or linear primary alkyl groups containing from about 1 to about 18 carbon atoms.

### Claim 21 (depends on 2)

The process of claim 2 wherein R.sup.5 and R.sup.6 form a heterocyclic ring containing from about 5 to about 7 members including the amide nitrogen atom.

### Claim 22 (depends on 2)

The process of claim 2 wherein R.sup.1 and R.sup.2 are selected from primary branched or linear alkyoxyl groups containing from about 4 to about 10 carbon atoms.

### Claim 23

A process for preparing an organophosphorus compound of the formula (Ia) ##STR28## said process comprising (a) reacting an organophosphorus compound of the formula (IIa) with a 2-substituted alkanoic amide of the formula (IIIa), ##STR29## wherein said reacting is conducted at a temperature in the range of about -20.degree. C. to about 40.degree. C. in a liquid-liquid two-phase system comprising a phase transfer catalyst in methylene chloride and an aqueous solution substantially saturated with respect to sodium hydroxide, said reacting being continued for sufficient time for said compound of formula (IIa) to substantially completely react with said 2-substituted alkanoic acid amide of formula (IIIa) to produce a reaction mixture containing said organophosphorus compound of formula (Ia) and for insufficient time for said organophosphorus compound of formula (Ia) to be appreciably degraded, as by hydrolysis said time being determined by analysis of the reaction mixture for said organophosphorus compound of formula (Ia) and degraded products of said organophosphorus compound of formula (Ia); and
(b) recovering said organophosphorus compound of formula (Ia) from said reaction mixture.