US4396556A
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Process of preparing organophosphorus compounds by phase transfer catalysis
Assignee: Occidental Research Corp
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Filing: 1981-03-02
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Granted: 1983-08-02
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Expires: 2001-03-02
Abstract
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.
Inventors
- 👤 Kenneth M. Kem
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 10:45
CPC Classifications
C; C22; C22B; C22B3/00; C22B3/20; C22B3/26; C22B3/38; C22B3/384; C22B3/3844; C01; C01G; C01G56/00; C01G56/001; C07; C07F; C07F9/00; C07F9/02; C07F9/28; C07F9/30; C07F9/32; C07F9/3205; C07F9/3211; C07F9/38; C07F9/40; C07F9/4003; C07F9/4006; C07F9/50; C07F9/53; C07F9/5304; C22B3/382; Y; Y02; Y02P; Y02P10/00; Y02P10/20
Claims Analysis
Total Claims: 26
Claim 1
Independent Claim
251 words
Process for preparing an organophosphorus compound of the formula (I): ##STR22## wherein R 1 and R 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 1 and R 2 can be in connection forming a heterocyclic ring structure of about 5 to about 7 members including the phosphorus atom; R 3 , R 4 , R 5 and R 6 can be different or the same and are selected from the group consisting of hydrogen, alkyl, or aryl groups and where R 5 and R 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 1 and R 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 3 , R 4 , R 5 and R 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
Dependent Claim
251 words
Process for preparing an organophosphorus compound of the formula (I): ##STR22## wherein R 1 and R 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 1 and R 2 can be in connection forming a heterocyclic ring structure of about 5 to about 7 members including the phosphorus atom; R 3 , R 4 , R 5 and R 6 can be different or the same and are selected from the group consisting of hydrogen, alkyl, or aryl groups and where R 5 and R 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 1 and R 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 3 , R 4 , R 5 and R 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 3
Dependent Claim
202 words
Process for preparing carbamoylmethylphosphonates comprising: (a) reacting (i) a secondary phosphite ester of the formula ##STR25## wherein R 1 and R 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 1 and R 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 3 , R 4 , R 5 and R 6 are the same or different and are selected from the group consisting of hydrogen, alkyl, aryl, and where R 5 and R 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 4
Dependent Claim
202 words
Process for preparing carbamoylmethylphosphonates comprising: (a) reacting (i) a secondary phosphite ester of the formula ##STR25## wherein R 1 and R 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 1 and R 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 3 , R 4 , R 5 and R 6 are the same or different and are selected from the group consisting of hydrogen, alkyl, aryl, and where R 5 and R 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 5
Dependent Claim
37 words
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 6
Dependent Claim
40 words
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 7
Dependent Claim
47 words
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 8
Dependent Claim
18 words
The process of claim 4 wherein said temperature range is between about -20° C. to about 50° C.
Claim 9
Dependent Claim
27 words
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 10
Dependent Claim
9 words
The process of claim 2 wherein X is chlorine.
Claim 11
Dependent Claim
20 words
The process of claim 2 wherein said phase transfer catalyst is selected from quaternary ammonium compounds and quaternary phosphonium compounds.
Claim 12
Dependent Claim
64 words
The process of claim 9 wherein said catalyst has the formula (Z) 4 NX' or (Z) 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 13
Dependent Claim
57 words
Th process of claim 9 wherein said catalyst has the structure (Z) 4 NX' or (Z) 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 14
Dependent Claim
23 words
The process of claim 10 wherein said catalyst is selected from methyltricaprylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrahexylammonium chloride, and tetrabutylphosphonium chloride.
Claim 15
Dependent Claim
58 words
The process of claim 2 wherein the 2-substituted alkanoic amide comprises an N,N-dialkylchloroacetamide of the formula: ##STR27## wherein R 5 and R 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 16
Dependent Claim
75 words
The process of claim 2 wherein R 1 and R 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 17
Dependent Claim
21 words
The process of claim 14 wherein one of R 1 and R 2 is aryl and the other is not aryl.
Claim 18
Dependent Claim
17 words
The process of claim 2 wherein at least one of R 3 and R 4 is hydrogen.
Claim 19
Dependent Claim
30 words
The process of claim 16 wherein one of R 3 and R 4 is selected from the group consisting of alkyl groups of about 1 to about 18 carbon atoms.
Claim 20
Dependent Claim
20 words
The process of claim 2 wherein one of R 5 and R 6 is hydrogen and the other is aryl.
Claim 21
Dependent Claim
34 words
The process of claim 2 wherein one of R 5 and R 6 is hydrogen and the other is a linear or branched primary alkyl group containing about 4 to about 18 carbon atoms.
Claim 22
Dependent Claim
33 words
The process of claim 2 wherein one or both of R 5 and R 6 is selected from branched or linear primary alkyl groups containing from about 1 to about 18 carbon atoms.
Claim 23
Dependent Claim
28 words
The process of claim 2 wherein R 5 and R 6 form a heterocyclic ring containing from about 5 to about 7 members including the amide nitrogen atom.
Claim 24
Dependent Claim
29 words
The process of claim 2 wherein R 1 and R 2 are selected from primary branched or linear alkyoxyl groups containing from about 4 to about 10 carbon atoms.
Claim 25
Dependent Claim
173 words
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° C. to about 40° 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.
Claim 26
Dependent Claim
173 words
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° C. to about 40° 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.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-08-01 | 1987-01-31 | 1987-08-02 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-08-01 | 1991-01-31 | 1991-08-02 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-08-01 | 1995-01-31 | 1995-08-02 | $7700.00 | Window Closed / Lapsed |