Process for the preparation of n- (phosphonomethyl) glycine by oxidizing n-substituted n-(phosphonomethyl) glycine

A process for the preparation of N-(phosphonomethyl)glycine, a salt of N-(phosphonomethyl)glycine, or an ester of N-(phosphonomethyl)glycine, the process comprising combining an N-substituted N-(phosphonomethyl)glycine reactant with oxygen in the presence of a catalyst comprising a noble metal and a promoter,

• wherein
• the N-substituted N-(phosphonomethyl)glycine reactant has formula (V):
• 33
• R1 and R2 are independently selected from the group consisting of hydrogen, halogen, —PO3R12R13, —SO3R14, —NO2, hydrocarbyl, and substituted hydrocarbyl other than —CO2R15;
• R7, R8, R9, R12, R13, R14, and R15 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, and an agronomically acceptable cation;
• the promoter comprises a metal selected from the group consisting of aluminum, ruthenium, osmium, indium, gallium, tantalum, tin, and antimony;
• and
• at least about 0.05% by weight of the catalyst consists of the promoter.

A process for the preparation of N-(phosphonomethyl)glycine, a salt of N-(phosphonomethyl)glycine, or an ester of N-(phosphonomethyl)glycine, the process comprising:

• contacting a surface of a carbon support with an oxidizing agent;
• depositing a noble metal onto the oxidized surface to form a carbon-supported oxidation catalyst;
• and
• combining an N-substituted N-(phosphonomethyl)glycine reactant with oxygen in the presence of the carbon-supported oxidation catalyst,
• wherein the N-substituted N-(phosphonomethyl)glycine reactant has formula (V):
• 34
• R1 and R2 are independently selected from the group consisting of hydrogen, halogen, —PO3R12R13, —SO3R14, —NO2, hydrocarbyl, and substituted hydrocarbyl other than —CO2R15;
• and R7, R9, R9, R12, R13, R14, and R15 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, and an agronomically acceptable cation.

A process for the preparation of N-(phosphonomethyl)glycine, a salt of N-(phosphonomethyl)glycine, or an ester of N-(phosphonomethyl)glycine, the process comprising:

• combining an N-substituted N-(phosphonomethyl)glycine mixture comprising an N-substituted N-(phosphonomethyl)glycine reactant with oxygen in the presence of a noble metal catalyst in an oxidation reaction zone to form an N-(phosphonomethyl)glycine mixture comprising N-(phosphonomethyl)glycine, the salt of N-(phosphonomethyl)glycine, or the ester of N-(phosphonomethyl)glycine;
• separating N-(phosphonomethyl)glycine, the salt of N-(phosphonomethyl)glycine, or the ester of N-(phosphonomethyl)glycine from the N-(phosphonomethyl)glycine mixture to recover the separated N-(phosphonomethyl)glycine, salt of N-(phosphonomethyl)glycine, or ester of N-(phosphonomethyl)glycine and form a residual mixture;
• feeding at least a portion of the residual mixture back into the oxidation reaction zone,
• wherein the N-substituted N-(phosphonomethyl)glycine reactant has formula (V):
• 35
• R1 and R2 are independently selected from the group consisting of hydrogen, halogen, —PO3R12R13, —SO3R14, —NO2, hydrocarbyl, and substituted hydrocarbyl other than —CO2R15;
• and R7, R8, R9, R12, R13, R14, and R15 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, and an agronomically acceptable cation.

A process for the preparation of N-(phosphonomethyl)glycine, a salt of N-(phosphonomethyl)glycine, or an ester of N-(phosphonomethyl)glycine, the process comprising introducing oxygen into a mixture comprising an N-substituted N-(phosphonomethyl)glycine reactant and a noble metal catalyst,

• wherein
• the oxygen is introduced into the mixture through a membrane;
• the N-substituted N-(phosphonomethyl)glycine reactant has formula (V):
• 36
• R1 and R2 are independently selected from the group consisting of hydrogen, halogen, —PO3R12R13, —SO3R14, —NO2, hydrocarbyl, and substituted hydrocarbyl other than —CO2R15;
• and
• R7, R8, R9, R12, R13, R14, and R15 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, and an agronomically acceptable cation.

A process for the preparation of N-(phosphonomethyl)glycine, a salt of N-(phosphonomethyl)glycine, or an ester of N-(phosphonomethyl)glycine, the process comprising forming a reaction mixture by combining an N-substituted N-(phosphonomethyl)glycine reactant with oxygen in the presence of a noble metal catalyst,

• wherein
• no greater than about 10% by volume of the reaction mixture consists of undissolved oxygen;
• the N-substituted N-(phosphonomethyl)glycine reactant has formula (V):
• 37
• R1 and R2 are independently selected from the group consisting of hydrogen, halogen, —PO3R12R13, —SO3R14, —NR2, hydrocarbyl, and substituted hydrocarbyl other than —CO2R15;
• and
• R7, R8, R9, R12, R13, R14, and R15 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, and an agronomically acceptable cation.

A process for the preparation of N-(phosphonomethyl)glycine, a salt of N-(phosphonomethyl)glycine, or an ester of N-(phosphonomethyl)glycine, the process comprising introducing oxygen into a mixture comprising an N-substituted N-(phosphonomethyl)glycine reactant and a noble metal catalyst in a stirred tank reactor,

• wherein
• the oxygen is introduced into the mixture as gas bubbles in a manner such that essentially no gas bubbles enter a region of the reactor through which an impeller passes;
• the N-substituted N-(phosphonomethyl)glycine reactant has formula (V):
• 38
• R1 and R2 are independently selected from the group consisting of hydrogen, halogen, —PO3R12R13, —SO3R14, —NO2, hydrocarbyl, and substituted hydrocarbyl other than —CO2R15;
• and
• R7, R8, R9, R12, R13, R14, and R15 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, and an agronomically acceptable cation.

A process for the preparation of N-(phosphonomethyl)glycine, a salt of N-(phosphonomethyl)glycine, or an ester of N-(phosphonomethyl)glycine, the process comprising:

• combining an N-substituted N-(phosphonomethyl)glycine reactant with oxygen in the presence of a noble metal catalyst in an oxidation reaction zone to form an oxidation product comprising (a) a ketone, and (b) N-(phosphonomethyl)glycine, the salt of N-(phosphonomethyl)glycine, or the ester of N-(phosphonomethyl)glycine;
• separating the ketone from the oxidation product to recover the ketone;
• using the recovered ketone as a starting material to form the N-substituted N-(phosphonomethyl)glycine reactant;
• and
• combining the N-substituted N-(phosphonomethyl)glycine reactant derived from the ketone with oxygen in the presence of the noble metal catalyst in the oxidation reaction zone,
• wherein the N-substituted N-(phosphonomethyl)glycine reactant has formula (V):
• 39
• the ketone has formula (VIII):
• 40
• R1 and R2 are independently selected from the group consisting of hydrocarbyl and substituted hydrocarbyl other than —CO2R15;
• and R7, R8, R9, and R15 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, and an agronomically acceptable cation.

A process for the preparation of N-(phosphonomethyl)glycine or a salt thereof, the process comprising:

• converting an N-substituted glycine salt into an N-substituted glycine free acid,
• phosphonomethylating the N-substituted glycine free acid to form an N-substituted N-(phosphonomethyl)glycine, and
• combining the N-substituted N-(phosphonomethyl)glycine or a salt thereof with oxygen in the presence of a noble metal catalyst in an oxidation reaction zone,
• wherein the N-substituted glycine free acid has formula (XII):
• 47
• the N-substituted glycine salt has formula (XIII):
• 48
• the N-substituted N-(phosphonomethyl)glycine has formula (I):
• 49
• R1 and R2 are independently selected from the group consisting of hydrogen, halogen, —PO3R12R13, —SO3R14, —NO2, hydrocarbyl, and substituted hydrocarbyl other than —CO2R15;
• R6 is an agronomically acceptable cation;
• R12, R13, and R14 are independently selected from the group consisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl;
• and R15 is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, and an agronomically acceptable cation.

A process for the preparation of an N-substituted N-(phosphonomethyl)glycine or a salt thereof, the process comprising:

• combining a source of H3PO3, a source of CH2O, and an N-substituted glycine salt in a reaction zone to form a first mixture which comprises (a) the N-substituted N-(phosphonomethyl)glycine or the salt thereof, and (b) a salt precipitate;
• separating salt precipitate from the first mixture to form a second mixture which comprises the N-substituted N-(phosphonomethyl)glycine or the salt thereof;
• adding a base to the second mixture to precipitate N-substituted N-(phosphonomethyl)glycine or the salt thereof;
• and
• separating the precipitated N-substituted N-(phosphonomethyl)glycine or salt thereof from the second mixture to recover the precipitated N-substituted N-(phosphonomethyl)glycine or salt thereof and form a residual mixture,
• wherein the N-substituted N-(phosphonomethyl)glycine has formula (I):
• 50
• the N-substituted glycine salt has formula (XIII):
• 51
• R1 and R2 are independently selected from the group consisting of hydrogen, halogen, —PO3R12R13, —SO3R14, —NO2, hydrocarbyl, and substituted hydrocarbyl other than —CO2R15;
• R6 is an agronomically acceptable cation;
• R12, R13, and R14 are independently selected from the group consisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl;
• and R15 is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, and an agronomically acceptable cation.

A process for the preparation of an N-substituted N-(phosphonomethyl)glycine or a salt thereof, the process comprising:

• combining a source of H3PO3 and an N-substituted glycine salt in a reaction zone to form a first mixture which comprises (a) an N-substituted glycine free acid, and (b) a salt precipitate;
• separating salt precipitate from the first mixture to form a second mixture comprising the N-substituted glycine free acid;
• adding a source of CH2O to the second mixture to form a third mixture which comprises the N-substituted N-(phosphonomethyl)glycine or the salt thereof;
• adding a base to the third mixture to precipitate N-substituted N-(phosphonomethyl)glycine or the salt thereof;
• and
• separating precipitated N-substituted N-(phosphonomethyl)glycine or the salt thereof from the third mixture to recover the precipitated N-substituted N-(phosphonomethyl)glycine or salt thereof and form a residual mixture;
• wherein the N-substituted N-(phosphonomethyl)glycine has formula (I):
• 52
• the N-substituted glycine salt has formula (XIII):
• 53
• the N-substituted glycine free acid has formula (XII):
• 54
• R1 and R2 are independently selected from the group consisting of hydrogen, halogen, —PO3R12R13, —SO3R14, —NO2, hydrocarbyl, and substituted hydrocarbyl other than —CO2R15;
• R6 is an agronomically acceptable cation;
• R12, R13, and R14 are independently selected from the group consisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl;
• and R15 is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, and an agronomically acceptable cation.

A process for the preparation of an N-substituted monoethanolamine, the process comprising combining a ketone, monoethanolamine, and H2 in the presence of a metal-containing catalyst and essentially in the absence of any non-reactive solvent,

• wherein the N-substituted monoethanolamine has formula (XI):
• 55
• the ketone has formula (VIII):
• 56
• R1 and R2 are independently selected from the group consisting of hydrocarbyl and substituted hydrocarbyl.