Granted Patent B2

US 12,358,934 · App. 17/755,076 · Granted Jul 15, 2025

Inventors: Minyang Zhuang (Beijing, CN); Hui Zheng (Beijing, CN); Xinyang Liu (Beijing, CN); Wei Liu (Beijing, CN); Yifeng He (Beijing, CN)

Assignees: CHINA PETROLEUM & CHEMICAL CORPORATION; RESEARCH INSTITUTE OF PETROLEUM PROCESSING, SINOPEC

C07F9/11C07F9/094C10M137/04

Abstract

Claims (45)

1. A phosphorus-containing compound of formula (I):

wherein, in formula (I),

n is 0, 1, 2, 3, or 4;

the plural R groups, identical to or different from each other, are independently selected from C 1 -C 6 alkylene group;

the R b group is H or C 1 -C 6 linear or branched alkyl;

the plural R 0 groups, identical to or different from each other, are independently selected from H, C 1 -C 10 linear alkyl, C 1 -C 10 branched alkyl, and

with the proviso that at least one R 0 in formula (I) is

in

x is 1, 2, or 3, y is an integer of 1 to 5, and a sum of x+y is less than or equal to a number of hydrogen atoms available to be substituted on the Ar group;

the plural R 1 groups, identical to or different from each other, are independently selected from H, C 1 -C 6 linear alkyl, and C 1 -C 6 branched alkyl, the plural Ar groups, are benzene rings, R 2 group is a single bond or C 1 -C 6 alkylene;

the plural A groups, identical to or different from each other, are independently selected from

and C 1 -C 10 linear or branched alkyl group substituted by

each X group is O, a is 1, each R′ is independently selected from C 1 -C 10 linear alkyl, C 1 -C 10 branched alkyl, benzyl optionally substituted by C 1 -C 10 linear or branched alkyl, and phenyl optionally substituted by C 1 -C 10 linear or branched alkyl.

2. The phosphorus-containing compound according to claim 1 , wherein, in

the Ar group is a benzene ring, x is 2, y is 1, OH is located at the para-position of the R 2 group, two R 1 are respectively located at the two neighboring positions of OH, and two R 1 are independently selected from C 1 -C 4 linear alkyl and C 1 -C 4 branched alkyl.

3. The phosphorus-containing compound according to claim 1 , wherein, in formula (I), each A group is independently selected from

C 1 -C 4 linear alkyl substituted by

and C 1 -C 4 branched alkyl substituted by

4. The phosphorus-containing compound according to claim 1 , wherein the phosphorus-containing compound is selected from

5. A method for preparing a phosphorus-containing compound according to claim 1 comprising:

step (1): reacting the compound of formula (II) and/or inorganic acid salt thereof with the compound of formula (III) to obtain the product of step (1),

in formula (II), n is 0, 1, 2, 3, or 4 the plural R groups, identical to or different from each other, are independently selected from C 1 -C 6 alkylene group; the R b group is H, C 1 -C 6 linear alkyl, or C 1 -C 6 branched alkyl;

the plural R 0 ′ groups, identical to or different from each other, are independently selected from H, C 1 -C 10 linear alkyl, and C 1 -C 10 branched alkyl, with the proviso that at least one R 0 ′ is H,

the plural A′ groups, identical to or different from each other, are independently selected from XA′″, C 1 -C 10 linear alkyl optionally substituted by XA′″, and C 1 -C 10 branched alkyl substituted by XA′″, A′″ is H,

X group is O;

the inorganic acid salt of the compound of formula (II) is

wherein M is the inorganic acid radical, j is the absolute value of the charge number of said inorganic acid radical, z is an integer between 1 and 10, and each of the other groups is defined as in formula (II), the inorganic acid salt of said compound of formula (II) is hydrochloride salt, nitrate salt, or sulfate salt;

in formula (III), each X group is O, a is 1, each R″ is independently selected from C 1 -C 10 linear or branched alkyl, benzyl optionally substituted by C 1 -C 10 linear or branched alkyl, and phenyl optionally substituted by C 1 -C 10 linear or branched alkyl;

and step (2): reacting the product of step (1) with the compound of formula (IV) to obtain the product of step (2),

wherein x is 1, 2, or 3, y is an integer between 1 and 5, and the sum of x+y is less than or equal to the number of hydrogen atoms available for subsitution on the Ar group; the plural R 1 groups, identical to or different from each other, and are independently selected from H, C 1 -C 6 linear alkyl, and C 1 -C 6 branched alkyl, the Ar group is a benzene ring, the R 2 group is a single bond or C 1 -C 6 alkylene, and X′ is F, Cl, Br, I or OH.

6. The method according to claim 5 , wherein the compound of formula (II) and/or the inorganic acid salt thereof is one or more selected from an amino acid, a condensate of amino acids, an inorganic salt of an amino acid, and an inorganic salt of a condensate of amino acids.

7. The method according to claim 5 , wherein the compound of formula (II) and/or the inorganic acid salt thereof is selected from one or more of the following compounds: L-serine, L-serine ester hydrochloride, L-leucine, L-leucine ester hydrochloride, L-isoleucine, L-isoleucine ester hydrochloride, glycine, glycine ester hydrochloride, L-phenylalanine, L-phenylalanine ester hydrochloride, L-valine, and L-valine ester hydrochloride, and

the compound of formula (III) is selected from phosphorous acid, dimethyl phosphite, diethyl phosphite, dipropyl phosphite, diisopropyl phosphite, di-n-butyl phosphite, diisobutyl phosphite, di-tert-butyl phosphite, (2-ethylhexyl) phosphite, dibenzyl phosphite, diphenyl phosphite, thiophosphorous acid, dimethyl thiophosphite, diethyl thiophosphite, dipropyl thiophosphite, diisopropyl thiophosphite, di-n-butyl thiophosphite, diisobutyl thiophosphite, di-tert-butyl thiophosphite, 2-ethylhexyl thiophosphite, dibenzyl thiophosphate, and diphenyl thiophosphite.

8. The method according to claim 5 , wherein, in step (1), the reaction molar equivalent ratio of the compound of formula (II) and/or the inorganic acid salt thereof (calculated as XA′″) to the compound of formula (III) (calculated as P-H) is 1:5 to 5:1; and the reaction temperature is −40 to 80° C.

9. The method according to claim 5 , wherein, in step (1), a solvent is added to the reaction of the compound represented of formula (II) and/or the inorganic acid salt thereof with the compound of formula (III);

a catalyst is optionally added;

a chloride is optionally added;

and optionally the reaction is carried out at pH 8-10.

10. The method according to claim 5 , wherein, in step (1), after the reaction of the compound of formula (II) and/or the inorganic acid salt thereof with the compound of formula (III), the reaction product is subject to one or more of extraction treatment, a drying treatment, or an ultrasonic treatment;

wherein the extraction treatment is carried out by a solvent in an acidic environment;

wherein the drying treatment is an ultrasonic treatment in the presence of a solvent for 1-10 hours.

11. The method according to claim 5 , wherein, in step (2), the compound of formula (IV) is selected from one or more of the following compounds: 3,5-bis(tert-butyl)-4-hydroxyphenylacetyl chloride, 3,5-bis(tert-butyl)-4-hydroxyphenylpropionyl chloride, p-hydroxyphenylacetyl chloride, 3-hydroxyphenylacetyl chloride, 2-hydroxyphenylacetyl chloride, 3,4-dihydroxyphenylacetyl chloride, 3,5-dihydroxyphenylacetyl chloride, 3-methyl-4-hydroxyphenylacetyl chloride, 3,5-dimethyl-4-hydroxyphenylacetyl chloride, 2,4-dihydroxyphenylpropionyl chloride, and 3,4-dihydroxyphenylpropionyl chloride.

12. The method according to claim 5 , wherein, in an optional step (2), the reaction molar equivalent ratio of the compound (calculated as X′) of the formula (IV) to the reaction product (calculated as NH) of the step (1) is 5:1-1:5; the reaction temperature is −40 to 60° C.

13. The phosphorus-containing compound according to claim 1 , wherein the plural R 0 groups, identical to or different from each other, are independently selected from H, C 1 -C 4 linear alkyl, C 1 -C 4 branched alkyl, and

with the proviso that at least one R 0 in formula (I) is

Assignments (1)

Priority Claims (1)

Continuity (1)

References Cited (23)