# US 11,306,112 B2 · Biphenyl tetradentate phosphite compound: preparation method and application thereof

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- Number: US 11,306,112 B2
- Document ID: US11306112B2
- Status: Granted
- Kind: B2
- Application number: 17/172,021
- Filed: 2021-02-09
- Published: 2021-08-26
- Granted: 2022-04-19
- Earliest claimed: 2020-02-10
- Assignees: Guangdong Oxo Chem Ltd.
- Applicants: Huizhou Catalys Technology Co., Ltd
- Inventors: Runtong Zhang; Xin Yan; Jianghua Peng; Jianxin Wang; Xintong He
- Web page: https://patentgrep.com/patent/US11306112B2

## CPC

- C07F 9/65746: {the molecule containing more than one cyclic phosphorus atom}
- B01J 31/2213: {At least two complexing oxygen atoms present in an at least bidentate or bridging ligand}
- B01J 31/223: {At least two oxygen atoms present in one at least bidentate or bridging ligand}
- C07C 37/60: by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
- C07C 45/50: by oxo-reactions
- C07C 45/505: {Asymmetric hydroformylation}
- B01J 2231/321: Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
- B01J 2531/0266: Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
- B01J 2531/822: Rhodium
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

The disclosure relates to chemical synthesis, and more particularly to a biphenyltetradentate phosphite compound and a preparation and application thereof. The compound has a structure of formula(I):

## Claims

### Claim 1

A biphenyl tetradentate phosphite compound of formula(I):
wherein R is selected from the group consisting of:
and hydrogen.

### Claim 2 (depends on 1)

A method of preparing the biphenyl tetradentate phosphite compound of claim 1, comprising:
reacting a biphenyl tetraphenol compound with phosphorochloridite in an organic solvent in the presence of n-butyl lithium to produce the biphenyl tetradentate phosphite compound;
wherein the phosphorochloridite is selected from L1-L26.

### Claim 3 (depends on 2)

The method of claim 2, the step of “reacting a biphenyl tetraphenol compound with phosphorochloridite” comprises:
adding the biphenyl tetraphenol compound and the organic solvent to a reactor successively under a nitrogen atmosphere; dropwise adding the n-butyl lithium at a low temperature; and heating the reaction mixture to room temperature followed by reaction under reflux; and
dropwise adding a phosphorochloridite solution of the biphenyl, methylene dibenzyl, binaphthyl, benzoyloxy, ortho-phenyl, phenyl, naphthyl or aryl group at low temperature; and reacting the reaction mixture at room temperature followed by concentration to obtain the biphenyl tetradentate phosphite compound.

### Claim 4 (depends on 3)

The method of claim 3, wherein the biphenyl tetraphenol compound is prepared by a reaction of 4,6-di(tert-butyl)benzene-1,3-diol under the action of a metallic oxidant, an acid and a reaction solvent.

### Claim 5 (depends on 3)

The method of claim 3, wherein the biphenyl tetraphenol compound is prepared through steps of:
dissolving 4,6-di(tert-butyl)benzene-1,3-diol in an acid in a reacting kettle; dropwise adding a metallic oxidant and a reaction solvent; and reacting the reaction mixture at −20-50° C. for 1-12 h followed by filtration to obtain the biphenyl tetraphenol compound; wherein a molar ratio of the metallic oxidant to the 4,6-di(tert-butyl)benzene-1,3-diol is (0.1-1.5):1.

### Claim 6 (depends on 4)

The method of claim 4, wherein the acid is selected from the group consisting of concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid, phosphonic acid, hexafluorophosphoric acid, hypochlorous acid, chlorous acid, formic acid, glacial acetic acid, peroxyacetic acid, 3-chloroperoxybenzoic acid, acetic anhydride, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, capric acid, adipic acid, oxalic acid, malonic acid, succinic acid and a combination thereof.

### Claim 7 (depends on 4)

The method of claim 4, wherein the metallic oxidant is selected from the group consisting of cuprous chloride, copper chloride, cuprous iodide, copper iodide, cuprous bromide, cupric bromide, copper sulfate, cupric nitrate, copper trifluoromethanesulfonate, ferrous chloride, ferric trichloride, nickel oxide, nickel dioxide, manganese trioxide, active manganese dioxide, potassium permanganate, cobalt(III) fluoride, cobaltic oxide, chromium trioxide, chromium dioxide, chromium(III) oxide, chromic acid, potassium dichromate, sodium dichromate, magnesium oxide, sodium iodate, sodium periodate, sodium hypochlorite, sodium chlorite, sodium chlorate, sodium perchlorate, potassium iodate, potassium periodate, potassium hypochlorite, potassium chlorite, potassium chlorate, potassium perchlorate, potassium persulfate, potassium hydrogen persulfate and a combination thereof.

### Claim 8 (depends on 3)

The method of claim 3, wherein the biphenyl tetraphenol compound is prepared by a reaction of 4,6-di(tert-butyl)benzene-1,3-diol under the action of a metal complex, a basic compound, an oxygen source and a reaction solvent.

### Claim 9 (depends on 3)

The method of claim 3, wherein the biphenyl tetraphenol compound is prepared through steps of:
adding a reaction solvent, an basic compound and a metal complex sequentially to a reacting kettle: reacting the reaction mixture at room temperature under stirring in the presence of an oxygen source to prepare a metal-organic base complex; dropwise adding 4,6-di(tert-butyl)benzene-1,3-diol to the reacting kettle, wherein the oxygen source is continuously introduced; and reacting the reaction mixture at −20-50° C. for 24-28 h followed by filtration to obtain the biphenyl tetraphenol compound, wherein a molar ratio of the metal complex to the 4,6-di(tert-butyl)benzene-1,3-diol is (0.005-0.1):1.

### Claim 10 (depends on 4)

The method of claim 4, wherein the reaction solvent is selected from a group consisting of water, methanol, ethanol, isopropanol, n-butanol, tert-butanol, dichloromethane, dichloroethane, trichloromethane, benzene, toluene, xylene, 1,2-dichlorobenzene, ethyl acetate, dioxane, tetrahydrofuran, acetone, glacial acetic acid, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and a combination thereof.

### Claim 11 (depends on 5)

The method of claim 5, wherein the reaction solvent is selected from a group consisting of water, methanol, ethanol, isopropanol, n-butanol, tert-butanol, dichloromethane, dichloroethane, trichloromethane, benzene, toluene, xylene, 1,2-dichlorobenzene, ethyl acetate, dioxane, tetrahydrofuran, acetone, glacial acetic acid, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and a combination thereof.

### Claim 12 (depends on 8)

The method of claim 8, wherein the oxygen source is selected from the group consisting of oxygen, air, ozone, diacetoxyiodobenzene, hydrogen peroxide, tert-butyl hydroperoxide, dibenzoyl peroxide, cyclohexanone peroxide, p-benzoquinone, dichlorodicyanobenzoquinone and a combination thereof.

### Claim 13 (depends on 8)

The method of claim 8, wherein the metal complex is selected from the group consisting of CuOAc, Cu(OAc)2, Cu(OTf)2, [Cu(NH3)4]SO4, [Cu(NH3)4](OH)2, CuCl(OH)TMEDA, Cu(TMEDA)Cl, Cu(TMEDA)Cl2, Cu(Et3N)Cl2, Cu(DTEDA)Cl2, Cu(morpholine)2Cl2, Cu(PDA)2Cl2, Cu2(TEEDA)2Br2, [Cu(MeCN)4][PF6], Cu(PPh3)2Cl2, K3[Fe(CN)6], K4[Fe(CN)6], K3[Fe(NCS)6], Na3[Fe(CN)], Na4[Fe(CN)6], Na3[Fe(NCS)6], Fe(PPh3)Cl, Ni(acac)2, Ni(OAc)2, Ni(CO)4, Mn(acac)2, Mn(OAc)2, Co(acac)2, Co(acac)3, [Co(NH3)3]Cl, [Co(NH3)6]Cl3, [Co(NO2)3(NH3)3], Co(OAc)2, CrCl3.6H2O, [Cr(H2O)6]Cl3, [CrCl(H2O)5]Cl2, [CrCl2(H2O)4]Cl, [CrCl2(H2O)4]Cl.2H2O, pyridinium chlorochromate, pyridinium dichromate, [Mg(ClO4)2].6H2O and a combination thereof.

### Claim 14 (depends on 8)

The method of claim 8, wherein the basic compound is selected from the group consisting of methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, N,N′-dimethylaniline, N-methylaniline, aniline, diphenylamine, ethylenediamine, N-methylethylenediamine, N,N-dimethylethylenediamine, N,N′-dimethylethylenediamine, N,N,N′-trimethylethylenediamine, N,N,N′,N′-tetramethylethylenediamine, N-ethylethylenediamine, N,N′-diethylethylenediamine, N,N-diethylethylenediamine, N,N,N′-triethylethylenediamine, N,N,N′,N′-tetradiethylethylenediamine, N,N-di-tert-butylethylenediamine, N,N,N′,N′-Tetramethylpropylenediamine, carbonamide, tetrahydropyrrole, imidazole, pyridine, piperidine, morpholine, potassium hydroxide and a combination thereof.

### Claim 15 (depends on 3)

The method of claim 3, wherein the biphenyl tetraphenol compound is prepared through steps of:
grinding resorcinol and sodium bicarbonate into powders followed by adding dimethyl sulfate; and reacting the reaction mixture under stirring at high temperature followed by washing and filtration to obtain 3-methoxyphenol;
adding toluene and an acid to the 3-methoxyphenol, and reacting the reaction mixture at a high temperature to produce 2,4-di-tert-butyl-5-methoxyphenol, wherein isobutylene is continuously introduced;
adding methanol and a mixture of potassium ferricyanide and potassium hydroxide to the 2,4-di-tert-butyl-5-methoxy-phenol; reacting the reaction mixture at room temperature to obtain 3,3′,5,5′-tetra-tert-butyl-6,6′-dimethoxy-2,2′-dihydroxy-1,1′-biphenyl; and
adding dichloromethane to the 3,3′,5,5′-tetra-tert-butyl-6,6′-dimethoxy-2,2′-dihydroxy-1,1′-biphenyl under nitrogen atmosphere; and dropwise adding boron tribromide for a reaction to obtain the biphenyl tetraphenol compound.

### Claim 16 (depends on 3)

The method of claim 3, wherein the biphenyl tetraphenol compound is prepared through steps of:
adding toluene and an acid to resorcinol followed by a high-temperature reaction to obtain 4,6-di-tert-butyl-1,3-dihydroxy benzene, wherein isobutylene is continuously introduced;
dissolving the 4,6-di-tert-butyl-1,3-dihydroxy benzene in dichloromethane; adding successively a hydroxyl protecting agent and N,N-diisopropylethylamine; and reacting the reaction mixture at room temperature to obtain 2,4-di-tert-butyl-5-methoxy methyl ether-phenol;
adding methanol to the 2,4-di-tert-butyl-5-methoxy methyl ether-phenol, and dropwise adding a mixture of potassium ferricyanide and potassium hydroxide; reacting the reaction mixture at room temperature to obtain 3,3′,5,5′-tetra-tert-butyl-6,6′-dimethoxy-2,2′-dihydroxy-1,1′-biphenyl; and
dissolving the 3,3′,5,5′-tetra-tert-butyl-6,6′-dimethoxy-2,2′-dihydroxy-1,1′-biphenyl in isopropanol; dropwise adding concentrated hydrochloric acid; and reacting the reaction mixture under stirring to obtain the biphenyl tetraphenol compound.

### Claim 17 (depends on 3)

The method of claim 3, wherein the biphenyl tetraphenol compound is prepared through steps of:
sequentially adding tetrahydrofuran and tetramethylethylenediamine tom-dimethoxybenzene; adding n-butyl lithium and ferric chloride under an argon atmosphere and a low temperature; and reacting the reaction mixture at room temperature to obtain 2,2′,6,6′-tetramethoxy-1,1′-biphenyl;
adding dichloromethane to the 2,2′,6,6′-tetramethoxy-1,1′-biphenyl; adding dropwise boron tribromide at the low temperature: reacting the reaction mixture under heating to obtain 2,2′,6,6′-tetrahydroxy-1,1′-biphenyl; and
adding tetrahydrofuran and an acid to the 2,2′,6,6′-tetrahydroxy-1,1′-biphenyl in nitrogen atmosphere for a reaction to obtain the biphenyl tetraphenol compound, wherein isobutylene is continuously introduced.

### Claim 18 (depends on 15)

The method of claim 15, wherein the acid is selected from the group consisting of formic acid, acetic acid, oxalic acid, dichloroacetic acid, trifluoroacetic acid, propionic acid, malonic acid, pyruvic acid, butyric acid, valeric acid, caproic acid, adipic acid, benzoic acid, p-nitrobenzoic acid, terephthalic acid, benzenesulfonic acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluene sulfonic acid, hydrobromic acid, hydrochloric acid, hydrofluoric acid, sulfurous acid, sulfuric acid, perchloric acid, phosphonic acid, pyrophosphoric acid, nitric acid, nitrous acid, chromic acid, fluoroantimony sulfonic acid, fluoroantimonic acid and a combination thereof.

### Claim 19 (depends on 16)

The method of claim 16, wherein the hydroxyl protecting agent is selected from the group consisting of 2-chlorotetrahydro-2H-pyran, 2-chloro-2-methylpropane, allyl chloride, benzyl chloride, tert-butyldiphenylchlorosilane, acetyl chloride, trimethylacetyl chloride, benzoyl chloride, tert-butyldimethylsilyl chloride and a combination thereof.

### Claim 20 (depends on 1)

An application of the biphenyl tetradentate phosphite compound of claim 1 in the hydroformylation reaction of a C2-C10 olefin, comprising:
adding the biphenyl tetradentate phosphite compound and a rhodium catalyst successively to a reactor in an inert gas, wherein a molar ratio of the biphenyl tetradentate phosphate compound to the rhodium catalyst is (1-5):1; and subjecting the biphenyl tetradentate phosphite compound to complexation in an organic solvent at room temperature under stirring;
adding a mixed butene, a etherified butene, cis-2-butene or trans-2-butene to the reactor under inert gas such that a concentration of the rhodium catalyst is controlled at 50-200 ppm; and subjecting the reaction mixture to a reaction at room temperature under stirring; and
introducing hydrogen and carbon monoxide into the reactor, wherein a pressure or volume ratio of the hydrogen to the carbon monoxide is (1-1.5):1 or 1:(1-1.5) and a total pressure is 0.5-1.5 MPa; and reacting the reaction mixture at 40-80° C. under stirring for 1-4 h.