LU103171B1 - Efficient and safe preparation method for 6-chloro-(6 hydrogen)-diphenyl [c,e][1,2]-phosphaphenanthrene (cdop) - Google Patents
Efficient and safe preparation method for 6-chloro-(6 hydrogen)-diphenyl [c,e][1,2]-phosphaphenanthrene (cdop) Download PDFInfo
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- LU103171B1 LU103171B1 LU103171A LU103171A LU103171B1 LU 103171 B1 LU103171 B1 LU 103171B1 LU 103171 A LU103171 A LU 103171A LU 103171 A LU103171 A LU 103171A LU 103171 B1 LU103171 B1 LU 103171B1
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- temperature
- cdop
- phosphorus trichloride
- phosphaphenanthrene
- diphenyl
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000004305 biphenyl Substances 0.000 title claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 21
- 239000001257 hydrogen Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 56
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 26
- 235000010292 orthophenyl phenol Nutrition 0.000 claims abstract description 24
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 13
- 239000011592 zinc chloride Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- SMWKVQOIYUNKNV-UHFFFAOYSA-N dichloro-(2-phenylphenoxy)phosphane Chemical compound ClP(Cl)OC1=CC=CC=C1C1=CC=CC=C1 SMWKVQOIYUNKNV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 238000005804 alkylation reaction Methods 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 2
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/146—Esters of phosphorous acids containing P-halide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
Disclosed is an efficient and safe preparation method for 6-Chloro-(6 hydrogen)-diphenyl [C,E][1,2]-phosphaphenanthrene (CDOP). The efficient and safe preparation method includes: 1. dropwise adding molten o-phenyl phenol into a rapidly stirred mixed solution of excessive phosphorus trichloride and anhydrous zinc chloride, rapidly dispersing the material, performing reaction to obtain a mixed solution of o-phenylphenyl dichlorophosphite and the excessive phosphorus trichloride; 2. distilling and recovering phosphorus trichloride until phosphorus trichloride is distilled off; and 3. continuously heating for reaction to obtain CDOP.
Description
H109WO6LU-PCT23017 30.06.2023
EFFICIENT AND SAFE PREPARATION METHOD FOR 6-CHLORO-(6 LU103171
HYDROGEN)-DIPHENYL [C,E][1,2]-PHOSPHAPHENANTHRENE (CDOP)
[01] The present invention relates to an efficient and safe preparation method for 6-Chloro-(6 hydrogen)-diphenyl [C,E][1,2]-phosphaphenanthrene (CDOP).
[02] 6-Chloro-(6 hydrogen)-diphenyl [C,E][1,2]-phosphaphenanthrene (CDOP) is an important fine chemical intermediate. CDOP reacts with water, after crystallization, washing and dehydration, the flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) can be prepared, the obtained product DOPO is an excellent halogen-free environment-friendly flame retardant, which can be used for flame retardant treatment of linear polyester, polyamide, epoxy resin, polyurethane and other polymer materials. CDOP contains active P-CI bonds, and can also directly react with alcohols, phenols, epoxy compounds, etc., which can be used to prepare new flame retardant products.
[03] At present, the traditional process of synthesizing CDOP is mainly the process of dropwise adding phosphorus trichloride to o-phenyl phenol (OPP) or adding phosphorus trichloride in batches under the catalysis of Lewis acid, but the process parameters are different, such as the temperature of adding phosphorus trichloride, reaction temperature and temperature keeping time. For example, in the patent CN1709897A, phosphorus trichloride was dropwise added into OPP solution with anhydrous zinc chloride added at 168-180°C to prepare CDOP, and the dropwise adding time was 7-10 h, the temperature keeping time was 9 h, and the excessive reflux of phosphorus trichloride was maintained in the whole process. In the patent CN103073597A, at 70°C, 1.1 molar equivalent of phosphorus trichloride was dropwise added into OPP solution containing anhydrous zinc chloride for 3-5 h, then temperature was raised to 180°C, and 0.2-0.4 molar equivalent of phosphorus trichloride was dropwise added for dropwise adding reaction time of 8-10h to obtain CDOP. Similarly, patents CN102229624A, CN102219806A, CN102146097A, 1
H109WO6LU-PCT23017 30.06.2023
CN10110886, US5650530 and US5391798 all use the process to prepare CDOP. LU103171
[04] The traditional process is used, CDOP is prepared by dropwise adding phosphorus trichloride or in batches to o-phenyl phenol under the catalysis of Lewis acid.
In the process of dropwise adding phosphorus trichloride or in batches, the amount of OPP in the system is more than the content of P-CI in phosphorus trichloride or intermediate product in a certain period of time, and the o-phenylphenyl dichlorophosphite generated by esterification reaction continues to react with OPP to obtain di-o-phenyl monochlorophosphite and tri-o-phenyl phosphite. The reaction is reversible with the further addition of phosphorus trichloride, the generated di-o-phenyl monochlorophosphite and tri-o-phenyl phosphite react with the added phosphorus trichloride to obtain o-phenylphenyl dichlorophosphite, and then further alkylation reaction is performed at 160-180°C to obtain CDOP. The principle is described as follows: y
[05] wo :
[06] Due to the generation of di-o-phenyl monochlorophosphite and tri-o-phenyl phosphite in the reaction process, phosphorus trichloride needs to be further added to convert di-o-phenyl monochlorophosphite and tri-o-phenyl phosphite into o-phenylphenyl dichlorophosphite, and then the target product CDOP can be obtained by reaction, such that the whole reaction process becomes complicated, and the reaction efficiency is greatly reduced. In the process of obtaining CDOP by alkylation reaction, it is still necessary to add phosphorus trichloride or keep excessive reflux of phosphorus trichloride. Because of the high reaction temperature, phosphorus trichloride is decomposed to produce elemental phosphorus, and the risk factor of the process is high. Therefore, it is particularly important to study 6-Chloro-(6 hydrogen)-diphenyl [C,F][1,2]-phosphaphenanthrene (CDOP) with 2
H109WO6LU-PCT23017 30.06.2023 simple operation and high safety factor. LU103171
[07] In view of the above problems existing in the prior art, an objective of the present invention is to provide an efficient and safe preparation method for 6-Chloro-(6 hydrogen)-diphenyl [C,E][1,2]-phosphaphenanthrene (CDOP), and the method may effectively reduce reaction complexity, improve reaction efficiency and greatly improve safety of a process.
[08] The efficient and safe preparation method for 6-Chloro-(6 hydrogen)-diphenyl [C,F][1,2]-phosphaphenanthrene (CDOP) is provided by the present invention and specifically includes:
[09] 1) dropwise adding molten o-phenyl phenol into a rapidly stirred mixed solution of phosphorus trichloride and a catalyst anhydrous zinc chloride, rapidly dispersing the dropwise added material, performing reaction at low temperature for a certain time to obtain a mixed solution of o-phenylphenyl dichlorophosphite and the excessive phosphorus trichloride; according to the present invention, excessive phosphorus trichloride is added into raw materials, molar amount of P-CI is far greater than that of phenolic hydroxyl group, such that the phenolic hydroxyl group is completely reacted, and other reactions at low temperature are avoided,
[10] 2) gradually heating up the mixed solution in step 1) for distillation, recovering excessive phosphorus trichloride, and keeping the temperature for distillation at certain temperature until no phosphorus trichloride is distilled off; and
[11] 3) continuously heating the mixed solution after the phosphorus trichloride is distilled off in step 2) to certain temperature, and keeping the temperature at the temperature for reaction for a certain time to obtain 6-Chloro-(6 hydrogen)-diphenyl [C,F][1,2]-phosphaphenanthrene, that is CDOP, with a reaction equation as follows: po, + 4 4 2 — VE y no Nn + * M Mi 0 Fai
A
[12] OPP O-phenvipheny! dichlorophespinte CDOP 3
H109WO6LU-PCT23017 30.06.2023
[13] Further, the present invention further discloses that in step 1), the dropwise LU103171 adding time of the o-phenyl phenol is 2-4 hours, and the dropwise adding temperature is 0-10C.
[14] Further, the present invention further discloses that an adding molar ratio of the o-phenyl phenol to the phosphorus trichloride in step 1) is 1:1.5-2.5.
[15] Further, the present invention further discloses that mass amount of the catalyst anhydrous zinc chloride in step 1) is 0.5-1.2% of mass of the o-phenyl phenol.
[16] Further, the present invention further discloses that in step 1), the reaction temperature is 5-25°C, and the reaction time is 3-6 h.
[17] Further, the present invention further discloses that in step 1), rotation speed of rapid stirring 1s 300-500 r/min.
[18] Further, the present invention further discloses that in step 2), the phosphorus trichloride is distilled off until the temperature is raised to 120-140°C, and the temperature is kept for 2-4 h.
[19] Further, the present invention further discloses that in step 2), a recovery rate of the excessive phosphorus trichloride is greater than 95%.
[20] Further, the present invention further discloses that in step 3), temperature of keeping the temperature for reaction is 160-180°C, and time for keeping the temperature for reaction 1s 3-8 h.
[21] By using the above technology, compared with the prior art, the present invention has the following beneficial effects:
[22] According to the present invention, CDOP is prepared by using a limited method, that is, firstly, the mixed solution of the o-phenylphenyl dichlorophosphite and the phosphorus trichloride is obtained by reaction at low temperature, the excessive phosphorus trichloride is recovered by distillation, and then the CDOP is obtained by alkylation reaction and dehydrochlorination reaction at 160-180°C, and cyclization. In a
CDOP preparation process defined by the present invention, there is basically no generation of di-o-phenyl monochlorophosphite and tri-o-phenyl phosphite in a reaction process thereof, which reduces the complexity of the reaction, and greatly improves the reaction efficiency; and further, compared with a traditional method, participation of the 4
H109WO6LU-PCT23017 30.06.2023 phosphorus trichloride in the whole reaction process is avoided, thus solving the problem LU103171 of generation of elemental phosphorus and improving safety of the reaction process thereof essentially.
[23] The present invention will be further described by the following examples and comparative examples, which should not be regarded as limiting the scope of protection of the present invention.
[24] An efficient and safe preparation method for 6-Chloro-(6 hydrogen)-diphenyl [C,F][1,2]-phosphaphenanthrene (CDOP) in the examples of the present invention specifically includes: adding phosphorus oxychloride and a catalyst anhydrous zinc chloride into a jacketed reactor provided with mechanical stirring, controlling temperature to be 0-25°C by a low-temperature circulating bath, starting mechanical stirring, dropwise adding molten (65°C) o-phenyl phenol (OPP) under rapid stirring (300-500 r/min), keeping the temperature for 3-6 h after dropwise adding, slowly raising the temperature and distilling excessive phosphorus trichloride until the temperature is raised to 120-140°C, keeping the temperature for 2-4 h until no phosphorus trichloride is distilled off, then continuously heating a reaction solution to 160-180°C, keeping the temperature for 3-8 h, performing alkylation reaction for dehydrochlorination to obtain the product 6-Chloro-(6 hydrogen)-diphenyl [C,F][1,2]-phosphaphenanthrene, namely CDOP.
[25] Example 1 565 g of phosphorus trichloride and 3.5 g of anhydrous zinc chloride were added into a jacketed reactor having a capacity of 1000 ml provided with mechanical stirring, stirring (rotation speed of 400 r/min) and low-temperature circulating bath were started, temperature of the materials in the reactor was reduced to 15°C, 350 g of molten
OPP (65°C) was started to be dropwise added, temperature was kept at 15 + 2°C during dropwise addition, the temperature was kept for 4 h for reaction after the dropwise addition was completed, and then the temperature was raised to 130°C for 3 h until no phosphorus trichloride was distilled out in the system; and after the recovery of excessive phosphorus trichloride was completed, the temperature was raised to 175°C for 4 h for reaction to obtain CDOP, a yield was 94.8%, content of CDOP in the product was detected to be 96.6% by PNMR, and the product does not contain elemental phosphorus.
H109WO6LU-PCT23017 30.06.2023
[26] Example 2 425g of phosphorus trichloride and 2.8g of anhydrous zinc chloride LU103171 were added into a jacketed reactor having a capacity of 1000 ml provided with mechanical stirring, stirring (rotation speed of 500 r/min) and low-temperature circulating bath were started, temperature of the materials in the reactor was reduced to 20°C, 350 g of molten
OPP (65°C) was started to be dropwise added, temperature was kept at 20 + 2°C during dropwise addition, the temperature was kept for 3 h for reaction after the dropwise addition was completed, and then the temperature was raised to 140°C for 2 h until no phosphorus trichloride was distilled out in the system; and after the recovery of excessive phosphorus trichloride was completed, the temperature was raised to 180°C for 3 h for reaction to obtain CDOP, a yield was 89.7%, content of CDOP in the product was detected to be 93.2% by PNMR, and the product does not contain elemental phosphorus.
[27] Example 3 700 g of phosphorus trichloride and 4.2 g of anhydrous zinc chloride were added into a jacketed reactor having a capacity of 1000 ml provided with mechanical stirring, stirring (rotation speed of 300 r/min) and low-temperature circulating bath were started, temperature of the materials in the reactor was reduced to 10°C, 350 g of molten
OPP (65°C) was started to be dropwise added, temperature was kept at 10 + 2°C during dropwise addition, the temperature was kept for 5 h for reaction after the dropwise addition was completed, and then the temperature was raised to 120°C for 4 h until no phosphorus trichloride was distilled out in the system; and after the recovery of excessive phosphorus trichloride was completed, the temperature was raised to 165°C for 7 h for reaction to obtain CDOP, a yield was 96.9%, content of CDOP in the product was detected to be 98.0% by PNMR, and the product does not contain elemental phosphorus.
[28] Example 4 565 g of phosphorus trichloride and 2.8 g of anhydrous zinc chloride were added into a jacketed reactor having a capacity of 1000 ml provided with mechanical stirring, stirring (rotation speed of 400 r/min) and low-temperature circulating bath were started, temperature of the materials in the reactor was reduced to 10°C, 350 g of molten
OPP (65°C) was started to be dropwise added, temperature was kept at 10 + 2°C during dropwise addition, the temperature was kept for 4 h for reaction after the dropwise addition was completed, and then the temperature was raised to 130°C for 3 h until no phosphorus trichloride was distilled out in the system; and after the recovery of excessive phosphorus 6
H109WO6LU-PCT23017 30.06.2023 trichloride was completed, the temperature was raised to 170°C for 8 h for reaction to LU103171 obtain CDOP, a yield was 93.6%, content of CDOP in the product was detected to be 95.8% by PNMR, and the product does not contain elemental phosphorus.
[29] Comparative Example: 340 g of phosphorus trichloride and 2.8 g of anhydrous zinc chloride were added into a jacketed reactor having a capacity of 1000 ml provided with mechanical stirring, stirring (rotation speed of 300 r/min) and low-temperature circulating bath were started, temperature of the materials in the reactor was reduced to 60°C, 350 g of molten OPP (65°C) was started to be dropwise added, temperature was kept at 60 + 2°C during dropwise addition, the temperature was kept for 2 h for reaction after the dropwise addition was completed, and then the temperature was raised to 130°C for 2 h until no phosphorus trichloride was distilled out in the system; and after the recovery of excessive phosphorus trichloride was completed, the temperature was raised to 180°C for 3 h for reaction to obtain CDOP, content of CDOP in the product was detected to be 65.8% by PNMR, and a yield was 55.1%. 7
Claims (9)
1. An efficient and safe preparation method for 6-Chloro-(6 hydrogen)-diphenyl [C,F][1,2]-phosphaphenanthrene (CDOP), comprising: 1) dropwise adding molten o-phenyl phenol into a rapidly stirred mixed solution of phosphorus trichloride and a catalyst anhydrous zinc chloride, rapidly dispersing the dropwise added material, performing reaction at low temperature for a certain time to obtain a mixed solution of o-phenylphenyl dichlorophosphite and the excessive phosphorus trichloride: 2) gradually heating up the mixed solution in step 1) for distillation, recovering excessive phosphorus trichloride, and keeping the temperature for distillation at certain temperature until no phosphorus trichloride is distilled off, and 3) continuously heating the mixed solution after the phosphorus trichloride is distilled off in step 2) to certain temperature, and keeping the temperature at the temperature for reaction for a certain time to obtain 6-Chloro-(6 hydrogen)-diphenyl [C,F][1,2]-phosphaphenanthrene, with a reaction equation as follows: A { NT teeta IN 5 HO Py ci OPP O-phenvipheny] dichiorophospiute CDOP
2. The efficient and safe preparation method for 6-Chloro-(6 hydrogen)-diphenyl [C,F][1,2]-phosphaphenanthrene (CDOP) according to claim 1, wherein in step 1), the dropwise adding time of the o-phenyl phenol is 2-4 hours, and the dropwise adding temperature is 0-10°C.
3. The efficient and safe preparation method for 6-Chloro-(6 hydrogen)-diphenyl [C,F][1,2]-phosphaphenanthrene (CDOP) according to claim 1, wherein an adding molar ratio of the o-phenyl phenol to the phosphorus trichloride in step 1) is 1:1.5-2.5.
4. The efficient and safe preparation method for 6-Chloro-(6 hydrogen)-diphenyl 1
H109WO6LU-PCT23017 30.06.2023 [C,F][1,2]-phosphaphenanthrene (CDOP) according to claim 1, wherein mass amount of LU103171 the catalyst anhydrous zinc chloride in step 1) is 0.5-1.2% of mass of the o-phenyl phenol.
5. The efficient and safe preparation method for 6-Chloro-(6 hydrogen)-diphenyl [C,F][1,2]-phosphaphenanthrene (CDOP) according to claim 1, wherein in step 1), the reaction temperature is 5-25°C, and the reaction time is 3-6 h.
6. The efficient and safe preparation method for 6-Chloro-(6 hydrogen)-diphenyl [C,F][1,2]-phosphaphenanthrene (CDOP) according to claim 1, wherein in step 1), rotation speed of rapid stirring is 300-500 r/min.
7. The efficient and safe preparation method for 6-Chloro-(6 hydrogen)-diphenyl [C,F][1,2]-phosphaphenanthrene (CDOP) according to claim 1, wherein in step 2), the phosphorus trichloride is distilled off until the temperature is raised to 120-140°C, and the temperature is kept for 2-4 h.
8. The efficient and safe preparation method for 6-Chloro-(6 hydrogen)-diphenyl [C,F][1,2]-phosphaphenanthrene (CDOP) according to claim 1, wherein in step 2), a recovery rate of the excessive phosphorus trichloride is greater than 95%.
9. The efficient and safe preparation method for 6-Chloro-(6 hydrogen)-diphenyl [C,F][1,2]-phosphaphenanthrene (CDOP) according to claim 1, wherein in step 3), temperature of keeping the temperature for reaction is 160-180‘C, and time for keeping the temperature for reaction is 3-8 h. 2
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211445449.XA CN115838384A (en) | 2022-11-18 | 2022-11-18 | Efficient and safe preparation method of 6-chloro- (6-hydrogen) -diphenyl [ C, E ] [1,2] -phosphaphenanthrene |
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| Publication Number | Publication Date |
|---|---|
| LU103171B1 true LU103171B1 (en) | 2024-05-24 |
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| LU103171A LU103171B1 (en) | 2022-11-18 | 2023-06-06 | Efficient and safe preparation method for 6-chloro-(6 hydrogen)-diphenyl [c,e][1,2]-phosphaphenanthrene (cdop) |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN115838384A (en) |
| LU (1) | LU103171B1 (en) |
| WO (1) | WO2024103693A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115838384A (en) * | 2022-11-18 | 2023-03-24 | 浙江万盛股份有限公司 | Efficient and safe preparation method of 6-chloro- (6-hydrogen) -diphenyl [ C, E ] [1,2] -phosphaphenanthrene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2053053A1 (en) * | 2007-10-26 | 2009-04-29 | Ems-Patent Ag | Method for continuous manufacture of an organophosphorus compound and its utilisation |
| CN107556343B (en) * | 2017-10-20 | 2020-08-21 | 利尔化学股份有限公司 | Preparation method of DOPO and intermediate thereof |
| CN115838384A (en) * | 2022-11-18 | 2023-03-24 | 浙江万盛股份有限公司 | Efficient and safe preparation method of 6-chloro- (6-hydrogen) -diphenyl [ C, E ] [1,2] -phosphaphenanthrene |
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2022
- 2022-11-18 CN CN202211445449.XA patent/CN115838384A/en active Pending
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2023
- 2023-06-06 WO PCT/CN2023/098550 patent/WO2024103693A1/en unknown
- 2023-06-06 LU LU103171A patent/LU103171B1/en active IP Right Grant
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|---|---|
| CN115838384A (en) | 2023-03-24 |
| WO2024103693A1 (en) | 2024-05-23 |
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