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Chemical Structure| 1184-10-7 Chemical Structure| 1184-10-7

Structure of 1184-10-7

Chemical Structure| 1184-10-7

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Product Details of [ 1184-10-7 ]

CAS No. :1184-10-7
Formula : C36H30N3O6P3
M.W : 693.56
SMILES Code : C1(OP2(OC3=CC=CC=C3)=NP(OC4=CC=CC=C4)(OC5=CC=CC=C5)=NP(OC6=CC=CC=C6)(OC7=CC=CC=C7)=N2)=CC=CC=C1
MDL No. :MFCD00183774
InChI Key :RNFJDJUURJAICM-UHFFFAOYSA-N
Pubchem ID :136917

Safety of [ 1184-10-7 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Computational Chemistry of [ 1184-10-7 ] Show Less

Physicochemical Properties

Num. heavy atoms 48
Num. arom. heavy atoms 36
Fraction Csp3 0.0
Num. rotatable bonds 12
Num. H-bond acceptors 9.0
Num. H-bond donors 0.0
Molar Refractivity 200.44
TPSA ?

Topological Polar Surface Area: Calculated from
Ertl P. et al. 2000 J. Med. Chem.

121.89 Ų

Lipophilicity

Log Po/w (iLOGP)?

iLOGP: in-house physics-based method implemented from
Daina A et al. 2014 J. Chem. Inf. Model.

0.0
Log Po/w (XLOGP3)?

XLOGP3: Atomistic and knowledge-based method calculated by
XLOGP program, version 3.2.2, courtesy of CCBG, Shanghai Institute of Organic Chemistry

11.75
Log Po/w (WLOGP)?

WLOGP: Atomistic method implemented from
Wildman SA and Crippen GM. 1999 J. Chem. Inf. Model.

11.17
Log Po/w (MLOGP)?

MLOGP: Topological method implemented from
Moriguchi I. et al. 1992 Chem. Pharm. Bull.
Moriguchi I. et al. 1994 Chem. Pharm. Bull.
Lipinski PA. et al. 2001 Adv. Drug. Deliv. Rev.

5.93
Log Po/w (SILICOS-IT)?

SILICOS-IT: Hybrid fragmental/topological method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

7.73
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

7.32

Water Solubility

Log S (ESOL):?

ESOL: Topological method implemented from
Delaney JS. 2004 J. Chem. Inf. Model.

-11.31
Solubility 0.0000000034 mg/ml ; 0.0 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Insoluble
Log S (Ali)?

Ali: Topological method implemented from
Ali J. et al. 2012 J. Chem. Inf. Model.

-14.3
Solubility 0.0 mg/ml ; 0.0 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Insoluble
Log S (SILICOS-IT)?

SILICOS-IT: Fragmental method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

-13.47
Solubility 0.0 mg/ml ; 0.0 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Insoluble

Pharmacokinetics

GI absorption?

Gatrointestinal absorption: according to the white of the BOILED-Egg

Low
BBB permeant?

BBB permeation: according to the yolk of the BOILED-Egg

No
P-gp substrate?

P-glycoprotein substrate: SVM model built on 1033 molecules (training set)
and tested on 415 molecules (test set)
10-fold CV: ACC=0.72 / AUC=0.77
External: ACC=0.88 / AUC=0.94

Yes
CYP1A2 inhibitor?

Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.83 / AUC=0.90
External: ACC=0.84 / AUC=0.91

No
CYP2C19 inhibitor?

Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.80 / AUC=0.86
External: ACC=0.80 / AUC=0.87

No
CYP2C9 inhibitor?

Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set)
and tested on 2075 molecules (test set)
10-fold CV: ACC=0.78 / AUC=0.85
External: ACC=0.71 / AUC=0.81

No
CYP2D6 inhibitor?

Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set)
and tested on 1068 molecules (test set)
10-fold CV: ACC=0.79 / AUC=0.85
External: ACC=0.81 / AUC=0.87

No
CYP3A4 inhibitor?

Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set)
and tested on 2579 molecules (test set)
10-fold CV: ACC=0.77 / AUC=0.85
External: ACC=0.78 / AUC=0.86

Yes
Log Kp (skin permeation)?

Skin permeation: QSPR model implemented from
Potts RO and Guy RH. 1992 Pharm. Res.

-2.19 cm/s

Druglikeness

Lipinski?

Lipinski (Pfizer) filter: implemented from
Lipinski CA. et al. 2001 Adv. Drug Deliv. Rev.
MW ≤ 500
MLOGP ≤ 4.15
N or O ≤ 10
NH or OH ≤ 5

2.0
Ghose?

Ghose filter: implemented from
Ghose AK. et al. 1999 J. Comb. Chem.
160 ≤ MW ≤ 480
-0.4 ≤ WLOGP ≤ 5.6
40 ≤ MR ≤ 130
20 ≤ atoms ≤ 70

None
Veber?

Veber (GSK) filter: implemented from
Veber DF. et al. 2002 J. Med. Chem.
Rotatable bonds ≤ 10
TPSA ≤ 140

1.0
Egan?

Egan (Pharmacia) filter: implemented from
Egan WJ. et al. 2000 J. Med. Chem.
WLOGP ≤ 5.88
TPSA ≤ 131.6

1.0
Muegge?

Muegge (Bayer) filter: implemented from
Muegge I. et al. 2001 J. Med. Chem.
200 ≤ MW ≤ 600
-2 ≤ XLOGP ≤ 5
TPSA ≤ 150
Num. rings ≤ 7
Num. carbon > 4
Num. heteroatoms > 1
Num. rotatable bonds ≤ 15
H-bond acc. ≤ 10
H-bond don. ≤ 5

2.0
Bioavailability Score?

Abbott Bioavailability Score: Probability of F > 10% in rat
implemented from
Martin YC. 2005 J. Med. Chem.

0.17

Medicinal Chemistry

PAINS?

Pan Assay Interference Structures: implemented from
Baell JB. & Holloway GA. 2010 J. Med. Chem.

0.0 alert
Brenk?

Structural Alert: implemented from
Brenk R. et al. 2008 ChemMedChem

1.0 alert: heavy_metal
Leadlikeness?

Leadlikeness: implemented from
Teague SJ. 1999 Angew. Chem. Int. Ed.
250 ≤ MW ≤ 350
XLOGP ≤ 3.5
Num. rotatable bonds ≤ 7

No; 1 violation:MW<3.0
Synthetic accessibility?

Synthetic accessibility score: from 1 (very easy) to 10 (very difficult)
based on 1024 fragmental contributions (FP2) modulated by size and complexity penaties,
trained on 12'782'590 molecules and tested on 40 external molecules (r2 = 0.94)

5.83

Application In Synthesis of [ 1184-10-7 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Upstream synthesis route of [ 1184-10-7 ]

[ 1184-10-7 ] Synthesis Path-Upstream   1~12

  • 1
  • [ 139-02-6 ]
  • [ 1184-10-7 ]
YieldReaction ConditionsOperation in experiment
95.24% With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In acetonitrile at 30 - 80℃; for 5 h; In the same reaction vessel, was added 1000g of acetonitrile, cooled to 30°C using a solid funnel was slowly added hexachlorocyclotriphosphazene 120g (0.345mol), 1 hour addition time, the final temperature of the feed 45°C, heated up to 80 deg.] C, began to reflux, 4 hours after the reaction by HPLC timing hexachloro cyclotriphosphazene residual content of 0.20percent, the reaction was complete. first atmospheric distillation of acetonitrile, to be distilled slowly, slowly open the vacuum distillation under reduced pressure the remaining acetonitrile recovered acetonitrile 980g.Acetonitrile evaporated after addition of 2percent sodium hydroxide solution and 600ml of toluene obtained in Step 1 was heated to 55°C, stirring for 1 hour, points to the water layer, and then separately with 600ml of 5percent sodium chloride solution and 600ml of pure water, and washed once by the same method of layering a final product to obtain a toluene solution. Toluene was distilled under reduced pressure to complete a total of recovered toluene 490g. After distillation of the residual material in toluene was added 300g of dry ethanol and heated to reflux for 1 hour, then cooled to 20 deg.] C and held for one hour, centrifuged, and dried 60 deg.] C for 5 hours to obtain a white hexaphenoxycyclotriphosphazene228g, HPLC content of 99.25percent is detected, a yield of 95.24percent, a chlorine ion content was 100ppm.
References: [1] Patent: CN103435654, 2016, B, . Location in patent: Paragraph 0031; 0032.
[2] Journal of the American Chemical Society, 1976, vol. 98, p. 4143 - 4149.
[3] Journal of the Chemical Society, 1964, p. 1735 - 1741.
[4] Macromolecules, 2012, vol. 45, # 3, p. 1182 - 1189.
  • 2
  • [ 108-95-2 ]
  • [ 1184-10-7 ]
YieldReaction ConditionsOperation in experiment
98.1%
Stage #1: With potassium hydroxide; sodium hydroxide In 1,2-dichloro-benzene at 190℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,2-dichloro-benzene at 20 - 180℃; for 1 - 4 h;
Example 1; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 30 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. 3.63 g (0.031 mol) of synthesized phosphonitrile dichloride dissolved in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.010 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 175° C. The reaction was followed by HPLC and terminated 4 hours after the reaction system reached 170° C. (hereinafter the same). After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.17 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.7percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.; Second Step; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 25 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, the reaction solution of the first step was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.021 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 180° C. The reaction was followed by HPLC and terminated 1 hour after the reaction system reached 175° C. The reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 6.80 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.2percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.; Second Step; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 25 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, the reaction solution of the first step was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.211 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 180° C. The reaction was followed by HPLC and terminated 3 hours after the temperature of the reaction system reached 171° C. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water. Then, the reaction solvent was distilled off under reduced pressure. As a result, 6.80 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.1percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
98.4%
Stage #1: With potassium hydroxide; sodium hydroxide In chlorobenzene at 140℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In chlorobenzene at 20 - 140℃; for 5 h; Heating / reflux
Example 4; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 25 g of monochlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 140° C. After cooling to room temperature, 0.015 g (0.05 mmol) of (NH4)3ZnCl5 prepared was added thereto and 3.63 g (0.031 mol) of synthesized phosphonitrile dichloride dissolved in 25 g of monochlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.012 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 140° C. The reaction was followed by HPLC and terminated 5 hours after the reaction system reached a reflux state. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.14 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.4percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
98%
Stage #1: With potassium hydroxide; sodium hydroxide In 1,2-dichloro-benzene at 190℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,2-dichloro-benzene at 20 - 180℃; for 1.5 - 2.5 h;
Example 18; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 25 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, 5.00 mg of the insoluble component prepared in the above <Synthesis of phosphonitrile dichloride> was added thereto and 3.63 g (0.031 mol) of synthesized phosphonitrile dichloride dissolved in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.010 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 180° C. The reaction was followed by HPLC and terminated 1.5 hours after the reaction system reached 175° C. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.14 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.3percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.; Example 20; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 25 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, 5.00 mg of the insoluble component prepared in the above <Synthesis of phosphonitrile dichloride> was added thereto and 3.63 g (0.031 mol) of phosphonitrile dichloride purified by recrystallization dissolved in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.013 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 180° C. The reaction was followed by HPLC and terminated 1.5 hours after the reaction system reached 175° C. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.15 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.5percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.; Example 21; 5.11 g (0.054 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 25 g of o-dichlorobenzene were put in a 100 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel, a thermometer and a Dean-Stark trap. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, 2.50 mg of the insoluble component prepared in the above <Synthesis of phosphonitrile dichloride> was added thereto with stirring and 2.50 g (0.022 mol) of synthesized phosphonitrile dichloride dissolved in 15 g of o-dichlorobenzene was added dropwise thereto over 10 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.217 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating and stirring were performed at an oil bath temperature of 180° C. The temperature in the reaction system at that stage was 171° C. The reaction was followed by HPLC and terminated 2.5 hours after the reaction system reached 171° C. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. When the reaction solution was further washed with 50 ml of distilled water, oil-water separation was poor as a whole. Then, the reaction solvent was distilled off under reduced pressure. As a result, 4.90 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.0percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.; Second Step; 6.77 g (0.072 mol) of phenol, 2.64 g (0.066 mol) of sodium hydroxide, 0.34 g (0.006 mol) of potassium hydroxide and 25 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, the reaction solution of the first step was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.015 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 180° C. The reaction was followed by HPLC and terminated 1 hour after the temperature of the reaction system reached 175° C. The reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 6.77 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.4percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
98.3%
Stage #1: With potassium hydroxide; sodium hydroxide In 1,2-dichloro-benzene at 190℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,2-dichloro-benzene at 20 - 180℃; for 2 h;
Example 12; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 25 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, 0.007 g (0.05 mmol) of CoCl2 was added thereto and 3.63 g (0.031 mol) of synthesized phosphonitrile dichloride dissolved in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.018 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 180° C. The reaction was followed by HPLC and terminated 2 hours after the reaction system reached 175° C. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.14 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.3percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
98.2%
Stage #1: With potassium hydroxide; sodium hydroxide In 1,2-dichloro-benzene at 190℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,2-dichloro-benzene at 20 - 180℃; for 2 h;
Example 14; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 25 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, 0.005 g (0.05 mmol) of CuCl was added thereto and 3.63 g (0.031 mol) of synthesized phosphonitrile dichloride dissolved in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.012 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 180° C. The reaction was followed by HPLC and terminated 2 hours after the reaction system reached 175° C. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.13 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.2percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
98.6%
Stage #1: With potassium hydroxide; sodium hydroxide In 1,2-dichloro-benzene at 190℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,2-dichloro-benzene at 20 - 180℃; for 2 h;
Example 10; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 25 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, 0.007 g (0.05 mmol) of ZnCl2 was added thereto and 3.63 g (0.031 mol) of synthesized phosphonitrile dichloride dissolved in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.017 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 180° C. The reaction was followed by HPLC and terminated 2 hours after the reaction system reached 175° C. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.16 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.6percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
98.1%
Stage #1: With potassium hydroxide; sodium hydroxide In 1,2-dichloro-benzene at 190℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,2-dichloro-benzene at 20 - 180℃; for 2 h;
Example 11; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 25 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, 0.005 g (0.05 mmol) of MgCl2 was added thereto and 3.63 g (0.031 mol) of synthesized phosphonitrile dichloride dissolved in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.019 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 180° C. The reaction was followed by HPLC and terminated 2 hours after the reaction system reached 175° C. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.12 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.1percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
98.5%
Stage #1: With potassium hydroxide; sodium hydroxide In 1,2-dichloro-benzene at 190℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,2-dichloro-benzene at 20 - 175℃; for 3 h;
Example 5; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 25 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, 0.015 g (0.05 mmol) of (NH4)3ZnCl5 prepared was added thereto and 3.63 g (0.031 mol) of synthesized phosphonitrile dichloride dissolved in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.015 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 150° C. The reaction was followed by HPLC and terminated 3 hours after the reaction system reached 175° C. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.15 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.5percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
98.2%
Stage #1: With potassium hydroxide; sodium hydroxide In 1,2-dichloro-benzene at 190℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,2-dichloro-benzene at 20 - 180℃; for 2 h;
Example 9; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 25 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, 0.007 g (0.05 mmol) of NH4MgCl3 prepared was added thereto and 3.63 g (0.031 mol) of synthesized phosphonitrile dichloride dissolved in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.014 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 180° C. The reaction was followed by HPLC and terminated 2 hours after the reaction system reached 175° C. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.13 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.2percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
98.7%
Stage #1: With potassium hydroxide; sodium hydroxide In 1,2-dichloro-benzene at 190℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,2-dichloro-benzene at 20 - 180℃; for 1.5 h;
Example 13; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 25 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, 0.012 g (0.05 mmol) of (NH4)2CoCl4 prepared was added thereto and 3.63 g (0.031 mol) of synthesized phosphonitrile dichloride dissolved in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.016 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 180° C. The reaction was followed by HPLC and terminated 1.5 hours after the reaction system reached 175° C. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.17 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.7percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
98.4%
Stage #1: With potassium hydroxide; sodium hydroxide In 1,2-dichloro-benzene at 190℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,2-dichloro-benzene at 20 - 180℃; for 2 h;
Example 15; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 25 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, 0.012 g (0.05 mmol) of (NH4)2CoCl4 prepared was added thereto and 3.63 g (0.031 mol) of synthesized phosphonitrile dichloride dissolved in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.013 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 180° C. The reaction was followed by HPLC and terminated 2 hours after the reaction system reached 175° C. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.14 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.4percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
98.1%
Stage #1: With potassium hydroxide; sodium hydroxide In xylene at 150℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In xylene at 20 - 150℃; for 7 h;
Example 17; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 20 g of xylene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 150° C. After cooling to room temperature, 5.00 mg of the insoluble component prepared in the above <Synthesis of phosphonitrile dichloride> was added thereto and 3.63 g (0.031 mol) of synthesized phosphonitrile dichloride dissolved in 20 g of xylene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.009 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 150° C. The reaction was followed by HPLC and terminated 7 hours after the reaction system reached 140° C. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.12 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.1percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
98.9%
Stage #1: With potassium hydroxide; sodium hydroxide In xylene at 150℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In xylene at 20 - 150℃; for 8 h; Heating / reflux
Example 3; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 20 g of xylene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 150° C. After cooling to room temperature, 0.015 g (0.05 mmol) of (NH4)3ZnCl5 prepared was added thereto and 3.63 g (0.031 mol) of synthesized phosphonitrile dichloride dissolved in 20 g of xylene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.014 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 150° C. The reaction was followed by HPLC and terminated 8 hours after the reaction system reached a reflux state. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.18 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.9percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
98.5%
Stage #1: With potassium hydroxide In 1,2-dichloro-benzene at 190℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,2-dichloro-benzene at 20 - 175℃; for 2 h;
Comparative Example 1; 7.05 g (0.075 mol) of phenol, 4.20 g (0.075 mol) of potassium hydroxide and 25 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Potassium phenoxide was prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, a solution of 3.63 g (0.031 mol) of phosphonitrile dichloride, which was prepared in the above <Synthesis of phosphonitrile dichloride>, in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.019 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 175° C. The reaction was followed by HPLC and terminated 2 hours after the reaction system reached 170° C. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.15 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.5percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 2.
98.1%
Stage #1: With cesium hydroxide; sodium hydroxide In 1,2-dichloro-benzene at 190℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,2-dichloro-benzene at 20 - 180℃; for 1 h;
Example 19; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.93 g (0.0062 mol) of cesium hydroxide and 25 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, 5.00 mg of the insoluble component prepared in the above <Synthesis of phosphonitrile dichloride> was added thereto and 3.63 g (0.031 mol) of synthesized phosphonitrile dichloride dissolved in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.021 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 180° C. The reaction was followed by HPLC and terminated 1 hour after the reaction system reached 175° C. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.12 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.1percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
98.2%
Stage #1: With cesium hydroxide; sodium hydroxide In 1,2-dichloro-benzene at 190℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,2-dichloro-benzene at 20 - 180℃; for 1 - 3 h; Heating / reflux
Example 6; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.93 g (0.0062 mol) of cesium hydroxide and 30 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Cesium phenoxide and sodium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, 0.015 g (0.05 mmol) of (NH4)3ZnCl5 prepared was added thereto and 3.63 g (0.031 mol) of synthesized phosphonitrile dichloride dissolved in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.011 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 175° C. The reaction was followed by HPLC and terminated 1 hour after the reaction system reached a reflux state. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.14 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.4percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.; Example 7; 6.54 g (0.070 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.0093 g (0.062 mmol) of cesium hydroxide and 30 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Cesium phenoxide and sodium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, 0.015 g (0.05 mmol) of (NH4)3ZnCl5 prepared was added thereto and 3.63 g (0.031 mol) of synthesized phosphonitrile dichloride dissolved in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.018 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 175° C. The reaction was followed by HPLC and terminated 3 hours after the reaction system reached a reflux state. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.13 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.2percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.; Example 16; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.35 g (0.0062 mol) of potassium hydroxide and 25 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Sodium phenoxide and potassium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, 0.015 g (0.05 mmol) of (NH4)3ZnCl5 prepared was added thereto and 3.63 g (0.031 mol) of phosphonitrile dichloride purified by recrystallization dissolved in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.014 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 180° C. The reaction was followed by HPLC and terminated 2 hours after the reaction system reached 175° C. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.14 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.4percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
98%
Stage #1: With cesium hydroxide; sodium hydroxide In 1,2-dichloro-benzene at 190℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,2-dichloro-benzene at 20 - 175℃; for 3 h; Heating / reflux
Example 2; 7.05 g (0.075 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide, 0.93 g (0.0062 mol) of cesium hydroxide and 30 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Cesium phenoxide and sodium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, 3.63 g (0.031 mol) of synthesized phosphonitrile dichloride dissolved in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.018 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 175° C. The reaction was followed by HPLC and terminated 3 hours after the reaction system reached a reflux state. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.12 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 98.0percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
98% With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine; potassium hydroxide In chlorobenzene at 40 - 130℃; for 6 h; Inert atmosphere Hexachlorocyclotriphosphazene (348 g, 1 mol), phenol (677 g, 7.2 mol),Granular potassium hydroxide (403.2g, 7.2mol), added with chlorobenzene (2500ml), nitrogen protection, stirring at 40 degrees for 1 hour, heating to 130 degrees and continuing reaction for 5 hours.After the reaction was completed, 17 g of alumina powder was added to cool to room temperature, suction filtration, and the filtrate was directly concentrated.The solid product hexaphenoxycyclotriphosphazene was obtained in a yield of 98percent.
97.6%
Stage #1: With calcium hydroxide; cesium hydroxide In 1,2-dichloro-benzene at 190℃;
Stage #2: With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,2-dichloro-benzene at 20 - 175℃; for 3 h;
Example 8; 7.05 g (0.075 mol) of phenol, 3.40 g (0.046 mol) of calcium hydroxide, 0.93 g (0.0062 mol) of cesium hydroxide and 30 g of o-dichlorobenzene were put in a 200 ml four-neck flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Potassium phenoxide and calcium phenoxide were prepared by azeotropic dehydration under nitrogen flow at an oil bath temperature of 190° C. After cooling to room temperature, 0.015 g (0.05 mmol) of (NH4)3ZnCl5 prepared was added thereto and 3.63 g (0.031 mol) of the synthesized phosphonitrile dichloride trimer dissolved in 25 g of o-dichlorobenzene was added dropwise thereto over 15 minutes. Part of the reaction solution was collected by a microsyringe and the moisture content was measured. As a result, the moisture content was 0.019 mole based on 1 mole of phosphonitrile dichloride. Subsequently, heating was performed at an oil bath temperature of 175° C. The reaction was followed by HPLC and terminated 3 hours after the reaction system reached 175° C. After completion of the reaction, the reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water and the reaction solvent was distilled off under reduced pressure. As a result, 7.09 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 97.6percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
96.68% for 0.0833333 h; Microwave irradiation; Green chemistry (1) Condensation of hexachlorocyclotriphosphazene and phenol: 1.04 g (0.003 mol) of hexachlorocyclotriphosphazene, 1.86 g (0.0198 mol) of phenol,0.825g (0.0198 mol, content 96percent) sodium hydroxide into the grinding bowl thoroughly ground for about 10min, then poured into a 100mL beaker, and placed 700W Glanz home microwave oven for 5min. (2) Product purification: After the reaction, the material is taken out of the microwave oven, cooled to room temperature and stirred for 4min with water for 10min, filtered, and the filter cake is washed twice with 2mL × 2 water and dried at 90 ~ Oxycyclotriphosphazene crude 2.17 g.The crude product is heated and dissolved with 6 mL of anhydrous ethanol, then cooled to -10 ~ 0 ° C for crystallization for 4~8 h, filtered, and the filter cake is washed twice with 2 mL × 2 anhydrous ethanol and dried at 90 ° C.~100 ° C. until constant weight 2.01 g (theoretical amount 2.079 g) of hexaphenoxy cyclotriphosphazene, yield 96.68percent, melting point 109-110 ° C, purity 99.2percent.
96.81% With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine; sodium hydroxide In water; 1,1,2,2-tetrachloroethane at 145℃; for 12 h; Autoclave Into the autoclave was added an inert solvent tetrachloroethane, phenol, sodium hydroxide and water, stirred to dissolve and then heated to 145 ° C, water / azeotropic separation of water azeotropy,The solution of hexachlorocyclotriphosphazene in tetrachloroethane was added dropwise. After the addition was completed, the mixture was incubated under reflux for 12 hours, and 0.5percent of the hexachlorocyclotriphosphazene was detected.The mass ratio of phenol to sodium hydroxide is 1: 0.45. The total amount of tetrachloroethane used in inert solvent is 18 times that of hexachlorocyclotriphosphazene. The feed liquid was cooled down to 110 ° C, epoxidized soybean oil was added with a chloride ion scavenger that was greater than the chlorine content of the hexaphenoxycyclotriphosphazene, and the reaction was continued at 120 ° C for 3 hours.Then by caustic washing, pickling, washing, steam distillation and dried to give a particulate low chlorine content hexaphenoxy cyclotriphosphazene.
82% With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine; potassium carbonate In chlorobenzene at 40 - 135℃; Inert atmosphere 330.3 g of phenol and 1650 ml of chlorobenzene are added to a 2000 ml four-necked flask under nitrogen atmosphere, and stirred at room temperature for 20 to 30 minutes, and are used. 200 g of a hexachlorocyclotriphosphazene compound (which may be selected from the products of the foregoing examples as a raw material) under nitrogen protection, 485g of acid-binding agent potassium carbonate and 1650ml of chlorobenzene were added to a 5000 ml four-necked flask, and the chlorobenzene solution of phenol was slowly added dropwise at a temperature below 40 ° C, and then the temperature was raised to a reflux temperature of 130 to 135 ° C and stirred at reflux temperature. 3 to 5 hours end; After cooling to room temperature, filtration, the filter cake was discarded, the filtrate was retained, and the filtrate was washed twice with 1000 ml of deionized water, and then several layers were concentrated to remove the solvent to give a crude product. Crystallization step: the above crude product compound and 400 ml of absolute ethanol were added to a 1000 ml pressure-resistant four-necked flask, and the temperature was refluxed to 78 ° C and stirred at this temperature for 2 to 3 hours, and then 0.5 to 1 ° C / minute. The rate was slowly lowered to 12 to 15 ° C, and stirred at 12 to 15 ° C for 3 hours, filtered, and the filter cake was dried under vacuum to obtain 327.2 g of Compound 4 as white crystals, yield 82percent.

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[2] Patent: US2008/91050, 2008, A1, . Location in patent: Page/Page column 15; 23.
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  • 3
  • [ 940-71-6 ]
  • [ 108-95-2 ]
  • [ 1184-10-7 ]
YieldReaction ConditionsOperation in experiment
95.04%
Stage #1: at 50℃; for 0.5 h;
Stage #2: at 90℃; for 9 h;
(1) Condensation of hexachlorocyclotriphosphazene and phenol: In a 250 mL three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 23.3 g of phenol, 1.0 g of tetrabutylammonium bromide, and 40 mL Chlorobenzene, 40g glass beads, then add 16. 1g powdered potassium hydroxide (potassium hydroxide content of 86percent), the control temperature does not exceed 50 °C, after adding potassium hydroxide and stirring 0.5h; at 50 °C or less hexachlorocyclotriphosphazene chlorobenzene solution (13.05g hexachlorocyclotriphosphazene dissolved in 40mL chlorobenzene),About 0.5h drops, then heated to 90 C reaction 9h. (2) purification of hexaphenoxy cyclotriphosphazene: After the reaction was cooled to 20 ~ 30 °C, filtered, the filter cake (referred to as cake 1) was washed twice with 15mL of X 2 chlorobenzene, the filtrate was Washed with 50mL X 3 water three times, each time for 5min washing and stirring; the washed oil phase evaporated 116.8g of chlorobenzene, chlorobenzene recovery 95.7percent, by gas chromatography, chlorobenzene purity of about 99percent; evaporated chlorobenzene After the material was added 80mL anhydrous ethanol at -10 ~ 0 °C crystallization 4 ~ 8h, filtered, the filter cake was washed with 15mL X 2 ethanol 2 times, and then dried at 90 ~ 100 °C until constant weight hexaphenoxycyclotriphosphazene 24.7g (theoretical yield 25.99g), product yield 95.04percent
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[2] Chemistry of Materials, 2011, vol. 23, # 22, p. 4947 - 4953.
[3] Asian Journal of Chemistry, 2015, vol. 27, # 3, p. 919 - 924.
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YieldReaction ConditionsOperation in experiment
97.9% With cesium hydroxide; 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,2-dichloro-benzene at 175℃; Example 25; While heating a cylindrical reactor measuring 5 mm in inner diameter and 200 mm in length equipped with a stirring blade and a jacket to 175° C., o-dichlorobenzene (moisture content: 10 ppm or less) was fed to the reactor from the lower part to the upper part at a rate of 15 ml/minute. A solution of 3.63 g (0.031 mol) of phosphonitrile dichloride in 50 ml of o-dichlorobenzene and a solution of a mixture of potassium phenoxide and sodium phenoxide, which was previously prepared from 6.54 g (0.070 mol) of phenol, 2.76 g (0.069 mol) of sodium hydroxide and 0.0093 g (0.062 mmol) of cesium hydroxide, in 25 ml of o-dichlorobenzene were each fed to the reactor through raw material feeding ports a, b disposed at the lower part of the reactor at 0.21 ml/minute. The reaction solution was successively recovered from the reactor through a reaction solution collecting port disposed at the upper part of the reactor. The recovered reaction solution was washed with 50 ml of a 10percent aqueous potassium hydroxide solution twice and neutralized by diluted hydrochloric acid. Further, the reaction solution was washed with 50 ml of distilled water. Then, the reaction solvent was distilled off under reduced pressure. As a result, 7.11 g of the reaction product was obtained (yield calculated based on phosphonitrile dichloride: 97.9percent). Results of 31P-NMR measurement and UV-Vis measurement are shown in Table 1.
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References: [1] Patent: US2008/91050, 2008, A1, . Location in patent: Page/Page column 21; 23-25.
[2] Patent: US2008/91050, 2008, A1, . Location in patent: Page/Page column 22-24.
[3] Patent: US2008/91050, 2008, A1, . Location in patent: Page/Page column 23-24.
[4] Patent: US2008/91050, 2008, A1, . Location in patent: Page/Page column 22; 24.
[5] Patent: US2008/91050, 2008, A1, . Location in patent: Page/Page column 21-22; 24.
[6] Patent: US2008/91050, 2008, A1, . Location in patent: Page/Page column 22; 24.
[7] Patent: US2008/91050, 2008, A1, . Location in patent: Page/Page column 22; 24.
[8] Patent: US2008/91050, 2008, A1, . Location in patent: Page/Page column 22; 24.
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[2] Patent: EP1403273, 2004, A1, . Location in patent: Page 19.
[3] Patent: EP1403273, 2004, A1, . Location in patent: Page 19-20.
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