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UAN DANIEL DÍAZ SANTIBÁÑEZ ;

Abstract: In the first part of this thesis work, a series of tetrabutyl ammonium (TBA) salts of Keggintype polyoxoanions with V included instead of W (TBA4PW11V1O40 and TBA5PW10V2O40) and Mo(TBA4PMo11V1O40 and TBA5PMo10V2O40) as added atoms were prepared by a hydrothermal method. These synthesized materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), diffuse reflectance UV-Vis (DRS UV-Vis), thermogravimetric analysis (TGA), CHN elemental analysis (EA), inductively coupled plasma spectrometry (ICP-MS) and N2 physisorption techniques to evaluate their physicochemical/textural properties and correlate them with their catalytic performances. According to FT-IR and DRS UV-Vis, (PVXW(Mo)12-XO40)(3+X)-anions are the main species present in TBA salts. In addition, CHN-EA and ICP-MS revealed that the desired stoichiometry was obtained. In summary, the results showed that the proposed catalysts were successfully synthesized, preserving the Keggin structure and confirming the successful inclusion of V in the structure, and in the expected number. Then, in both Mo and W series, it was found that after substitution of the addenda atoms by V, there was an improvement in catalytic activity concerning the unsubstituted atoms. Subsequently, their catalytic activities were studied in the liquid-phase, aerobic oxidation of benzyl alcohol to benzaldehyde at 5 bar O2 and 170℃. Regardless of the nature of the addition atom, the catalytic activity increased with the number of V in the Keggin anion structure. For both series of catalysts, the TBA salts of polyoxometalates with the highest degree of V substitution (TBA5PMo10V2O40 and TBA5PW10V2O40) showed the highest activity. The maximum benzyl alcohol conversion obtained was 93% and 97% using (TBA)5PMo10V2O40 and (TBA)5PW10V2O40 as catalysts, respectively. In all cases, the selectivity towards benzaldehyde was higher than 99%. In the second part of this thesis work, a study was carried out for the optimization of the operational conditions in the catalytic oxidation reaction of phenethoxybenzene with (TBA)5[PMo10V2O40] catalyst. The optimization was carried out in two stages, the first one consisted of the determination of the variables A fractional factorial design of 4 variables was used, which were temperature (T, ℃), time (t, h) O2 pressure (PO2, bar) and catalyst mass (Mcat, mg).Statistical validation of the model using an ANOVA analysis of the model, showed to be significant for 95% confidence (P ˂0.05) and presents a good fit to explain the variability of the response from the variables, with an R2 of 0.984. The statistically significant variables according to the model are temperature (X1) and time (X2), with P-values ˂0.05. For the second stage, a central circumscribed composite design (CCC) was used for three variables (T, t and Mcat) and three levels (with star points). The model was analyzed and statistically validated by ANOVA, which was significant for 95% confidence and had an R2 of 0.948, ensuring an adequate fit to the data. As a result, the significant independent variables (P ˂ 0.05) were the quadratic terms temperature (X12), time (X22), and catalyst mass (X32). The optimum conditions to obtain 77.0 % phenethoxybenzene conversion were a temperature of 137℃, time of 3.5 h and catalyst mass of 200 mg. Finally, the experimental validation of the mathematical model yielded an experimental conversion value (%) of 76.7+ -0.2. Furthermore, depolymerization was confirmed by GPC with the decrease of the Mw molar mass distribution from 7.34 kDa to 1.97 kDa, a decrease of the PDI polydispersity index from 6 to 3 was also detected. Also, the successful cleavage of the β-O-4 bond was verified by GC-MS analysis of the reaction products. Finally, the optimization approach through the experimental design of the operational variables for the catalytic oxidation reaction of phenethoxybenzene with the Keggin-type catalyst(TBA)5[PMo10V2O40] proved to be a useful tool in the design of a catalytic system for the oxidation of phenethoxybenzene with Keggin-type polyoxometalate catalysts, with a view to the valorization of lignin. The characteristics studied above, clearly demonstrate the effects of the structural features of the Keggin-type POMs on the catalytic activity in the selective catalytic oxidation reaction of lignin model substrates.

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Product Details of [ 101-84-8 ]

CAS No. :101-84-8 MDL No. :MFCD00003034
Formula : C12H10O Boiling Point : -
Linear Structure Formula :- InChI Key :USIUVYZYUHIAEV-UHFFFAOYSA-N
M.W : 170.21 Pubchem ID :7583
Synonyms :
Chemical Name :Diphenyl oxide

Calculated chemistry of [ 101-84-8 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 13
Num. arom. heavy atoms : 12
Fraction Csp3 : 0.0
Num. rotatable bonds : 2
Num. H-bond acceptors : 1.0
Num. H-bond donors : 0.0
Molar Refractivity : 52.96
TPSA : 9.23 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : Yes
CYP2C9 inhibitor : Yes
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -4.35 cm/s

Lipophilicity

Log Po/w (iLOGP) : 2.55
Log Po/w (XLOGP3) : 4.21
Log Po/w (WLOGP) : 3.48
Log Po/w (MLOGP) : 3.34
Log Po/w (SILICOS-IT) : 3.11
Consensus Log Po/w : 3.34

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 2.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -4.1
Solubility : 0.0136 mg/ml ; 0.0000797 mol/l
Class : Moderately soluble
Log S (Ali) : -4.11
Solubility : 0.0131 mg/ml ; 0.000077 mol/l
Class : Moderately soluble
Log S (SILICOS-IT) : -4.65
Solubility : 0.00383 mg/ml ; 0.0000225 mol/l
Class : Moderately soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 2.0
Synthetic accessibility : 1.44

Safety of [ 101-84-8 ]

Signal Word:Danger Class:9
Precautionary Statements:P273-P280-P302+P352+P312-P305+P351+P338+P310-P312-P362+P364-P391-P501 UN#:3077
Hazard Statements:H303-H312-H318-H411 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 101-84-8 ]

* 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 [ 101-84-8 ]
  • Downstream synthetic route of [ 101-84-8 ]

[ 101-84-8 ] Synthesis Path-Upstream   1~42

  • 1
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Reference: [1] J. Gen. Chem. USSR (Engl. Transl.), 1961, vol. 31, p. 776 - 780[2] Zhurnal Obshchei Khimii, 1961, vol. 31, p. 845 - 849
  • 2
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Reference: [1] Journal of the Chemical Society, <1957> 4625,
  • 3
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  • [ 213699-53-7 ]
  • [ 13425-93-9 ]
YieldReaction ConditionsOperation in experiment
95% at 120 - 230℃; for 0.0833333 h; 5-((3,4-Dimethoxyphenylamino)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione (16.1 g, 52 mmol) was added to a pre-heated 1000 mL round-bottom flask containing 1-phenoxy benzene (100 mL) at 230 °C.
The reaction was stirred for 5 min, and then cooled to 120°C. n-Hexane (100 mL) was added to the solution to allow the product to precipitate out from the reaction solution.
The mixture was further stirred at rt overnight.
The solid was collected and crystallized in a solution of EtOAc/ n-hexane (50 mL, v/v = 10/1) to afford the title compound as a brown solid (10.2 g, 95percent).
Reference: [1] Patent: US2010/239576, 2010, A1,
[2] Patent: EP2408300, 2016, B1, . Location in patent: Paragraph 0354
  • 4
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  • [ 92-52-4 ]
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  • [ 26892-90-0 ]
Reference: [1] Journal of the American Chemical Society, 1946, vol. 68, p. 1264
  • 5
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  • [ 100124-07-0 ]
Reference: [1] Patent: CN107325090, 2017, A,
  • 6
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  • [ 21454-19-3 ]
Reference: [1] Journal of Organic Chemistry, 1963, vol. 28, p. 2725 - 2728
[2] Chinese Chemical Letters, 2010, vol. 21, # 10, p. 1157 - 1161
  • 7
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  • [ 139-59-3 ]
  • [ 2688-84-8 ]
Reference: [1] Journal of the American Chemical Society, 2013, vol. 135, # 13, p. 5000 - 5003
[2] Science, 2015, vol. 349, # 6254, p. 1326 - 1330
  • 8
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  • [ 101-80-4 ]
  • [ 139-59-3 ]
  • [ 2688-84-8 ]
Reference: [1] Chemistry - A European Journal, 2017, vol. 23, # 3, p. 563 - 567
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  • [ 591-50-4 ]
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Reference: [1] Journal of the American Chemical Society, 1982, vol. 104, # 14, p. 3917 - 3923
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Reference: [1] Journal of the American Chemical Society, 1982, vol. 104, # 14, p. 3917 - 3923
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  • [ 71-43-2 ]
Reference: [1] Journal of the American Chemical Society, 1982, vol. 104, # 14, p. 3917 - 3923
  • 12
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  • [ 2217-65-4 ]
  • [ 101-63-3 ]
  • [ 5950-83-4 ]
Reference: [1] Journal of Organic Chemistry, 1981, vol. 46, # 15, p. 3056 - 3060
  • 13
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  • [ 591-50-4 ]
  • [ 69113-59-3 ]
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Reference: [1] Journal of the American Chemical Society, 1982, vol. 104, # 14, p. 3917 - 3923
  • 14
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  • [ 2050-47-7 ]
YieldReaction ConditionsOperation in experiment
99% With bromine In 1,2-dichloroethane (EDC); water; 1,2-dichloro-ethane Example 3
Bromination of DPE in EDC/H2O in the presence of NaBrO3
Bromine (176g, 1.1 moles) was added to a stirred mixture of diphenylether (170g, 1.0 mole) in 1,2-dichloroethane (EDC) (300ml), water (200ml) and NaBrO3 (55g, 0.36 mole) in a four-necked round bottomed flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer.
The addition of the Br2 took place over one hour at 25°C, without any noticeable liberation of HBr from the reaction apparatus.
The progress of the reaction and its completion were followed by means of GC.
Full conversion was achieved after two hours, after which the phases were separated.
Crude 4,4'-dibromodiphenylether was obtained (324.8g) in a yield of 99percent and a selectivity of 99.5percent.
96% With bromine In 1,2-dichloroethane (EDC); water; 1,2-dichloro-ethane Example 2
Bromination of DPE in EDC/H2O in the presence of 30percent H2O2
Bromine (176g, 1.1 moles) was added to a stirred mixture of diphenylether (170g, 1.0 mole) in 1,2-dichloroethane (EDC) (300ml) and water (200ml) in a four-necked round-bottomed flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer.
The addition of the Br2 took place over one hour at 5°C, without any noticeable liberation of HBr from the reaction apparatus.
Thereafter, 30percent H2O2 (130g, 1.15 moles) was added gradually to the reaction mixture at 50°C for a further one hour.
The progress of the reaction and its completion were monitored by GC.
Full conversion was achieved after three hours, after which the phases were separated.
After distillation of the solvent, crude 4,4'-dibromodiphenylether was obtained (318.1g) in a yield of 96percent and a selectivity of 99percent.
Reference: [1] Patent: EP429975, 1991, A1,
[2] Angewandte Chemie - International Edition, 2018, vol. 57, # 20, p. 5938 - 5942[3] Angew. Chem., 2018, vol. 130, p. 6044 - 6049,6
[4] Monatshefte fuer Chemie, 1992, vol. 123, # 12, p. 1153 - 1162
[5] Patent: EP429975, 1991, A1,
[6] Journal of Organic Chemistry, 2018, vol. 83, # 2, p. 930 - 938
[7] Tetrahedron Letters, 2003, vol. 44, # 49, p. 8781 - 8785
[8] Advanced Synthesis and Catalysis, 2006, vol. 348, # 7-8, p. 862 - 866
[9] Zeitschrift fuer Naturforschung, B: Chemical Sciences, 1993, vol. 48, # 4, p. 521 - 538
[10] Chemistry - A European Journal, 2016, vol. 22, # 30, p. 10459 - 10474
[11] Inorganic Chemistry, 2018, vol. 57, # 5, p. 2381 - 2385
[12] Chem.Abstr., 1946, p. 557
[13] Justus Liebigs Annalen der Chemie, 1871, vol. 159, p. 210
[14] Bulletin of the Chemical Society of Japan, 1988, vol. 61, p. 2226 - 2228
[15] Journal of the Chemical Society, 1932, p. 2880,2881
  • 15
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  • [ 107-06-2 ]
  • [ 2050-47-7 ]
YieldReaction ConditionsOperation in experiment
97% With bromine In 1,2-dichloroethane (EDC) Bromination of DPE using 1,2-dichloroethane (EDC) as the solvent
To a four-necked round-bottomed flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, containing a stirred solution of diphenylether (170 g, 1.0 mole) in 1,2-dichloroethane (EDC) (300 ml), there were added 336 g. (2.1 moles) of Br2.
To the top of the condenser there was attached a trap to absorb HBr released during the reaction.
The addition of the Br2 took place over one hour at 5°C, after which the reaction mixture was stirred at 50°C for a further one hour.
The progress of the reaction and its completion were monitored by GC. Excess Br2 and traces of HBr were neutralized with 10percent ammonia (70ml).
The phases were separated and the organic layer was rinsed with water (100ml).
After the distillation of the solvent from the organic phase, crude 4,4'-dibromodiphenylether (320.2g) was obtained in a yield of 97percent and a selectivity of 99percent. GC analyses were conducted on a Varian Model 3400.
The column used was an HP-1 (100percent dimethyl polysiloxane) Megabore 5m x 0.53mm at a flow of 8ml/min.
The conditions were an initial temperature of 110°C for one minute then a rise to 250°C at 15 deg./min.
giving a retention time for the 4,4'-dibromodiphenylether of 7.6 min.
Reference: [1] Patent: EP429975, 1991, A1,
  • 16
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  • [ 1972-28-7 ]
  • [ 4114-28-7 ]
  • [ 2050-47-7 ]
Reference: [1] Tetrahedron Letters, 2008, vol. 49, # 11, p. 1729 - 1733
  • 17
  • [ 101-84-8 ]
  • [ 591-50-4 ]
  • [ 2050-47-7 ]
Reference: [1] Journal of Chemical Research, Miniprint, 1982, # 6, p. 1649 - 1660
  • 18
  • [ 101-84-8 ]
  • [ 101-55-3 ]
  • [ 2050-47-7 ]
Reference: [1] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1912, vol. 154, p. 603[2] Bulletin de la Societe Chimique de France, 1912, vol. <4> 11, p. 293
[3] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1912, vol. 154, p. 603[4] Bulletin de la Societe Chimique de France, 1912, vol. <4> 11, p. 293
  • 19
  • [ 56-23-5 ]
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  • [ 7726-95-6 ]
  • [ 7553-56-2 ]
  • [ 101-55-3 ]
  • [ 2050-47-7 ]
Reference: [1] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1912, vol. 154, p. 603[2] Bulletin de la Societe Chimique de France, 1912, vol. <4> 11, p. 293
  • 20
  • [ 80-05-7 ]
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  • [ 1568-80-5 ]
Reference: [1] Journal of Organic Chemistry, 1990, vol. 55, # 16, p. 4966 - 4969
  • 21
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  • [ 1163-19-5 ]
YieldReaction ConditionsOperation in experiment
99.436 - 99.71 %Chromat.
Stage #1: at 20℃; for 0.166667 h;
Stage #2: at 53 - 60℃; for 3.55 - 7.32 h;
EXAMPLE 6; Preparation of Partially brominated DPO[0056] To the 500 mL flask (equipped as described in Example 4) containing 47.3 g of DPO was added over about 10 minutes, 28.0 g of bromine with stirring and cooling at room temperature. Catalyzed Bromination [0057] In a 1 -liter jacketed flask equipped with mechanical stirrer, Friedrich condenser(water cooled at about 250C), and with a 1/32-inch diptube but without a fractionation column were placed 3.8 g of AlCl3 and 885 g of bromine. After a feed time of about 7.25 hours, all of the partially brominated DPO had been fed from the flask. The reaction temperature was maintained at 56.30C to 57.20C throughout the addition. The reaction mixture was refluxed for 4 minutes as the temperature rose to 58.40C, then 450 mL of water was added and the reactor was set for distillation. The product was distilled to 1700F (about 770C) and 312 g of bromine was collected. The water layer was decanted from the reactor, 400 mL of water was added, stirred, and discarded. Then 400 mL of water and 10 g of NaOH were added, the mixture was stirred well and product was collected and water washed on a filter. GC analysis showed the product was composed of 99.71percent of decabromodiphenyl oxide, and 0.034 and0.259percent of the first and second nonabromodiphenyl oxide isomers, respectively. The product was placed in a 1250C oven and after drying overnight weighed 252.0 g. EXAMPLE 7Preparation of Partially brominated DPO [0058] To the 500 mL flask (equipped as described in Example 4) containing 49.1 g of DPO <n="14"/>was added over aboutlO minutes, 29.7 g of bromine. This was purged with nitrogen to remove HBr. Catalyzed Bromination[0059] In a 1 -liter jacketed flask equipped as in Example 6 (no fractionation column) were placed 3.8 g of AlCl3 and 884 g of bromine. The mixture was heated to 59°C and a feed of the partially brominated DPO formed above was initiated. The feed through the 1/32-inch diptube was set at a rate of about 0.21 mL per minute. All the partially brominated DPO was added over 3 hours and 23 minutes, The reaction mixture had been maintained at a temperature of 56.10C to 57.10C throughout the addition time reflux was continued for about 10 more minutes as the temperature rose to 59.60C. Then 450 mL of water was added to the reaction mixture and the reactor was set for distillation. The mixture was distilled to 770C and 294.5 g of bromine was collected. The mixture was worked up as in Example 6. GC analysis of the product showed 99.59percent of decabromodiphenyl oxide and 0.11percent and 0.296percent of first and second nonabromodiphenyl oxide peaks, respectively. Present in the product were a few "lumps". One was removed and a GC showed it contained 99.61percent of decabromodiphenyl oxide and 0.100 and 0.291percent of the first and second nonabromodiphenyl oxide isomers, respectively. The product was oven dried. EXAMPLE 8Preparation of Partially brominated DPO [0060] To the 500 mL flask (equipped as in Example 4) containing 49.00 g of DPO was added 31.4 g of bromine over about 10 minutes. Then the mixture was purged with nitrogen. Catalyzed Bromination[0061] In a 1 -liter jacketed flask, equipped as in Example 6, were placed 3.82 g OfAlCl3 and 988 g of bromine The mixture was heated to 56.O0C and addition of the partially brominated DPO begun at a feed rate of about 0.18 mL per minute. This feed was maintained for a period of about 4 hours with the temperature fluctuating between 53.O0C and 54.O0C. The mixture was allowed to reflux for about another 7 minutes with the temperature reaching about 600C. Then, 450 mL of water was added to the reaction mixture and the reaction vessel was set for distilling bromine. The distillation was conducted to 770C whereby an amount of 400.2 g of bromine was recovered. Product was isolated as in Example 5 and oven dried. GC analysis showed 0.093percent and 0.471percent of the first and second nonabromodiphenyl oxide peaks, respectively, and 99.436percent of decabromodiphenyl oxide. After drying over the weekend the product weighed 260.1 g.
Reference: [1] Russian Journal of Applied Chemistry, 1994, vol. 67, # 8.2, p. 1167 - 1169[2] Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation), 1994, vol. 67, # 8, p. 1324 - 1327
[3] Bulletin de la Societe Chimique de France, 1910, vol. &lt;4&gt; 7, p. 779
[4] Patent: US2008/58555, 2008, A1, . Location in patent: Page/Page column 6-7
[5] Patent: US2008/58558, 2008, A1, . Location in patent: Page/Page column 4
[6] Patent: US2008/58557, 2008, A1, . Location in patent: Page/Page column 4-5
[7] Patent: US2008/15394, 2008, A1, . Location in patent: Page/Page column 3-4
[8] Patent: WO2008/27776, 2008, A2, . Location in patent: Page/Page column 12-13
[9] Patent: WO2008/26215, 2008, A2, . Location in patent: Page/Page column 16-20
[10] Patent: WO2008/26215, 2008, A2, . Location in patent: Page/Page column 17-18
[11] Patent: WO2008/26215, 2008, A2, . Location in patent: Page/Page column 21
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YieldReaction ConditionsOperation in experiment
99.44 - 99.70 %Chromat.
Stage #1: at 40℃;
Stage #2: at 56.5 - 78.4℃; for 3.65 - 4.36667 h;
EXAMPLE 9; Preparation of Partially brominated DPO[0062] A batch of partially brominated DPO was prepared by slowly adding 131 g of bromine to 236 g of DPO while cooling in a water bath so that the temperature did not exceed 400C. The resultant partially brominated DPO contained about 0.59 atom of bromine per molecule of DPO. Catalyzed Bromination[0063] In a 1 -liter jacketed reactor equipped with 00C Friedrich condenser, mechanical stirrer, thermocouple well, and 1/32-inch LD. diptube was placed 4.0 g AlCl3 and 1021 g of bromine. To this was fed 64.3 g of a portion of the above batch of partially brominated DPO.The feed rate was approximately 0.17 mL per minute with the condenser water set at +10C. The feed occurred over a period of 4 hours and 17 minutes during which time the reaction temperature was maintained at 56.5 to 56.90C. The mixture was refluxed for an additional period of about 5 minutes as the temperature rose to 590C and then 450 mL of water was added to it. Bromine was distilled off from the reaction mixture up to a temperature of ca800C. The amount of bromine collected was 502 g. Water was then decanted from the reaction mixture, and the remainder of the reaction mixture was stirred in 400 mL of water and this wash water was decanted. Then 500 mL of 2percent NaOH was added. Product was collected and water washed. GC analysis showed 0.067percent and 0.233percent of the first and second nonabromodiphenyl oxide isomers, respectively, the second being the ortho isomer, and99.70percent of decabromodiphenyl oxide. EXAMPLE 10Catalyzed Bromination[0064] Another portion of the same partially brominated DPO as used in Example 9 was used as the feed in this Example. The reactor was a 500 mL pressure reactor (Ace glassNo.6438-17) with jacket, equipped with a mechanical stirrer, a 1/32-inch diptube to feed the partially brominated diphenyl oxide, 1/4-inch O. D. diptube for takeoff, and a 9 inch x 3/4-inch LD. (ca. 22.8 cm x 1.91 cm) uninsulated fractionation column packed with 5 mm x 5 mm Raschig rings. The column was fitted at the top with a 00C condenser. The condenser was connected to a backpressure regulator to maintain the desire pressure. To this reactor were changed 3.9 g OfAlCl3 and 940 g of bromine. A 90 mL pressure bottle was charged with 59.8 g of the above partially brominated diphenyl oxide having about 0.6 bromine atom per molecule of diphenyl oxide. The pressure bottle was equalized with reactor via a nitrogen purge that entered the system at a back pressure regulator. The contents of the 500 mL pressure reactor were heated to a refluxing temperature of 78.4°C at a pressure of 12.1 psig(ca. 1.85x 105 Pa). Then a feed of the partially brominated DPO was maintained at a flow rate <n="16"/>of about 0.17 niL per minute for an overall period of about 3 hours and 39 minutes. The reaction mixture was maintained at a temperature of 74.30C to 76.20C and at 12.1 to 13.5 psig (ca. 1.85x105 to 1.94x105 Pa) pressure. Operational difficulties in the system were encountered during this time. Nevertheless, 100 mL of water was then charged to the reactor and the reaction mixture was poured into a 1 -liter flask. The reaction mixture was stripped of bromine up to a temperature of 1000C. Solids remaining in the reactor were treated with dilute sodium hydroxide solution and combined with the product that had been stripped. This mixture was filtered and washed giving a product containing 0.034percent and 0.526percent of the first and second nonabromodiphenyl oxide isomers, respectively, the second being the ortho isomer, and 99.44percent of DBDPO.
Reference: [1] Patent: WO2008/27776, 2008, A2, . Location in patent: Page/Page column 14-15
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  • [ 1163-19-5 ]
YieldReaction ConditionsOperation in experiment
99.54 %Chromat. at 55 - 61℃; for 6.25 h; EXAMPLE 1; Catalyzed Bromination [0047] A reactor was configured from a 1 -liter Morton flask with a mechanical stirrer, thermometer, 60 mL addition funnel, and fractionation column (10" x 1" (ca. 25.4 cm x 2.54 cm) with 5 mm x 5 mm Raschig rings) topped by a O0C reflux condenser. The outlet of the condenser was connected to a H2O trap. A small N2 purge was added to the line from the condenser to the H2O trap. The reactor was charged with 3.5 g OfAlCl3 and 1577g of bromine (containing 11 ppm H2O). The addition funnel was charged with 47.04 g of diphenyl oxide.The reactor was heated to 550C and the diphenyl oxide was added drop-wise supersurface. <n="10"/>The time for the initiation of the diphenyl oxide addition was noted. The reactor was heated by a mantle. Twenty-seven minutes into the diphenyl oxide feed, half of the diphenyl oxide had been added and the reaction mass temperature was 560C. One and a quarter hours after the diphenyl oxide feed was initiated, all of the diphenyl oxide had been added and the reaction mass temperature was 570C. The compressor on the refrigeration system was shut off to allow slow warm-up of the condenser. The reaction mass was refluxed through the fractionation column. At one hour and 18 minutes after feed initiation, the reaction mass temperature was 590C. Two hours and three minutes after diphenyl oxide feed initiation the condenser water was at 2O0C and the reaction temperature was at 610C. At two hours and seven minutes after feed initiation, the condenser water was at 3O0C. Thirty two minutes later the addition funnel was replaced with a N2 inlet. A slow N2 purge of the reactor was started. The reaction mass temperature was 610C. The N2 purge was at 100 mL/min into the vapor space of the reactor. Four hours and fifty minutes after the initiation of the diphenyl oxide feed, the reaction mass temperature was 610C and the condenser water was at 370C. At six hours and 15 minutes after the initiation of the diphenyl oxide feed the reaction mass was cooled to 550C, 350 mL deionized H2O was added, the fractionation column was removed, and the reactor was set for distillation. Br2 was distilled off. When most of the Br2 was gone 150 mL more deionized water was added. The remaining Br2 was distilled off to 1000C. The remaining mixture was cooled to 6O0C, and 30 mL of 25percent NaOH was added to pH 13-14. The resultant mix was filtered and washed well with deionized water. A sample was subjected to GC analysis. The GC trace showed the product to contain 0.21percent of the first nonabromodiphenyl oxide peak (deemed to be meta- and para-hydrogen isomers), 0.24percent of the second nonabromodiphenyl oxide peak (deemed to be the ortho-hydrogen isomer) and 99.54percent of decabromodiphenyl oxide. The sample was oven dried.
0.031 - 0.205 %Chromat.
Stage #1: for 0.416667 - 1.41667 h; Heating / reflux
Stage #2: at 56.1 - 59℃; for 7.13333 - 9.78333 h;
EXAMPLE 3; Preparation of Partially brominated DPO[0050] To the 500 mL 4-neck flask equipped as in Example 2 was added 732g of Br2. Molten diphenyl oxide (49.3 g) was added dropwise at bromine reflux over 40 minutes. The solution was refluxed (O0C condenser) 45 minutes longer. Catalyzed Bromination[0051] To the 1-liter flask, equipped as in Example 2, were added 4.0 g of AlCl3 and 595 g of bromine. This mixture was brought to reflux through the fractionation column and the contents of the 500 mL flask were pumped in at -0.5 niL/min via the 1/16" (ca. 0.16 cm) O. D., 1/32" (ca. 0.08 cm) LD. diptube subsurface to the resulting reaction mass. The reaction mass temperature was 590C. The reaction mass was kept at hard reflux throughout the solution addition. The temperature of the cooling water on condenser was 170C. Eight hours later, all of the contents of the 500 mL flask had been pumped into the 1 -liter flask. About 5 mL of bromine was added to the 500 mL flask and this bromine was pumped into the 1 -liter flask. The reaction mass was then refluxed 15 minutes longer with a N2 purge (about 100-200 niL/min. down the diptube). The reaction mass was cooled partially, and 50O mL of H2O was added and the reactor was set for distillation. Bromine was distilled to 1000C and the reaction mass was cooled to 6O0C. Excess 5percent NaOH added to pH 12. The solid product was collected and washed well with H2O. A sample was analyzed by GC. GC analysis showed the product to contain 0.017percent of the first nonabromodiphenyl oxide peak (meta and para isomers), 0.031percent of the second nonabromodiphenyl oxide peak (ortho isomer) and 99.95percent of <n="12"/>decabromodiphenyl oxide. The remainder of the product was dried overnight at 13O0C and, after drying, weighed 263 g. EXAMPLE 4; Preparation of Partially brominated DPO [0052] To 50.0 g of DPO in a 500 rnL flask equipped with magnetic stirrer, addition funnel, thermometer, and condenser was added 29 g of bromine dropwise over 30 minutes. The reactor was cooled in a water bath. When all the bromine had been added, the reactor was purged with nitrogen to facilitate pumping and prevent HBr breakout in the line. Catalyzed Bromination [0053] In a 1-liter 4-neck Morton flask were placed 4.05 g of AlCl3 and 1230 g of bromine.The flask was equipped with 1/32-inch (ca. 0.08 cm) LD. diptube (subsurface) and a fractionation column as described in Example 2 and topped with a tap water cooled Friedrich condenser. This mixture was brought to reflux and the DPO mixture was pumped into the reactor via the 1/32-inch diptube. Reaction temperature was 590C. Heating was such that bromine vapor rose to about 1A of the height of the condenser before totally condensing. The temperature of the cooling water exiting the condenser was 25.6°C. After 6 hours and 58 minutes of feeding, all of the DPO had been added except for about Ig remaining in the flask. The diptube was removed and the reaction mixture was refluxed 10 minutes longer. Water (500 mL) was added and the reactor was set for bromine distillation. Bromine was distilled to a reaction temperature of 1000C. 658 g of bromine was collected. The reactor was cooled,5percent NaOH was added to pH of about 13, and the product was collected and washed. GC analysis showed the product to contain 0.020percent of the first nonabromodiphenyl oxide peak (meta and para isomers), 0.080percent of the second nonabromodiphenyl oxide peak (ortho isomer) and 99.90percent of decabromodiphenyl oxide. The product was dried overnight at 1300C. After drying overnight the product weighed 265.2 g. EXAMPLE 5Preparation of Partially brominated DPO[0054] To the 500 mL flask (equipped as described in Example 4) containing 51.67 g ofDPO was added 30.0 g of bromine over about 10 minutes with cooling in a water bath. After stirring for 15 minutes this mixture was nitrogen sparged to remove HBr.Catalyzed Bromination[0055] In a 1 -liter jacketed 4-neck flask equipped with a thermocouple, 1/32-inch LD. dip tube, mechanical stirrer and 9 inch x 1 inch (ca. 22.8 cm x 2.54 cm) column (packed with 5 mm x 5 mm Raschig rings) and topped with a water-cooled Friedrich condenser, and heated by circulating hot water through the jacket, the water temperature being controlled to give the <n="13"/>desire reaction temperature, were placed 4.0 g OfAlCl3 and 1240 g of bromine. This mixture was heated to 56.70C and DPO addition initiated. After a DPO feed time of 9 hours and 42 minutes, during which time the reaction temperature was maintained mainly at 56.10C to 57.10C, the feed was stopped and the mixture was refluxed 5 minutes longer under a nitrogen purge of the reaction flask. Then 500 mL of water was added and the flask was set for distillation. 617 Grams of bromine was distilled to a temperature of 800C. The stirrer in the flask was stopped and the resultant water phase was decanted. The solids were washed with 500 mL of water and the water was decanted. Then 500 mL of water and 10 g of NaOH were added to the solids and the mixture was stirred well. Then the mixture was filtered and washed well on the filter leaving the product as a filter cake. A sample after drying was shown by GC analysis to contain 0.031percent of the first nonabromodiphenyl oxide peak (meta and para isomers), 0.205percent of the second nonabromodiphenyl oxide peak (ortho isomer) and 99.764percent of decabromodiphenyl oxide. The product was oven dried and weighed 267.2 g.
99.634 - 99.696 %Chromat.
Stage #1: at 40℃;
Stage #2: at 56.9 - 60.4℃; for 1.83333 - 1.85 h;
EXAMPLE 11; Catalyzed Bromination[0065] Into a 1 -liter Morton flask equipped with a Vigreux column (10-inches x 1-inch), a0-50C cooled Friedrich condenser, a 1/32-inch diptube, a mechanical stirrer, heating mantle, and a thermocouple well and thermocouple were placed 6.9 g Of AlCl3 and 909 g of bromine.This was brought to a hard reflux (90 volts of heating mantle) as a total of 56.5 g of another portion of the same partially brominated DPO as used in Example 9 was pumped into this reactor at a rate of 0.4 mL per minute. The reaction was maintained mainly at 58.50C to 59.40C with one excursion at the beginning to 56.90C. Reflux was 2/3 up the Friedrich condenser during the addition, which occurred over 100 minutes. The mixture was refluxed10 more minutes, during which time the reaction temperature rose to 60.40C. The reaction mixture was then cooled in a water bath to 400C and 500 mL of tap water was added to the reaction mixture. The Vigreux column was removed and the reactor set for distillation. Bromine was stripped from the reaction mixture up to 1000C, and a total of 430 g of bromine was recovered. The reaction mixture was cooled to 600C and 25percent aqueous caustic solution was added to a pH of 13. The solid product was collected and water washed and then oven dried. GC of a sample of the product showed 0.084percent of the first nonabromodiphenyl oxide isomer (a mixture of meta and para hydrogen containing isomers) and 0.220percent of a second nonabromodiphenyl oxide isomer (ortho-hydrogen isomer) and 99.696percent of decabromodiphenyl oxide. After oven drying for 2 hours the product weighed 242.8 g.EXAMPLE 12Catalyzed Bromination[0066] Example 11 was reproduced as exactly as possible using the same equipment, except less catalyst was used. Charged to the reactor were 3.00 g of AlCl3 and 913 g of bromine.56.5 g of the same partially brominated DPO as used in Example 9 was pumped in over 101 <n="17"/>minutes as the temperature was maintained at 58.30C to 59.10C. Heating via the heating mantle using the same voltage setting as in Example 11. It was heated at reflux 10 minutes longer as the temperature rose to 60.40C. The product was isolated in the same manner as in Example 11, 431 grams bromine being recovered. GC analysis ofthe product showedO.185percent of a first nonabromodiphenyl oxide isomer (believed to be a mixture of meta and para hydrogen containing isomers) and 0.181percent of a second nonabromodiphenyl oxide (believed to be ortho-hydrogen isomer) and 99.634percent of decabromodiphenyl oxide. After oven drying for 2 hours the product weighed 246.0 g.
Reference: [1] Patent: WO2008/27776, 2008, A2, . Location in patent: Page/Page column 8-9
[2] Patent: WO2008/27776, 2008, A2, . Location in patent: Page/Page column 10-12
[3] Patent: WO2008/27776, 2008, A2, . Location in patent: Page/Page column 15-16
  • 24
  • [ 101-84-8 ]
  • [ 437701-78-5 ]
  • [ 437701-79-6 ]
  • [ 918947-03-2 ]
  • [ 1163-19-5 ]
YieldReaction ConditionsOperation in experiment
97.2 %Chromat. at 55 - 57℃; for 2.23333 h; Heating / reflux The reactor was charged with 3.16 g of AlCl3 and 711 g of bromine. Diphenyl oxide (46.1 g, 0.271 mol) and the Br2/Cl2 mixture (BrCl) were cofed to the reactor during 124 minutes at 55 ° C to 57 °C. The rate of addition was at a proportion of about 8.2 g Br2/Cl2 mixture (BrCl) per gram of DPO, such that the addition of both was completed at the same time. The mixture in the reactor was refluxed for 10 minutes after the cofeeds had ended, and deionized H2O was added. The reactor was set for distillation. The halogen (mostly Br2, but <n="13"/>also comprised of BrCl and Cl2) was distilled off. When most of the halogen was gone, more deionized water was added. The remaining halogen was distilled off to 1000C. The remaining mixture was cooled to 6O0C, and 30 mL of 25percent NaOH was added to pH 13-14. The resultant mixture was filtered and washed well with deionized water. A sample was subjected to GC analysis. The GC trace showed the product to contain 0.26percent Br9DPO (meta and para hydrogen isomers only), 2.52percent Br9ClDPO, and 97.2percent Br10DPO. None (less than 0.02percent) of the ortho hydrogen isomer of Br9DPO was detected. The sample was oven dried. [0043] The drawings show illustrative GC traces formed using the recommended gas chromatographic procedure described hereinabove. In these traces, the abscissa is time in minutes and the ordinate is the detector response. A copy of the GC trace of the product formed in Example 1 appears as Fig. 1. In Fig. 1, the peak at 1.358 represents the area percentage of what is deemed to be the meta and para isomers of nonabromodiphenyl oxide. No peak for the ortho-isomer of nonabromodiphenyl oxide was observed. The peaks at 2.103 and 2.200 were deemed to be Br9ClDPO isomers. The peak at 2.649 represents the area percentage of decabromodiphenyl oxide.
Reference: [1] Patent: WO2008/27780, 2008, A1, . Location in patent: Page/Page column 11-12
  • 25
  • [ 101-84-8 ]
  • [ 437701-78-5 ]
  • [ 63387-28-0 ]
  • [ 437701-79-6 ]
  • [ 918947-03-2 ]
  • [ 1163-19-5 ]
YieldReaction ConditionsOperation in experiment
99.29 %Chromat. at 56℃; for 0.0666667 h; Heating / reflux EXAMPLE 2; [0044] Example 1 was repeated, with the following differences. A Vigreux column was placed between the reactor and the condenser. The amounts of the reagents were 302 g of Br2 and 53.1 g of Cl2 in the pressure bottle, 3.4 g Of AlCl3 and 698 g of bromine charged to the reactor, and 47.4 g of diphenyl oxide. Diphenyl oxide (2 grams) was added to the reactor before the BrCl addition was begun, after which the diphenyl oxide and BrCl were added at rates such that addition of both was completed at about the same time. Reaction temperature was 56 °C throughout the additions. The mixture was refluxed 4 minutes longer, and then worked up as in Example 1. The GC trace showed the product to contain 0.31percent Br9DPO (0.17percent combined of the meta and para hydrogen isomers, and 0.14percent of the ortho hydrogen isomer), 0.40percent Br9ClDPO, and 99.29percent Br10DPO.
Reference: [1] Patent: WO2008/27780, 2008, A1, . Location in patent: Page/Page column 12
  • 26
  • [ 101-84-8 ]
  • [ 7726-95-6 ]
  • [ 7727-15-3 ]
  • [ 1163-19-5 ]
Reference: [1] Bulletin de la Societe Chimique de France, 1910, vol. &lt;4&gt; 7, p. 779
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  • [ 591-50-4 ]
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  • [ 34883-46-0 ]
Reference: [1] Chemistry - A European Journal, 2017, vol. 23, # 53, p. 13249 - 13258
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  • [ 71-43-2 ]
  • [ 101-84-8 ]
  • [ 34883-46-0 ]
Reference: [1] Chemistry - A European Journal, 2017, vol. 23, # 53, p. 13249 - 13258
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Reference: [1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1992, # 15, p. 1969 - 1974
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Reference: [1] Advanced Synthesis and Catalysis, 2001, vol. 343, # 1, p. 57 - 60
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Reference: [1] , Gmelin Handbook: B: B-Verb.9, 5.2.7, page 215 - 219,
[2] Journal of the American Chemical Society, 1960, vol. 82, p. 4163 - 4166
[3] Organic and Biomolecular Chemistry, 2012, vol. 10, # 33, p. 6693 - 6704
[4] Journal of Materials Chemistry C, 2016, vol. 4, # 25, p. 6016 - 6026
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Reference: [1] Patent: EP1444981, 2004, A1, . Location in patent: Page/Page column 61
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  • [ 166330-10-5 ]
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[2] Phosphorus, Sulfur and Silicon and Related Elements, 1996, vol. 109, # 1-4, p. 545 - 548
[3] Patent: US2011/124904, 2011, A1, . Location in patent: Page/Page column 3
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  • [ 166330-10-5 ]
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  • [ 434336-16-0 ]
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Reference: [1] Organic and Biomolecular Chemistry, 2015, vol. 13, # 41, p. 10336 - 10340
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