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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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CAS No. : | 101-84-8 |
Formula : | C12H10O |
M.W : | 170.21 |
SMILES Code : | C1(OC2=CC=CC=C2)=CC=CC=C1 |
MDL No. : | MFCD00003034 |
InChI Key : | USIUVYZYUHIAEV-UHFFFAOYSA-N |
Pubchem ID : | 7583 |
GHS Pictogram: |
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Signal Word: | Danger |
Hazard Statements: | H303-H312-H318-H411 |
Precautionary Statements: | P273-P280-P302+P352+P312-P305+P351+P338+P310-P312-P362+P364-P391-P501 |
Class: | 9 |
UN#: | 3077 |
Packing Group: | Ⅲ |
* 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.
Yield | Reaction Conditions | Operation in experiment |
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Example 1; Step A: Formation of Partially Brominated Diphenyl Oxide; A 250-mL four-necked flask equipped with a mechanical stirrer, a glycol-cooled reflux condenser maintained at 0 C., an addition funnel, a thermometer with a temperature regulator and an ice-cold caustic scrubber, was charged with 0.2 mol (34.0 g) of diphenyl oxide. The addition funnel was charged with bromine (1.2 mol, 192 g, approximately 62 mL). Diphenyl oxide was heated to about 25 C. and stirred. With stirring under nitrogen, bromine was now added, drop-wise, to the stirred diphenyloxide over a period of 55 minutes. The reaction mixture was now heated and stirred at 45 C. for another 45 minutes. The reaction mixture was now allowed to cool to room temperature. A drying tube containing Drierite was installed on the condenser and the reaction mixture was stored overnight under nitrogen, for use the next day. The total volume of this solution was approximately 67 mL.; Step B: Bromination of Partially Brominated Diphenyl Oxide; Prepared in Step a, AboveA 1-L four-necked round bottom flask was equipped in a manner identical to what was used in step A, above, except that the addition funnel was also equipped with a Teflon dip tube approximately 1/16 in diameter and of sufficient length to reach well beneath the bromine surface for sub-surface feeding. Also, a vigreux column, approximately seven inches in length and ½ in. in diameter, was installed on the reactor before the condenser to provide additional fractionation of the liquid and vapor phases. The reactor was charged with bromine (3.97 moles, 635.5 g, approx. 2055 mL), followed by 3.4 g of anhydrous aluminum chloride catalyst. The bromine/catalyst mixture was stirred and heated to 60 C. Partially brominated DPO (prepared before as described in step A, above), was now added, subsurface to bromine/catalyst at 60 C., over a period of about three hours and twenty three minutes. The reaction mixture was allowed to reflux at 60 C. for an additional three hours, while using the same dip tube to allow a slow nitrogen sweep through the reaction mixture. After the reflux time was over, the reaction mixture was allowed to cool to room temperature. Water (250 mL) was now added to decompose the catalyst. Excess bromine was now removed by steam distillation until the vapor temperature of 100 C. was reached. The aqueous slurry of the product was allowed to cool to 40 C. Aqueous sodium hydroxide (50 wt. % solution) was now added until a pH of about 9-10 was reached. The product was now filtered using a sintered glass funnel and the cake was washed once with 200 mL of fresh water. The cake was allowed to dry in air overnight. This gave a shiny crystalline solid powder, weighing 185.9 grams. A GC analysis of the sample indicated the product to be 100 area % decabromodiphenyl oxide. Further analytical analysis of product sample using other protocols confirmed decabromodiphenyl oxide purity of no less than about 99.7 area %.; Example 2; Step A: Formation of Partially Brominated Diphenyl Oxide; This step was performed in a manner identical to step A of example 1 as described above, except that a 1-L round bottom flask was used. This flask was charged with 170 g (1.0 mol) of diphenyloxide to which a total of 960 g (309.6 mL) of bromine was fed over a period of 1 hour and thirty eight minutes. The reaction temperature was maintained between 25-35 C. during the addition, followed by a reflux at 50-58 C. for thirty minutes. This reaction mixture was stored overnight as described in part A of Example 1, above. Total volume of this mixture was approximately 300 mL.Step B: Bromination of Partially Brominated Diphenyl OxideThis procedure was also performed in a manner identical to step B as described for example 1 above. The equipment design was also identical to the one used in step B, above. A brief description is as follows:A 3-L round bottom flask was equipped with a mechanical stirrer, a 7 in.×½ in. vigreux column to which was attached a glycol-cooled reflux condenser, an addition funnel with a 1/16 in. Teflon dip tube for sub-surface feed, a thermometer with a temperature regulator and an ice cold caustic scrubber. The reactor was charged with bromine (19.85 mol, 3177.5 g, 1025 mL) and 17.0 g of anhydrous aluminum chloride catalyst. The bromine/catalyst mix was stirred under nitrogen and heated to 55 C. The addition funnel was charged with partially brominated DPO feed, prepared earlier as described in step A above. Partially brominated DPO was then added, sub-surface, to the reactor containing bromine and catalyst, over a period of 4.5 hours, at a temperature of 55-60 C. The contents were then heated at reflux for an additional two hours. The reaction mixture was now cooled to room temperature and 250 mL of water was added to decompose the catalyst. An exotherm to 43 C. was observed upon water addition. After this another 950 mL of water (total=1200 mL) was added. The reaction mixture was now heated and exc... | ||
With bromine;aluminum (III) chloride; at 55℃; | EXAMPLE 1; A reactor is configured from a 1-liter Morton flask with a mechanical stirrer, thermometer, a 60 mL addition funnel, and a distillation column. The condenser from the distillation column is connected to a H2O trap. A small N2 purge is added to the line from the condenser to the H2O trap. The reactor is charged with AlCl3 and bromine. The addition funnel is charged with diphenyl oxide. The reactor is heated to 55 C. and the diphenyl oxide is added drop-wise supersurface to the bromine. The reactor is heated by a mantle. After all of the diphenyl oxide has been added, the addition funnel is replaced with a Br2 feed line. After several minutes of refluxing, the distillation of Br2 (containing HBr) is initiated. At the same time, the Br2 feed is initiated. As needed, the feed rate of the Br2 is adjusted so that the volume in the reactor remains fairly constant. After the distillation and concurrent replacement feed of Br2 are conducted for an hour, the liquid mixture is cooled to 55 C., some deionized H2O is added, and most of the Br2 is distilled off. When most of the Br2 is gone, more deionized water is added. The remaining Br2 is then distilled. The remaining mixture is cooled to 60 C., and a portion of an aqueous 25% NaOH solution is added to make the pH 13-14. The resultant mixture is filtered and washed well with deionized water. A sample is subjected to GC analysis and then is oven dried. | |
With bromine;aluminum (III) chloride; In 1,2-dibromomethane; at 55 - 69℃; for 4.78333 - 6h;Product distribution / selectivity; | EXAMPLE 1; A reactor was configured using a heating mantle, a 1-liter, 4 neck flask equipped with a mechanical stirrer, a thermometer, an addition funnel equipped with a 1/16 inch Teflon dip tube, an ice cold caustic scrubber and a nitrogen gas inlet to sweep the reactor with nitrogen gas (N2). The reactor was charged with 323 mL of bromine (Br2) and 4.3 g of AlCl3 catalyst. The resulting mixture was stirred and heated to a temperature of 55 C. The addition funnel was then charged with a solution of diphenyl oxide (42.5 g) in dibromomethane (75 mL), which solution was then added, sub-surface, to the bromine/AlCl3 reactor mixture using the dip tube and with agitation of that reactor mixture. Addition was complete after 52 minutes, after which time the reactor mixture was stirred and heated to about 69 C. The scrubber weight gain observed was 255.6 g after the first hour and 10 minutes of refluxing at 69 C. After 2 hours and 10 minutes of refluxing at 69 C., an additional 50 mL of fresh dibromomethane was added to the reaction mixture to increase reflux temperature to 73 C., and the reflux at this temperature was continued for an additional 45 minutes, after which time the heat source was removed and the mixture was allowed to cool slowly. The total reflux time was 2 hours and 10 minutes at 69 C. followed by 1 hour and 45 minutes at 73 C. After cooling overnight, 300 mL of water was added to the reaction mixture, the reactor was set to stir the reaction mixture and distill therefrom the excess bromine. In fifteen minutes the reaction mixture reached 67 C. and distillation of bromine/dibromomethane/water began. Distilled bromine and dibromomethane were continuously removed and distilled water was recycled back to the reactor vessel during the next 25 minutes, at which time the mixture temperature was 69 C. and 100 mL of bromine/dibromomethane had been distilled. Distillation continued for another 1 hour and 20 minutes until substantially all bromine/dibromomethane was distilled. Heat was removed and the reactor content was allowed to cool to room temperature. Caustic then was added to the contents, with stirring, to a pH in the range of 12-13. The contents then was filtered and the resulting cake washed with water (6×150 mL) and allowed to dry in air overnight. The cake when wet weighed 246.3 g, and when dried in air overnight to shiny crystals, it weighed 233.9 g. GC analysis of those crystals revealed nonabromodiphenyl oxide (isomer 1) content of 0.50 area %, nonabromodiphenyl oxide (isomer 2) content of 0.65 area %, and decabromodiphenyl oxide content of 98.84 area %.; EXAMPLE 2; Using equipment identical to that of Example 1, 42.5 g of diphenyl oxide was dissolved in 125 mL methylene bromide and charged to the additional funnel. The reactor was charged with bromine (226 mL Br2) and catalyst (4.25 g AlCl3). The reactor contents was stirred and heated to 60 C. Then addition of the additional funnel charge was initiated via the dip tube. After feeding the funnel contents over a period of 1 hour and 15 minutes, the temperature of the reactor was 63 C. Additional heat was applied to the reactor and 11 minutes later the temperature was 80 C. with the reaction mass refluxing. After 35 minutes of refluxing the temperature remained at 80 C. and the scrubber gain was 257.2 g (compared to theoretical gain of 2.5 moles HBr, 202.5 g). Reflux was continued for a total reflux time of 6 hours, whereupon heat source was cut and the reaction mass was allowed to cool. Agitation of the reaction mass was stopped 36 minutes after the heat source was cut, and the reactor content was allowed to stand overnight. The next morning, 350 mL of water was added to the reactor and the content was stirred well. Steam distillation of the reactor content was commenced with heating. Bromine and methylene bromide began to distill over at 71 C., and water was recycled back to the reactor with separation of the bromine and methylene bromide into a flask. After 1 hour and 10 minutes, the distillation was complete and the reactor temperature was 100 C. The heat source was cut and contents allowed to cool. Sodium hydroxide (aqueous) was added to a pH of 10-11 with stirring. Reactor content was filtered and the resulting cake was washed with water (4×150 mL). The wet cake weight was 253.0 g, and it was allowed to air dry overnight. The dried wet cake weight was 235.0 g (0.244 mole, 98%). GC analysis of the dried product revealed 98.54 area % DBDPO. |
With bromine;aluminum (III) chloride; at 25 - 59℃; for 2.08333 - 25.0833h;Product distribution / selectivity; | Comparative Example; A 500 milliliter four-neck round bottom flask was fitted with a mechanical stirrer, a double walled reflux condenser, a thermocouple, a temperature controller, a heating mantle, and a syringe pump fitted with a Teflon needle. The flask was vented to a water trap for collection of by-product hydrogen bromide. Dry bromine (929.5 grams, 5.82 moles, 200% excess) was charged into the reaction flask, followed by 4.1 grams of aluminum chloride (0.031 mole). The reaction was stirred for 5 minutes.Addition of 33.0 grams (0.19 mole) of diphenyl ether was initiated to the bromine-catalyst mixture at a temperature of 25C. The diphenyl ether addition was maintained at a constant rate by use of a syringe pump over a period of about 180 minutes. The reaction temperature was allowed to increase by way of exotherm to about 35C. Additional heat was applied after the diphenyl ether addition had been completed, and the reaction temperature increased to about 59C within about 20 minutes. After 180 minutes of post addition heating, the heat input was removed and the reaction allowed to cool to room temperature in about 90 minutes.A two liter four-neck round bottom flask was fitted with a mechanical stirrer, a distilling head, a double walled reflux condenser, a thermocouple, a temperature controller, and a heating mantle. One liter of water and the reaction slurry were charged to the flask and the excess bromine was distilled off until a temperature of 100C was achieved.Decabromodiphenyl ether was filtered from the aqueous slurry, washed with water, and dried at 100 C. in a forced air oven.Gas chromatographic analysis of the resulting product showed decabromodiphenyl ether 96.93 area percent, nonabromodiphenyl ether isomers totaling 2.79%, octabromodiphenyl ether isomers totaling 0.25%, and heptabromodiphenyl ether isomers totaling 0.02%.; Example 1; A two liter four-neck round bottom flask was fitted with a mechanical stirrer, a double walled reflux condenser, a thermocouple, a temperature controller, a heating mantle, and a syringe pump fitted with a Teflon needle. The flask was vented to a water trap for collection of by-product hydrogen bromide. Dry bromine (3,410 grams, 21.34 moles, 1000% excess) was charged into the reaction flask, followed by 17.9 grams of aluminum chloride (0.13 mole). The reaction was stirred for five minutes.Addition of 33.0 grams (0.19 mole) of diphenyl ether was initiated to the bromine-catalyst mixture at a temperature of 25 C. The diphenyl ether addition was maintained at a constant rate by use of a syringe pump over a period of about 60 minutes. The reaction temperature was allowed to increase by way of exotherm to about 35 C. Additional heat was applied after the diphenyl ether addition had been completed, and the reaction temperature increased to about 59 C. within about 20 minutes. After about 60 minutes of post addition heating, the heat input was removed and the reaction allowed to cool to room temperature in about 90 minutes.A three liter four-neck round bottom flask was fitted with a mechanical stirrer, a distilling head, a double walled reflux condenser, a thermocouple, a temperature controller, and a heating mantle. One liter of water and the reaction slurry were charged to the flask and the excess bromine was distilled off until a temperature of 100 C. was achieved.Decabromodiphenyl ether was filtered from the aqueous slurry, washed with water, and dried at 100 C. in a forced air oven.Gas chromatographic analysis of the resulting product showed decabromodiphenylether 99.95 area percent, nonabromodiphenyl ether isomers totaling 0.05%, with no other isomers present.; Example 2; The procedure of Example 1 was repeated except that the amount of aluminum chloride was reduced to 6.2 grams (0.047 mole).Gas chromatographic analysis of the resulting product showed decabromodiphenylether 99.90 area percent and nonabromodiphenyl ether 0.1%, with no other isomers present.; Example 3; A two liter four-neck round bottom flask was fitted with a mechanical stirrer, a double-walled reflux condenser, a thermocouple, a temperature controller, a heating mantle, and a syringe pump fitted with a Teflon needle. The flask was vented to a water trap for collection of by-product hydrogen bromide. Dry bromine (3410.1 grams, 21.34 moles, 1000% excess) was charged into the reaction flask, followed by 6.5 grams of aluminum chloride (0.049 mole). The reaction was stirred for five minutes.Addition of 33.0 grams (0.19 mole) of diphenyl ether was initiated to the bromine-catalyst mixture at a temperature of 25 C. The diphenyl ether addition was maintained at a constant rate by use of a syringe pump over a period of about 60 minutes. The reaction temperature was allowed to increase by way of exotherm to about 31 C. Additional heat was applied after the diphenyl ether addition had been completed, and the reaction temperature increased to about 59 C. within about 20 minutes. After about 24 hours of post... | |
99.436 - 99.71%Chromat. | 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 99.71% of decabromodiphenyl oxide, and 0.034 and0.259% 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 59C 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 99.59% of decabromodiphenyl oxide and 0.11% and 0.296% 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 99.61% of decabromodiphenyl oxide and 0.100 and 0.291% 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 0.093% and 0.471% of the first and second nonabromodiphenyl oxide peaks, respectively, and 99.436% of decabromodiphenyl oxide. After drying over the weekend the product weighed 260.1 g. | |
With bromine;aluminum (III) chloride; In dichloromethane; chlorobromomethane; 1,2-dibromomethane; at 7℃; for 3.5 - 8h;Heating / reflux;Product distribution / selectivity; | Example 1; Decabromodiphenyl ether - Simultaneous bromination and milling in a mixed solvent; To a 1 liter round bottomed flask equipped with a mechanical stirrer, a dropping funnel, a thermocouple and a reflux condenser was added 440 g of solvent mixture (DCM 20 %, CBM 40 %, and DBM 40 % w/w) ; bromine, 475 g; AlCl3,4.3 g; and ceramic beads (1.5-3.5 mm diameter), 814 g-A solution of diphenyl oxide (42.5 g, ) in 20 ml of solvent mixture was dropped into the flask during 70 minutes with stirring while keeping the temperature at 7- 13 C . The reaction mixture was refluxed for 4.5 hours, the flask was cooled and 55 ml of water was carefully added to destroy the catalyst. Excess bromine was bleached with sodium bisulfite solution, the aqueous phase was separated and the organic phase was washed with water. The product mixture was passed through a sieve to remove the ceramic beads and the mixture was filtered, washed with water and dried. The product comprised 99.4 % decabromodiphenyl ether and 0.1 % nonabromodiphenyl ether (in the Examples sometimes abbreviated "Deca" and "Nona", respectively). Particle size 7.1 microns (dg0) .; Example 2 (comparative); Decabromodiphenyl ether - Bromination without milling in a mixed solvent.; The procedure of Experiment 1 was repeated without the ceramic beads present. The product consisted of 94.1 % Deca and 5.8 % Nona. Particle size 98 microns (d90).; Example 3; Decabromodiphenyl ether- increasing the crystal size of milled Deca in a simulated reaction mixture after bromination and destruction of the catalyst.; The product of Example 1, having a particle size of 7.1 microns (dgo) and an assay of 99.4 %, was charged to a 1 liter flask followed by 440 g of solvent mixture (DCM 20 %, CBM 40 %, and DBM 40 %); 4.3 g AlCl3, 50 g of bromine and 50 ml of water to destroy the catalyst. The mixture was refluxed for 5.3 hours, cooled and bleached with bisulfite. The product was filtered, washed with water and dried. The particle size v/as 28.8 microns (dgo), had an assay of 99.7 % and was easily filtered.; Example 7; Decabromodiphenyl ether - Bromination of pre-milled Deca precursor; To a 2 liter jacketed reaction vessel equipped with a mechanical stirrer, a dropping funnel, a thermocouple and a reflux condenser was added 500 g of milled Deca (content 97.3 %, particle size 3.8 microns (d90) ) , 1945 g of solvent mixture, 444 g bromine and 22 g AICI3. The <n="20"/>mixture was heated at reflux for 3.5 hours. Water, 260 ml, was added and the excess bromine was bleached with sodium bisulfite solution. To the thick slurry was added 150 ml of water. The mixture was filtered and the dried solid comprised 99.6 % Deca with particle size 38.5 microns (dgo).; Example 8; Decabromodiphenyl ether- Bromination of pre-milled Deca precursor on an industrial scale; A reactor vessel of 16 cubic meters capacity was charged with 7500 liters of solvent consisting of 12.6 % dichloromethane, 32.5 % bromochloromethane and 54.9 % dibromomethane . Aluminum chloride, 150 kg, 8 tons of pre- milled Deca (Deca content 97.9 % with particle size 14 microns (dg0) ) and 1000 kg of bromine were added. The mixture was heated at reflux for 8 hours and was then bleached with 1340 liters of 38 % sodium bisulfite solution. The upper aqueous solution was decanted and the mixture was washed with two 1200 liters portions of water. Sodium hydroxide, 20 %, was added to neutralize the mixture which was then centrifuged. The product was dried and was found to contain 99.3 % Deca with particle size 42 microns (d90).; Example 9; Decabromodiphenyl ethane - Simultaneous bromination and milling in a mixed solvent; To a 1 liter round bottomed flask equipped with a mechanical stirrer, a dropping funnel, a thermocouple and a reflux condenser was added 520 g of solvent mixture <n="21"/>(DCM 6 %, CBM 20 %, and DBM 74 % ) ; bromine, 539 g; AlCl3, 9 g; and ceramic beads (1.5-3.5 mm diameter), 840 g.A 55 % solution of diphenyl ethane in DCM (91.1 g, ) was dropped into the flask during 30 minutes with stirring while keeping the temperature at 21-26 0C. The reaction mixture was refluxed for 6.7 hours, and 120 ml of water was carefully added to destroy the catalyst. Bromine was bleached with sodium bisulfite solution, the aqueous phase was separated and the organic phase was washed with water and was neutralized with 20 % NaOH. The product mixture was passed through a sieve to remove the ceramic beads and the mixture was filtered, washed with water and dried. The product comprised 91.4 % decabromodiphenyl ethane and 7.8 % nonabromodiphenyl ethane. Particle size was 6.1 microns (d90).; Example 10 (comparative); Decabromodiphenyl ethane - Bromination without milling in a mixed solvent.; The procedure of Example 9 was repeated without the ceramic beads present. The product comprised 80.6 % decabromodiphenyl ethane and 18.6 % nonabromodiphenyl ethane. Particle size 22 .microns (dgo). | |
With bromine;aluminum (III) chloride; at 6℃; for 7.2h;Heating / reflux;Product distribution / selectivity; | Example 4; Decabromodiphenyl ether- Simultaneous bromination and milling in bromine solvent; To a 1 liter round bottomed flask equipped with a mechanical stirrer, a dropping funnel, a thermocouple and a reflux condenser was added 1200 g bromine, 6.8 g AlCl3, and 840 g ceramic beads (1.5-3.5 mm diameter). Molten DPO, 60 g was dropped into the flask from the heated funnel during 1 hour while keeping the temperature at about 6 0C. The contents of the flask were heated at reflux for' 6.2 hours and were then cooled to room temperature. Water, 100 ml, was carefully added to destroy the catalyst. The excess bromine was then distilled with the simultaneous addition of 165 ml of water. Some residual bromine was bleached with sodium bisulfite solution and the product mixture was passed <n="19"/>through a sieve to remove the ceramic beads. The mixture was filtered, washed with water and dried. The product comprised 99.9 % Deca and 0.1 % Nona. Particle size 14 microns (dgo).; Example 5 (comparative); Decabromodiphenyl ether- Bromination without milling in bromine solvent.; The procedure of Experiment 4 was repeated without the ceramic beads present. The product comprised 98.3 % Deca and 1.2 % Nona. Particle size 143 microns (d90). | |
With bromine;aluminum tri-bromide; for 5h;Heating / reflux;Product distribution / selectivity; | Example 12 (comparative)Decabromodiphenyl ether - Bromination of Deca completely dissolved in bromine.; The solubility of Deca in bromine was determined as 2.64 g Deca in 100 g bromine at 200C.To a 1 liter round bottomed flask equipped with a mechanical stirrer, a dropping funnel, a thermocouple and a reflux condenser was added 22 g of non milled Deca (content 97.1 %) and 1642 g bromine to produce a 1.32 % solution. AlBr3, 14.1 g, was added and the mixture was heated at reflux for 5 hours. After cooling to room temperature, water, 250 ml, was carefully added. The bromine was distilled and an additional 520 g of water was added. The solid was filtered and dried and consisted of 99.6 % Deca. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With cadmium selenide; triethylamine; In N,N-dimethyl-formamide; at 20℃; for 24h;Irradiation; Sealed tube; | Using CdSe quantum dots as photocatalyst, take 10 mL of quantum dot stock solution, add appropriate amount of hydrochloric acid, centrifuge, discard the supernatant to retain solids, and redistribute the quantum dot solids to 4 mL of N,N-dimethylformamide (DMF). The concentration of the quantum dots was 2.47×10-5 M; decabromodiphenyl ether (0.05 mmol) and triethylamine (2.5 mmol) were added to DMF, the rubber stopper was sealed, and the atmosphere was degassed for 20 min to remove the system. The oxygen in the room was irradiated for 24 hours at room temperature with an LED lamp (lambda > 460 nm). After the reaction, the yield and selectivity of diphenyl ether were determined by GC (FID) using diphenylacetonitrile as an internal standard. The debromination efficiency of decabromodiphenyl ether was determined by ion chromatography using sodium chloride as an internal standard. The experimental results show that decabromodiphenyl ether can be completely removed by quantum dot photocatalytic reduction and dehalogenation hydrogenation. The debromination efficiency is 65%, the yield of diphenyl ether is 54%, and the selectivity is as high as 83%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.24%Chromat.; 99.54%Chromat. | With bromine;aluminum (III) chloride; at 55 - 61℃; for 6.25h;Product distribution / selectivity; | 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 25% 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 0.21% of the first nonabromodiphenyl oxide peak (deemed to be meta- and para-hydrogen isomers), 0.24% of the second nonabromodiphenyl oxide peak (deemed to be the ortho-hydrogen isomer) and 99.54% of decabromodiphenyl oxide. The sample was oven dried. |
0.031 - 0.205%Chromat.; 99.90 - 99.95%Chromat. | 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 5% 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 0.017% of the first nonabromodiphenyl oxide peak (meta and para isomers), 0.031% of the second nonabromodiphenyl oxide peak (ortho isomer) and 99.95% 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 25.6C. 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,5% NaOH was added to pH of about 13, and the product was collected and washed. GC analysis showed the product to contain 0.020% of the first nonabromodiphenyl oxide peak (meta and para isomers), 0.080% of the second nonabromodiphenyl oxide peak (ortho isomer) and 99.90% 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 ... | |
0.181 - 0.220%Chromat.; 99.634 - 99.696%Chromat. | 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 25% 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 0.084% of the first nonabromodiphenyl oxide isomer (a mixture of meta and para hydrogen containing isomers) and 0.220% of a second nonabromodiphenyl oxide isomer (ortho-hydrogen isomer) and 99.696% 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.185% of a first nonabromodiphenyl oxide isomer (believed to be a mixture of meta and para hydrogen containing isomers) and 0.181% of a second nonabromodiphenyl oxide (believed to be ortho-hydrogen isomer) and 99.634% of decabromodiphenyl oxide. After oven drying for 2 hours the product weighed 246.0 g. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.233 - 0.526%Chromat.; 99.44 - 99.70%Chromat. | 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 2% NaOH was added. Product was collected and water washed. GC analysis showed 0.067% and 0.233% of the first and second nonabromodiphenyl oxide isomers, respectively, the second being the ortho isomer, and99.70% 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 78.4C 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 0.034% and 0.526% of the first and second nonabromodiphenyl oxide isomers, respectively, the second being the ortho isomer, and 99.44% of DBDPO. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97.2%Chromat. | With bromine; bromine chloride;aluminum (III) chloride; at 55 - 57℃; for 2.23333h;Heating / reflux;Product distribution / selectivity; | 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 25% 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 0.26% Br9DPO (meta and para hydrogen isomers only), 2.52% Br9ClDPO, and 97.2% Br10DPO. None (less than 0.02%) 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. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.14%Chromat.; 99.29%Chromat. | With bromine; bromine chloride;aluminum (III) chloride; at 56℃; for 0.0666667h;Heating / reflux;Product distribution / selectivity; | 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 0.31% Br9DPO (0.17% combined of the meta and para hydrogen isomers, and 0.14% of the ortho hydrogen isomer), 0.40% Br9ClDPO, and 99.29% Br10DPO. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methanol; n-propanol water; ethanol; water; | A mixture of ethyl alpha-(2,5-dimethoxybenzylacetoacetate (21.2 g) <strong>[1004-38-2]2,4,6-triaminopyrimidine</strong> (10 g) and diphenylether (100 ml) was heated at 190-230C for 1.5 hours in an apparatus fitted with a Dean-Stark trap and water-ethanol (4 ml) was collected. Methanol (200 ml) and ethanol (50 ml) were added to the cooled reaction mixture. The resulting solid was collected by filtration and treated with boiling water (1 l) to give 2,4,-diamino-5-methyl-6-(2,5-dimethoxybenzyl)-7-oxo-7,8-dihydropyrido[2,3- d ]pyrimidine (17 g), m.p. 325-326C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Boron triiodide (156 mg, 0.40 mmol) and diphenyl ether (287 mg, 1.6 mmol) under a nitrogen atmosphere,It heat-stirred at 180 degreeC for 12 hours.After cooling the reaction solution to room temperature, it is distilled off under reduced pressure.1-diiodoboryl-4-phenoxybenzene (Y-8)And 1-diiodoboryl-3-phenoxybenzene (Y-9)Was obtained as a mixture.Then triethylamine (0.670 ml, 4.8 mmol),Add pinacol (142 mg, 1.2 mmol),Stir at room temperature. Thereafter, the solvent was distilled off under reduced pressure.Gel permeation chromatography of the obtained crude productWhen isolated and purified with (eluent: toluene),Compound (Y'-2-9) and Compound (Y'-2-10)(60.1 mg, yield 5 1percent)In a ratio of 75:25 as a yellow liquid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | General procedure: To a solution of anisole 3A (3.0 mmol, 324.4 mg) in THF (3.0 mL) was added n-BuLi (4.5 mmol,1.55 M in hexane, 2.87 mL) at 0 C. The mixture was stirred for 2 h at 0 C under an argon atmosphere. Then, pivalonitrile (9.0 mmol, 748.2 mg) in THF (2.0 mL) was added to the mixture at 0 C and the obtained mixture was stirred for 30 min in the temperature range of 0 C to room temperature. MeOH (2.0 mL) was added to the mixture. Then, I2 (12.0 mmol, 3045.6 mg) and K2CO3 (12.0 mmol, 1658.4 mg) were added to the mixture at room temperature, and the obtained mixture was stirred for 6 h at 70 C. Sat. aq. Na2SO3 solution (20.0 mL) was added to the reaction mixture, and the product was extracted with AcOEt (10.0 mL x 3). The organic layer was dried over Na2SO4. After filtration and removal of the solvent, the residue was purified by silica-gel column chromatography (chloroform: n-hexane 1:1) to give 2-methoxybenzonitrile 2A (315.6 mg, 79%). |
Tags: 101-84-8 synthesis path| 101-84-8 SDS| 101-84-8 COA| 101-84-8 purity| 101-84-8 application| 101-84-8 NMR| 101-84-8 COA| 101-84-8 structure
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P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
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