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CAS No. : | 80-08-0 | MDL No. : | |
Formula : | C12H12N2O2S | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | MQJKPEGWNLWLTK-UHFFFAOYSA-N |
M.W : | 248.30 | Pubchem ID : | 2955 |
Synonyms : |
4,4′-Diaminodiphenyl sulfone;DDS;Sulfona;4,4'-Sulfonyldianiline;Diaphenylsulfone;NSC 6091;4,4'-Diaminodiphenyl sulfone;Dapson
|
Chemical Name : | 4,4'-Sulfonyldianiline |
Num. heavy atoms : | 17 |
Num. arom. heavy atoms : | 12 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 2 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 2.0 |
Molar Refractivity : | 67.19 |
TPSA : | 94.56 Ų |
GI absorption : | High |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -7.13 cm/s |
Log Po/w (iLOGP) : | 1.28 |
Log Po/w (XLOGP3) : | 0.97 |
Log Po/w (WLOGP) : | 2.78 |
Log Po/w (MLOGP) : | 1.87 |
Log Po/w (SILICOS-IT) : | 0.85 |
Consensus Log Po/w : | 1.55 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.38 |
Solubility : | 1.03 mg/ml ; 0.00416 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.54 |
Solubility : | 0.71 mg/ml ; 0.00286 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -4.13 |
Solubility : | 0.0185 mg/ml ; 0.0000746 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.92 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302 | Packing Group: | N/A |
GHS Pictogram: |
* 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 |
---|---|---|
64% | In methanol; at 65℃; for 4h; | General procedure: To a solution of isobenzofuran-1,3-dione (1.48 g, 10 mmol) in methanol (4 mL/1 mmol) at room temperature was added aliphatic or aromatic amine (10 mmol) and the reaction mixture was refluxed at 65 C for 4 h. After completion of the reaction as indicated by the TLC, the reaction was cooled to room temperatureand purified by column chromatography using petroleum ether:ethyl acetate (7:3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91.9% | With ammonium chloride; In ethanol; for 5h;Reflux; | 50.0 ml of ethanol was taken in a 250 ml three-necked flask, And then slowly adding <strong>[80-07-9]4,4'-dichlorodiphenylsulfone</strong> 10.0 g (40.27 mmol), 4.30 g (80.54 mmol) of ammonium chloride solid, while stirring while adding 50.0 ml of ethanol, heating reflux reaction 5h, TLC point The reaction was completed, 30ml of distilled water slowly quenched the reaction, stirring cooling, to be a large number of solid precipitation, filtration, with a small amount of ethanol washing filter cake three times, at 40 blast drying, to obtain white crystalline powder 7.9g, Yield: 91.9%. |
With ammonium hydroxide; copper(I) bromide; at 200℃; for 40h; | Into the copper liner of an Adkins rocking bomb is placed 20 g. of 4,4'- dichlorodiphenyl sulfone, 1 g. of cuprous bromide, 0.5 g. copper bronze and 170 cc. of 28% aqueous ammonia. The bomb is shaken at 200 for about 40 hours and shaking is continued during the cooling period to avoid solidification of the product as a solid cake. The solid is filtered from the ammoniacal liquid, washed with water, and dissolved in 10% hydrochloric acid. A small amount of tar and the copper bronze are removed by treatment with Darco activated carbon and filtration. The solution is cooled and the clear brownish liquid is basified with ammonia. The collected precipitate is washed with ammonium hydroxide and water and dissolved in 150 cc. of ethanol and 50 cc. of water. A voluminous precipitate of ferric hydroxide is left undissolved, and it is filtered with addition of standard Super Cel calcined diatomaceous earth filter aid. The slightly brownish filtrate is clarified with Darco activated carbon and diluted with boiling water to a volume of about 800 cc. Flat needles of 4,4'- diaminodiphenylsulfone crystallize on cooling. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Synthesis of N,N'-diamino-diphenyl sulfone N,N'-Diamino-diphenyl sulfone can be synthesized in various ways, but the following synthesis route is offered as an example. This synthesis was performed in two steps: 1. 60 g of acetanilide were poured into an Erlenmeyer flask and heated slowly with flame until the melting of the solid was complete. The resulting viscous liquid was cooled in a glass of ice, ensuring that the solidified material stayed at the bottom of the flask. 165 ml of chloro-sulfonic acid were added in a single portion, without removal from the ice bath. Subsequently, the flask was removed from the ice, mixing carefully, and the reaction was allowed to be take place for 10 minutes, at the end of which the reaction mixture was again heated until the total solubilization of the remaining acetanilide, allowing it to react again for 10 more minutes. The product was allowed to cool and was carefully poured into a container with ice and water, filtering the precipitate and washing it with cold water. The precipitate was collected, dissolved in chloroform and extracted three times with water, collecting the chloroform phase, which was placed in an ice bath, precipitating the purified thionyl chloride (Reported melting point of the intermediary: 149C). 2. 123.6 ml of anhydrous nitrobenzene were poured into a glass reactor, 89.2 g of aluminum chloride were added and heated slowly; then, 41.3 g of thionyl chloride was added to the hot mixture, heating the reaction mixture at a temperature of 140 - 145 C, and 13 g of acetanilide were slowly added, maintaining the reaction temperature for two hours. At the end of this period, the product of the reaction was poured into 104 ml of water acidified with hydrochloric acid then dark crystals were precipitated, and were recrystallized with dilute acetic acid. These crystals were refluxed with 5N hydrochloric acid for 30 minutes, then neutralizing the reaction mixture, with which white crystals were precipitated (raw DDS), which was recrystallized again with ethanol. | ||
114 g | With hydrogenchloride; In water; at 100℃; for 6h; | Oxidation:In a 5L three-necked flask with mechanical stirring, 4,4'-bis (N-acetyl) diphenylsulfoxide (Compound 1,158 g, 500 mmol) was dissolved in 2000 ml of isopropanol, and then added A copper complex catalyst (CuL2-Cat.) (2.8 g, 7.5 mmol) was used as a catalyst. Under agitation conditions, oxygen was continuously introduced and a catalytic oxidation reaction was performed at 80 C. After stirring for 24 hours, the reaction was completed. The reaction was lowered to room temperature, and CuL2-Cat. Was separated by filtration. The filtrate was concentrated under reduced pressure to remove the isopropanol solvent. After vacuum drying, 4,4'-bis (N-acetyl) di Phenylsulfone (compound 2), all solids were used directly in the next hydrolysis reaction.Hydrolysis reaction: Suspend the solid obtained in the above reaction in 1000 ml of a 2.0 mol / L hydrochloric acid solution, and then raise the temperature of the reaction solution to 100 C. and stir for 6 hours. After the hydrolysis is completed, reduce to room temperature and use 10% (mass) Fractional) sodium hydroxide solution adjusted the pH of the solution to 12, and precipitated a large amount of solids. The product was filtered and washed with water to obtain a crude 4,4'-diaminodiphenylsulfone, which was a crude 4,4'-diaminodiphenylsulfone. After recrystallization from acetone, 114 g of a white solid was obtained, which was pure 4,4'-diaminodiphenylsulfone (compound 3). The yield was 92% in two consecutive steps. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
5 mg | With water; sodium hydroxide; In methanol; at 35℃; for 2h; | In a reaction flask 10 mg of N-(4-(4-aminophenylsulfonyl)phenyl)acetamide (0.00008 mol), 2 ml di methanol, 1 ml of water and 6 mg of NaOH (0.00016 mol) were charged, the temperature was brought to about 35C and the reaction mixture was kept under in these conditions for about 2 hours. At the end of the reaction, 2 ml of ethyl acetate were added, the aqueous phase was extracted with ethyl acetate (1 x 1 ml), and the collected organic phases were reduced to a residue by distillation under vacuum to give 5 mg of Dapsone. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With pyridine; dmap; at 20℃; for 10h; | To a solution of 4,4'-sulfonyldianiline (283 mg, 1.1 mmol, 3 equiv.) in pyridine (1 mL) was added Ac2O (36 muL, 0.38 mmol, 1 equiv.) and catalytic amounts of DMAP and the reaction stirred for 10 h at RT. Column chromatography on silica gel (DCM/MeOH) afforded the desired product as a white solid (100 mg, 0.034 mmol, 88%). Rf=0.51 (DCM/MeOH, 10:1). LC-MS: m/z=291.05 [M+H]+. 1H NMR (DMSO-d6, 400 MHz) delta ppm 10.31 (s, 1H), 7.70-7.77 (m, 2H), 7.50 (d, J=8.8 Hz, 2H), 6.60 (d, J=8.8 Hz, 2H), 6.13 (s, 2H), 2.06 (s, 3H). 13C NMR (DMSO-d6, 101 MHz) delta ppm 169.0, 153.4, 142.9, 136.8, 129.2, 127.7, 126.1, 118.8, 112.9, 24.1, 22.8. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34% | With pyridine; In 1,4-dioxane; at 20℃; | General procedure: Dapsone (3 mmol) is dissolved in pyridine (5 mL/mmol). The acyl chloride (1 mmol) is dissolved in dioxane (5 mL/mmol) and added dropwise to the reaction mixture which is then stirred over night at room temperature. To purify the crude product, approximately 50 mL of diethylether are added to the solution. The formed precipitate is separated and dissolved in DMF. The solution is poured into 200 mL of 2 M hydrochloric acid and the resulting precipitate is filtered off and washed thoroughly with water. The product is dried in vacuo and can be further purified by flash column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
12.5% | With triethylamine; In acetone; at 20℃;Cooling with ice; | General procedure: Mono-chloromethyl-acetamido- derivatives were preparedas described earlier [24]. Briefly: To a magneticallystirred, ice-bathed, solution or suspension of the particularcommercially available sulfanilamide or aniline (1.0 equivalent)and triethylamine (2.0 equivalents) in dry acetone (25ml), chloroacetylchloride (1.5 equivalents) in dry acetone (25ml) was gradually added over 30 minutes. The reaction mixturewas stirred at room temperature until TLC revealedcomplete consumption of the starting amine. Subsequently,the reaction mixture was poured slowly onto ice water (100ml). The precipitated crude products were purified by recrystallizationfrom acetone/water. Scheme 1 shows the preparedcompounds and their corresponding starting materials. |
6% | With pyridine; In 1,4-dioxane; at 20℃; | General procedure: Dapsone (3 mmol) is dissolved in pyridine (5 mL/mmol). The acyl chloride (1 mmol) is dissolved in dioxane (5 mL/mmol) and added dropwise to the reaction mixture which is then stirred over night at room temperature. To purify the crude product, approximately 50 mL of diethylether are added to the solution. The formed precipitate is separated and dissolved in DMF. The solution is poured into 200 mL of 2 M hydrochloric acid and the resulting precipitate is filtered off and washed thoroughly with water. The product is dried in vacuo and can be further purified by flash column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With Na+-MMT-[pmim]HSO4; In neat (no solvent); at 60℃; for 0.416667h; | General procedure: Amine (1 mmol) was added to a mixture of Na+-MMT-[pmim]HSO4 (10 mg, 1 mol %) and formic acid (2 mmol) and the resulting mixture was stirred at 60 C for the appropriate time. After completion of the reaction (monitored by TLC), ethyl acetate (10 mL) was added and the catalyst was separated by filtration. The organic phase was washed with water (2 x 10 mL) and dried over Na2SO4. The solvent was removed under reduced pressure to afford the desired product. |
In toluene; for 8h;Reflux; | General procedure: General procedure for the isonitrile synthesis: The mixture of diamine 1 (0.050 mol), toluene (100 ml) and 98% formic acid (7.5 ml, 0.2 mol) was refluxed for 8 h. After cooling, the mixture was evaporated to dryness, the residue was treated with a new portion of toluene (100 ml) and evaporated again to give the crude diformamide 2. To a flask with crude diformamide 2 was added triethylamine (51 ml, 0.36 mol) and dichloromethane (200 ml). The resulting solution (or suspension) of crude diformamide 2 was cooled to 0oC (ice-water bath) and phosphorous oxychloride (11.3 ml, 0.12 mol) was added dropwise over 20-30 minutes. After the addition of the POCl3, the mixture was stirred for about 1 h at 0oC (ice-water bath) and 2 h at room temperature. The reaction mixture was cooled again (0oC, ice-water bath) and a solution of about 25 g of Na2CO3 in 100 ml of water was added dropwise over 15-20 minutes. The final two-phase mixture was stirred for about 1 h. The organic phase was separated and the aqueous phase was extracted with dichloromethane (3×50 ml). The combined organics were washed with brine (4×50 ml), dried over anhydrous Na2SO4, and concentrated in vacuo, yielding crude isocyanide 3.The oily isocyanide 3m was used for the next step without purification, 3l was purified by bulb to bulb distillation, while the remaining solid isocyanides were crystallized from an appropriate solvent (see Table 1 at page 3). 1,6-Diisocyanohexane was purchased from Sigma-Aldrich, Germany. Isocyanides 3a,3-6 3b,5-7 3c,7 3d,7-9 3e,4,10 3f,7 3g,4,11,12 3h,12,13 3j,4,7 3k,14,15 and 3m9,16 are known in the literature. Spectroscopic data for the new isocyanides 3i and 3l are shown below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium azide; sodium nitrite; In hydrogenchloride; water; | 4-Azidophenyl sulfone A solution of NaNO2 (0.48 g, 7.00 mmol) in water was added dropwise to a solution of 4-aminophenyl sulfone (0.83 g, 3.33 mmol) in 2 N HCl (14 mL) at 0-5 C. with vigorous stirring. The mixture was kept below 5 C. for 30 min followed by neutralization with calcium carbonate. Then, a solution of NaN3 (0.49 g, 7.53 mmol) in water (3 mL) was added dropwise while the temperature was kept below 5 C. The solid precipitate was filtered, washed with water (3*30 mL) and finally recrystallized from ethanol. Yield: 2.73 mmol, 82%, yellow solid. 1H: [300 MHz, CDCl3] delta=7.10-7.13 (m, 4H), 7.89-7.91 (m, 4H) ppm. 13C: [75 MHz, CDCl3] delta=119.7, 129.5, 137.6, 145.4 ppm. MS-EI: [C11H8N6O2S] m/z cal. [M]+·=300.0429, m/z found [M]+·=300.0429. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In diethylene glycol dimethyl ether Heating; | ||
In diethylene glycol dimethyl ether for 15h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
2.5 kg | With triethylamine In acetonitrile for 45h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: N,N,Ν',N'-tetraglycidyl-4,4'-diaminodiphenylmethane; dapsone at 140℃; for 16h; Stage #2: at 200℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | In methanol Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In methanol Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With dihydrogen peroxide; In water; acetonitrile; at 50℃; for 3h; | General procedure: A solution of sulfide (1 mmol) and catalyst (100 mg), in acetonitrile (9 mL), was added to H2O2 35% (w/v) (10 mmol). The mixture was stirred at 50 C for a time period (see Tables 1 and 2). The solvent was evaporated and then H2O (5 mL) was added. The substrate was extracted with toluene (2 × mL) and dried with anhydrous Na2SO4; filtration and evaporation afforded the corresponding sulfoxides. The crude solids were purified by recrystallization to affordthe pure sulfones |
With dihydrogen peroxide; In acetonitrile; at 25℃; for 24h; | General procedure: Diphenyl sulfide was used as the model reagent for sulfide oxidationstudies. They were performed with H2O2 (aq. solution) as the oxidant,acetonitrile as the solvent, in a batch reactor at 25 C, using POTV (PVWand PV2W) and synthesized hybrid materials (PAACA-PVWX andPAACA-PV2WX) as homogeneous or heterogeneous catalysts respectively. We made experiments using excess of H2O2 (10 mmol ofH2O2 per 1 mmol of sulfide). We also tested the oxidation reaction usinglower amount of oxidant (0.3 and 0.5 ml of 35% w/v H2O2) but verylong reaction times were required to obtain suitable conversion values.So we decided to use 1 ml of 35% w/v H2O2 for the catalytic test. More details about the experimental conditions and the identification of theproducts were added in the supplementary information. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | Example 6: preparation of Dapsone; In a hydrogenation vessel 4-(4'-Nitro-benzenesulfonyl)-phenylmanine (100 g), p-toluensulfonic acid (68.4 g), methanol (350 ml), water (150 ml) and 10% palladium on charcoal (7.6 g) are charge. The mixture is allowed to react with hydrogen at approximately 50C and 5 bar pressure. At reaction completion, hydrochloric acid is added, the catalyst is filtered and dried. 82 g of crude Dapsone are obtained (82% yield; >99.5% purity). | |
80% | Example 5: preparation of Dapsone; Charge an hydrogenation vessel with 4-(4'-nitro-benzenesulfonyl)-phenylmanine(380g;1.36 mole), water (220 ml), methanol (910 ml) and methansulfonic acid (187kg; 1.95 mole). Then charge under nitrogen, 5% palladium on charcoal (14.4g;0.0067 mole). After inertization, the mixture is added with hydrogen under vigorousstirring up to 4 bar and then heated to 50C. The mixture is maintained under theabove conditions for the least 4 hours. After reaction completion the reactor ispurged with nitrogen several times and the catalyst filtered off. The filter is washedwith methanol (25 ml) and water (200 ml) and the solution is concentrated undervacuum below 50C to remove the organic solvent. A the end, then the mixture isneutralised with 15% ammonia at 50C, then cooled and the product isolated byfiltration.After drying, 315 g of crude product is obtained . Product is crystallised from iso-propanol (1000 ml) and water (700 ml) to give 302 g of pure product (80% yield;>90% purity). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In 1,4-dioxane | 7 4'4"'-Sulfonybis(2-methylaminoacetanilide) EXAMPLE 7 4'4"'-Sulfonybis(2-methylaminoacetanilide) To a stirred solution of 24.83 g of bis(p-aminophenyl)sulfone in 100 ml of dioxane and 200 ml of dimethoxyethyl ether at 50° C. was added a 1:1 mixture of chloroacetyl chloride and dimethoxyenthyl ether. The mixture was heated at 90° C. for 3.5 hours and then allowed to stand at ambient temperature. The solid was collected and crystallized giving 10.2 g of bis[(p-chloroacetamido)phenyl]sulfone. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Sodium phenylphosphinate; In 1,2-dichloro-benzene; at 180 - 230℃; for 7h;Product distribution / selectivity; | Comparative Example-2; Imidization in Parr Reactor with Up-Front CLPA Addition; A 450 ml Parr pressure-rated reactor equipped as in Comparative Example-1 with two side quartz windows and a partial condenser was charged with solid <strong>[117-21-5]3-chlorophthalic anhydride</strong> (3-ClPA, 21.578 g; 118.2 mmol), phthalic anhydride (0.2664 g; 1.8 mmol), DDS (14.898 g; 60 mmol), sodium phenylphosphinate (50 mg; 0.3 mmol) and o-DCB (85 ml). The reactor was sealed and the temperature was gradually raised. At about 180 C. the reaction mixture was observed to become homogeneous. As water of imidization was removed via the partial condenser the reaction gradually became heterogeneous and eventually the mixture became so thick that mixing of the solid adhering to the quartz window ceased to occur. As the temperature of the reaction mixture was raised further to about 190 C. the heterogeneous reaction mixture began to thin and the viscosity of the heterogeneous mixture was visibly diminished by the time the reaction mixture reached 200 C. Between about 210 C. and about 215 C. most of the solid material present in the reaction mixture dissolved. Thereafter the temperature was raised to 230 C. After about 7 hours imidization was deemed to be complete. Heating was discontinued and as the temperature decreased to about 215 C. the product bisimide began to precipitate from solution. When the temperature had decreased to about 200 C. the product mixture became so thick that efficient stirring could no longer be effected. This Comparative Example illustrates the limitations of “up-front” addition of all of the reactants. Thus, when each of the reactants is added to the reaction vessel at ambient temperature and thereafter the temperature of the reaction mixture is raised. While the reaction mixture is initially homogenous at about 180 C., as water of imidization is removed, the reaction mixture exhibits thick phase behavior which persists until the temperature reaches a higher threshold temperature, in this Comparative Example about 215 C., at which the reaction mixture becomes homogeneous again. The thick phase behavior is undesirable in that it prevents the efficient mixing of the reaction mixture while the thick phase persists and makes accurate measurement of reaction stoichiometry difficult.; Example-1; Imidization in Parr Reactor with Melt CLPA Addition-Procedure:; A 450 ml Parr pressure-rated reactor equipped as in Comparative Example-1 was charged with DDS (14.898 g; 60 mmol), sodium phenylphosphinate (50 mg, 0.3 mmole) and o-DCB (85 mL). The temperature was gradually raised to about 225-230 C. The resultant homogeneous solution was maintained at about 230 C. for 1 hr after which time molten <strong>[117-21-5]3-chlorophthalic anhydride</strong> (3-ClPA, 21.578 g, 118.2 mmole) and phthalic anhydride (0.2664 g; 1.8 mmol) at about 130 C. was added from a stainless steel bomb mounted on top of the reactor. The addition of 3-ClPA was carried out over a period of about 30 to 40 minutes. Water of imidization was azeotropically removed from the reactor via the partial condenser. Throughout the 3-ClPA/PA addition, and thereafter, the reaction mixture was observed to remain a homogeneous solution while at 230 C. No thick phase behavior was observed during the reaction. As the reactor was cooled, the product bisimide was observed to precipitate over a temperature range from about 215 to about 210 C. The reactor was vented when the temperature had decreased to about 170 C. and a sample of the pasty product mixture was withdrawn and analyzed by HPLC. The quality of the product bisimide (“ClPAMI”) was found to be equivalent to the quality of ClPAMI made using known methods.Larger scale imidization reactions using the method of the present invention were conducted in a 5 gallon reactor. The larger reactor was equipped with sampling features which allowed the withdrawal of samples of the reaction mixture as a homogeneous solution without venting the reactor or causing the product bisimide to precipitate during sampling. Examples 2 and 3 are illustrative.A reactor system 10 utilized in various embodiments of the invention is shown in FIG. 1. The reactor system comprised a 5-gallon stainless steel reactor 12 connected directly to monomer and catalyst feed lines 14 and inert gas purge line 15, and indirectly to feed lines 16 for addition of molten reactants. The reactor 12 was connected via distillation line 17 to a partial reflux condenser 18, a total condenser 20 and a back-pressure regulator 22. Feed lines 14 were employed for the batchwise addition of DDS, SSP catalyst, and optionally a portion of the ClPA, whereas, monomer feed lines 16 served for the semi-batch mode introduction of a molten mixture of ClPA and the chain stopper phthalic anhydride (PA). Solvent could be introduced into the reactor via solvent feed line 23.Reactant DDS, ODCB solvent and SPP catalyst were charged to the reactor 12 in batch mode, i.e. prior to starting the reaction. In some reactions a portion of th... | |
Sodium phenylphosphinate; In 1,2-dichloro-benzene; at 184.1 - 230.7℃; for 0.05 - 2.41667h;Product distribution / selectivity; | Example 2; The 5-gallon reactor described above and shown in FIG. 1 was equipped with 2 flights of 4-blade pitched turbines, and was charged according to Table I below. TABLE I Component Mass (g) Moles Source 4,4 Diamino Diphenyl Sulfone 1520.8 6.125 Atul (DDS) Phthalic Anhydride (PA) 27.19 0.184 Aldrich Sodium Phenyl Phosphinate 5.0 0.030 Akzo (SPP) 3-Chloro Phthalic Anhydride 2202.8 12.066 Pressure Chem. (ClPA) 1,2 Dicholoro Benzene (ODCB) 9756 66.37 PPG Grade F The reactor was purged with inert gas at 100 SCCM, and the agitation rate was set to 200 rpm. The partial condenser was heated by means of an oil jacket to a temperature of about 130 C. The reactor was heated by setting the reactor oil jacket temperature to 200 C. After 30-minutes of heating, the reactor oil jacket temperature was increased to 230 C. The reactor internal temperature reached a temperature of about 177 C. Water and ODCB were collected as condensed distillate. The reactor pressure was 26.3 psig. Amounts of distillate collected of the course of the reaction, reactor temperature and pressure are shown-in Table II. TABLE II Reactor P Time (min) Reactor T ( C.) (PSIG)H2O (ml) ODCB (ml) 3 184.1 26.3 36 25 6 190.4 26.3 86 52 8 197.4 26.0 114 76 10 205.9 26.4 132 92 16 219.2 25.0 171 117 22 223.5 26.4 186 128 26 225.6 26.4 191 134 30 226.7 26.3 194 138 35 227.7 26.3 198 140 57 230.7 26.2 207 145 After about 1.4 hrs of distillation, the reaction mixture was sampled via the heated sampling port. HPLC analysis of the homogeneous sample indicated that additional 3-ClPA (6.1 grams) was needed to adjust the stoichiometry to within the specified limits. At 2.5 hours of distillation, the 6.1 grams of 3-ClPA was added as a solution of about 9.8 wt % in ODCB.After a total of 4.5 hours the reaction mixture was again sampled. Sample analysis by HPLC indicated that ratio of anhydride to amine was in the range required, from about 1.00 to about 1.03. Therefore, there was no need for any further stoichiometry correction. Heating was continued for a total 9.5 hours at a reactor oil jacket set temperature of 230 C. The reaction was then cooled and diluted with ODCB to provide a slurry of the product so that approximately 3500 grams of solids was obtained as a slurry in 17.8 Kg of ODCB.; Example 3; Melt 3-CLPA Semi-Batch Reaction Mode; The 5-gallon reactor described above and shown in FIG. 1 was equipped with 2 flights of 4-blade pitched turbines, and was charged according to Table III below. TABLE III Component Mass (g) Moles Source 4,4 Diamino Diphenyl Sulfone 1520.8 6.125 Atul Inc. (DDS) Sodium Phenyl Phosphinate 5.0 0.030 Akzo Inc. (SPP) 1,2-Dicholoro Benzene 9991 68.0 PPG Grade F (ODCB) Heated tank 24 (FIG. 1) was charged with phthalic anhydride (PA) and <strong>[117-21-5]3-chlorophthalic anhydride</strong> (3-ClP) in the amounts shown in Table IV and heated to 140 C. in order to melt the 3-ClPA/PA solids. ODCB (240 grams) was then added to the molten mixture of 3-ClPA and PA which was completely miscible with the ODCB. Thus, the mixture in heated tank 24 comprised 3-ClPA (89.2 wt %), ODCB (9.7 wt %), and PA (1.1 wt %). The small amount of ODCB solvent employed helped to facilitate complete transfer of the anhydride reactants into the reaction mixture. TABLE IV Component Mass (g) Moles Source Phthalic Anhydride 27.20 0.184 Aldrich 3-Chlorophthalic Anhydride 2203.0 12.067 Pressure Chem. 1,2-Dicholorobenzene 240.0 1.63 PPG Grade F The 5-gallon reactor was purged with inert gas at 100 SCCM, and the agitation rate was set to 200 rpm. The partial condenser was heated by means of an oil jacket to a temperature of 130 C. The reactor was heated commenced by setting the reactor oil jacket temperature to 180 C. After 30-minutes, the oil jacket temperature was increased to 225 C. At the 1.0-hour mark, the reactor reached a temperature of 226 C., at which point the melt addition of the 3-ClPA-PA-ODCB melt mixture from heated tank 24 was commenced. The reactor pressure was 25.1 PSIG. The 3-ClPA-PA-ODCB melt mixture was pumped via melt feed pump 26 and melt feed line 27 into reactor 12 at an average rate of about 21.5 grams/minute. Addition of the 3-ClPA at a temperature in excess of 210 C. avoided the thick phase reaction stage observed when the reactants are brought into contact at temperatures below about 190 C.About 15 minutes after the addition of the 3-ClPA-PA-ODCB melt mixture was initiated, water and ODCB distillate were observed in the overheads from the partial reflux condenser 18. Addition of the 3-ClPA-PA-ODCB melt mixture required about 2 hours to complete. During the addition of the 3-ClPA-PA-ODCB melt mixture, the amounts of water and ODCB condensed from the overheads emerging from the partial reflux condenser were recorded as a function of time and are recorded in Table V, along with the reactor temperature and pressure profiles. TABLE V Reactor P Time (min)* Reactor T ( C.) (PSIG)H2O (ml) ODCB (ml) 10 222.4 26.5 23 20 20 223.1 26.4 42 33 25 223.2 26.4 53 39 30 223.3 26.5 63 46... |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97.1% | With toluene-4-sulfonic acid; In chloroform; for 8h;Inert atmosphere; Reflux; | S1, the synthesis of intermediates: 1 mol of 4,4'-diaminophenylsulfone and 200 ml of trichloromethane were mixed, Under nitrogen protection, the temperature was raised to the reflux temperature of chloroform, Then 2.5 mol of 2-hydroxybenzaldehyde and 0.1 g of p-toluenesulfonic acid were added and reacted for 8 hours. After the end of the reaction, the mixture was filtered and washed with trichloromethane three times and dried to obtain 0.97 mol of orange-red intermediate, The yield of the intermediate was 97.1% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | In methanol; at 20℃; for 1.5h; | General procedure: All the tetra dentate Schiff base ligands were prepared by condensation between diamines and 2-hydroxy-1-naphthaldehyde in methanol and purified by recrystallization from a methanol through the partial evaporation ofthe more volatile dichloromethane. Schiff base ligands prepared by dissolving 2-hydroxy-1-naphthaldehyde (0.5 g, 2.9 mmol) and diamine (0.15 g, 1.45 mmol) in methanol with stirring inone portion. The stirring was continued to completion of the reaction. The progress of the reaction was monitored by thin layer chromatography (TLC). After the completion of the reaction, a colored substance was obtained. The solid product was filtered and washed with cold MeOH. The crude product was purified by recrystallization from methanol and the pure Schiff base was obtained in high yield after leaving for the appropriate time. The Schiff bases were characterized by physical and spectroscopic data [15]. |
In methanol; | General procedure: All tetradentate Schiff bases were prepared by the condensation of diamines (1 mmol) with 2-hydroxy-1-naphtaldehyde (2 mmol) in methanol under stirring. After the completion of the reaction (TLC monitoring), the obtained colored substances were collected by filtration and washed with cold MeOH. The crude products were purified by recrystallization from ethanol. The physical and spectroscopic data for the synthesized Schiff bases were in good agreement with the published data. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With CeCl3·7H2O-SiO2; In neat liquid; for 0.0666667h;Microwave irradiation; | General procedure: The mixture of Dapsone (3) (1 mmol, 248 mg), 3-nitrobenzaldehyde (4c) (1.1 mmol, 167 mg), diethylphosphite (5) and the catalyst, CeCl3·7H2O-SiO2 (12 mol%) was placed into a 50 mL flat-bottomed flask. The reaction mixture was irradiated under microwave radiations using catalyst systems (CATA-4R), % power is 65% and 465 W. After completion of the reaction (monitored by TLC), DCM (15 mL) was added to the reaction mixture. The catalyst was filtered and washed with DCM (5 mL) to recover it. The combined filtrates and washings were concentrated under reduced pressure, followed by purification on column chromatography using ethylacetate:n-hexane in the ratio of 4:6 as an eluent to afford pure tetraethyl[4,4'-sulfonylbis(4,1-phenylene)bis(azanediyl)]bis[(3-nitrophenyl)methylene]diphosphonate (6c). The filtered residue catalyst was dried under vacuum and reused for the next reaction. This same procedure was adopted for preparing the remaining title products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With CeCl3·7H2O-SiO2; In neat liquid; for 0.0666667h;Microwave irradiation; | General procedure: The mixture of Dapsone (3) (1 mmol, 248 mg), 3-nitrobenzaldehyde (4c) (1.1 mmol, 167 mg), diethylphosphite (5) and the catalyst, CeCl3·7H2O-SiO2 (12 mol%) was placed into a 50 mL flat-bottomed flask. The reaction mixture was irradiated under microwave radiations using catalyst systems (CATA-4R), % power is 65% and 465 W. After completion of the reaction (monitored by TLC), DCM (15 mL) was added to the reaction mixture. The catalyst was filtered and washed with DCM (5 mL) to recover it. The combined filtrates and washings were concentrated under reduced pressure, followed by purification on column chromatography using ethylacetate:n-hexane in the ratio of 4:6 as an eluent to afford pure tetraethyl[4,4'-sulfonylbis(4,1-phenylene)bis(azanediyl)]bis[(3-nitrophenyl)methylene]diphosphonate (6c). The filtered residue catalyst was dried under vacuum and reused for the next reaction. This same procedure was adopted for preparing the remaining title products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With CeCl3·7H2O-SiO2; In neat liquid; for 0.0833333h;Microwave irradiation; | General procedure: The mixture of Dapsone (3) (1 mmol, 248 mg), 3-nitrobenzaldehyde (4c) (1.1 mmol, 167 mg), diethylphosphite (5) and the catalyst, CeCl3·7H2O-SiO2 (12 mol%) was placed into a 50 mL flat-bottomed flask. The reaction mixture was irradiated under microwave radiations using catalyst systems (CATA-4R), % power is 65% and 465 W. After completion of the reaction (monitored by TLC), DCM (15 mL) was added to the reaction mixture. The catalyst was filtered and washed with DCM (5 mL) to recover it. The combined filtrates and washings were concentrated under reduced pressure, followed by purification on column chromatography using ethylacetate:n-hexane in the ratio of 4:6 as an eluent to afford pure tetraethyl[4,4'-sulfonylbis(4,1-phenylene)bis(azanediyl)]bis[(3-nitrophenyl)methylene]diphosphonate (6c). The filtered residue catalyst was dried under vacuum and reused for the next reaction. This same procedure was adopted for preparing the remaining title products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: Heating 2: Heating |
Yield | Reaction Conditions | Operation in experiment |
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83% | With phosphotungstic acid; In ethanol; at 80℃; for 12h;Green chemistry; | General procedure: A mixture of barbituric acid (0.26 g, 2 mmol), aldehyde(1 mmol), amine (1 mmol), and H3PW12O40 (0.04 g, 2 mol %) inethanol (5 mL) at 80 C was stirred for 12 h. As completion ofthe reaction confirmed by TLC (eluent EtOAc/MeOH), thereaction mixture was cooled to room temperature. Then, theprecipitated product was filtered and washed withwater (2 10 mL) and ethanol (2 5 mL) to afford the pureproduct.4.1.7 9-[4-(4-Amino-benzenesulfonyl)-phenyl]-10-(3-hydroxy-4-methoxy-phenyl)-9,10-dihydro-1H,8H-1,3,6,8,9-pentaaza-anthracene-2,4,5,7-tetraone (L5) Yield: 83%; yellow solid; mp >350 C. IR (KBr): 3374, 3115, 1693, 1677, 935, 807 cm-1. 1H NMR (250 MHz, DMSO-d6/TMS): delta = 3.86 (s, 3H, OCH3), 4.82 (s, 1H, CH), 6.68 (s, 1H, Ar), 6.85 (d, J = 9.5 Hz, 2H, Ar), 7.02 (d, J = 9.2 Hz, 4H, Ar), 7.83 (d, J = 9.5 Hz, 4H, Ar), 9.43 (br s, 1H, OH), 11.12 (s, 2H, NH), 11.25 (s, 2H, NH). 13C NMR (62.9 MHz, DMSO-d6/TMS): delta = 27.1, 57.0, 80.4, 115.8, 116.8, 118.1, 123.5, 127.9, 129.2, 132.1, 143.5, 146.9, 151.8, 152.5, 166.3. MS: 602.11 (8.9%, M+). Anal. Calcd for C28H22N6O8S (602.57): C, 55.81; H, 3.68; N, 13.95. Found: C, 55.93; H, 3.73; N, 14.06. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With triethylamine; In tetrahydrofuran; at 20 - 45℃; for 16h;Inert atmosphere; | DDS (1.24 g, 5 mmol) was dissolved in THF/Et3N (40/10 mL) mixed solvent at room temperature. Trimethylchlorosilane (2.17 g, 20 mmol) was then added dropwise into the solution. After completion of dropping, the reaction mixture was further stirred for 16 h at 45 C. Then the mixture was filtered and concentrated under reduced pressure. To further purify the product, the resulting orange powder was dissolved in THF (20 mL) and filtered. All volatiles were removed under reduced pressure. 1.79 g compound 1 was obtained in 91% yield as a gray white powder. |
91% | With pyridine; In acetone; at 40℃; for 0.5h;Inert atmosphere; | Example 1Preparation of 4,4'-bis(N,N'-trimethylsilyl)aminodiphenyl sulfoneUnder nitrogen atmosphere, to two-necked flask were successively added 4,4'-diaminodiphenylsulfone(1. 24g, 5mmol), acetone (20 mL) and pyridine (20 mL), stirred to dissolve, warmed to 40 C, the trimethylchlorosilane(1. 09g, lOmmol) was added dropwise After into the solution, after the addition was complete the reaction solution to amine 0.5 hours, cooled to room temperature, filtered, and the solvent was removed under reduced pressure50 C and dried in vacuo to give a pale yellow solid, yield 91%, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With triethylamine; In tetrahydrofuran; at 20 - 45℃; for 16h;Inert atmosphere; | General procedure: DDS (1.24 g, 5 mmol) was dissolved in THF/Et3N (40/10 mL) mixed solvent at room temperature. Trimethylchlorosilane (2.17 g, 20 mmol) was then added dropwise into the solution. After completion of dropping, the reaction mixture was further stirred for 16 h at 45 C. Then the mixture was filtered and concentrated under reduced pressure. To further purify the product, the resulting orange powder was dissolved in THF (20 mL) and filtered. All volatiles were removed under reduced pressure. 1.79 g compound 1 was obtained in 91% yield as a gray white powder. |
92% | With N-ethyl-N,N-diisopropylamine; In tetrahydrofuran; at 20℃; for 2h;Inert atmosphere; | Example 2Preparation of 4,4'-bis(N,N'-dimethylvinylsilyl)aminodiphenyl sulfoneUnder nitrogen atmosphere, two-necked flask were successively added 4,4'-diaminodiphenylsulfone(1. 74g, 7mmol),In tetrahydrofuran (30 mL) and diisopropylethylamine amine (20 mL), stirred and dissolved, 20 C, a solution of chloro(dimethyl)vinylsilane(2. llg, 17. 5_1) was added dropwise to the above solution, after the addition was complete amidation reaction for 2 hours, filtered, and solvent was removed under reduced pressure. after the addition was complete amidation reaction for 2 hours, filtered, and solvent was removed under reduced pressureAfter the agent is 50 C and dried in vacuo to give a pale yellow solid, yield 92%, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | In water; for 2h;Reflux; | A mixture of 2,3-dichloro-1,4-naphthoquinone (2.270 g,10 mmol) and 4-aminophenyl sulfone (2.048 g, 10 mmol) wasadded to distilled water (800 mL) and refluxed for 2 h. The reactionmixture was cool to room temperature. The red precipitate formed,separated by filtration, washed with hot water (200 mL), dried at80 C, and crystallized from 95% ethyl alcohol to give compound1 (3.850 g, 88%) as red crystals; mp-239.5-240.5 C [18]; IR(KBr): 1259, 1317, 1516, 1585, 1627, 1676, 1699, 2312, 3286,3707 cm1; 1H NMR (500 MHz, DMSO-d6) d: 6.12 (s, 2H), 6.60 (d,2H, J = 5.2 Hz), 7.17 (d, 2H, J = 4.8 Hz), 7.52 (d, 2H, J = 6.8 Hz),7.70 (d, 2H, J = 6.8 Hz), 7.80 (t, 1H, J = 7.2 Hz), 7.85 (t, 1H,J = 7.0 Hz), 8.02 (t, 2H, J = 8.0 Hz), 9.50 (s, 1H); 13C NMR(125 MHz, DMSO-d6) d: 112.9, 119.0, 122.1, 125.9, 126.1, 126.5,126.6, 129.1, 130.4, 131.6, 133.4, 134.6, 137.0, 142.5, 143.1,153.3, 176.9, 179.7; HRMS (EI) m/z: Calcd for C22H15ClN2O4S:438.8835 found: 438.8832. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | In acetone; at 20℃; for 3h;Glovebox; | A vigorously stirring solution of BSDA (5 mmol), anhydrous acetone (15 g), and m-dichlorobenzene (15 g) were added into a polyfluoroalkoxy(PTA) cylindrical reactor. COF2 was induced to the mixture with the flow amount of 12 ml/min for 3 h at room temperature. COF2 and HF left in the reactor and pipeline were removed by nitrogen gas, and white intermediate 15 (100% yield) with the structure of N-fluoroformyl was gained. After heating the mixture under reflux temperature 171C with a nitrogen gas stream for 3 h, isocyanate 16 was obtained (97% yield) as a yellow solid after evaporating solvent under reduced pressure. The colorless needle crystal was gained by the recrystallization in toluene. |
In acetone; at 20℃; for 3h; | The 298g (1.2 muM) 4, 4' - sulfonyl diphenyl diamine (BSDA) and 300 ml acetone, 300 ml of dichlorobenzene to join with mixer 1.50L stainless steel reactor, filled with 396g (6.0 muM) after the carbonyl of the closed system, reacting at room temperature 3h after, to reactor as rectification, direct rectification, regulating the sump temperature, to ensure that the system pressure is 1 mpa, tower-top temperature is -40 C, carbonyl fluoride extracted 219g, recovery is 92.3%, then the sump heating up to 100 C the left and right, to ensure that the system pressure is 0.6 mpa, tower-top temperature is 20 C, is extracted hydrogen fluoride 42g, recovery is 87.5%. Then in normal pressure, temperature 140 C lower reaction 2h removing hydrogen fluoride, after the reaction is completed, the top of the coolant temperature is 20 C, extracted hydrogen fluoride 40g, recovery is 83.3%, the system after cooling down to room temperature, filter to get a yellow solid 4, 4' - sulfonyl diphenyl diisocyanate (BSDI) crude 364g, purity of 96.0%, the product yield 97.1%. Recovery of the solvent the crude product after the water washing, alkali cleaning, distillation 290 ml acetone and 287 ml dichlorobenzene, to return to the solvent storage tank |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | General procedure: A mixture of 0.272 g(2 mmol) of 1,3,6-oxadithiepane (1) and 0.022 g (0.05 mmol) of Sm(NO3)3 · 6H2O in 10 mL of chloroform was stirred for 30 min at room temperature under argon, 1 mmol of the corresponding diamine in 10 mL of ethanol was added, and the mixture was stirred for 3 h at room temperature. The mixture was then treated with 2 mL of water, stirred for 30 min, and extracted with chloroform (20 mL). The extract was evaporated,and the residue was subjected to column chromatographyon silica gel. Compound 4 was isolated as colorless oily material, and compounds 2, 3, and 5-8 were colorless crystals (recrystallized from CHCl3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With triethylamine; In N,N-dimethyl-formamide; for 24h;Reflux; | A mixture of (II) (1.52 g, 0.01 mol) anddapsone (2.48 g, 0.01 mol) in dry dimethylformamide(10 mL) containing 3 drops of trimethylamine was refluxed for 24 h. The obtained solid while hot was recrystallized from dioxane to give (XXI). Yield 63%; mp139.3C. IR: 3401, 3361 (NH, NH2), 3079 (CHarom.), 2971, 2836 (CH aliph.), 2228 (C?N), 1618(C=N), 1377, 1154 (SO2). 1H NMR: 2.3 (s, 3H,CH3), 6.6 (s, 2H, NH2, exchangeable with D2O), 6.9-8.2 (m, 10H, ArH), 11.0 (s, 1H, NH, exchangeablewith D2O). 13C NMR: 25.1, 112.4, 112.7 (2), 114.4,115.9 (2), 117.0, 128.3 (4), 130.0 (2), 142.4, 144.9,149.2, 153.4, 158.9. MS, m/z (%): 364 (M+) (14.1165), 347 (100). Calcd. for C19H16N4O2S(364.42): C, 62.62; H, 4.43; N, 15.37. Found: C,62.94; H, 4.11; N, 15.07. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With triethylamine; In N,N-dimethyl-formamide; for 24h;Reflux; | A mixture of (II)(3.04 g, 0.02 mol) and dapsone (2.48 g, 0.01 mol) indry dimethylformamide (10 mL) containing 3 drops oftrimethylamine was refluxed for 24 h. The obtainedsolid after poured onto ice water was recrystallizedfrom dioxane to give (XXII). Yield 56%; mp 173.9C.IR: 3404, 3171(NH), 3079 (CH arom.), 2966, 2836(CH aliph.), 2226 (C?N), 1622 (C=N), 1377, 1141(SO2). 1H NMR: 2.4 (s, 6H, 2CH3), 6.5-8.6 (m, 12H,ArH), 10.6 (s, 2H, 2NH, exchangeable with D2O).13CNMR: 25.4 (2), 109.6 (2), 112.8 (2), 113.7 (4), 114.0(2), 128.8 (4), 129.3 (2), 139.9 (2), 144.9 (2), 155.5 (2),160.1 (2). MS, m/z (%): 480 (M+) (44.6408), 240 (100).Calcd. for C26H20N6O2S (480.54): C, 64.98; H, 4.20; N,17.49. Found: C, 64.64; H, 4.51; N, 17.87. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; for 16h; | A mixture of 4,4?-Diaminodiphenyl Sulfone 1 (481mg, 1.94mmol), N-Boc-l-proline (1.00g, 4.65mmol), and EDCI (945mg, 5.03mmol) in CH2Cl2 (10mL) was stirred at room temperature for 16h. The mixture was then poured in 1N aq. HCl solution and extracted with CH2Cl2. The organic layer dried over magnesium sulfate, filtered, and concentrated in vacuo. Then without any purification, tert-Butyl (S)-2-((4-((4-((R)-1-(tert-butoxycarbonyl)pyrrolidine-2-carboxamido)phenyl)sulfonyl)phenyl)carbamoyl)pyrrolidine-1-carboxylate 2 was obtained as white solid (544mg, 44%). 1H NMR (DMSO-d6, delta=2.5ppm, 400MHz): 10.43 (s, 2H), 7.89-7.79 (m, 8H), 4.27-4.18 (m, 2H), 3.44-3.39 (m, 4H), 2.19-2.16 (m, 2H), 1.99-1.78 (m, 6H), 1.38-1.23 (app br s, 18H). 13C NMR (DMSO-d6, delta=39.52ppm, 100MHz): 172.3, 153.0, 143.4, 135.3, 128.5, 119.2, 113.0, 78.6, 62.8, 60.4, 46.5, 45.1, 33.1, 30.9, 30.1, 27.9, 26.7, 26.6, 24.0, 23.4, 13.1. HRMS (ESI) m/z: Anal. calcd. for [M+Na]+ C32H42N4NaO8S: 665.2616; found 665.2613. |
44% | With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; for 16h; | 4,4'-diaminodiphenyl sulfone (481 mg, 1.94 mmol), N-Boc-L-proline (1.00 g, 4.65 mmol) And ethyl 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDCI) (945 mg, 5.03 mmol) Was dissolved in dichloromethane (10 mL) The mixture was stirred at room temperature for 16 hours. The reaction mixture was diluted with 1 N aqueous hydrochloric acid solution and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, The mixture was concentrated in vacuo to give the desired compound (S) -2 - ((4 - ((R) -1- (tert-butoxycarbonyl) pyrrolidine- 2- carboxamido) phenyl) sulfonyl) phenyl) Carbamoyl) pyrrolidine-1-carboxylate (544 mg, 44% yield) as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | at 150℃; for 24h; | In the presence of a magnet, 4-(4-aminobenzenesulfonyl)aniline (1 mmol) and 1,2-<strong>[628-36-4]diformylhydrazine</strong> (4 mmol) were added to a 50 mL three-neck round bottom flask equipped with a reflux condenser and a thermometer respectively. Start stirring at 150°C for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature and filtered. The resulting precipitate was added to 100 mL of hot methanol. After stirring and dissolving, filter. The filtrate was slowly evaporated to give a white solid, yield 85percent. |
85% | at 150℃; for 24h; | The molar ratio of 4- (4-aminobenzenesulfonyl) aniline: bisformylhydrazide was 1: 4A 50 mL three-necked round-bottomed flask equipped with a magnetron, a reflux condenser and a thermometer was charged with 4- (4-aminobenzenesulfonylYl) aniline (1 mmol) and bisformylhydrazide (4 mmol) were added and the mixture was stirred for 24 hours at 150 ° C. After completion of the reaction,The solution was cooled to room temperature and the resulting precipitate was added to 100 mL of hot methanol. After stirring, the solution was filtered and the filtrate was slowly evaporated to obtain whiteColor solid, yield 85percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With copper(ll) bromide In ethanol; water Reflux; Green chemistry; | Synthesis of compounds 4a-g; general procedure General procedure: A mixture of α-ketobutyric acid (2 mmol), dapsone (1 mmol) andaldehyde (2 mmol) in water and ethanol (1:1, 10 mL) was stirredthoroughly with CuBr2 (25 mol%, 0.25 mmol) under reflux for theappropriate time. When the reaction was complete as monitored byTLC, the reaction was filtered to obtain the crude product. This cruderesidue was added to aq. NaOH (1 M, 10 mL) under reflux for a further0.5 h, and then the resulting solution was acidified with HCl (1 M). Theprecipitate was filtered and recrystallised with acetic acid to give thepure product. The catalyst CuBr2 remained in the solvent phase. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With copper(ll) bromide In ethanol; water Reflux; Green chemistry; | Synthesis of compounds 4a-g; general procedure General procedure: A mixture of α-ketobutyric acid (2 mmol), dapsone (1 mmol) andaldehyde (2 mmol) in water and ethanol (1:1, 10 mL) was stirredthoroughly with CuBr2 (25 mol%, 0.25 mmol) under reflux for theappropriate time. When the reaction was complete as monitored byTLC, the reaction was filtered to obtain the crude product. This cruderesidue was added to aq. NaOH (1 M, 10 mL) under reflux for a further0.5 h, and then the resulting solution was acidified with HCl (1 M). Theprecipitate was filtered and recrystallised with acetic acid to give thepure product. The catalyst CuBr2 remained in the solvent phase. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With copper(ll) bromide In ethanol; water Reflux; Green chemistry; | Synthesis of compounds 4a-g; general procedure General procedure: A mixture of α-ketobutyric acid (2 mmol), dapsone (1 mmol) andaldehyde (2 mmol) in water and ethanol (1:1, 10 mL) was stirredthoroughly with CuBr2 (25 mol%, 0.25 mmol) under reflux for theappropriate time. When the reaction was complete as monitored byTLC, the reaction was filtered to obtain the crude product. This cruderesidue was added to aq. NaOH (1 M, 10 mL) under reflux for a further0.5 h, and then the resulting solution was acidified with HCl (1 M). Theprecipitate was filtered and recrystallised with acetic acid to give thepure product. The catalyst CuBr2 remained in the solvent phase. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With copper(ll) bromide In ethanol; water Reflux; Green chemistry; | Synthesis of compounds 4a-g; general procedure General procedure: A mixture of α-ketobutyric acid (2 mmol), dapsone (1 mmol) andaldehyde (2 mmol) in water and ethanol (1:1, 10 mL) was stirredthoroughly with CuBr2 (25 mol%, 0.25 mmol) under reflux for theappropriate time. When the reaction was complete as monitored byTLC, the reaction was filtered to obtain the crude product. This cruderesidue was added to aq. NaOH (1 M, 10 mL) under reflux for a further0.5 h, and then the resulting solution was acidified with HCl (1 M). Theprecipitate was filtered and recrystallised with acetic acid to give thepure product. The catalyst CuBr2 remained in the solvent phase. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With copper(ll) bromide In ethanol; water Reflux; Green chemistry; | Synthesis of compounds 4a-g; general procedure General procedure: A mixture of α-ketobutyric acid (2 mmol), dapsone (1 mmol) andaldehyde (2 mmol) in water and ethanol (1:1, 10 mL) was stirredthoroughly with CuBr2 (25 mol%, 0.25 mmol) under reflux for theappropriate time. When the reaction was complete as monitored byTLC, the reaction was filtered to obtain the crude product. This cruderesidue was added to aq. NaOH (1 M, 10 mL) under reflux for a further0.5 h, and then the resulting solution was acidified with HCl (1 M). Theprecipitate was filtered and recrystallised with acetic acid to give thepure product. The catalyst CuBr2 remained in the solvent phase. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With copper(ll) bromide In ethanol; water Reflux; Green chemistry; | Synthesis of compounds 4a-g; general procedure General procedure: A mixture of α-ketobutyric acid (2 mmol), dapsone (1 mmol) andaldehyde (2 mmol) in water and ethanol (1:1, 10 mL) was stirredthoroughly with CuBr2 (25 mol%, 0.25 mmol) under reflux for theappropriate time. When the reaction was complete as monitored byTLC, the reaction was filtered to obtain the crude product. This cruderesidue was added to aq. NaOH (1 M, 10 mL) under reflux for a further0.5 h, and then the resulting solution was acidified with HCl (1 M). Theprecipitate was filtered and recrystallised with acetic acid to give thepure product. The catalyst CuBr2 remained in the solvent phase. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | at 150℃; for 0.0333333h;Microwave irradiation; | General procedure: Hexahydroisobenzofuran-1,3-dione (1a; 308 mg; 2mmol) and 2-(2-(2-aminoethoxy)ethoxy)ethanamine (2a; 148 mg; 1mmol) were mixed thoroughly and subjected to a focused microwave irradiation at 120 C for 4 minutes. TLC of reaction mixture over silica gel G using CHCl3: MeOH (9.5:0.5) as mobile phase showed absence of starting materials and presence of a new spot of the product. Hence, the reaction is complete. Crude product, so obtained was purified by column chromatography over silica gel using solvent of elution: CHCl3:MeOH (9.7:0.3) to give pure product 3a. Yield: 85%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In ethanol; at 70℃; for 1h; | General procedure: The macrocyclic tetradentate Schiff base ligands (L10, L20, L30)were prepared, by condensation of phthalaldehyde (1 mmol;0.134 g) and the dianilines including 4,40-sulfonyldianiline(1 mmol; 0.248 g), 4,40-oxydianiline (1 mmol; 0.20 g), 4,40-methylenedianiline(1 mmol; 0.19 g), in ethanol, respectively (Scheme 1).The reaction mixture was stirred at 70 C for 1 h on a water baththen put in a refrigerator for 1 h. The progress of the reaction andpurity of the product were checked by TLCtest. The obtained yellowprecipitation was filtered, washed with ethanol and dried at 80 Cover CaCl2 in vacuum.C40H28N4O4S2 (L10): Mw 692.80 g/mol, yellow solid, yield: 85%;m.p. 215 C, 1H NMR d (400 MHz, DMSO-d6, ppm): 8.50 (4H, s,HeC]N), 7.82 (4H, m, Hd), 7.70 (4H, dd, J1 7.6, J2 2.4, Hc), 7.35(8H, d, J 8.0, Ha), 7.30 (8H, d, J 8.0, Hb), 13C NMR d (400 MHz,DMSO-d6, ppm): 168.69 (Ciminic), 152.74, 125.80, 125.24, 121.87,114.11 (CAr). IR (KBr, cm1): 3062 (nCeH, Ar), 2864 (nCeH, iminic), 1662(nC]N), 1629 (nC]C), 1369, 1171, 1369, 1171, 546 (nS]O). Elementalanalysis, Found (calculated): C, 68.21 (69.35), H, 3.62 (4.07), N, 8.99(8.09), S, 9.33 (9.26) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With thionyl tetrafluoride; triethylamine; In acetonitrile;Sealed tube; | A round-bottom flask (500 mL) with a magnetic stir bar was charged with 4,4?-sulfonyldianiline (24.8 g, 0.10 mol), acetonitrile (200 mL) and triethylamine (20.2 g, 27.9 mL,0.20 mol). The flask was then sealed with a SUBA-SEAL Septum, and an empty balloon,attached to a needle fixed syringe, was inserted into the flask. A needle linked to a vacuumpump was then inserted into the flask, and the atmosphere evacuated under reduced pressureuntil bubbles formed and the balloon became tense. The flask was immersed into an ice waterbath and allowed to cool. Then, 50F4 was slowly introduced into the flask via a needle, untilthe reaction had completed (TLC). The CH3CN was removed under reduced pressure androtary evaporation. The mixture was dissolved in EtOAc (500 mL) and washed with PBSbuffer (pH = 7.0, 2 x 100 mL) and brine (100 mL). After removing the solvent, the product was purified by flash column chromatography over silica gel (hex/EA = 4/1) to give 2-6 (38.3g 92%) as a white solid. Mp: 111 C; ?H NIVIR (600 MHz, CDC13) 7.94 (d, J 8.7 Hz, 4H),7.25 (d, J 8.7 Hz, 4H). ?3C NIVIR (150 IVIFIz, CDC13) 140.8, 138.9, 129.5, 124.5 (m); ?9FNIVIR (376 IVIFIz, CDC13) 46.9; ESI-MS (m/z): 417 [M+H]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With hydrogenchloride; chlorosulfonic acid; In dichloromethane; at 20℃; for 2.33333h;Cooling with ice; | A 25-mL suction flask charged with a solution of 4,4?-sulfonyldianiline(2.843 g, 10 mmol) in dry CH2Cl2(5 mL)was equipped with a constant pressure-dropping funnelcontaining 1.165 g chlorosulfonic acid (10 mmol) and agas inlet tube for conducting HCl gas over an adsorbingsolution, i.e., water. Chlorosulfonic acid was added dropwise over a period of 20 min, while the reaction mixturewas stirred slowly in an ice bath. The mixture was thenheated to room temperature and stirred for additional 2 h.The mixture was filtered, and the solid residue was washedwith ether (3 × 5 mL) and dried under vacuum. SPSA wasobtained as a white-colored solid, 3.119 g (95% yield).Spectral data of SPSA catalystWhite-colored solid: M.p. 244-248 C; FT-IR (KBr):3424, 2412-3378, 3123, 1632, 1589, 1277, 1143 cm-1;1H NMR (400 MHz, DMSO-d6): delta(ppm) 6.85 (d, 4H,J = 8.8 Hz, 2CH), 7.61 (d, 4H, J = 8.8 Hz, 2CH), 7.95(s, 2H, 2OH), 10.92 (s, 2H, 2NH); 13C NMR (100 MHz, CDCl3):delta(ppm) 118.6, 129.6, 133.7, 146.9. MS: (70 eV),m/z = 409 (M+ + 1), 408 (M+), 407 (M+-H), 406(M+-2H), 327 (M+-SO3H), 248 (M+-2SO3H), 248 (<strong>[80-08-0]dapsone</strong>),64 (-SO2-). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium carbonate; nickel(II) hydroxide; In dimethyl sulfoxide; at 35℃; for 2h; | In the preparation method of the trifluoromethyl aromatic amine of the present embodiment, the aromatic amine is 4,4'-diaminodiphenyl sulfone, and the other reaction and post-treatment processes are the same as in the embodiment 28. The preparation method of the trifluoromethyl aromatic amine of the present embodiment, the aromatic amine is aniline, and the nickel compound is nickel hydroxide.The base is potassium carbonate, and the reaction process parameters are: 1-trifluoromethyl-1,2-phenyliodo-3(H)-one (0.5 mmol, 1.0 eq).Aromatic amine (1.5 mmol, 3.0 eq), nickel hydroxide 10 mol%, potassium carbonate (1.5 mmol, 3.0 eq),DMSO (2 mL) was reacted at 35 C for 2 h, and the other reactions and workup procedures were the same as in Example 1. |
81% | With potassium carbonate; In acetonitrile; at 75℃; for 6h;Schlenk technique; Inert atmosphere; | General procedure: Experimental Procedure: A dried 25 mL Schlenk tube equipped with a magnetic stir bar was charged with Togni?s Reagent 2 (0.25 mmol, 1.0 equiv), free anilines 1 (0.75 mmol, 3.0 equiv), K2CO3 (0.375 mmol, 1.5 equiv) and CH3CN (1.5 mL). The reaction mixture was then stirred at 75 C for 6 h under an argon atmosphere. The reaction progress was monitored by TLC. After cooling to room temperature, the mixture was washed with water and extracted with CH2Cl2 three times, then washed with saturated NaCl solution. The combined organic layer was dried with anhydrous Na2SO4 and filtered. The filtrate was concentrated in vacuo. The crude product was purified by flash column chromatography on silica gel (Elutent: petroleum ether-EtOAc) to give the pure product. The products were characterized by 1H NMR, 13C NMR, 19F NMR, GC -MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91.5% | at 180℃; for 12h; | 365.1 g (2.0 mol) of chlorophthalic anhydride obtained in the step (1) and 198.6 g (0.8 mol)4,4'-diaminodiphenyl sulfone is put into3000g of polychlorinated benzene,Stir and evenly disperse and mixHeat the reaction system to 180 C,Pumped to a negative pressure of -0.04MPa,The reaction was continuously stirred for 12 hours, and then suction filtration was performed.The filtrate is recycled and recycled.The filter cake is 513.0 g of crude bis(substituted phthalimide).The crude product yield is 95.9%.The crude product is put into boiling water and stirred for washing.After boiling,Removal of impurities on the surface of the product and inside the particles,After suction filtration,Obtaining 489.4 g of a bis(chlorophthalimide) product having an aromatic sulfone structure,Product yield 91.5%;By high performance liquid chromatography,The purity is 99.7%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67.1% | With dmap; N-ethyl-N,N-diisopropylamine; In acetonitrile; at 70 - 80℃;pH 7 - 9; | 2.48 g (0.01 mol) of diaminodiphenyl sulfone and 0.12 g of 4-dimethylaminopyridine (catalyst) was placed in a 250 mL dry four-necked flask with mechanical stirring and condensing reflux. Pour 100 mL of anhydrous acetonitrile. Stir well, The solution was gradually warmed to 70 to 80 C. 13.43 g (0.05 mol) of diphenyl chlorophosphate was dissolved in 100 mL of anhydrous acetonitrile. It was slowly added dropwise to the above four-necked flask using a constant pressure dropping funnel; During the reaction, The pH of the reaction was adjusted to 7-9 with N,N-diisopropylethylamine. The progress of the reaction was detected by thin layer chromatography (developing solvent: methanol: toluene = 1: (4) ~8), volume ratio).After the reaction was completed, the solvent was removed by a rotary evaporator to give a viscous solid. Use the viscous solid first The 0.01 mol/L HCl solution was washed three times, and then washed with a 0.01 mol/L NaOH solution until the viscous solid was in the middle. Sex. The viscous solid was dissolved in 30 mL of methanol to obtain a solution B, and the solution B was slowly poured while stirring. In a 0.05 mol/L CaCl 2 solution, precipitation A precipitated, and the precipitate A was a brown solid. After filtration, the precipitate A is obtained. The precipitate A is recrystallized with methanol and water to obtain a target product diaminodiphenyl sulfone derivative flame retardant, namely: tetrakis(diphenyl phosphate)-4,4'-diphenylsulfone tetraphosphoramide ( TPDDS), The yield was 67%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | With potassium pyrosulfite; palladium diacetate; N-ethyl-N,N-diisopropylamine; tri tert-butylphosphoniumtetrafluoroborate; In N,N-dimethyl-formamide; at 100℃; for 20h;Inert atmosphere; | General procedure: K2S2O5 (33.3 mg, 0.150 mmol, 0.75 equiv), Pd(OAc)2 (4.5 mg, 20.0 mumol, 10 mol%), P(t-Bu)3HBF4 (11.6 mg, 40.0 mumol, 20 mol%), and 4-iodoanisole (93.6 mg, 0.400 mmol, 2.0 equiv)were added into a screw-capped 10-mL test tube containing a magnetic stirring bar. The tube wascapped with a septum, evacuated, and backfilled with Ar three times. DMF (0.40 mL) and iPr2NEt(77.5 mg, 0.600 mmol, 3.0 equiv) were added to the tube. The septum was replaced with a screwcap. The tube was warmed to 100 C in an oil bath and stirred for 20 h. The reaction mixture wascooled to rt, diluted with EtOAc, washed with H2O and brine, dried over Na2SO4, filtered, andconcentrated. The residue was purified by preparative TLC (SiO2, hexane/CHCl3 = 1/3) to afford2 (44.7 mg, 0.161 mmol, 81%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With potassium pyrosulfite; palladium diacetate; N-ethyl-N,N-diisopropylamine; tri tert-butylphosphoniumtetrafluoroborate; In N,N-dimethyl-formamide; at 100℃; for 20h;Inert atmosphere; | General procedure: K2S2O5 (33.3 mg, 0.150 mmol, 0.75 equiv), Pd(OAc)2 (4.5 mg, 20.0 mumol, 10 mol%), P(t-Bu)3HBF4 (11.6 mg, 40.0 mumol, 20 mol%), and 4-iodoanisole (93.6 mg, 0.400 mmol, 2.0 equiv)were added into a screw-capped 10-mL test tube containing a magnetic stirring bar. The tube wascapped with a septum, evacuated, and backfilled with Ar three times. DMF (0.40 mL) and iPr2NEt(77.5 mg, 0.600 mmol, 3.0 equiv) were added to the tube. The septum was replaced with a screwcap. The tube was warmed to 100 C in an oil bath and stirred for 20 h. The reaction mixture wascooled to rt, diluted with EtOAc, washed with H2O and brine, dried over Na2SO4, filtered, andconcentrated. The residue was purified by preparative TLC (SiO2, hexane/CHCl3 = 1/3) to afford2 (44.7 mg, 0.161 mmol, 81%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70.4% | With sulfuric acid; at 80℃; for 7h; | S1: taking 40 g of concentrated sulfuric acid having a mass fraction of 98% and 40 g of fuming sulfuric acid having a mass fraction of 65%, stirring uniformly to obtain a sulfonating agent;S2: at room temperature, 24.83 g of 4,4'-diaminodiphenyl sulfone was uniformly added to the sulfonating agent in 30 min; then the temperature was raised to 80 C at a rate of 2 C / min, and reacted for 5 h to obtain a reaction liquid;S3: After the reaction solution is cooled to room temperature, it is added to 200 g of ice water while stirring; the pH of the solution is adjusted to 4 with sodium hydroxide solution, stirred for 20 minutes, and then filtered under reduced pressure to obtain 4,4'- a yield of 65.8% filter cake of diamino-3,3'-disulfonic acid diphenyl sulfone;S4: 200 g of water was added to the filter cake, stirred for 30 min, and filtered under reduced pressure to remove insoluble matter; a filtrate volume of 10% sodium chloride solid was added to the filtrate for salting out, and the mixture was filtered under reduced pressure to obtain a purity of 95%. 4,4'-3,3'-diaminodisulfonic acid diphenyl sulfone. |
65.8% | With sulfuric acid; at 80℃; for 5h; | (1) Take 40g of concentrated sulfuric acid with a mass fraction of 98% and 40g of fuming sulfuric acid with a mass fraction of 65%, stir evenlyTo the sulfonating agent;(2) at room temperature, 24.83 g of 4,4'-diaminodiphenyl sulfone was added to the sulfonating agent at a constant rate within 30 min; then the temperature was raised to 80 C at a rate of 2 C / min, and reacted for 5 h to obtain a reaction liquid;(3) After the reaction solution is cooled to room temperature, it is added to 200 g of ice water while stirring; the pH of the solution is adjusted to 4 with sodium hydroxide solution, stirred for 20 minutes, and then filtered under reduced pressure to obtain 4, 4'. a filter cake having a yield of 65.8 % of diamino-3,3'-disulfonate diphenyl sulfone;(4) 200 g of water was added to the filter cake, stirred for 30 min, and filtered under reduced pressure to remove insolubles; a filtrate volume of 10% sodium chloride solid was added to the filtrate for salting out, and the purity was 95% after filtration under reduced pressure. 4,4'-3,3'-diaminodisulfonic acid diphenyl. |
With sulfuric acid; at 80℃; for 5.5h; | (1) taking 40 g of concentrated sulfuric acid having a mass fraction of 98% and 40 g of fuming sulfuric acid having a mass fraction of 65%, stirring uniformly to obtain a sulfonating agent;(2) at room temperature, 24.83 g of 4,4'-diaminodiphenyl sulfone was uniformly added to the sulfonating agent in 30 min;Then, the temperature was raised to 80 C at a rate of 2 C / min, and reacted for 5 hours to obtain a reaction liquid;(3) After the reaction solution is cooled to room temperature, it is added to 200 g of ice water while stirring;The pH of the solution was adjusted to 4 with a sodium hydroxide solution, stirred for 20 minutes, and then filtered under reduced pressure.a filter cake having a yield of 65.8% of 3,3?-disulfonated-4,4?-dichlorodiphenyl sulfoneis obtained;(4) adding 200 g of water to the filter cake, stirring for 30 min, filtering under reduced pressure, removing insoluble matter;A filtrate volume of 10% sodium chloride solid was added to the filtrate for salting out, and filtered under reduced pressure to give 3,3?-disulfonated-4,4?-dichlorodiphenyl sulfonehaving a purity of 95%. |
With sulfuric acid; sulfur trioxide; at 80℃; for 5.5h; | (1) Taking 40 g, the mass fraction is 98% concentrated sulfuric acid and 40 g, the mass fraction is 65% of a fuming sulfuric acid, stir, get the sulfonating agent; (2) Under the room temperature condition, in the 30 min in the sulfonating agent within the uniform adding 24 . 83 g4, 4' - diamino diphenyl sulfone; then 2 C/min of the rate of rise to 80 C, reaction 5 h, get the reaction solution; (3) In the reaction solution after cooling to room temperature, while stirring it added to the 200 g ice water; sodium hydroxide for solution of the solution is adjusted to pH 4, stirring 20 min after, by vacuum filtering, to obtain the 4,4'-diamino-3,3'-disulfonic acid diphenyl sulfone in the yield of 65.8% of the filter cake; (4) Adding to the filter cake in 200 g water, stirring 30 min, decompression after filtration, to remove the insoluble; in the filtrate and adding to the volume of 10% of the sodium chloride solid salt out, pressure reducing obtained after filtering the purity is 95% of the 4, 4 '- 3, 3' - diamino acid diphenyl sulfone. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | Compound 1 (0.77 mmol) was dissolved in a minimumamount of ethanol and cooled to 0-5 C in an ice-NaClbath. NaNO2 [31.05 mg (0.45 mmol)] with 0.35 ml distilledwater and 4,4?-diaminodiphenyl sulphone [37.2 mg(0.15 mmol)] with 0.3 ml of HCl (37.5%) were preparedin separate beakers at 0-5 C. NaNO2/water solutionwas added dropwise to the solution of 4,4?-diaminodiphenyl sulfone/HCl solution with stirring.KOH [29.4 mg (0.525 mmol)] in ethanol was addedinto the solution of compound 1 and stirred for 5 min,followed by the addition of 0.38 mmol of the prepareddiazonium chloride solution. The reaction was monitoredby TLC. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | In dichloromethane | General procedure for the synthesis bischroman-3,4-dicarboxamide derivatives General procedure: To the magnetically stirred diamine (1 mmol) and coumarin-3-carboxylic acid (2 mmol) in CH2Cl2 (10 mL) was added alkyl isocyanide (2 mmol) via a syringe at room temperature. After the completion of the reaction (28-32 h, monitored by TLC (silica gel, eluent: n-hexane/ethyl acetate, 70/30)), the volatiles (consisting mostly of CH2Cl2) were evaporated and the residue was diluted with methanol, precipitating the product. The precipitated solid product was washed with hot methanol and CHCl3. In some cases (4a, 4b, 4g and 4z), further purification was done by column chromatography (silica gel) with n-hexane/ethyl acetate (80/20) as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | In dichloromethane | General procedure for the synthesis bischroman-3,4-dicarboxamide derivatives General procedure: To the magnetically stirred diamine (1 mmol) and coumarin-3-carboxylic acid (2 mmol) in CH2Cl2 (10 mL) was added alkyl isocyanide (2 mmol) via a syringe at room temperature. After the completion of the reaction (28-32 h, monitored by TLC (silica gel, eluent: n-hexane/ethyl acetate, 70/30)), the volatiles (consisting mostly of CH2Cl2) were evaporated and the residue was diluted with methanol, precipitating the product. The precipitated solid product was washed with hot methanol and CHCl3. In some cases (4a, 4b, 4g and 4z), further purification was done by column chromatography (silica gel) with n-hexane/ethyl acetate (80/20) as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80.6% | at 200℃; for 4h; | In a 300-mL round-bottomed flask, bis(4-aminophenyl)sulfone (5.52 g, 23.2 mmol) and phenyl salicylate (8.91 g, 20.8 mmol) were dissolved in 30 mL of 1,3-dimethyl-2-imidazolidinone. The mixture was heated at 200 oC. After 4 h, the reaction mixture was added into 400 mL of hot brine. Precipitates were collected and washed with water thoroughly. After drying, the powder was washed with hot ethyl acetate two times. Pale pink powder (8.75 g. 80.6 %). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | General procedure: A mixture of 0.22 g (1 mmol) [or 0.44 g (2 mmol) in the reactions with dianilines] of compound 1 [14], 10 mL of chloroform, and 0.022 g (0.05 mmol) of Sm(NO3)3·6H2O was stirred for 30 min at room temperature, and 1 mmol of the corresponding amine or diamine in 10 mL of ethanol was added dropwise. The mixture was stirred for 3 h at ~20C and evaporated, and the residue was purified by silica gel column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | Stage #1: dapsone With potassium carbonate In acetone at 80℃; for 0.5h; Stage #2: n-decanoyl chloride In acetone for 8h; Reflux; | 2.1. Synthesis of Dapsone based nonionic surfactant (DC-DDS) The Dapsone based nonionic surfactant (DC-DDS) was prepared in aneasy single step reaction as shown in Scheme 1. Briefly, in a roundbottom flask, 4, 4’-Diamino diphenyl sulfone (Dapsone; 500 mg; 2.0136mmol) was dissolved and stirred in 30 mL acetone with K2CO3 (1667mg; 6 mmol). The resultant mixture was refluxed at 80 C for 30 min.After refluxing for 30 min, Decanoyl chloride (0.43 mL; 2.3 mmol) wasadded to reaction mixture drop-wise and kept on refluxing for 8 h. Thereaction progress was periodically monitored through Thin LayerChromatography (TLC). After reaction completion, the reaction mixturewas cooled to room temperature, excess acetone was removed via rotaryevaporation and crude product was extracted using Dichloromethane(35 mL × 3). The crude organic product in organic phase was collected,dried using rotary evaporator and further purified with silica-gel columnchromatography using n-hexane and ethyl acetate (60:40 V/V). Theresulted yield was 75 %, m.p. 178-182 C, EI-MS 556 m/z, 1H NMR (300MHz, MeOH) δ ppm: 0.86 (t, 6H, CH3), 1.21 (m, 24H, CH2), 1.68 (m, 4H,CH2), 2.37 (t, 4H, CH2-CO), 4.68 (s, 2H, NH-CO), 7.83 (dd, 8H, ArH). |
Tags: 80-08-0 synthesis path| 80-08-0 SDS| 80-08-0 COA| 80-08-0 purity| 80-08-0 application| 80-08-0 NMR| 80-08-0 COA| 80-08-0 structure
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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 |
Sorry,this product has been discontinued.
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