Purity | Size | Price | VIP Price | USA Stock *0-1 Day | Global Stock *5-7 Days | Quantity | |||||
{[ item.p_purity ]} | {[ item.pr_size ]} |
{[ getRatePrice(item.pr_usd, 1,1) ]} {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} |
{[ getRatePrice(item.pr_usd, 1,1) ]} | Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} {[ getRatePrice(item.pr_usd,1,item.mem_rate) ]} | {[ item.pr_usastock ]} | Inquiry - | {[ item.pr_chinastock ]} | Inquiry - |
* Storage: {[proInfo.prStorage]}
CAS No. : | 1668-53-7 | MDL No. : | MFCD16251125 |
Formula : | C25H23N3O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | FROCQMFXPIROOK-UHFFFAOYSA-N |
M.W : | 397.47 | Pubchem ID : | 74276 |
Synonyms : |
|
Num. heavy atoms : | 30 |
Num. arom. heavy atoms : | 24 |
Fraction Csp3 : | 0.16 |
Num. rotatable bonds : | 3 |
Num. H-bond acceptors : | 5.0 |
Num. H-bond donors : | 2.0 |
Molar Refractivity : | 120.04 |
TPSA : | 79.13 Ų |
GI absorption : | High |
BBB permeant : | No |
P-gp substrate : | Yes |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | Yes |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -4.67 cm/s |
Log Po/w (iLOGP) : | 4.07 |
Log Po/w (XLOGP3) : | 5.71 |
Log Po/w (WLOGP) : | 5.52 |
Log Po/w (MLOGP) : | 3.68 |
Log Po/w (SILICOS-IT) : | 6.03 |
Consensus Log Po/w : | 5.0 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -6.3 |
Solubility : | 0.000201 mg/ml ; 0.000000506 mol/l |
Class : | Poorly soluble |
Log S (Ali) : | -7.14 |
Solubility : | 0.0000289 mg/ml ; 0.0000000727 mol/l |
Class : | Poorly soluble |
Log S (SILICOS-IT) : | -9.15 |
Solubility : | 0.000000279 mg/ml ; 0.0000000007 mol/l |
Class : | Poorly soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 3.02 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319 | 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 |
---|---|---|
79% | Stage #1: With aluminum (III) chloride In chlorobenzene at 25℃; for 0.5 h; Inert atmosphere Stage #2: at 85℃; for 5 h; |
General procedure: To astirred anhydrous chlorobenzene (15 mL) under dry N2 protectionin a 50mL three-necked flask were added 5 (1.6mmol)and anhydrous AlCl3 (0.32 g, 2.4 mmol),the mixture wasstirred for 0.5 h at 25 °C. Then resorcinol (0.24 g, 2.2 mmol)was added, and the mixture was stirred for 5 h at 85 °C. Aftercooling to room temperature, ice water (10 mL) was addedslowly and then chlorobenzene was evaporated under reducedpressure. The mixture was filtered and washed with water(3 × 10 mL), the filter cake was recrystallized with EtOA togive the corresponding products 8a, 8e 9a-9d. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With methanesulfonic acid In methanol; m-xylene | EXAMPLE 4 4,6-Bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine To a 500 mL four-necked, round-bottomed flask fitted with a mechanical stirrer, a nitrogen atmosphere and an oil bath are added 20.0 g (0.0524 mol) of the product of Example 2, 23.0 g (0.209 mol) of resorcinol. 7.6 g (0.079 mol) of methanesulfonic acid and 25 mL of m-xylene. The mixture is stirred at 120° C. for 20 hours and then allowed to cool to room temperature. A 200 mL portion of heptane and 200 g of ice are added. The contents are warmed to 55° C. and then allowed to cool to below 40° C. The crude solid formed is isolated by filtration, washed with water and heptane and then dried under reduced pressure to yield 17.5 g of yellow-orange crude product. The material is ground in a mortar, taken up in 170 mL of methanol, cooled to -20° C. and then filtered to afford 12.8 g (62percent yield) of the title compound as a yellow solid melting at 203-205° C. |
62% | With hydrogenchloride In n-heptane; m-xylene | EXAMPLE 6 4,6-Bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine To a 250 mL round-bottomed flask fitted with a magnetic stirrer, a condenser and a nitrogen atmosphere are charged 7.85 g (0.0206 mol) of the product of Example 2, 13.5 g (0.123 mol) of resorcinol, 4 mL of m-xylene and 0.954 g (7.16 mmol) of aluminum chloride. The mixture is heated to 150° C. for 13.5 hours and then allowed to cool to 90° C. Portions of 2N hydrochloric acid and heptane are added and the mixture is stirred at 90° C. for 30 minutes followed by stirring for 18 hours at room temperature. The mixture is then warmed to 35° C. The crude solid formed is collected by vacuum filtration and is washed with portions of water and heptane. The solid is then recrystallized twice from methanol to afford 4.76 g (62percent yield) of the title compound as a yellow solid melting at 194-196° C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | Stage #1: With hydrogenchloride; aluminum (III) chloride In water; chlorobenzene at 20℃; for 1 h; Cooling with ice Stage #2: at 90℃; for 2 h; |
In a 5-liter three-necked flask equipped with mechanical stirring, 3 liters of chlorobenzene, 184 grams of cyanuric chloride, 212 grams of m-xylene were added(2 times the amount) and 400 g of aluminum trichloride (3 times the amount); under ice-cooling, 20 ml of concentrated hydrochloric acid (0.2 times) was added, the reaction was stirred for 1 hour, and the temperature was raised to room temperature and 121 g of resorcinol was added ( 1.1 times) and then heated to 90°C for 2 hours. After the reaction was completed, the reaction solution was slowly added to 5 liters of 10percent hydrochloric acid with stirring, and the precipitated solid was filtered and washed with water.Recrystallization yielded 365 g (yield 92percent) of 2,4-bis(m-xylyl)-6-(1-m-xylenol)-1,3,5-triazine product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With hydrogenchloride In ethyl acetate | EXAMPLE 7 4,6-Bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine To a 250 mL round-bottomed flask equipped with a magnetic stirrer, a condenser and a nitrogen atmosphere are added 6.00 g (0.0157 mol) of the product of Example 2, 2.08 g (0.0189 mol) of resorcinol, 2.09 g (0.0157 mol) of aluminum chloride and 6 mL of tetramethylene sulfone (sulfolane). The mixture is stirred at 138° C. for six hours, 147° C. for seven hours, 160° C. for 10.5 hours and then allowed to cool to room temperature. A portion of 2N hydrochloric acid is added and the mixture is refluxed for two hours and then allowed to cool to room temperature. The solids formed are collected by vacuum filtration and then washed with portions of water and heptane. The crude solid is taken up in ethyl acetate and passed through a plug of silica gel. The solvent is removed under reduced pressure to give 5.25 g of crude product. The crude product is recrystallized from methanol to afford 4.29 g (69percent yield) of the title compound as a yellow solid melting at 199-201° C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | After 5 h, analysis by HPLC showed the formation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (73%) and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine (21%), with 3% of unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. | |
Examples of the 2-(2-hydroxyphenyl)-1,3,5-triazines of group x) are 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis-(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis-(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine, ... | ||
Example 5 Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 1 eq Resorcinol and 2.5 eq AlCl3 Cyanuric chloride (1.84 g) was allowed to react with 2.05 eq of m-xylene, in the presence of 2.5 eq of AlCl3 (3.35 g) and 1 eq of resorcinol, in 25 mL chlorobenzene at about 5 C. for 2 h and then at 15 C. for 4 h. Analysis by HPLC showed 70% conversion of cyanuric chloride, mainly to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a 59:41 ratio. Two minor components were also present, 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine (5%) and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (3%). The reaction mixture was allowed to warm to room temperature, and after about 16 h at room temperature, HPLC analysis showed 92% cyanuric chloride conversion, mainly to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine (66%), 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (25%), 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (4.5%), and 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4-(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine (3%). |
To the reaction mixture was added 1.1 eq of resorcinol, and the reaction mixture was heated at 85 C. for 4.5 h. HPLC analysis showed the formation of 78% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 19% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1.6% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 1.4% 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine. The reaction was allowed to cool to room temperature, and 2% ice-cold aqueous HCl was added. A yellow precipitate was formed, separated by filtration, washed with water, and dried to yield 7.7 g of crude 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. | ||
Thereafter, the reaction mixture was allowed to react with 1.1 eq of resorcinol and subsequently heated at 85 C. for 1 h. HPLC analysis showed the formation of 83.3% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 14.9% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 1.7% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. | ||
Further stirring gave 99.5% cyanuric chloride conversion, with the ratio of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine unchanged and no other products were detected. Thereafter, the reaction mixture was allowed to react with 1.1 eq of resorcinol at 85 C. for 1.5 h. HPLC analysis of the reaction mixture showed the formation of 92.7% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 5% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 2.3% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. The product was isolated by treating the reaction mixture with cold 2% aqueous HCl. Precipitate was collected by filtration, washed with water, and dried to give 92% yield of crude 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. | ||
Example 28 Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 3 eq AlCl3 and 6.5% Concentrated HCl To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl3 in chlorobenzene, was added 0.24 eq of concentrated HCl at ice-bath temperature. After 45 min, 0.95 eq of m-xylene and 0.95 eq of toluene were added. After 45 min at ice bath temperature, the reaction was stirred at 9 C. for 1 h and then at room temperature for 2 h. HPLC analysis showed 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine as the major product with lesser amounts of 2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazine, and 2-chloro-4-(4-methylphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine. The reaction mixture was allowed to react with 1.1 eq of resorcinol and subsequently heated to 85 C. for 2 h. HPLC analysis of the reaction mixture showed 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine as the major product with lesser amounts of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4-(4-methylphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine. | ||
...e, N,N'-bis (3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- and para-methoxy-as well as of o- and p-ethoxy-disubstituted oxanilides. 2.8. Hydroxyphenyl-s-triazines, for Example 2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine; 2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine; 2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)-phenyl]-6-(4-bromophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine. N-salicylal-N'-salicyloyl-hydrazine, ... | ||
...de, N,N'-bis (3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- and para-methoxy- as well as of o- and p-ethoxy-substituted oxanilides. 2.8. Hydroxyphenyl-s-triazines, for Example 2,6bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine; 2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine; 2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)-phenyl]-6(4-bromophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine. N-salicylal-N'-salicyloylhydrazine, ... | ||
Example 2 Preparation of 2-(2.4-dihydroxyphenyl)-4.6-bis(2.4-dimethylphenyl)-1,3,5-triazine To a stirring solution of 2-(2,4-dihydroxyphenyl)-4,6-dichloro-1,3,5-triazine (257 mg) in 5 mL of m-xylene was added aluminum chloride (200 mg). The reaction mixture was stirred at room temperature for 24 hr. The reaction mixture was analyzed by TLC after usual work-up to contain mainly one product which was identical with 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. | ||
Examples of such compounds include 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, | ||
...ethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of o- and p-methoxy-disubstituted oxanilides, and o- and p-ethoxy-disubstituted oxanilides. 2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. | ||
...xalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixtures with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- and para-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides. 2.8 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. | ||
...de, N,N'-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, and mixtures of o- and p-methoxy- and of o- and p-ethoxy-disubstituted oxanilides. 7. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine 2-[2-hydroxyl4-(2-hydroxyl3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxyl4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and | ||
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazine Process step a) 200 g (1.50 mol) of aluminium chloride are added to 110.7 g (0.60 mol) of cyanuric chloride, dissolved in 360 g of 1,2-dichlorobenzene, with stirring (about 200 rpm). The readily stirrable suspension is then heated to 84 to 86 C. in the course of 30 minutes and kept at this temperature for 15 minutes. At about 200 rpm, 67.9 ml (58.6 g, 0.55 mol) of m-xylene are metered in at 84 to 86 C. in the course of 4 hours (exothermic reaction|), then the suspension is cooled as evenly as possible to 34 to 36 C. in the course of 1.5 hours. The addition of a further 101.8 ml (87.95 g, 0.83 mol) of m-xylene is carried out at 34 to 36 C. (exothermic reaction|) in a period of 6 hours. Shortly before the end of addition, a little HCl gas is released, which is neutralized by means of NaOH (40%). After addition of xylene is complete, the readily stirrable dark-brown reaction mixture is additionally stirred at 34 to 36 C. for a further 15 minutes. | ||
EXAMPLE 8A 2,4-Bis(2,4-dimethylphenyl)-6-(2,4-dihydroxyphenyl)-s-triazine The title compound is prepared by the reaction of cyanuric chloride with m-xylene followed by reaction with resorcinol. Aluminum chloride is used as a reagent in both reactions. | ||
Example 2 Isolation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine by Treating with 3% Aqueous Sodium Carbonate To a reaction flask equipped with a reflux condenser, a Dean-Stark apparatus, a nitrogen inlet, and a mechanical stirrer was added 112.5 mL of 3% aqueous sodium carbonate and 50 gm crude 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine from Example 1a containing polyresorcinol-triazines as impurities. The resulting mixture was heated to reflux, and it was held at reflux for 2 hours while residual ODCB was collected as azeotropic mixture in the Dean-Stark apparatus. The heating was discontinued, and the mixture filtered around 80 C. The filter cake was washed with 112.5 mL of 3% aqueous sodium carbonate solution followed by 300 mL of 50 C. water. The 47 gm of residue thus obtained was analyzed by HPLC to be 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine containing no polyresorcinol impurities. | ||
Example 10 Process to Isolate 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine by Removing Trisxylyl-triazine A mixture of 20 gm of crude 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine prepared by the procedure of WO 00/29392 (about 40% wet; which had been treated with 3% aqueous sodium carbonate to remove polyresorcinol-triazines), 20 mL toluene and 80 mL heptane was heated to reflux for 1 hour. The heating was discontinued and the mixture cooled to 30 C. The mixture was filtered, the filter cake washed with a mixture of 20 mL toluene and 80 mL heptane and dried to give 11.7 gm of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine which was analyzed by HPLC to be free of trisxylyl-triazine impurity. | ||
a. Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5triazine with High Levels of Polyresorcinol-triazines: To a reaction flask equipped with a reflux condenser, a nitrogen inlet, and a magnetic stirrer was added 2 gm of cyanuric chloride, 25 mL chlorobenzene, 4.4 gm of aluminum chloride and 2.34 gm of m-xylene. The reaction mixture was stirred at room temperature for about 40 hours. To it was then added 3.6 gm of resorcinol and heated to 90 C. for 2 hours. The reaction mixture was quenched with water, and chlorobenzene removed azeotropically. The precipitated material was filtered, the filter cake washed with water and dried to give 4.5 gm of a crude product. | ||
b. Isolation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine: To a reaction flask, 1 gm of the above mixture in Example 7a was heated with 30 mL of 5% aqueous sodium carbonate solution for 2 hours. The pH of the mixture was about 10. The heating was discontinued and the mixture was filtered, the filter cake was first washed with 5% aqueous sodium carbonate solution, and then with water. The solid product (300 mg) isolated was identified by HPLC to be 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, which was free of polyresorcinol-triazine impurities. | ||
The mixture was cooled, filtered and the filter cake washed with additional heptane and dried to give 4.5 gm of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine which by HPLC analysis has only 0.9% trisxylyl-triazine remaining, but there was no change in the level of polyresorcinol-triazine impurity. | ||
EXAMPLE 10 4,6-Bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine To a 250 mL round-bottomed flask fitted with a condenser, magnetic stirrer and a nitrogen atmosphere are added 1.44 g (4.16 mmol) of the product of Example 9, 1.98 g (0.0180 mol) of resorcinol, 0.59 g (6.2 mmol) of methanesulfonic acid and 2.7 mL of m-xylene. The mixture is stirred at 125 C. for one hour and then refluxed for an additional five hours. The mixture is allowed to cool to room temperature and portions of heptane and water are added. The gooey mixture is encouraged to form solids by scratching with a glass rod. The solids formed are collected by vacuum filtration and dried to give 1.04 g of a red-brown solid. 1H nmr (CDCl3) reveals that the title compound makes up approximately 15 molar percent of the recovered solid. | ||
EXAMPLE 13 4,6-Bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine A 350 mL Paar reaction vessel equipped with a magnetic stirrer is charged with 4.12 g (6.02 mmol) of the product of Example 12, 7.00 g (0.0636 mol) of resorcinol and 4.3 mL of m-xylene. The vessel is connected to a hydrogen chloride lecture bottle via TEFLON (duPont) tubing and the system includes a MONEL (Inco Alloys) gauge and MONEL valves. The system is flushed once with hydrogen chloride and is brought to a pressure of 5.5 lb/in2 of hydrogen chloride. The system is brought to an external temperature of 170 C. and the pressure increases to 14.5 lb/in2. The mixture is stirred at this temperature for eight hours and at an external temperature of 160 C. for an additional 17 hours. The mixture is allowed to cool to room temperature and portions of water and heptane are added. The mixture is stirred with warming and allowed to cool. The solids formed are collected by vacuum filtration to afford 5.10 g of crude product as a yellow-brown powder. The crude product is recrystallized from methanol to give 1.92 g of the title compound as a yellow solid. | ||
...lide, N,N'-bis(3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixes of ortho- and para-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides. 2.8. Hydroxyphenyl-s-triazines, for Example 2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine; 2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine; 2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine. N-salicylal-N'-salicyloyl-hydrazine, ... |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
The reaction mixture was then allowed to react with 0.9 eq of resorcinol at 60 C. for 5 h. HPLC analysis showed the formation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 77:21 with 1% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Example 3 Reaction of Cyanuric Chloride with Resorcinol Followed by m-xylene: One-pot Preparation of a Combination of 2-(2.4-dihydroxyphenyl)-4.6-bis(2.4-dimethylphenyl)-1,3.5-triazine and 2,4-bis(2,4-dihydroxylphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With methanesulfonic acid; In water; ethyl acetate; | EXAMPLE 5 2-[2,4-Dihydroxy-5-(1,1-dimethylethyl)phenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine To a 250 mL round-bottomed flask equipped with a magnetic stirrer, condenser, and a nitrogen atmosphere are charged 440 mg (1.11 mmol) of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine, 2 mL of diisobutylene, and 6 mL of methanesulfonic acid. The mixture is stirred at an external temperature of 75 C. for three hours. The mixture is allowed to cool to room temperature, and equal portions of ethyl acetate and water are added. The layers are separated and the organic layer is washed once with water, twice with saturated sodium bicarbonate solution, once with brine and is dried over anhydrous magnesium sulfate. Following filtration, the solvent is removed under reduced pressure to yield 1.28 g of yellow solid. The crude solid is purified with medium pressure chromatography with 3:1 heptane:ethyl acetate to afford 59 mg of the title compound as a yellow solid. 1 H nmr (CDCl3) and mass spectra are consistent with the desired compound; UV lambdamax (ethyl acetate) 290; 346 nm (epsilon29,400; 16,600). | |
With methanesulfonic acid; In water; ethyl acetate; | EXAMPLE 5 2-[2,4-Dihydroxy-5-(1,1-dimethylethyl)phenyl]-4,6--bis-(2,4-dimethylphenyl)-s-triazine To a 250 mL round-bottomed flask equipped with a magnetic stirrer, condenser, and a nitrogen atmosphere are charged 440 mg (1.11 mmol) of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine, 2 mL of diisobutylene, and 6 mL of methanesulfonic acid. The mixture is stirred at an external temperature of 75 C. for three hours. The mixture is allowed to cool to room temperature, and equal potions of ethyl acetate and water are added. The layers are separated and the organic layer is washed once with water, twice with saturated sodium bicarbonate solution, once with brine and is dried over anhydrous magnesium sulfate. Following filtration, the solvent is removed under reduced pressure to yield 1.28 g of yellow solid. The crude solid is purified with medium pressure chromatography with 3:1 heptane:ethyl acetate to afford 59 mg of the title compound as a yellow solid. 1 H nmr (CDCl3) and mass spectra are consistent with the desired compound; UV lambdamax (ethyl acetate) 290; 346 nm (epsilon 29,400; 16,600). | |
With methanesulfonic acid; In water; ethyl acetate; | Example 5 2-[2,4-Dihydroxy-5-(1,1-dimethylethyl)phenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine To a 250 mL round-bottomed flask equipped with a magnetic stirrer, condenser, and a nitrogen atmosphere are charged 440 mg (1.11 mmol) of 2-(2,4-dihydroxy-phenyl)-4,6-bis- (2,4-dimethylphenyl)-s-triazine, 2 mL of diisobutylene, and 6 mL of methanesulfonic acid. The mixture is stirred at an external temperature of 75 C. for three hours. The mixture is allowed to cool to room temperature, and equal portions of ethyl acetate and water are added. The layers are separated and the organic layer is washed once with water, twice with saturated sodium bicarbonate solution, once with brine and is dried over anhydrous magnesium sulfate. Following filtration, the solvent is removed under reduced pressure to yield 1.28 g of yellow solid The crude solid is purified with medium pressure chromatography with 3:1 heptane:ethyl acetate to afford 59 mg of the title compound as a yellow solid. 1 H nmr (CDCl3) and mass spectra are consistent with the desired compound; UV lambdamax (ethyl acetate) 290; 346 nm (epsilon29,400; 16,600). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With aluminum isopropoxide; | EXAMPLE 6 2-[2,4-Dihydroxy-5-(1-methyl-1-phenylethyl)phenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine To a 1 L three-necked, round-bottomed flask equipped with a magnetic stirrer, condenser, dropping funnel, thermometer, and a nitrogen atmosphere are charged 15.0 g (37.8 mmol) of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine and 390 mg of aluminum isopropoxide. The mixture is heated to 175 C. and 4.47 g (37.9 mmol) of alpha-methylstyrene are added dropwise at a rate of one drop every two seconds. A total of six equivalents of a-methyl styrene are added in this fashion over a 4.5 hour period. After cooling to room temperature, the mixture is diluted with ethyl acetate, washed twice with water and once with brine, and is dried over anhydrous magnesium sulfate. Following filtration, the solvent is removed under reduced pressure to yield a yellow solid. The crude product is purified with medium pressure chromatography with 12% ethyl acetate/heptane to afford 13.2 g of the title compound as a yellow solid; mp 168-170 C. 1 nmr (CDCl3) spectrum is consistent with the desired product; UV lambdamax (ethyl acetate) 290; 347 nm (epsilon45,700; 23,300). | |
With aluminum isopropoxide; | Example 6 2-[2,4-Dihydroxy-5-(1-methyl-1-phenylethyl)phenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine To a 1L three-necked, round-bottomed flask equipped with a magnetic stirrer, condenser, dropping funnel, thermometer, and a nitrogen atmosphere are charged 15.0 g (37.8 mmol) of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine and 390 mg of aluminum isopropoxide. The mixture is heated to 175 C. and 4.47 g (37.9 mmol) of alpha-methylstyrene are added dropwise at a rate of one drop every two seconds. A total of six equivalents of alpha-methyl styrene are added in this fashion over a 4.5 hour period. After cooling to room temperature, the mixture is diluted with ethyl acetate, washed twice with water and once with brine, and is dried over anhydrous magnesium sulfate. Following filtration, the solvent is removed under reduced pressure to yield a yellow solid. The crude product is purified with medium pressure chromatography with 12% ethyl acetate/heptane to afford 13.2 g of the title compound as a yellow solid; mp 168-170 C. 1 H nmr (CDCl3) spectrum is consistent with the desired product; UV lambdamax (ethyl acetate) 290; 347 nm (epsilon45,700; 23,300). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; In water; ethyl acetate; 1,1,2,2-tetrachloroethane; | EXAMPLE 47 2-(5-Benzoyl-2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine To a 500 mL three-necked, round-bottomed flask equipped with a mechanical stirrer, condenser, dropping funnel, and a nitrogen atmosphere are charged 5.57 g (14.0 mmol) of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine and 25 mL of tetrachloroethane. The mixture is warmed to an external temperature of 90 C. and 2.88 g (20.5 mmol) of benzoyl chloride in 20 mL of tetrachloroethane are added dropwise over 45 minutes. The mixture is stirred at an external temperature of 145 C. for six hours and is allowed to sit at room temperature overnight. Fifty mL of water and 5 mL of concentrated hydrochloric acid are added and the mixture is stirred with warming for three hours. A portion of ethyl acetate is added and the mixture is warmed to dissolve any organic solids. The layers are separated, the aqueous layer is washed with ethyl acetate and the combined organic layers are dried over anhydrous magnesium sulfate and filtered. The product is allowed to crystallize from solution and 3.55 g of the title compound (off-white needles) are collected by vacuum filtration. 1 H nmr (CDCl3) and mass spectra are consistent with the desired compound; UV lambdamax (ethyl acetate) 282; 340 nm (epsilon61,400; 15,600). | |
With hydrogenchloride; In water; ethyl acetate; 1,1,2,2-tetrachloroethane; | EXAMPLE 47 2-(5-Benzoyl-2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine To a 500 mL three-necked, round-bottomed flask equipped with a mechanical stirrer, condenser, dropping funnel, and a nitrogen atmosphere are charged 5.57 g (14.0 mmol) of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine and 25 mL of tetrachloroethane. The mixture is warmed to an external temperature of 90 C. and 2.88 g (20.5 mmol) of benzoyl chloride in 20 mL of tetrachloroethane are added dropwise over 45 minutes. The mixture is stirred at an external temperature of 145 C. for six hours and is allowed to sit at room temperature overnight. Fifty mL of water and 5 mL of concentrated hydrochloric acid are added and the mixture is stirred with warming for three hours. A portion of ethyl acetate is added and the mixture is warmed to dissolve any organic solids. The layers are separated, the aqueous layer is washed with ethyl acetate and the combined organic layers are dried over anhydrous magnesium sulfate and filtered. The product is allowed to crystallize from solution and 3.55 g of the title compound (off-white needles) are collected by vacuum filtration. 1 H nmr (CDCl3) and mass spectra are consistent with the desired compound; UVlambdamax (ethyl acetate) 282; 340 nm(epsilon 61,40; 15,600). | |
With hydrogenchloride; In water; ethyl acetate; 1,1,2,2-tetrachloroethane; | Example 47 2-(5-Benzoyl-2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine To a 500 mL three-necked, round-bottomed flask equipped with a mechanical stirrer, condenser, dropping funnel, and a nitrogen atmosphere are charged 5.57 g (14.0 mmol) of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine and 25 mL of tetrachloroethane. The mixture is warmed to an external temperature of 90 C. and 2.88 g (20.5 mmol) of benzoyl chloride in 20 mL of tetrachloroethane are added dropwise over 45 minutes. The mixture is stirred at an external temperature of 145 C. for six hours and is allowed to sit at room temperature overnight. Fifty mL of water and 5 mL of concentrated hydrochloric acid are added and the mixture is stirred with warming for three hours. A portion of ethyl acetate is added and the mixture is warmed to dissolve any organic solids. The layers are separated, the aqueous layer is washed with ethyl acetate and the combined organic layers are dried over anhydrous magnesium sulfate and filtered. The product is allowed to crystallize from solution and 3.55 g of the tide compound (off-white needles) are collected by vacuum filtration. 1 H nmr (CDCl3) and mass spectra are consistent with the desired compound; UV lambdamax (ethyl acetate) 282; 340 nm (epsilon61,400, 15,600). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride;aluminium trichloride; In water; ethyl acetate; 1,1,2,2-tetrachloroethane; | EXAMPLE 12 2-(2,4-Dihydroxy-5-propionylphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine To a 500 mL three-necked, round-bottomed flask equipped with a mechanical stirrer, condenser, and a nitrogen atmosphere are charged 5.33 g (13.0 mmol) of 2-(2,4-di-hydroxyphenyl)-4,6-bis -(2,4-dimethylphenyl)-s-triazine and 20 mL of tetrachloroethane. The mixture is warmed to an external temperature of 40 C. and 4.33 g (32.5 mmol) of aluminum chloride are added quickly in small portions. A solution of 1.20 g (13.0 mmol) of propionyl chloride in 20 mL tetrachloroethane is added dropwise over 15 minutes. The mixture is stirred at an external temperature of 110 C. for four hours. After cooling to room temperature, 50 mL of water and 6 mL of concentrated hydrochloric acid are added and the mixture is stirred with warming for two hours. A portion of ethyl acetate is added with warming to dissolve all of the solids. The layers are separated and the aqueous layer is extracted once more with ethyl acetate. The combined organic layers are dried over anhydrous magnesium sulfate and filtered. The product is allowed to crystallize and 2.14 g of the title compoundcompound is collected by vacuum filtration as a yellow solid. 1 H nmr (CDCl3), infrared and mass spectra are consistent with the desired compound; UV lambdamax (ethyl acetate) 270; 338 nm (epsilon49,500; 17,500). | |
With hydrogenchloride;aluminium trichloride; In water; ethyl acetate; 1,1,2,2-tetrachloroethane; | EXAMPLE 12 2-(2,4-Dihydroxy-5-propionylphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine To a 500 mL three-necked, round-bottomed flask equipped with a mechanical stirrer, condenser, and a nitrogen atmosphere are charged 5.33 g (13.0 mmol) of 2-(2,4-dihydroxyphenyl)4,6-bis-(2,4-dimethylphenyl)-s-triazine and 20 mL of tetrachloroethane. The mixture is warmed to an external temperature of 40 C. and 4.33 g (32.5 mmol) of aluminum chloride are added quickly in small portions. A solution of 1.20 g (13.0 mmol) of propionyl chloride in 20 mL tetrachloroethane is added dropwise over 15 minutes. The mixture is stirred at an external temperature of 110 C. for four hours. After cooling to room temperature, 50 mL of water and 6 mL of concentrated hydrochloric acid are added and the mixture is stirred with warming for two hours. A portion of ethyl acetate is added with warming to dissolve all of the solids. The layers are separated and the aqueous layer is extracted once more with ethyl acetate. The combined organic layers are dried over anhydrous magnesium sulfate and filtered. The product is allowed to crystallize and 2.14 g of the title compoundcompound is collected by vacuum filtration as a yellow solid. 1 H nmr (CDCl3), infrared and mass spectra are consistent with the desired compound; UV lambdamax (ethyl acetate) 270; 338 nm (epsilon 49,500; 17,500). | |
With hydrogenchloride;aluminium trichloride; In water; ethyl acetate; 1,1,2,2-tetrachloroethane; | Example 12 2-(2,4-Dihydroxy-5-propionylphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine To a 500 mL three-necked, round-bottomed flask equipped with a mechanical stirrer, condenser, and a nitrogen atmosphere are charged 5.33 g (13.0 mmol) of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine and 20 mL of tetrachlorcethane. The mixture is warmed to an external temperature of 40 C. and 4.33 g (32.5 mmol) of aluminum chloride are added quickly in small portions. A solution of 1.20 g (13.0 mmol) of propionyl chloride in 20 mL tetrachloroethane is added dropwise over 15 minutes. The mixture is stirred at an external temperature of 110 C. for four hours. After cooling to room temperature, 50 mL of water and 6 mL of concentrated hydrochloric acid are added and the mixture is stirred with warming for two hours. A portion of ethyl acetate is added with warming to dissolve all of the solids. The layers are separated and the aqueous layer is extracted once more with ethyl acetate. The combined organic layers are dried over anhydrous magnesium sulfate and filtered. The product is allowed to crystallize and 2.14 g of the title compoundcompound is collected by vacuum filtration as a yellow solid. 1 H nmr (CDCl3), infrared and mass spectra are consistent with the desired compound; UV lambdamax (ethyl acetate) 270; 338 nm (epsilon49,500; 17,500). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; potassium iodide; In water; 4-methyl-2-pentanone; acetone; | EXAMPLE 1 A mixture of 2,4-di-(2,4-dimethylphenyl)-6(2,4-dihydroxyphenyl)-1,3,5-triazine (20 g, 0.049 mole), 6-chloro-1-hexanol (7.04 g, 0.05 mole), available from Aldrich Chemicals, Milwaukee, Wis., potassium iodide (0.37 g, 0.0022 mole), PEG 400 (1.9 g, 0.005 mole), available from Aldrich Chemicals, Milwaukee, Wis., sodium hydroxide (2.0 g, 0.05 mole) in methyl isobutyl ketone was reflux (120-122 C.) for 16 hrs. After cooling to 85 C., water (50 ml) was added and the reaction mixture was acidified with 37% hydrochloric acid to pH 1, and the resulting aqueous layer was removed. The organic layer was washed twice with warm water (75 ml per each washing) and the volatiles were removed under reduced pressure. The oily residue was dissolved in acetone and decolorized with activated charcoal and filtered. Cooling to 22 C. gave 2,4-di-(2,4-dimethylphenyl)-6-[2-hydroxy-4-(6-hydroxy-1-hexyloxy)phenyl]-1,3,5-triazine (I-E) as a pale yellow solid (10 g), m.p. 117-118 C. The filtrate was concentrated under a reduced pressure to give a second crop of triazine I-E bringing the total weight of product to 21 g (87% yeild). It was characterized to be 2,4-di-(2,4,dimethylphenyl)-6-[ 2-hydroxy-4-(6-hydroxy-1-hexyloxy)phenyl]-1,3,5-triazine (I-E). This example illustrates the preparation of triazine I-E, which is an ultraviolet light stabilizer useful in preparing the composition of this invention, in either of the following two forms: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With aluminum isopropoxide; | EXAMPLE 6 2-[2,4-Dihydroxy-5-(1-methyl-1 -phenylethyl)phenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine To a 1 L three-necked, round-bottomed flask equipped with a magnetic stirrer, condenser, dropping funnel, thermometer, and a nitrogen atmosphere are charged 15.0 g (37.8 mmol) of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine and 390 mg of aluminum isopropoxide. The mixture is heated to 175 C. and 4.47 g (37.9 mmol) of alpha-methylstyrene are added dropwise at a rate of one drop every two seconds. A total of six equivalents of or-methyl styrene are added in this fashion over a 4.5 hour period. After cooling to room temperature, the mixture is diluted with ethyl acetate, washed twice with water and once with brine, and is dried over anhydrous magnesium sulfate. Following filtration, the solvent is removed under reduced pressure to yield a yellow solid. The crude product is purified with medium pressure chromatography with 12% ethyl acetate/heptane to afford 13.2 g of the title compound as a yellow solid; mp 168-170 C. 1 H nmr (CDCl3) spectrum is consistent with the desired product; UV lambdamax (ethyl acetate) 290; 347 nm (epsilon 45,700; 23,300). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | With hydrogenchloride; sodium hydroxide; In water; N,N-dimethyl-formamide; | EXAMPLE 8B 2,4-Bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-((1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yloxy)carbonylmethoxy)-phenyl]-s-triazine A solution of 14.5 g (40.0 mmol) of 1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl chloroacetate in 25 ml of N,N-dimethylformamide is rapidly added to a mixture of 20.0 g (50.2 mmol) of 2,4-bis(2,4-dimethylphenyl)-6-(2,4-dihydroxyphenyl)-1,3,5-triazine (Example 8A), 125 ml of N,N-dimethylformamide, and 4.0 g of 50% sodium hydroxide solution that has been stirred at ambient temperature for 30 minutes. The reaction mixture is then heated at 70 C. for 1 hour and stirred at ambient temperature for 17 hours. The reaction mixture is partitioned between ethyl acetate (300 ml) and a mixture of water (1000 ml) and 1N hydrochloric acid (10 ml). The aqueous layer is extracted with diethyl (2*500 ml) and saturated sodium chloride solution (500 ml), dried over magnesium sulfate, and concentrated to an oil. Purification by flash chromatography on silica gel (5:1 heptane: ethyl acetate) affords 14.0 g (48% yield) of the title compound, a yellow solid, mp 86-90 C. Anal. Calcd. for C44 H58 N4 O5: C, 73.1; H, 8.1; N, 7.7. Found: C, 72.8; H, 8.1; N, 7.6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | EXAMPLE 23 2,4-Bis(2,4-dimethylphenyl)-6-{2-hydroxy-4-[(1-cyclohexyloxy -2,2,6,6-tetramethylpiperidin-4-yloxy)carbonylmethoxy]phenyl}-s-triazine The title compound, a yellow solid with mp 105-109 C., is prepared in 54% yield from 1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl chloroacetate and 2,4-bis(2,4-dimethylphenyl)-6-(2,4-dihydroxyphenyl)-s-triazine according to the procedure of Example 8B. Anal. Calcd. for C42 H52 N4 O5: C, 72.8; H, 7.6; N, 8.1. Found: C, 72.2, H, 7.6; N, 7.9. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
aluminium trichloride; In hydrogenchloride; water; m-xylene; | a. Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (Following a Procedure in WO 00/29392): To a reaction flask equipped with a reflux condenser, a nitrogen inlet, and a mechanical stirrer was added 50 g of cyanuric chloride, 191 mL of ortho-dichlorobenzene (ODCB), and 108.5 gm of aluminum chloride. The mixture was cooled in an ice-bath to 5 C. and 6.5 gm of concentrated HCl was added over a period of 20 minutes. The mixture was allowed to warm room to temperature, and stirred for 2 hours. It was cooled back to 5 C. and then 51.8 gm of m-xylene was slowly added over a period of 4 hours, while allowing the temperature to go up to 21 C. The mixture was stirred at room temperature for additional 16 hours. The reaction mixture was heated to about 69 C. and 32.8 gm of resorcinol was added over a period of 30 minutes. The mixture was held at about 65 C. for 4 hours. It was then added to 500 mL water and ODCB distilled off azeotropically. The precipitated solid was filtered off to give 120 gm of water wet 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. The HPLC analysis showed it to contain about 7% of polyresorcinols consisting mainly of trisresorcinol-triazine and bisresorcinol-monochloro-triazine. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
EXAMPLE 2 4,6-Bis-(2,4-dimethylphenyl)-2-phenoxy-s-triazine To a 1 L four-necked, round-bottomed flask equipped with a mechanical stirrer and an addition funnel is charges 37.5 g (0.203 mol) of cyanuric chloride and 200 mL of m-xylene. The suspension/solution is chilled below 5 C. and 34.5 g of sodium bicarbonate, 200 mL of water and 1.4 g of benzyltrimethylammonium chloride are added. The contents of the flask are again cooled below 5 C. A solution of phenol (19.2 g, 0.203 mol) in 100 mL of m-xylene is charged to the addition funnel and then added over a 10-minute period to the reaction flask while the temperature is maintained between 1 C. and 3 C. The mixture is then stirred at 2-7 C. for five hours. The mixture is then warmed to 50 C. and the phases are separated. The organic phases is returned to the reaction flask and 32.5 g (0.244 mol) of aluminum chloride are added at 35 C. The mixture is then heated at about 130 C. for three hours. The contents are cooled below 120 C. and poured into 500 mL of cold 2N hydrochloric acid. The phases are separated and the organic phases is washed twice with water and one with saturated sodium bicarbonate solution. After drying over anhydrous potassium carbonate, the solvent is removed under reduced pressure to afford an oil which crystallized upon cooling. The crude solid is recrystallized from isopropanol to afford 57.7 g (75% yield) of the title compounds melting at 96-98 C. Examples 3-8, 10 and 13 below represent some of the various novel methods which can be used to prepare 4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | In 5,5-dimethyl-1,3-cyclohexadiene; | Example 1 23.8 g (0.06 mol) of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl) 1,3,5-triazine (prepared as described in U.S. Pat. No. 3,244,708 Example 16) are suspended in 300 ml of xylene. 12.1 g (0.09 mol) of 97% butyl glycidyl ether and 0.75 g (0.006 mol) of dimethylbenzylamine are added to this suspension, and the mixture is heated to reflux temperature. After a reaction time of 5 hours the clear, brownish solution is cooled and clarified by filtration through 100 g of silica gel. The yellow solution is evaporated and the residue is recrystallized from hexaneltoluene. This gives 27.3 g of pale yellow crystals of 2-[2-hydroxy4(3-butoxy-2-hydroxypropyloxy)-phenyl]4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin (=86% yield). Melting point: 80-83 C. (Compound 1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With hydrogenchloride;aluminium trichloride; In ethyl acetate; | EXAMPLE 7 4,6-Bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine To a 250 mL round-bottomed flask equipped with a magnetic stirrer, a condenser and a nitrogen atmosphere are added 6.00 g (0.0157 mol) of the product of Example 2, 2.08 g (0.0189 mol) of resorcinol, 2.09 g (0.0157 mol) of aluminum chloride and 6 mL of tetramethylene sulfone (<strong>[126-33-0]<strong>[126-33-0]sulfolan</strong>e</strong>). The mixture is stirred at 138 C. for six hours, 147 C. for seven hours, 160 C. for 10.5 hours and then allowed to cool to room temperature. A portion of 2N hydrochloric acid is added and the mixture is refluxed for two hours and then allowed to cool to room temperature. The solids formed are collected by vacuum filtration and then washed with portions of water and heptane. The crude solid is taken up in ethyl acetate and passed through a plug of silica gel. The solvent is removed under reduced pressure to give 5.25 g of crude product. The crude product is recrystallized from methanol to afford 4.29 g (69% yield) of the title compound as a yellow solid melting at 199-201 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With aluminium trichloride; In m-xylene; chlorobenzene; | A mixture of 10 g cyanuric chloride (0.0542 mol), 11.51 g of m-xylene (2 eq.), and 5.97 g of resorcinol (1 eq.) in 100 mL chlorobenzene under a nitrogen atmosphere was cooled to 20 C. under a nitrogen atmosphere. Aluminum trichloride (16.26 g, 2.25 eq.) was added over 25 min. such that the temperature was maintained below 5 C. The mixture was then warmed to 25 C. with stirring, and the progress of the reaction was monitored by HPLC (area % at 290 nm). After 24 hr. at 25 C., HPLC analysis showed 37.6% of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine (4) and only 1.0% of 1,4.4% of 2, and 5.1% of 3. Additional m-xylene (2 eq.) and aluminum trichloride (0.25 eq.) were added, and the mixture was heated to 32-35 C. for 20 hr. HPLC analysis indicated that the yield of 1 was increased to 45.3% and there was only 1.9% 2,4,6-tris-(2.4-dihyroxyphenyl)-5-triazine and 5.6% 2,4-bis-(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-5-triazine. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; sodium iodide; In acetone; | Example 1 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-(4-tert-butyl-2,6-dimethyl-3-hydroxybenzyl)phenyl)-1,3,5-triazine (Compound C) was synthesised using the following reaction scheme: To a stirred mixture of 2 g of 2,4-bis(2,4-dimethylphenyl)-6-(2,4-dihydroxyphenyl)-1,3,5-triazine (Compound A), 4.15 g of anhydrous K2CO3 and 40 mL acetone was added a solution of 1.25 g 3-chloromethyl-2,4-dimethyl-6-tert-butylphenol (Compound B) in 10 mL acetone followed by 50 mg NaI. The reaction mixture was heated to reflux for 4 hours. The thin layer chromatography (hereafter "TLC") analysis at this stage showed the absence of Compound A and the formation of a new major product. The heating was discontinued and the reaction mixture cooled to room temperature. The reaction mixture was diluted with methylene chloride and filtered through Celite brand filter agent. The filtrate was concentrated under reduced pressure and the residue crystallized from hexane/methylene chloride to give 2.5 g of a pale yellow solid which was characterized to be Compound C on the basis of NMR and mass spectra. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.8% | In 1,2-dichloro-benzene; at 20 - 100℃; for 8h; | Add 300 ml of N-hexylpyridine tetrafluoroborate and 200 ml 1-butyl-3-methylimidazolium tetrafluoroborate to the reactor,80ml o-dichlorobenzene,55.4g (0.30mol) of cyanuric acid, reduce the temperature to 5 with stirring,63.7 g (0.60 mol) of m-xylene was added dropwise, and the drop time was 2 h.While adding m-xylene dropwise, 2.2 g of initiator HCl gas was passed in (through 1 h), keeping the temperature at 5-10 C.After the addition of m-xylene was completed, the reaction was held at 10-15 C for 6 hours.The content of 2-chloro-4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine in the reaction solution was detected by HPLC at 95.5%,The HPLC spectrum is shown in Figure 3. The peak time is consistent with the peak time of the standard.Add 34.2 g (0.31 mol) of resorcinol, heat up to 90-100 C with stirring, and hold the reaction for 8 hours.Reduce the temperature to 20 and filter out the crude product.The filtrate was recovered and used, and the crude product was purified by methanol.Products with 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine content of 99.4%,The HPLC chart is shown in Figure 4. The peak time was consistent with the peak time of the standard, and the yield was 93.8%. |
79% | General procedure: To astirred anhydrous chlorobenzene (15 mL) under dry N2 protectionin a 50mL three-necked flask were added 5 (1.6mmol)and anhydrous AlCl3 (0.32 g, 2.4 mmol),the mixture wasstirred for 0.5 h at 25 C. Then resorcinol (0.24 g, 2.2 mmol)was added, and the mixture was stirred for 5 h at 85 C. Aftercooling to room temperature, ice water (10 mL) was addedslowly and then chlorobenzene was evaporated under reducedpressure. The mixture was filtered and washed with water(3 × 10 mL), the filter cake was recrystallized with EtOA togive the corresponding products 8a, 8e 9a-9d. | |
EXAMPLE 3 4,6-Bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine To a 50 mL round-bottomed flask equipped with a magnetic stirrer, condenser and nitrogen atmosphere are charged 1.00 g (3.10 mmol) of 4,6-bis-(2,4-dimethylphenyl)-2-chloro-s-triazine and 1.70 g (15.5 mmol) of resorcinol. The mixture is stirred at 180 C. for five hours at which point 1H nmr (CDCI3) of an aliquot reveals a 72% overall conversion to the title compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With aluminium trichloride; In m-xylene; 1,2-dichloro-benzene; | Use of Ortho-dichlorobenzene as the Solvent. The basic procedure of Example 3 was followed, except ortho-dichlorobenzene was used as the solvent in place of chlorobenzene. A mixture of 1.84 g cyanuric chloride (10 mmol), 2.12 g of m-xylene (2 eq.), and 1.10 g of resorcinol (1 eq.) in 20 mL o-dichlorobenzene under a nitrogen atmosphere was cooled to 4 C. Aluminum trichloride (3.00 g) was added over 20 mm. such that the temperature was maintained below 6 C. The mixture was then warmed to 35 C. with stirring, and the progress of the reaction was monitored by HPLC. After 17.5 hr. at 35 C., HPLC analysis (area % at 290 nm) showed 37.1% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-5-triazine (4) with 9.0% bis-resorcinol-triazine products: 2-chloro-4,6-bis-(2,4-dihydroxyphenyl)-s-triazine (2, 3.0%) and 2,4-bis-(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine (3, 6.0%). This experiment demonstrates that 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazine can be prepared and the yield of bis-resorcinol-s-triazine products can be minimized using solvents other than chlorobenzene. The use of solvents other than chlorobenzene for this process is therefore considered within the scope of this invention. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With methanesulfonic acid; In methanol; m-xylene; | EXAMPLE 4 4,6-Bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine To a 500 mL four-necked, round-bottomed flask fitted with a mechanical stirrer, a nitrogen atmosphere and an oil bath are added 20.0 g (0.0524 mol) of the product of Example 2, 23.0 g (0.209 mol) of resorcinol. 7.6 g (0.079 mol) of methanesulfonic acid and 25 mL of m-xylene. The mixture is stirred at 120 C. for 20 hours and then allowed to cool to room temperature. A 200 mL portion of heptane and 200 g of ice are added. The contents are warmed to 55 C. and then allowed to cool to below 40 C. The crude solid formed is isolated by filtration, washed with water and heptane and then dried under reduced pressure to yield 17.5 g of yellow-orange crude product. The material is ground in a mortar, taken up in 170 mL of methanol, cooled to -20 C. and then filtered to afford 12.8 g (62% yield) of the title compound as a yellow solid melting at 203-205 C. |
62% | With hydrogenchloride;aluminium trichloride; In n-heptane; m-xylene; | EXAMPLE 6 4,6-Bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine To a 250 mL round-bottomed flask fitted with a magnetic stirrer, a condenser and a nitrogen atmosphere are charged 7.85 g (0.0206 mol) of the product of Example 2, 13.5 g (0.123 mol) of resorcinol, 4 mL of m-xylene and 0.954 g (7.16 mmol) of aluminum chloride. The mixture is heated to 150 C. for 13.5 hours and then allowed to cool to 90 C. Portions of 2N hydrochloric acid and heptane are added and the mixture is stirred at 90 C. for 30 minutes followed by stirring for 18 hours at room temperature. The mixture is then warmed to 35 C. The crude solid formed is collected by vacuum filtration and is washed with portions of water and heptane. The solid is then recrystallized twice from methanol to afford 4.76 g (62% yield) of the title compound as a yellow solid melting at 194-196 C. |
57% | In n-heptane; water; toluene; | EXAMPLE 8 4,6-Bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine A 300 mL three-necked, round-bottomed flask fitted with a magnetic stirrer, an acid trap, a gas inlet and a heat lamp to prevent sublimation is charged with 29.9 g (0.272 mol) of resorcinol and 2.00 g (0.00525 mol) of the product of Example 2. The mixture is heated to 150 C. and hydrogen chloride gas is bubbled slowly through the molten mixture for 25 minutes. The mixture is stirred at this temperature for another 4.5 hours and then allowed to cool to room temperature. Portions of water and toluene are added and the mixture is refluxed till the solids are dissolved. The mixture is allowed to cool to room temperature and the layers separated. The organic layer is washed once with water, twice with saturated sodium bicarbonate solution and once with brine. After drying over anhydrous magnesium sulfate and filtering, the solvent is removed under reduced pressure to afford 1.56 g of crude product. Purification by flash chromatography on silica gel with 3:1 heptane:ethyl acetate gives 1.19 g (57% yield) of the title compound as a yellow solid. |
With hydrogenchloride;aluminium trichloride; In 5,5-dimethyl-1,3-cyclohexadiene; | EXAMPLE 5 4,6-Bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine To a 250 mL round-bottomed flask fitted with a magnetic stirrer, a condenser and a nitrogen atmosphere are charged 6.26 g (0.0164 mol) of the product of Example 2, 12.8 g (0.116 mol) of resorcinol, 2,4 g of NAFION NR50 beads 10-35 and 2 mL of xylene. The mixture is heated to 160 C. for 8.5 hours and then allowed to cool to room temperature. A 2.13 g (0.0160 mol) of aluminum chloride is added all at once. The mixture is then heated to 160 C. for two hours. An aliquot is worked up by adding portions of 2N hydrochloric acid and heptane and collecting the solid by vacuum filtration. 1H nmr (CDCl3) reveals a complete conversion to the title compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Weighing 1.98g dihydroxybenzene (5.39mmol) added to the 250 ml flask in three port, three-port flask is then placed in a constant temperature oil bath boiler. Add 70 ml xylene, open heating and stirring, and then adding the same equivalent NaOH (the NaOH dissolved in 10 ml deionized water, and adding 0.1 times equivalent quaternary ammonium salt), the temperature is increased to 70 C. Reaction 1h, the 1.67 ml dodecyl glycidyl ether (6.2mmol) dissolved in 30 ml of xylene in the above-mentioned solution is dripped into the in, in the 70 C reaction under 24h. By a water washing after the reaction of the catalyst removal method, rotary evaporation to remove the solvent, the chromatographic column for separating and purifying, to obtain the corresponding product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With tetrabutylammomium bromide; potassium iodide; In 5,5-dimethyl-1,3-cyclohexadiene; at 135℃;Inert atmosphere; | Nitrogen protection, 550 g of xylene, 100 g of a triazine fragment (2- [2,4-dihydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine), 1 g of potassium iodide, 1 g of tetrabutylammonium bromide, 98 g of isomeric tridecylglycidyl ether were added and the temperature was raised to 135 C. The micro refluxing reaction was carried out for 12 to 15 hours, 95%. After cooling to room temperature, the filtrate was washed once with water. The filtrate was concentrated and the crude crystals crystallized to give 145 g of product in 89% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | General procedure: DBDT (1 equiv), solid K2CO3 (1.1 equiv) and 18-crown-6 were dissolved in acetone and stirred at room temperature for 30 min.Then dibromoalkane (1.1 equiv) was slowly added into this solution. The reaction was conducted at 50 C until the thin-layer chromatography showed the DBDT disappeared. After the solvent was removed in vacuum, the crude product was purified by silica gel column chromatography with ethyl acetate/petroleum ether (1/100, V/V) as the eluent to get the pure intermediate products (ABs) with yields 86-92%. And then, ABs, solid K2CO3, 18-crown-6 and fluorinated alcohol were added into acetone with a mole ratio of 1:1.1: 1.1. The mixture was heated at the temperature of 50 C with stirring for 6 h. After the solvent was removed in vacuum, the crude product was purified by silica gel column chromatography withethyl acetate/petroleum ether (1/100, V/V) as the eluent to get the target compounds with yields 55-61%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | General procedure: DBDT (1 equiv), solid K2CO3 (1.1 equiv) and 18-crown-6 were dissolved in acetone and stirred at room temperature for 30 min.Then dibromoalkane (1.1 equiv) was slowly added into this solution. The reaction was conducted at 50 C until the thin-layer chromatography showed the DBDT disappeared. After the solvent was removed in vacuum, the crude product was purified by silica gel column chromatography with ethyl acetate/petroleum ether (1/100, V/V) as the eluent to get the pure intermediate products (ABs) with yields 86-92%. And then, ABs, solid K2CO3, 18-crown-6 and fluorinated alcohol were added into acetone with a mole ratio of 1:1.1: 1.1. The mixture was heated at the temperature of 50 C with stirring for 6 h. After the solvent was removed in vacuum, the crude product was purified by silica gel column chromatography withethyl acetate/petroleum ether (1/100, V/V) as the eluent to get the target compounds with yields 55-61%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With tetraethylammonium bromide; In N,N-dimethyl-formamide; at 150℃; for 16h; | A three liter 3-neck round bottom flask was equipped with a temperature probe, condenser and mechanical stirrer. The flask was charged with 500 grams (1.26 moles) of 2,4-di-(2,4-dimethylphenyl)-6-(2,4-dihydroxyphenyl)-triazine, 124 grams (1.4 moles) of ethylene carbonate, 18 grams (0.085 moles) tetraethylammonium bromide and 475 grams of dimethyl formamide. The batch was heated to 150 C. and maintained at that temperature for five hours. The evolution of CO2 from the batch was observed. After five hours, 15 grams additional ethylene carbonate and 2 grams additional tetraethylammonium bromide were added. The batch was heated at 150 C. for three hours, and then 15 grams additional ethylene carbonate and 2 grams additional tetraethylammonium bromide were added. The batch was heated at 150 C. for three more hours, after which time no more starting material was observed by thin layer chromatography. The batch was allowed to cool to 80 C., and 1360 grams of isopropanol (IPA) was added with good agitation. The mixture was cooled to room temperature, and the solid product was collected by filtration onto a Buchner funnel. The solid product was taken up into 1000 grams each of water and IPA, stirred well, and collected by filtration onto a Buchner funnel. The product was air-dried to give 540 grams (96%) of an off-white solid product, 2-[4,6-bis-(2,4-dimethylphenyl)-[1,3,5]triazin-2-yl]-5-(2-hydroxyethoxy)phenol, mp=172 C.-173 C. The product was used without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With sodium hydroxide; In ethanol; at 65℃; for 12.5h;Inert atmosphere; | (1) Weighing compound I-1 39.7 g (0.1 mol), NaOH 6.0g (0.15mol) was added to the four-neck bottle. Add absolute ethanol, Protected and stirred with nitrogen. Set the reaction temperature to 65 C, After the raw material is completely dissolved, Starting to add 13.8 g (0.15 mol) of epichlorohydrin, and the addition was completed in 30 min, and the reaction was carried out at 65 C for 12 h; After the reaction was completed, the system was washed 3 times with water. Chloroform extraction, Drying with anhydrous MgSO4; After removing some of the solvent, Crystallization of the product, Filtering, A light yellow intermediate III-1 solid powder of 34 g was obtained in a yield of 75%. |
With fluorapatite; In chloroform; at 100℃; for 12h; | 20% fluorapatite and 100 C reaction temperature(Chloroform dissolution reaction product)5 grams4- [4,6-bis (2,4-xylyl) -1,3,5-triazine-2-yl] -1,3-resorcinol,1 gram of fluorapatite,Add 50 ml of epichlorohydrin100 ml three-necked flask,Install reflux condenser and thermometer.Heated to 100 C,Heated at this temperature for 12 hours,Using thin-layer tomography,Raw material consumption is complete.Cool to room temperature,filter.The incomeThe solid was dissolved in 5 ml of chloroform,filter,Fluoride apatite was filtered off.The filtrate was concentrated to dryness,Vacuum dried,The yield was 5.25 g (yield 92%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | In a 5-liter three-necked flask equipped with mechanical stirring, 3 liters of chlorobenzene, 184 grams of cyanuric chloride, 212 grams of m-xylene were added(2 times the amount) and 400 g of aluminum trichloride (3 times the amount); under ice-cooling, 20 ml of concentrated hydrochloric acid (0.2 times) was added, the reaction was stirred for 1 hour, and the temperature was raised to room temperature and 121 g of resorcinol was added ( 1.1 times) and then heated to 90C for 2 hours. After the reaction was completed, the reaction solution was slowly added to 5 liters of 10% hydrochloric acid with stirring, and the precipitated solid was filtered and washed with water.Recrystallization yielded 365 g (yield 92%) of 2,4-bis(m-xylyl)-6-(1-m-xylenol)-1,3,5-triazine product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92.5% | With calcium hydroxide In sulfolane at 70 - 110℃; for 7h; Inert atmosphere; | 5-8; 1 Equipped with stirring, thermometer,Add 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to the reactor with reflux condenser column and nitrogen conduit 119.3 g (0.30mol, abbreviation: DHDMT), calcium hydroxide 26.7g (0.36mol), sulfolane 600ml, under nitrogen protection, stirring and heating to 70-75, dropwise add bromooctane 61.0g (0.32mol), at this temperature Stir for 5h, then heat to 100-110 and stir for 2h, add 600ml of deionized water dropwise at 95-105 for 2.0h, then cool to room temperature, filter with Buchner funnel, rinse with appropriate amount of water, and dry 145.6 g of UV1164 product was obtained, the content was 99.3%, and the yield was 95.2%. |
With sodium hydroxide In N,N-dimethyl-formamide at 70℃; | Synthesis of 2- (4,6-bis(2,4-dimethyl phenyl)-l,3,5-triazin-2-yl)-5- (octyloxy) phenol (A4): To a stirred solution of a compound formula (A3) (0.2 mol) i n DM F (250 g) was added sodium hydroxide (0.1 mol). The tem perature was raised to 70° C, octyl bromide (0.2 mol) was added dropwise. The reaction was continued at this temperature 4-5h. , After the reaction was com pleted, the reaction mixture was cooled, submitted to suction filtration and recrystal lized to obtain a compou nd of formula (A4). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71.66% | With potassium bromide In N,N-dimethyl-formamide at 105℃; for 8h; | 1; 2 In the etherification reactor, drop into 50g acylation intermediate (already 100%), 1g potassium bromide, 2.5g PEG-400, dimethylformamide 200g and 25g 1-chloro-n-octane, stir and be warming up to 105 , then Incubate for 8h.The reaction solution was filtered, cooled and temperature-controlled at 5-10 °C for the first crystallization, and then 180 g of ethanol was mixed with crude UV-1164 and heated to reflux, and kept at the reflux temperature for 1 h, and the temperature was controlled at 5-10 °C for the second time. Secondary crystallization to obtain UV-1164 finished product.After testing, the content of the finished product is 99.14%, (as shown in the map in Figure 3, and the data after the area normalization method is shown in Figure 4) the weight of the finished product: 60.10 g, and the total molar yield is 71.66%. |
Tags: 1668-53-7 synthesis path| 1668-53-7 SDS| 1668-53-7 COA| 1668-53-7 purity| 1668-53-7 application| 1668-53-7 NMR| 1668-53-7 COA| 1668-53-7 structure
[ 106556-36-9 ]
2-(4,6-Diphenyl-1,3,5-triazin-2-yl)-5-methoxyphenol
Similarity: 0.87
[ 7753-13-1 ]
4,4',4''-(1,3,5-Triazine-2,4,6-triyl)triphenol
Similarity: 0.84
Precautionary Statements-General | |
Code | Phrase |
P101 | If medical advice is needed,have product container or label at hand. |
P102 | Keep out of reach of children. |
P103 | Read label before use |
Prevention | |
Code | Phrase |
P201 | Obtain special instructions before use. |
P202 | Do not handle until all safety precautions have been read and understood. |
P210 | Keep away from heat/sparks/open flames/hot surfaces. - No smoking. |
P211 | Do not spray on an open flame or other ignition source. |
P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
P223 | Keep away from any possible contact with water, because of violent reaction and possible flash fire. |
P230 | Keep wetted |
P231 | Handle under inert gas. |
P232 | Protect from moisture. |
P233 | Keep container tightly closed. |
P234 | Keep only in original container. |
P235 | Keep cool |
P240 | Ground/bond container and receiving equipment. |
P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
P242 | Use only non-sparking tools. |
P243 | Take precautionary measures against static discharge. |
P244 | Keep reduction valves free from grease and oil. |
P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
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 |
Sorry,this product has been discontinued.
Home
* Country/Region
* Quantity Required :
* Cat. No.:
* CAS No :
* Product Name :
* Additional Information :