Tetramethylolacetylenediurea

Liquid

Into a suitable reaction vessel equipped with a stirrer, thermometer and reflux condenser, there was introduced 688 parts (10 mol) of aqueous formaldehyde (44percent), and the pH was adjusted to 8.7 with 22 parts of 0.5 N NaOH solution. To this solution, there was added 284 parts (2 mol) of acetylene carbamide at 40° C. During the resulting reaction, the temperature was allowed to rise up to 55° C. At this stage, most of the acetylene carbamide entered into solution. After about 15 minutes, the pH was adjusted to 8.0 with five parts of 0.5 N NaOH. A clear, pale yellow colored solution was obtained. The clear solution was distilled at 50° C, under reduced pressure, to remove water until the reaction vessel content was about 640 parts. The resulting syrup in the vessel was poured into 800 parts of methanol. The resulting white crystalline precipitate was filtered and dried. The total yield of the tetramethylol acetylene carbamide was 483 parts (92percent) and had a melting point of 132° - 136° C.Into a suitable reaction vessel equipped with a stirrer, thermometer and reflux condenser, there was introduced 688 parts (10 mol) of aqueous formaldehyde (44percent), and the pH was adjusted to 8.7 with 22 parts of 0.5 N NaOH solution. To this solution, there was added 284 parts (2 mol) of acetylene carbamide at 40° C. Duringthe reaction, the temperature was allowed to rise up to 55° C. At this stage, most of the acetylene carbamide had gone into solution. After about 15 minutes, the pH was adjusted to 8.0 with five parts of 0.5 N NaOH. A clear, pale yellow colored solution was obtained. The clear solution was distilled at 50° C, under reduced pressure to remove water, until the reaction vessel content was about 640 parts. The syrup inthe vessel was poured into 800 parts of methanol. The white crystalline precipitate was filtered and dried. The total yield of the tetramethylol acetylene carbamide was 483 parts (92percent) and melting point of 132° - 136° C.A suspension of 28.4 g (0.2 mol) of glycoluril 1 and 80 g of 40percent formaldehyde solution was alkalized with a 20percent NaOH solution to 9–10, after which the mixture was stirred at 50 °C for 2 h. 70percent of water was distilled off, and tetra-N-hydroxymethyl glycoluril was separated and washed with acetone. Yield of 2 26.2 g (50percent), mp 136.5 °C. IR spectrum(KBr), ν, cmIn a 50 mL flask equipped with a thermometer, 1.31 g (5.0 mmol) of 1, 3, 4, 6-tetrakis (hydroxymethyl) glycoluril, Pyridine 3.90 g (50.0 mmol)And 25 mL of N, N-dimethylformamide.To the resulting mixture was added, under ice cooling, After 5.33 g (50.0 mmol) of methacryloyl chloride was added dropwise, And the mixture was stirred overnight at room temperature.After this, 100 mL of water was added to the obtained reaction mixture, Extraction operation was carried out with 100 mL of ethyl acetate.The obtained organic layer was concentrated under reduced pressure, The obtained concentrate was purified by silica gel chromatography (ethyl acetate / hexane = 1/1 (volume ratio)), 733 mg of 1, 3, 4, 6-tetrakis (methacryloyloxymethyl) glycoluril was obtained as a colorless liquid.Yield 27%.1 , 3, 4, 6-tetrakis(hydroxymethyl)tetrahydroimidazo [4, 5-d]imidazole-2, 5(1H, 3H)-dione (1.25 g, 4.8 mmol) in 3 ml of DMSO was dissolved. Then, 0.3 ml nitric acid (65%) and 4-methylcyclohexanol (5.9 ml, 47.7 mmol) were added to the solution and the mixture was heated at 60 C for 16 hours. Afier the reaction was over, the reaction liquid was cooled and iN NaOH was added around pH 7. Around 100 ml ethyl acetate was used to extract with mixture and the organic phase was washed by saturated NaC1(aq) solution for 2 times. After being dried by Na2504, the solvent was removed1 , 3, 4, 6-tetrakis(hydroxymethyl)tetrahydroimidazo [4, 5-d]imidazole-2, 5(1H, 3H)-dione (1.99 g, 7.6 mmol) in 1.5 ml of DM50 was dissolved. Then, 0.3 ml nitric acid (65%) and 4-ethylcyclohexanol (10.5 ml, 75.9 mmol) were added to the solution and the mixture was heated at 60 C. for 16 hours. After the reaction was over, the reaction liquid was cooled and iN NaOH was added around pH 7. Around 100 ml ethyl acetate was used to extract with mixture and the organic phase was washed by saturated NaC1(aq) solution for 2 times. Afier being dried by Na2SO4, the solvent was removed1 , 3, 4, 6-tetrakis(hydroxymethyl)tetrahydroimidazo [4, 5-d]imidazole-2, 5(1H, 3H)-dione (3 g, 11.4 mmol) in tetrahydro-4-pyranol (11 ml, 114 mmol) was dissolved. Then, 0.15 ml nitric acid (65%) was added to the solution and the mixture was heated at 60 C. for 16 hours. Afier the reaction was over, the reaction liquid was cooled and iN NaOH was added around pH 7. Around 100 ml ethyl acetate was used to extract with mixture and the organic phase was washed by saturated NaC1(aq) solution for 2 times. After being dried by Na2504, the solvent was removed. The crude compound was purified by flash chromatography (MC/acetone). The product was obtained colorless viscous oil. 'H NMR (600 MHz, DMSO-d6): oe (ppm) 5.57 (s, 2H), 4.84 (m, 8H), 3.78 (m, 8H), 3.57 (m, 4H), 3.29 (m, 8H), 1.82 (m, 8H), 1.40 (m, 8H)1 , 3, 4, 6-tetrakis(hydroxymethyl)tetrahydroimidazo [4, 5-d]imidazole-2, 5(1H, 3H)-dione (1.88 g, 7.2 mmol) in 1.5 ml of DMSO was dissolved. Then, 0.15 ml nitric acid (65%) and n-l3uOH (13.12 ml, 143 mmol) were added to the solution and the mixture was heated at 60 C. for 16 hours. After the reaction was over, the reaction liquid was cooled and iN NaOH was added around pH 7. Around 100 ml ethyl acetate was used to extract with mixture and the organic phase was washed by saturated NaC1(aq) solution for 2 times. After being dried by Na2504, the solvent was removed. The crude compound was purified by flash chromatography (Heptane/EtOAc). The product was obtained colorless viscous oil in 0.38 g, yield (11%) 'H NMR (600 MHz, DMSO-d6): oe (ppm) 5.52 (s, 2H), 4.73 (m, 8H), 3.35 (m, 8H), 1.46 (m, 8H), 1.29 (m, 8H), 0.85 (t, 12H)To tetra(hydroxymethyl)glycoluril (1.0 eq.) suspended in cyclohexanol (20.0 eq.) is added concentrated nitric acid (4.4 eq.). This mixture is heated to dissolve the glycoluril and then stirred at the elevated temperature until the reaction is completed. The final reaction mixture is cooled to ambient temperature, neutralized with dilute caustic, dried over magnesium sulfate, and then concentrated by rotary evaporation. The final product is isolated by either crystallization from the crude reaction mixture or by purification via column chromatography (EtOAc:Hex) to give the target compound as a white crystalline solid1 , 3, 4, 6-tetrakis(hydroxymethyl)tetrahydroimidazo [4, 5-d]imidazole-2, 5(1H, 3H)-dione (1 g, 3.8 mmol) in 2 ml of DM50 was dissolved. Then, 0.15 ml nitric acid (65%) and n-hexylalcohol (9.5 ml, 76.3 mmol) were added to the solution and the mixture was heated at 60 C. for 16 hours. After the reaction was over, the reaction liquid was cooled and iN NaOH was added around pH 7. Around 100 ml ethyl acetate was used to extract with mixture and the organic phase was washed by saturated NaC1(aq) solution for 2 times. After being dried by Na2SO4, the solvent was removed. The crude compound was purified by flash chromatography (Heptane/EtOAc). The product was obtained colorless viscous oil in 0.15 g, yield (%) 'H NMR (600 MHz, DMSO-d6): oe ppm) 5.50 (s, 2H), 4.73 (m, 8H), 3.36 (m, 8H), 1.46 (m, 8H), 1.24 (m, 26H), 0.85 (t, 12H)To 3.5 g (0.013 mol) of 2 in toluene, 18.08 g (0.06 mol) of phosphorus tribromide was added. The mixture was heated at 60-90 C for 24 h. The resulting precipitate was filtered off and washed with diethyl ether. Yield of 4 3.5 g (62.5%), mp 160 C. 1H NMR spectrum (400 MHz, DMSO), delta, ppm: 5.46 s (2H, CH), 7.14-7.21 m (4H, CH2Br), 4.67-4.73 m (4H, CH2OH).2.0 g (0.0076 mol) of 2 in acetonitrile, 8.4 g (0.0608 mol) of phosphorus trichloride was added at 0-10 C. After that, the mixture was stirred at 70-80 C for 24 h, and the precipitate was filtered off and washed with acetonitrile. Yield of 3 1.89 g (60.96%), mp 180 C. 1H NMRspectrum (400 MHz, DMSO), delta, ppm: 5.48 s (2H, CH), 7.12-7.23 m (4H, CH2Cl), 4.65-4.76 m (4H, CH2OH).To 2.62 g (0.01 mol) of 2 and1.58 g (0.02 mol) of pyridine in benzene, 2.89 g (0.02mol) of dimethyl phosphorochloridate was added at 0 C. The mixture was heated at 60-70 C for 24 h. The reaction progress was constantly monitored by TLC. The precipitate was filtered off and washed with acetone. Yield of 5, 6 2.0 g (50.25%). 1H NMR spectrum (400 MHz, DMSO), delta, ppm: 3.16 s [12H, 2P(OCH3)2], 4.34 s [4H, 2CH2P(O)], 4.52-4.62 m (4H, 2CH2-OH), 5.64 s (2H, CHCH), 3.21 s [6H, 2P(O)OCH3], 2.51-2.53 m [8H, 2P(CH2)2]. In the 31P NMR spectrum, there are two signals at 1.0 [(CH2)2P(O)OCH3] and 4.0 ppm[CH2P(O)(OCH3)2]. However, we failed to separate these products because of their affinity for the solvents.

Crosslinker, Fungicide, Concrete additive Tetramethylol acetylene diurea is a formaldehyde type of textile-finish resin.

Intermediates

Molecular Weight:262.22
XLogP3:-2.1
Hydrogen Bond Donor Count:4
Hydrogen Bond Acceptor Count:6
Rotatable Bond Count:4
Exact Mass:262.09133418
Monoisotopic Mass:262.09133418
Topological Polar Surface Area:128
Heavy Atom Count:18
Complexity:304
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes