三羟甲基乙烷

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a stirred solution of 1,1,1-tris(hydroxymethyl)ethane (13.1 g, 109 mmol), (2S)-2-(6-methoxy(2-naphthyl))propanoic acid (naproxen, 5.00 g, 21.7 mmol), 1-(3-(dimethylamino)propyl)-3-ethylcarbodiimide hydrochloride (4.80 g, 25 mmol), and N,N-dimethylaminopyridine (DMAP, 20 mg, catalytic amount) in acetonitrile (200 mL) was added triethylamine (4.2 mL, 30 mmol). The reaction mixture was stirred at ambient temperature for 25 hours, filtered, and the filtrate was concentrated to dryness. The residue was diluted with EtOAc, washed with 1N HCl (2×), saturated NaHCO3, and brine, dried over Na2SO4, filtered, and concentrated. The resulting material was purified by crystallization (2×) from EtOAc/Hexanes (1:3 v:v) to give the title compound (4.72 g, 66% yield) as white flakes. Mp 105° C. 1H NMR (300 MHz, CDCl3) δ 7.72 (d, J=2.0 Hz, 1H), 7.69 (d, J=2.5 Hz, 1H), 7.66 (s, 1H), 7.39 (dd, J=8.5, 1.7 Hz, 1H), 7.17-7.10 (m, 2H), 4.25 (d, J=11.3 Hz, 1H), 4.09 (d, J=11.3 Hz, 1H), 3.90 (s, 3H), 3.88 (q, J=7.1 Hz, 1H), 3.46-3.25 (m, 4H), 2.65-2.55 (m, 2H), 1.60 (d, J=7.1 Hz, 3H), 0.67 (s, 3H). 13C NMR (75 MHz, CDCl3) δ175.8, 157.7, 135.3, 133.8, 129.2, 128.9, 127.3, 126.0, 119.2, 105.6, 67.7. 67.5, 66.8, 55.3, 45.6, 40.9, 18.1, 16.7. LRMS (API-TIS) m/z 350.2 ((M+NH4)+). filtered the filtrate was concentrated to dryness The residue was diluted with EtOAc washed with 1N HCl (2×), saturated NaHCO3, and brine dried over Na2SO4 filtered concentrated The resulting material was purified by crystallization (2×) from EtOAc/Hexanes (1:3 v:v)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: As a compound having at least one addition polymerizable ethylenically unsaturated group and a boiling point of 100° C. or more under normal pressure, there can be exemplified a monofunctional acrylate and methacrylate such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl(meth)acrylate; compounds obtained by the addition of ethylene oxide or propylene oxide to polyfunctional alcohol such as polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane, tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl)isocyanurate, glycerin, and trimethylolethane, and then having (meth)acrylated; urethane acrylates as disclosed in JP-B-48-41708, JP-B-50-6034, and JP-A-51-37193; polyester acrylates as disclosed in JP-A-48-64183, JP-B-49-43191, and JP-B-52-30490; and polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acids. Further, photocurable monomers and oligomers described in Nihon Setchaku Kyokai Shi (Bulletin of Japan Adhesion Association), Vol. 20, No. 7, pp. 300 to 308 can also be used. As a compound having at least one addition polymerizable ethylenically unsaturated group

反应条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 22.4 g DP9C/012, 3.9 g Poly G 83-34, 1.0 g Pluronic L-62, 0.4 g trimethylolethane, 2.0 g Cirrasol G-265, 1.0 g DMAMP DBS, and 0.11 g tin catalyst are added to 2.6 g N-methyl pyrrolidone plus 4.7 g methylethylketone, 2.8 g tertiary amyl alcohol, 0.6 g 2,4-pentanedione and 4.0 g diacetone alcohol and are mixed together. The mixture is heated to 60° C. and then reacted for 6 hours in a nitrogen atmosphere. Following the reaction, the resulting polyurethane prepolymer mixture is cooled and then dispersed in 59.0 g of distilled water, 0.1 g trimethylolethane, and 0.2 g triethanolamine with a high shear disperser, resulting in a stable aqueous polyurethane dispersion having about 24% solids by weight of the dispersion. The resulting polyurethane comprises about 3% polyethylene oxide side chains by weight of the solids of the polyurethane, about 12% polyethylene oxide main chains by weight of the solids of the polyurethane, and about 48% blocked polyisocyanates by weight of the solids of the polyurethane. are mixed together reacted for 6 hours in a nitrogen atmosphere the reaction

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of acetic acid 1-acetoxymethyl-2-[3-(2,3-diacetoxy-propylcarbamoyl)-2,4,6-triiodo-5-isocyanato-benzoylamino]-ethyl ester in dichloromethane was added 1,1,1-tris(hydroxymethyl)ethane (0.3 equivalent). The reaction mixture was stirred for 18 hours and then purified by column chromatography to give acetic acid 2-acetoxy-3-[3-{2-[3,5-bis-(2,3-diacetoxy-propylcarbamoyl)-2,4,6-triiodo-phenylcarbamoyloxymethyl]-3-hydroxy-2-methyl-propoxycarbonylamino}-5-(2,3-diacetoxy-propylcarbamoyl)-2,4,6-triiodo-benzoylamino]propyl ester. This was dissolved in methanol and treated with aquesous ammonia. The material was purified by preparatie HPLC to give 1,3-bis-[N,N′-Bis-(2,3-dihydroxy-propyl)-2,4,6-triiodo-5-carbamido-isophthalamide]-2-methyl-2-hydroxymethylpropane as a white powder after freeze drying. purified by column chromatography

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of acetic acid 1-acetoxymethyl-2-[3-(2,3-diacetoxy-propylcarbamoyl)-2,4,6-triiodo-5-isocyanato-benzoylamino]-ethyl ester in dichloromethane was added 1,1,1-tris(hydroxymethyl)ethane (0.3 equivalent). The reaction mixture was stirred for 18 hours and then purified by column chromatography to give acetic acid 2-acetoxy-3-[3-{2-[3,5-bis-(2,3-diacetoxy-propylcarbamoyl)-2,4,6-triiodo-phenylcarbamoyloxymethyl]-3-hydroxy-2-methyl-propoxycarbonylamino}-5-(2,3-diacetoxy-propylcarbamoyl)-2,4,6-triiodo-benzoylamino]propyl ester. This was dissolved in methanol and treated with aquesous ammonia. The material was purified by preparatie HPLC to give 1,3-bis-[N,N′-Bis-(2,3-dihydroxy-propyl)-2,4,6-triiodo-5-carbamido-isophthalamide]-2-methyl-2-hydroxymethylpropane as a white powder after freeze drying. purified by column chromatography

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The dendrimers selected for the toner additives of the present invention are, for example, illustrated in the documents mentioned herein. Dendrimers are known, and can be considered radially symmetrical molecules of a STARBURST topology comprised of an initiator core, such as nitrogen, ethylenediimine, silicon, and the like, interior layers attached to the core and comprised of, for example, three, four or more arms, each arm being composed of repeating units with the number of repeating units in each arm being considered the generation of the dendrimer, and terminal covalently bonded stable free radical functional groups, such as for example a nitroxyl compound attached to the outermost generation, which dendrimers having related terminal amine terminated groups are illustrated, for example, in U.S. Pat. Nos. 4,507,466; 4,631,337; 4,558,120; 4,568,737 and 4,587,329; and in D. A. Tomalia, A. M. Naylor, and W. A. Goddard, Angewandte Chemie, Int. Ed. Engl., 29, 138 (1990), the disclosures of which are totally incorporated herein by reference. The size and shape of the STARBURST dendrimer molecule and the functional groups present in the dendrimer molecule can be controlled by the choice of the initiator core, the number of generations, and the choice of repeating units employed at each generation. The choice of the dendrimer components can affect the properties of the dendrimers. The initiator core type can affect the dendrimer shape producing, for example, spheroid-shaped dendrimers, cylindrical- or rod-shaped dendrimers, or ellipsoid-shaped dendrimers. Sequential building of generations determines the dimensions of the dendrimers and the nature of its interior. Examples of core materials which have been successfully used include ammonia, polyfunctional alcohols, such as pentaerythritol or tris-(hydroxymethyl)ethane, 1,1,1-tris-(4'-hydroxyphenyl)-ethane, polyfunctional amines, such as ethylene diamine, linear polyethyleneimines, and the like, carbosilanes such as tetravinylsilane as described, for example, in J. Roovers, P. M. Toporowski and L-L. Zhou, Polymer Preprints, American Chemical Society, Division of Polymer Chemistry, 33, (1), 182 (1992), and the like; polysiloxysilanes, such as those described, for example, in L. J. Mathias and T. W. Carothers, J. Am. Chem. Soc., 113, 4043 (1991), in H. Uchida, Y. Kabe, K. Yoshino, A. Kawamata, T. Tsumuraya, and S. Masamune, J. Am. Chem, Soc., 112, 7077 (1990), in A. Morikawa, M. Kakimoto, and Y. Imai, Macromolecules, 24, 3469 (1991), and the like; polyfunctional aromatic rings, such as benzoic acids, such as 3,5-diacetoxybenzoic acid, as illustrated, for example, in B. I. Voit and S. R. Turner, in Polymer Preprints, American Chemical Society, Division of Polymer Chemistry, 33, (1), 184 (1992); hyperbranched polyphenylenes such as those described by Y. H. Kim and O. W. Webster, in J. Am. Chem. Soc., 112, 4592 (1990), hyperbranched polyarylenes, such as those described in U.S. Pat. Nos. 4,857,630 and 5,070,183 to E.I. DuPont de Nemours and Company, and the like. The chemical functionality of the repeating unit in the interior layers can include, for example, amidoamines, such as amino-ethyl acetamide, imines, such as diethylene diimine, ethers such as those obtained from materials such as, for example, 3,5-dihydroxyethyl benzyl alcohol, siloxanes, such as dimethylsiloxane, diethylsiloxane, diphenylsiloxane, and the like, carbosilanes, such as ethyl silane and the like. The terminal functionalities include, for example, amino groups, quaternary ammonium salts, phosphonium salts, hydroxyl groups, carboxylic acid groups, carboxylates, esters, amides, phosphates, sulfonates, and the like. The synthesis of dendrimers usually occurs by a linear, convergent, or divergent aproaches. The divergent approach involves the initial reaction of a monomer with the initiator core, followed by exhaustive reaction of the resulting functional groups with a difunctional compound, such as a diamine, including, for example, ethylene diamine, to afford the next generation of reactive amino groups. Repetition of the two-step procedure leads to subsequent generations. An alternate synthetic route uses a convergent growth synthesis as described in detail in C. J. Hawker and J. M. J. Frechet, J. Am. Chem. Soc., 112, 7638 (1990), the disclosure of which is totally incorporated herein by reference. Examples of dendrimers prepared by the divergent method include STARBURST dendrimers available from the Michigan Molecular Institute, Dendrimer Microparticles available from Polysciences, Inc., in which the terminal functional groups are primary amino groups, and which range in average diameter of from about 10.8 Angstroms (first generation) to about 83.9 Angstroms (8th generation). Other dendrimers of interest, in embodiments, of the present invention include those as illustrated in U.S. Pat. Nos. 5,041,516; 4,857,599 and 4,694,064, the disclosures of which are totally incorporated herein by reference.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The dendrimers selected for the toner additives of the present invention are, for example, illustrated in the documents mentioned herein. Dendrimers are known, and can be considered radially symmetrical molecules of a STARBURST topology comprised of an initiator core, such as nitrogen, ethylenediimine, silicon, and the like, interior layers attached to the core and comprised of, for example, three, four or more arms, each arm being composed of repeating units with the number of repeating units in each arm being considered the generation of the dendrimer, and terminal covalently bonded stable free radical functional groups, such as for example a nitroxyl compound attached to the outermost generation, which dendrimers having related terminal amine terminated groups are illustrated, for example, in U.S. Pat. Nos. 4,507,466; 4,631,337; 4,558,120; 4,568,737 and 4,587,329; and in D. A. Tomalia, A. M. Naylor, and W. A. Goddard, Angewandte Chemie, Int. Ed. Engl., 29, 138 (1990), the disclosures of which are totally incorporated herein by reference. The size and shape of the STARBURST dendrimer molecule and the functional groups present in the dendrimer molecule can be controlled by the choice of the initiator core, the number of generations, and the choice of repeating units employed at each generation. The choice of the dendrimer components can affect the properties of the dendrimers. The initiator core type can affect the dendrimer shape producing, for example, spheroid-shaped dendrimers, cylindrical- or rod-shaped dendrimers, or ellipsoid-shaped dendrimers. Sequential building of generations determines the dimensions of the dendrimers and the nature of its interior. Examples of core materials which have been successfully used include ammonia, polyfunctional alcohols, such as pentaerythritol or tris-(hydroxymethyl)ethane, 1,1,1-tris-(4'-hydroxyphenyl)-ethane, polyfunctional amines, such as ethylene diamine, linear polyethyleneimines, and the like, carbosilanes such as tetravinylsilane as described, for example, in J. Roovers, P. M. Toporowski and L-L. Zhou, Polymer Preprints, American Chemical Society, Division of Polymer Chemistry, 33, (1), 182 (1992), and the like; polysiloxysilanes, such as those described, for example, in L. J. Mathias and T. W. Carothers, J. Am. Chem. Soc., 113, 4043 (1991), in H. Uchida, Y. Kabe, K. Yoshino, A. Kawamata, T. Tsumuraya, and S. Masamune, J. Am. Chem, Soc., 112, 7077 (1990), in A. Morikawa, M. Kakimoto, and Y. Imai, Macromolecules, 24, 3469 (1991), and the like; polyfunctional aromatic rings, such as benzoic acids, such as 3,5-diacetoxybenzoic acid, as illustrated, for example, in B. I. Voit and S. R. Turner, in Polymer Preprints, American Chemical Society, Division of Polymer Chemistry, 33, (1), 184 (1992); hyperbranched polyphenylenes such as those described by Y. H. Kim and O. W. Webster, in J. Am. Chem. Soc., 112, 4592 (1990), hyperbranched polyarylenes, such as those described in U.S. Pat. Nos. 4,857,630 and 5,070,183 to E.I. DuPont de Nemours and Company, and the like. The chemical functionality of the repeating unit in the interior layers can include, for example, amidoamines, such as amino-ethyl acetamide, imines, such as diethylene diimine, ethers such as those obtained from materials such as, for example, 3,5-dihydroxyethyl benzyl alcohol, siloxanes, such as dimethylsiloxane, diethylsiloxane, diphenylsiloxane, and the like, carbosilanes, such as ethyl silane and the like. The terminal functionalities include, for example, amino groups, quaternary ammonium salts, phosphonium salts, hydroxyl groups, carboxylic acid groups, carboxylates, esters, amides, phosphates, sulfonates, and the like. The synthesis of dendrimers usually occurs by a linear, convergent, or divergent aproaches. The divergent approach involves the initial reaction of a monomer with the initiator core, followed by exhaustive reaction of the resulting functional groups with a difunctional compound, such as a diamine, including, for example, ethylene diamine, to afford the next generation of reactive amino groups. Repetition of the two-step procedure leads to subsequent generations. An alternate synthetic route uses a convergent growth synthesis as described in detail in C. J. Hawker and J. M. J. Frechet, J. Am. Chem. Soc., 112, 7638 (1990), the disclosure of which is totally incorporated herein by reference. Examples of dendrimers prepared by the divergent method include STARBURST dendrimers available from the Michigan Molecular Institute, Dendrimer Microparticles available from Polysciences, Inc., in which the terminal functional groups are primary amino groups, and which range in average diameter of from about 10.8 Angstroms (first generation) to about 83.9 Angstroms (8th generation). Other dendrimers of interest, in embodiments, of the present invention include those as illustrated in U.S. Pat. Nos. 5,041,516; 4,857,599 and 4,694,064, the disclosures of which are totally incorporated herein by reference.

反应条件: temp:30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: One loopful bacterial cells of Agrobacterium sp. SD807 strain were inoculated in 5 ml of a culture medium having the same composition as culture medium 2 shown in Table 3 and incubated with shaking at 30° C. for 1 day. After completion of the cultivation, the bacterial cells were harvested by centrifugation and a 50 mM potassium phosphate buffer solution containing 1,1,1-tris(hydroxymethyl)ethane in a concentration of 5 g/l was added thereto to prepare a resting cell suspension reaction mixture. This was shaken at 30° C. The reaction mixture had a turbidity in terms of absorbance of 0.2 at 660 nm. A portion of the reaction mixture was analyzed by high performance liquid chromatography and as a result, it was found that 4.9 g/l of 1,1,1-tris(hydroxymethyl)ethane had been oxidized at 66 hours of the reaction to produce 0.1 g/l of 2,2-bis (hydroxymethyl)propionaldehyde and 4.8 g/l of 2,2-bis (hydroxymethyl)propionic acid. Conversion rate of 1,1,1-tris(hydroxymethyl)ethane to 2,2-bis(hydroxymethyl)propionic acid was about 88%. was added to prepare a resting cell suspension reaction mixture This was shaken at 30° C had been oxidized at 66 hours of the reaction

反应条件: temp:30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: One loopful bacterial cells of Rhodococcus erythropolis SD806 strain were inoculated in 200 ml of a culture medium having the same composition as culture medium 1 shown in Table 3 and incubated with shaking at 30° C. for 2 days. After completion of the incubation, the bacterial cells were harvested by centrifugation and 1 liter of a 50 mM potassium phosphate buffer solution containing 5 g of 1,1,1-tris(hydroxymethyl)ethane was added thereto to prepare a resting cell suspension reaction mixture. The reaction mixture had a turbidity in terms of absorbance of 0.8 at 660 nm. This was shaken at 30° C. for 24 hours. A portion of the reaction mixture was analyzed by high performance liquid chromatography and as a result, it was found that 3.3 g of 1,1,1-tris(hydroxymethyl)ethane was oxidized and decomposed to produce 1.1 g of 2,2-bis (hydroxymethyl)propionaldehyde and 2.0 g of 2,2-bis (hydroxymethyl)propionic acid. was added to prepare a resting cell suspension reaction mixture This was shaken at 30° C. for 24 hours

反应条件: temp:30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: One loopful bacterial cells of Rhodococcus erythropolis SD806 strain were inoculated in 200 ml of a culture medium having the same composition as culture medium 1 shown in Table 3 and incubated with shaking at 30° C. for 2 days. After completion of the incubation, the bacterial cells were harvested by centrifugation and 1 liter of a 50 mM potassium phosphate buffer solution containing 5 g of 1,1,1-tris(hydroxymethyl)ethane was added thereto to prepare a resting cell suspension reaction mixture. The reaction mixture had a turbidity in terms of absorbance of 0.8 at 660 nm. This was shaken at 30° C. for 24 hours. A portion of the reaction mixture was analyzed by high performance liquid chromatography and as a result, it was found that 3.3 g of 1,1,1-tris(hydroxymethyl)ethane was oxidized and decomposed to produce 1.1 g of 2,2-bis (hydroxymethyl)propionaldehyde and 2.0 g of 2,2-bis (hydroxymethyl)propionic acid. was added to prepare a resting cell suspension reaction mixture This was shaken at 30° C. for 24 hours