4559-86-8

Usage

Uses

Plasticizer.

InChI:InChI=1/C17H36N2O/c1-5-9-13-18(14-10-6-2)17(20)19(15-11-7-3)16-12-8-4/h5-16H2,1-4H3

Synthetic route

Tetrabutyl-selenourea (160594-75-2) → N,N,N',N'-Tetrabutylurea (4559-86-8)

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 3h;	100%

bis(trichloromethyl) carbonate (32315-10-9) + dibutylamine (111-92-2) → N,N,N',N'-Tetrabutylurea (4559-86-8)

Conditions	Yield
In water at 0 - 5℃; for 2h; Temperature;	92.4%

dibutylamine (111-92-2) + carbonic acid dimethyl ester (616-38-6) → N,N,N',N'-Tetrabutylurea (4559-86-8)

Conditions	Yield
With sodium methylate In methanol at 30 - 60℃; for 5h; Temperature; Solvent; Reagent/catalyst; Reflux;	90.9%

phosgene (75-44-5) + dibutylamine (111-92-2) → N,N,N',N'-Tetrabutylurea (4559-86-8)

Conditions	Yield
With sodium hydroxide In H20 at 75 - 85℃; for 5.75 - 7h; pH=10 - 11; Product distribution / selectivity;	88%
With potassium carbonate
With potassium carbonate In benzene

carbon dioxide (124-38-9) + dibutylamine (111-92-2) → N,N,N',N'-Tetrabutylurea (4559-86-8)

Conditions	Yield
Stage #1: carbon dioxide; dibutylamine In dimethyl sulfoxide at 20℃; Stage #2: dibutylamine With triphenylphosphine; diethylazodicarboxylate In dimethyl sulfoxide at 20℃; for 3h; chemoselective reaction;	84%
With potassium hydroxide at 149.84℃; under 60006 Torr; for 10h; Autoclave;	36.7%
Stage #1: carbon dioxide; dibutylamine With 1,8-dimethylaminonaphthalene In tetrahydrofuran at 20℃; under 750.075 Torr; for 1h; Stage #2: dibutylamine In tetrahydrofuran; tetrachloromethane at 60℃; for 23h; Further stages.;	99 % Spectr.

O-trifluoromethanesulfonyl-N,N,N',N'-tetrabutyluronium triflate + diethylamine (109-89-7) → N,N-diethyl-1,1,1-trifluoromethanesulfonamide (357-39-1) + N,N,N',N'-Tetrabutylurea (4559-86-8) + diethylammonium trifluoromethanesulfonate (60933-18-8)

Conditions	Yield
In chloroform at 4℃; for 72h;	A 55% B 74% C n/a

carbon monoxide (201230-82-2) + dibutylamine (111-92-2) → N,N,N',N'-Tetrabutylurea (4559-86-8) + N,N,N',N'-Tetrabutyl-2-oxo-malonamide (132279-00-6) + N,N-dibutylglyoxylamide hemihydrate (83862-73-1)

Conditions	Yield
Yield given. Multistep reaction. Yields of byproduct given;

N-phenylacetoacetamide (102-01-2) + dibutylamine (111-92-2) → N,N,N',N'-Tetrabutylurea (4559-86-8) + 1,1'-dibutyl-3-phenylurea (2589-21-1)

Conditions	Yield
With zeolite HSZ-360 at 180℃; for 3h; Condensation;

O-trifluoromethanesulfonyl-N,N,N',N'-tetrabutyluronium triflate + diisopropylamine (108-18-9) → C7H14F3NO2S + N,N,N',N'-Tetrabutylurea (4559-86-8) + diisopropylammonium trifluoromethanesulfonate (77534-66-8)

Conditions	Yield
In chloroform at 4℃; for 72h;

O-trifluoromethanesulfonyl-N,N,N',N'-tetrabutyluronium triflate + dibutylamine (111-92-2) → C9H18F3NO2S + dibutylammonium trifluoromethanesulfonate + N,N,N',N'-Tetrabutylurea (4559-86-8)

Conditions	Yield
In chloroform at 4℃; for 72h;

dibutylamine (111-92-2) + 2-bromo-1-<7-chloro-naphthyl-(1)>-ethanol-(1) → N,N,N',N'-Tetrabutylurea (4559-86-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 22 percent / Se, NaH, HMPA / 0.5 h / 80 °C 2: 100 percent / m-chloroperbenzoic acid / CH2Cl2 / 3 h / 0 °C View Scheme

N,N,N',N'-Tetrabutylurea (4559-86-8) + trifluoromethylsulfonic anhydride (358-23-6) → bis(tetrabutylamidinio) ether bis(trifluoromethanesulfonate)

Conditions	Yield
In dichloromethane for 12h; Heating;	84%

N,N,N',N'-Tetrabutylurea (4559-86-8) → N-butyl-N-(chloro(dibutylamino)methylene)butan-1-aminium chloride (81363-13-5)

Conditions	Yield
With COCl2 at 80℃; for 2h;	83%
With phosgene In acetonitrile 1.) 6 h, -5 deg C, 2.) 24 h, room temp.;
With phosgene In acetonitrile 1) 6 h, -5 deg C, 2) 24 h, room temperature;
With oxalyl dichloride In dichloromethane at 60℃; for 18h; Inert atmosphere;
With oxalyl dichloride In toluene at 60℃; for 20h; Inert atmosphere; Cooling with ice;

N,N,N',N'-Tetrabutylurea (4559-86-8) + trifluoromethylsulfonic anhydride (358-23-6) → O-trifluoromethanesulfonyl-N,N,N',N'-tetrabutyluronium triflate

Conditions	Yield
In chloroform at 0℃;

N,N,N',N'-Tetrabutylurea (4559-86-8) → 1,1,2,2-Tetrabutyl-3,3-dipropylguanidiniumchlorid (89609-85-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: phosgene / acetonitrile / 1) 6 h, -5 deg C, 2) 24 h, room temperature 2: 83 percent / triethylamine / 1 h / Ambient temperature View Scheme

N,N,N',N'-Tetrabutylurea (4559-86-8) → 1,1-Dially-2,2,3,3-tetrabutylguanidiniumchlorid (89609-86-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: phosgene / acetonitrile / 1) 6 h, -5 deg C, 2) 24 h, room temperature 2: 82 percent / triethylamine / 1 h / Ambient temperature View Scheme

N,N,N',N'-Tetrabutylurea (4559-86-8) → 1-pyrrolidiniumchlorid

Conditions	Yield
Multi-step reaction with 2 steps 1: phosgene / acetonitrile / 1) 6 h, -5 deg C, 2) 24 h, room temperature 2: 85 percent / triethylamine / 1 h / Ambient temperature View Scheme

N,N,N',N'-Tetrabutylurea (4559-86-8) → 1-piperidiniumchlorid

Conditions	Yield
Multi-step reaction with 2 steps 1: phosgene / acetonitrile / 1) 6 h, -5 deg C, 2) 24 h, room temperature 2: 82 percent / triethylamine / 1 h / Ambient temperature View Scheme

N,N,N',N'-Tetrabutylurea (4559-86-8) → 1-morpholiniumchlorid

Conditions	Yield
Multi-step reaction with 2 steps 1: phosgene / acetonitrile / 1) 6 h, -5 deg C, 2) 24 h, room temperature 2: 87 percent / triethylamine / 1 h / Ambient temperature View Scheme

N,N,N',N'-Tetrabutylurea (4559-86-8) → 1,1,2,2,3,3-Hexabutylguanidiniumchlorid (89450-31-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: phosgene / acetonitrile / 1) 6 h, -5 deg C, 2) 24 h, room temperature 2: 88 percent / triethylamine / 1 h / Ambient temperature View Scheme
Multi-step reaction with 2 steps 1: phosgene / acetonitrile / 1.) 6 h, -5 deg C, 2.) 24 h, room temp. 2: triethylamine / acetonitrile / 1 h / Ambient temperature View Scheme

Upstream product

• 13358-73-1 N,N-dibutylcarbamoyl chloride 
• 75-44-5 phosgene 
• 111-92-2 dibutylamine 
• 201230-82-2 carbon monoxide 
• 25440-26-0 lithium dibutylamide 
• 124-38-9 carbon dioxide 
• 108-18-9 diisopropylamine 
• 109-89-7 diethylamine 
• 32315-10-9 bis(trichloromethyl) carbonate 
• 616-38-6 carbonic acid dimethyl ester 
• 536-74-3 phenylacetylene 
• 102-01-2 N-phenylacetoacetamide 
• 160594-75-2 Tetrabutyl-selenourea 
• 650-51-1 sodium trichloroacetate 

Downstream Products

• 128838-18-6 4-Phenyl-1,1,3,3-tetrabutylguanidine 
• 114591-53-6 1,1,3,3,4-Pentabutylguanidine 

Relevant academic research and scientific papers

Method for preparing tetrabutylurea by oil-water two-phase reaction system

The invention discloses a method for preparing tetrabutylurea by using an oil-water two-phase reaction system, which is characterized in that bis (trichloromethyl) carbonate and dibutylamine are used as raw materials, the oil-water two-phase reaction system is designed and provided, a solvent capable of effectively dissolving bis (trichloromethyl) carbonate and dibutylamine is adopted, meanwhile, a water phase is added into the reaction system to perform liquid seal on the reaction system, can absorb hydrogen chloride gas generated by the reaction at the same time, and promotes the forward proceeding of the whole reaction, and the method has the characteristics of high conversion rate, high selectivity and the like. The method for preparing tetrabutylurea by using the oil-water two-phase reaction system comprises the following steps: dissolving bis (trichloromethyl) carbonate in an organic solvent, placing the solution in a reactor, and simultaneously adding water into the reactor to perform liquid seal on the reaction system; and dissolving dibutylamine in an organic solvent, slowly injecting the dibutylamine into the organic solution of bis (trichloromethyl) carbonate through a micro-injection pump, carrying out chemical reaction, and carrying out refining treatment to obtain the product tetrabutylurea.

Organic ligand and solvent free oxidative carbonylation of amine over Pd/TiO2 with unprecedented activity

A highly active Pd/TiO2 catalyst system was prepared and applied in the oxidative carbonylation of amines to ureas with ultra-low Pd content under organic ligand and solvent free conditions. The catalytic turnover frequencies (TOFs, moles of amines converted per mole of Pd per h) were 126000 and 250000 h-1 for the production of diphenylurea and dibenzylurea, respectively. An expanded substrate scope including the electron-rich and electron-deficient anilines, primary aliphatic amines, secondary amines was also established. This work offers a straightforward, step economic, and green methodology for the efficient synthesis of valuable ureas.

Synthesis method of tetrabutylurea

The invention provides a synthesis method of tetrabutylurea. The synthesis method comprises the following steps: dissolving an organic strong base catalyst and dimethyl carbonate into a solvent; raising temperature to 30 DEG C to 50 DEG C to obtain mixed liquid; dropwise adding dibutylamine into the mixed liquid at 50 DEG C to 80 DEG C; after dropwise adding, heating to reflux and keeping the heat and reacting for 5h to 8h to obtain reaction liquid; rectifying the reaction liquid under normal pressure to obtain condensed liquid containing the solvent and residual liquid; decompressing and rectifying the residual liquid to obtain a tetrabutylurea product and residues. According to the synthesis method of the tetrabutylurea, provided by the invention, a toxic raw material, namely phosgene, is not used and hydrogen chloride gas is not generated, so that equipment is not corroded and requirements on the equipment are relatively low; meanwhile, three wastes are avoided; the mass content of the tetrabutylurea in an obtained tetrabutylurea product is 99 percent or more and the yield is 75 percent or more.

Method for preparation of 1, 1, 3, 3-tetrabutylurea by aqueous phase process

The invention discloses a method for preparation of 1, 1, 3, 3-tetrabutylurea by aqueous phase process. The method includes: adding bis(trichloromethyl)carbonate into a reaction container, and adding water; adding dibutylamine into the aqueous solution of bis(trichloromethyl)carbonate, and controlling the reaction temperature at 0-10DEG C; at the end of charging, further carrying out reaction for 1-9h; at the end of the reaction, separating the organic phase from the aqueous phase, conducting pickling and washing on the organic phase to remove impurities and a small amount of dibutylamine, and drying the organic phase to obtain 1, 1, 3, 3-tetrabutylurea; adding sodium hydroxide into the separated aqueous phase to conduct neutralization, and separating the organic phase to obtain dibutylamine, which can be directly used for reaction. The method takes water as the solvent, the reaction process is carried out at low temperature, and the method has the advantages of safety, environmental protection, low cost and strong operability.

Palladium-Catalyzed Oxidative N-Dealkylation/Carbonylation of Tertiary Amines with Alkynes to α,β-Alkynylamides

The first highly effective Pd/C-catalyzed oxidative N-dealkylation/carbonylation of various aliphatic as well as cyclic tertiary amines with alkynes has been described. The selective sp3 C-N bond activation of tertiary amines at the less steric side using O2 as a sole oxidant and a plausible reaction pathway for the reaction are discussed. The general and operationally simple methodology provides an alternative for the synthesis of a wide range of alk-2-ynamide derivatives under mild conditions. The present protocol is ecofriendly and practical, and it shows significant recyclability.

Synthesis of urea derivatives from CO2 and amines catalyzed by polyethylene glycol supported potassium hydroxide without dehydrating agents

Polyethylene glycol supported potassium hydroxide (KOH/PEG1000) was developed as a recyclable catalyst for facile synthesis of urea derivatives from amines and CO2 without utilization of additional dehydrating agents. Primary aliphatic amines, secondary aliphatic amines, and diamines can be converted into the corresponding urea derivatives in moderate yields. Furthermore, the catalyst can be recovered after a simple separation procedure, and reused over 5 times with retention of high activity. Georg Thieme Verlag Stuttgart.

Cobalt/rhodium heterobimetallic nanoparticle-catalyzed oxidative carbonylation of amines in the presence of carbon monoxide and molecular oxygen to ureas

An environmentally friendly oxidative carbonylation of aliphatic and aromatic primary amines to ureas has been successfully achieved in the presence of a catalytic amount of cobalt/rhodium heterobimetallic nanoparticles without any promoters. The catalyst system could be reused with only a slight loss of catalytic activity.

A high yielding, one-pot synthesis of substituted ureas from the corresponding amines using Mitsunobu's reagent

A Mitsunobu-based protocol has been developed for the synthesis of symmetrically and unsymmetrically substituted ureas from a variety of primary and secondary amines using gaseous carbon dioxide, in good to excellent yields. This protocol is mild and efficient compared to other reported methods.

Hexaalkylguanidinium trifluoromethanesulfonates - A general synthesis from tetraalkylureas and triflic anhydride, and properties as ionic liquids

More than thirty hexaalkylguanidinium trifluoromethanesulfonates 12 were prepared from N,N-diethyl-N′,N′-dimethylurea, N,N-dibutyl-N′, N′-diethylurea, or tetrabutylurea, triflic anhydride, and a dialkylamine or cyclic sec-amine in two steps. The combination of the urea and triflic anhydride first yields a bis(tetraalkylamidinio)ether bis(triflate) 10, which is then converted into a salt 12 by reaction with the amine component. The reaction sequence can also be carried out as a one-pot procedure. Eighteen of the prepared guanidinium triflates 12 constitute room-temperature ionic liquids, which were characterized for their melting point, glass transition temperature, viscosity, and refractive index. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

METHOD FOR THE CONTINUOUS PRODUCTION OF TETRA-SUBSTITUTED UREAS

The invention relates to a method for producing tetra-substituted ureas by reacting the corresponding amines with phosgene in the presence of an aqueous inorganic base at a temperature ranging of from 0 to 150 °C. According to the inventive method, the corresponding amine, the phosgene and the aqueous inorganic base are on average continuously fed to the reactor, a two-phase system is formed in the reactor by selecting the tetra-substituted ureas to be produced, by selecting the quantitative ratio of the substances and substance mixtures to be added, by selecting the temperature during reaction and optionally by adding an organic solvent that is not completely miscible with water, and the reaction mixture is discharged from the reactor in an on average continuous manner.