- Process method for increasing yield of N, N '-diisopropylcarbodiimide product
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The invention discloses a process method for improving the yield of an N, N '-diisopropylcarbodiimide product, and relates to the technical field of organic chemical synthesis, and the process methodcomprises the following steps: reacting isopropylamine and carbon disulfide by using chlorobenzene as a solvent to generate diisopropylthiourea, and carrying out suction filtration; using hydrogen peroxide as an oxidizing agent, using ethyl tert-butyl ether as a solvent, performing primary oxidation, removing hydrogen sulfideafter oxidation to generate N, N '-diisopropylcarbodiimide and sulfur; carrying out secondary oxidation, removing sulfur by using sodium hydrosulfide, washing with water, drying, evaporating out the solvent, adding potassium carbonate into the DIC crude product without thesolvent, controlling the temperature to be 55-65 DEG C, stirring for 0.3-1 hour, controlling the pressure to be less than -0.08 MPa, and distilling to obtain qualified DIC; by adding potassium carbonate, the stability of N, N '-diisopropylcarbodiimide is facilitated, and the N, N'-diisopropylcarbodiimide is prevented from being decomposed at a high temperature so that the yield is increased.
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Paragraph 0019-0023
(2021/01/29)
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- Method for synthesizing N, N'-diisopropylcarbodiimide by using oxygen as oxidant
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The invention relates to a method for synthesizing N, N'-diisopropylcarbodiimide by using oxygen as an oxidant, which comprises the following steps: adding N, N'-diisopropylthiourea and a xylene solvent into a high-pressure reaction kettle in a mass ratio of 1-2:1; adding a MoO3 or Sb2O4 catalyst, wherein the use amount of the MoO3 or Sb2O4 catalyst is 1-3% of the amount of the added materials; introducing oxygen, wherein the mass ratio of the N, N'-diisopropylthiourea to the oxygen is 1:0.2-0.4, and an oxidation reaction is carried out for 3-4 h under the conditions that the pressure is controlled to be 5-10 MPa and the temperature is controlled to be 110-120 DEG C; and cooling to 5-15 DEG C, carrying out suction filtration, decolorizing, and carrying out reduced pressure distillation toobtain the DIC. Oxygen is used as an oxidizing agent, the reaction selectivity is high, the risk is low, meanwhile, the wastewater yield is greatly reduced, treatment is easy, and the problem that waste brine in a traditional process is large in amount and difficult to treat is solved; and the method is easy to control, the reaction yield is increased, and the production cost is reduced.
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Paragraph 0016-0018
(2021/01/11)
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- N,N'-diisopropyl carbodiimide preparation method
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The invention belongs to the technical field of organic synthesis and particularly relates to an N,N'-diisopropyl carbodiimide preparation method. The method includes steps: adopting isopropylamine and carbon disulfide to synthesize N,N'-diisopropyl thiourea in a solvent; subjecting the N,N'-diisopropyl thiourea to suction filtration, drying and primary oxidization; performing secondary oxidization reaction, adding a catalyst and an oxidant, and performing reaction for 1h at 60-65 DEG C; performing desulfurizing treatment, adding sodium sulfide solution into oxidation liquid, heating to 70-75DEG C, and performing reaction for 1-2h; adding caustic soda flakes to neutralize, washing, separating a water layer, adding a drying agent for drying, evaporating out the solvent, and performing vacuum rectification to obtain N,N'-diisopropyl carbodiimide. The N,N'-diisopropyl carbodiimide preparation method has advantages that wastewater recycling can be realized, emission is avoided, and accordingly environmental pollution is avoided; simplicity in feeding and aftertreatment, low production cost, high yield and high purity are realized.
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Paragraph 0039-0042; 0043; 0045-0048; 0051-0054
(2019/04/06)
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- Multicomponent Approach to Libraries of Substituted Dihydroorotic Acid Amides
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A process featuring a sequential multicomponent reaction followed by a regioselective postcyclization strategy was implemented for the facile synthesis of N,N′-disubstituted dihydroorotic acid amides under mild conditions. We obtained, for the first time, a library of 29 derivatives, encompassing 19 Nα-substituted-N4-dihydroorotyl-4-aminophenylalanine derivatives, a key residue of gonadotropin-releasing hormone antagonist Degarelix. The corresponding products were prepared from easily accessible starting materials in good to excellent yields with broad substrate scope.
- Bellucci, Maria Cristina,Sacchetti, Alessandro,Volonterio, Alessandro
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supporting information
p. 705 - 715
(2019/10/02)
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- Synthesis and Characterization of Tungsten Nitrido Amido Guanidinato Complexes as Precursors for Chemical Vapor Deposition of WNxCy Thin Films
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Tungsten nitrido amido guanidinato complexes of the type WN(NR2)[(NR′)2C(NR2)]2 (R = Me, Et; R′ = iPr, Cy) were synthesized as precursors for aerosol-assisted chemical vapor deposition (AACVD) of WNxCy thin films. The reaction of tungsten nitrido amido complexes of the type WN(NR2)3 (R = Me, Et) with two equivalents of a carbodiimide R′N=C=NR′ (R′ = iPr, Cy) resulted in two insertions of a carbodiimide into W–N(amido) bonds, affording bis(guanidinato) amido nitrido tungsten complexes. These compounds were characterized by 14N NMR, indicating distinctive chemical shifts for each type of N-bound ligand. Crystallographic structure determination of WN(NMe2)[(NiPr)2C(NMe2)]2 showed the guanidinato ligands to be non-equivalent. The complex WN(NMe2)[(NiPr)2C(NMe2)]2 was demonstrated to serve as a precursor for AACVD of WNxCy thin films, resulting in featureless, X-ray amorphous thin films for growth temperatures 200–400 °C.
- Nolan, Michelle M.,Touchton, Alexander J.,Richey, Nathaniel E.,Ghiviriga, Ion,Rocca, James R.,Abboud, Khalil A.,McElwee-White, Lisa
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- A method of manufacturing a carbodiimide compound
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PROBLEM TO BE SOLVED: To provide a novel method that can efficiently produce a carbodiimide compound without using substances that are harmful, hazardous, expensive, or difficult to obtain.SOLUTION: The method of producing a carbodiimide compound includes converting a thiourea compound having a specific structure to a carbodiimide compound having a specific structure in the presence of at least one of an iron compound and a molybdenum compound.
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Paragraph 0054-0059; 0062; 0063; 0064
(2018/03/02)
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- Cross-linked peptides containing non-peptide cross-linked structure, method for synthesizing cross-linked peptides, and novel organic compound used in method
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The purpose of the present invention is to provide a cross-linked peptide containing a novel non-peptide cross-linked structure, and a method for synthesizing the same. A cross-linked peptide having a novel non-peptide cross-linked structure, a useful intermediate for synthesizing the cross-linked peptide, and a method for synthesizing the novel cross-linked peptide and the intermediate are provided. The cross-linked peptide is characterized by having an —NR— bond in the cross-linked structure. By using the method for synthesizing the cross-linked peptide, a cross-link can be freely designed and an change can be freely made to a cross-link.
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Page/Page column 176
(2016/09/26)
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- ORGANIC METAL COMPOUND AND ORGANIC LIGHT-EMITTING DEVICE EMPLOYING THE SAME
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Organic metal compounds and organic electroluminescence devices employing the same are provided. The organic metal compound has a chemical structure represented below: wherein R1, R2, R3, R4, and R5 are independent and can be hydrogen, halogen, C1-8 alkyl or C1-8alkoxy; L can be acetylacetone ligand, picolinic acid ligand, N,N′-diisopropylbenzamidinate, or N,N′-diisopropyl-diisopropyl-guanidinate.
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- Stimuli-Responsive Frustrated Lewis-Pair-Type Reactivity of a Tungsten Iminoazaphosphiridine Complex
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Reactions of 3-imino-azaphosphiridine complexes 1 a,b with carbodiimides 2 a,b, isocyanates 3 a,b, and carbon dioxide are described. Whereas exchange of the carbodiimide unit occurs in the first case, an overall ring expansion takes place with phenyl isocyanate (3 a) and carbon dioxide to yield complexes 4 and 5 bearing novel 1,3,5-oxazaphospholane ligands; the isopropyl derivative 3 b did not react under these conditions. DFT calculations provide insight into the pathway of the reaction with carbon dioxide with model complex 1 c, revealing effects of initial non-covalent interactions with the substrate onto the ring bonding, thus triggering an initially masked frustrated Lewis-pair-type behavior.
- Villalba Franco, José Manuel,Schnakenburg, Gregor,Sasamori, Takahiro,Espinosa Ferao, Arturo,Streubel, Rainer
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p. 9650 - 9655
(2015/06/30)
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- Synthesis of carbodiimides by I2/CHP-mediated cross-coupling reaction of isocyanides with amines under metal-free conditions
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An I2/CHP-mediated cross-coupling reaction of isocyanides with readily accessible amines via C-N formation is described for carbodiimide synthesis in moderate to excellent yields. This represents a metal-free strategy for a coupling reaction of isocyanides with amines, and it provides an efficient approach for symmetric and unsymmetric functionalized carbodiimide derivative synthesis under mild conditions.
- Zhu, Tong-Hao,Wang, Shun-Yi,Tao, Yang-Qing,Ji, Shun-Jun
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p. 1974 - 1977
(2015/04/27)
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- Dehydrogenative desulfurization of thiourea derivatives to give carbodiimides, using hydrosilane and an iron complex
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Dehydrogenative desulfurization of thiourea derivatives (RNHC(S)NHR′) has been achieved, to give carbodiimides (RNCNR′), in the reaction with hydrosilane and (η5-C5H5)Fe(CO) 2Me. The obtained carbodiimide reacted with (η5-C 5H5)Fe(CO)(SiR3) formed in the reaction to give an N-silylated η2-amidino iron complex, which was isolated and then characterized by X-ray analysis.
- Hayasaka, Kazumasa,Fukumoto, Kozo,Nakazawa, Hiroshi
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supporting information
p. 10271 - 10276
(2013/07/26)
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- Copper iminopyrrolidinates: A study of thermal and surface chemistry
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Several copper(I) iminopyrrolidinates have been evaluated by thermogravimetric analysis (TGA) and solution based 1H NMR studies to determine their thermal stability and decomposition mechanisms. Iminopyrrolidinates were used as a ligand for copper(I) to block previously identified decomposition routes of carbodiimide deinsertion and β-hydrogen abstraction. The compounds copper(I) isopropyl-iminopyrrolidinate (1) and copper(I) tert-butyl-iminopyrrolidinate (2) were synthesized for this study, and compared to the previously reported copper(I) tert-butyl-imino-2,2- dimethylpyrrolidinate (3) and the copper(I) guanidinate [Me2NC( iPrN)2Cu]2 (4). Compounds 1 and 2 were found to be volatile yet susceptible to decomposition during TGA. At 165 C in C 6D6, they had half-lives of 181.7 h and 23.7 h, respectively. The main thermolysis product of 1 and 2 was their respective protonated iminopyrrolidine ligand. β-Hydrogen abstraction was proposed for the mechanism of thermal decomposition. Since compound 3 showed no thermolysis at 165 C, it was further studied by chemisorption on high surface area silica. It was found to eliminate an isobutene upon chemisoption at 275 C. Annealing the sample at 350 C showed further evidence of the decomposition of the surface species, likely eliminating ethene, and producing a surface bound methylene diamine.
- Coyle, Jason P.,Pallister, Peter J.,Kurek, Agnieszka,Sirianni, Eric R.,Yap, Glenn P. A.,Barry, Seán T.
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p. 910 - 917
(2013/03/13)
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- Synthesis, structure, tautomerism, and reactivity of methanetrisamidines
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Tout au contraire: Both tautomeric forms of a methanetrisamidine were structurally characterized for the first time by X-ray diffraction and by ab initio calculations (see structures; gray C, red H, blue N). Their reactivity as proton acceptors and multia
- Gutschank, Benjamin,Schulz, Stephan,Marcinkowski, Michael,Jansen, Georg,Bandmann, Heinz,Blaeser, Dieter,Woelper, Christoph
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supporting information
p. 10893 - 10897
(2013/01/15)
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- A New synthetic protocol for the preparation of carbodiimides using a hypervalent iodine(III) reagent
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A new, simple, and efficient preparation of symmetrical and unsymmetrical carbodiimides from the corresponding thioureas via dehydrosulfurization using a hypervalent iodine(III) reagent is described. The oxidation afforded carbodiimides in excellent yields and high selectivity. A possible mechanism for the transformation is proposed. Georg Thieme Verlag Stuttgart New York.
- Zhu, Chenjie,Xu, Dan,Wei, Yunyang
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supporting information; experimental part
p. 711 - 714
(2011/04/24)
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- Crystal structure of dimerized 1,3-diisopropyl carbodiimide
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A crystal structure of dimerized 1,3-diisopropyl carbodiimide (CDI) has been obtained and its synthesis through a reaction of CDI with aluminum chloride (AlCl3) has been studied. It possesses space group P21/c, with a = 9.352(5), b = 7.956(4), c = 11.405(6) A and β = 112.465(5)°. It has been observed that this reaction is catalytic with respect to AlCl3. Kinetic studies of the dimer show that its decomposition into CDI is first order with respect to the dimer. The reactivity of the dimer with metals has been investigated through reactions with methyl lithium and alane. The thermal stability of the dimer has been investigated by thermal gravimetric analysis and differential scanning calorimetry.
- Gordon, Peter George,Yap, Glenn P. A.,Barry, Sean Thomas
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body text
p. 375 - 378
(2011/10/12)
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- Gas-phase thermolysis of a guanidinate precursor of copper studied by matrix isolation, time-of-flight mass spectrometry, and computational chemistry
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The fragmentation of the copper(i) guanidinate [Me2NC(N/Pr) 2Cu]2 (1) has been investigated with time-of-flight mass spectrometry (TOF MS), matrix-isolation FTIR spectroscopy (Ml FTIR spectroscopy), and density functional theory (DFT) calculations. Gas-phase thermolyses of 1 were preformed in the temperature range of 100-800 °C. TOF MS and Ml FTIR gave consistent results, showing that precursor 1 starts to fragment at oven temperatures above 150 °C, with a close to complete fragmentation at 260 °C. Precursor 1 thermally fragments to Cu( S), H2(g), and the oxidized guanidine Me 2NC(=N/Pr)(N=CMe2) (3). In TOF MS experiment, 3 was clearly indentifled by its molecular ion at 169.2 u. Whereas H2+ was detected, atomic Cu was not found in gas-phase thermolysis. In addition, the guanidine Me2NC(N/Pr)(NH/Pr) (2) was detected as a minor component among the thermolysis products. Ml thermolysis experiments with precursor 1 were performed, and species evolving from the thermolysis oven were trapped in solid argon at 20 K. These species were characterized by FTIR spectroscopy. The most indicative feature of the resulting spectra from thermolysis above 150 °C was a set of intense and structured peaks between 1600 and 1700 cm-1, an area where precursor 1 does not have any absorbances. The guanldine 2 was matrix-isolated, and a comparison of its FTIR spectrum with the spectra of the thermolysis of 1 indicated that species 2 was among the thermolysis products. However, the main IR bands In the range of 1600 and 1700 cm-1 appeared at 1687.9,1668.9,1635.1, and 1626.6 cm-1 and were not caused by species 2. The oxidized guanldine 3 was synthesized for the first time and characterized by1H NMR and FTIR spectroscopy. A comparison of an FTIR spectrum of matrix isolated 3 with spectra of the thermolysis of 1 revealed that the main IR bands in the range of 1600 and 1700 cm -1 are due to the presence of 3. The isomers exhibit the NMe2 group cis or trans to the /Pr group, with c/s-3 being significantly less stable than trans-3. At higher temperature secondary thermal fragments had been observed. For example at 700 °C, TOF MS and Ml FTIR data showed that species 2 and 3 both eliminate HNMe2 to give the carbodilmides /PrNCNPr (CDI) and /PrNCN[C(=CH 2)Me] (4), respectively. A DFT study of the decomposition of compound 1 was undertaken at the B3LYP/6-31+G(d,p) level of theory employing dispersion-correcting potentials (DCPs). The DFT study rationalized both carbodilmide delnsertion and β-hydrogen elimination as exergonic decomposition pathways (AG = -44.4 kcal/mol in both cases), but experiment showed β-hydrogen elimination to be the favorable route.
- Coyle, Jason P.,Johnson, Paul A.,Dilabio, Gino A.,Barry, Sean T.,Mueller, Jens
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body text
p. 2844 - 2850
(2010/05/14)
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- Silver(I) fluoride and related compounds in chemical synthesis
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Silver(I) fluoride is a versatile tool in desulfuration-fluorination reactions with thiuram disulfides and thioureas. Reactions of AgF and trimethyl(perfluoroorgano)- and trimethyl(alkynyl)-silanes offer a convenient approach to the corresponding organosilver derivatives, which are excellent reagents for oxidative organylations of group 12-16 elements. Reactions of AgF and elements of groups 13-16 open a convenient access to the corresponding fluorides.
- Tyrra, Wieland
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p. 561 - 566
(2007/10/03)
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- Catalytic double-bond metathesis without the transition metal
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Iminophosphoranes of the type X3P=NR (X = CI, pyrrolyl; R = alkyl, aryl) catalytically metathesize C=N bonds of carbodiimides via an addition/elimination mechanism that, despite the lack of d orbital participation in P-N bonding, conserves the key features of metal-catalyzed olefin metathesis. Diazaphosphetidine intermediates, produced by the formal [2 + 2] addition of carbodiimides to the P=N bond, have been isolated and characterized. All phosphorus-containing species in the complex catalytic reaction mixtures have been identified and their origins explained. The kinetics of addition of diisopropylcarbodiimide to Cl3P=NPri and subsequent elimination were studied, and rate constants were determined: kadd 1.7 × 10-3 (±0.1 × 10-3) M s-1 and kelim = 4.0 × 10-4 (±0.3 × 10-4) s-1. The rate of these reactions corresponds well with the observed catalytic TOF of 1.44 TO/P/h.
- Bell, Stephen A.,Meyer, Tara Y.,Geib, Steven J.
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p. 10698 - 10705
(2007/10/03)
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- Reaction of Electrochemically Generated Triphenylphosphine Radical Cation with Amides and Ureas
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Constant-current electrolysis of triphenylphosphine in dichloromethane in the presence of primary amides and N,N'-disubstituted ureas resulted in the formation of nitriles and carbodiimides, respectively.Dehydrosulfurization of thiobenzamide and N,N'-dicyclohexylthiourea was also effected by electrlysis under the same conditions, but probably through mechanisms different from those of dehydration of the corresponding amide and urea.Keywords-constant-current electrolysis; triphenylphosphine; primary amide; N,N'-disubstituted urea; nitrile; carbodiimide
- Ohmori, Hidenobu,Sakai, Kiyoshi,Nagai, Noriko,Mizuki, Yasuyuki,Masui, Masaichiro
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p. 373 - 376
(2007/10/02)
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- The Dehydration of Ureas by Two-Phase Dichlorocarbene Reaction, a Synthetic Access to Substituted Cyanamides
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A wide variety of N,N-disubstituted ureas are dehydrated in the CHCl3/NaOH catalytic two-phase system under mild conditions.The sequence of urea-transamidation and dehydration thus offers a profitable approach to aprotic cyanamides.Among various tested PT-catalysts tertiary amines prove to be the most efficient and favourable ones.Tertiary amines may also be used advantageously in the transformation of carboxylic amides and thioamides to the corresponding nitriles.The application of the same technique is less suitable in the case of N-mono-substituted ureas, N,N'-disubstituted ureas as well as N(dialkylaminomethylidene)ureas, because consequent reactions of the primarily formed cyanamides predominate.Problems concerning the dehydration mechanism are elucidated in terms of HMO-perturbation theory.
- Schroth, W.,Kluge, H.,Frach, R.,Hodek, W.,Schaedler, H. D.
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p. 787 - 802
(2007/10/02)
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- Synthesis and Decomposition of Functionalized Diaziridinimines
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The conversion of guanidines into diaziridinimines on treatment with t-BuOCl and t-BuOK can be applied to the synthesis of sulfonyl-, phosphoryl-, and cyano-substituted derivatives bearing two additional tert-butyl groups.Carbethoxy- and benzoyl-substituted guanidines give N-carbonyl-substituted diaziridinimines only as elusive intermediates which rearrange into 5-imino-Δ2-1,3,4-oxadiazolines.Other decomposition pathways observed are (i) rearrangement of sulfonylimino- and phosphorylimino-substituted diaziridines into hydrazine derivatives and (ii) cheletropic decomposition of N-cyano-substituted diaziridinimines into carbodiimides and cyanonitrene.
- L'abbe, Gerrit,Verbruggen, Andre,Minami, Toru,Toppet, Suzanne
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p. 4478 - 4481
(2007/10/02)
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- Nucleophilic Substitution on Dialkoxy Disulfides. III. Reaction with Thioureas
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1,3- and 1,1-Disubstituted thioureas reacted with diethoxy disulfide to give carbodiimides and 1,2,4-thiadiazoles respectively. 1,1,3-Trisubstituted thioureas and diethoxy disulfide afforded trialkyl(trialkylamidino)thioureas.
- Kagami, Hiroaki,Hanzawa, Takashi,Suzuki, Nobuo,Yamaguchi, Shoso,Saito, Masami,Motoki, Shinichi
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p. 3658 - 3660
(2007/10/02)
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- Oxidation of Mixtures of Thioureas: Part VII - Formation of 4-Alkyl-5-alkylimino-3-amino-4,5-dihydro-1,2,4-thiadiazoles
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Oxidation of acidic ethanolic solutions of binary mixtures of 1,3-diethyl, 1,3-di-n-propyl, 1,3-diisopropyl, 1,3-di-n-butyl, 1,3-dibenzyl, 1-benzyl-3-methyl, 1-benzyl-3-ethyl, 1-benzyl-3-n-propyl, 1-benzyl-3-n-butyl, 1-n-butyl-3-n-propyl-thioureas with thiourea has been found to yield the related 4-alkyl-5-alkylimino-3-amino-4,5-dihydro-1,2,4-thiadiazoles (3).The mechanism of formation of these thiadiazoles has been discussed.One of the intermediates, viz. bis(formamidino)sulphide salt has been alternatively prepared and its further reactions studied.
- Indukumari, P. V.,Joshua, C. P.
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p. 667 - 671
(2007/10/02)
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