- A safe production method for acetone cyanohydrin
-
An easily amenable method is presented to produce acetone cyanohydrin on mole scale (output 39 g/h), using a continuous flow system to overcome the high risks associated with the large-scale use of hydrogen cyanide.
- Heugebaert, Thomas S.A.,Roman, Bart I.,De Blieck, Ann,Stevens, Christian V.
-
-
Read Online
- Anchimeric-Assisted Spontaneous Hydrolysis of Cyanohydrins Under Ambient Conditions: Implications for Cyanide-Initiated Selective Transformations
-
Nitrile/cyanide hydrolysis is of importance from the perspective of organic chemistry, especially, prebiotic chemistry. Herein we report that cyanohydrins, generated by the reaction of cyanide with β-keto acids and γ-keto-alcohols, spontaneously hydrolyze
- Yerabolu, Jayasudhan Reddy,Liotta, Charles L,Krishnamurthy, Ramanarayanan
-
supporting information
p. 8756 - 8765
(2017/06/30)
-
- DEUTERATED COMPOUNDS FOR TREATING HEMATOLOGIC MALIGNANCIES, AND COMPOSITIONS AND METHODS THEREOF
-
The invention provides novel chemical compounds useful for treating various hematologic malignancies, or a related disease or disorder thereof, and pharmaceutical composition and methods of preparation and use thereof.
- -
-
Paragraph 00113; 00114
(2017/05/10)
-
- Common origins of RNA, protein and lipid precursors in a cyanosulfidic protometabolism
-
A minimal cell can be thought of as comprising informational, compartment-forming and metabolic subsystems. To imagine the abiotic assembly of such an overall system, however, places great demands on hypothetical prebiotic chemistry. The perceived differences and incompatibilities between these subsystems have led to the widely held assumption that one or other subsystem must have preceded the others. Here we experimentally investigate the validity of this assumption by examining the assembly of various biomolecular building blocks from prebiotically plausible intermediates and one-carbon feedstock molecules. We show that precursors of ribonucleotides, amino acids and lipids can all be derived by the reductive homologation of hydrogen cyanide and some of its derivatives, and thus that all the cellular subsystems could have arisen simultaneously through common chemistry. The key reaction steps are driven by ultraviolet light, use hydrogen sulfide as the reductant and can be accelerated by Cu(I)-Cu(II) photoredox cycling.
- Patel, Bhavesh H.,Percivalle, Claudia,Ritson, Dougal J.,Duffy, Colm D.,Sutherland, John D.
-
p. 301 - 307
(2015/04/14)
-
- Metal bridging for directing and accelerating electron transfer as exemplified by harnessing the reactivity of AIBN
-
A new strategy for tuning the electron transfer between radicals and enolates has been developed. This method elicits the innate reactivity of AIBN with a copper catalyst and enables a cascade reaction with cinnamic acids. Electron paramagnetic resonance studies and control experiments indicate that the redox-active copper species not only activates the radical by coordination, but also serves as a bridge to bring the radical and nucleophile within close proximity to facilitate electron transfer. By exploiting possible combinations of redox-active metals and radical entities with suitable coordinating functional groups, this strategy should contribute to the development of a broad range of radical-based reactions.
- Xie, Yinjun,Guo, Shengmei,Wu, Longmin,Xia, Chungu,Huang, Hanmin
-
supporting information
p. 5900 - 5904
(2015/05/13)
-
- Method for producing acetone cyanohydrin and the subsequent products thereof by specific cooling
-
The present invention relates in general terms to a process for preparing acetone cyanohydrin, comprising as steps: A. contacting acetone and hydrocyanic acid in a reactor to give a reaction mixture, the reaction mixture being circulated, to obtain acetone cyanohydrin;B. cooling at least some of the reaction mixture by flowing it through a cooling region of a cooler, the cooler including one cooling element or at least two cooling elements;C. discharging at least a portion of the acetone cyanohydrin obtained from the reactor, the volume of the cooling region of the cooler based on the total internal volume of the cooler being greater than the volume of the cooling element or of the at least two cooling elements of the cooler, to a process for preparing an alkyl methacrylate, to a process for preparing a methacrylic acid, to an apparatus for preparing alkyl methacrylates, to a process for preparing polymers based at least partly on alkyl methacrylates, to the use of the alkyl methacrylates obtainable from the process according to the invention in chemical products, and to chemical products based on the alkyl methacrylates obtainable by the processes according to the invention.
- -
-
Page/Page column 24-25
(2013/02/27)
-
- Synthesis and evaluation of anti-inflammatory and antitussive activity of hydantion derivatives
-
1-Methylhydantion is a compound, which was isolated from Oviductus Ranae for the first time. In our study, we found that it showed good antitussive and anti-inflammatory activity. It is also the first report which illustrates the antitussive activity of hydantion derivative. A series of hydantion derivatives were synthesized and evaluated for their anti-inflammatory and antitussive activity in vivo. The pharmacological tests showed that compounds 7a, 7c and 7d have good anti-inflammatory and antitussive activity compared to Ibuprofen and codeine. Compound 7a in particular showed two-fold stronger anti-inflammatory activity than Ibuprofen.
- Lu, Haibin,Kong, Dejuan,Wu, Bin,Wang, Shihan,Wang, Yongsheng
-
experimental part
p. 638 - 642
(2012/08/28)
-
- METHOD FOR PRODUCING A CARBOXYLIC ACID AMIDE FROM A CARBONYL COMPOUND AND HYDROCYANIC ACID
-
The invention relates to a method for producing a carboxylic acid amide from a carbonyl compound and hydrocyanic acid, comprising the steps of A) reacting a carbonyl compound with hydrocyanic acid to produce a hydroxycarboxylic acid nitrile, B) hydrolysis of the hydroxycarboxylic acid nitrile obtained in step A) in the presence of a catalyst comprising manganese dioxide, wherein a molar excess of carbonyl compound is used in relation to the hydrocyanic acid to react the carbonyl compound with hydrocyanic acid according to step A), and the reaction mixture obtained in step A) is not purified by distillation before the hydrolysis according to step B) is carried out. The invention furthermore relates to a method for producing alkyl(meth)acrylates from polymers, moulding compounds and moulded bodies, wherein a method for producing a carboxylic acid amide from a carbonyl compound and hydrocyanic acid is carried out in accordance with the method described above.
- -
-
Page/Page column 12
(2012/01/03)
-
- BIOMASS-DERIVED METHYL METHACRYLATE AND CORRESPONDING MANUFACTURING METHOD, USES AND POLYMERS
-
The invention relates to methyl methacrylate characterized in that at least one portion of the carbons thereof is biologically sourced and, more specifically, in that it contains between 0.2×10?10 and 1.2×10?10 wt.-% of 14C in relation to total carbon weight according to the ASTM D6866 standard. The preparation method comprises the use of acetone cyanohydrin as a raw material, said acetone cyanohydrin being obtained by condensing cyanohydric acid on acetone, and the methyl methacrylate is prepared using a process involving the addition of methanol. According to the invention, at least one from among the acetone, cyanohydric acid and methanol is obtained by means of a reaction or series of reactions involving the biomass.
- -
-
Page/Page column 6-7
(2012/01/13)
-
- NOVEL INHIBITORS OF POLY(ADP-RIBOSE)POLYMERASE (PARP)
-
A compound having the structure set forth in Formula (I): wherein the variables Y, R1, R2, R3, R4 and R5 are as defined herein. Compounds described herein are inhibitors of poly(ADP-ribose)polymerase activity. Also described herein are pharmaceutical compositions that include at least one compound described herein and the use of such compounds and pharmaceutical compositions to treat diseases, disorders and conditions that are ameliorated by the inhibition of PARP activity
- -
-
Page/Page column 46
(2009/04/24)
-
- Nitrile hydratase and a method for producing amides
-
An objective of the present invention is to provide a nitrile hydratase capable of producing 2-hydroxy-4-methylthiobutyroamide. The present invention provides a novel nitrile hydratase producing α-hydroxyamide using, α-hydroxnitrile as the substrate, and the encoding DNA thereof. The enzyme can be obtained from Rhodococcus sp. Further, the enzymatic activity of the enzyme can he maintained stably during the reaction. The present invention provides a method for producing amide compounds, the method comprising the step of reacting this enzyme to nitrile compounds. According to the present invention, from hydroxy nitrile compounds, corresponding amide compounds can be produced biochemically without reducing the enzyme activity of nitrile hydratase.
- -
-
-
- METHOD FOR PRODUCING ALPHA-HYDROXYCARBOXYLIC ACIDS AND THE ESTERS THEREOF
-
The invention relates to a method for the selective, economical production of methacrylic acid and methacrylic esters on the basis of acetone cyanhydrin. According to the inventive method, 2-hydroxy-2-methylpropionic acid is produced by reacting acetone cyanhydrin with sulfuric acid in the presence of water and a suitable polar solvent, and is isolated. The 2-hydroxy-2-methylpropionic acid so produced is used to produce methacrylic acid by β elimination of water.
- -
-
Page/Page column 41
(2008/06/13)
-
- CATHEPSIN INHIBITORS
-
This invention relates to a novel class of compounds, represented by the formula (I) below, wherein the meanings of R1, R2, R3 and R4 are indicated therein, which are cysteine protease inhibitors, including but not limited to, inhibitors of cathepsins K, L, S and B. These compounds are useful for treating diseases in which inhibition of bone resorption is indicated, such as osteoporosis, osteoarthritis and rheumatoid arthritis.
- -
-
Page/Page column 64-65
(2010/02/11)
-
- Remarkably Facile Solvolyses of Triflates via Carbocationic Processes in Dimethyl Sulfoxide
-
A number of triflates have been shown to undergo clean pseudo-first-order solvolysis reactions in DMSO-d6 to give products derived from carbocationic intermediates. Thus, t-BuCH(OTf)CO-t-Bu (5) and t-BuCH 2OTf (9) react readily in DMSO-d6 at 25 °C to give a rearranged oxosulfonium salts, and subsequent alkene products where methyl migration to the incipient cationic center occurs. t-BuCH(OTf)CO 2CH3 (14) gives analogous rearranged products, and 1-methylcyclopropyl triflate (21) gives a ring-opened allylic oxosulfonium salt. These triflates react primarily via kΔ pathways. 6-Methylbicyclo[3.1.0]hex-6-yl triflate (23), bicyclo[2.2.1hept-1-yl triflate (24), 1,6-methano[10]-annulen-11-yl triflate (25), (CH3) 2C(OTf)CO2CH3 (26), and (CH3) 2CCN(OTf) (29) all react in DMSO-d6 to give carbocation-derived products. PhCH(OTf)CF3 (33) and substituted analogues also react readily in DMSO-d6, and the Hammett ρ + value is -3.7. This suggests a "borderline" mechanism where the transition state has substantial charge development. The primary feature of these solvolyses is the high reactivity of all of these triflates in DMSO-d6. Thus, these triflates are all more reactive in DMSO-d 6 than in HOAc, and for most, rates are faster than in CF 3CH2OH. Triflates 5, 21, 29, and 33 are 10 8-109 times more reactive in DMSO-d6 than the corresponding mesylates. It is suggested that the decreased need for electrophilic solvation of trifiate anion, and the high cation solvating ability of DMSO, are the reasons for the high triflate reactivity in DMSO-d 6.
- Creary, Xavier,Burtch, Elizabeth A.
-
p. 1227 - 1234
(2007/10/03)
-
- Process for producing acetone cyanohydrin
-
An improved process for the production of acetone cyanohydrin by the reaction of acetone and HCN under basic pH conditions comprises supplying a metal cyanide composition and an HCN composition to the reaction.
- -
-
Page column 5-6
(2008/06/13)
-
- Enantioselective formation of mandelonitrile acetate - Investigation of a dynamic kinetic resolution
-
Investigations into the separate reactions of a dynamic kinetic resolution and the combined reactions revealed that the overall sequence is highly susceptible to the water content of the reaction mixture. While the racemization and formation of mandelonitrile as well as its kinetic resolution proceeded rapidly when performed independently, the dynamic kinetic resolution was severely hampered by the undesired formation of acetic acid during the reaction. The utilization of drying reagents and neutralizing agents in order to suppress the formation of acetic acid or its consequences were investigated.
- Li, Yu-Xin,Straathof, Adrie J.J.,Hanefeld, Ulf
-
p. 739 - 743
(2007/10/03)
-
- Studies on phosphoroheterocycle chemistry III: An unusual way to 1,3,2-thiazaphospholidine-4-thione 2-sulfide derivatives
-
An unusual but efficient method for the synthesis of phosphoroheterocycles, 1,3,2-thiazaphospholidine-4-thione 2-sulfide derivatives, by the reaction of Lawesson's reagent with a variety of α-hydroxy nitriles has been developed. The possible mechanism of the reaction is proposed to involve thiation of hydroxy group in a first step, sequential addition of P-SH to the nitrile and rearrangement resulting in the title phosphoroheterocycles. The preliminary bioassays show that these heterocyclic compounds have herbicidal properties.
- Deng, ShengLou,Chen, RuYu
-
p. 2527 - 2531
(2007/10/03)
-
- Fluorination with aminosulfur trifluorides
-
A fluorination method of oxygen and halogen sites with diaryl-, dialkoxyalkyl-, alkylalkoxyalkyl-, arylalkoxyalkyl- and cyclic aminosulfur trifluorides fluorinating reagents is disclosed.
- -
-
-
- Naturally occurring cyanohydrins, analogues and derivatives as potential insecticides
-
Several naturally occurring cyanohydrins were tested for fumigation toxicity to two insect species, the house fly (Musca domestica L) and the lesser grain borer (Rhyzopertha dominica (F)). Synthetic analogues of these compounds were tested as well. Most of the cyanohydrins tested were more toxic as fumigants to M domestica and R dominica than chloropicrin; some compounds were nearly as toxic as dichlorvos. Naturally occurring cyanohydrins were among the most toxic tested. (C) 2000 Society of Chemical Industry.
- Peterson, Chris J.,Tsao, Rong,Coats, Joel R.
-
p. 615 - 617
(2007/10/03)
-
- Fluorination with aminosulfur trifluorides
-
A fluorination method of oxygen and halogen sites with diaryl-, dialkoxyalkyl-, alkylalkoxyalkyl-, arylalkoxyalkyl- and cyclic aminosulfur trifluorides fluorinating reagents is disclosed.
- -
-
-
- Process for producing methyl methacrylate
-
There is provided a process for producing MMA characterized by comprising the steps of: introducing an α-hydroxyisobutyric acid amide (HAM) production solution 5 into a thermal decomposition reactor 6; decomposing and separating non-reacted acetone cyanohydrin (ACH) to produce a HAM aqueous solution 11; contacting the HAM aqueous solution with ion exchange resins 12 and 13; dehydrating-hydrating it at a dehydration-hydration reactor 17 to produce methacrylic acid and/or methacrylamide 18 to which methanol 21 is added, which is esterified at an esterification reactor 22 to produce methyl methacrylate (MMA); contacting the MMA product 23 with a hydrophobic organic solvent 25 to extract MMA; separating MMA 42 by distillation; using the solvent 25, from which MMA is separated, for the liquid-liquid extraction; recovering methanol and by-product ammonia contained in the raffinate solution 27; using the methanol 37 as the starting material for the esterification reaction; using, for the ACH synthesis, a mixture 10 of the acetone and the hydrocyanic acid discharged from the thermal decomposition reactor 6; and recycling the resultant ACH as a starting material for the hydration reaction. The present invention permits production of MMA of high purity, elongating the lifetime of the catalyst. In addition, the recovered product(s) may be recycled. The present invention is thus suitable for industrial production of MMA.
- -
-
-
- Free Radical Pathways in the Nitrous Acid Deamination of α-Aminonitriles
-
Free radicals and carbocations are generated competitively in nitrous acid deamination reactions of α-aminonitriles: in the absence of added scavengers the radicals are trapped by NO2 and by NO.
- Bunse, Michael,Joedicke, Dirk,Kirmse, Wolfgang
-
-
- Process for preparation of cyanohydrins
-
This invention relates to the discovery that high yields of excellent quality cyanohydrins can be prepared by reacting certain carbonyl compounds in a solution of metallic cyanide and hydrochloric acid.
- -
-
-
- Process for purifying methacrylamide
-
In a conventional process for the purification of crude methacrylamide by the recrystallization from an aqueous medium, pH of the aqueous methacrylamide solution is controlled to a value in alkaline range of at least 8 and then methacrylamide is crystallized out. As the alkali used for the pH control, there have been used alkali metal and alkaline earth metal carbonates and hydroxides. Methacrylamide to be recrystallized is crude methacrylamide obtained by neutralizing methacrylamide sulfate obtained from acetone cyanhydrin and sulfuric acid with ammonia in the presence of water.
- -
-
-
- Synthesis of alpha-amino acids
-
A method for synthesizing alpha amino acids proceding through novel intermediates of the formulas: wherein R1 and R2 are each selected from hydrogen monovalent substituted and unsubstituted hydrocarbon radicals of 1 to 10 carbon atoms. The use of these intermediates allows the synthesis steps to be exothermic and results in an overall synthesis method which is faster than the snythesis methods of the prior art.
- -
-
-
- Process for the manufacture of α-hydroxycarboxylic acid amides
-
Process for the manufacture of α-hydroxycarboxylic acid amides by adding water onto cyanohydrins in an aqueous medium containing 10-60% by weight of the oxo compound on which the cyanohydrin is based, with the aid of a catalyst dissolved in the reaction medium and selected from the group consisting of alkali metal-, alkaline earth metal- and alkylammonium salts of boric acid, at a pH from 7-11.
- -
-
-