- CO2-Enabled Cyanohydrin Synthesis and Facile Iterative Homologation Reactions**
-
Thermodynamic and kinetic control of a chemical process is the key to access desired products and states. Changes are made when a desired product is not accessible; one may manipulate the reaction with additional reagents, catalysts and/or protecting groups. Here we report the use of carbon dioxide to accelerate cyanohydrin synthesis under neutral conditions with an insoluble cyanide source (KCN) without generating toxic HCN. Under inert atmosphere, the reaction is essentially not operative due to the unfavored equilibrium. The utility of CO2-mediated selective cyanohydrin synthesis was further showcased by broadening Kiliani–Fischer synthesis under neutral conditions. This protocol offers an easy access to a variety of polyols, cyanohydrins, linear alkylnitriles, by simply starting from alkyl- and arylaldehydes, KCN and an atmospheric pressure of CO2.
- Juhl, Martin,Petersen, Allan R.,Lee, Ji-Woong
-
supporting information
p. 228 - 232
(2020/11/30)
-
- Radical-mediated aerobic oxidation of substituted styrenes and stilbenes
-
A 2,2-azobis(isobutyronitrile)-catalyzed oxidative cleavage of alkenes with molecular oxygen as the oxidant was described. Carbonyl compounds and oxiranes were obtained in moderate yield under mild conditions. This study provided useful insights into the mechanism of aerobic oxidative cleavage of alkenes.
- Aman, Hasil,Chiu, Wei-Hua,Chuang, Gary Jing,Liu, Pin-Heng
-
p. 20103 - 20106
(2021/12/02)
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- Production process of high-purity and high-yield spirodiclofen
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The invention relates to the technical field of synthesis of compounds and specifically relates to a production process of high-purity and high-yield spirodiclofen. The production process comprises the following steps: performing an addition reaction on cyclohexanone which is taken as a starting material, so as to obtain 1-cyano-cyclohexanol; hydrolyzing and esterifying the 1-cyano-cyclohexanol, so as to obtain 1-hydroxylethyl formate; performing a condensation ring-closing reaction on the 1-hydroxylethyl formate, so as to obtain an intermediate caproate; and performing a reaction on the caproate and 2, 2-dimethylbutyryl chloride, so as to obtain the spirodiclofen. According to the production process, the problem in the prior art that the prepared spirodiclofen is low in purity and yield is solved; the spirodiclofen prepared by adopting the production process is high in purity and yield; and in addition, the raw material for preparing the spirodiclofen is easily obtained, and the operation is convenient.
- -
-
Paragraph 0046; 0051; 0067
(2019/03/08)
-
- Anesthetic compounds and related methods of use
-
Provided herein are compounds according to formula (I): Provided herein is also a pharmaceutical composition comprising a compound according to formula (I) and a pharmaceutically acceptable carrier, and a method for providing anesthesia in a subject by administering such a pharmaceutical composition.
- -
-
Page/Page column 65
(2015/11/09)
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- SPIRO-OXAZOLONES
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The present invention provides spiro-oxazolones, which act as V1a receptor modulators, and in particular as V1a receptor antagonists, their manufacture, pharmaceutical compositions containing them and their use as medicaments. The present compounds are useful as therapeutics acting peripherally and centrally in the conditions of inappropriate secretion of vasopressin, anxiety, depressive disorders, obsessive compulsive disorder, autistic spectrum disorders, schizophrenia, aggressive behavior and phase shift sleep disorders, in particular jetlag.
- -
-
Page/Page column 75
(2015/09/28)
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- The continuous reaction device and method of using the continuous composite (by machine translation)
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PROBLEM TO BE SOLVED: compounds with high productivity can be generated. SOLUTION: 1 the raw material supply section 12 and a first, a second and 2 the raw material supply section 14, and a reaction part 18, the first reaction part 1 from the raw material supply section 1 and a second quantity of raw material, the raw material supply section 2 from the first reaction part 2 and a second quantity of raw material, the raw material supply section 1 from the first reaction part 1 and a second temperature of the raw material, the raw material supply section 2 from the first reaction part 2 and supplied to the temperature of the raw material, and having a control part 22, a continuous reaction device as shown in the drawing. Selected drawing: fig. 1 (by machine translation)
- -
-
Paragraph 0174
(2017/01/02)
-
- A magnetic nanoparticle catalyzed eco-friendly synthesis of cyanohydrins in a deep eutectic solvent
-
Magnetic Fe3O4 nanoparticles in deep eutectic solvents (DESs) have been regard as excellent catalysts for highly efficient cyanosilylation of various aldehydes and epoxides using trimethylsilyl cyanide TMSCN in high yields with excellent selectivity. Fe3O4 nanoparticles were synthesized and applied as a catalyst for the preparation of a wide variety of cyanohydrins (α-hydroxy nitriles and β-hydroxy nitriles) in readily available urea-choline chloride deep eutectic solvent DES as the most promising environmentally benign and cost-effective green solvent. Magnetic DES operates at very mild reaction conditions and can be easily recycled without significant loss of its catalytic activity.
- Azizi, Najmedin,Rahimi, Zahra,Alipour, Masoumeh
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p. 61191 - 61198
(2015/07/28)
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- Synthesis, spectral, and structural characteristics of cyanohydrines derived from aliphatic cyclic ketones1
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A series of cyanohydrines derived from cyclic aliphatic ketones was synthesized by acid-catalyzed nucleophilic addition reaction under the action of potassium cyanide. The products were characterized by means of multi-nuclear NMR spectroscopy (1H, 13C, 14N, 15N), mass spectrometry, elemental analysis, UV-Vis spectroscopy, refraction index measurements as well as vibrational spectroscopy. The structure of the cyanohydrine of cyclohexanone was elucidated by means of single crystal X-ray diffraction.
- Hosten,Betz
-
p. 2222 - 2227
(2015/02/02)
-
- ANESTHETIC COMPOUNDS AND RELATED METHODS OF USE
-
Provided herein are compounds according to formula (I): Provided herein is also a pharmaceutical composition comprising a compound according to formula (I) and a pharmaceutically acceptable carrier, and a method for providing anesthesia in a subject by administering such a pharmaceutical composition.
- -
-
Paragraph 00201
(2013/07/25)
-
- Novel 4H-1,2,4-triazol-3-yl cycloalkanols as potent antitubercular agents
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Enzymes of shikimate pathway, dehydroquinase and shikimate kinase represent comparatively newer targets for antitubercular research. Molecular hybridization approach was implemented by integrating the essential features of inhibitors acting on these enzymes of shikimate pathway. Considering the flexibility of alicyclic ring of reported dehydroquinase (DHQ) inhibitors and triazole ring, key feature of the virtual hits of Mtb shikimate kinase, a series of structurally novel, substituted 4H-1,2,4-triazol-3-yl cycloalkanols were designed as antimycobacterial agents. Docking studies of the molecules was carried out on the enzyme DHQ. All the synthesized compounds exhibited promising activity (MIC 0.59-15.5 μg/ml) against H37Rv strains of Mycobacterium tuberculosis using resazurin microtiter assay. Five of the evaluated compounds exhibit MIC 50 values indicate compounds are non-toxic, with selectivity indices >28. These compounds could serve as leads for further optimization to obtain novel antimycobacterial agents.
- Desai, Nutan H. Palsule,Bairwa, Ranjeet,Kakwani, Manoj,Tawari, Nilesh,Ray,Rajan,Degani, Mariam
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p. 401 - 408
(2013/03/13)
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- Asymmetric synthesis of both the enantiomers of antidepressant venlafaxine and its analogues
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Chemoenzymatic asymmetric synthesis of antidepressant agent venlafaxine and its analogue have been reported in this communication. The main highlight of the reported synthesis is the stereoselective synthesis of cyanohydrins by (S)-hydroxynitrile lyase (Hevea brasiliensis) followed by lipase catalyzed kinetic resolution.
- Bhuniya, Rajib,Nanda, Samik
-
scheme or table
p. 1990 - 1992
(2012/05/05)
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- A single-step, mild, neutral, catalyst-free method for cyanohydrin synthesis
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A wide variety of carbonyl compounds can be transformed to their corresponding cyanohydrins in a single step using a dimethyl sulfoxide (DMSO)-water system in excellent yields (75-94%). The major advantages of this system are that the reaction conditions are mild and neutral; the reaction proceeds without catalyst and gives the corresponding cyanohydrins in short time (15-120 min).
- Degani, Mariam S.,Kakwani, Manoj D.,Palsule Desai, Nutan H.,Bairwa, Ranjeet
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experimental part
p. 461 - 465
(2012/06/15)
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- Preparation and reactions of optically active cyanohydrins derived from 4-chlorobenzaldehyde, cyclohexanone and 2-methylcyclohexanone using the (R) hydroxynitrile lyase from Prunus amygdalus
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CYANURATION of 4-chlorobenzaldehyde (1), cyclohexanone (2a) and 2-methylcyclo-hexanone (2b) yielded the racemic 2-hydroxy-2-(4-chlorophenyl) ethanenitrile (R,S)-3, cyclohexanone cyanohydrin 21a and (R,S)-2- methylcyclohexanone cyanohydrin (R,S)-21b. The same reaction can be completed by using acetone cyanohydrin (4) as a transcyanating agent. The optically active cyanohydrins (R)-3 and (R)-21b could be respectively obtained by hydrocyanation of 1 and 2b using (R)-hydroxynitrile lyase (R) PaHNL [EC 4.1.2.10] from almonds (Prunus amygdalus) as a chiral catalyst. Cyanohydrins 3 and 21 in their racemic and optically active forms undergo a number of transformations which involve either the hydroxyl group or the cyanide function. Moreover, derivatization of 3 and 21b with (S)-Naproxen chloride (S)-7 gave the respective diastereoisomers 8 and 22b. The optical activities of (R)-3 and 21b as well as their derivatives were recorded. The postulated structures of the new products were supported with compatible elementary and spectroscopic (IR, 1H NMR, 13C NMR, MS and X-ray crystallography) analyses. The antitumor activity of some selected racemic new products and their respective optically active analogues were undertaken. The structure-activity relationship (SAR) was also discussed.
- Yosef,Elmasry,Ismael, Eman H. I.,Mahran
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p. 745 - 755
(2013/05/21)
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- Bradykinin B1 receptor antagonists: An α-hydroxy amide with an improved metabolism profile
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A series of carbo- and heterocyclic α-hydroxy amide-derived bradykinin B1 antagonists was prepared and evaluated. A 4,4-difluorocyclohexyl α-hydroxy amide was incorporated along with a 2-methyl tetrazole in lieu of an oxadiazole to afford a suitable compound with good pharmacokinetic properties, CNS penetration, and clearance by multiple metabolic pathways.
- Kuduk, Scott D.,Chang, Ronald K.,DiPardo, Robert M.,Di Marco, Christina N.,Murphy, Kathy L.,Ransom, Richard W.,Reiss, Duane R.,Tang, Cuyue,Prueksaritanont, Thomayant,Pettibone, Douglas J.,Bock, Mark G.
-
scheme or table
p. 5107 - 5110
(2009/05/26)
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- Novel uncatalyzed hydrocyanation of ketones utlizing tetrachlorosilane- potassium cyanide reagent
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A combination of tetrachlorosilane and potassium cyanide (in situ trichlorosilyl cyanide) was found to work efficiently for hydrocyanation of ketones to afford the corresponding cyanohydrins in high yield under mild conditions. Copyright Taylor & Francis Group, LLC.
- Salama, Tarek A.,Elmorsy, Saad S.,Khalil, Abdel-Galel M.,Girges, Margret M.,El-Ahl, Abdel-Aziz S.
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p. 1313 - 1319
(2008/02/01)
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- An R-selective hydroxynitrile lyase from Arabidopsis thaliana with an α/β-hydrolase fold
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Folding and selectivity: The noncyanogenic plant Arabidopsis thaliana contains a new hydroxynitrile lyase, which was cloned and characterized. This enzyme is readily available form a recombinant source, has a broad range of substrates, and enantioselectively transforms aliphatic and aromatic aldehydes as well as ketones into the corresponding R-cyanohydrins. (Chemical Equation Presented).
- Andexer, Jennifer,Von Langermann, Jan,Mell, Annett,Bocola, Marco,Kragl, Udo,Eggert, Thorsten,Pohl, Martina
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p. 8679 - 8681
(2008/09/18)
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- Tandem alkylation-cyclization process via an O,C-dianion
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A general protocol for preparing densely functionalized cyclopentenones through a tandem nucleophilic addition-deprotonation-alkylation-cyclization process is described. Addition of lithioallene 2 to enamides 1 generates tetrahedral intermediate 3. Deprotonation of the γ carbon atom of the allene function in situ, followed by trapping by a suitable electrophile and cyclization during workup leads to C6 substituted cyclopentenones 6.
- Banaag, April R.,Berger, Gideon O.,Dhoro, Francis,Delos Santos, Derrick B.,Dixon, Darryl D.,Mitchell, James P.,Tokeshi, Bradley K.,Tius, Marcus A.
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p. 3419 - 3428
(2007/10/03)
-
- Spirodiclofen and spiromesifen - Novel acaricidal and insecticidal tetronic acid derivatives with a new mode of action
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The broad spectrum acaricides spirodiclofen (BAJ2740, trade name: Envidor) and spiromesifen (BSN2060, trade name: Oberon) with an additional excellent activity against whiteflies, both belong to the new chemical class of tetronic acid derivatives discovered at Bayer CropScience during the 1990s. The discovery process starting from herbicidal PPO (protoporphyrinogen oxidase) chemistry, the synthetic routes leading to the products, and some insight into process development of central intermediates is given. Spirodiclofen and spiromesifen have a new mode of action (interference with lipid biosynthesis), show no cross-resistance to any resistant mite or whitefly field population and are therefore valuable tools for resistance management.
- Bretschneider, Thomas,Benet-Buchholz, Jordi,Fischer, Reiner,Nauen, Ralf
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p. 697 - 701
(2007/10/03)
-
- Studies on phosphoroheterocycle chemistry III: An unusual way to 1,3,2-thiazaphospholidine-4-thione 2-sulfide derivatives
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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)
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- Behavior of biradicals generated from a Norrish type-I reaction of 2,2- diphenylcycloalkanones. Chain-length dependence and magnetic field effects
-
The reaction course of acyl-diphenylmethyl biradicals (α-oxo-ω, ω- diphenyl-α,ω-alkanediyl biradicals), O=C↑(CH2)η-2-C↑Ph2 (3BR-η), generated from the Norrish type-I reaction of 2,2-diphenylcycloalkanones (CK- η) with various ring sizes in methanol, is switched from intramolecular disproportionation (n = 6, 7), giving a diphenylalkenal, to acylphenyl recombination (n ≥ 9), affording a cyclophane derivative. The behavior of 3BR-9 derived from CK-9 was studied in detail; the photolysis of CK-9 afforded an open-chain and a cyclic decarbonylation product together with an unsaturated aldehyde and a 4-methylene-2,5-cyclohexadienyl ketone (a pre- cyclophane). The photolysis of this ketone gave the same products that arose from the photolysis of CK-9, presenting the possibility that the decarbonylation products and a part of the aldehyde are formed as secondary products during irradiation. The magnetic field dependence of the lifetimes of 3BR-η (η = 12 and 13) generated from CK-12 and 13, respectively, was measured in methanol by means of a pulsed-laser excitation technique. The rate constants for intersystem crossing showed a maximum at a relatively low field strength, which decreased with increasing the field strength to level off to an asymptotic value at > 1.5 kG. The results show that the role of hyperfine coupling in intersystem crossing is less important in these systems, presumably because of the presence of a carbonyl oxygen and the absence of a hydrogen atom at the radical center.
- Suzuki, Itsuko,Tanaka, Ryoko,Yamaguchi, Akinori,Maki, Shin-Ichiro,Misawa, Hiroaki,Tokumaru, Katsumi,Nakagaki, Ryoichi,Sakuragi, Hirochika
-
p. 103 - 113
(2007/10/03)
-
- Bismuth bromide as an efficient and versatile catalyst for the cyanation and allylation of carbonyl compounds and acetals with organosilicon reagents
-
Bismuth bromide was found to work efficiently as a versatile catalyst for the cyanation and allylation of carbonyl compounds and acetals with organosilicon reagents, affording the corresponding alcohols and ethers in high yields.
- Komatsu, Naoki,Uda, Masato,Suzuki, Hitomi,Takahashi, Toshikazu,Domae, Terutomo,Wada, Makoto
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p. 7215 - 7218
(2007/10/03)
-
- Trimethylsilyl bis(fluorosulfonyl)imide: An efficient catalyst for the addition of trimethylsilyl cyanide to carbonyl compounds
-
In the presence of 1 mol% of trimethylsilyl bis(fluorosulfonyl)imide, trimethylsilyl cyanide adds efficiently to carbonyl compounds. The catalyst has been found to be more active than trimethylsilyl triflate for the above reaction.
- Kaur, Harpinder,Kaur, Gurmeet,Trehan, Sanjay
-
p. 1925 - 1929
(2007/10/03)
-
- Lanthanoid(III) Alkoxides as Novel Catalysts for a Rapid Transhydrocyanation from Acetone Cyanohydrin to Aldehydes and Ketones
-
A rapid transhydrocyanation from acetone cyanohydrin to several aldehydes and ketones is promoted by a catalytic amount of lanthanoid(III) alkoxide to provide the corresponding cyanohydrins.
- Ohno, Hiroshi,Mori, Atsunori,Inoue, Shohei
-
p. 375 - 378
(2007/10/02)
-
- A Novel Rate Enhancement in Titanium and Zirconium Alkoxide Mediated Cyano Group Transfer by the Addition of Salycylal Type Schiff Base, dl-3-(2-Hydroxy-1-naphthylidene)-imino ε-caprolactame. A Neighboring Amide Effect
-
The addition of a salycylal type Schiff base containing amide, dl-3-(2-hydroxy-1-naphthylidene)imino-ε-caprolactam (Nap-ACL) to titanium (IV) 2-propoxide or zirconium (IV) 1-propoxide accelerates cyano group transfers of acetone cyanohydrin with various carbonyl and imino compounds to give the corresponding cyanated products.
- Mori, Atsunori,Inoue, Shohei
-
p. 145 - 148
(2007/10/02)
-
- Addition of diphenylphosphine to Michael-type olefins: the preparation of phosphine-nitrile and phosphine-ester ligands
-
The reactions of five Michael-type olefins with diphenylphosphine have been carried out. 1-Cyanocyclopentene, 1-cyanocyclohexene, and 4-t-butyl-1-cyanocyclohexene all provide the corresponding 2-diphenylphosphino-1-cyanocycloalkanes, and both methyl acrylate and ethyl methacrylate yield to corresponding 2-diphenylphosphinopropionates.For the products from 1-cyanocyclopentene and 1-cyanocyclohexene, 13C and 31P NMR data are consistent with the formation of both trans (Ph2P equatorial and CN axial) and cis (both Ph2P and CN equatorial) isomers.The morpholine amide of 3-diphenylphosphinopropionic acid has been obtained by treatment of methyl-3-diphenylphosphinopropionate with the dimethylaluminum adduct of morpholine.This phosphine, Ph2Pmorph, has been isolated as its palladium(II) complex, (Ph2Pmorph)2PdCl2.A phosphine-benzaldimine, Ph2P(CH2)3NC(H)C6H5, has been obtained by reacting Ph2P(CH2)3NH2, from the reduction of PhP(CH2)2CN, with benzaldehyde in the presence of molecular sieves.
- Blinn, D.A.,Button, R.S.,Farazi, V.,Neeb, M.K.,Tapley, C.L.,et al.
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p. 143 - 152
(2007/10/02)
-
- Cyclic Ether Formation in Superacid Media
-
The formation of ethers in superacids by interaction of a primary hydroxy group with a carbocation centre has been investigated by a study of cyclisation of suitable substrates, mainly 1-(2-hydroxyethyl)cyclohexanols to give hydrobenzofurans.Cyclisation traps thermodynamically stable ionic species, with rates of reaction dependent upon the size of the ether ring formed.Three- and four-membered ether rings were not formed, five-membered ether rings formed readily, the reaction being comparable in rate with a 1,2-methyl shift.Six-membered rings formed a little less readily and seven-membered rings less readily still, though a yield of 34 percent from a suitable substrate has been recorded.An unexpected feature of the reactions was their stereospecificity; in one case, this is believed to result from a methyl shift concerted with attack of the primary hydroxy group, the reaction proceeding through hindered transition state, in which methyl loss, probably as CH3+, competes with a 1,2-methyl shift.
- Carr, Graham,Whittaker, David
-
p. 359 - 366
(2007/10/02)
-
- Lactone Formation in Superacidic Media
-
The reaction of substituted 1-hydroxycyclohexanecarboxylic acids in fluorosulphuric acid has been studied.Cyclisation takes place around 0 deg C, accompanied by rearrangement in appropriate cases, yielding the thermodynamically stable lactone or mixture of lactones.An unexpected feature of these reactions is that the carboxy-substituted cyclohexyl carbocation does not undergo ring contraction, unlike the unsubstituted cyclohexyl carbocation, although the cycloheptyl system contracts to cyclohexyl.We suggest that the cyclohexyl carbocation is strongly stabilised by carboxyl substitution, as a result of through-space interaction between the carboxyl oxygen atom and the carbocation centre.
- Carr, Graham,Whittaker, David
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p. 1877 - 1880
(2007/10/02)
-
