- Atom- and Mass-economical Continuous Flow Production of 3-Chloropropionyl Chloride and its Subsequent Amidation
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3-Chloropropionyl chloride is a chemically versatile building block with applications in the field of adhesives, pharmaceuticals, herbicides and fungicides. Its current production entails problems concerning safety, prolonged reaction times and the use of excessive amounts of chlorinating reagents. We developed a continuous flow procedure for acid chloride formation from acrylic acid and a consecutive 1,4-addition of hydrogen chloride generating 3-chloropropionyl chloride, as presented in this paper. Up to 94 % conversion was reached in 25 minutes at mild temperatures and pressures. This continuous flow method offers a safer alternative and is highly efficient in terms of consumption of starting product and shorter residence time. Valorization of this building block is exemplified by the synthesis of beclamide, a compound with sedative and anticonvulsant properties. Over 80 % conversion towards this drug was achieved in 1 minute in a continuous flow setup. Further research is needed to telescope the synthesis of 3-chloropropionyl chloride and subsequent beclamide formation without intermediate purification.
- Movsisyan, Marine,Heugebaert, Thomas S. A.,Roman, Bart I.,Dams, Rudolf,Van Campenhout, Rudy,Conradi, Matthias,Stevens, Christian V.
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- Initiation of Cationic Polymerization of Cyclic Ethers by Redox Radical-Chain Reactions of Onium Salts
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Redox radical-chain reactions of diaryliodonium halides (Ar2I(+)X(-)) with tetrahydrofuran (THF) and 1,3-dioxolane to give arenes (ArH) and iodoarenes (ArI) are reported.When the reactions are initiated by irradiation at 313 nm, the quantum yield for the formation of iodoarene is substantially greater than 1 (Φ ca. 2-20).Nonphotochemical radical initiators give the same reaction, showing that the photochemical step is simply an initiation step.The key propagation step in these reactions is a single-electron reduction of the onium salts by ether-derived radicals.The photoinitiated reaction with THF follows zero-order kinetics, showing that termination does not compete with electron transfer.In addition, the same nonphotochemical conditions that give radical-chain reduction of the diaryliodonium halides give rapid cationic polymerization of the ethers when the iodonium hexafluorophosphates are used.These observations establish the connection between the redox chemistry of the iodonium salt and the cationic polymerization of the eters.The polymerization of THF by iodonium salt in the presence of free radicals is accelerated by the addition of trimethyl phosphite (TMP).Furthermore, triarylsulfonium salts will initiate polymerization of THF in the presence of TMP and radical sources.Therefore, redox-chain reduction of these onium salts by TMP can also initiate cationic polymerization of the cyclic ethers.
- Kampmeier, J. A.,Nalli, Thomas W.
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- Effect of Structure and Substituents in the Aqueous Phase Oxidation of Alcohols and Polyols Over Au, Pd, and Au-Pd Catalysts
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Abstract Reactivity trends for oxidation of various alcohols and polyols have been examined for carbon-supported Au, Pd, and Au-Pd catalysts. A Hammett σρ approach was used to study substituent effects, with Hammett factors (ρ) of 1.27, 1.31, and 0.40 obtained for Pd, Au, and Au-Pd catalysts, suggesting the formation of a net negative charge at the transition state of the rate limiting step. The lower ρ for the Au-Pd catalyst versus Au and Pd monometallic catalysts indicates the ability of the Au-Pd catalyst to stabilize the negative charge at the transition state, explaining the improved performance of Au-Pd bimetallic catalysts for alcohol oxidation. Hammett-Taft factors were used to explain the low selectivity of terminal diols and polyols to diacids.
- Rodriguez, Abraham A.,Williams, Christopher T.,Monnier, John R.
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- Gas-Phase Elimination Kinetics of Ethyl Esters of Chloroacetate, 3-Chloropropionate, and 4-Chlorobutyrate. The Electronic Effects of Substituents at the Acyl Carbon
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Several ethyl chloroesters were pyrolyzed in a static reactor in the presence of a propene inhibitor at temperatures between 360 and 420 deg C and pressures between 49 and 209 torr.The reactions are homogeneous, unimolecular, and follow a first-order rate law.The temperature dependence of the rate coefficients is given by the following Arrhenius equations: for ethyl chloroacetate, log k(s-1) = (12.70+/-0.50) - (197.0+/-6.1)kJ mol-1 (2.303RT)-1; for ethyl 3-chloropropionate, log k(s-1) = (12.54+/-0.22) - 196.8+/-2.7) kJ mol-1 (2.303RT)-1; and ethyl 4-chlorobutyrate, log k(s-1) = (12.67+/-0.31) - (198.7+/-3.8) kJ mol-1 (2.303RT)-1.The data from the rate coefficients give an approximate correlation only with ?* values (ρ*=0.357, r=0.903, and intercept =0.048 at 400 deg C).The present work together with those reported in the literature suggests, that electron-withdawing substituents at the acyl carbon of ethyl, isopropyl, and tert-butyl esters of substituted acetates enhance the rate of elimination, whereas electron-releasing substituents decrease it.
- Chuchani, Gabriel,Triana, Juana L.,Rotinov, Alexandra,Caraballo, Darlo F.
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- Preparation method of 3-chloropropionyl chloride
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The invention relates to the technical field of organic synthesis, in particular to a preparation method of 3-chloropropionyl chloride. The preparation method provided by the invention comprises the following steps: 1) introducing hydrogen chloride gas into acrylic acid to carry out addition reaction, and keeping the gas introduction pressure to be less than or equal to 0.15 MPa to obtain a reaction solution; and 2) pumping the reaction liquid in the step 1) into a reaction kettle in vacuum, heating to 30-80 DEG C, dropwise adding thionyl chloride, carrying out negative pressure distillation to 70 DEG C after dropwise adding is finished, and collecting a steamed product at 70-80 DEG C, namely the finished product 3-chloropropionyl chloride. According to the preparation method of the 3-chloropropionyl chloride, the process is simple, the preparation of the 3-chloropropionyl chloride can be realized by adopting extremely simple equipment, the cost is greatly reduced, the total yield (based on acrylic acid) is 90-92%, and the content is greater than or equal to 98.5%.
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Paragraph 0017-0019; 0021-0023; 0025-0027
(2021/05/08)
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- A production device for 5-chloro-indanone and a production method thereof
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The present invention relates to a production device for 5-chloro-indanone, including an acrylic acid storage tank, at least two gas liquid reactors connected in series, a thionyl chloride storage tank, at least two first flow reactors connected in series, a 3-chloropropionyl chloride storage tank, a chlorobenzene storage tank, at least two second flow reactors connected in series, and at least two third flow reactors connected in series. A gas outlet of each first flow reactor is connected to a gas inlet of the gas liquid reactor at the rearmost end through a pipeline provided with a condenser. A feeding port of the second flow reactor in the front end is provided with a first aluminium chloride feeding device. A feeding port of the third flow reactor in the front end is provided with a second aluminium chloride feeding device. The invention relates to a method for producing the 5-chloro-indanone by utilizing the production device. The production device and method can achieve continuous cyclic production and a high product yield.
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Paragraph 0023
(2019/04/10)
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- 3 - Chloropropionyl production device
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The utility model relates to a 3 - chloropropionyl production device, including acrylic acid storage tank, at least two serially connected gas-liquid reactor, thionyl chloride storage tank, at least two serially connected continuous reactor and 3 - chloropropionyl storage tank; acrylic acid storage tank with the discharge port of the foremost end of the pipeline located in the gas-liquid reactor is connected with feed opening; at the last end of the discharge port of the gas-liquid reactor through the pipeline with the locates at foremost a continuous reactor connected to the feed ports of the, the discharge port of the thionyl chloride storage tank through the pipeline with the locates at foremost a continuous reactor is connected with feed opening; at the last end of the discharge port of the continuous reactor through the pipeline with 3 - chloropropionyl connected to the feed ports of the storage tank; the air outlet of the continuous reactor is provided with a condenser through a pipeline with the last end of the gas-liquid located connected with the inlet of the reactor. The utility model of the 3 - chloropropionyl production equipment to achieve continuous circulation production, high product yield.
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Paragraph 0016; 0020; 0021; 0022
(2019/06/24)
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- Catalytic Bromination of Alkyl sp3C-H Bonds with KBr/Air under Visible Light
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Alkyl sp3C-H bonds of cycloalkanes and functional branch/linear alkanes have been successfully brominated with KBr using air or O2 as an oxidant at room temperature to 40 °C. The reactions are carried out in the presence of catalytic NaNO2 in 37% HCl (aq)/solvent under visible light, combining aerobic oxidations and photochemical radical processes. For various alkane substrates, CF3CH2OH, CHCl3, or CH2Cl2 is employed as an organic solvent, respectively, to enhance the efficiency of bromination.
- Zhao, Mengdi,Lu, Wenjun
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supporting information
p. 5264 - 5267
(2018/09/12)
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- Visible Light-Induced Oxidative Chlorination of Alkyl sp3 C-H Bonds with NaCl/Oxone at Room Temperature
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A visible light-induced monochlorination of cyclohexane with sodium chloride (5:1) has been successfully accomplished to afford chlorocyclohexane in excellent yield by using Oxone as the oxidant in H2O/CF3CH2OH at room temperature. Other secondary and primary alkyl sp3 C-H bonds of cycloalkanes and functional branch/linear alkanes can also be chlorinated, respectively, under similar conditions. The selection of a suitable organic solvent is crucial in these efficient radical chlorinations of alkanes in two-phase solutions. It is studied further by the achievement of high chemoselectivity in the chlorination of the benzyl sp3 C-H bond or the aryl sp2 C-H bond of toluene.
- Zhao, Mengdi,Lu, Wenjun
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supporting information
p. 4560 - 4563
(2017/09/11)
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- Ketone-catalyzed photochemical C(sp3)–H chlorination
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Photoexcited arylketones catalyze the direct chlorination of C(sp3)–H groups by N- chlorosuccinimide. Acetophenone is the most effective catalyst for functionalization of unactivated C–H groups while benzophenone provides better yields for benzylic C–H functionalization. Activation of both acetophenone and benzophenone can be achieved by irradiation with a household compact fluorescent lamp. This light-dependent reaction provides a better control of the reaction as compared to the traditional chlorination methods that proceed through a free radical chain propagation mechanism.
- Han, Lei,Xia, Ji-Bao,You, Lin,Chen, Chuo
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p. 3696 - 3701
(2017/06/13)
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- HYDROCHLORINATION OF ELECTRON-DEFICIENT ALKENES
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The present invention pertains to a method for the hydrochlorination of electron deficient alkenes, particularly alkenes having the functional groups COOH, CONH2, and CN. Specific alkenes discussed include acrylic acid, crotonic acid, methacrylic acid, acrylonitrile, acrylamide, and methacrylonitrile. The alkene is combined with a primary or secondary alcohol (e.g., isopropanol) and an acid chloride (e.g., acetyl chloride) under conditions suitable to chlorinate the alkene. Products formed by the invention include 3-chorosubstituted carbonyl compounds such as 3-chlorpropionic acid (3-CPA), 3-chloropropionamide (3-CPAD), and 3-chloropropionitrile among other products.
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Page/Page column 4-5
(2012/07/31)
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- Nitrile biotransformation by whole cells of Aspergillus sp. PTCC 5266
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Aspergillus sp. PTCC 5266 exhibited nitrile-hydrating activity over a broad pH range from 6.0 to 10.0 at 26°C. It hydrated 4-nitrophenylacetonitrile, 2-chlorobenzonitrile and 3-chlorobenzonitrile to their corresponding carboxylic acids and amides, while benzyl cyanide, benzonitrile, 4-tolunitrile, cyclohexanecarbonitrile, 4-chlorobutyronitrile and isobutyronitrile gave carboxylic acids as the sole products. The maximum whole-cell nitrile-hydrating activity was observed at pH 7.0.
- Yousefi,Mohammadi,Habibi,Cheraghi
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experimental part
p. 54 - 59
(2012/03/10)
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- An efficient method for the synthesis of aliphatic acids using microwaves
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Aliphatic acids are prepared by reaction of nitriles with phtalic acid by irradiation under microwaves in a domestic oven.
- Brǎtulescu, George
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p. 161 - 163
(2007/10/03)
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- Kinetics and mechanism of the hydrolysis of 1-aryloxyethyl alkanoates
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The kinetics and mechanism of the hydrolysis of 1-aryloxyethyl alkanoates are reported.In acidic media, 18O isotope exchange studies, kinetics, activation parameters and substituent effects point clearly to an AAl-1 mechanism with the formation of an alkoxycarbonium ion as the rate-limiting step.In basic media the data indicate a conventional BAc-2 mechanism through attack of hydroxide ion on the carbonyl carbon.In neutral medium (pH 2.5-8.8) there is a certain amount of conflicting evidence which leads, however, to the proposal that hydrolysis occurs via attack of a water molecule on the acyl carbon as the rate-limiting step.
- Hall, C. Dennis,Goulding, Celia W.
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p. 1471 - 1478
(2007/10/02)
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- 'Dry' Hydrolysis of Nitriles Effected by Microwave Heating
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The preparation of carboxylic acids from their corresponding nitriles by a 'dry hydrolysis' with dicarboxylic acids, in the absence of solvent, has been investigated.The reaction proceeds very slowly at atmospheric pressure, but high yields can be obtained in much shorter reaction times under pressure.The mechanism of the reeaction has been studied and its rate constant and activation energy determined in the case of a model reaction (preparation of phenylacetic acid from benzyl cyanide with phthalic acid) under both microwave and conventional heating.No 'microwave kinetic effect' has been detected, but at high temperatures microwave heating gives better yields and selectivities.
- Chemat, Farid,Poux, Martine,Berlan, Jacques
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p. 2597 - 2602
(2007/10/02)
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- Preparation of D- or L-alanine or high enantiomeric purity
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A pure D- or L-alanine enantiomer is prepared by reacting an optically active chloropropionic acid with ammonia in water or a water/alcohol mixture at from 50° to 110° C.
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- Microbial Dehalogenation of Haloalkanes Mediated by Oxygenase or Halidohydrolase
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Microorganisms utilizing 1-chlorobutane as a sole carbon and energy source for growth could release halogens under anaerobic conditions, while microorganisms which could utilize 1,9-dichlorononane released the halogens only under aerobic conditions.A 1-chlorobutane-utilizing bacterium, strain m 15-3, converted 1-chlorobutane to butiric acid and 1,3-dichloropropane to 3-chloropropionic acid under aerobic conditions and 1-chlorobutane to butanol under anaerobic conditions.In the latter case, the participation of halidohydrolase was suggested.Methane-utilizing bacteria catalyzed the removal of halogens from the terminal positions of short chained chlorinated hydrocarbons.Methane-utilizing bacteria dehalogenated 1,2-dichloroethane to 18O-incorporeted 2-chloroacetic acid in the presence of 18O2 gas.All of the seven bacterial strains used in this study dehalogenated 3-chlorinated aliphatic acids, but only one strain out of seven could dehalogenate 2-chlorinated aliphatic acids.
- Yokota, Toyokazu,Fuse, Hiroyuki,Omori, Toshio,Minoda, Yasuji
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p. 453 - 460
(2007/10/02)
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- Influence of Nitrogen Base Ligation and Hydrogen Bonding on the Rate Constants for Oxygen Transfer from Percarboxylic Acids and Alkyl Hydroperoxides to (meso-Tetraphenylporphinato>manganese(III) Chloride
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Equilibrium constants for axial ligation of imidazole (ImH), N-methylimidazole (N-MeIm), 4'-(imidazo-1-yl)-acetophenone (NAcPhIm), 2,6-lutidine (2,6-Py), and 3,4-lutidine (3,4-Py) with (meso-tetraphenylporphinato)manganese chloride ((TPP)MnIIICl) have been determined.The rates of oxygen atom transfer from percarboxylic acids and alkyl hydroperoxides (YOOH) to the manganese(III) porphyrin in the presence of varying concentrations of the nitrogen bases were determined.For this purpose, 2,2-diphenyl-1-picrylhydrazine (DPPH) was employed as a trap for the generated higher valent oxo-manganese porphyrin species.From the equilibrium and kinetic data, there was then calculated the second-order rate constants for oxygen atom transfer from YOOH compounds to the species (TPP)MnIIICl, TPP(Cl)MnIIIN, and TPP(Cl)MnIIIN2 (where N = ImH, N-MeIm, and 3,4-Py).Only the percarboxylic acids exhibit measurable rate constants for oxygen transfer to (TPP)MnIIICl, whereas alkyl hydroperoxides and percarboxylic acids transfer oxygen to the TPP(Cl)MnIIIN species.Of the species TPP(Cl)MnIIIN2, reaction with YOOH compounds is seen only when N is imidazole.This is attributed to an equilibrium of the unreactive bis axially ligated TPP(Cl)MnIII(ImH)2 with the reactive isomeric mono axial-ligated complex Cl(1-)...H-Im...H-Im...MnIIITPP.Nitrogen base ligation of (TPP)MnIIICl provides minimally a 1E3 increase in the rate constants for oxygen transfer in methylene chloride.Linear free-energy plots of the log of the second-order rate constants for oxygen transfer from YOOH vs. the pKa of YOH establish that β1g for oxygen transfer in which heterolytic O-O bond scission is rate-determining is large and negative.The value of β1g when oxygen transfer involves rate-determining homolytic O-O bond scission is small and negative.
- Yuan, Lung-Chi,Bruice, Thomas C.
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p. 1643 - 1650
(2007/10/02)
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- RING-CLOSURE REACTIONS. XXV. WHY ARE STRAINED SMALL RINGS SO EASILY FORMED IN INTRAMOLECULAR NUCLEOPHILIC SUBSTITUTION REACTIONS?
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The leaving group effect (kBr/kCl) has been determined for two typical series of SN2 cyclisation reactions in the ring size range of 3 to 6 in order to probe the effect of ring strain on transition state structure.The general increase of the magnitude of the leaving group effect on going from the less strained to the more strained ring systems indicates that bond making and bond breaking is significant also in the small ring transition states.The apparent unimportance of strain in the products to the ease of closure of the smallest rings is tentatively explained by the hypothesis that the adverse effect of ring strain is partially offset by a significant reduction of non-bonded interactions in the transition states.
- Casadei, Maria Antonietta,Martino, Alessandro di,Galli, Carlo,Mandolini, Luigi
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p. 659 - 664
(2007/10/02)
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- 3-Trehalosamine compounds
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Novel antibiotic 3-trehalosamine (U-59,834) producible in a fermentation under controlled conditions using the new microorganism Nocardiopsis trehalosei sp. nov., NRRL 12026. This antibiotic is active against Gram-positive bacteria, for example, Staphylococcus aureus, Bacillus subtilis, and Diplococcus pneumoniae. Thus, 3-trehalosamine can be used in various environments to eradicate or control such bacteria. Antibiotic 3-trehalosamine can be shown by the following structural formula: STR1
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- Tetrapeptidehydrazide derivatives
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Novel tetrapeptidehydrazide derivatives, inclusive of a pharmacologically acceptable acid addition salt thereof, which has the general formula (I): STR1 [wherein R1 is hydrogen or lower alkyl; R2 is hydrogen or the side chain of a D-α-amino acid; R3 is hydrogen or lower alkyl; R4 is hydrogen, or a saturated or unsaturated and straight or branched lower aliphatic acyl group which may optionally be substituted by hydroxy, amino, lower alkoxy, halogen, oxo, lower alkylthio or lower alkylthiooxide], are useful as analgesics.
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- Antibiotic 354 and process for producing same
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Novel antibiotic 354 (U-54,703) producible in a fermentation under controlled conditions using the new microorganism Streptomyces puniceus subsp. doliceus, NRRL 11160. This antibiotic is active against Gram-negative bacteria, for example, Pseudomonas and Proteus species. Thus, antibiotic 354 can be used in various environments to eradicate or control such bacteria.
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- Composition of matter and process
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Novel antibiotic formulations of antibiotic 354 (U-54,703) and their use in treating susceptible infectious disease in humans and animals.
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- Aminoglycoside antibiotics
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6-0- AND 3'-0-D-glycosyl analogs of 4-0-(α-D-glycosyl)-2-deoxystreptamine, 6-0- and 3'-0-D-glycosyl ortho esters of 4-0-(α-D-glycosyl)-2-deoxystreptamine, novel aminoglycoside antibiotics, and novel intermediates are prepared by a new chemical process. The compounds have utility as antibacterial agents or as intermediates to make antibacterially-active compounds.
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