- Syntheses of [13C,15N]-Labeled Polyamines
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[1,4-13C2, 1,4-15N2]butanediamine (1), a key compound in the syntheses of [5,8-13C2, 1,4,8-15N3]spermidine (2) and [5,8-13C2, 1,4,8,12-15N4]spermine (3), has been prepared as part of a 6-step process from 1,2-dibromoethane using potassium [13C]cyanide and potassium [15N]phthalimide. In the course of the syntheses, it was found that 1,4-dibromobutane was generated from tetrahydrofuran when bromination using triphenylphosphine and tetrabromomethane took place. A high-yield preparation of monobenzyloxycarbonyl (Z) derivative of 1, a precursor for 2, was obtained using a water-soluble Z reagent, Z-DSP, in a two-phase system of alkaline solution and chloroform. All the steps for 1, 2, and 3, were aimed at minimizing the loss of stable isotopes.
- Hara, Takeshi,Xu, Yong Ji,Sasaki, Hitomi,Niitu, Masaru,Samejima, Keijiro
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Read Online
- A New and Efficient One-Pot Preparation of Alkyl Halides From Alcohols
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Primary alkanols and 2-alkenols are converted into the corresponding halides in high yield by a one-pot, two-step reaction via transformation into intermediate trifluoroacetates followed by nucleophilic substitution with lithium halides.
- Camps, Francisco,Gasol, Vicens,Guerrero, Angel
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Read Online
- Boron tribromide as a reagent for anti-Markovnikov addition of HBr to cyclopropanes
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Although radical formation from a trialkylborane is well documented, the analogous reaction mode is unknown for trihaloboranes. We have discovered the generation of bromine radicals from boron tribromide and simple proton sources, such as water ortert-butanol, under open-flask conditions. Cyclopropanes bearing a variety of substituents were hydro- and deuterio-brominated to furnish anti-Markovnikov products in a highly regioselective fashion. NMR mechanistic studies and DFT calculations point to a radical pathway instead of the conventional ionic mechanism expected for BBr3
- Chen, Shuming,Gieuw, Matthew H.,Houk, K. N.,Ke, Zhihai,Yeung, Ying-Yeung
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p. 9426 - 9433
(2020/10/02)
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- Continuous method for preparation of dihalogenated alkane from diol compound
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The invention discloses a continuous method for preparation of dihalogenated alkane from a diol compound. A diol compound and haloid acid are used as the substrate, a microchannel reactor is utilizedto synthesize dihalogenated alkane continuously. Synthesis of the dihalogenated alkane includes the steps of: inputting the diol compound and haloid acid into a mixer respectively by a metering pump at room temperature, conducting premixing, then sending the mixture into a high-temperature section of the microchannel reactor at for reaction, and controlling the reaction temperature by an externalcirculating heat exchange system; at the end of the reaction, letting the product flow out from an outlet of the microchannel reactor and enter a cooling section, letting the cooled material enter a liquid separation kettle for standing and liquid separation, and collecting an organic layer; and preheating the organic layer, then feeding the preheated organic layer into a rectifying tower by a metering pump, controlling the temperature and reflux ratio of a reboiler, and collecting fractions at a specific temperature, thus obtaining the target product in a product collecting tank. The method provided by the invention has the characteristics of high reaction efficiency, safety, environmental protection, convenience and rapidity.
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Paragraph 0055-0061
(2020/03/16)
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- 1,2-Dibromotetrachloroethane: An efficient reagent for many transformations by modified Appel reaction
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An efficient and facile method has been developed for the synthesis of alkyl bromides from various alcohols under mild conditions using a triphenylphosphine (PPh 3) /1,2-dibromotetrachloroethane (DBTCE) complex in excellent yields and very short time (5 min). This method can also be applied for the transformation of chiral alcohols to their corresponding bromides in very high enantiomeric excess. The PPh 3 /DBTCE complex is also successfully applied to ring-opening reactions of cyclic ethers in mild conditions. Esterification, amidation, and formation of acid anhydrides under very mild experimental conditions are also successfully accomplished by following a modification of the Appel reaction protocol in this work.
- Essiz, Sel?uk,Da?tan, Arif
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p. 150 - 156
(2019/05/16)
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- Method for preparation of (4Ｅ, 10Ｚ)-tetradecadienylacetate as major sex pheromone of apple leaf miner moth, Phyllonorycter ringoniella
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The present invention relates to a method for preparing sex pheromone of apple leaf miner moth (Phyllonorycter ringoniella) for controlling apple leaf miner moth and, more specifically, to a method for efficiently, simply and economically preparing (4E, 10Z)-tetradecadienylacetate which is a major component of sex pheromone of apple leaf miner moth from a cheap starting material in excellent purity and yield.COPYRIGHT KIPO 2015
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Paragraph 0053; 0057; 0058
(2016/10/20)
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- Mild one-step synthesis of dibromo compounds from cyclic ethers
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A novel one-step method for mildly converting cyclic ethers into dibromo compounds is reported. Alcohols, oximes, aldehydes, and ketones are known to react under Appel or Corey-Fuchs reaction conditions, but apparently these have never been applied to oxetanes or larger cyclic ethers. Treatment of 3,3-dimethyloxetane (1) with tetrabromomethane and triphenylphosphine gave the corresponding dibromo compound 1,3-dibromo-2,2-dimethylpropane (2). The less-strained homologue oxolane (6) was also reacted giving 1,4-dibromobutane (7) in a 93% yield. Mechanistic interpretations are offered to explain the observed reaction rates of the conversions described.
- Billing, Peter,Brinker, Udo H.
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p. 11227 - 11231
(2013/02/23)
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- Redox-responsive morphology transformation of self-assembled nanostructures based on thiol-disulfide interconversion
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One dimensional (1D) nanotubes and three dimensional (3D) flowerlike supernanostructures were transformed reversibly, which was controlled by the oxidation and reduction cycle of aromatic diamide-derived thiol 1 and disulfide 2, as evidenced by SEM study.
- Tao, Zhi-Gang,Xiao, Ze-Yun,Zhao, Xin,Jiang, Xi-Kui,Li, Zhan-Ting
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supporting information; experimental part
p. 4447 - 4451
(2012/09/25)
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- Superelectrophilic sp3 C-H carbonylation of n-octyl acetate as a way to new bifunctional neo-octanes
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Carbonylation of n-octyl acetate in the presence of CBr4· 2AlBr3 followed by treatment with nucleophiles such as alcohols, amines or (het)arenes affords 7-acetoxy-2,2-dimethylheptanoyl-containing products.
- Akhrem, Irena S.,Avetisyan, Dzhul'Etta V.,Afanas'Eva, Lyudmila V.,Orlinkov, Alexander V.,Kagramanov, Nikolai D.,Petrovskii, Pavel V.
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experimental part
p. 323 - 325
(2012/02/04)
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- Synthesis and characterization of tetraazaparacyclophane disulfone
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1,6,20,25-Tetraaza[6.1.6.1]paracyclophane-13,32-disulfone D was synthesized under a very dilute condition by the cyclization between tetramethylene dibromide and N,N′-di-p-tosylaminodiphenylsulfone B, which was prepared using N,N′-diaminodiphenyl sulfone and p-toluenesulfonyl as raw materials. 1,6,20,25-Tetra-sulfoferrocene-1,6,20,25-tetraaza[6.1.6.1]paracyclophane-13,32- disulfone E was prepared by modifying D with the bioactive unit ferrocene. The structures were confirmed by IR, 1H NMR, and elemental analysis. Copyright Taylor & Francis Group, LLC.
- Yang, Ya-Ting,Yang, Bing-Qin,Li, Min,Ning, Wei,Lu, Zhen-Huan
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p. 530 - 536
(2008/04/12)
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- Low-energy collision-induced fragmentation of negative ions derived from diesters of aliphatic dicarboxylic acids made with hydroxybenzoic acids
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Diesters of ortho-hydroxybenzoic acid (salicylic acid) made with glutaric, adipic, and pimelic acids are the monomers of some potential drug candidates for aspirin patches. Collision-induced dissociation (CID) spectra of negative ion derived from these compounds show a 120-Da 'neutral loss' specific to the ortho isomers. In contrast, the anions derived from diesters of meta- and para-hydroxybenzoic acids show a 138-Da loss for an elimination of elements of hydroxybenzoic acid by a charge-remote mechanism. Deuterium labeling studies confirmed that the hydrogen atom transferred for hydroxybenzoic acid loss originates specifically from the α position of the dicarboxylic acid moiety. Although all spectra showed a peak at m/z 137, a charge-mediated process specific for the ortho compounds renders it the most prominent peak in the spectra of ortho compounds. Appropriate deuterium labeling experiments demonstrated that the hydrogen atom transferred for the formation of the m/z 137 ion in ortho compounds is specifically derived from the α position of the dicarboxylic acid moiety. Copyright
- Nishshanka, Upul,Attygalle, Athula B.
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experimental part
p. 1502 - 1511
(2009/10/10)
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- Substitute 1-(piperidin-4-yl)-3-(aryl)-isothioureas, their preparation and therapeutic use
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The invention concerns compounds of formula (I) wherein: R1 and R2, identical or different, represent a saturated or unsaturated alkyl radical, branched or not and containing 1 to 7 carbon atoms; R3 to R8, identical or different, represent a hydrogen, an alkyl branched or not and containing 1 to 5 carbon atoms, an acyloxy, branched or not and containing 1 to 5 carbon atoms, a halogeno, nitro, hydroxy, acyl or alkoxy group containing 1 to 5 carbon atoms, a dialkylamino group containing 1 to 5 carbon atoms, a trifluoromethyl or trifluoro methoxyl group; Z represents an oxygen or sulphur atom or methylene; m represents an integer between 0 and 4 inclusively; n represents an integer between 2 and 7 inclusively; and their pure enantiomers and mixtures, the therapeutically acceptable mineral or organic salts of the compounds of formula (I) and their possible hydrates.
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- 2,3-oxidosqualene-lanosterol cyclase inhibitors
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The present invention relates to aminocyclohexanol derivatives useful for the treatment and/or prophylaxis of diseases which are associated with 2,3-oxidosqualene-lanosterol cyclase such as hypercholesterolemia, hyperlipemia, arteriosclerosis, vascular diseases, mycoses, gallstones, tumors and/or hyperproliferative disorders, and treatment and/or prophylaxis of impaired glucose tolerance and diabetes.
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- Analine derivatives as OSC inhibitors
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The present invention relates to compounds of formula (I) wherein U, Y, V, W, L, X, A1, A2, A3, A4, A5 and A6 are as defined in the description and claims and pharmaceutically acceptable salts and/or pharmaceutically acceptable esters thereof. The compounds are useful for the treatment and/or prophylaxis of diseases which are associated with 2,3-oxidosqualene-lanosterol cyclase such as hypercholesterolemia, hyperlipemia, arteriosclerosis, vascular diseases, mycoses, parasite infections, gallstones, tumors and/or hyperproliferative disorders, and/or treatment and/or prophylaxis of impaired glucose tolerance and diabetes.
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- Sodium channel drugs and uses
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The compounds of this invention comprise 2-10 ligands covalently connected, each of the ligands being capable of binding to a ligand binding site in a Na+channel, thereby modulating the biological activities thereof.
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- Group 5 and group 6 metal halides as very efficient catalysts for acylative cleavage of ethers
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Group 5 and 6 metal chlorides such as MoCl5, WCl6, NbCl5 and TaCl5 were found as very efficient catalysts for acylative cleavage of the C-O bond of ethers. Compared with conventional Lewis acid catalysts such as ZnCl2, AlCl3, SnCl4 and TiCl4, group 5 and 6 metal chlorides showed better results in the catalytic C-O bond cleavage of dibutyl ether with benzoyl chloride.
- Guo, Qiaoxia,Miyaji, Taichi,Hara, Ryuichiro,Shen, Baojian,Takahashi, Tamotsu
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p. 7327 - 7334
(2007/10/03)
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- A new route to δ-(2,4-di-tert-amylphenoxy)butylamine
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A new route to δ-(2,4-di-tert-amylphenoxy)butylamine, the main intermediate in production of the blue protectable component for color motion picture and photographic materials, was proposed.
- Yutilov,Svertilova,Minkina,Shcherbina,Kirillova
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p. 1220 - 1225
(2007/10/03)
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- Heterocyclic compounds for treating myocardial ischemia
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PCT No. PCT/FR96/01176 Sec. 371 Date Jan. 26, 1998 Sec. 102(e) Date Jan. 26, 1998 PCT Filed Jul. 25, 1996 PCT Pub. No. WO97/05134 PCT Pub. Date Feb. 13, 1997Substituted N-heterocyclyl-1-aryloxyalkyl-4-piperldineamines of formula (I) wherein each of R1 to R4, which are the same or different, is hydrogen, optionally branched C1-4 alkyl, optionally branched C1-4 alkyloxy, halo, nitro, hydroxy, or trifluoromethyl or trifluoromethoxyl; R5 is hydrogen, optionally branched C1-6 alkyl, optionally branched C7-12 phenylalkyl optionally substituted on the phenyl by one or more radicals having the same definition as R1; W and X are oxygen or sulphur; Y is C2-6 polymethylene or -CH2-CH(OH)-CH2-; and n is 0 or 1; and pure R or S isomers of said compounds, where applicable, as well as mixtures thereof, as well as therapeutically-acceptable organic or inorganic salts and hydrates of the compounds and a method for preparing the compounds and their use as drugs are all disclosed.
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- The versatile behavior of the PdCl2/Et3SiH system. Conversion of alcohols to the corresponding halides and alkanes
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The versatility of the palladium(II) chloride/triethylsilane system has been tested in the transformation of alcohols. The conversion to the corresponding halides and alkanes has been achieved in good yields and in the absence of solvent for a variety of substrates.
- Ferreri,Costantino,Chatgilialoglu,Boukherroub,Manuel
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p. 135 - 137
(2007/10/03)
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- Brominative Deoxygenation of Some Aldehydes and Ethers
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Three aldehydes (4a-c) are transformed into 1,1-dibromides (6a-c) by 2,2,2-tribromo-2,2-dihydro-1,3,2-benzodioxaphosphole (2).This reagent (2) is also very active in the cleavage of ethers; its reactions may show some features of carbonium as well as of SN2 character.
- Roman, Ulrich von,Knorr, Rudolf,Behringer, Claudia,Ruhdorfer, Jakob
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p. 260 - 262
(2007/10/02)
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- Sequential π-ligand exchange from metallacyclopentanes: Synthesis and structure of 1,1 -bis(cyclopentadienyl)-2,3-diphenyl-1-hafnacyclopent-2-ene
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Bis(cyclopentadienyl)hafnacyclopentane was prepared by reaction of Cp2HfCl2 and 1,4-dilithiobutane. Thermolysis of the five-membered metallacycle at 80°C with butadiene results in liberation of 1 equiv of ethylene and formation of an (ethylene)hafnocene/butadiene (1:1) addition product: (1-3:6-η-2-hexenediyl)hafhocene. Similarly, the hafnacyclopentane reacted with diphenylcetylene under suitable controlled reaction conditions at 80°C in benzene to give a 36% yield of the title compound. 1,1-Bis(cyclopentadienyl)-2,3-diphenyl-1-hafnacyclopent-2-ene crystallizes in the triclinic space group P1 with cell constants a = 8.901 (2) A?, b = 9.871 (2) A?, c = 13.199 (3) A?, α = 78.19 (2)°, β = 72.49 (2)°, γ = 65.62 (2)°, V = 1003.0 (4) A?3, Z = 2, and R(F) = 2.76%. The four ring carbons are nearly planar. Bond distances within the metallacyclic five-membered ring system are Hf-C(1) = 2.255 (7), C(1)-C(2) = 1.529 (7), C(2)-C(3) = 1.513 (8), C(3)-C(4) = 1.337 (8), and C(4)-Hf = 2.268 (4) A?. Though the ring system is somewhat strained (bond angles C(1)-C(2)-C(3) = 115.6 (5)° and Hf-C(4)-C(3) = 110.6 (3)°), the strong hafnium to carbon σ-bonds protect it from rapidly reacting further with additional diphenylacetylene to give the very stable metallacycle Cp2Hf(-CPh=CPhCPh=CPh).
- Erker, Gerhard,Dorf, Ulrich,Rheingold, Arnold L.
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p. 138 - 143
(2008/10/08)
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- Metal-assisted Reactions. Part 17. Ring-opening and Dimerization of Cyclic Ethers by Titanium Halides
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Reaction of TiCl4 or TiBr4 with a variety of cyclic ethers gives, predominantly, products resulting from simple ring-opening or from ring-opening with simultaneous condensation to dimeric species.The variations in yields of these two kinds of products might be correlated qualitatively with an initial formation of the complex TiX4*2E (X = Cl or Br; E = cyclic ether) in which the ethers were held in a cis or trans relationship.Although such a correlation might suggest that TiCl4 but not TiBr4 exerts a template effect on the condensation, stereochemical considerations of the reaction products indicate otherwise.TiCl3 and VCl3 do not give similar results and TiF4 gives no reaction.
- Delaney, Paul A.,Johnstone, Robert A. W.,Entwistle, Ian D.
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p. 1855 - 1860
(2007/10/02)
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- SELECTIVITIES OF pi - AND sigma -SUCCINIMIDYL RADICALS IN SUBSTITUTION AND ADDITION REACTIONS. APPENDIX: RESPONSE TO WALLING, EL-TALIAWI, AND ZHAO.
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A new method for studies of pi -succinimidyl (S// pi ) radicals is described, one that makes possible the study of reactions of this radical with a variety of substrates not accessible by the use of Br//2-NBS. NBS systems containing BrCCl//3 at mole fractions greater than 0. 3 show all the characteristics associated with S// pi behavior, and they function in the presence of olefins which serve as Br//2 scavengers. If CCl//4 is substituted for BrCCl//3, the system is clearly S// sigma . The S// pi behavior is contrasted with S// sigma and Br multiplied by (times) reactivities for H abstractions from a variety of substrates and for additions to tert-butylethylene, isobutylene, and 1,3-butadiene. In early-transition-state systems, for H transfer, the strength of the bond being broken and the strength of the bond being made are not the major factors in determining reactivities. The behavior in late-transition-state systems is influenced by both bond strengths. The S// pi radical shows intermediate behavior. These conclusions are supported by primary deuterium isotope effects for methylene chloride and chlororoform. The Appendix addresses a number of questions raised by the preliminary study of NBS reactions by Walling et al.
- Skell,Tlumak,Seshadri
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p. 5125 - 5131
(2007/10/02)
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- 4-PYRIMIDONE COMPOUNDS
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The compounds are substituted isocytosines which are histamine H 2-antagonists. Two specific compounds of the present invention are 2-2-(5-methyl-4-imidazolylmethylthio)-ethylamino!-5-(3-methoxybenzyl)-4-pyrim idone and 2-2-(5-methyl-4-imidazolylmethylthio)ethylamino!-5-benzyloxy-4-pyrimidone.
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- ALKOXY PYRIDINE COMPOUNDS
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The compounds are alkoxypyridine compounds which are histamine H 2-antagonists. Two specific compounds of the present invention are N-cyano-N'-methyl-N"-2-((3-methoxy-2-pyridyl)methylthio)ethyl!guanidine and 1-methylamino-1-2-(3-methoxy-2-pyridyl)methylthio)ethylamino!-2-nitroethylene. "
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