- Bambusurils Bearing Nitro Groups and Their Further Modifications
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Bambusurils are recently developed neutral anion receptors that show a high affinity towards many inorganic anions, not only in organic solvents but also in water. However, the number of water-soluble bambusurils and also those bearing functional groups is very limited. In this paper we report the synthesis of four- and six-membered bambusurils containing eight and twelve nitro groups. All the nitro groups on the bambusuril portals could be transformed into amino functions, which provided the macrocycles with water solubility and allowed their further modification. For example, we have demonstrated the conversion of amino groups on the bambusurils into the corresponding urea-functionalized bambusuril derivatives. We also report the first example of a bambusuril bearing only two functional groups, which was prepared by the condensation of two different glycolurils.
- Yawer, Mirza Arfan,Sleziakova, Kristina,Pavlovec, Lukas,Sindelar, Vladimir
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- Synthetic method for o-nitrobenzyl chloride
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The invention discloses a synthetic method for o-nitrobenzyl chloride. The synthetic method comprises the following steps: adding a catalyst into o-nitrotoluene, carrying out heating and stirring, slowly introducing chlorine and recovering o-nitrotoluene after completion of reaction so as to obtain o-nitrobenzyl chloride. The synthetic method provided by the invention overcomes defects like low yield and a great number of by-products of conventional thermal chlorination methods and luminescence methods for synthesis of o-nitrobenzyl chloride; the catalyst is added into o-nitrotoluene, chlorine is introduced after heating and stirring, and o-nitrotoluene is recovered after completion of the reaction, so o-nitrobenzyl chloride is obtained; and with the synthetic method provided by the invention, o-nitrobenzyl chloride (in terms of actual consumption of o-nitrotoluene) with a purity of no less than 99% and a yield of no less than 80% can be obtained, higher than the purity and yield of o-nitrobenzyl chloride produced by using the thermal chlorination methods and luminescence methods.
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Paragraph 0044; 0045
(2016/12/22)
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- Ortho-nitro benzyl chloride by a synthetic method of preparing pyraclostrobin intermediate (by machine translation)
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This invention relates to a kind of the ortho-nitro benzyl chloride preparation pyraclostrobin method for synthesizing intermediate, comprising the following steps: in the ortho-nitro toluene, a catalyst is added, heating and stirring, and slowly inject chlorine, after the end of reaction, recovering O-nitro-toluene, ortho-nitro benzyl chloride obtained; the ortho-nitro benzyl chloride and 1 the [...] (the 4 [...] chlorolphenyl) - 3 the the pyrazole is mellow[...] for etherification reaction, to obtain the 2 [...] [(N -4 the [...] chlorolphenyl) - 3 the pyrazole oxygen radical[...] methyl] nitrobenzene. In this invention to replace nitryl chlorine animal pennitryl bromination animal pen and adjacent to the 1 [...] (the 4 [...] chlorolphenyl) - 3 the reaction the pyrazole is mellow[...], pyraclostrobin intermediates prepared by the 2 [...] [(N -4 the [...] chlorolphenyl) - 3 the pyrazole oxygen radical[...] methyl] nitrobenzene, avoid the use of a defect method for synthesis of O- nitryl bromination animal pen, content can be used for preparing ≥ 98%, yield ≥ 90% ether product. (by machine translation)
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Paragraph 0042
(2016/10/31)
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- Treatment of alcohols with tosyl chloride does not always lead to the formation of tosylates
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Treatment of substituted benzyl alcohols with tosyl chloride resulted in the formation of the corresponding chlorides, not the usual tosylates. A series of experiments demonstrated that it was possible to predict whether chlorination or tosylation would occur for substituted benzyl alcohols and pyridine methanols. Treatment of electron withdrawing group-substituted benzyl alcohols with tosyl chloride gave the corresponding chlorides in moderate yields under mild conditions, which provided a simple way to directly prepare chlorides from alcohols.
- Ding, Rui,He, Yong,Wang, Xiao,Xu, Jingli,Chen, Yurong,Feng, Man,Qi, Chuanmin
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experimental part
p. 5665 - 5673
(2011/09/20)
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- 4-Aminophenyldiphenylphosphinite (APDPP), a new heterogeneous and acid scavenger phosphinite - Conversion of alcohols, trimethylsilyl, and tetrahydropyranyl ethers to alkyl halides with halogens or N-halosuccinimides
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A new heterogeneous phosphinite, 4-aminophenyldiphenylphosphinite (APDPP), is prepared and used for the efficient conversion of alcohols, trimethylsilyl ethers, and tetrahydropyranyl ethers to their corresponding bromides, iodides, and chlorides in the presence of molecular halogens or N-halosuccinimides. The amino group in this phosphinite acts as an acid scavenger and removes the produced acid. A simple filtration easily removes the phosphinate by-product.
- Iranpoor, Nasser,Firouzabadi, Habib,Gholinejad, Mohammad
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p. 1006 - 1012
(2007/10/03)
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- Oxidation of benzylic alcohols and ethers to carbonyl derivatives by nitric acid in dichloromethane
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Nitric acid in dichloromethane may be successfully employed for the oxidation of benzylic alcohols and ethers to the corresponding carbonyl compounds. The proposed method proved to be of general applicability, affording very good yields of aldehydes and ketones and showing interesting chemoselectivity in many instances, allowing competitive aromatic nitration to be avoided, as well as - in the case of aldehydes - any further oxidation to carboxylic acids. The reaction probably proceeds by a radical mechanism, the active species in the oxidation process being NO2. Competitive formation of nitro esters was observed in some cases, whereas poor results were obtained with allylic and non-benzylic substrates. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Strazzolini, Paolo,Runcio, Antonio
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p. 526 - 536
(2007/10/03)
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- Nickel-catalyzed benzylic oxidation with NaOCl
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Ni(bpy)2Cl2 has been found to be an efficient catalyst for the oxidation of various alkylbenzenes with hypochlorite. Substituted toluenes having electron withdrawing group at 4-position were oxidized to the corresponding substituted benzoic acids in excellent yields.
- Yamazaki, Shigekazu
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p. 2211 - 2216
(2007/10/03)
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- trans-2,2′-dinitrostilbene as a precursor of 0-nitrobenzaldehyde, a key intermediate for pharmaceuticals: Reactivity and molecular structure studies
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A novel synthesis of o-nitrobenzaldehyde by means of the ozonolysis-reductive hydrolysis of symmetrical trans-2,2′-dinitrostilbene is reported, yielding only the ortho isomer of nitrobenzaldehyde. This new route reduces environmental hazards in the synthesis of o-mtrobenzaldehyde. The central ethylene bond of trans-2,2′-dinitrostilbene showed a high reactivity for the ozonolysis reaction. The molecular structures of 2-nitrobenzaldehyde and trans-2,2′-dinitrostilbene were studied theoretically by means of ab initio quantum mechanical calculations at the 6-31G*//6-31G* level. A non-coplanar conformer was found for o-nitrobenzaldehyde, where the carbonyl and nitro groups are slightly twisted with respect to the phenyl ring. Also, a non-coplanar minimal s-trans-gauchels-transgauche conformer (NO2-aryl-C=C-aryl-NO2) was found for trans-2,2′-dinitrostilbene, where the aromatic groups are twisted with respect to the central double bond, and the nitro groups are also twisted out the planes of the aromatic rings. This structure is consistent with certain experimental physical-chemical properties of this molecule.
- Sainz-Diaz, Claro I.,Hernandez-Laguna, Alfonso
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p. 1489 - 1495
(2007/10/03)
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- New applications of tungsten hexachloride (WCl6) in organic synthesis. Halo-de-hydroxylation and dihalo-de-oxo-bisubstitution reactions
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Tungsten hexachloride (WCl6) has been used for the halo-de-hydroxylation and dihalo-de-oxo-bisubstitution reactions of benzylic alcohols, benzaldehydes, acyloins, and epoxides to their chlorides, gem-dichlorides, vic-trichlorides, and vic-dichlorides respectively.
- Firouzabadi, Habib,Shiriny, Farhad
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p. 14929 - 14936
(2007/10/03)
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- Substitution Reactions toward 2-Nitrobenzyl Pseudohalides. The Crystal Structure of 2-Nitrobenzyl Tellurocyanate
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The reactions between 2-nitrobenzyl pseudohalides, 2-NO2-PhCH2XCN, and pseudohalide ions, NCX- (X = S, Se or Te) have been studied kinetically in acetonitrile at 25.0 deg C.The reactions proceed through nucleophilic attack at the methylene carbon atom, forming exclusively the exchange products.The average nucleophilicity order, NCTe- >> NCSe- > NCS-, and the average leaving group order, NCTe- >/= NCSe- >/= NCS-, lead to a carbon basicity order NCTe- > NCSe- >/= NCS-, which is confirmed with equilibrium studies.A crystal structure determination of 2-nitrobenzyl tellurocyanate at ca. 135 deg C has revealed that the TeCN group is syn-clinal (gauche) to the C(CH2)-C(Ar) bond with a torsion angle of -48.5(5) deg.The TeCC plane forms an angle of 103.4(5) deg with the phenyl ring plane.In this conformation the steric influence of the 2-NO2 group in substitution reactions at the methylene carbon atom will be negligible except for bulky nucleophiles.The tellurium atom forms two fairly strong intermolecular bonds to nitrogen atoms from neighbouring tellurocyanate groups, viz. 2.889(6) Angstroem trans to the cyano group and 3.382(6) Angstroem trans to the methylene group.In the crystalline state the compound may be considered both as a tellurium(II) complex and as an organic pseudohalide.No intermolecular tellurium-oxygen contacts could be observed.
- Grung, Knut Eric,Roemming, Christian,Songstad, Jon
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p. 518 - 526
(2007/10/02)
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