- Synthesis method of tert-amylbenzene with controllable isomer content
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The invention provides a synthesis method of tert-amylbenzene with controllable isomer content. The synthesis method comprises the following steps: 1) carrying out a substitution reaction on tert-amylalcohol and haloid acid to obtain a halopentane intermediate; 2) carrying out a Friedel-Crafts alkylation reaction on the halopentane intermediate and benzene under the catalysis of a Lewis acid to obtain tert-amylbenzene; wherein the Lewis acid is one of ZnCl2 and FeCl3 or a mixture of the ZnCl2 and the FeCl3; the temperature of the Friedel-Crafts alkylation reaction is -10 to 40 DEG C; the vacuum degree is absolute pressure of 2-75kPa; and the reaction time is 0.5-4 h. According to the synthesis method, by setting reasonable reaction steps, controlling reaction conditions, selecting a proper catalyst and the like, the isomerization ratio is reduced, and the tert-amyl product with high yield and high selectivity is obtained.
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Paragraph 0025-0026
(2020/06/17)
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- A 2, 2 - dimethyl butyric acid
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The invention relates to a pesticide synthesis technology field, discloses a 2, 2 - dimethyl butyric acid, use chloro- uncle pentane preparing Grignard reagent, then with the ester compound produced by the reaction of 2, 2 - dimethyl ester, followed by hydrolysis to obtain 2, 2 - dimethyl butyric acid. To avoid the traditional production of large amount of sulfuric acid used in the method of defect, reducing the risk of the working personnel, and the use of some conventional chemical reagent can prepare 2, 2 - dimethyl butyric acid, convenient to make the 2, 2 - dimethyl butyric acid.
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Paragraph 0018-0021
(2019/04/13)
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- In Situ Formation of Al(Fe)/Cl Metal Chloride Complexes and Evaluation of Their Catalytic Properties in the Reaction of Ethylene Oligomerization
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The reactivity of the Al/Fe alloy with respect to organochlorine compounds for producing in situ catalytic (Fe-, Al/Cl) complexes from the systems Al/Fe/ tert-butyl chloride (TBC) and Al/Fe/TBC in n-hexane was investigated, together with their catalytic p
- Arbuzov,Kudrya,Trenikhin,Drozdov
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p. 1926 - 1930
(2018/04/17)
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- In situ study of the interaction between tert-butyl chloride and aluminum activated with liquid in-ga eutectic
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The interaction between tert-butyl chloride and activated aluminum was studied by attenuated total reflectance Fourier transform infrared spectroscopy near room temperature (18-25°C). A long induc- tion period of ?240-260 min was observed. The AlCl4- ionic aluminum chloride complexes [AlnCl3n+1]-(n = 1, 2) and the molecular species AlCl3 were identified at the activated aluminum/tert-butyl chloride interface during the reaction. The formation of the ion in the liquid medium and the presence of the same ion and a molecular AlCl3 -tert-butyl chloride complex in the resinous products of the reaction were confirmed by 27Al NMR spectroscopy. The reaction products were analyzed qualitatively by GC/MS. The reactivities of activated aluminum and anhydrous aluminum chloride toward tert-butyl chloride under the same conditions were compared. A distinctive feature of the interaction activated aluminum and tert-butyl chloride is the dominant formation of the AlCl4 -ion. By contrast, the interaction between aluminum chloride and tert-butyl chloride yields the polynuclear ion and,Al2Cl7 - likely,Al3Cl10-. Pleiades Publishing, Ltd., 2010.
- Arbuzov,Drozdov,Likholobov,Trenikhin,Talsi,Kudrya
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experimental part
p. 354 - 358
(2011/01/05)
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- The AZARYPHOS family of ligands for ambifunctional catalysis: Syntheses and use in ruthenium-catalyzed anti-markovnikov hydration of terminal alkynes
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The family of AZARYPHOS (aza-aryl-phosphane) phosphane ligands, containing a phosphine unit and sterically shielded nitrogen lone pairs in the ligand periphery, is introduced as a tool for developing ambifunctional catalysis by the metal center and nitrogen lone pairs in the ligand sphere. General synthetic strategies have been developed to synthesize over 25 examples of structurally diverse (6-aryl-2pyridyl)phosphanes (ARPYPHOS), (6alkyl-2-pyridyl)phosphanes (ALPY-PHOS), 4,6-disubsituted l,3-diazin-2ylphosphanes or l,3,5-triazin-2- ylphosphanes, quinazolinylphosphanes, quinolinylphosphanes, and others. The scalable syntheses proceed in a few steps. The incorporation of AZARYPHOS ligands (L) into complexes [RuCp(L)2(MeCN)][PF6] (Cp = cyclopentadieny1)gives catalysts for the anti-Markovnikov hydration of terminal alkynes of the highest known activities. Electronic and steric ligand effects modulate the reaction kinetics over a range of two orders of magnitude. These results highlight the importance of using structurally diverse ligand families in the process of developing cooperative ambifunctional catalysis by a metal and its ligand.
- Hintermann, Lukas,Dang, Tuan Thanh,Labonne, Aurelie.,Kribber, Thomas,Xiao, Li,Naumov, Pance
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supporting information; experimental part
p. 7167 - 7179
(2010/02/28)
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- Rapid conversion of hindered arylsulfonates to alkyl chlorides with retention of configuration
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Arylsulfonates of hindered secondary alcohols are converted to the corresponding alkyl chlorides very rapidly and in good yields in the presence of titanium tetrachloride at low temperatures. These reactions proceed with exclusive retention of configuration.
- Lepore, Salvatore D.,Bhunia, Anjan K.,Mondal, Deboprosad,Cohn, Pamela C.,Lefkowitz, Craig
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p. 3285 - 3286
(2007/10/03)
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- Determination and interpretation of second order rate constants for the addition of hydrogen halides to alkenes
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An extensive range of second order rate constants for the addition of hydrogen halides to alkenes in 98% v/v ethanoic acid (acetic acid)-water have been obtained by conductivity measurements. The rate constants are in the expected order of HF HCl HBr HI. The rates with different alkenes cannot be rationalised solely by a consideration of carbocation stability and it has been necessary to consider steric effects in order to explain the observed order.
- Borgeaud, Robert,Newman, Henry,Schelpe, Arabella,Vasco, Veronica,Peter Hughes
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p. 810 - 813
(2007/10/03)
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- Reactivity of bismuth(III) halides towards alcohols. A tentative to mechanistic investigation
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The reactivity of bismuth(III) halides (BiX3; X=Cl, Br and I) towards a series of alcohols has been investigated. Three different reactions have been studied, namely: halogenation, dehydration and etherification. The behaviour of these bismuth derivatives was found to depend on the nature of the halide bonded to the bismuth atom. Their reactivities can be interpreted on the basis of the Hard and Soft Acids and Bases (HSAB) principle. A mechanism is proposed which involves the formation of a complex of the alcohol with Bi(III).
- Keramane, El Mehdi,Boyer, Bernard,Roque, Jean-Pierre
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p. 1909 - 1916
(2007/10/03)
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- BiX3 as an efficient and selective reagent for the halogen exchange reaction
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Bismuth halides are efficient and selective reagents in the halogen exchange reactions carried out under mild conditions. This rapid, high yield reaction proceeds mainly with retention of configuration.
- Boyer, Bernard,Keramane, El Mehdi,Arpin, Severine,Montero, Jean-Louis,Roque, Jean-Pierre
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p. 1971 - 1976
(2007/10/03)
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- BiCl3 : An efficient agent for selective chlorination of alcohols or for halogen exchange reaction
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BiCl3 was found to be an effective reagent for an improved chlorination of alcohols and for a convenient halogen exchange reaction.
- Boyer, Bernard,Keramane, El Mehdi,Montero, Jean-Louis,Roque, Jean-Pierre
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p. 1737 - 1741
(2007/10/03)
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- Process for the preparation of alkyl halides
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In the continuous preparation of alkyl halides from branched olefins and hydrohalic acids, the reaction is carried out without the addition of catalysts and without solvents. With a high olefin conversion, alkyl halides are obtained with high selectivity and with very good color quality.
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- Activation of the silicon-halogen bond by bismuth (III) halides. Halogenation of alcohols: prospective and mechanism
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In the presence of catalytic amount of BiCl3, chloromethylsylanes can be used as chlorinating agents for alcohols, and as chloro-dealkylating agents for silyl ethers and carboxylic and sulfonic esters.The chlorination of (R)-(-)-octan-2-ol and the (R)-(-)-2-mesyloctane by TMSCl gave predominantly the (S)-(+)-2-chlorooctane with inversion of configuration at secondary carbon.According to the class of alcohol, the mechanism involves SN2, SN2' or SN1 processes.This new activation of the Si-Cl bond, probably trough a Si-Cl...BiCl3 interaction gives a hard-soft reagent that can generate a silicenium cation, was also observed with Me3SiBr, BiBr3 and Me3SiI, BiI3 systems.The reaction is also presented as a possible alcoholysis of chlorosilanes, which can lead to siloxanes in non-aqueous conditions. catalysis / halogenation / alcohol / ester / silyl ether / chlorosilane / chlorotrimethylsilane / bromotrimethylsilane / iodotrimethylsilane / siloxane / bismuth (III) halide
- Labrouillere, Mireille,Roux, Christophe Le,Oussaid, Abdelouahad,Gaspard-Iloughmane, Hafida,Dubac, Jacques
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p. 522 - 530
(2007/10/02)
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- Synthesis of new 7-benzofuranmethanamines as heterocyclic analogues of the squalenepoxidase-inhibitor Butenafine
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Selected title compounds (6a-f, 7a-d) were synthesized by RedAl(R)-reduction of the carboxamides 4a-f and 5a-d, easily available from the corresponding (2,3-dihydro-)7-benzofurancarboxylic acids 1a-f or 2a-d, respectively. For practical reasons, the preparation of the 2,3-dihydro-2-methyl-7-benzofuranmethanamines 6h-k with varied N-substitution by alkylation of the N-methyl-benzofuranmethanamine 6g with preformed aralkylbromides 9a-d was preferred.
- Stanetty,Koller,Purstinger,Grubner
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p. 351 - 358
(2007/10/02)
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- Surprising Reactivity of (Methyl 2-Acetamidoacrylate)tricarbonyliron(0) leading to the Synthesis of β,β,β-Trialkyl α-Amino Acids
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Addition of methyllithium followed by tertiary haloalkanes to readily available and air-stable (methyl 2-acetamidoacrylate)tricarbonyliron(0) 1, gives protected β,β,β-trialkyl α-amino acids which are hydrolysed to give tert-leucine 10 and the new α-amino acids 2-amino-3,3-dimethylpentanoic acid 11 and 2-amino-3,3-dimethylhexanoic acid 12.
- Barker, James,Cook, Stephen L.,Lasterra-Sanches M. Elena,Thomas, Susan E.
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p. 830 - 832
(2007/10/02)
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- α,α-DICHLOROALDEHYDES AND α,α-DICHLOROCARBOXYLIC ACIDS FROM LONG CHAIN 1-ALKANOLS. IMPROVED CHLORINATION IN THE SYSTEM DMF-CHCl3-MgCl2
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Production of α,α-dichloroaldehydes by direct chlorination of 1-alkanols with chlorine gas, catalyzed by DMF and DMF*HCl, was extended to long chain compounds (CnH2n+1OH; n = 5, 6, 8, 10, 12, 14, 16, 18).Two problems specific to the longer chains were solved to obtain isolated yields in the range 70-85 percent; a) parasitic radical chlorination was largely controlled by shielding from light; b) alkyl alkanoate side product (8 percent for n = 8 but 25 percent for n = 16 or 18) was decreased to 0-2 percent in the presence of MgCl2*H2O.Homogeneity of the reaction medium was improved with chloroform as a cosolvent.Oxidation of the aldehydes to dichlorocarboxylic acids proceeded smoothly with aqueous KMnO4 up to the tetradecanal.For the longer chains 30 percent hydrogen peroxide-NaHCO3 in acetone (overnight at 48-52 deg C) was the preferred oxidant.
- Buyck, L. De,Casaert, F.,Lepeleire, C. De,Schamp, N.
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p. 525 - 534
(2007/10/02)
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- Preparation of indanes
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Indanes are prepared by reacting substituted or unsubstituted benzyl halides with olefins in the presence of a Lewis acid as catalyst by reacting benzyl halides I STR1 (where R1 and R2 =hydrogen, alkyl, alkoxy, cycloalkyl, aryl, aryloxy, aralkyl R3 =R1, halogen or an ortho-fused ring system X=halogen) with olefins II STR2 (where R4 to R7 =hydrogen or alkyl unbranched at alpha) in the presence of catalytic amounts of titanium tetrachloride.
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- THE MECHANISM OF 2-METHYLBUTENE-2 HYDROHALOGENATION IN SOLID PHASE
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Complexes and reactions of 2-methylbutene-2 with hydrohalogen (HCl, HBr) have been studied in solid phase at 80-150 deg K.It has been found that 2-methylbutene-2 forms with HX complexes of 1:1 and 1:2 composition.Hydrohalogenation proceeds via the rearrangement of complex 2HX*C5H10 into complex of addition product with HX.Kinetic equation depends on the reagents ratio.In excess of HX (1HX:C5H1010)reaction can be described by the first order kinetic equation.If the ratio HX:C5H10 is more then 10, reaction is described by polychronous kinetic law.The effective activation energy of solid phase hydrohalogenation does not exceed 20 kJ/mole.The molecular mechanism of hydrohalogenation in solid phase has been proposed
- Sergeev, G. B.,Smirnov, V. V.,Rostovshchikova, T. N.,Komissarovan N. V.,Indoleva, Ye. V.
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p. 5853 - 5864
(2007/10/02)
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- Silylaminyl Radicals. Part 2. Free Radical Chain Halogenation of Hydrocarbons using N-Halogenobis(trialkylsilyl)amines
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The liquid-phase halogenation of a number of hydrocarbons and of 1-chlorobutane by N-halogenobis(trialkylsilyl)amines has been studied using product analysis techniques.The reactions take place by free radical chain mechanisms which involve the propagation steps generalised in equations (A) and (B) (X=Br or Cl).At 353 K, the molar reactivities of toluene (benzylic C-H) and cyclohexane towards (R3Si)2N+RH(R3Si)2NH+R (A) R+(R3Si)2NXRX+(R3Si)2N (B) (Me3Si)2N are approximately equal and toluene is 5.2 times more reactive than perdeuteriotoluene.The relative rates of hydrogen abstraction by (Me3Si)2N and (ButMe2Si)2N from the primary, secondary, and tertiary C-H groups in 2-methylbutane show that the silylaminyl radicals are not only highly reactive but also sterically demanding.Thus, at 333 K the average primary C-H reactivity is 0.6 times that of the tertiary C-H towards attack by (Me3Si)2N, but 4.2 times that of the tertiary C-H towards attack by the more bulky (ButMe2Si)2N.Silylaminyl radicals are much more reactive in hydrogen abstraction than are analogous dialkylaminyl radicals and this difference is interpreted in terms of thermodynamic and polar effects which arise because of the ?-donor-?-acceptor nature of the trialkylsilyl substituent.
- Cook, Malcolm D.,Roberts, Brian P.,Singh, Karamjit
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p. 635 - 644
(2007/10/02)
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- Selectivity in the Halogenation of Hexane by Tertiary Aminium Radicals from the Photodecomposition of N-Halogenoammonium Perchlorates
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The photochlorination of hexane with tertiary N-chloroammonium perchlorates in trifluoroacetic acid gives monochlorohexanes in high yield and with a striking preference for the 2-isomer.It is shown that free-radical chains are involved in which hydrogen-atom abstraction is by tertiary aminium radicals.The marked preference for 2- compared with 3-chlorination is attributed mainly to the bulky aminium radical attacking the relatively more accessible 2-position; an alternative explanation involving a reversible hydrogen-atom abstraction is ruled out.The magnitude of the primary deuterium kinetic isotope effect in these photochlorinations gives information about the dependence of the extent of C-H bond breakage in the transition state on the structure of the abstracting aminium radical.
- Fuller, Steven E.,Smith, John R. Lindsay,Norman, Richard O. C.,Higgins, Raymond
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p. 545 - 552
(2007/10/02)
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- Studies on Sulphochlorination of Paraffins. IX. Regularities of the Sulphochlorination of Branched-chain Paraffins
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In the cases of 2-methylbutane and 2-methylpentane the formation of tertiary sulphochlorides in the sulphochlorination of the parent hydrocarbons could be established by means of 13C-n.m.r.-spectroscopy.The relative rates of the various C-H-bonds in 2-methylbutane, 2-methylpentane and 3-methylpentane in the sulphochlorination reaction were determined.The relative rates of the tertiary C-H-bonds in the sulphochlorination were considerably lower than the corresponding values for the chlorination of the branched-chain paraffins.
- Estel, D.,Mateew, K.,Pritzkow, W.,Schmidt-Renner, W.
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p. 262 - 268
(2007/10/02)
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- Stabilities of Carbonium Ions in Solution. 12. Heats of Formation of Alkyl Chlorides as an Entree to Heats of Solvation of Aliphatic Carbonium Ions
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Heats of formation (ΔHf) of tertiary alkyl chlorides may be calculated from measurements of the heats of hydrochlorination of appropriate olefins at -50 deg C in CH2Cl2.Since many good values for heats of formation of the olefins have been published, the heats of hydrochlorination lead directly to ΔHf for the chlorides, for which few previous values are available.The new data, when combined with previously reported heats of ionization for the chlorides, provide heats of formation for the carbonium ions.Relative values for ΔHf for the carbonium ions are remarkably similar in the gas phase and in SO2ClF, thus supporting the proposal that differential solvation of carbonium ions is small in solvents such as SO2ClF.Because solvation energies are nearly constant for carbonium ions, their relative energies as calculated from quantum theory should apply directly to nonnucleophilic condensed phase values - a situation which is drastically different from that for ammonium or oxonium ions.We have shown previously the close relationship between ionization energies for alkyl chlorides in SO2ClF and their solvolysis rates in ethanol.The present results complete the series of data which are necessary for rigorously relating theoretical calculations of carbonium ion stability to solvolysis reaction rates in solution.Thereby, they help to explain the great success of the carbonium ion theory of organic chemistry.
- Arnett, Edward M.,Pienta, Norbert J.
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p. 3329 - 3334
(2007/10/02)
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- (E-Z)-ISOMERISATION OF CHLOROOLEFINS
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Equilibrium constants for the (E-Z)-isomerisation of the compounds R-CH=CH-Cl were determined and the experimental values compared with energy differences, calculated by the CNDO/2 method.
- Prochazka, Milos,Adamcova, Jindriska,Palecek, Milos
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p. 1388 - 1400
(2007/10/02)
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