- Preparation method of 4 -tert-butyl phthalonitrile (by machine translation)
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The invention discloses a preparation method of 4 -tert-butylphthalonitrile, and belongs to the technical field of organic synthesis. To the technical scheme, o-xylene and chlorobutane are reacted under the action of catalyst iodine to obtain 4 -tert-butylphthalyl chloride; 4 -tert-butyl phthalic acid is reacted with ammonia solution to obtain 4 -tert-butylphthalamide; 4 -tert-butylphthalamide and dehydrating agent are subjected to dehydration reaction to obtain 4 - 4 - 4 -tert-butylphthalonitrile; and the tert-butylphthalonitrile is obtained through dehydration 4 - 4 . The method has the advantages of mild reaction conditions, high yield, low cost and suitability for industrial production, and is a synthetic method with industrial production value. (by machine translation)
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Paragraph 0023; 0028; 0029; 0034; 0035; 0040-0041
(2020/09/20)
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- Preparation method of di-tert-butyl o-phthalodinitrile
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The invention discloses a preparation method of di-tert-butyl o-phthalodinitrile and belongs to the technical field of organic synthesis. According to the technical scheme disclosed by the invention,a specific process of the preparation method of the di-tert-butyl o-phthalodinitrile comprises the following steps: taking the di-tert-butyl o-dibromobenzene as a starting raw material, 1,8-diazabicycloundec-7-ene as a solvent, potassium ferricyanide as a cyanation reagent and silver carbonate and copper acetylacetonate as catalysts, and reacting at 80 to 100 DEG C to prepare a target product di-tert-butyl o-phthalodinitrile. The preparation method disclosed by the invention has the advantages of moderate reaction conditions, relatively high yield and low cost and is suitable for industrialized application.
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Paragraph 0019
(2018/05/01)
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- Synthesis of phthalonitriles using a palladium catalyst
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An easy synthetic method to obtain phthalonitriles from o-dibromobenzenes under mild conditions in high yields using Zn(CN)2 and a catalytic amount of tris(dibenzylideneacetone)dipalladium and 1,1′- bis(diphenylphosphino)ferrocene is described. Georg Thieme Verlag Stuttgart.
- Iqbal, Zafar,Lyubimtsev, Alexey,Hanack, Michael
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experimental part
p. 2287 - 2290
(2009/05/07)
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- Reductive activation of arenes. XII. Reaction of the product of phthalonitrile one-electron reduction with butyl halides in liquid ammonia
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The product of one-electron reduction of the phthalonitrile with metallic potassium in liquid ammonia reacts with butyl halides (BuCl, BuBr, BuI, s-BuBr, t-BuBr, t-BuI) to yield compounds of alkyl bonding in ipso(2-butylbenzonitriles) and unsubstituted (4-butyl-1,2-dicyanobenzenes and 2,5-dibutylbenzonitriles) positions of the aromatic ring of the original dinitrile. The dependence of the product composition on the character of alkyl moiety and halogen atom in the butyl halide is rationalized by reaction mechanism including at the first stage electron transfer from the anion-radical of the phthalonitrile to the alkyl halide and followed by recombination of the alkyl radical produced with another molecule of anionradical.
- Panteleeva,Bilkis,Steingarts
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p. 1632 - 1639
(2007/10/03)
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- Homolytic base-promoted aromatic alkylations by alkyl halides
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Electron-transfer chain reactions leading to regioselective alkylations of benzenes bearing electron-withdrawing substituents can be observed with alkyl halides in the presence of the radical initiator (Bu3Sn)2 and the proton acceptor 1,4-diazabicyclo[2.2.2]octane (DABCO). Yields vary from low to high depending on the benzene derivatives. The role of DABCO is to abstract a proton from the substituted cyclohexadienyl adduct radical to form a radical anion which then transfers an electron to RX and is converted to the alkylated product itself. The rate of this electron-transfer step is probably not fast enough to sustain a good radical chain reaction so that further generation of R· from excess (Bu3Sn)2 and RX is necessary.
- Wang, Chen,Russell, Glen A.,Trahanovsky, Walter S.
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p. 9956 - 9959
(2007/10/03)
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- Homolytic base-promoted aromatic alkylations by alkylmercury halides
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Electron transfer chain reactions leading to substitution in electronegatively substituted benzene derivatives can be observed with alkylmercury halides in the presence of proton accepters such as DABCO. Promotion by base involves the abstraction of a proton from the substituted cyclohexadienyl adduct radical to form a radical anion which readily transfers an electron to RHgX with the regeneration of R.. Aromatic substitutions involving t-Bu. are highly regioselective and yield products of only para attack for PhCHO, PhCOCH3, PhCOCMe3, PhCOPh, PhCN, phthalimides, or 1,2-dicyanobenzene. The ortho/para substitution products are observed for isophthaldehyde or 1,3-dicyanobenzene, while 1,4-dicyanobenzene yields the ortho substitution product. At 25-35°C substitution by t-Bu. ortho to an ester group is not observed and m- or p-cyanobenzoate esters yield only products of substitution ortho to the cyano group. With the isopropyl radical substitution ortho to the ester function is observed with diethyl isophthalate. Intramolecular radical cyclizations of the radical adducts of 1-aryl-4-penten-1-ones leading to α-tetralones is also promoted by the presence of DABCO. When the aryl group contains a para ester function, spirocyclizatien occurs leading to a rearrangement acyl radical which can be oxidized by t-BuHgCl to the acyl cation and the carboxylic acid.
- Russell, Glen A.,Chen, Ping,Kim, Byeong Hyo,Rajaratnam, Ragine
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p. 8795 - 8801
(2007/10/03)
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- Association and Orientation of Copper(II) Tetra-t-butylphthalocyaninate in Multilayer Langmuir-Blodgett Films as determined by Electron Paramagnetic Resonance Spectroscopy
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E.s.r. spectra obtained at 20 or 25 K, electronic absorption spectra measured at ambient temperature, and vapour-phase osmometry show that copper tetra-t-butylphthalocyaninate (1) is associated in dilute solutions in dichloromethane but unassociated in toluene.The corresponding spectra within single- and multi-component Langmuir-Blodgett films on silica slides are also reported.Films containing complex (1) either alone or admixed with eicosanoic acid gave spectra characteristic of the associated material.However, a three-component film containing (1), tetra-t-butylphthalocyanine (2), and eicosanoic acid (ratio 5:50:400) gave an e.s.r. spectrum showing hyperfine and superhyperfine structure.The orientational dependence of the e.s.r. spectrum was investigated and reveals that the molecules of (1) are aligned with the plane of the ring at 80 +/- 10 deg to the substrate surface.Some orientational disorder is also present and can be detected in the g region.
- Cook, Michael J.,Dunn, Adrian J.,Gold, Andrew A.,Thomson, Andrew J.,Daniel, Mervyn F.
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p. 1583 - 1590
(2007/10/02)
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- Soluble trans-Di-1-alkynyl- and Poly-trans-ethynyl(tetraalkylphthalocyaninato)metal IVB Derivatives
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The hitherto unknown peripheric substituted trans-dihalogeno(tetra-tert-butylphthalocyaninato)metal IVB derivatives 5a,b and 6a,b as well as trans-dichlorogermanium (6c) were converted into the monomeric, soluble trans-di-1-alkynyl(tetra-tert-butylphthalocyaninato)metal IVB compounds 10a - h and trans-di-1-alkynylgermanium compounds 10i - l, respectively, by the reaction with various 1-alkynyl Grignard derivatives 9a - e.The high solubility of all products in organic solvents and the strong ring-current effect of the macrocycle on the axial ligands are remarkable.The formally analogous reaction with the bidentate ethynediyldi-Grignard compound 9f leads to the soluble, acetylene-bridged polymers 12a - c.These are considered as model compounds for a new kind of one-dimensional conductors proposed by us.
- Hanack, Michael,Metz, Josef,Pawlowski, Georg
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p. 2836 - 2853
(2007/10/02)
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