- SYSTEMS AND METHODS FOR SYNTHESIS OF PHENOLICS AND KETONES
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Embodiments herein relate to apparatus and systems for phenolic and ketone synthesis and methods regarding the same. In an embodiment, a method of producing phenolics and ketones is included. The method can specifically include forming a reaction mixture comprising nanocrystalline cellulose (NCC) and water. The method can also include contacting the reaction mixture with a metal oxide catalyst at a temperature of 350 degrees Celsius or higher and a pressure of at least about 3200 psi to form a reaction product mixture. The reaction product mixture can include at least about 20 wt. % phenolics and at least about 10 wt. % ketones as a percentage of the total mass of nanocrystalline cellulose (NCC). Other embodiments are also included herein.
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Paragraph 0080-0088
(2018/11/21)
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- 2,2,5,5-Tetramethyltetrahydrofuran (TMTHF): A non-polar, non-peroxide forming ether replacement for hazardous hydrocarbon solvents
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An inherently non-peroxide forming ether solvent, 2,2,5,5-tetramethyltetrahydrofuran (2,2,5,5-tetramethyloxolane), has been synthesized from readily available and potentially renewable feedstocks, and its solvation properties have been tested. Unlike traditional ethers, its absence of a proton at the alpha-position to the oxygen of the ether eliminates the potential to form hazardous peroxides. Additionally, this unusual structure leads to lower basicity compared with many traditional ethers, due to the concealment of the ethereal oxygen by four bulky methyl groups at the alpha-position. As such, this molecule exhibits similar solvent properties to common hydrocarbon solvents, particularly toluene. Its solvent properties have been proved by testing its performance in Fischer esterification, amidation and Grignard reactions. TMTHF's differences from traditional ethers is further demonstrated by its ability to produce high molecular weight radical-initiated polymers for use as pressure-sensitive adhesives.
- Byrne, Fergal,Forier, Bart,Bossaert, Greet,Hoebers, Charly,Farmer, Thomas J.,Clark, James H.,Hunt, Andrew J.
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supporting information
p. 3671 - 3678
(2017/08/15)
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- Oxidative coupling reactions of grignard reagents with nitrous oxide
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Catalysis with laughing gas: N2O in combination with transition-metal catalysts allow the oxidative homo- and cross-coupling of Grignard reagents. The reactions can be performed under mild conditions despite the inert character of N2O. Copyright
- Kiefer, Gregor,Jeanbourquin, Loic,Severin, Kay
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supporting information
p. 6302 - 6305
(2013/07/19)
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- VARIATIONS ON PRINS-LIKE CHEMISTRY TO PRODUCE 2,5-DIMETHYLHEXADIENE FROM ISOBUTANOL
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The method of the present invention provides a high yield pathway to 2,5-dimethylhexadiene from renewable isobutanol, which enables economic production of renewable p-xylene (and subsequently, terephthalic acid, a key monomer in the production of PET) from isobutanol. In addition, the present invention provides methods for producing 2,5-dimethylhexadiene from a variety of feed stocks that can act as “equivalents” of isobutylene and/or isobutyraldehyde including isobutanol, isobutylene oxide, and isobutyl ethers and acetals. Catalysts employed in the present methods that produce 2,5-dimethylhexadiene can also catalyze alcohol dehydration, alcohol oxidation, epoxide rearrangement, and ether and acetal cleavage.
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Page/Page column 6
(2012/11/07)
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- METHOD OF RAPID METHYLATION OF ALKENE COMPOUND AND KIT FOR PET TRACER PREPARATION USING THE SAME
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To provide a method of rapid methylation of alkenes, which is applicable to the preparation of a PET tracer and which enables alkenes to be methylated through cross coupling between SP2 (alkenyl) and SP3 (alkyl) carbon atoms rapidly and in a high yield. Methyl iodide and an alkenyltrialkylstannane are subjected to cross coupling in an aprotic polar solvent in the presence of a palladium complex having a valence of 0, a phosphine ligand, a cuprous halide, and a carbonate and/or alkali metal fluoride.
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Page/Page column 5; 6
(2008/12/07)
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- Rapid methylation on carbon frameworks useful for the synthesis of 11CH3-incorporated PET tracers: Pd(0)-mediated rapid coupling of methyl iodide with an alkenyltributylstannane leading to a 1-methylalkene
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The Pd(0)-mediated rapid coupling of methyl iodide with an excess of alkenyltributylstannane was examined with the aim of incorporating a short-lived 11C-labeled methyl group into a biologically significant organic compound with a 1-methylalkene unit for the synthesis of a PET tracer. Four sets of reaction conditions (A-D) were used, all performed in DMF at 60 °C for 5 min. Condition B, using CH3I/stannane/Pd2(dba) 3/P(o-tolyl)3/CuCl/K2CO3 (1: 40: 0.5: 4-6: 2: 5), works well in almost all cases. Condition D, using CH 3I/stannane/Pd2(dba)3/P(o-tolyl) 3/CuX (X = Br, Cl, or I)/CsF (1: 40: 0.5-5: 2-20: 2-20: 5-50), shows the best results with regard to general applicability to tin substrates, affording the corresponding methylated product in >90% yield based on consumption of methyl iodide. P(t-Bu)2Me was less effective than P(o-tolyl)3, particularly for α,β-unsaturated carbonyl substrates. No regio- or stereoisomerization occurred under these reaction conditions. The efficiency of the protocol was demonstrated by synthesis of an 11C-methylated compound. The Royal Society of Chemistry 2006.
- Hosoya, Takamitsu,Sumi, Kengo,Doi, Hisashi,Wakao, Masahiro,Suzuki, Masaaki
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p. 410 - 415
(2007/10/03)
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- Efficient palladium-catalyzed nucleophilic addition of triorganoindium reagents to carbocyclic derivatives
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Palladium (0)-catalyzed allylic substitution reactions employing triorganoindium reagents have been investigated. In situ generated vinyl- and arylindiums react with substituted and unsubstituted cyclohex-2-enyl esters in the presence of 1-3 mol % Pd2(dba)3 to produce vinyl- or arylcyclohexenes in moderate to excellent yields. The stereoselectivity of this process was also examined, and evidence is presented that the reaction proceeds with inversion of stereochemical configuration.
- Baker, Lucas,Minehan, Thomas
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p. 3957 - 3960
(2007/10/03)
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- Asymmetric copper complex and cyclopropanation reaction using the same
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There are disclosed asymmetric copper complex comprising, as components, (a) an optically active bisoxazoline compound of formula (1): wherein R1 and R2 are different and each represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a phenyl or aralkyl group which may be substituted, R3 and R4 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a phenyl or aralkyl group which may be substituted, or R3 and R4 may be bonded to each other to form a C3-5 cyclic alkylene group, R5 represents a hydrogen atom or a C1-6 alkyl group, or the two R5 groups may be bonded to each other to represent a C3-5 cyclic alkylene group, (b) a monovalent or divalent copper compound, and (c) a strong acid or a Lewis acid or a mixture thereof, and a process for producing an optically active cyclopropanecarboxylate using the same.
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- Polylithiumorganic compounds. Part 27: C,C-bond forming reactions of 3,4-dilithio-2,5-dimethyl-2,4-hexadiene
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The reaction of the title compound 3,4-dilithio-2,5-dimethyl-2,4- hexadiene (4) with various mono- and bifunctional carbon-centered electrophiles is investigated, with special emphasis on carbonyl and carbonic acid derivatives. Depending on the nature of the electrophile, mono- and disubstituted derivatives with either butadiene, allene, or alkyne skeleton are obtained. Ring forming reactions in the second derivatization step are only observed in a few cases. Electrophiles bearing halogens as leaving groups react by a different mechanism and are not suitable in C,C-bond forming reactions. The compounds obtained in this investigation are suitable and highly reactive building blocks for further modifications. (C) 2000 Elsevier Science Ltd.
- Maercker, Adalbert,Van De Flierdt, Joachim,Girreser, Ulrich
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p. 3373 - 3383
(2007/10/03)
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- Controlled Rearrangement of 2,3-Dilithio-1,3-butadienes to 2,5-Dilithio-1,3-butadienes: Synthesis of 2-Isopropylidene-2,5-dihydrosilols
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3,4-Dilithio-2,5-dimethyl-2,4-hexadiene (4a) rearranges to the cross-conjugated 2,5-dimethylhexadienediyl dianion 11a. A mechanistic investigation proves the intermolecularity of this rearrangement, which is also observed when starting from 4b. The 3-lithio-2,5-dimethylhexadienyl anion 10a with one vinyllithium and one allyllithium group, is a true intermediate in this rearrangement, its synthetic potential is employed in the reaction with dichlorosilanes to form 2-isopropylidene-2,5-dihydrosilols 8.
- Maercker, Adalbert,Wunderlich,Girreser, Ulrich
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p. 793 - 798
(2007/10/03)
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- Thermal isomerisations, XXIV. Gas phase kinetics of the pyrolysis of some 3,3-dimethyl-1-alkyl-cyclopropenes: Some surprising substituent activation effects and the intramolecular trapping of vinylidene intermediates
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The gas phase pyrolyses of four 3,3-dimethyl-1-alkylcyclopropenes were studied for which the 1-alkyl substituents are ethyl- (6), isopropyl- (7), 1′-butyl- (8) and 1′-isoamyl- (9). Rate data over a 50°C temperature range were obtained and Arrhenius parameters are reported both for overall reactions and individual pathways for all compounds. Tests confirm all reactions to be unimolecular and homogeneous. For 8 and 9, noteworthy products are cyclopentenes, whose presence demonstrates the involvement of vinylidene intermediates. The substantial product yields of 2,4-alkadienes together with dramatic rate enhancement effects of these 1-alkyl substituents (relative to 1-methyl) are explained by the involvement of vinylcarbene intermediates in this pathway. Minor, transient products from 6, 8 and 9 are probably isomeric cyclopropenes. This suggests further pathways for vinylidene intermediates, whose reactivity pattern is briefly reviewed. VCH Verlagsgesellschaft mbH, 1996.
- Hopf, Henning,Plagens, Andreas,Walsh, Robin
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p. 825 - 835
(2007/10/03)
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- Photochemical nucleophile-olefin combination, aromatic substitution (photo-NOCAS) reaction. Part 6: methanol, nonconjugated dienes, and 1,4-dicyanobenzene
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Irradiation, through Pyrex, of an acetonitrile-methanol (3:1) solution of 1,4-dicyanobenzene (1) and 1,5-hexadiene (9) leads to formation of ortho and metal cyclic adducts (13-16) arising from the intermediate exciplex.There was no evidence for interaction between the two double bonds of this nonconjugated diene.The oxidation potential of 9 is high enough (>3 V vs. sce) to preclude single electron transfer (SET); no photo-NOCAS products are formed.Similar irradiation of acetonitrile-methanol solutions of 1 and 2-methyl-1,5-hexadiene (10) does yield a photo-NOCAS product (17); reaction occurs only on the more heavily substituted double bond.The additional substitution on the double bond lowers the oxidation potential (2.70 V vs. sce) of this diene to the point where SET from 10 to the excited singlet state of 1 can occur.In this case, no cycloaddition products are formed; the exciplex is quenched by electron transfer.There was no evidence for interaction between the two double bonds of the initially formed radical cation 10, or between the terminal double bond and the β-alkoxyalkyl radical of the intermediate leading to the photo-NOCAS product.The photo-NOCAS product (19) was also formed when 2,5-dimethyl-1,5-hexadiene (11) was subjected to these reaction conditions.In this case, when biphenyl (4) was added as a codonor, in addition to the photo-NOCAS product, products (21 cis and trans) resulting from cyclization of the initially formed acyclic radical cation 11 to give the 1,4-dimethylcyclohexane-1,4-diyl radical cation were also observed.This 1,6-endo, endo cyclization of 11 cation radical must be rapid enough to compete with reaction with methanol.There was no evidence for cyclization (neither 1,4-exo nor 1,5-endo) of the intermediate β-alkoxyalkyl radical.When the radical cation of 2,5-dimethyl-1,4-hexadiene (12 cation radical) is generated under these reaction conditions, photo-NOCAS products 22 and 23 are formed at the more heavily substituted double bond, along with the conjugated tautomer 2,5-dimethyl-2,4-hexadiene (24).The mechanisms for these transformations are discussed.
- Arnold, Donald R.,McManus, Kimberly A.,Du, Xinyao
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p. 415 - 429
(2007/10/02)
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- Ni(0)-Triphenylphosphine Complex-Catalyzed Homo-Coupling of 1-Alkenyl Halides with Zinc Powder
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The homo-coupling of 1-alkenyl halides was examined in the presence of NiBr2(PPh3)2, PPh3, and excess zinc.The reactions proceed under very mild conditions to give high yields of conjugated dienes.The addition of KI or thiourea was unnecessary for a successful reaction, in contrast with systems without an external phosphine ligand.
- Sasaki, Ken,Nakao, Kikuji,Kobayashi, Yoshihiko,Sakai, Mutsuji,Uchino, Norito,et al.
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p. 2446 - 2448
(2007/10/02)
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- STUDIES ON THE CHEMISTRY OF DIOLS AND CYCLIC ETHERS-52. MECHANISM AND STEREOCHEMISTRY OF DEHYDRATION OF OXOLANES TO DIENES
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On γ-Al2O3, BPO4 and NaX zeolite, the dehydration of (+/-)-2,2,3,4,5,5-hexamethyloxolane (2) in the vapour phase leads to the formation of 2,3,4,5-tetramethyl-1,5-hexadiene (8) in a slow process, while meso-2,2,3,4,5,5-hexamethyloxolane (3) is converted to 2,3,4,5-tetramethyl-2,4-hexadiene (7) with high selectivity in a fast reaction.These differences in reaction rate and selectivity indicate that the dehydration of 2 takes place by an E2 mechanism.In contrast, the steric strain in 3 results in ring opening by an E1 mechanism.These conclusions are supported by the nonselective transformations of 2,2,5,5-tetramethyloxolane (1) and 2,2,6,6-tetramethyloxane (4), and the dehydration of 1, 2 and 3 in the presence of formic acid in the liquid phase.The experimental observation prove that both the reactivity and the reaction directions in the dehydration of stereoisomeric oxolanes are determined by steric factors.
- Molnar, Arpad,Bartok, Mihaly
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p. 131 - 142
(2007/10/02)
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- PHOTOCHEMISTRY OF BIS(2-METHYL-1-PROPENYL)ETHER AND 2,2,4,4-TETRAMETHYL-6-OXABICYCLOHEXAN-3-ONE: ON THE SEARCH FOR THE OXYDI-?-METHANE REARRANGEMENT
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?,?*-Excitation of bis(2-methyl-1-propenyl)ether leads to products derived from a vinyl-vinyloxy radical pair; photochemical decarbonylation (n,?*) of the title ketone provides an entry into the diradical manifold of the oxydi-?-methane rearrangement.
- Adam, Waldemar,Berkessel, Albrecht,Krimm, Stefan
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p. 619 - 622
(2007/10/02)
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- IN SITU-GENERATED NICKEL(0)-CATALYZED HOMO-COUPLING OF ALKENYL HALIDES WITH ZINC POWDER. A SPECIFIC OUTCOME IN STEREOCHEMISTRY.
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The catalytic activity of nickel(0) generated in situ from nickel(II) salt was examined in a dehalogenative coupling of alkenyl halides with zinc powder. The reaction of alkenyl bromides took place provided that potassium iodide was present to assist the reduction of nickel(II) with zinc powder, and also to convert the alkenyl bromides to the corresponding alkenyl iodides. A speculative view concerning the disproportionation step is advanced in an attempt to explain the unique sterochemistry observed.
- Takagi,Mimura,Inokawa
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p. 3517 - 3522
(2007/10/02)
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- A Synthesis of Conjugated Dienes from Aromatic, Five-membered Heterocycles
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Reactions of furan, thiophene, selenophene, and tellurophene as well as 2-methyl and 2,5-dimethyl derivatives of the first two heterocycles with phenyl-, methyl-, and n-butyl-magnesium bromides in the presence of ligated nickel dichloride are shown to yield buta-1,3-dienes mostly with retention of configuration.
- Wenkert, Ernest,Leftin, Michael H.,Michelotti, Enrique L.
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p. 617 - 618
(2007/10/02)
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- Ni(0)-TRIALKYLPHOSPHINE COMPLEXES. EFFICIENT HOMO-COUPLING CATALYST FOR ARYL, ALKENYL, AND HETEROAROMATIC HALIDES.
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Bis(trialkylphosphine)nickel(0) generated in situ from bis(trialkylphosphine)nickel(II) chloride was found to be an effective catalyst for a homo-coupling of aryl, alkenyl, or heteroaromatic halides with zinc powder. The catalytic reaction proceeded very well in NMP or HMPA solvent under mild conditions to afford dehalogenative-coupling products in good yields.
- Takagi,Hayama,Sasaki
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p. 1887 - 1890
(2007/10/02)
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- Process for preparing 2,5-dimethyl-2,4-hexadiene
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2,5-Dimethyl-2,4-hexadiene is prepared by dehydrating 2,5-dimethyl-2,5-hexanediol in liquid phase. The reaction takes place by contacting 2,5-dimethyl-2,5-hexanediol, melted or dissolved in an appropriate solvent, with acids, heating the mixture at a temperature of 100° C.-160° C. and distilling off water from the reaction environment as it is being formed. The pressure can range between 1 and 10 bars.
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- Titanium Catalyzed Cyclization of 1,5-Hexadienes
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Cp2TiCl (1) and Cp2TiCl2 (2) combined with isopropylmagnesium bromide (molar ratio 1:1 and 1:2, resp.) catalyze the conversion of 1,5-hexadiene into a mixture of the five-membered ring compounds 3 and 4 as well as the linear isomeric hexadienes 5, 6, and 7.THF is most effective in both promoting cyclization as well as suppressing isomerization (3 -> 4 and 5 -> 6 or 7).The ratio of cyclic to linear products in reactions involving substituted 1,5-hexadienes is found to be dependent upon the position of the substituents.Substitution in the 2- or 2- and 5-position leads to the formation of the open-chain isomers 11 and 12 or 13 and 14, while 3,4-substituted 1,5-hexadienes react to give > 99percent of the five-membered ring systems 15 and 16 or 17 and 18.A reaction mechanism is discussed which involves Cp2TiH and Cp2(alkenyl)Ti intermediates.
- Lehmkuhl, Herbert,Tsien, Yen-Lung
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p. 2437 - 2446
(2007/10/02)
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- NICKEL-CATALYZED ULLMANN-TYPE COUPLING OF ALKENYL HALIDES WITH ZINC POWDER
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Convenient procedure for an Ullmann-type coupling of alkenyl halides using zinc powder, nickel(II) chloride, and potassium iodide and/or thiourea is presented.One double bond in the produced diene retained the configuration of a starting material, while partial cis-trans isomerization was observed in the second one.
- Takagi, Kentaro,Hayama, Naomi
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p. 637 - 638
(2007/10/02)
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- REARRANGEMENT OF CYCLOPROPYL, SUBSTITUTED VINYL AND ALKYL GROUPS TO DIVALENT CARBON.
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The relative carbenic migratory abilities of cyclopropyl, β,β-dimethylvinyl, methyl,ethyl and isopropyl groups have been determined.
- Kraska, A. R.,Cherney, L. I.,Shechter, H.
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p. 2163 - 2166
(2007/10/02)
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