Halomethyl-Metal Compounds. II. The Preparation of gem-Dihalocyclopropanes by the Reaction of Phenyl(trihalomethyl)mercury Compounds with Olefins<sup>1</sup>

Seyferth, Dietmar; Burlitch, James M.; Minasz, Richard J.; Mui, J. Y. P.; Simmons, Harry D.; Treiber, Arno; Dowd, Susan R.

doi:10.1021/ja00947a009

Cited by 187 publications

(59 citation statements)

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“…The notable difference between geometry 1 and 6 is the NPA charge of fragment CCl 2 in 6 being 0.278 higher than that of in geometry 1, because the electronegativity of the S atom is weaker than that of O, resulting in electron of S flow to the vacant p orbit of C7 easier. ReactionⅡ(3) occurred easily because of the energy of precursor complex 10, barrier transition state of TS 10-P8 and the eventual abstraction product P8 is relatively low compared to that of the corresponding geometry in reactionsⅡ(1) andⅡ (2). In addition, the NPA analysis shows that reactionⅡ(3) possesses the neucleophilic and electrophilic characters.…”

Section: (2) Insertion Reaction Of CCL 2 With C-h [Reactionⅰ(2)]mentioning

confidence: 98%

“…The carbene 2p unoccupied orbital is directly toward high negative charge O2 (NPA: −0.680) atom that is beneficial to the charge from O2 transferring to 2p unorbital. The NBO analysis shows that the main interaction between fragments CCl 2 and CH 3 OH in intermediate 1 is the lone electron pair of O2 transferring to the antibonding σ* unoccupied orbital of C7-Cl8 [LP(O2)→ σ*(C7-Cl8)] (Figure 4(a)), and their E (2) is 58 kJ⋅mol −1 beneficial to the stabilization of intermediate 1.…”

Section: Singlet Potential Energy Surfacementioning

confidence: 99%

“…The mechanisms for reactionⅡ(2) involve three kinds of transition state and three intermediates like reaction I(2). In reactionⅡ (2), the product P7 is generated by the 1,7-H transferring and the C1-C7 bond forming with the dihedral angel D2179 and D6279 changing. In course of R→7→TS 7-8 →8, the NPA charge sequence of fragment CCl 2 is 0.000→−0.004→ −0.283→−0.239.…”

Section: (2) Insertion Reaction Of CCL 2 With C-h [Reactionⅰ(2)]mentioning

confidence: 99%

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Quantum chemical study on insertion and abstraction reaction of dichlorocarbene with methyl alcohol and methyl mercaptan

Zhu

et al. 2009

Sci. China Ser. B-Chem.

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The insertion and abstraction reaction mechanisms of singlet and triplet CCl 2 with CH 3 MH (M=O, S) have been studied by using the DFT, NBO and AIM methods. The geometries of reactions, the transition state and products were completely optimized by B3LYP/6-311G(d, p). All the energy of the species was obtained at the CCSD(T)/6-311G(d, p) level. The calculated results indicated that the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CCl 2 can not only trigger the insertion reaction with C-H and M-H in four pathways, by which the products P1 [CH 3 OCHCl 2 , reactionⅠ(1)], P3[Cl 2 HCCH 2 OH, reactionⅠ(2)], P5[CH 3 SCHCl 2 , reactionⅡ(1)] and P7[Cl 2 HCCH 2 SH, reaction Ⅱ(2)] are produced respectively, but also abstract M-H, resulting P4 [CH 2 O+CH 2 Cl 2 , reactionⅠ(3)] and P8[CH 2 S+CH 2 Cl 2 , reactionⅡ(3)]. In addition, the important geometries in domain pathways have been studied by AIM and NBO theories.

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Section: (2) Insertion Reaction Of CCL 2 With C-h [Reactionⅰ(2)]mentioning

confidence: 98%

Section: Singlet Potential Energy Surfacementioning

confidence: 99%

Section: (2) Insertion Reaction Of CCL 2 With C-h [Reactionⅰ(2)]mentioning

confidence: 99%

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Quantum chemical study on insertion and abstraction reaction of dichlorocarbene with methyl alcohol and methyl mercaptan

Zhu

et al. 2009

Sci. China Ser. B-Chem.

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“…Herein, the reactions of carbene with mulriple bond, such as , and have been reported systemically [4][5][6] . Also, the addition reactions between dihalocarbenes and carbonyl compounds have been studied more and more deeply [7][8][9] .…”

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confidence: 99%

Density functional theory study on the insertion reaction mechanism of dibromocarbene with formaldehyde

Kang

et al. 2007

CHINESE SCI BULL

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The insertion reaction mechanism of CBr 2 with CH 3 CH 2 O has been studied by using the B3LYP/6-311G(d) and CCSD(T)/6-311G(d) at single point. The geometries of reactions, transition state and products were completely optimized. All the transition state is verified by the vibrational analysis and the internal reaction coordinate (IRC) calculations. The results show that reaction (1) is the dominant reaction path, which proceeds via two steps: i) two reactants form an intermediate (IM1), which is an exothermal reaction of 8.62 kJ·mol −1 without energy barrier; ii) P1 is obtained via the TS1 and the H-shift, in which the energy barrier is 44.53 kJ·mol −1 . The statistical thermodynamics and Eyring transition state theory with Wigner correction are used to study the thermodynamic and kinetic characters of this reaction in temperature range from 100 to 2200 K. The results show that the appropriate reaction temperature ranges from 200 to 1900 K at 1.0 atm, in which the reaction has a bigger spontaneity capability, equilibrium constant (K) and higher rate constant (k).dibromocarbene, formaldehyde, insertion reaction, density functional theory, thermodynamic and kinetic characters Carbene has been paid more attention to because it has some advantages, such as significant role in medicament synthesization and tensile annulet, and can speed up the reaction and make the reaction readily [1][2][3] . Herein, the reactions of carbene with mulriple bond, such as , and have been reported systemically [4][5][6] . Also, the addition reactions between dihalocarbenes and carbonyl compounds have been studied more and more deeply [7][8][9] . Methods of calculating quantum chemistry are effective tool to study the mechanisms of reactions [10][11][12] and further, the cycloaddition reactions of carbene with formaldehyde have been studied deeply by using calculating methods of quantum [13,14] . The insertion reactions between carbene and organic compounds also are reported [15,16] . Recently, the insertion reactions of carbene with ethers have been studied systemically [17][18][19] . However, to our knowledge, up to the present, there have been few literatures on the study of the insertion reactions between the carbene and formaldehyde. In the present work, both the insertion reaction mechanism between singlet CBr 2 and CH 2 O and the characters of thermodynamics and kinetics have been studied by using density functional theory (DFT) in B3LYP/6-311G(d) level. Moreover, our study can make up for the shortage of the study on insertion reaction between CBr 2 and CH 2 O in theories and experiments. Calculation methodsB3LYP/6-311G(d) implemented in the Gaussian 2003 package were employed to locate all the stationary points along the reaction pathways. Full optimization and vibrational analysis were done for the stationary points on the reaction profile. Zero-point energy and

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“…Wir verwendeten eine modifizierte Vorschrift des Verfahrens von Jefford et al [31], welche es erlaubte, 10 in 5 ± 10-g-Quantitäten herzustellen. Bei der DibromocarbenAddition an 10 3 11 waren aufgrund von Vorversuchen nach Seyferth et al [17] Schwierigkeiten zu erwarten, doch führt das Phasentransfer-Verfahren nach Makosza [19] mit überraschend hohen Ausbeuten (80%) zu 9. Auch die abschliessende CuCl 2 -induzierte Carben-Dimerisierung [14] [1] von 11 zu 5 liess sich unter StandardBedingungen 9 ) mit mässigen Ausbeuten (23%) realisieren.…”

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Synthese und1H-NMR-Analyse von Triafulvalen-Vorstufen

Huwyler¹,

Li²,

Bönzli³

et al. 1999

HCA

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Halomethyl-Metal Compounds. II. The Preparation of gem-Dihalocyclopropanes by the Reaction of Phenyl(trihalomethyl)mercury Compounds with Olefins¹

Cited by 187 publications

References 1 publication

Quantum chemical study on insertion and abstraction reaction of dichlorocarbene with methyl alcohol and methyl mercaptan

Quantum chemical study on insertion and abstraction reaction of dichlorocarbene with methyl alcohol and methyl mercaptan

Density functional theory study on the insertion reaction mechanism of dibromocarbene with formaldehyde

Synthese und1H-NMR-Analyse von Triafulvalen-Vorstufen

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Halomethyl-Metal Compounds. II. The Preparation of gem-Dihalocyclopropanes by the Reaction of Phenyl(trihalomethyl)mercury Compounds with Olefins1

Cited by 187 publications

References 1 publication

Quantum chemical study on insertion and abstraction reaction of dichlorocarbene with methyl alcohol and methyl mercaptan

Quantum chemical study on insertion and abstraction reaction of dichlorocarbene with methyl alcohol and methyl mercaptan

Density functional theory study on the insertion reaction mechanism of dibromocarbene with formaldehyde

Synthese und1H-NMR-Analyse von Triafulvalen-Vorstufen

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Product

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Halomethyl-Metal Compounds. II. The Preparation of gem-Dihalocyclopropanes by the Reaction of Phenyl(trihalomethyl)mercury Compounds with Olefins¹