Reduction of 2,2,2-trichloro-1-arylethanones by RMgX: mechanistic investigation and the synthesis of substituted alpha,alpha-dichloroketones
Ali H. Essa; Reinner I. Lerrick; Floriana Tuna; Ross W. Harrington; William Clegg; Michael J. Hall; Chem.Commun. 49 (2013) 2756–; doi:10.1039/c3cc39147g

data_7109025
_publ_section_title
;
 Reduction of 2,2,2-trichloro-1-arylethanones by RMgX: mechanistic
 investigation and the synthesis of substituted
 alpha,alpha-dichloroketones
;
_journal_name_full               Chem.Commun.
_journal_page_first              2756
_journal_paper_doi               10.1039/c3cc39147g
_journal_volume                  49
_journal_year                    2013
_chemical_formula_moiety         'C14 H13 Cl2 N O2'
_chemical_formula_sum            'C14 H13 Cl2 N O2'
_chemical_formula_weight         298.15
_space_group_IT_number           60
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  '-P 2n 2ab'
_symmetry_space_group_name_H-M   'P b c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   21.1956(11)
_cell_length_b                   7.5271(4)
_cell_length_c                   17.1302(14)
_cell_measurement_reflns_used    3920
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      28.61
_cell_measurement_theta_min      2.87
_cell_volume                     2733.0(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET)
(compiled Jan 20 2011,15:58:25)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET)
(compiled Jan 20 2011,15:58:25)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET)
(compiled Jan 20 2011,15:58:25)
;
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL and local programs'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_structure_solution    'Bruker SHELXTL'
_diffrn_ambient_temperature      150(2)
_diffrn_detector_area_resol_mean 10.3968
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.847
_diffrn_measurement_device_type
'Oxford Diffraction Gemini A Ultra diffractometer'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  none
_diffrn_radiation_source         'sealed tube with Enhance optics'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0337
_diffrn_reflns_av_sigmaI/netI    0.0342
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            9986
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         28.64
_diffrn_reflns_theta_min         2.87
_exptl_absorpt_coefficient_mu    0.471
_exptl_absorpt_correction_T_max  0.912
_exptl_absorpt_correction_T_min  0.872
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET)
(compiled Jan 20 2011,15:58:25)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.449
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1232
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_refine_diff_density_max         0.489
_refine_diff_density_min         -0.239
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     177
_refine_ls_number_reflns         2977
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0606
_refine_ls_R_factor_gt           0.0429
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0457P)^2^+1.9653P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0981
_refine_ls_wR_factor_ref         0.1091
_reflns_number_gt                2347
_reflns_number_total             2977
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            c3cc39147g.txt
_cod_data_source_block           mjh78_3a
_cod_database_code               7109025
_computing_special_details
;
TITL mjh78 in Pbcn
CELL 0.71073 21.1956 7.5271 17.1302 90.000 90.000 90.000
ZERR 8.00 0.0011 0.0004 0.0014 0.000 0.000 0.000
LATT 1
SYMM 0.5-X, 0.5-Y, 0.5+Z
SYMM -X, Y, 0.5-Z
SYMM 0.5+X, 0.5-Y, -Z
SFAC C H N O CL
UNIT 112 104 8 16 16
TEMP -123
L.S. 8
BOND $H
CONF
REM colourless block
SIZE 0.30 0.20 0.20
ACTA 50
FMAP 2
PLAN 5
HTAB O2 O1_$1
EQIV $1 -x+1, -y, -z
HTAB O2 O1
REM EXTI 0.000088
WGHT 0.045700 1.965300
FVAR 0.24719
CL1 5 0.368559 0.333884 0.150662 11.00000 0.03940 0.03042 =
0.02939 -0.00664 0.00728 0.00059
CL2 5 0.303536 0.113477 0.036550 11.00000 0.02713 0.03845 =
0.03323 -0.00048 -0.00362 0.00116
O1 4 0.459362 0.149001 -0.018661 11.00000 0.04668 0.06142 =
0.03804 0.01387 0.01900 0.02701
O2 4 0.472002 0.051825 0.135106 11.00000 0.02784 0.05638 =
0.02728 -0.00148 0.00118 0.00516
H2 2 0.495975 0.037739 0.097691 11.00000 0.07242
N 3 0.433981 0.479666 -0.092307 11.00000 0.04334 0.03701 =
0.03308 -0.00014 0.00513 -0.00738
C1 1 0.489974 0.406440 -0.129879 11.00000 0.04717 0.05363 =
0.04096 0.00300 0.01364 -0.01377
AFIX 137
H1A 2 0.505427 0.490119 -0.169317 11.00000 -1.50000
H1B 2 0.479270 0.293370 -0.154959 11.00000 -1.50000
H1C 2 0.522854 0.386622 -0.090612 11.00000 -1.50000
AFIX 0
C2 1 0.405114 0.630276 -0.115120 11.00000 0.07101 0.03632 =
0.04532 0.00851 0.00054 -0.00913
AFIX 43
H2A 2 0.418473 0.703330 -0.157214 11.00000 -1.20000
AFIX 0
C3 1 0.353878 0.662839 -0.069028 11.00000 0.06425 0.03437 =
0.05240 0.00548 -0.00163 0.00990
AFIX 43
H3 2 0.325645 0.760373 -0.073323 11.00000 -1.20000
AFIX 0
C4 1 0.350883 0.526582 -0.014790 11.00000 0.04341 0.03718 =
0.03564 -0.00190 -0.00002 0.00498
AFIX 43
H4 2 0.320031 0.513922 0.025052 11.00000 -1.20000
AFIX 0
C5 1 0.400891 0.411727 -0.028869 11.00000 0.03438 0.03433 =
0.02844 -0.00059 0.00185 -0.00328
C6 1 0.417676 0.245169 0.006082 11.00000 0.02894 0.03828 =
0.02518 -0.00006 0.00252 0.00249
C7 1 0.379114 0.171711 0.076380 11.00000 0.02421 0.03278 =
0.02276 -0.00519 0.00290 0.00158
C8 1 0.410355 0.003534 0.110893 11.00000 0.02813 0.03383 =
0.02297 -0.00408 -0.00088 0.00590
AFIX 13
H8 2 0.413907 -0.087706 0.068689 11.00000 -1.20000
AFIX 0
C9 1 0.375117 -0.077119 0.178795 11.00000 0.03146 0.02916 =
0.02209 -0.00297 -0.00029 0.00786
C10 1 0.392027 -0.034343 0.254656 11.00000 0.03845 0.03233 =
0.02739 -0.00466 -0.00267 0.00188
AFIX 43
H10 2 0.425807 0.045868 0.263951 11.00000 -1.20000
AFIX 0
C11 1 0.359735 -0.108404 0.316871 11.00000 0.05309 0.04293 =
0.02334 0.00195 -0.00001 0.00436
AFIX 43
H11 2 0.371271 -0.077755 0.368740 11.00000 -1.20000
AFIX 0
C12 1 0.311041 -0.226098 0.304320 11.00000 0.04962 0.04103 =
0.03369 0.01150 0.00720 0.00314
AFIX 43
H12 2 0.288966 -0.275761 0.347369 11.00000 -1.20000
AFIX 0
C13 1 0.294360 -0.271796 0.228986 11.00000 0.04324 0.03298 =
0.04687 0.00673 -0.00309 -0.00515
AFIX 43
H13 2 0.261176 -0.354067 0.219888 11.00000 -1.20000
AFIX 0
C14 1 0.326436 -0.196620 0.166989 11.00000 0.04274 0.02855 =
0.02977 -0.00366 -0.00466 0.00010
AFIX 43
H14 2 0.314818 -0.227640 0.115190 11.00000 -1.20000
HKLF 4
REM mjh78 in Pbcn
REM R1 = 0.0429 for 2347 Fo > 4sig(Fo) and 0.0606 for all 2977 data
REM 177 parameters refined using 0 restraints
END
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