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_7109027
_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 H12 Cl2 N2 O4'
_chemical_formula_sum            'C14 H12 Cl2 N2 O4'
_chemical_formula_weight         343.16
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 112.479(7)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   8.4490(5)
_cell_length_b                   21.9722(12)
_cell_length_c                   8.5158(6)
_cell_measurement_reflns_used    3678
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      28.5309
_cell_measurement_theta_min      3.0277
_cell_volume                     1460.78(17)
_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 0.983
_diffrn_measured_fraction_theta_max 0.834
_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  0.0288
_diffrn_reflns_av_sigmaI/netI    0.0342
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            9235
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         28.59
_diffrn_reflns_theta_min         3.03
_exptl_absorpt_coefficient_mu    0.464
_exptl_absorpt_correction_T_max  0.875
_exptl_absorpt_correction_T_min  0.840
_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    1.560
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             704
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.20
_refine_diff_density_max         0.305
_refine_diff_density_min         -0.237
_refine_diff_density_rms         0.052
_refine_ls_extinction_coef       0.0018(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     205
_refine_ls_number_reflns         3125
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0467
_refine_ls_R_factor_gt           0.0335
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0233P)^2^+0.7057P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0681
_refine_ls_wR_factor_ref         0.0753
_reflns_number_gt                2589
_reflns_number_total             3125
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            c3cc39147g.txt
_cod_data_source_block           mjh75_3f
_cod_original_cell_volume        1460.78(16)
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               7109027
_computing_special_details
;
TITL mjh75 in P2(1)/c
CELL 0.71073 8.4490 21.9722 8.5158 90.000 112.479 90.000
ZERR 4.00 0.0005 0.0012 0.0006 0.000 0.007 0.000
LATT 1
SYMM -X, 0.5+Y, 0.5-Z
SFAC C H N O CL
UNIT 56 48 8 16 8
TEMP -123
SIZE 0.30 0.30 0.20
L.S. 8
BOND $H
CONF
FMAP 2
PLAN 5
HTAB O2 O3_$1
EQIV $1 x+1, y, z+1
HTAB O2 O1
ACTA 50
WGHT 0.023300 0.705700
EXTI 0.001845
FVAR 0.71085
CL1 5 0.124584 0.380698 0.493212 11.00000 0.02169 0.03318 =
0.02095 -0.00057 0.00909 0.00017
CL2 5 0.023977 0.463829 0.703201 11.00000 0.02307 0.02638 =
0.02973 -0.00104 0.00946 0.00372
N1 3 0.604429 0.434464 0.931138 11.00000 0.01955 0.02547 =
0.02153 -0.00396 0.00751 -0.00180
N2 3 -0.640831 0.287221 0.236762 11.00000 0.02448 0.03814 =
0.02144 0.00205 0.00787 -0.00831
O1 4 0.345717 0.355090 0.946003 11.00000 0.02146 0.05044 =
0.03364 0.01954 0.00198 -0.00511
O2 4 -0.002843 0.352503 0.891043 11.00000 0.02045 0.05239 =
0.02152 0.00497 0.00653 -0.00206
H2 2 0.092014 0.345349 0.979581 11.00000 0.05413
O3 4 -0.759672 0.320903 0.227845 11.00000 0.02006 0.07092 =
0.02350 -0.00668 0.00374 0.00566
O4 4 -0.657174 0.243184 0.145081 11.00000 0.03991 0.03796 =
0.04385 -0.01531 0.00753 -0.01441
C1 1 0.687683 0.392612 1.071904 11.00000 0.02202 0.03548 =
0.02884 0.00081 0.00481 -0.00009
AFIX 137
H1A 2 0.810353 0.401857 1.123664 11.00000 -1.50000
H1B 2 0.671739 0.350694 1.029355 11.00000 -1.50000
H1C 2 0.636829 0.397199 1.157158 11.00000 -1.50000
AFIX 0
C2 1 0.687967 0.479299 0.887080 11.00000 0.02343 0.03134 =
0.02949 -0.00872 0.01205 -0.00761
AFIX 43
H2A 2 0.806047 0.488583 0.944232 11.00000 -1.20000
AFIX 0
C3 1 0.577419 0.509558 0.747571 11.00000 0.03407 0.02712 =
0.03181 -0.00162 0.01794 -0.00577
AFIX 43
H3A 2 0.604638 0.542985 0.691688 11.00000 -1.20000
AFIX 0
C4 1 0.418038 0.482151 0.703235 11.00000 0.02657 0.02683 =
0.02718 0.00002 0.01128 0.00173
AFIX 43
H4A 2 0.316074 0.493543 0.611235 11.00000 -1.20000
AFIX 0
C5 1 0.434306 0.435176 0.817259 11.00000 0.01852 0.02623 =
0.02055 -0.00234 0.00752 0.00046
C6 1 0.311350 0.392670 0.833104 11.00000 0.01899 0.02915 =
0.02253 0.00205 0.00719 0.00129
C7 1 0.123237 0.392346 0.699839 11.00000 0.01862 0.02570 =
0.01951 0.00272 0.00763 0.00308
C8 1 0.021697 0.339900 0.739647 11.00000 0.01737 0.02776 =
0.02336 0.00363 0.00728 0.00177
AFIX 13
H8A 2 0.091060 0.301798 0.756958 11.00000 -1.20000
AFIX 0
C9 1 -0.152048 0.328157 0.602107 11.00000 0.01803 0.02148 =
0.02371 0.00331 0.00880 0.00084
C10 1 -0.172091 0.282081 0.484963 11.00000 0.02234 0.02419 =
0.03849 -0.00134 0.01367 0.00294
AFIX 43
H10A 2 -0.074933 0.259557 0.488147 11.00000 -1.20000
AFIX 0
C11 1 -0.332081 0.268439 0.363210 11.00000 0.03001 0.02390 =
0.03232 -0.00682 0.01489 -0.00368
AFIX 43
H11A 2 -0.346039 0.237186 0.281895 11.00000 -1.20000
AFIX 0
C12 1 -0.470248 0.301594 0.363732 11.00000 0.02015 0.02536 =
0.02006 0.00148 0.00683 -0.00521
C13 1 -0.455032 0.347193 0.478986 11.00000 0.01840 0.02648 =
0.02337 0.00383 0.01005 0.00239
AFIX 43
H13A 2 -0.552912 0.369138 0.476310 11.00000 -1.20000
AFIX 0
C14 1 -0.294403 0.360492 0.598923 11.00000 0.02121 0.02423 =
0.02030 -0.00143 0.00873 0.00040
AFIX 43
H14A 2 -0.281354 0.391912 0.679569 11.00000 -1.20000
HKLF 4
REM mjh75 in P2(1)/c
REM R1 = 0.0335 for 2589 Fo > 4sig(Fo) and 0.0467 for all 3125 data
REM 205 parameters refined using 0 restraints
END
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