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_7109028
_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 O3'
_chemical_formula_sum            'C14 H12 Cl2 N2 O3'
_chemical_formula_weight         327.16
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                88.060(6)
_cell_angle_beta                 72.636(10)
_cell_angle_gamma                80.267(8)
_cell_formula_units_Z            2
_cell_length_a                   8.8490(11)
_cell_length_b                   8.8572(6)
_cell_length_c                   9.6786(9)
_cell_measurement_reflns_used    2302
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      28.67
_cell_measurement_theta_min      3.08
_cell_volume                     713.48(13)
_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 0.998
_diffrn_measured_fraction_theta_max 0.806
_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  0.0211
_diffrn_reflns_av_sigmaI/netI    0.0369
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            5166
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         28.73
_diffrn_reflns_theta_min         3.09
_exptl_absorpt_coefficient_mu    0.466
_exptl_absorpt_correction_T_max  0.955
_exptl_absorpt_correction_T_min  0.873
_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    1.523
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       slab
_exptl_crystal_F_000             336
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.337
_refine_diff_density_min         -0.295
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         2967
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0422
_refine_ls_R_factor_gt           0.0331
_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^)+(0.0249P)^2^+0.3136P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0711
_refine_ls_wR_factor_ref         0.0768
_reflns_number_gt                2526
_reflns_number_total             2967
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            c3cc39147g.txt
_cod_data_source_block           mjh79_3g
_cod_original_cell_volume        713.48(12)
_cod_database_code               7109028
_computing_special_details
;
TITL mjh79 in P-1
CELL 0.71073 8.8490 8.8572 9.6786 88.060 72.636 80.267
ZERR 2.00 0.0011 0.0006 0.0009 0.006 0.010 0.008
LATT 1
SFAC C H N O CL
UNIT 28 24 4 6 4
TEMP -123
L.S. 8
LIST 1
FMAP 2
PLAN 5
ACTA 50
BOND $H
CONF
REM colourless slab
SIZE 0.30 0.30 0.10
REM EXTI 0.003834
WGHT 0.024900 0.313600
FVAR 0.32778 0.57907
CL1 5 -0.054903 0.286801 0.991070 11.00000 0.01467 0.03327 =
0.02611 -0.00174 -0.00435 -0.00508
CL2 5 0.180452 0.075665 0.775987 11.00000 0.02476 0.02175 =
0.02937 -0.00541 -0.01165 -0.00398
N1 3 0.409705 0.194421 1.100964 11.00000 0.01491 0.02553 =
0.02240 -0.00096 -0.00722 -0.00291
N2 3 -0.341159 0.297938 0.451947 11.00000 0.03236 0.04265 =
0.02975 -0.00047 -0.01695 -0.01037
O1 4 0.341122 0.390165 0.877189 11.00000 0.02703 0.03082 =
0.03889 0.00908 -0.01738 -0.01651
PART 1
O2 4 -0.297255 0.238774 0.339835 -21.00000 0.07414 0.05187 =
0.05016 -0.03471 -0.04648 0.02377
O3 4 -0.483851 0.357970 0.509151 21.00000 0.02239 0.10983 =
0.04242 -0.01781 -0.01349 -0.00704
PART 2
O2A 4 -0.293768 0.253606 0.322640 21.00000 0.03639 0.04959 =
0.02489 0.00030 -0.01714 -0.01173
O3A 4 -0.475656 0.283031 0.530121 -21.00000 0.02732 0.08890 =
0.04333 -0.00498 -0.01320 -0.02386
PART 0
C1 1 0.531476 0.293703 1.062678 11.00000 0.02102 0.04082 =
0.03102 0.00226 -0.01369 -0.01300
AFIX 137
H1A 2 0.604610 0.268512 1.121854 11.00000 -1.50000
H1B 2 0.479213 0.400923 1.080438 11.00000 -1.50000
H1C 2 0.592338 0.278314 0.960045 11.00000 -1.50000
AFIX 0
C2 1 0.402526 0.088253 1.204998 11.00000 0.02302 0.03390 =
0.02354 0.00021 -0.00920 0.00125
AFIX 43
H2A 2 0.471535 0.070840 1.264644 11.00000 -1.20000
AFIX 0
C3 1 0.279742 0.009211 1.211201 11.00000 0.03032 0.02652 =
0.02730 0.00501 -0.00606 -0.00322
AFIX 43
H3A 2 0.248701 -0.071090 1.275484 11.00000 -1.20000
AFIX 0
C4 1 0.209517 0.068488 1.106114 11.00000 0.02160 0.02479 =
0.02795 -0.00087 -0.00670 -0.00721
AFIX 43
H4A 2 0.122030 0.035462 1.084909 11.00000 -1.20000
AFIX 0
C5 1 0.290472 0.185252 1.037240 11.00000 0.01568 0.02176 =
0.02152 -0.00337 -0.00612 -0.00335
C6 1 0.265868 0.286784 0.922378 11.00000 0.01459 0.02087 =
0.02296 -0.00368 -0.00536 -0.00418
C7 1 0.133856 0.265371 0.852265 11.00000 0.01385 0.02113 =
0.02259 -0.00347 -0.00452 -0.00462
C8 1 0.124036 0.382154 0.733969 11.00000 0.01936 0.02435 =
0.02395 0.00139 -0.00820 -0.00657
AFIX 23
H8A 2 0.097770 0.486417 0.777558 11.00000 -1.20000
H8B 2 0.230870 0.373105 0.660823 11.00000 -1.20000
AFIX 0
C9 1 0.001283 0.363829 0.658669 11.00000 0.02015 0.02157 =
0.02171 0.00344 -0.00863 -0.00604
C10 1 -0.158754 0.432714 0.713727 11.00000 0.02350 0.02977 =
0.02326 -0.00562 -0.01010 -0.00039
AFIX 43
H10A 2 -0.190497 0.495629 0.798460 11.00000 -1.20000
AFIX 0
C11 1 -0.272454 0.411375 0.647516 11.00000 0.01913 0.03750 =
0.02409 -0.00286 -0.00683 -0.00062
AFIX 43
H11A 2 -0.382032 0.455989 0.687282 11.00000 -1.20000
AFIX 0
C12 1 -0.222066 0.323603 0.522353 11.00000 0.02345 0.02918 =
0.02208 0.00295 -0.01082 -0.00820
C13 1 -0.064538 0.257135 0.461459 11.00000 0.02984 0.02765 =
0.01858 -0.00270 -0.00842 -0.00250
AFIX 43
H13A 2 -0.032917 0.198868 0.373871 11.00000 -1.20000
AFIX 0
C14 1 0.046664 0.277201 0.530849 11.00000 0.02088 0.03073 =
0.02124 0.00036 -0.00487 -0.00070
AFIX 43
H14A 2 0.155752 0.231209 0.490769 11.00000 -1.20000
HKLF 4
REM mjh79 in P-1
REM R1 = 0.0331 for 2526 Fo > 4sig(Fo) and 0.0422 for all 2967 data
REM 210 parameters refined using 0 restraints
END
;