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«Supporting Information for One-pot odourless synthesis of thioesters via in situ generation of thiobenzoic acids using benzoic anhydrides and ...»

-- [ Page 1 ] --

Supporting Information

for

One-pot odourless synthesis of thioesters via in situ

generation of thiobenzoic acids using benzoic

anhydrides and thiourea

Mohammad Abbasi*1 and Reza Khalifeh2

Address: 1Chemistry Department, Faculty of Sciences, Persian Gulf University, Bushehr

75169, Iran and 2Department of Chemistry, Shiraz University of Technology, Shiraz,

Iran

Email: Mohammad Abbasi - abbassi@pgu.ac.ir

* Corresponding author

Analytical data

S1

General procedure A mixture of a well-powdered benzoic anhydride (1.2 mmol), thiourea (1.3 mmol) and Et3N (0.5 mL) was stirred at 40–80 °C until the starting anhydride was completely consumed and a twophase system containing Et3N and a thick brick-red liquid was formed. Then, water (1 mL) and an electron-deficient alkene or an alkyl halide (1 mmol) were added to the mixture and stirring was continued at room temperature. After consumption of starting alkene or halide (1–3 h), the crude product was extracted with EtOAc (3 × 2 mL), concentrated and purified by chromatography on silica gel respectively. The desired thioesters were produced in good to excellent yields.

S-3-Oxobutyl benzothioate (1) Colorless oil; 1H NMR (250 MHz, CDCl3) δ: 7.95-7.91 (m, 2H), 7.58-7.52 (m, 1H), 7.45-7.39 (m, 2H), 3.24 (t, J = 6.7 Hz, 2H), 2.86 (t, J = 6.7 Hz, 2H), 2.16 (s, 3H); 13C NMR (62.5 MHz, CDCl3) δ:

206.5, 191.9, 136.8, 133.5, 128.6, 127.2, 43.4, 29.9, 22.7; IR (neat): ν (cm-1) = 1717 (C=O ketone), 1655 (C=O thioester); Anal. Calcd for (C11H12O2S): C, 63.43; H, 5.81; S, 15.40. Found: C, 63.51; H, 5.77; S, 15.42.

S-2-Cyanoethyl benzothioate (2) Colorless oil; 1H NMR (250 MHz, CDCl3) δ: 7.96-7.92 (m, 2H), 7.63-7.57 (m, 1H), 7.50-7.43 (m, 2H), 3.30 (t, J = 6.9 Hz, 2H), 2.77 (t, J = 6.9 Hz, 2H); 13C NMR (62.5 MHz, CDCl3) δ: 190.8, 136.2, 134.0, 128.8, 127.4, 118.0, 24.7, 18.7; IR (neat): ν (cm-1) = 2251 (CN), 1666 (C=O thioester) ;

Anal. Calcd for (C10H9NOS): C, 62.80; H, 4.74; N, 7.32; S, 16.77. Found: C, 62.77; H, 4.83; N, 7.30;

S, 16.81.

S2 Ethyl 3-(benzoylthio)propanoate (3) Colorless oil; 1H NMR (250 MHz, CDCl3) δ: 7.88-7.85 (m, 2H), 7.51-7.45 (m, 1H), 7.38-7.32 (m, 2H), 4.09 (q, J = 7.1 Hz, 2H), 3.24 (t, J = 6.9 Hz, 2H), 2.64 (t, J = 6.9 Hz, 2H), 1.18 (t, J = 7.1 Hz, 3H);

C NMR (62.5 MHz, CDCl3) δ: 191.5, 171.7, 136.8, 133.4, 128.6, 127.2, 60.7, 34.5, 24.0, 14.2; IR (neat): ν (cm-1) = 1736 (C=O ester), 1666 (C=O thioester) ; Anal. Calcd for (C12H14O3S): C, 60.48;

H, 5.92; S, 13.46. Found: C, 60.40; H, 5.93; S, 13.50.

Butyl 3-(benzoylthio)propanoate (4) Colorless oil; 1H NMR (250 MHz, CDCl3) δ: 7.95-7.91 (m, 2H), 7.54-7.51 (m, 1H), 7.44-7.38 (m, 2H), 4.09 (t, J = 6.6 Hz, 2H), 3.30 (t, J = 7.0 Hz, 2H), 2.71 (t, J = 7.0 Hz, 2H), 1.65-1.54 (m, 2H), 1.43-1.31 (m, 2H), 0.90 (t, J = 7.3 Hz, 3H); C NMR (62.5 MHz, CDCl3) δ: 191.5, 171.8, 136.8, 133.5, 128.6, 127.2, 64.7, 34.5, 30.6, 24.1, 19.1, 13.7; IR (neat): ν (cm-1) = 1732 (C=O ester), 1666 (C=O thioester); Anal. Calcd for (C14H18O3S): C, 63.13; H, 6.81; S, 12.04. Found: C, 63.19; H, 6.85; S, 11.98.

The IR spectrum of the product showed characteristic signal of ester functional group (1732 cm and phenyl thioester (1666 cm-1). The 1H-NMR spectrum of this compound consists of four triplet signals at 0.90, 2.71, 3.30 and 4.09 ppm which were respectively correlated to the resonances of CH3, CH2CO, CH2S and CH2O hydrogen atoms. It is also consists of multiple resonances between 1.31-1.43, 1.54-1.65 and 7.38-7.95 ppm due to resonances of hydrogens on CH2 linked to methyl group, CH2 linked to CH2O and benzene ring. The C NMR spectrum contained 12 resonances, which were assigned to the methyl (δ = 13.7), methylenes (δ = 19.1, 24.1, 30.6, 34.5, 64.7), aromatic (δ = 127.2, 128.6, 133.5, 136.8), ester (δ = 171.8) and thioester (191.5) carbons (Figure S1).

–  –  –

S-(3-Oxobutyl) 4-methylbenzothioate (5) H NMR (250 MHz, CDCl3) δ: 7.75 (d, J = 8.1 Hz, 2H), 7.17 (d, J = 8.1 Hz, 2H), 3.14 (t, J = 6.7 Hz, 2H), 2.74 (t, J = 6.7 Hz, 2H), 2.30 (s, 3H), 2.07 (s, 3H); 13C NMR (62.5 MHz, CDCl3) δ:206.5, 191.4, 144.3, 134.3, 129.3, 127.6, 43.4, 29.9, 22.6, 21.6; IR (neat): ν (cm-1) = 1717 (C=O ketone), 1659 (C=O thioester); Anal. Calcd for (C12H14O2S): C, 64.83; H, 6.35; S, 14.42. Found: C, 64.80; H, 6.43;

S, 14.47.

S-(2-Cyanoethyl) 4-methylbenzothioate (6) H NMR (250 MHz, CDCl3) δ: 7.77 (d, J = 8.1 Hz, 2H), 7.18 (d, J = 8.1 Hz, 2H), 3.20 (t, J = 7 Hz, 2H), 2.68 (t, J = 7 Hz, 2H), 2.33 (s, 3H); C NMR (62.5 MHz, CDCl3) δ:190.1, 145.0, 133.7, 129.5, 127.4, 118.1, 24.7, 21.7, 18.7; IR (neat) : ν (cm-1) =2253 (CN), 1663 (C=O thioester); Anal. Calcd for (C11H11NOS): C, 64.36; H, 5.40; N, 6.82; S, 15.62. Found: C, 64.41; H, 5.35; N, 6.82; S, 15.70.

Ethyl 3-((4-methylbenzoyl)thio)propanoate (7) H NMR (250 MHz, CDCl3) δ: 7.76 (d, J = 8.1 Hz, 2H), 7.14 (d, J = 8.1 Hz, 2H), 4.08 (q, J = 7.1 Hz, 2H), 3.22 (t, J = 7 Hz, 2H), 2.63 (t, J = 7 Hz, 2H), 2.31 (s, 3H), 1.18 (t, J = 7.1 Hz, 3H); 13C NMR (62.5 MHz, CDCl3) δ:191.1, 171.7, 144.3, 134.3, 129.3, 127.3, 60.7, 34.5, 23.9, 21.6, 14.2; IR (neat) : ν (cm-1) =1736 (C=O ester), 1659 (C=O thioester); Anal. Calcd for (C13H16O3S): C, 61.88;

H, 6.39; S, 12.71. Found: C, 61.93; H, 6.33; S, 12.66.

–  –  –





2H, 3.29 (t, J = 7.0 Hz, 2H), 2.71 (t, J = 7.0 Hz, 2H), 2.39 (s, 3H), 1.66-1.54 (m, 2H), 1.44-1.35 (m, 2H), 0.91 (t, J = 7.3 Hz, 3H); C NMR (62.5 MHz, CDCl3) δ:191.1, 171.8, 144.3, 134.3, 129.3, 127.3, 64.7, 34.6, 30.6, 24.0, 21.7, 19.1, 13.7; IR (neat) : ν (cm-1) =1736 (C=O ester), 1663 (C=O thioester); Anal. Calcd for (C15H20O3S): C, 64.26; H, 7.19; S, 11.44. Found: C, 64.33; H, 7.24; S, 11.38.

S-(3-Oxobutyl) 4-chlorobenzothioate (9) H NMR (250 MHz, CDCl3) δ: 7.80 (d, J = 8.7 Hz, 2H), 7.34 (d, J = 8.7 Hz, 2H), 3.20 (t, J = 6.7 Hz, 2H), 2.80 (t, J = 6.7 Hz, 2H), 2.10 (s, 3H); 13C NMR (62.5 MHz, CDCl3) δ: 206.3, 190.7, 139.8, 135.2, 128.9, 128.5, 43.3, 29.9, 22.8; IR (neat): ν (cm-1) =1717 (C=O ketone), 1666 (C=O thioester); Anal. Calcd for (C11H11ClO2S): C, 54.43; H, 4.57; S, 13.21. Found: C, 54.50; H, 4.53; S, 13.13.

S-(2-Cyanoethyl) 4-chlorobenzothioate (10) H NMR (250 MHz, CDCl3) δ: 7.82 (d, J = 8.7 Hz, 2H), 7.37 (d, J = 8.7 Hz, 2H), 3.24 (t, J = 6.9 Hz, 2H), 2.70 (t, J = 6.9 Hz, 2H); C NMR (62.5 MHz, CDCl3) δ:189.4, 140.5, 134.5, 129.1, 128.7, 117.9, 28.8, 18.6; IR (neat): ν (cm-1) =2249 (CN), 1659 (C=O thioester); Anal. Calcd for (C10H8ClNOS): C, 53.22; H, 3.57; N; 6.21; S, 14.21. Found: C, 53.20; H, 3.64; N; 6.29; S, 14.14.

Ethyl 3-((4-chlorobenzoyl)thio)propanoate (11) H NMR (250 MHz, CDCl3) δ: 7.81 (d, J = 8.5 Hz, 2H), 7.34 (d, J = 8.5 Hz, 2H), 4.10 (q, J = 7.1 Hz, 2H), 3.24 (t, J = 6.9 Hz, 2H), 2.65 (t, J = 6.9 Hz, 2H), 1.19 (t, J = 7.1 Hz, 3H); 13C NMR (62.5 MHz, CDCl3) δ:190.4, 171.6, 139.9, 135.1, 128.9, 128.6, 60.8, 34.4, 23.9, 14.2; IR (neat): ν (cm-1) =

–  –  –

Found: C, 52.91; H, 4.87; S, 11.75.

Butyl 3-((4-chlorobenzoyl)thio)propanoate (12) H NMR (250 MHz, CDCl3) δ: 7.81 (d, J = 8.6 Hz, 2H), 7.34 (d, J = 8.6 Hz, 2H), 4.04 (t, J = 6.6 Hz, 2H), 3.24 (t, J = 6.9 Hz, 2H), 2.65 (t. J = 6.9 Hz, 2H)1.59-1.58 (m, 2H), 1.37-1.22 (m, 2H), 0.84 (t, J = 7.3 Hz, 3H); 13C NMR (62.5 MHz, CDCl3) δ: 190.3, 171.7, 139.8, 135.1, 128.9, 128.5, 64.7, 34.4, 30.6, 24.2, 19.1, 13.7; IR (neat): ν (cm-1) =1732 (C=O ester), 1666 (C=O thioester); Anal. Calcd for (C14H17ClO3S): C, 55.90; H, 5.70; S, 10.66. Found: C, 55.96; H, 5.61; S, 10.71.

S-(3-Oxobutyl) 4-methoxybenzothioate (13) H NMR (250 MHz, CDCl3) δ: 7.84 (d, J = 8.9 Hz, 2H), 6.83 (d, J = 8.9 Hz, 2H), 3.77 (s, 3H), 3.15 (t, J = 6.8 Hz, 2H), 2.78 (t, J = 6.8 Hz, 2H), 2.06 (s, 3H); 13C NMR (62.5 MHz, CDCl3) δ: 206.6, 190.3, 163.8, 132.8, 129.3, 113.8, 55.5, 43.6, 29.9, 22.6; IR (neat): ν (cm-1) =1717 (C=O ketone), 1651 (C=O thioester); Anal. Calcd for (C12H14O3S): C, 60.48; H, 5.92; S, 13.46. Found: C, 60.55; H, 6.00;

S, 13.39.

S-(2-Cyanoethyl) 4-methoxybenzothioate (14) H NMR (250 MHz, CDCl3) δ: 7.85 (d, J = 8.9 Hz, 2H), 6.86 (d, J = 8.9 Hz, 2H), 3.79 (s, 3H), 3.20 (t, J = 6.9 Hz, 2H), 2.68 (t, J = 6.9 Hz, 2H); 13C NMR (62.5 MHz, CDCl3) δ:188.9, 164.2, 129.6, 129.0, 118.1, 114.0, 55.6, 24.6, 18.8; IR (neat): ν (cm-1) =2249 (CN), 1651(C=O thioester); Anal. Calcd for (C11H11NO2S): C, 59.71; H, 5.01; N, 6.33; S, 14.49. Found: C, 59.70; H, 5.09; N, 6.39; S, 14.42.

Ethyl 3-((4-methoxybenzoyl)thio)propanoate (15) H NMR (250 MHz, CDCl3) δ: 7.85(d, J = 9 Hz, 2H), 6.84 (d, J = 9 Hz, 2H), 4.09 (q, J = 7.1 Hz, 2H), 3.78 (s, 3H), 3.22 (t, J = 7 Hz, 2H), 2.64 (t, J = 7 Hz, 2H), 1.19 (t, J = 7.1 Hz, 3H); 13C NMR (62.5

–  –  –

(cm-1) =1736 (C=O ester), 1659 (C=O thioester); Anal. Calcd for (C13H16O4S): C, 58.19; H, 6.01; S,

11.95. Found: C, 58.13; H, 5.97; S, 11.98.

Butyl 3-((4-methoxybenzoyl)thio)propanoate (16) H NMR (250 MHz, CDCl3) δ: 7.86 (d, J = 8.9 Hz, 2H), 6.84 (d, J = 8.9 Hz, 2H), 4.04 (t, J = 6.6 Hz, 2H), 3.79 (s, 3H), 3.22 (t, J = 6.9 Hz, 2H), 2.65 (t, J = 6.9 Hz, 2H), 1.61-1.49 (m, 2H), 1.35-1.18 (m, 2H), 0.82 (t, J = 7.3 Hz, 3H); C NMR (62.5 MHz, CDCl3) δ:190.0, 171.9, 163.8, 129.7, 129.4, 113.8, 64.6, 55.5, 34.6, 30.6, 23.9, 19.1, 13.7; IR (neat): ν (cm-1) =1732 (C=O ester), 1659 (C=O thioester); Anal. Calcd for (C15H20O4S): C, 60.79; H, 6.80; S, 10.82. Found: C, 60.85; H, 6.80; S, 10.84.

S-Decyl benzothioate (17) H NMR (250 MHz, CDCl3) δ: 7.91-7.86 (m, 2H), 7.51-7.33 (m, 3H), 2.99 (t, J = 7.3 Hz, 2H), 1.65m, 2H), 1.38-1.19 (m, 14H), 0.83-0.78 (m, 3H); 13C NMR (62.5 MHz, CDCl3) δ:192.0, 137.3, 133.1, 128.9, 127.4, 31.9, 29.6, 29.6, 29.5, 29.3, 29.2, 29.0, 29.0, 22.7, 14.1; IR (neat): ν (cm-1) =1666 (C=O thioester); ; Anal. Calcd for (C17H26OS): C, 73.33; H, 9.41; S, 11.52. Found: C, 73.31;

H, 9.48; S, 11.46.

S-(2-Methylallyl) benzothioate (18) H NMR (250 MHz, CDCl3) δ: 7.92-7.88 (m, 2H), 7.51-7.32 (m, 3H), 4.97-4.96 (m, 1H), 4.82-4.80 (m, 1H), 3.67 (s, 2H), 1.74 (s, 3H); C NMR (62.5 MHz, CDCl3) δ: 191.4, 140.7, 137.0, 133.4, 128.6, 127.3, 114.3, 35.8, 21.3; IR (neat): ν (cm-1) = 1666 (C=O thioester); Anal. Calcd for (C11H12OS): C, 68.71; H, 6.29; S, 16.68. Found: C, 68.67; H, 6.36; S, 16.60.

–  –  –

127.3, 78.9, 71.1, 17.5; IR (neat): ν (cm-1) =3294, 2125, 1670; Anal. Calcd for (C10H8OS): C, 68.15;

H, 4.58; S, 18.19. Found: C, 68.20; H, 4.55; S, 18.26.

S-Methyl benzothioate (20) H NMR (250 MHz, CDCl3) δ: 7.91-7.87 (m, 2H), 7.52-7.32 (m, 3H), 2.39 (s, 3H); 13C NMR (62.5 MHz, CDCl3) δ: 192.4, 137.7, 133.3, 128.6, 127.1, 11.7; IR (neat): ν (cm-1) =1666; Anal. Calcd for (C8H8OS): C, 63.13; H, 5.30; S, 21.07. Found: C, 63.05; H, 5.31; S, 21.08.

S-Octyl benzothioate (21) H NMR (250 MHz, CDCl3) δ: 7.77-7.71 (m, 2H), 7.33-7.16 (m, 3H), 2.83 (t, J = 7.3 Hz, 2H), 1.46m, 2H), 1.21-1.04 (m, 10H), 0.67-0.62 (m, 3H); 13C NMR (62.5 MHz, CDCl3) δ:192.0, 137.3, 133.2, 128.5, 127.2, 31.8, 29.5, 29.3, 29.2, 29.1, 29.0, 22.7, 14.1; IR (neat): ν (cm-1) =1666; Anal.

Calcd for (C15H22OS): C, 71.95; H, 8.86; S, 12.81. Found: C, 72.03; H, 8.81; S, 12.77.

S-4-Methylbenzyl benzothioate (22) H NMR (250 MHz, CDCl3) δ: 7.86-7.83 (m, 2H), 7.44-7.21 (m, 3H), 7.15 (d, J = 8 Hz, 2H), 6.99 (d, J = 8 Hz, 2H), 4.17 (s, 2H), 2.19 (s, 3H); 13C NMR (62.5 MHz, CDCl3) δ: 191.4, 137.1, 136.9, 134.4, 133.4, 129.4, 128.9, 128.7, 127.6, 33.2, 21.2; IR (neat): ν (cm-1) =1663; Anal. Calcd for (C15H14OS): C, 74.34; H, 5.82; S, 13.23. Found: C, 74.33; H, 5.90; S, 13.20.

S-Benzyl 4-methylbenzothioate (23) H NMR (250 MHz, CDCl3) δ: 7.77 (d, J = 8.1 Hz, 2H), 7.30-7.17 (m, 5H), 7.14 (d, J = 8.1 Hz, 2H), 4.21 (s, 2H), 2.29 (s, 3H); 13C NMR (62.5 MHz, CDCl3) δ:190.8, 144.4, 137.7, 134.3, 129.3, 129.0,

–  –  –

5.82; S, 13.23. Found: C, 74.27; H, 5.90; S, 13.30.

S-Prop-2-yn-1-yl 4-methylbenzothioate (24) H NMR (250 MHz, CDCl3) δ: 7.77 (d, J = 8.2 Hz, 2H), 7.17 (d, J = 8.2 Hz, 2H), 3.73 (d, J = 2.7 Hz, 2H), 2.33 (s, 3H), 2.14 (t, J = 2.7 Hz, 1H); C NMR (62.5 MHz, CDCl3) δ:189.6, 144.7, 133.7, 129.4, 127.4, 79.0, 71.0, 21.7, 17.3; IR (neat): ν (cm-1) =3294, 2122, 1666; Anal. Calcd for (C11H10OS): C, 69.44; H, 5.30; S, 16.85. Found: C, 69.36; H, 5.33; S, 16.91.

S-Octyl 4-methylbenzothioate (25) H NMR (250 MHz, CDCl3) δ: 7.69 (d, J = 8.2 Hz, 2H), 7.05 (d, J = 8.2 Hz, 2H), 2.87 (t, J = 7.3 Hz, 2H), 2.22 (s, 3H), 1.54-1.43 (m, 2H), 1.24-1.10 (m, 10H), 0.72-0.68 (m, 3H); 13C NMR (62.5 MHz, CDCl3) δ: 190.8, 144.0, 134.8, 129.2, 127.2, 31.8, 29.6, 29.2, 29.1, 29.0, 22.6, 21.6, 14.1; IR (neat): ν (cm-1) =1663; Anal. Calcd for (C16H24OS): C, 72.67; H, 9.15; S, 12.13. Found: C, 72.74; H, 9.10; S, 12.08.

S-Methyl 4-methylbenzothioate (26) H NMR (250 MHz, CDCl3) δ: 7.78 (d, J = 8.1 Hz, 2H), 7.18 (d, J = 8.1 Hz, 2H), 2.38 (s, 3H), 2.35 (s, 3H); 13C NMR (62.5 MHz, CDCl3) δ: 192.0, 144.1, 134.5, 129.2, 127.2, 21.6, 11.6; IR (neat): ν (cmAnal. Calcd for (C9H10OS): C, 65.02; H, 6.06; S, 19.29. Found: C, 65.01; H, 6.15; S, 19.22.

S-(2-Methylallyl) 4-methylbenzothioate (27) H NMR (250 MHz, CDCl3) δ: 7.79 (d, J = 8.1 Hz, 2H), 7.14 (d, J = 8.1 Hz, 2H), 4.95 (s, 1H), 4.80m, 1H), 3.62 (s, 2H), 2.31 (s, 3H), 1.73 (s, 3H); 13C NMR (62.5 MHz, CDCl3) δ:191.0, 144.2, 140.9, 134.4, 129.3, 127.3, 114.2, 35.7, 21.7, 21.3; IR (neat) : ν (cm-1) =1659; Anal. Calcd for (C12H14OS): C, 69.86; H, 6.84; S, 15.54. Found: C, 69.80; H, 6.88; S, 15.61.

–  –  –

δ:191.0, 139.5, 135.6, 128.8, 128.5, 31.9, 30.0, 29.5, 29.5, 29.3, 29.2, 29.1, 28.9, 22.7, 14.1; IR (neat): ν (cm-1) =1666; Anal. Calcd for (C17H25ClOS): C, 65.26; H, 8.05; S, 10.25. Found: C, 65.33;

H, 8.13; S, 10.16.

S-Methyl 4-chlorobenzothioate (29) H NMR (250 MHz, CDCl3) δ: 7.75 (d, J = 8.7 Hz, 2H), 7.26 (d, J = 8.7 Hz, 2H), 2.32 (s, 3H); C NMR (62.5 MHz, CDCl3) δ: 191.2, 139.6, 135.3, 128.9, 128.5, 11.8; IR (neat): ν (cm-1) =1666;

Anal. Calcd for (C8H7ClOS): C, 51.48; H, 3.78; S, 17.18. Found: C, 51.51; H, 3.86; S, 17.10.

S-(2-Methylallyl) 4-chlorobenzothioate (30) H NMR (250 MHz, CDCl3) δ: 7.83 (d, J = 8.5 Hz, 2H), 7.34 (d, J = 8.5 Hz, 2H), 4.96 (s, 1H), 4.82 (s, 1H), 3.67 (s, 2H), 1.73 (s, 3H); 13C NMR (62.5 MHz, CDCl3) δ: 190.2, 140.5, 139.7, 135.3, 128.9, 128.6, 114.5, 36.0, 21.3; IR (neat): ν (cm-1) =1666; Anal. Calcd for (C11H11ClOS): C, 58.27; H, 4.89;

S, 14.14. Found: C, 58.35; H, 4.81; S, 14.09.



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«Valley Philanthropy Forum Hiding in Plain Sight San Fernando Valley Santa Clarita Valley Tuesday December 3, 2013 Universal City Hilton Hotel Edison International is proud to sponsor the San Fernando Valley Community Foundation’s Valley Philanthropy Forum 2013. LIFE, POWERED BY EDISON The Southern California Gas Company a Sempra Energy Utility is proud to be a supporter of the Valley Philanthropy Forum Valley Philanthropy Forum 2013 Hiding in Plain Sight Philanthropy in the San Fernando and...»

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«A 3D Simulator of Multiple Legged Robots based on USARSim Marco Zaratti, Marco Fratarcangeli, Luca Iocchi Dipartimento di Informatica e Sistemistica Universit` “La Sapienza”, Rome, Italy a Via Salaria 113 00198 Rome Italy E-mail: lastname@dis.uniroma1.it Abstract. This paper presents a flexible 3D simulator able to reproduce the appearance and the dynamics of generic legged robots and objects in the environment at full frame rate (30 frames per second). Such a simulator extends and...»

«Biographical Details of Directors and Senior Management Executive Directors Dr the Hon. LEE Shau Kee, GBM, DBA (Hon), DSSc (Hon), LLD (Hon), aged 83, is the founder of the Company. He has been the Chairman and Managing Director of the Company since 1976 and has been engaged in property development in Hong Kong for more than 55 years. He is also the Chairman of the Nomination Committee and a member of the Remuneration Committee of the Company. He is the founder and the chairman and managing...»

«This chapter will appear in: Sustainable Security: Rethinking American National Security Strategy, edited by Jeremi Suri and Benjamin Valentino. Copyright © 2016 The Tobin Project. Reproduced with the permission of Oxford University Press. Please note that the final chapter in the published volume may differ slightly from this text Climate Change and US National Security: Sustaining Security Admidst Unsustainability Joshua William Busby Climate Change and US National Security: Sustaining...»

«Handbook of Abhidhamma Studies by Venerable Sayādaw U Sīlānanda (Volume III) First edition: October 2012 © 2012 Copyright by SBVMS. Selangor Buddhist Vipassana Meditation Society (SBVMS) 23, Jalan SS3/37, 47300 Petaling Jaya, Selangor, West Malaysia. Printed and Bound in Kuala Lumpur, Malaysia by Majujaya Indah Sdn Bhd Tel: 034291 6001 / 6002 Fax: 034292 2053 Sabbadānaṃ dhammadānaṃ jināti The Gift of Dhamma excels all gifts Handbook of Abhidhamma Studies Venerable Sayādaw U...»

«England’s ‘examinations industry’: deterioration and decay A report from HMC on endemic problems with marking, awarding, re-marks and appeals at GCSE and A level, 2007-12 September 2012 Contents Preface Letter to the Secretary of State SUMMARY The nature of the problems 1 Overall diagnosis Hidden problems – their nature and scope What is the evidence and who suffers?The school sample Methods of collecting data Who suffers? What is to blame? What should be done? Seven failings of...»

«FOR PUBLICATION UNITED STATES COURT OF APPEALS FOR THE NINTH CIRCUIT  DAVID LAHOTI, an individual, Plaintiff-Appellant, No. 08-35001  v. D.C. No. CV-06-01132-JLR VERICHECK, INC, a Georgia Corporation, OPINION  Defendant-Appellee. Appeal from the United States District Court for the Western District of Washington James L. Robart, District Judge, Presiding Argued and Submitted March 9, 2009—Seattle, Washington Filed November 16, 2009 Before: William A. Fletcher, Ronald M. Gould, and...»





 
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