Electronic upplementary Material (EI) for ChemComm. This journal is The Royal ociety of Chemistry upporting Information Controllably, C C Triple Bond as One-Carbon ynthon to Assembly of Benzothiazole Framework Yubing Huang, Donghao Yan, Xu Wang, Peiqi Zhou, Wanqing Wu,* and Huanfeng Jiang* Key Laboratory of Functional Molecular Engineering of Guangdong Province, chool of Chemistry and Chemical Engineering, outh China University of Technology, Guangzhou, P. R. China E-mail: cewuwq@scut.edu.cn, jianghf@scut.edu.cn Contents A. General Methods... B. General Procedures... C. Optimization of the Reaction Conditions... D. Free Radical Verification Experiments... E. Deuterium-labeling Experiments... F. Characterization Data for Products... G. References... H. X-ray Diffraction Parameters and Data for d... I. MR pectra...
A. General Methods Melting points were determined with a Buchi Melting Point B- instrument. H and C MR spectra were recorded using a Bruker DRX- spectrometer with CDCl as solvent. The chemical shifts are referenced to signals at. and. ppm, respectively, and chloroform is solvent with TM as the internal standard. IR spectra were obtained either as potassium bromide pellets or as liquid films between two potassium bromide pellets with a Bruker TEOR spectrometer. Mass spectra were recorded on a Thermo cientific IQ gas chromatograph-mass spectrometer. The data of HRM was carried out on a high-resolution mass spectrometer (LCM- IT-TOF). TLC was performed by using commercially prepared - mesh silica gel plates and visualization was effected at nm. Unless otherwise noted, all reagents and solvents were obtained from commercial suppliers and used without further purification. B. General Procedures General procedure A: the synthesis of benzo[d]thiazole products au: In a test tube, a mixture of -iodoaniline (. mmol), (. mmol), phenylacetylene (. mmol), CuI (. mmol), K PO (. mmol) and,-phen (. mmol) was stirred in DMO (. ml). The reaction was allowed to stir at C under atm O for h. After that, water was added and extracted with ethyl acetate twice. The combined organic phase was dried over a O and concentrated. The residue was purified by flash column chromatography on silica gel with petroleum ether/ethyl acetate (PE/EA = : :) as the eluent to afford the desired product. General procedure B: the synthesis of benzo[d]thiazole products a-p: In air, a ml chlenk tube was charged with -iodoaniline (. mmol), (. mmol), phenylacetylene (. mmol), CuTC (. mmol), DBU (. mmol) and. ml MeC/H O (:). The flask was evacuated and filled with nitrogen for three cycles. The reaction was allowed to stir at C for h. After that, water was added and extracted with ethyl acetate twice. The combined organic phase was dried over a O and concentrated. The residue was purified by flash column chromatography on silica gel with petroleum ether/ethyl acetate (PE/EA = : :) as the eluent to afford the desired product. C. Optimization of the Reaction Conditions Table. Optimization of the Reaction Conditions a,b entry [Cu] base additive (equiv) solvent Yield d (%) CuI K CO - DMO n.d CuI K CO - dioxane trace n.d CuI K CO - IPA n.d n.d CuI K PO - DMO n.d CuI KOAc - DMO n.d a a
CuI K PO TBAI () DMO n.d CuI K PO,-phen (.) DMO () e n.d CuTC DBU MeC CuTC DBU MeC c trace CuTC DBU MeC/H O (:) n.d () e CuTC DBU MeC/H O (:) n.d CuTC DBU MeC/H O (:) n.d CuTC DBU H O n.d CuTC DBU,-phen (.) MeC/H O (:) n.d a Reaction conditions (entries -): a (. mmol), (. mmol), a (. mmol), CuI ( mol %), base ( equiv), additive in. ml solvent at C under atm of O for h unless otherwise noted. b Reaction conditions (entries -): a (. mmol), (. mmol), a (. mmol), CuTc ( mol %), DBU ( equiv) in. ml solvent at C under for h unless otherwise noted. c uper dry acetonitrile. d GC-M yield using n-dodecane as an internal standard. e Isolated yield. As indicated in Table, -Iodoaniline (. mmol), (. mmol) and phenylacetylene (. mmol) were chosen as initially investigated substrates. Through series of copper salts and alkali screening, we believed that the use of CuI and potassium is more conducive to the formation of -phenylbenzo[d]thiazole (a). When the reaction was performed in the presence of CuI ( mol %) and K CO ( equiv) using DMO as solvent at C under atm of O, - phenylbenzo[d]thiazole (a) was obtained in % yield (entry ). Other solvents including dioxane, IPA and MeC did not effect on improving the yield of a (entries ). When K CO was replaced by K PO or KOAc, % and % yields were obtain, respectively (entries -). In order to further improve the yield, different additives were tested in the system (entries -). The result showed that the addition of phase transfer reagent (TBAI) did not work in the reaction system, while the yield increased to % when using,-phenanthroline as a ligand (entry ). ext, when the reaction was performed in the presence of CuTC ( mol %) and DBU ( equiv) using. ml of MeC as solvent at C under, -benzylbenzo[d]thiazole (a) was delivered in % yield and % yield of product a was detected (entry ). The use of super dry acetonitrile was not conducive to the conversion, making the yield of a drop to % (entry ). ubsequently, we replaced MeC with a mixed solvent MeC/H O (:), and the desired product a was delivered in % yield (entry ) with no product a detected. When increasing the proportion of water in the mixed solvent, the yield was decreased slightly (entries -). However, the reaction could not proceed well when water was used as a solvent (entry ). Besides, when adding a ligand in the system, the yield was reduced to % (entry ). D. Free Radical Verification Experiments
cheme. Free radical verification experiments. Condition A: CuI ( mol %), K PO ( equiv),,-phen ( mol %), DMO, O, C, h. Condition B: CuTC ( mol %), DBU ( equiv), MeC/H O (:),, C, h. E. Deuterium-labeling Experiments cheme. Deuterium-labeling experiments. Reaction conditions: a (. mmol), (. mmol), a (. mmol), CuTC ( mol %), DBU ( equiv) in. ml MeC/D O (:) at C under for h unless otherwise noted. Isolated yield. The product d -a was determined by H MR.
F. Characterization Data for Products -Phenylbenzo[d]thiazole (a). White solid, yield mg (%), mp - ºC. H MR ( MHz, CDCl ): δ.-. (m, H),. (d, J =. Hz, H),.-. (m, H),.-. (m, H). C MR ( MHz, CDCl ): δ.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -(p-tolyl)benzo[d]thiazole (b). White solid, yield mg (%), mp - ºC. H MR ( MHz, CDCl ): δ. (tt, J =.,. Hz, H),.-. (m, H),. (s, H). C MR ( MHz, CDCl ): δ.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -(-Ethylphenyl)benzo[d]thiazole (c). Yellow solid, yield mg (%), mp - ºC. H MR ( MHz, CDCl ): δ. (dd, J =.,. Hz, H),. (d, J =. Hz, H),. (t, J =. Hz, H),.-. (m, H),. (dd, J =.,. Hz, H),. (t, J =. Hz, H). C MR ( MHz, CDCl ): δ.,.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -(-Methoxyphenyl)benzo[d]thiazole (d). White solid, yield mg (%), mp ºC. H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (t, J =. Hz, H),. (t, J =. Hz, H),. (d, J =. Hz, H),. (s, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,,,. HRM (EI) (m/z): calcd for C H O [M+H] + :., found:.. -(-Chlorophenyl)benzo[d]thiazole (e). White solid, yield mg (%), mp - ºC. H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),.-. (m, H),. (t, J =. Hz, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,,,. HRM (EI) (m/z): calcd for C H Cl [M+H] + :., found:.. -(Benzo[d]thiazol-yl)benzonitrile (f). White solid, yield mg (%), mp ºC. H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (t, J =. Hz, H),. (t, J =
. Hz, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -([,'-Biphenyl]--yl)benzo[d]thiazole (g). Yellow solid, yield mg (%), mp ºC. H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (dd, J =.,. Hz, H),. (t, J =. Hz, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -(m-tolyl)benzo[d]thiazole (h). Yellow oil, yield mg (%). H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (s, H),.-. (m, H),. (t, J =. Hz, H),. (t, J =. Hz, H),. (d, J =. Hz, H),. (s, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -(Thiophen-yl)benzo[d]thiazole (i). White solid, yield mg (%), mp ºC. H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (dd, J =.,. Hz, H),. (t, J =. Hz, H),.-. (m, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -(Pyridin-yl)benzo[d]thiazole (j). White solid, yield mg (%), mp - ºC. H MR ( MHz, CDCl ) δ. (s, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (t, J =. Hz, H),. (t, J =. Hz, H),.-. (m, H). C MR ( MHz, CDCl, ppm) δ.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -(aphthalen-yl)benzo[d]thiazole (k). White solid, yield mg (%), mp - ºC. H MR ( MHz, CDCl ) δ. (s, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (dd, J =.,. Hz, H),.-. (m, H),.-. (m, H),. (t, J =. Hz, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:..
-Methyl-phenylbenzo[d]thiazole (l). Yellow solid, yield mg (%), mp - ºC. H MR ( MHz, CDCl ) δ.-. (m, H),. (d, J =. Hz, H),. (s, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (s, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -Fluoro-phenylbenzo[d]thiazole (m). Yellow solid, yield mg (%), mp - ºC. H MR ( MHz, CDCl, ppm) δ. (ddd, J =.,.,. Hz, H),. (dd, J =.,. Hz, H),.-. (m, H),.-. (m, H). C MR ( MHz, CDCl ) δ. (d, J =. Hz),. (d, J =. Hz),.,. (d, J =. Hz),.,.,.,.,. (d, J =. Hz),. (d, J =. Hz),. (d, J =. Hz). IR (KBr, cm ):,,,,,,. HRM (EI) (m/z): calcd for C H F [M+H] + :., found:.. -Bromo-phenylbenzo[d]thiazole (n). White solid, yield mg (%), mp - ºC. H MR ( MHz, CDCl ) δ.-. (m, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,,,. HRM (EI) (m/z): calcd for C H Br [M+H] + :., found:.. -Methoxy-phenylbenzo[d]thiazole (o). White solid, yield mg (%), mp - ºC. H MR ( MHz, CDCl ) δ.-. (m, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (s, H),. (dd, J =.,. Hz, H),. (d, J =. Hz, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,,,. HRM (EI) (m/z): calcd for C H O [M+H] + :., found:.. -Phenyl--(trifluoromethyl)benzo[d]thiazole (p). Yellow solid, yield mg (%), mp ºC. H MR ( MHz, CDCl ) δ. (s, H),. (dd, J =.,. Hz, H),. (d, J =. Hz, H),.-. (m, H). C MR ( MHz, CDCl ) δ.,. (d, J =. Hz),.,.,.,.,.,. (q, J =. Hz),. (q, J =. Hz),.,. (q, J =. Hz),. (q, J =. Hz). IR (KBr, cm ):,,,,,,,. HRM (EI) (m/z): calcd for C H F [M+H] + :., found:..
-Methyl-phenylbenzo[d]thiazole (q). White solid, yield mg (%), mp - ºC. H MR ( MHz, CDCl ) δ.-. (m, H),. (s, H),. (d, J =. Hz, H),.-. (m, H),. (d, J =. Hz, H),. (s, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -Chloro-phenylbenzo[d]thiazole (r). White solid, yield mg (%), mp - ºC. H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,,,,. HRM (EI) (m/z): calcd for C H Cl [M+H] + :., found:.. Methyl -phenylbenzo[d]thiazole--carboxylate (s). White solid, yield mg (%), mp ºC. H MR ( MHz, CDCl ) δ. (s, H),.-. (m, H),. (d, J =. Hz, H),.-. (m, H),. (s, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,,. HRM (EI) (m/z): calcd for C H O [M+H] + :., found:..,-dichloro-phenylbenzo[d]thiazole (t). White solid, yield mg (%), mp ºC. H MR ( MHz, CDCl ) δ.-. (m, H),. (s, H),.-. (m, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,. HRM (EI) (m/z): calcd for C H Cl [M+H] + :., found:.. -Chloro--fluoro-phenylbenzo[d]thiazole (u). White solid, yield mg (%), mp - ºC. H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (s, H),. (d, J =. Hz, H),. (d, J =. Hz, H). C MR ( MHz, CDCl ) δ.,. (d, J =. Hz),. (d, J =. Hz),. (d, J =. Hz),.,.,. (d, J =. Hz),.,.,. (d, J =. Hz),. (d, J =. Hz). IR (KBr, cm ):,,,,,,,,,. HRM (EI) (m/z): calcd for C H ClF [M+H] + :., found:..
-Benzylbenzo[d]thiazole (a). Brown oil, yield mg (%). H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (t, J =. Hz, H),. (m, H),. (s, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -(-Methylbenzyl)benzo[d]thiazole (b). Brown oil, yield mg (%). H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (t, J =. Hz, H),. (t, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (s, H),. (s, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -(-Fluorobenzyl)benzo[d]thiazole (c). Brown oil, yield mg (%). H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (dd, J =.,. Hz, H),. (ddd, J =.,.,. Hz, H),. (m, H),. (s, H). C MR ( MHz, CDCl ) δ.,. (d, J =. Hz),.,.,. (d, J =. Hz),. (d, J =. Hz),.,.,.,.,. (d, J =. Hz),.. IR (KBr, cm ):,,,,,,. HRM (EI) (m/z): calcd for C H F [M+H] + :., found:.. -(-Bromobenzyl)benzo[d]thiazole (d). Yellow solid, yield mg (%), mp - ºC. H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (t, J =. Hz, H),. (t, J =. Hz, H),. (t, J =. Hz, H),. (s, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,. HRM (EI) (m/z): calcd for C H Br [M+H] + :., found:..
-(-Methoxybenzyl)benzo[d]thiazole (e). Brown oil, yield mg (%). H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (t, J =. Hz, H),. (m, H),. (m, H),. (s, H),. (s, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,. HRM (EI) (m/z): calcd for C H O [M+H] + :., found:.. -(aphthalen-ylmethyl)benzo[d]thiazole (f). Brown oil, yield mg (%). H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (m, H),. (d, J =. Hz, H),. (m, H),. (t, J =. Hz, H),. (s, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -Hexylbenzo[d]thiazole (g). Yellow oil, Yield mg (%). H MR ( MHz, DMO-d ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (m, H),. (m, H),. (t, J =. Hz, H),. (dd, J =.,. Hz, H),. (m, H),. (dd, J =.,. Hz, H),. (d, J =. Hz, H). C MR ( MHz, DMO-d ) δ.,.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -Heptylbenzo[d]thiazole (h). Yellow oil, yield mg (%). H MR ( MHz, DMO-d ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (m, H),. (dd, J =.,. Hz, H),. (t, J =. Hz, H),. (dd, J =.,. Hz, H),. (m, H),. (t, J =. Hz, H). C MR ( MHz, DMO-d ) δ.,.,.,.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:..
-Octylbenzo[d]thiazole (i). Yellow oil, yield mg (%). H MR ( MHz, DMO-d ) δ. (dd, J =.,. Hz, H),. (d, J =. Hz, H),. (m, H),. (m, H),. (t, J =. Hz, H),. (m, H),. (m, H),. (t, J =. Hz, H). C MR ( MHz, DMO-d ) δ.,.,.,.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -(-Cyclopentylethyl)benzo[d]thiazole (j). Yellow oil, yield mg (%). H MR ( MHz, DMO-d ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (dd, J =.,. Hz, H),.-. (m, H),.. (m, H),.. (m, H),.. (m, H),.. (m, H),. (dd, J =.,. Hz, H). C MR ( MHz, DMO-d ) δ.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -(Hex--yn-yl)benzo[d]thiazole (k). Yellow oil, Yield mg (%). H MR ( MHz, DMO-d ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (m, H),. (m, H),. (t, J =. Hz, H),. (t, J =. Hz, H),. (td, J =.,. Hz, H),. (dt, J =.,. Hz, H),. (dt, J =.,. Hz, H). C MR ( MHz, DMOd ) δ.,.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -(-Phenylpropyl)benzo[d]thiazole (l). Brown oil, yield mg (%). H MR ( MHz, DMO-d ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (t, J =. Hz, H),. (d, J =. Hz, H),. (m, H),. (t, J =. Hz, H),. (m, H),. (dd, J =.,. Hz, H). C MR ( MHz, DMO-d ) δ.,.,.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm - ):,,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:..
-(Pyridin-ylmethyl)benzo[d]thiazole (m). Yellow oil, yield mg (%). H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (dd, J =.,. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (m, H),. (m, H),. (m, H),. (s, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -(Thiophen-ylmethyl)benzo[d]thiazole (n). Brown oil, yield mg (%). H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (m, H),. (m, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (s, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -Benzyl--methylbenzo[d]thiazole (o). Brown oil, yield mg (%). H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (s, H),. (d, J =. Hz, H),. (dd, J =.,. Hz, H),. (d, J =. Hz, H),. (s, H),. (s, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. -Benzyl--fluorobenzo[d]thiazole (p). Brown solid, yield mg (%), mp - ºC. H MR ( MHz, CDCl ) δ. (dd, J =.,. Hz, H),. (dd, J =.,. Hz, H),. (d, J =. Hz, H),. (m, H),. (dt, J =.,. Hz, H),. (s, H). C MR ( MHz, CDCl ) δ. (d, J =. Hz),. (d, J =. Hz),.,.,. (d, J =. Hz),.,.,.,. (d, J =. Hz),. (d, J =. Hz),. (d, J =. Hz),.. IR (KBr, cm ):,,,,,,,,. HRM (EI) (m/z): calcd for C H F [M+H] + :., found:.. -Benzyl--(trifluoromethyl)benzo[d]thiazole (q). Brown oil, yield mg (%). H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (dd, J =.,.
Hz, H),. (m, H),. (s, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,. (q, J =. Hz),. (q, J =. Hz),.,. (q, J =. Hz),. (q, J =. Hz),.. IR (KBr, cm ):,,,,,. HRM (EI) (m/z): calcd for C H F [M+H] + :., found:.. -Benzyl--methylbenzo[d]thiazole (r). Yellow solid, yield mg (%), mp ºC. H MR ( MHz, CDCl ) δ. (s, H),. (s, H),. (m, H),. (d, J =. Hz, H),. (s, H),. (s, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. Benzo[d]thiazol-yl(phenyl)methanone (). White solid, yield mg (%), mp - ºC. H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (t, J =. Hz, H),. (dt, J =.,. Hz, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,,. HRM (EI) (m/z): calcd for C H ao [M+a] + :., found:.. -(-Phenylbut-en-yl)benzo[d]thiazole (). Yellow oil, yield mg (%). H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (m, H),. (m, H),. (ddt, J =.,.,. Hz, H),. (d, J =. Hz, H),. (d, J =. Hz, H),. (t, J =. Hz, H),. (dt, J =.,. Hz, H),. (dt, J =.,. Hz, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. (E)-(,-Diphenylvinyl)benzo[d]thiazole (). Yellow solid, yield mg (%), mp - ºC. H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (s, H),. (d, J =. Hz, H),.-. (m, H),. (dt, J =.,. Hz, H),. (t, J =. Hz, H),.-. (m, H),. (dt, J =.,. Hz, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.,.,.,.,.,
.. IR (KBr, cm ):,,,,,,,. HRM (EI) (m/z): calcd for C H [M+H] + :., found:.. [D ]-benzylbenzo[d]thiazole (d -a). Brown oil, yield mg (%). H MR ( MHz, CDCl ) δ. (d, J =. Hz, H),. (d, J =. Hz, H),. (dd, J =.,. Hz, H),. (m, H),. (m, H). C MR ( MHz, CDCl ) δ.,.,.,.,.,.,.,.,.,.,.,.. IR (KBr, cm ):,,,,,. HRM (EI) (m/z): calcd for C H D [M+H] + :., found:.. G. References. H. terckx, J. De Houwer, C. Mensch, I. Caretti, K. A. Tehrani, W. A. Herrebout,. Van Doorslaer, B. U. W. Maes, Chem. ci.,,,.. (a) G. Kaupp, D. Lübben, O. auerland, Phosphorus, ulfur, and ilicon,,, -. (b) G. Kaupp, Chem. Ber.,,,. H. X-ray Diffraction Parameters and Data for d d Br X-ray of d Table Crystal data and structure refinement for d. Identification code Empirical formula d C H Br Formula weight. Temperature/K.() Crystal system triclinic pace group P a/å.() b/å.() c/å.() α/.()
β/.() γ/.() Volume/Å.() Z ρ calc g/cm. μ/mm. F(). Crystal size/mm... Radiation CuKα (λ =.) Θ range for data collection/. to. Index ranges - h, - k, - l Reflections collected Independent reflections [R int =., R sigma =.] Data/restraints/parameters // Goodness-of-fit on F. Final R indexes [I>=σ (I)] R =., wr =. Final R indexes [all data] R =., wr =. Largest diff. peak/hole / e Å./-.
I. MR pectra H MR ( MHz, CDCl ) spectrum of compound a........................ f (ppm) C MR ( MHz, CDCl ) spectrum of compound a.......... f (ppm)
H MR ( MHz, CDCl ) spectrum of compound b......................... f (ppm) C MR ( MHz, CDCl ) spectrum of compound b
H MR ( MHz, CDCl ) spectrum of compound c........................ f (ppm) C MR ( MHz, CDCl ) spectrum of compound c
H MR ( MHz, CDCl ) spectrum of compound d............... O C MR ( MHz, CDCl ) spectrum of compound d
H MR ( MHz, CDCl ) spectrum of compound e............... Cl C MR ( MHz, CDCl ) spectrum of compound e
H MR ( MHz, CDCl ) spectrum of compound f.............. C MR ( MHz, CDCl ) spectrum of compound f
H MR ( MHz, CDCl ) spectrum of compound g................... - C MR ( MHz, CDCl ) spectrum of compound g
H MR ( MHz, CDCl ) spectrum of compound h................ C MR ( MHz, CDCl ) spectrum of compound h
H MR ( MHz, CDCl ) spectrum of compound i................ f (ppm) C MR ( MHz, CDCl ) spectrum of compound i
H MR ( MHz, CDCl ) spectrum of compound j.................. C MR ( MHz, CDCl ) spectrum of compound j
H MR ( MHz, CDCl ) spectrum of compound k...................... C MR ( MHz, CDCl ) spectrum of compound k
H MR ( MHz, CDCl ) spectrum of compound l............. C MR ( MHz, CDCl ) spectrum of compound l
H MR ( MHz, CDCl ) spectrum of compound m...................... F C MR ( MHz, CDCl ) spectrum of compound m
H MR ( MHz, CDCl ) spectrum of compound n............. Br C MR ( MHz, CDCl ) spectrum of compound n
H MR ( MHz, CDCl ) spectrum of compound o.............. O - C MR ( MHz, CDCl ) spectrum of compound o
H MR ( MHz, CDCl ) spectrum of compound p............ F F F C MR ( MHz, CDCl ) spectrum of compound p
H MR ( MHz, CDCl ) spectrum of compound q.............. C MR ( MHz, CDCl ) spectrum of compound q
H MR ( MHz, CDCl ) spectrum of compound r.......... Cl C MR ( MHz, CDCl ) spectrum of compound r
H MR ( MHz, CDCl ) spectrum of compound s........... O O - C MR ( MHz, CDCl ) spectrum of compound s
H MR ( MHz, CDCl ) spectrum of compound t......... Cl Cl - C MR ( MHz, CDCl ) spectrum of compound t
H MR ( MHz, CDCl ) spectrum of compound u........ Cl F C MR ( MHz, CDCl ) spectrum of compound u
H MR ( MHz, CDCl ) spectrum of compound a............... - C MR ( MHz, CDCl ) spectrum of compound a
H MR ( MHz, CDCl ) spectrum of compound b................. C MR ( MHz, CDCl ) spectrum of compound b
H MR ( MHz, CDCl ) spectrum of compound c........................ F C MR ( MHz, CDCl ) spectrum of compound c
H MR ( MHz, CDCl ) spectrum of compound d............... Br C MR ( MHz, CDCl ) spectrum of compound d
H MR ( MHz, CDCl ) spectrum of compound e................... O C MR ( MHz, CDCl ) spectrum of compound e
H MR ( MHz, CDCl ) spectrum of compound f...................... C MR ( MHz, CDCl ) spectrum of compound f
H MR ( MHz, DMO-d ) spectrum of compound g................................ C MR ( MHz, DMO-d ) spectrum of compound g
H MR ( MHz, DMO-d ) spectrum of compound h............................... C MR ( MHz, DMO-d ) spectrum of compound h
H MR ( MHz, DMO-d ) spectrum of compound i................................... C MR ( MHz, DMO-d ) spectrum of compound i
H MR ( MHz, DMO-d ) spectrum of compound j.................. C MR ( MHz, DMO-d ) spectrum of compound j
H MR ( MHz, DMO-d ) spectrum of compound k................................. C MR ( MHz, DMO-d ) spectrum of compound k
H MR ( MHz, DMO-d ) spectrum of compound l................................... C MR ( MHz, DMO-d ) spectrum of compound l
H MR ( MHz, CDCl ) spectrum of compound m............ C MR ( MHz, CDCl ) spectrum of compound m
H MR ( MHz, CDCl ) spectrum of compound n.................. C MR ( MHz, CDCl ) spectrum of compound n
H MR ( MHz, CDCl ) spectrum of compound o............... C MR ( MHz, CDCl ) spectrum of compound o
H MR ( MHz, CDCl ) spectrum of compound p.......... F C MR ( MHz, CDCl ) spectrum of compound p
H MR ( MHz, CDCl ) spectrum of compound q.............. F F F C MR ( MHz, CDCl ) spectrum of compound q
H MR ( MHz, CDCl ) spectrum of compound r.......... C MR ( MHz, CDCl ) spectrum of compound r
H MR ( MHz, CDCl ) spectrum of compound................ O C MR ( MHz, CDCl ) spectrum of compound
H MR ( MHz, CDCl ) spectrum of compound................................ C MR ( MHz, CDCl ) spectrum of compound
H MR ( MHz, CDCl ) spectrum of compound................................ C MR ( MHz, CDCl ) spectrum of compound
H MR ( MHz, CDCl ) spectrum of compound d -a C MR ( MHz, CDCl ) spectrum of compound d -a............