Question

Answer ALL of the questions and show ALL of your work/ reasoning.

1. (16 points) Using the COSY and HSQC spectra below assign all the protons and carbon resonances in 3- octanone recorded in C.D. solution at 298K at 600 MHz. Complete the table below to indicate which carbon is attached to which protons and at which position (#1-#8) using the numbering system provided. TH-TH COSY Spectrum 1000 MHZ. Benzene-Og solution Position # SH OC 0.82 0.92 1.11 1.19 1.47 20 1.8 1.6 1.4 1.2 1.0 0.8 ppm 1.92 1.94 C-H Correlation Spectrum 'H600 MHz, 3c 150 MHZ. Benzene-Og solution) Carbon chemical shifts are: 8c 209 (not shown in HSQC on right), 42, 35, 31, 25, 22, 14, 8 ppm 2018 16 14 12 1008 ppm

Answer 1

Date Page 'H -H COSY Spectrum all the 0.8 El.0 1.6 -7.8 -2 .o 1.0 1.2 0.8 2.0 1.8 16 14 of proton. other K This cosy spectrum shows ppairs molecule which are coupled to each Here ; 0.82S is coupled with. l. lgs 0.92 S is coupled with log2 or 1.84 § lolls is coupled with 1.475. 1.478 is coupled with lolls & l.gzorigys

Date Page spectrum. C-4 correlation All ulli to +40 1.2 0 0.8 * This HS ge is the heteronuclear anologue of Cosy Spectrum This hsgc spectrum shows which protons are coupled to which carbon in the given molecule

Page om 3-octanone position # Su 0.82 0.92 31 22 This value Y are identified by a 25 1.19 1.47 1.92 7.94 35 This value are identified by HSGC Cc-t correlation spectrum) 42 H-H-Cosy

Date Page ON. me ICCH cca * NMR Date: (15.6ppm multiplet ² show olefinic proton value (3) (2) 5.2 ppm dd. J= llogg.2 H2 = this value indicate attachment of nitro group 4.1 ppm broad doublet 9.2 H2 =) This indicato attachment of nitrogen atom. (4 13.36 ppm. didd llog 9.2 667 Hz This is the value indicate attachment of Phenyl group Here I value of 9.2 Hz is similar Lin in three values (5.2, 4.1 a 3. 362 In case of value 3.36 ppm shows d.d.d. that means there is nearer three proton. According to cosp 2.36 s value is of. -cthe group which is attached to olefinla carbon shows coupling with 3.365 that means definis carbon atom which is attached to Phenyl a NO 4.18 value is a proton which is nearer to nitrogen can shows coupling with proton containing carbon which is attached to nitro group

H-cosy Date Page 3/36 $1.2 401 3.361 236 1.78 coupled to The roton molecule which are each other are's (1) 2.365 is coupled with 3.36 5 , 5.6s (2) 3.36 s is coupled with 2.368, 5.25 (3 4.15 is coupled with. d. 5.25 (4 5: 26 is coupled with 401, 3.368 15 5.6s is coupled with 2.36 s

Dale Page * And soos which is a olefinic proton value coupled with 2-36 s. valce which shows -cth attached to carbon containing Phenyt ring so according to this overallo value final structure arised by the Diels, Alder reaction is -2.36 5 ph THE 3.368 HT I NCH N Ceth 2 5.28 4:15