C8953 NMR strukturní analýza seminář Identification of an unknown compound Jan Novotný, Ondřej Jurček 17 6003@is.muni.cz, ondrej.jurcek@ceitec.muni.cz April 18, 2018 □ if? Task 0: Classification of an unknown substance Assign the general name to displayed substances: CARBOHYDRATE PEPTIDE STEROID TERPENE ALKALOID COUMARINE □ g - g ► -El = "O Q. O Äri' 26, 2S.7 O^VO^ Task 0: Classification of an unknown substance JUÜilii A I AAftA A A J>----_ 1 I I 11. 1 J—--ft A a JA A Task 1: Ci0Hi3NO 5[ppm] Multiplicity Integral 1.05 triplet 3 1.75 singlet 3 3.70 quartet 2 7-7.60 complex multiplet 5 Ondřej Jurček ^5sri' 26, 2S.7 0*3/^ Task 2: CnHi5N02 5[ppm] Multiplicity -/(Hz) Integral 1.30 triplet 7 3 3.00 singlet - 6 4.25 quartet 7 2 6.65 dublet 8 2 7.80 dublet 8 2 ^5sri' 26, 2S.7 O^VC^ Task 3: Ci2H17NO - ^/COSY *H NMR (300 MHz, CDCI3) Ol CO H CD 1" Ifl Ol Cl 10 r| •3" CN O r- M tH CO U> CN O Cl Cl M N Cl (S H H Ol Ol in on in «o ri' 26, 2m7 0«V(^ Task 3: d2Hi7NO - ^-"C/HSQC.HMBC HSQC (300 MHz, CDCI3) F2 (ppm) 1- I 1 l I I l I I (III I I I I I I I I I I I I I I I 1 [Ml I I I I I I I I lili I I I I i I I I lili lili 1111 140 120 100 80 60 Fl (ppm) 40 20 Ondřej Jurček ^5sri' 26, 2S.7 O^C^ Task 3: Ci2Hi7NO - ^-"C/HSQC.HMBC HMBC (300 MHz, CDCI3) wméym^m^tm**mH wh—i F2 (ppm) 1- 2 3- 4 5 I I I I I I I I l I I I I I I I I I I I I I I I 1 Q o - i i i i i i ' l l f i I i I I l I I I I I 1 I I I I I I I I 1 1 1 I I I ! I I I I I I l l I l 1 I l l ' I I I I I I I I I 200 180 160 140 120 100 80 60 40 20 0 Ondřej Jurček ^5sri' 26, 2S.7 O^C^ General comments • inspect molecular formula CmHh0oNnXx: Degree of unsaturation m + 1 — 0.5(h + x — n) • identify signals of CH3 and exchangeable protons in ID 1H sectrum • arbitrary numbering (e.g., from lower to higher value of chemical shift) of resolved resonances in all spectra • identification of the individual spin systems using DQF-COSY • resolve geminal protons using HSQC • connect molecular fragments/isolated spins using HMBC, NOESY o specify the stereochemistry (relative configuration) by means of J— and NOE interaction • in ID spectrum bottom blue numbers are integrals, labels in violet frames contains the arbitrary label (A-N), multiplet specification (use with caution, automatically determined), and position of a signal in ppm 9 UnHa-UnHb in 2D reffers to correlation of protons a and b of unknown compound Un < n ► < g ► < II ► < ^1 ► 1: 'O^O ■3 QicV(> ID XH of Ci0H20O 1H ID ).8M DMSO 25CTXI 4.0 Jan Novotný Tr r 3.5 3.0 2.5 fl (ppm) —1— 2.0 —1— 1.5 —1— 1.0 —r 0.5 1H-13C HSQC and NOESY 20 i 30-\ & 40H O 50H 60-^ 70 UnC1-Ha UnC2-Hd > UnC3-H^^ UnC4 _ UnC5-Hk—-- j UnC6-Hh. UnC4-Hf UnC7-Hj [ 30 \ i UnC7-Hb UnC8-Hk UnC8-Hc \ \ / UnC9-Hg UnC10-Hm \ 20 40 50 [ 60 70 E Ä 2 3^ 4^ 4 2 C02-1H (ppm) 6 _i_ uhHa-Hn J_u _1_ UnHd-Hk UnHd UnHk-Hr \ UnHe-Hm Un„s_Hm UnHa-H, J UnHb-Hj^ UnHg-Hn UnHg UnHh-Hm V UnHI-H UnHk-Hm X j " 1 If unMD-j \/ UnHd-HL 1 / I/(/UrÚ / / UnHf-Hj YY |nUf*S / UnHg-Hľ V UnHf-Hi. UnHf-Hm y , . .1 UnHm-Hn « a e I I 4 C02- 1H (ppm) -r- 2 h3 Task 1: J-connectivity of C10H20O E o. 2 Q. 1111 UnHc-Hm UnHg-Hm' UnHk-Hmi UnHJ-Hj w 3H UnHm-Hn Jan Novotný □ ť5> Task 1: ./-connectivity of CioH2oO Task 1: J-connectivity of C10H20O E o. 2 Q. 3H 1111 UnHc-Hm UnHg-Hm' UnHk-Hmi UnHm-Hn Jan Novotný UnHdl-Hj \ UnHf-Hb 1 <^P Q3CVP Task 1: -/-connectivity of C10H20O Jan Novotný Task 1: J-connectivity of CiqH2oO 30- 35- E Cl O. O co 40- 45- 50- Jan Novotný j_i_ j_i_ j_i_ HSQC HMBC „ IT.UnC6-He UnC6-Hki----^' x - 30 UnC7-He^ UnC6-Hf UnC7-Hk - 35 UnC7-Hj UnC7-Hb UnC7-Hi - 40 UnC8-He UnC8-Hm UnC8-Hn UnC8-Hk„ „n TTl\ UnC8-Hb UnC8-Hh Hn \ xUnC8-Hh \ \ \\ - 45 UnC9-Hn UnC9-Hm UnC9;H1 UnC9-Hd °n""f \ UnC9-Hi \ Un""Ha Uneg-HgS1 4 □ fiP - 50 = 1= ^r) c\(y