C8953 NMR strukturní analýza seminář
Identification of an unknown compound Jan Novotný
176003@is.muni.cz
April 13, 2022
Task 0: Classification of an unknown substance
Assign the general name to displayed
substances:
CARBOHYDRATE PEPTIDE STEROID TERPENE ALKALOID COUMARINE
□ S ► < -š ►   -š | = 0,0
Aril 26, 2SL7 020/
Task 0: Classification of an unknown substance
a    k AVUa A
1
1
V   a   /A aA*.. . ,
JAJL
JÜU_UlJ_L
JL-IL.
—^_1*-
-i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—i—r~
2
Ondřej Jurček
9
1 ^
Äri' 26, 2SL7 O^Vd*
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
tori'. 26, 2SL7 O^VO
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
26, 2SL7 050/
Task 3: Ci2Hi7NO - ^/COSY
!H NMR (300 MHz, CDCI3)
cn   00   H oo oj  o r-
M    Cl    Cl M
in   cn   ro   vo h
01 H m W) N o oj   oj   H CTi cn
11[111111II1111111111111111 j 11111111111111111111II1111 7.7   7.5   7.3   7.1 ppm
m m
m m m
co • in in cm
« J 7
mHmHtniDtn^jicomcrtrncrtinH H<noor-u>infnHcou>ro<Ha>oio iĎini/imiíii/imi/icicicicioiaioi
LILII
11111111111 < 111111111111111111111111111111111111111111111111 [ 11111111111111111111111111111111111 2.6   2.4   2.2   2.0   1.8   1.6   1.4   1.2 ppm
J
"~|-1-1-1-1-1-1-r
9 8
I 1 1 7
I 1 1 6
—i—1—1—1—1—r~
5 4
I 1 1 3
~l-[—1-r
2
-|—l-1    i    i    | i
1 ppm
0.92 1.08
1.84 1.00
2.08 2.05 2.91
2.94 2.02
Ondřej Jurček
26, 2SL7 O&O/d*
Task 3: Ci2Hi7NO - ^/COSY
COSY (300 MHz, CDCI3)
Ondřej Jurček
F2
(ppm)
1-
3-
4
5
8
es &
9
26, 2SL7 O^Vd*
Task 3: Ci2Hi7NO - ^-"C/HSQC.HMBC
HSQC (300 MHz, CDCI3)
Ondřej Jurček
F2
(ppm)
1-
i i i i—i i i i
MM--MM
MM--MM
7  T  T  1       I   1   1 ■
MM--Mil
1   I   I   '   T  7   7 7
i i i i    r~i i r
MM--MM
140 120 100 80 60
Fl (ppm)
40
20
26, 2B.7 O^Vd*
Task 3: Ci2Hi7NO - ^-"C/HSQC.HMBC
HMBC (300 MHz, CDCI3)
F2
(ppm)
1-
2
3
4
5
0 o
rl II I 1111   I I I I I I I I I   I 1 1 I | I I l l   l l l i II i l l   li li   l li l   l l l l 11 l l l   l l i i | l l l l   I I I I I I I I I   I 1 I I 1 I I 1 1   l l l l II l l l
180        160        140        120        100 80 60 40 20
Ondřej Jurček
26, 2B.7 O^Vd*
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
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
Oi<V o
73
N)
o
-ŕ bo
O
U) U)
□
4
.....
9
149.55
■ 148.60 Q] -138.75 O
134.77
77.26 77.00 76.75 68.84
- 56.98 (J)
- 40.34 I -35.19 —
- 22.59 f
U) 4i
O D O
CO
CD
LU
Q O
CO <
3 4
C10H14N2 in CDCľ
56 7d
I i 10,11,12
LLjJL*m_
ppm
30 40 50 60 70 t- 80 90
t-100
110 120 -130 -140 150
(5
LU
Q O
DO <
3 4
56 78
iLJbr
" I " " I' " 11" '11" ■' 11''11 ■ ■" I " " I'1" I" ■1 ľ " ■ I" " I " " I " "-
8.5  8.0 7.5  7.0 6.5  6.0  5.5 5.0 4.5 4.0 3.5  3.0 2.5  2.0 ppm
■' i1" 11 ■1111" " ľ1" i " " i ■1" i " ■1 r 1 ■ ■ i1 ■ ■ ■ i " " i1" 1111 ■ ■ i "111 ■1 8.5  8.0  7.5  7.0 6.5  6.0 5.5  5.0 4.5  4.0 3.5  3.0 2.5 2.0
ppm
30 40
\r 50
60 f- 70 80 90
f-100
110 120 r 130 r 140 -150 ppm
"C^H HSQC
13C/H HMBC
ID *H of CioH200
1H ID
).8M DMSO 25CTXI
Jan Novotný
4.0
Tr
3.5
3.0
7ř
Tm
r
li
h o in md in o rn o i—1 o ■—i ■—i rsi rn <—i rn
2.5 fl (ppm)
2.0
1.5
1.0
0.5
1H-13C HSQC and NOESY
UnC1-Ha UnC2-Hd ^
UnC3-Hqs^^
UnC4 _
UnC5-HE— j
UnC6-HI\ UnC4-Hf
UnC7-Hj
\
Á
UnC7-Hb UnC8-Hk UnC8-Hc
\ 1 /
UnC9-Hg
UnC10-Hm
\
20
H
30
E
40   B 2
3
50 3
60
4^
70
4 2
C02-1H (ppm)
6
_i_
uhHa-Hn
4 —i—
_2
UnHd
UnHk-Hr
UnHd-Hk
UnHe-Hm llnHa Hm   Unŕla"HI   I UnHb-Hj , m   UnHa-Hm      i       f   . UnHb-^i
/
/ UnHf-Hj YV lnMÄ UnHg-H* \UnHf-Hi
UnHg-Hn UnHf-H«L-----uu Hm    J ^UjßHg-Hi
"UnHh-
UnHI-H
UnHk-Hm
UnHh-Hk£ří ©
UnHh-Hj . 4 #
UnHm-Hn
\
!
4
O 0
I
co2- 1H (ppm)
2
3
Task 1: J-con necti vity of C10H20O
Jan Novotný
□ t3
Task 1: J-connectivity of C10H20O
• CH2 8ck weakly coupled with CH2 7bj => closing ring
• protons b and k coupled to CH 6h which is connected to methyl 3e
9 other expected crosspeaks in DQ-COSY c rowd ed / ove r I a p p ed, found topology confirmed
in HMBC {3/4JHc)
a      1  H 2 d H3a M XH
MENTHOL
Jan Novotný
30-
35
CL Q.
O
co
40
45
50
4
_1_
UnC6-Hh
UnC6-He
HMBC
UnC6-Hi UnC6-Hk
^\ V
UnC6-Hb - 30
UnC7-He^ UnC6-Hf
UnC7-Hk'
UnC7-H] \
\
- 35
UnC7-Hb
UnC7-Hi
UnC8-He
UnC8-Hm   UnC8_Hk \ UnC8-Hb
UnC8-Hn \ xUnC8-Hh \ /
\ \ \\y
nnrQ-Hl UnC8-Hc UnC9-H„ UnC.-H, U„C9-Ha
\ \ \     -   \ ^/
UnC9-Hg
2
40
45
■ 50
C02-1H (ppm)
□ fl1
□
S1
4/5