[Thanks David - if you have any spectra of the starting materials it would be helpful to upload them on their respective ChemSpider entries. Just make sure that they are on the right scale. Have you been able to fix your product NMR on the right scale -you were still off by 1ppm last I checked. Once you do you can get the rotamer ratio from the diastereotopic protons around 4 ppm giving 2 nice doublets for each rotamer. JCB] Dr. Antony Williams processed the original JEOL files into the ACD/NMR Processor and exported them as JCAMP files. The new JCAMP files were scaled properly. For some reason, the JEOL conversion software didn't convert the files correctly. The spectra of the starting materials can now be found under the "Spectra of Starting Materials" section below.

Since Google Wave is "Sunsetting" in 2012, here's a zip file with all the files and discussion from the wave: Ugi Characterization Wave.zip

Researcher

David Bulger

Objective

To characterize the only Ugi product which precipitated from Ugi Reaction Blog#002
The list of attempted reactions is available on LaBLog.
Reactants: 3,5-bis(trifluoromethyl)benzaldehyde, phenylpropionic acid, benzylamine, and cyclohexylisocyanide

Procedure

Previous Experiment

The experiment can be found at Ugi Reaction Blog#002.

NMR Spectra: Sample 2, Sample 4. Note: Samples in deuterated chloroform and original solvent was methanol.
[Assuming that the peak at 8.2 ppm is residual CHCl3 and the other 2 are methanol it looks like your spectrum is shifted by 1 ppm and there is almost nothing else in there - how much material did you use to make up the NMR sample? JCB] I have redone the NMR analysis below with most of the methanol evaporated and a higher concentration of Ugi product in the solution. Furthermore, the most recent 1H NMR spectrum (uc234_2_2_hnmr) is not shifted as bad, although it does seem to be backwards.

Characterization by NMR


A concentrated sample of Ugi Product labeled "Ugi2.2" was prepared in CDCl3. Various 1H and 13C NMR runs will be performed on this sample, including some two-dimensional analyses. These will be used with NMR prediction software (HyperChem release 7.5 and HyperNMR) to confirm the identity. [You might get some info from the NMR prediction software but your best bet is to compare against **NMRs for Ugi products** with alkynes JCB] That is a great idea! Comparing with 173G19-4 in Exp193 should especially aid the characterization of the groups from the phenylpropionic acid and benzylamine as well as the rotamers. Infrared Spectroscopy will also be used to identify key functional groups and to compare with 173G19-4 in Exp193.

Results

ACD/NMR Processor 12.1 Corrected Spectra with XY conversion via JSpecView
Ugi234H1.jdx
Ugi234C13.jdx
Raw JCAMP-DX for Ugi234H1
Raw JCAMP-DX file for Ugi234C13
Ugi234NOESY.pdf
Ugi234COSY.pdf
Ugi234CHSHF.pdf
Note: Peak locations will be added to the 2D spectra later.

FT-IR: FTIRUgi2.1general

IR (KBr, thin film) (cm-1): 3400-3150 (s, NH), 3150-3000 (s, aromatic), 2930 (s, asymmetrical aliphatic), 2850 (s, symmetrical aliphatic), 2810 (w), 2210 (s, C≡C stretching), 1950 (w, 1,3,5-trisubstituted aromatic), 1880 (w), 1800 (w), 1650 (s, C=O), 1580 (s, Amide II NH bend), 1600 (s, 1,3,5-trisubstituted aromatic), 1490 (s, 1,3,5-trisubstituted aromatic), 1450 (s), 1410 (s), 1390 (s), 1290 (s, CF), 1190 (s, CF), 1120 (s, CF), 1020 (m), 1000 (w), 950 (w), 900 (m), 850 (m), 800-685 (m, overlap NH and 1,3,5-trisubstituted aromatic).
References: (Silverstein, 82,85,101) (Shriner, 210,214).

1H NMR with TMS converted by Dr. Williams:234hnmrtmsjdx

1H NMR: 234hnmrcorrected [it looks like the spectrum is off scale - I don't see CHCl3 peak at 7.27ppm and the high field protons are at very high ppm ranges JCB] It should be corrected now.[no still looks like it is off - see for example 241-8A the cyclohexyl group should be up to 1.5ppm but in your spectrum it is above 2 ppm - in the future add a tiny amount of TMS so that you can set the reference to the zero ppm peak JCB]
1H NMR with TMS: Ugi2.1tms.pdf, Ugi2.1tmsdoublet.pdf, Ugi2.1tmsclose.pdf


13C NMR: ugi2.2c13, ugi2.2c13close
Distortionless Enhancement by Polarization Transfer (DEPT) (135 deg) decoupled: ugi2.2dept135
DEPT (90 deg) decoupled: ugi2.2dept90, ugi2.2dept90close1, ugi2.2dept90close2
Double Quantum Filtered Correlation Spectroscopy (DQF COSY): ugi2.2cosy, ugi2.2cosycolor, ugi2.2cosyclose1, ugi2.2cosycolorcloseup1
Heteronuclear shift correlation (chshf): ugi2.2chshf
Nuclear Overhauser Effect Spectroscopy (NOESY): ugi2.2noesy
C13 Chemical Shift (ppm)
Area under C13 peak
Direction of DEPT 135 peak
DEPT135 (ppm)
DEPT90 (ppm)
chshf proton 1 (ppm)
chshf proton 2 (ppm)
24.7282
2.42G
down
24.7359
24.7359
1.55

25.4764
879.06M
down
25.4382
25.4458
1.62

32.6524
2.42G
down
32.5990
32.5990
1.19
1.95
48.9053
1.16G
up
48.9129
48.9053
3.82

52.3559
620.3M
down
52.3559
52.3635
5.12

60.8602
910.62M
up
60.8602
60.8678
6.05



up
65.4635
65.4559


76.6932






77.1131
42.95G
up
77.2429
77.3192
7.27

77.5406






81.3805
301.86M





92.5415
202.5M





119.7875
366.1M





121.1921
525.0M





122.2762
713.16M
up
122.2227
122.2685
7.70

124.8107
298.59M





127.2688
1.51G
up
127.2688
127.2688
7.14

127.7727
597.44M
up
127.7727
127.7650
7.225



up
127.9025
127.9025




up
128.0475
128.0475


128.6735
3.47G
up
128.6811
128.6735
7.282





128.7880






128.9331


129.8644
1.99G
up
129.8262
129.8186
7.755

130.7042
497.31M
up
130.7042
130.7042
7.485

131.4065
612.85M





131.8493
243.07M





132.2920
359.68M





132.6814
1.97G
up
132.6814
132.6814
7.462

136.4602
501.72M





136.9030
604.08M





156.2248
545.46M





166.5918
823.1M






HyperNMR Computed Coupling and Shielding Constants for all atoms with the propionic keto group in the closed position relative to the rest of the molecule: (C)
HyperNMR Computed Coupling and Shielding Constants for all atoms with the propionic keto group in the closed position after molecular dynamics (300K for 1ps in vacuum): (CMD)
HyperNMR Computed Coupling and Shielding Constants for all atoms with the propionic keto group in the open position: (O)
HyperNMR Computed Coupling and Shielding Constants for all atoms with the propionic keto group in the open position after molecular dynamics (300K for 0.1 ps in vacuum): (OMD)
Note: Each Index varies slightly between the closed and open positions. O and OMD have the same Index.
Screen Captures Indicating Index in Closed Position: Ugi2Closed1, Ugi2Closed2
Screen Captures Indicating Index in Open Position: Ugi2Open1, Ugi2Open2
Index (C)
Shift (C)
Index (CMD)
Shift (CMD)
Index (O)
Shift (O)
Index (OMD1)
Shift (OMD1)
Index (OMD2)
Shift (OMD2)
1-19H
0.83
1-19H
0.884
1-19H
0.907
1-11H
0.801
1-15H
0.704
1-20H
1.202
1-20H
1.239
1-20H
1.066
1-16H
1.027
1-20H
0.839
1-16H
1.35
1-16H
1.382
1-16H
1.324
1-12H
1.105
1-18H
0.894
1-18H
1.401
1-18H
1.453
1-18H
1.445
1-19H
1.405
1-14H
1.06
1-17H
1.469
1-17H
1.554
1-15H
1.538
1-17H
1.516
1-16H
1.156
1-15H
1.514
1-15H
1.555
1-14H
1.619
1-15H
1.533
1-19H
1.166
1-12H
1.7
1-12H
1.721
1-17H
1.606
1-18H
1.554
1-11H
1.195
1-14H
1.763
1-14H
1.783
1-11H
1.629
1-20H
1.822
1-17H
1.547
1-11H
1.809
1-11H
1.818
1-12H
1.625
1-10H
1.941
1-12H
1.655
1-10H
1.845
1-10H
1.869
1-10H
1.723
1-14H
2.507
1-10H
1.876
1-13H
2.117
1-13H
2.153
1-13H
1.971
1-33H
2.724
1-13H
2.34
1-46H
3.397
1-46H
3.46
1-33H
3.124
1-13H
3.008
1-32H
3.726
1-52H
3.921
1-52H
3.927
1-39H
3.816
1-39H
3.712
1-33H
3.952
1-45H
4.489
1-45H
4.5
1-32H
4.098
1-32H
3.91
1-39H
4.091
1-34H
6.633
1-34H
6.57
1-67H
6.854
1-55H
6.456
1-55H
6.606
1-37H
6.878
1-69H
6.65
1-36H
6.926
1-38H
6.53
1-67H
6.903
1-69H
6.938
1-37H
6.853
1-55H
6.972
1-36H
6.619
1-69H
6.957
1-49H
6.945
1-33H
6.908
1-38H
7.018
1-37H
6.689
1-65H
7.034
1-33H
6.996
1-49H
6.965
1-66H
7.054
1-67H
6.755
1-38H
7.054
1-68H
7.023
1-68H
6.995
1-37H
7.074
1-66H
6.927
1-34H
7.156
1-51H
7.044
1-36H
7.055
1-65H
7.176
1-54H
7.041
1-68H
7.171
1-36H
7.082
1-51H
7.069
1-68H
7.18
1-65H
7.264
1-66H
7.182
1-50H
7.121
1-50H
7.149
1-34H
7.266
1-68H
7.382
1-36H
7.214
1-35H
7.143
1-35H
7.207
1-35H
7.273
1-35H
7.433
1-37H
7.386
1-47H
7.251
1-47H
7.259
1-54H
7.299
1-69H
7.546
1-35H
7.394
1-48H
7.267
1-48H
7.282
1-56H
7.307
1-34H
7.581
1-54H
7.518
1-67H
7.39
1-67H
7.379
1-69H
7.593
1-56H
8.215
1-56H
7.574
1-9H
7.773
1-9H
7.872
1-9H
8.725
1-9H
9.505
1-9H
8.762

Discussion


Extra peaks appeared in DEPT135 that do not show protons on the chshf. There has been problems with the DEPT135 this semester. A quick fix was attempted by widening the peaks. However, this does not seem to have worked. The DEPT90 spectrum contains even more extra peaks and contains all of the peaks found in the DEPT135, which was not expected. This could be explained since the DEPT90 has had even more problems than the DEPT135 and a fix has not been attempted. I was informed of this after the spectra were collected.

Conclusion



Log

11.11.09
15.45 - Shimmed with CDCl3 (Z1:-1217;Z2:-1031;Z3:-166;Z4=981)
15.52 - Ran 1H NMR on CDCl3 sample - 8 scans (Gain:25)
Chemical Shift (ppm)
Area under peak
Interpretation
0.80
0.14
Impurity in NMR tube
1.25
0.12
Impurity in NMR tube
1.62
1.00
Impurity in CDCl3
7.27
0.39
CHCl3 residual
16.00 - Cleaned tube with CHCl3
16.05 - Ran 1H NMR on CDCl3 sample - 8 scans (Gain:22)
Chemical Shift (ppm)
Area under peak
Interpretation
1.60
0.39
Impurity in CDCl3
4.80
0.26
Impurity in CHCl3
7.27
1.00
CHCl3 residual and CHCl3 used in cleaning
16.18 - Ran 1H NMR on CDCl3 sampe in new clean tube - 8 scans (Gain:26)
Chemical Shift (ppm)
Area under peak
Interpretation
1.6
1.00
Impurity in CDCl3
7.27
0.40
CHCl3 residual
16.25 - vacuum desiccated with heat the two NMR tubes
16.31 - transferred Ugi Product solution 2.2 into bottle of remaining solid 2.2 dissolving remaining Ugi Product and increasing the concentration
16.36 - removed NMR tubes from vacuum desiccator
16.40 - shimmed and locked on Ugi2.2 (Z1:-1249;Z2:-1014;Z3:-151;Z4:635)
16.45 - tune and match for 1H and 13C NMR probes
16.56 - single pulse 1H NMR on Ugi2.2 - 8 scans (Gain:16)
17.06 - single pulse 1H NMR on Ugi2.2 - 64 scans (Gain:16) uc234_2_2_hnmr
- set-up computer experiment sequence to run the following overnight: 13C decoupled (Gain:28), DEPT (135 degree) decoupled, DEPT (90 degree) decoupled, DQF COSY, and Heteronuclear Shift Correlation.
11.16.09
16.00 - Collected and analyzed spectra from previous run: DEPT135, DEPT90, DQF COSY, and chshf
16.06 - Auto-gradient shim and lock (Z1:-1358;Z2:-1038;Z3:-313;Z4:547)
16.08 - Absolute Value NOESY submitted on Ugi 2.2
18.20 - Transferred Ugi Product solution 1.4 into bottle of remaining solid 1.4 dissolving remaining Ugi Product and increasing the concentration
18.35 - Collected and analyzed NOESY of Ugi 2.2 and cleaned NMR tube
11.23.09
16.45 - Dissolved Ugi 2.1 in Methylene Chloride
16.54 - Weighed 0.114 2 g KBr and placed in mortar
16.58 - Lightly pressed large chunks of KBr into sand-size particles with pestle
16.59 - KBr vaccum-dessicated with heat in mortar
17.04 - Removed from vacuum-dessicator
17.05 - Added dissolved Ugi 2.1 in methylene chloride to KBr in mortar
17.08 - Vaccum-dessicated with heat
17.10 - Cleaned blot and barrel with methylene chloride and vaccum dessicated with heat
17.18 - Removed both the mortar with Ugi 2.1 in KBr and the barrel with bolt from vaccum dessicator
17.19 - Transferred Ugi 2.1 in KBr from mortar to barrel with one bolt
17.20 - Barrel with Ugi 2.1/KBr vaccum-dessicated with heat
17.25 - Removed from vaccum dessicator and added second bolt
17.26 - Pressed with bolt on bench to generate disk
17.28 - Barrel with both bolts in vaccum dessicated with heat
17.33 - Removed bolts from vaccum dessicator and removed bolts revealing opaque disk
17.34 - Ran background and spectrum
17.38 - Removed disk from barrel, saving in original glass vial
12.01.09
15.30 Washed NMR tubes with CHCl3 and vacuum dessicated
16.00 Added 7 uL to about 1 mL of Ugi 2.1 in CDCl3 solution
16.17 Auto-gradient shim and lock (Z1:-1196,Z2:-1016,Z3:-152.Z4:800)
16.21 Proton NMR (128 scans) of Ugi 2.1 (Autogain: 17)
16.48 Added 4 uL to about 0.7 mL of Ugi 1.4 in CDCl3
16.50 Auto-gradient shim and lock (Z1:-1303,Z2:-1063,Z3:-223,Z4:781)
16.54 Proton NMR (128 scans) of Ugi 1.4 (Autogain: 14)


Spectra of Starting Materials

3,5-bis(trifluoromethyl)benzaldehyde
http://www.sigmaaldrich.com/spectra/ftir/FTIR004662.PDF (FTIR)
http://www.nmrdb.org/predictor?smiles=FC(F)(F)c1cc(C=O)cc(c1)C(F)(F)F (FTNMR predicted)

Phenylpropionic acid
http://webbook.nist.gov/cgi/cbook.cgi?ID=C501520&Units=SI&Type=IR-SPEC#IR-SPEC (FTIR)
http://www.sigmaaldrich.com/spectra/fnmr/FNMR000998.PDF (FTNMR)

Benzylamine
http://webbook.nist.gov/cgi/cbook.cgi?ID=C100469&Type=IR-SPEC&Index=1#IR-SPEC (FTIR)
http://www.sigmaaldrich.com/spectra/fnmr/FNMR002357.PDF (FTNMR)

Cyclohexylisocyanide
http://www.sigmaaldrich.com/spectra/ftir/FTIR000824.PDF (FTIR)
http://www.sigmaaldrich.com/spectra/fnmr/FNMR000952.PDF (FTNMR)

Methanol
http://www.astrochem.org/compare.html (FTIR Low-Quality)
http://www.hull.ac.uk/chemistry/spectroscopy/infrared_spectrum.php?res=high&molecule=methanol (FTIR High-Quality)
http://www.muhlenberg.edu/depts/chemistry/chem201woh/1Hmethanol.html (FTNMR)
http://www.chem.purdue.edu/gchelp/nmr/meoh4.html (FTNMR)

Acknowledgements

The author thanks Dr. William Collier (Instructor for CI) for his help with the characterization of these Ugi Products, and the Chemical Instrumentation (CI) Lab partners Chelsea Kimbrough, Jessica Jowers, Dustin Sprouse, and Gloria Jordan for helping with the project (use of camera) as part of the CI Lab Group Project.

Tags

SMILES:
c1ccc(cc1)CN(C(c2cc(cc(c2)C(F)(F)F)C(F)(F)F)C(=O)NC3CCCCC3)C(=O)C#Cc4ccccc4
InChI:
InChI=1/C32H28F6N2O2/c33-31(34,35)25-18-24(19-26(20-25)32(36,37)38)29(30(42)39-27-14-8-3-9-15-27)40(21-23-12-6-2-7-13-23)28(41)17-16-22-10-4-1-5-11-22/h1-2,4-7,10-13,18-20,27,29H,3,8-9,14-15,21H2,(H,39,42)
InChIKey:
UYXAPLVGIOTMNK-UHFFFAOYAP
Std. InChI:
InChI=1S/C32H28F6N2O2/c33-31(34,35)25-18-24(19-26(20-25)32(36,37)38)29(30(42)39-27-14-8-3-9-15-27)40(21-23-12-6-2-7-13-23)28(41)17-16-22-10-4-1-5-11-22/h1-2,4-7,10-13,18-20,27,29H,3,8-9,14-15,21H2,(H,39,42)
Std. InChIKey:
UYXAPLVGIOTMNK-UHFFFAOYSA-N