Exp234

media type="custom" key="4933637"
 * [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 CHCl 3 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 1 H 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 ** 1 **H and ** 13 **C 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).


 * 1 H NMR with TMS converted by Dr. Williams:[|234hnmrtmsjdx] **

1 H 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]** 1 H NMR with TMS: [|Ugi2.1tms.pdf], [|Ugi2.1tmsdoublet.pdf], [|Ugi2.1tmsclose.pdf]

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]
 * 13 **C NMR: [|ugi2.2c13], [|ugi2.2c13close]
 * 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 CDCl 3 (Z1:-1217;Z2:-1031;Z3:-166;Z4=981) 15.52 - Ran ** 1 **H NMR on CDCl 3 sample - 8 scans (Gain:25) 16.00 - Cleaned tube with CHCl 3 16.05 - Ran ** 1 **H NMR on CDCl 3 sample - 8 scans (Gain:22) 16.18 - Ran ** 1 **H NMR on CDCl3 sampe in new clean tube - 8 scans (Gain:26) 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 ** 1 **H and ** 13 **C NMR probes 16.56 - single pulse ** 1 **H NMR on Ugi2.2 - 8 scans (Gain:16) 17.06 - single pulse ** 1 **H NMR on Ugi2.2 - 64 scans (Gain:16) [|uc234_2_2_hnmr] - set-up computer experiment sequence to run the following overnight: ** 13 **C 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 CHCl 3 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 CDCl 3 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)
 * 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 ||
 * 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 ||
 * Chemical Shift (ppm) || Area under peak || Interpretation ||
 * 1.6 || 1.00 || Impurity in CDCl3 ||
 * 7.27 || 0.40 || CHCl3 residual ||

** Spectra of Starting Materials **

** [|3,5-bis(trifluoromethyl)benzaldehyde] ** [] (FTIR) [] (FTNMR predicted)

<span style="color: black; font-family: Arial,Helvetica,sans-serif; font-size: 10pt; line-height: normal; margin-bottom: 0pt; margin-left: 0in; margin-right: 0in; margin-top: 0in;">Phenylpropionic acid <span style="font-family: Arial,Helvetica,sans-serif; line-height: normal; margin-bottom: 0pt; margin-left: 0in; margin-right: 0in; margin-top: 0in;"> [|http://webbook.nist.gov/cgi/cbook.cgi?ID=C501520&Units=SI&Type=IR-SPEC#IR-SPEC] (FTIR) <span style="font-family: Arial,Helvetica,sans-serif; line-height: normal; margin-bottom: 0pt; margin-left: 0in; margin-right: 0in; margin-top: 0in;"> [] (FTNMR)

<span style="color: black; font-family: Arial,Helvetica,sans-serif; font-size: 10pt; line-height: normal; margin-bottom: 0pt; margin-left: 0in; margin-right: 0in; margin-top: 0in;">Benzylamine <span style="font-family: Arial,Helvetica,sans-serif; line-height: normal; margin-bottom: 0pt; margin-left: 0in; margin-right: 0in; margin-top: 0in;"> [|http://webbook.nist.gov/cgi/cbook.cgi?ID=C100469&Type=IR-SPEC&Index=1#IR-SPEC] (FTIR) <span style="font-family: Arial,Helvetica,sans-serif; line-height: normal; margin-bottom: 0pt; margin-left: 0in; margin-right: 0in; margin-top: 0in;"> [] (FTNMR)

<span style="color: black; font-family: Arial,Helvetica,sans-serif; font-size: 10pt; line-height: normal; margin-bottom: 0pt; margin-left: 0in; margin-right: 0in; margin-top: 0in;">Cyclohexylisocyanide <span style="font-family: Arial,Helvetica,sans-serif; line-height: normal; margin-bottom: 0pt; margin-left: 0in; margin-right: 0in; margin-top: 0in;"> [] (FTIR) <span style="font-family: Arial,Helvetica,sans-serif; line-height: normal; margin-bottom: 0pt; margin-left: 0in; margin-right: 0in; margin-top: 0in;"> [] (FTNMR)

<span style="color: black; font-family: Arial,Helvetica,sans-serif; font-size: 10pt; line-height: normal; margin-bottom: 0pt; margin-left: 0in; margin-right: 0in; margin-top: 0in;">Methanol <span style="font-family: Arial,Helvetica,sans-serif; font-size: 12pt; line-height: normal; margin-bottom: 0pt; margin-left: 0in; margin-right: 0in; margin-top: 0in;">[] (FTIR Low-Quality) <span style="font-family: Arial,Helvetica,sans-serif; font-size: 12pt; line-height: normal; margin-bottom: 0pt; margin-left: 0in; margin-right: 0in; margin-top: 0in;">[] (FTIR High-Quality) <span style="font-family: Arial,Helvetica,sans-serif; font-size: 12pt; line-height: normal; margin-bottom: 0pt; margin-left: 0in; margin-right: 0in; margin-top: 0in;">[] (FTNMR) <span style="font-family: Arial,Helvetica,sans-serif; font-size: 12pt; line-height: normal; margin-bottom: 0pt; margin-left: 0in; margin-right: 0in; margin-top: 0in;">[] (FTNMR)

<span style="font-family: Arial,Helvetica,sans-serif;">Acknowledgements
<span style="font-family: Arial,Helvetica,sans-serif;"> 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 ||