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Ezetimibe NMR

October 8, 2015 7:26 am / Leave a comment

Ezetimibe

Marcin Śnieżek, Sebastian Stecko, Irma Panfil, Bartłomiej Furman, and Marek Chmielewski *

Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland

J. Org. Chem., 2013, 78 (14), pp 7048–7057

DOI: 10.1021/jo400807c..http://pubs.acs.org/doi/full/10.1021/jo400807c

Ezetimibe (1)

ezetimibe 1 (1.08 g, 80%) as a white solid.

Mp 164–166 °C [lit.(11) 155–157 °C];

99% ee;

[α]²⁰_D −28.1 (c 0.15, MeOH) [lit.(11) −32.6 (c 0.34, MeOH)];

¹H NMR (600 MHz, DMSO-d₆) δ 9.49 (1H, s), 7.28–7.24 (2H, m), 7.19–7.16 (4H, m), 7.11–7.07 (4H, m), 6.75–6.71 (2H, m), 5.25 (1H, d, J 4.3 Hz), 4.77 (1H, d, J 2.2 Hz), 4.49–4.59 (1H, m), 3.07–3.04 (1H, m) 1.84–1.66 (4H, m);

¹³C NMR (150 MHz, CDCl₃) δ 167.8, 162.3, and 160.7 (d, J_C–F 240.3 Hz), 159.3, 157.9, 157.7, 142.5, 134.4, 128.7, 128.3, 128.0, 127.9, 118.7, and 118.6 (d, J_C–F 8.1 Hz), 116.3, 116.2, 115.2, and 115.0 (d, J_C–F 20.7 Hz), 71.5, 60.0, 59.9, 36.8, 24.9;

HRMS (EI, TOF) m/z calcd for C₂₄H₂₁F₂NO₃ [M] 409.1489 found 409.1478. Anal. Calcd for C₂₄H₂₁F₂NO₃: C 70.41, H 5.17, F 9.28, N 3.42. Found: C 70.46, H 5.23, F 9.24, N 3.34.

(3S,4S)-4-(4-(Benzyloxy)phenyl)-1-(4-fluorophenyl)-3-((S)-3-(4-fluorophenyl)-3′-hydroxypropyl)azetidin-2-one (20)

Method 1

To a cooled (0 °C) solution of lactone 19 (2.0 g, 4 mmol) in 160 mL of dry diethyl ether was added 12 mL of 1 M solution of t-BuMgCl in diethyl ether. After 2 h, 30 mL of aq NH₄Cl was added. The aqueous layer was extracted with ether (160 mL), the organic layer was washed with satd NaHCO₃ (50 mL) and dried (MgSO₄), and the solvent was removed under reduced pressure. Crude product 20 (1.64 g, 82%) obtained as a yellowish solid was used in the next step without further purification. An analytic sample was obtained by chromatography on silica gel (hexanes/ethyl acetate 7:3). Mp 130–133 °C [lit.(11) 132–134 °C]; [α]²⁰_D −42.2 (c 1.2, CHCl₃); ¹H NMR (600 MHz, CDCl₃) δ 7.42–7.20 (11H, m), 7.02–6.90 (6H, m), 5,04 (2H, s), 4.72–4.68 (1H, m), 4.55 (1H, d J 2.2 Hz), 3.07 (1H, dt J 7.1, 2.2 Hz), 2.05–1.93 (3H, m) 1.89–1.82 (2H, m); ¹³C NMR (150 MHz, CDCl₃) δ 167.6, 163.0, and 161.4 (d, J_C–F 244.2 Hz), 159.8 and 158.1 (d, J_C–F 241.8 Hz), 159.0, 140.0, 139.9, 136.6, 133.9, and 133.8 (d, J_C–F 2.9 Hz), 129.6, 128.6, 128.1, 127.5, 127.4 and 127.4, (d, J_C–F 8.0 Hz), 127.2, 118.4, 118.3, 115.8, 115.8, and 115.7 (d, J_C–F 22.0 Hz), 115.5, 115.4, and 115.3 (d, J_C–F 21.3 Hz), 73.3, 70.1, 61.1, 60.3, 36.5, 25.0; HRMS (ESI, TOF) m/z calcd for C₃₁H₂₇F₂NO₃Na [M + Na]⁺ 522.1851, found 522.1862; IR (KBr) v 3441, 1743, 1609, 1510 cm^–1. Anal. Calcd for C₃₁H₂₇F₂NO₃: C 74.53, H 5.45, N 2.80, F 7.61. Found: C 74.40, H 5.53, N 2.74, F 7.56.

Org. Process Res. Dev., 2009, 13 (5), pp 907–910

DOI: 10.1021/op900039z

http://pubs.acs.org/doi/abs/10.1021/op900039z

Preparation of 1-(4-Fluorophenyl)-3-(R)-[3-(4-fluorophenyl)-3(S)-hydroxypropyl]-4(S)-(4-hydroxyphenyl)-2-azetidinone 1 (Ezetimibe)

of compound 1. ¹H NMR (300 MHz, DMSO-d₆, δ) 1.72−1.84 (m, 4H), 3.08 (m, 1H), 4.45 (m, 1H), 4.8 (d, 1H, J = 2.0 Hz), 5.25 (d, 1H, J = 4.8), 6.75 (d, 2H, J = 8.4 Hz), 7.05−7.4 (m, 10H, Ar), 9.48 (s, 1H); IR: 3270.0, 2918, 1862, 1718.4, 1510 cm⁻¹. MS: m/z 409.2 (M⁺). Anal. Calcd for C₁₅H₁₇NO₅: C, 70.41; H, 5.17; N, 3.42. Found: C, 70.38; H, 5.27; N, 3.34.

Preparation of (3R,4S)-1-(4-Fluorophenyl)-3-[3-(4-fluorophenyl)-3(S)-hydroxypropyl]-4-(4-benzyloxyphenyl)-2-azetidinone 10

compound 9 as a white solid. ¹H NMR (200 MHz, DMSO-d₆, δ) 1.6−1.9 (m, 4H), 2.0−2.2 (bs, 1H), 3.0−3.2 (m, 1H), 4.4−4.6 (m, 1H), 4.74 (m, 1H), 5.05 (s, 2H), 6.95−7.9 (m, 17H, Ar); IR: 3492, 2922, 2852, 1719 cm⁻¹; MS: m/z 499.3 (M⁺).

….

doi:10.1016/j.jpha.2015.04.002

Scheme 1.

Synthesis of ezetimibe and desfluoro ezetimibe impurity.

http://www.sciencedirect.com/science/article/pii/S2095177915000386

Fig. 4.

Fig. 2.

Structures of ezetimibe, desfluoro impurity and intermediates.

Comparison of ¹H, ¹³C and ¹⁹F NMRs of ezetimibe and desfluoro ezetimibe impurity.

Table 2.¹H and ¹³C NMR assignments for Eze-1 and desfluoro Eze-1.

Position^a	¹H–δ ppm		¹³C–δ ppm (DEPT)
Position^a	Eze-1^b	Desfluoro Eze-1^b	Eze-1^b	Desfluoro Eze-1^b
1	10.15 (br, OH)	10.13 (br, OH)	–	–
2	–	–	161.3 (C)	161.3 (C)
3	6.87 (d, J=8.5 Hz, 2H)	6.87 (dd, J=8.4, 1.8 Hz, 2H)	116.3 (2CH)	116.3 (2CH)
4	7.74 (d, J=8.5 Hz, 2H)	7.75 (dd, J=8.4, 1.8 Hz, 2H)	131.4 (2CH)	131.4 (2CH)
5	–	–	128.1 (C)	128.2 (C)
6	8.43 (s, 1H)	8.43 (s, 1H)	160.8 (CH)	160.8 (CH)
7	–	–	149.0 (d, ⁴J=2.6 Hz, C)	152.7 (C)
8	7.15–7.26 (m, 4H)	7.36 (dd, J=8.1, 7.5 Hz, 2H)	123.3 (d, ³J=8.4 Hz, 2CH)	121.6 (2CH)
9	7.15–7.26 (m, 4H)	7.17 (d, J=7.8 Hz, 2H)	116.5 (d, ²J=22 Hz, 2CH)	129.8 (2CH)
10	–	7.18 (t, J=6.3 Hz, 1H)	160.8 (d, ¹J=242 Hz, C)	126.0 (CH)

Assignments: s: singlet; d: doublet; t: triplet; m: multiplet; br: broad singlet. Mean values used for coupled signals.

aNumbering of all compounds shown in Fig. 2 and copies of NMR spectra are presented in Appendix A.

bSolvent is DMSO-d6.

R-Enantiomer in Ezetimibe

R-Enantiomer in Ezetimibe

ABOVE 1H NMR OF R ENANTIOMER

Isolation and Characterization of R-Enantiomer in Ezetimibe

http://www.scirp.org/journal/PaperDownload.aspx?paperID=36901

by K Chimalakonda – ‎2013 – ‎Related articles

HPLC1H and 13C NMR. The purity of isolated R-Isomer is about 98%. Keywords: Isolation; Characterization; (R)-Isomer; Ezetimibe; Supercritical Fluid …

http://file.scirp.org/Html/10-2200417_36901.htm

1H NMR VALUES FOR R ENANTIOMER

13C NMR OF R ENANTIOMER

13C NMR VALUES OF R ENANTIOMER

IR OF R ENANTIOMER

Ezetimibe for reference

163222-33-1

Ezetimibe
Systematic (IUPAC) name

(3R,4S)-1-(4-fluorophenyl)-3-[(3S)-3-(4-fluorophenyl)-3-hydroxypropyl]-4-(4-hydroxyphenyl)azetidin-2-one
Clinical data
Trade names	Zetia
AHFS/Drugs.com	monograph
MedlinePlus	a603015
Pregnancy category	AU: C US: C
Legal status	AU: Prescription Only (S4) CA: ℞-only UK: POM US: ℞-only
Routes	Oral
Pharmacokinetic data
Bioavailability	35–65%
Protein binding	>90%
Metabolism	Intestinal wall, hepatic
Half-life	19–30 hours
Excretion	Renal 11%, faecal 78%
Identifiers
CAS number	163222-33-1
ATC code	C10AX09
PubChem	CID 150311
DrugBank	DB00973
ChemSpider	132493
UNII	EOR26LQQ24
KEGG	D01966
ChEBI	CHEBI:49040
ChEMBL	CHEMBL1138
Chemical data
Formula	C₂₄H₂₁F₂N O₃
Molecular mass	409.4 g·mol⁻¹
SMILES [show]
InChI [show]
Physical data
Melting point	164 to 166 °C (327 to 331 °F)
(what is this?) (verify)

1H NMR OF R ENANTIOMER PREDICTED

Ezetimibe NMR spectra analysis, Chemical CAS NO. 163222-33-1 NMR spectral analysis, Ezetimibe H-NMR spectrum

13C NMR OF R ENANTIOMER PREDICTED

Ezetimibe NMR spectra analysis, Chemical CAS NO. 163222-33-1 NMR spectral analysis, Ezetimibe C-NMR spectrum

cosy

Ezetimibe has the chemical name 1-(4-fluorophenyl)-3(R)-[3-(4-fluorophenyl)-3(S)-hydroxypropyl]-4(S)-(4-hydroxyphenyl)-2-azetidinone (hereinafter referred to by its adopted name “ezetimibe”) and is structurally represented by Formula I.

Ezetimibe is in a class of lipid lowering compounds that selectively inhibit the intestinal absorption of cholesterol and related phytosterols. It is commercially available in products sold using the trademark ZETIA as a tablet for oral administration containing 10 mg of ezetimibe, and in combination products with simvastatin using the trademark VYTORIN.

U.S. Pat. No. 6,096,883 discloses generically and specifically ezetimibe and its related compounds along with their pharmaceutical compositions. The patent also describes a process for the preparation of ezetimibe.

The process described in the patent involves the use of methyl-4-(chloroformyl) butyrate and also involves isolation of the compound (3R,4S)-1-(4-fluorophenyl)-3-[3-(chloroformyl)-3-oxo-propyl]-4-(4-benzyloxyphenyl)-2-azetidinone as an intermediate. Chlorinated compounds are unstable and difficult to handle in large scale productions. The process described in the patent also involves the purification of intermediates using column chromatography, thus making the process difficult to be scaled up.

Processes for preparation of ezetimibe and its intermediates have also been described in U.S. Pat. Nos. 6,207,822, 5,856,473, 5,739,321, and 5,886,171, International Application Publication No. WO 2006/050634, and in Journal of Medicinal Chemistry 1998, 41, 973-980, Journal of Organic Chemistry 1999, 64, 3714-3718, and Tetrahedron Letters, 44(4), 801-804.

http://www.google.com/patents/US20070049748

EXAMPLE 10 PREPARATION OF 1-(4-FLUOROPHENYL)-3(R)-[3-(4-FLUOROPHENYL)-3(S)-HYDROXYPROPYL]-4(S)-(4-HYDROXYPHENYL)-2-AZETIDINONE (FORMULA I)

50 g of (3R,4S)-1-(4-fluorophenyl)-3-[3-(4-fluorophenyl)-3(s)-hydroxypropyl]-4-(4-benzyloxyphenyl)-2-azetidinone and 475 ml of methanol were taken into a round bottom flask. A mixture of 15 g of 5% palladium on carbon and 25 ml of water was added to it. The reaction mass was flushed with hydrogen gas and a hydrogen pressure of 3 to 5 kg/cm2 was applied. The reaction mass was stirred for 3 hours. Reaction completion was checked using thin layer chromatography. After the reaction was completed, the pressure was released and the reaction mass was filtered through perlite. The filter bed was washed with 100 ml of methanol. The filtrate was distilled completely at 70° C., and 400 ml of isopropanol was added to it. The reaction mass was heated to 45° C. and maintained for 10 minutes. The reaction mass was then allowed to cool to 28° C. 400 ml of water was added to the reaction mass and stirred for 1 hour, 20 minutes. The separated compound was filtered and washed with 100 ml of water. The wet cake was taken into another round bottom flask and 500 ml of chlorobenzene and 40 ml of methanol were added to it. The reaction mass was heated to 65° C. and maintained for 15 minutes. 25 ml of water was added to the reaction mass and stirred for 2 hours. The separated compound was filtered and washed with 100 ml of chlorobenzene. The wet cake was taken into another round bottom flask and 375 ml of chlorobenzene, and 30 ml of methanol were added to it. The reaction mass was heated to 62° C. and maintained for 10 minutes. The reaction mass was then cooled to 28° C. and 20 ml of water was added to it. The reaction mass was stirred for 20 minutes and then filtered and washed with 100 ml of chlorobenzene. The wet cake was taken into another round bottom flask and 400 ml of isopropanol was added to it. The reaction mass was heated to 46° C. and maintained for 15 minutes. 800 ml of water was added to the reaction mass at 45 to 46° C. and stirred for one hour. The separated solid was filtered and washed with water. The process of recrystallization in a combination of isopropanol and water was repeated and the obtained compound was dried at 70° C. for 5 hours to get 19.8 g of the title compound. (Yield 49.2%)

Purity by HPLC: 99.68%.

EXAMPLE 11 PURIFICATION OF 1-(4-FLUOROPHENYL)-3(R)-[3-(4-FLUOROPHENYL)-3(S)-HYDROXYPROPYL]-4(S)-(4-HYDROXYPHENYL)-2-AZETIDINONE (FORMULA I)

15.0 g of ezetimibe obtained above and 120 ml of isopropanol were taken into a round bottom flask and the reaction mass was heated to 48° C. The reaction mass was filtered through a perlite bed in the hot condition to make the solution particle free. The filtrate was taken into another round bottom flask and heated to 47° C. 240 ml of water was added at 47° C. After completion of the addition, the reaction mass was maintained at 47° C. for 1 hour. The separated solid was filtered and washed with 30 ml of water. The wet compound was dried at 70° C. for 8 hours to get 13.4 g of the title compound. (Yield 89%)

Purity by HPLC: 99.92.

benzyl ezetimibe impurity: less than 0.0003 area-%,

benzyl ezetimibe diol impurity: 0.004 area-%,

lactam cleaved alcohol impurity: 0.003 area-%,

lactam cleaved acid impurity: 0.01 area-%,

ezetimibe diol impurity: less than 0.0007 area-%.

Residual solvent content by gas chromatography:

Isopropyl alcohol: 1454 ppm

All other solvents: Less than 100 ppm.

WO1997045406A1 *	May 28, 1997	Dec 4, 1997	Schering Corp	3-hydroxy gamma-lactone based enantioselective synthesis of azetidinones
WO2004099132A2	May 5, 2004	Nov 18, 2004	Ram Chander Aryan	Process for the preparation of trans-isomers of diphenylazetidinone derivatives
WO2008032338A2 *	Sep 10, 2007	Mar 20, 2008	Reddy Maramreddy Sahadeva	Improved process for the preparation of ezetimibe and its intermediates
EP0720599A1	Sep 14, 1994	Jul 10, 1996	Schering Corporation	Hydroxy-substituted azetidinone compounds useful as hypocholesterolemic agents
US20070049748	Aug 25, 2006	Mar 1, 2007	Uppala Venkata Bhaskara R	Preparation of ezetim

Citing Patent	Filing date	Publication date	Applicant	Title
US7470678	Jul 1, 2003	Dec 30, 2008	Astrazeneca Ab	Diphenylazetidinone derivatives for treating disorders of the lipid metabolism
US7842684	Apr 25, 2007	Nov 30, 2010	Astrazeneca Ab	Diphenylazetidinone derivatives possessing cholesterol absorption inhibitor activity
US7863265	Jun 19, 2006	Jan 4, 2011	Astrazeneca Ab	N-{[4-((2R,3R)-1-(4-fluorophenyl)-3-{[(2R or S)-2-(4-fluorophenyl)-2-hydroxyethyl]thio}-4-oxoazetidin-2-yl)phenoxy]acetyl}glycyl-D-lysine, used as anticholesterol agents
US7871998	Dec 21, 2004	Jan 18, 2011	Astrazeneca Ab	Diphenylazetidinone derivatives possessing cholesterol absorption inhibitory activity
US7893048	Jun 21, 2006	Feb 22, 2011	Astrazeneca Ab	2-azetidinone derivatives as cholesterol absorption inhibitors for the treatment of hyperlipidaemic conditions
US7906502	Jun 21, 2006	Mar 15, 2011	Astrazeneca Ab	2-azetidinone derivatives as cholesterol absorption inhibitors for the treatment of hyperlipidaemic conditions
US8013150 *	Feb 17, 2006	Sep 6, 2011	Msn Laboratories Ltd.	Process for the preparation of ezetimibe
US8383810	Dec 12, 2011	Feb 26, 2013	Merck Sharp & Dohme Corp.	Process for the synthesis of azetidinones
US20110130378 *	May 26, 2009	Jun 2, 2011	Lek Pharmaceuticals D.D.	Ezetimibe process and composition
US20110183956 *	Jul 29, 2009	Jul 28, 2011	Janez Mravljak	Process for the synthesis of ezetimibe and intermediates useful therefor
EP2128133A1	May 26, 2008	Dec 2, 2009	Lek Pharmaceuticals D.D.	Ezetimibe process and composition
WO2008096372A2 *	Feb 6, 2008	Aug 14, 2008	Pranav Gupta	Process for preparing highly pure ezetimibe using novel intermediates
WO2009150038A1	May 26, 2009	Dec 17, 2009	Lek Pharmaceuticals D.D.	Process for the preparation of ezetimibe and composition containing it
WO2009157019A2 *	Jun 23, 2009	Dec 30, 2009	Ind-Swift Laboratories Limited	Process for preparing ezetimibe using novel allyl intermediates

WO2005021497A2 *	Aug 27, 2004	Mar 10, 2005	Eduardo J Martinez	Tethered dimers and trimers of 1,4-diphenylazetidn-2-ones
WO2006127893A2 *	May 25, 2006	Nov 30, 2006	Microbia Inc	Processes for production of 4-(biphenylyl)azetidin-2-one phosphonic acids
WO2008096372A2 *	Feb 6, 2008	Aug 14, 2008	Pranav Gupta	Process for preparing highly pure ezetimibe using novel intermediates
US20070049748 *	Aug 25, 2006	Mar 1, 2007	Uppala Venkata Bhaskara R	Preparation of ezetimibe

/////

Your Aunt can teach you Organic Opectroscopy

August 2, 2014 3:10 am / Leave a comment

Organic spectroscopy should be brushed up and you get confidence

read my blog

ORGANIC SPECTROSCOPY INTERNATIONAL is the blog

Organic chemists from Industry and academics to interact on Spectroscopy techniques for Organic compounds ie NMR, MASS, IR, UV Etc. email me ……….. amcrasto@gmail.com

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feder-0005.gif from 123gifs.eu amcrasto@gmail.com

Oleanolic acid spectral data and interpretation

http://orgspectroscopyint.blogspot.in/2014/08/oleanolic-acid-spectral-data-and.html

Oleanolic acid
(4aS,6aR,6aS,6bR,8aR,10S,12aR,14bS)-10-hydroxy-2,2,6a,6b,9,9,12a-heptamethyl-1,3,4,5,6,6a,7,8,8a,10,11,12,13,14b-tetradecahydropicene-4a-carboxylic acid

Oleanic acid, Caryophyllin, Astrantiagenin C, Giganteumgenin C, Virgaureagenin B, 3beta-Hydroxyolean-12-en-28-oic acid, OLEANOLIC_ACID

Molecular Formula: C₃₀H₄₈O₃

Molecular Weight: 456.70032

http://orgspectroscopyint.blogspot.in/2014/08/oleanolic-acid-spectral-data-and.html

Ursolic acid [(3b)-3-Hydroxyurs-12-en-28-oic acid] rarely occurs without its isomer oleanolic acid [(3b)-3-Hydroxyolean-12-en-28-oic acid] They may occur in their free acid form, as shown in Figure 1, or as aglycones for triterpenoid saponins which are comprised of a triterpenoid aglycone linked to one or more sugar moieties. Ursolic and oleanolic acids are similar in pharmacological activity

A pentacyclic triterpene that occurs widely in many PLANTS as the free acid or the aglycone for many SAPONINS. It is biosynthesized from lupane. It can rearrange to the isomer, ursolic acid, or be oxidized to taraxasterol and amyrin.

MS
EIMS m/z (rel. int.) 456 [M]+ (5), 412 (3), 248 (100), 203 (50), 167 (25), 44 (51)

IR KBR
(KBr) 3500, 2950, 2850, 1715; 1H-NMR (250 MHz, pyridine-d5) δ: 5.49 (1H, s, H-12), 3.47 (1H, t, J = 8.0 Hz, H-3), 3.30 (1H, m, H-18), 1.12 (3H, s, CH3-27), 0.96 (3H, s, CH3-30), 0.91 (3H, s, CH3-25), 0.89 (3H, s, CH3-23), 0.87 (3H, s, CH3-24), 0.75 (3H, s, CH3-26)

http://orgspectroscopyint.blogspot.in/2014/08/oleanolic-acid-spectral-data-and.html

1H NMR

(250 MHz, pyridine-d5)δ: 5.49 (1H, s, H-12), 3.47 (1H, t, J = 8.0 Hz, H-3), 3.30 (1H, m, H-18), 1.12 (3H, s, CH3-27), 0.96 (3H, s, CH3-30), 0.91 (3H, s, CH3-25), 0.89 (3H, s, CH3-23), 0.87 (3H, s, CH3-24), 0.75 (3H, s, CH3-26)

13 C NMR

(63 MHz, pyridine-d5) δ: 180.2 (C-28), 144.8 (C-13), 122.5 (C-12), 78.0 (C-3), 55.7 (C-5), 48.0 (C-9), 46.6 (C-8, 17), 42.1 (C-14), 39.7 (C-4), 39.4 (C-1), 37.3 (C-10), 33.2 (C-7), 32.9 (C-29), 32.4 (C-21), 30.9 (C-20), 28.7 (C-23), 27.2 (C-2), 26.9 (C-15), 26.1 (C-30), 23.7 (C-11), 23.6 (C-16), 18.7 (C-6), 17.4 (C-26), 16.5 (C-24), 15.5 (C-25)

http://orgspectroscopyint.blogspot.in/2014/08/oleanolic-acid-spectral-data-and.html

http://www.google.com/patents/US20120237629

FIG. 4 shows the ¹H NMR spectrum of oleanolic acid;

FIG. 5 shows the ¹³C NMR spectrum of oleanolic acid;

FIG. 6 shows the ¹³C DEPT NMR spectrum of oleanolic acid;

FIG. 7 shows the ¹H ¹³C HSQC NMR spectrum of oleanolic acid;

see below

http://orgspectroscopyint.blogspot.in/2014/08/oleanolic-acid-spectral-data-and.html

EXAMPLE 2 Extraction and Isolation of Oleanolic Acid (9) and Maslinic Acid (10) from Cloves

Syzygium aromaticum dried buds or whole cloves were obtained commercially. The cloves (1.5 kg, whole) of Syzygium aromaticum were sequentially and exhaustively extracted with hexane and ethyl acetate to give, after solvent removal in vacuo, a hexane extract (68.8 g, 4.9%) and an ethyl acetate extract (34.1 g, 2.3%). A portion of the ethyl acetate extract (10.0 g), was subjected to chromatographic separation on silica gel (60-120 mesh) column (40×5.0 cm). Elution with hexane/ethyl acetate solvent mixtures (8:2→6:4) afforded pure oleanolic acid (9) (4.7 g, 1.06%), a mixture of oleanolic acid (9) and maslinic acid (10) (0.5 g), and pure maslinic acid (10) (0.25 g). The structures of oleanolic acid (9) and maslinic acid (10) (as 2,3-diacetoxyoleanolic acid) were confirmed by spectroscopic data analysis (1D and 2D ¹H NMR and ¹³C NMR experiments) (FIGS. 4-7 and FIGS. 8-10, respectively).

http://orgspectroscopyint.blogspot.in/2014/08/oleanolic-acid-spectral-data-and.html

THANKS AND REGARD’S
DR ANTHONY MELVIN CRASTO Ph.D

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GLENMARK SCIENTIST , INDIA
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Mom will teach you NMR

July 26, 2014 11:38 am / Leave a comment

Dedicated to all moms in the world

ETHYL PROPIONATE NMR, carbonyl is dad and oxygen mom, a methyl gets more attention

ORIGINALLY IN http://orgspectroscopyint.blogspot.in/2014/07/ethyl-propionate-nmr-carbonyl-is-dad.html

C=O group is dad

O atom is mom

Carbonyl is dad and oxygen mom hence c labelled methyl has higher chemical shift and gets a little more attention

SEE BELOW

NMR IS EASY

A chemical has Formula: C₅H₁₀O₂

C₅H₁₀O₂
Rule 2, omit O, gives C₅H₁₀
5 – 10/2 + 1 = 1 degree of unsaturation.
Look for 1 pi bond or aliphatic ring.

The band at 1740 indicates a carbonyl, probably a saturated aliphatic ester. The bands at 3000-2850 indicate C-H alkane stretches. The bands in the region 1320-1000 could be due to C-O stretch, consistent with an ester.

Structure answer

This is the structure. See if you can assign the peaks on your own.

NMR answer

C has a higher chemical shift than D because it’s closer to a more electron-withdrawing functional group.

Carbonyl is dad and oxygen mom, hence c has higher chemical shift and gets a little more attention in proton nmr

13 C NMR

Mass spectrum

RAMAN

WHAT HAPPENS WHEN A CHLORO IS INTRODUCED

THE INTERPRETATION IS BELOW

remember “a” labelled CH3 appears as a doublet

WHEN THERE IS ONE METHYL

WHEN THERE ONE CH2 SHORT

WHEN MOM HAS ONE MORE CH2

PROPYL PROPIONATE, try this on your own

1H NMR

see interpretation

BIGGER ONE THAN OBOVE

13C NMR

APT

COSY

WILL PASTE INTERPRETATION AFTER ONE WEEK……………….

13C NMR OF SIMPLE MOLECULES…………..Brush up….???

April 8, 2014 2:14 pm / 1 Comment on 13C NMR OF SIMPLE MOLECULES…………..Brush up….???

ما هو هذا، لماذا أنت قلق، فرشاة مع الأشياء البسيطة، وسوف يخرج عبقري، وتعلم معي، قطرات صغيرة من الماء جعلالمحيطات، وسوف يكون خبيرا في هذا

what is this, why are you worried, brush up with simple things, you will come out genius, learn with me, small drops of water make an ocean, you will be an expert in this

あなたが心配している理由は、これは簡単なことでブラッシュアップ、、何か、あなたは、天才が出てくる私と一緒に学ぶことが、水の小さな滴が海を作るには、この専門家になる

structure

Name: 1,2-dimethoxymethane

C₄H₁₀O₂

From the molecular formula, the compound has “0 degrees of unsaturation” (no double bonds or rings).

C13 Spectrum

The ¹³C NMR has two peaks, a quartet at 54 (a CH₃) and a triplet at 80 (a CH₂). Since the molecule has four carbons and only two ¹³C NMR peaks, there must be symmetry. Both peaks are in the regions where carbons next to electronegative atoms occur (oxygen).

τι είναι αυτό, γιατί είσαι ανήσυχος, βούρτσα με απλά πράγματα, θα βγει ιδιοφυΐα, να μάθουν μαζί μου, μικρές σταγόνες του νερού κάνει έναν ωκεανό, θα είστε ένας εμπειρογνώμονας σε αυτό

আপনি চিন্তিত কেন এই সহজ জিনিস নিয়ে ব্রাশ,, কি, আপনি, প্রতিভা বাইরে আসতে আমার সাথে শিখতে হবে, জলের ছোট ঝরিয়া একটি মহাসাগর না, আপনি এই একজন বিশেষজ্ঞ হতে হবে

C₅H₇O₂N

From the molecular formula, the compound has “3 degrees of unsaturation” (3 double bonds or rings).

structure

: ethyl cyanoacetate

C13 Spectrum

The ¹³C NMR has 5 peaks, a quartet at 14 (a CH₃), a triplet at 59 (a CH₂), another triplet at 22 (another CH₂), and two singlets, one at 118 and one at 172. Since the molecule has five carbons and five ¹³C NMR peaks, there must be no symmetry. The singlet at 172 is in the carbonyl region, most likely an acid or an ester. The CH₂ at 59 is in the region where carbons next to electronegative atoms occur (i.e., oxygen) and the CH₃ at 14 is a simple terminal methyl, suggesting an -O-CH₂CH₃ residue. The singlet at 118 would be consistent with a nitrile carbon and the shielded CH₂ at 22 suggests that it may be adjacent to the sp-carbon of the nitrile

מה זה, למה אתה מודאג, לרענן עם דברים פשוטים, אתה תצא גאון, ללמוד איתי, טיפות קטנות של מיםיגרמו לים, אתה תהיה מומחה בזה

C₆H₁₀OFrom the molecular formula, the compound has “2 degrees of unsaturation” (2 double bonds or rings).

C13 Spectrum

structure

2-butanon-4-ene

The ¹³C NMR has 6 peaks, a quartet at 25 (a CH₃), a triplet at 49 (a CH₂), another quartet at 17 (another CH₃), two doublets (a CH) , one at 124 and one at 131, and one singlet at 207. Since the molecule has six carbons and six ¹³C NMR peaks, there must be no symmetry. The singlet at 207 is in the carbonyl region, most likely an aldehyde or ketone. The CH₃ groups at 17 and 25 are consistent with simple terminal methyl groups, with one slightly shifted by an mildly electronegative group (a carbonyl?). The doublets at 124 and 131 are in the alkene region, suggesting a -CHCH- group. The remaining CH₂ group at 49 is probably deshielded by two electronegative groups.

o que é isso, por que você está preocupado, retocar com coisas simples, você vai sair gênio, aprender comigo, pequenas gotas de água fazem um oceano, você vai ser um especialista neste

C₈H₈O

From the molecular formula, the compound has “5 degrees of unsaturation” (5 double bonds or rings).

structure

acetophenone

C13 Spectrum

The ¹³C NMR has 6 peaks, a quartet at 27 (a CH₃), three doublets (CH groups), at 129, 128 and 133, and two singlets, one at 137 and one at 197. Since the molecule has eight carbons and six ¹³C NMR peaks, there must some degree of symmetry. The singlet at 197 is in the carbonyl region, most likely an aldehyde or ketone. The CH₃ groups at 27 is consistent with a simple terminal methyl group, slightly shifted by an mildly electronegative group (a carbonyl?). The doublets at 129, 128 and 133 and the singlet at 137 are in the aromatic region, suggesting a monosubstituted aromatic group, with symmetry in four of the six carbons.

நீங்கள் கவலை ஏன் இந்த எளிய பொருட்களை கொண்டு துலக்க, என்ன, நீங்கள், மேதை வெளியே வர எனக்கு கற்று, நீர் சிறு துளிகள் ஒரு கடல் செய்ய, நீங்கள் இந்த ஒரு நிபுணர் இருக்கும்

के तपाईं चिंतित हो किन यो सरल कुरा संग ब्रश,, के हो, तपाईं, प्रतिभा बाहिर आउन मलाई संग सिक्न हुनेछ, पानी सानो थोपा एक महासागर बनाउन, तपाईं यस मा एक विशेषज्ञ हुनेछ\

તમને ચિંતા થતી હોય કે શા માટે આ સરળ બાબતો સાથે બ્રશ, શું છે, તમે પ્રતિભા બહાર આવે મારી સાથે શીખશે, પાણી નાના ટીપાં સમુદ્ર કરો, તો તમે આ એક નિષ્ણાત હશે

kas tas ir, kāpēc jūs uztraucaties, suka ar vienkāršām lietām, jūs iznākt ģēnijs, mācīties kopā ar mani, nelieli ūdens pilieni veikt okeānu, jums būs eksperts šajā

что это такое, почему ты беспокоишься, освежить с простых вещей, вы будете выходить гений, узнать со мной, маленькие капли воды сделать океан, вы будете экспертом в этом

hvað er þetta, af hverju ert þú áhyggjur, bursta upp með einföldum hlutum, verður þú að koma út snillingur, læra með mér, litla dropa af vatni gera haf, verður þú að vera sérfræðingur í þessu

C₆H₈OFrom the molecular formula, the compound has “3 degrees of unsaturation” (3 double bonds or rings).

structure

cyclohexanon-2-ene

The ¹³C NMR has 6 peaks, three triplets (CH₂ groups) at

46, 30 and 41, two doublets (CH groups), at

129 and 145, and one singlet at

198. Since the molecule has six carbons and six ¹³C NMR peaks, there must be no symmetry. The singlet at

198 is in the carbonyl region, most likely an aldehyde or ketone. Two of the three CH₂ groups are shifted by electronegative groups, suggesting a X-CH₂-CH₂-CH₂-Y unit. The doublets at

129 and 145 are in the alkene region, suggesting a -CH

CH- group. The three degrees of unsaturation suggests that the molecule also has a ring.

这是什么，你为什么担心，刷了简单的事情，你会出来的天才，学我，小水珠做出的海洋，你将在这方面的专家

당신이 걱정하는 이유는 간단한 것들로 브러시, 무엇인가, 당신은 천재 나올 나와 함께 배울 것, 물 작은 방울은 바다를 만들어,이 분야의 전문가가 될 것입니다

Electronegative groups are “deshielding” and tend to move NMR signals from attached carbons further “downfield” (to higher ppm values).
The -system of alkenes, aromatic compounds and carbonyls strongly deshield C nuclei and move them “downfield” to higher ppm values.
Carbonyl carbons are strongly deshielded and occur at very high ppm values. Within this group, carboxylic acids and esters tend to have the smaller values, while ketones and aldehydes have values 200.

The ¹³C chemical shift is dependent both on the presence of electronegative groups and on the steric environment. This is best demonstrated by examining a variety of hexane isomers:

Simple interior (primary and secondary) carbons tend to be in the range 25 – 45. Methyl groups which terminate unbranched alkyl chains, however, are significantly shielded (moved to lower values), as shown by the examples above ( 14, 14.3 and 8.7). The origin of this effect is thought to be steric compression in the gamma () position due to gauche interactions. This is shown schematically below and the gamma position is marked above in the example for hexane.

The presence of an electronegative atom such as oxygen tends to move the chemical shift of the Œ-carbon down into the region 65 – 90, as shown in the examples below:

Halogens, however, have effects which are difficult to predict and carbons adjacent to halogens tend to have chemical shifts in the 30 – 50 region, as shown below. The effects are not simply additive, however, and multiple substitution can often be shielding (move the signal to lower values). The nitrile carbon is significantly shielding and adjacent carbons tend to occur in the 20 – 25 region.

Alkene carbons tend to have chemical shifts in the range 110 – 140, as shown in the examples below. Conjugation between alkene centers has little effect, as demonstrated by the two middle structures shown below. Conjugation with an oxygen, however, has a dramatic shielding effect, which is attributed to contributions from the resonance forms shown below.

Alkyne carbons occur in the region 65 -85, and are significantly shielding to the carbons which are immediately adjacent ( 1.5 for the terminal methyl of 2-pentyne).

Carbonyls are the most highly deshielded carbons which are typically encountered. Their intensity is usually weak, since there are no attached hydrogens to contribute to the Nuclear Overhauser Effect enhancement (with the exception of aldehydes). Typical chemical shifts occur in the region 170 – 210 with esters, carboxylic acids and amides at the low end, and simple ketones and aldehydes at the high end of the range.

Aromatic carbons have chemical shifts in the range 120 – 140 and are shifted within this range by the nature of the attached substituent. The multiplicity of aromatic peaks in the non-decoupled spectrum is useful for identifying aromatic substitution patterns.

آپ پریشان کیوں ہیں اس سادہ چیزوں کے ساتھ برش،، کیا ہے، آپ، ہوشیار باہر آ میرے ساتھ سیکھ جائے گی، پانی کے چھوٹے چھوٹے قطرے ایک سمندر بنانے کے لئے، آپ کو اس میں ایک ماہر ہو جائے گا

THANKS AND REGARD’S
DR ANTHONY MELVIN CRASTO Ph.D

amcrasto@gmail.com

MOBILE-+91 9323115463

GLENMARK SCIENTIST , INDIA
web link

ABOUTME

BRAND ANTHONYCRASTO

COLLECTION OF SITE LINKS

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Congratulations! Your presentation titled “Anthony Crasto Glenmark scientist, helping millions with websites” has just crossed MILLION views.

アンソニー安东尼 Энтони 안토니 أنتوني

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1H NMR OF SIMPLE MOLECULES.. Brush up

April 8, 2014 10:43 am / 1 Comment on 1H NMR OF SIMPLE MOLECULES.. Brush up

what is this, why are you worried, brush up with simple things, you will come out genius, learn with me, small drops of water make an ocean, you will be an expert in this

structure

4-methylbenzaldehyde

NMR Spectrum

The proton NMR has three peaks; a singlet at 2.2 (3H), and a singlet at 10 (1H) and two doublets centered around 7.6. The doublets centered at 7.6 are in the aromatic region; the fact that two doublets are observed (2H each) suggests a 1,4-disubstituted aromatic compound.

The peak at 2.2 is in the region for a methyl group adjacent a mildly electronegative group. The singlet at 10 is in the region observed for aldehydic protons. The presence of two doublets in the aromatic region is highly characteristic of 1,4-disubstitution.

structure

methyl acetate (methyl ethanoate)

NMR Spectrum

The proton NMR has two singlets of equal area. The fact that the molecule has 6 hydrogens means that there must be two non-identical CH₃ groups in the molecule and that they are non-adjacent. The peak at 1.95 is in the area generally observed for methyl groups adjacent to carbonyls; the peak at 3.85 is in the region for methyl groups adjacent to electronegative atoms, i.e., oxygen.

structure
diethyl ketone (3-pentanone)

NMR Spectrum

The proton NMR has a quartet and a triplet, indicating a CH₂ adjacent to a CH₃. The peak at 2.5 is in the area generally observed for methyl groups adjacent to mildly electronegative groups; the peak at 1.2 is in the region for simple methyl groups adjacent to carbons (CH₃CH₂). The molecule contains oxygen, but the peak at 2.5 is not shifted enough for this to represent an -O- linkage, so it must represent a carbonyl.

structure

acetaldehyde (ethanal)

NMR Spectrum

The proton NMR has two peaks; at high resolution, fine coupling is evident between them (J 1 Hz) with the peak at 9.7 being a quartet and the peak at 2.1 being a doublet, indicating a CH coupled to a CH₃. The peak at 9.7 is in the area generally observed for aldehydic protons; the peak at 2.1 is in the region for a methyl group adjacent a carbonyl. The molecule contains oxygen, but the peak at 2.1 is not shifted enough for this to represent an -O- linkage, so it must represent a carbonyl. The very small coupling constant suggests that the proton and the CH₃ group are not immediately adjacent, but that this represents an example of cross-space coupling.

o que é isso, por que você está preocupado, retocar com coisas simples, você vai sair gênio, aprender comigo, pequenas gotas de água fazem um oceano, você vai ser um especialista neste

structure

Name: ethyl acetate (ethyl ethanoate)

NMR Spectrum

The proton NMR has three peaks; a quartet at 4.1 (2H), a triplet at 1.2 (3H) and a singlet at 1.97 (3H). The quartet and triplet suggest a CH₂ coupled to a CH₃ in an ethyl group. The peak at 4.1 is in the area generally observed for CH groups adjacent to electronegative groups, i.e., oxygen. The peak at 2 is in the region for a methyl group adjacent a carbonyl.

kas tas ir, kāpēc jūs uztraucaties, suka ar vienkāršām lietām, jūs iznākt ģēnijs, mācīties kopā ar mani, nelieli ūdens pilieni veikt okeānu, jums būs eksperts šajā

methyl vinyl ether (methyl ethenyl ether)

The proton NMR has four groups of peaks; the singlet at

3.6 (3H) is consistent with an isolated CH₃ group adjacent to an electronegative center, such as oxygen. The sets of highly split doublets centered at

6.5, 4.2 and 4.0 (there is overlap of these at

4.1) span the region where alkene hydrogens are observed. The complex splitting pattern observed resembles an ABC pattern for a terminal alkene.

这是什么，你为什么担心，刷了简单的事情，你会出来的天才，学我，小水珠做出的海洋，你将在这方面的专家

Name: 1,2-dimethoxyethane

The proton NMR has two peaks; both singlets are consistent with isolated groups adjacent to an electronegative center, such as oxygen. The fact that the molecule contains ten hydrogens, but only shows singlets for two and three hydrogens requires a great deal of symmetry in the molecule, i.e., both CH₃ groups must be identical, as must both CH₂ groups.

4-isopropyl-1-methoxybenzene (4-(1-methylethyl)-1-methoxybenzene)

The proton NMR has four sets of peaks; a singlet at

3.6 (3H), two sets of doublets centered around

6.9 (4H), a septet at

2.7 (1H) and a doublet at

1.6. The singlet at

3.6 is consistent with an isolated CH₃adjacent to an electronegative center, such as an oxygen. The septet and doublet strongly suggest an isopropyl group

CH(CH₃) ₂ in which the carbon is bonded to something mildly electronegative and the two doublets centered at

6.9 strongly suggest a 1,4-disubstituted aromatic compound.

3-bromomethyltoluene (3-bromomethyl-1-methylbenzene)

The proton NMR has three sets of peaks; a singlet at

4.3 (2H), a messy singlet around

7.1 (4H), and a singlet at

2.3 (3H). The singlet at

2.3 is consistent with an isolated CH₃ adjacent to a mildly electronegative center. The singlet at 4.3 is consistent with a CH₂ group adjacent to two mildly electronegative centers (X-CH₂-Y), and the singlet at

7.1 is consistent with a disubstituted aromatic compound. The substitution pattern is not what is normally seen in 1,4-disubstitution (two doublets), suggesting 1,2 or 1,3-disubstitution.

THANKS AND REGARD’S
DR ANTHONY MELVIN CRASTO Ph.D

amcrasto@gmail.com

MOBILE-+91 9323115463

GLENMARK SCIENTIST , INDIA
web link

ABOUTME

BRAND ANTHONYCRASTO

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Diethyl benzylmalonate, IR, NMR, Mass

April 8, 2014 7:01 am / 1 Comment on Diethyl benzylmalonate, IR, NMR, Mass

structure

The mass spectrum displays a molecular ion, an m-45 and a peak at m/e = 91, all of which are consistent with a molecule containing benzyl and ethoxy groups.

The ¹³C spectrum contains six peaks, indicating that the molecule has some elements of symmetry. The quartet at 56 and the triplet at 71 represent a CH₃ and a CH₂ group which are deshielded by electronegative atoms (most likely oxygen); the peaks at 161 – 128 are in the aromatic region; the fact that three doublets and one singlet are observed strongly suggests monosubstitution.

The proton NMR also shows evidence for two ethyl groups, a CH-CH₂– group, and a monosubstituted aromatic group; the chemical shift suggests that the carbons of the CH-CH₂– adjacent to one or more electronegative groups.

The IR is consistent with an aromatic compound containing a carbonyl group.

The simplest structure which is consistent with all of these data would be an aromatic compound linked via a -CH₂CH group to a diethyl ester.

Structure:

IUPAC Name: ethyl ethyl benzylpropanedioate (diethyl benzylmalonate)

607-81-8

C₁₄H₁₈O₄; MW = 250.29

1H NMR

The proton NMR has a coupled quartet and a triplet, consistent with an ethyl group in which the CH₂ (at 4.1) is adjacent to an electronegative atom (most likely oxygen). The presence of a coupled triplet and doublet suggests the presence of a CH-CH₂– group in which both carbons are adjacent to one or more electronegative atoms. The singlet at 7.1 is consistent with a monosubstituted aromatic compound.

NMR Spectrum

13C NMR

The ¹³C spectrum contains nine peaks, indicating that the molecule has some elements of symmetry. The quartet at 14 and the triplet at 60 represent a simple CH₃ and a CH₂ which is deshielded by an electronegative atom (most likely oxygen); the doublet at 58 and the triplet at 36 are CH and CH₂ groups which are adjacent to one or more electronegative groups. The peaks at 141 – 125 are in the aromatic region; the fact that three doublets and one singlet are observed strongly suggests monosubstitution.

¹³C NMR Assignments: C-13 assignments

MASS

The mass spectrum consists of a molecular ion at 250, a base peak at 91 (a benzyl group), an m-45 peak at 205, indicating the presence of an ethoxy group; other significant peaks at 131 and 176 must be consistent with the proposed structure. The spectrum is consistent with a molecule containing ethoxy and benzyl groups.

Mass Spectrum

Mass Spectrum Fragments: C-13 assignments

3400-3200 cm^–¹: no OH peak 3100 cm^–¹: small peak, suggesting unsaturated CH 2900 cm^–¹: strong peak suggesting saturated CH 2200 cm^–¹: no unsymmetrical triple bonds 1730 cm^–¹: strong carbonyl 1610 and 1500 cm^–¹: weak peaks, vaguely consistent with aromatic carbon-carbon double bonds

ADDITIONAL INFO FOR READER ON SPECTROSCOPY

SEE THE FUN WHEN A CARBONYL IS INTRODUCED

BENZOYLMALONIC ACID DIETHYL ESTER Structure

1H NMR

13 C NMR

MASS

RAMAN

4-methoxyphenyl methanol, (4-メトキシフェニル)メタノール NMR, IR , MASS

April 8, 2014 6:19 am / 3 Comments on 4-methoxyphenyl methanol, (4-メトキシフェニル)メタノール NMR, IR , MASS

(4-methoxyphenyl)methanol

Structure:

IUPAC Name: 4-methoxyphenyl methanol

C₆H₁₀O₃; MW = 138.17

The molecule contains two oxygens, and from the analysis, contains four double bonds, carbonyls or rings. The large number of degrees of unsaturation strongly suggests an aromatic compound (DU = 4).

The mass spectrum displays a molecular ion, which is the base peak, an m-1 and an m-17, all of which are consistent with a simple alcohol.

The ¹³C spectrum contains six peaks, indicating that the molecule has some elements of symmetry. The quartet at 56 and the triplet at 71 represent a CH₃ and a CH₂ group which are deshielded by electronegative atoms (most likely oxygen); the peaks at 161 – 128 are in the aromatic region; the fact that two doublets and two singlets are observed strongly suggests 1,4-disubstitution.

The proton NMR also shows evidence for aromatic 1,4-disubstitution and suggests that the methyl and methylene are isolated and adjacent to electronegative groups. A peak consistent with an alcoholic OH can also be seen.

The IR is consistent with an aromatic alcohol containing no carbonyl group, suggesting that the second oxygen is involved in an ether linkage.

The simplest structure which is consistent with all of these data would be an aromatic compound containing an alcohol group and a methyl ether, situated 1,4 relative to each other.

IH NMR

The proton NMR has two doublets at 6.9, consistent with aromatic 1,4-disubstitution, and three singlets, areas 3, 2 and 1. The singlets at 3.6 and 4.7 are highly shifted and suggest isolated CH₃ and CH₂ groups adjacent to one or more electronegative atoms or groups. The singlet, area 1, would be consistent with an alcohol.

NMR Spectrum

Predict NMR spectrum

13C NMR

The ¹³C spectrum contains six peaks, indicating that the molecule has some elements of symmetry. The quartet at 56 and the triplet at 71 represent a CH₃ and a CH₂ group which are deshielded by electronegative atoms (most likely oxygen); the peaks at 161 – 128 are in the aromatic region; the fact that two doublets and two singlets are observed strongly suggests 1,4-disubstitution.

¹³C NMR Data: q-56.0; t-71.0; d-114.3; d-128.3; s-160.9; s-133.2

¹³C NMR Assignments: C-13 assignments

MASS

The mass spectrum consists of a molecular ion at 138, which is also the base peak, an m-1 peak at 137, indicating the presence of a labile hydrogen (OH or CHO), and an m-17 peak (loss of HO-). The spectrum is consistent with an alcohol which cannot readily break down to form other stable radical cations.

Mass Spectrum

Mass Spectrum Fragments: C-13 assignments

3400-3200 cm^–¹: strong OH peak 3100 cm^–¹: small peak, suggesting possible unsaturated CH 2900 cm^–¹: strong peak suggesting saturated CH 2200 cm^–¹: no unsymmetrical triple bonds 1710 cm^–¹: no carbonyl 1610 and 1500 cm^–¹: sharp peaks, consistent with aromatic carbon-carbon double bonds

Synthetic Communications, 18, p. 613, 1988 DOI: 10.1080/00397918808064019
Synthesis, p. 1081, 1984
Tetrahedron Letters, 32, p. 3243, 1991

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