Ethyl(1R,2S,3S,4S)-2-(furan-2-yl)-3-nitro-6-oxobicyclo[2.2.2]octane-1-carboxylate

Ethyl(1R,2S,3S,4S)-2-(furan-2-yl)-3-nitro-6-oxobicyclo[2.2.2]octane-1-carboxylate

Compound 7 Ethyl(1R,2S,3S,4S)-2-(furan-2-yl)-3-nitro-6-oxobicyclo[2.2.2]octane-1-carboxylate To a solution of CAT 10 (128 mg, 0.37 mmol) and the nitroolefin 9 (3.1 g, 22.3 mmol) in 10 mL anhydrous CH2Cl2 at room temperature was added enone 8 (1.8 g, 10.7 mmol). The resulting mixture was stirred at the same temperature until enone 8 is consumed as indicated by TLC. Then DBU (0.34 mL, 3.20 mmol) was added and the mixture was allowed to stir at ambient temperature until completion as indicated by TLC. The solution was concentrated in vacuo and purified by flash chromatography on silica gel (Hexane / EtOAc = 20 / 1) to give 7 (2 g, 61% yield) as a yellow solid. [α]D 23 28.0 (c = 1.0, CHCl3).

1H NMR (400 MHz, CDCl3): δ 7.29 (d, J = 0.8 Hz, 1H), 6.27 (dd, J = 2.0 Hz, J = 3.2 Hz, 1H), 6.14 (d, J = 4.0 Hz, 1H), 4.93 (m, 1H), 4.57 (d, J = 4.4 Hz, 1H), 4.11 (m, 2H), 3.04-3.02 (m, 1H), 2.80-2.75 (m, 1H), 2.60- 2.54 (m, 1H), 2.33-2.29 (m, 1H), 1.88-1.72 (m, 2H), 1.33-1.23 (m, 1H), 1.21 (t, J = 7.2 Hz, 3H).

13C NMR (100 MHz, CDCl3): δ 204.1, 168.7, 151.8, 142.5, 110.5, 108.1, 88.3, 61.3, 56.3, 42.0, 40.8, 33.7, 26.9, 19.2, 13.8.

IR (thin film): 3435, 3141, 3120, 2996, 2959, 1715, 1653, 1621, 1557, 1505, 1473, 1443, 1408, 1371, 1336, 1301, 1336, 1301, 1270, 1236, 1142, 1120, 1083, 1062, 1074, 1045, 1045, 1011, 996, 960, 930, 892, 884, 867, 803, 753, 628, 600, 508, 436 cm-1 .

LRMS (ESI): 308.0 (M+H)+ , 330.0 (M+Na)+ .

HRMS (ESI): calcd for C15H18O6N (M+H) + : 308.1129. Found: 308.1130.

Melting point: 117-118 oC.

Concise asymmetric total synthesis of (−)-patchouli alcohol

 Author affiliations

Abstract

The asymmetric total synthesis of (−)-patchouli alcohol was accomplished in a concise manner. Key reactions include a highly diastereo- and enantioselective formal organocatalytic [4 + 2] cycloaddition reaction, a radical denitration reaction, and an oxidative carboxylation reaction. The formal synthesis of norpatchoulenol was achieved as well.

Graphical abstract: Concise asymmetric total synthesis of (−)-patchouli alcohol

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2,5-Bis(ethoxymethyl)furan

2,5-Bis(ethoxymethyl)furan, 6

1H NMR (CDCl3) = 6.20 (s, 2H), 4.36 (s, 4H), 3.47 (q, 4H, J = 7.1 Hz), 1.16 (t, 6H, J = 7.1 Hz);

13C NMR (CDCl3) = 150.9, 109.7, 65.7, 64.7, 15.1 ppm

PREDICTS

Green Chem., 2017, Advance Article

DOI: 10.1039/C7GC02211E, Paper

F. A. Kucherov, K. I. Galkin, E. G. Gordeev, V. P. Ananikov

Efficient one-pot synthesis of tricyclic compounds from biobased 5-hydroxymethylfurfural (HMF) is described using a [4 + 2] cycloaddition reaction.

Efficient route for the construction of polycyclic systems from bioderived HMF

 Author affiliations

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NOESY experiment of diastereomer 10α (3S, 5R) …….(3S,5R)-3-Benzyl-5-isobutyl-1,3,4,5-tetrahydro-2H-thieno[3,2-e]- [1,4]diazepin-2-one (10α)

NOESY experiment of diastereomer 10α (3S, 5R)

(3S,5R)-3-Benzyl-5-isobutyl-1,3,4,5-tetrahydro-2H-thieno[3,2-e]- [1,4]diazepin-2-one (10α):

Pale yellow solid, 50% (64.0 mg),

m.p. 66.7–67.4 °C.

[α]D 29 = –122.2 (c = 1.0, MeOH).

1 H NMR (CDCl3, 300 MHz): δ = 0.90 (d, J = 6.3 Hz, 3 H), 0.92 (d, J = 6.6 Hz, 3 H), 1.36–1.54 (m, 2 H), 1.81 (m, 1 H), 2.08 (s, 1 H), 3.13 (d, J = 5.1 Hz, 2 H), 3.93 (t, J = 5.1 Hz, 1 H), 4.67 (dd, J = 3.0, J = 9.9 Hz, 1 H), 7.15–7.30 (m, 8 H) ppm.

13C NMR (CDCl3, 75 MHz): δ = 21.48, 23.79, 24.71, 36.81, 42.09, 59.63, 73.76, 111.68, 120.97, 125.09, 126.92, 126.97, 128.70, 129.83 (2 C), 135.11, 136.90, 172.65 ppm.

LC–MS (ESI+): m/z = 315.2 [M + H]+.

HRMS: calcd. for C18H23N2OS 315.1531 [M + H]+; found 315.1531

10.1002/ejoc.201500943

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trans-2-(benzo[d][1,3]dioxol-5-yl)-2-methylcyclopropane-1-carbonitrile

trans-2-(benzo[d][1,3]dioxol-5-yl)-2-methylcyclopropane-1-carbonitrile

yellowish solid (53 mg, 66%);

m.p. = 72 °C;

1 H-NMR (600 MHz, CDCl3): δ = 6.77 – 6.71 (m, 3H), 5.94 (s, 2H), 1.63 – 1.59 (m, 4H), 1.50 (dd, J = 9.1, 5.0 Hz, 1H), 1.26 (t, J = 5.3 Hz, 1H);

13CNMR (151 MHz, CDCl3): δ = 147.80, 146.73, 136.69, 120.64, 120.23, 108.28, 108.17, 101.19, 28.75, 23.86, 21.40, 11.30;

HRMS (ESI): m/z calc. for [C12H11O2NK]: 240.0414, found 240.04204;

IR (KBr): νmax/cm-1 = 2972, 2897, 2231, 1490, 1457, 1434, 1349, 1226, 1080, 1033, 924, 869, 808, 728.

1H NMR PREDICT

13C NMR PREDICT

 Green Chem., 2017, Advance Article

DOI: 10.1039/C7GC00602K, Communication

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C[C@@]1([C@H](C#N)C1)C2=CC(OCO3)=C3C=C2

2-{[6-Chloro-3-methyl-2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl]methyl}-4-fluorobenzonitrile

2-{[6-Chloro-3-methyl-2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl]methyl}-4-fluorobenzonitrile (4)

white solid . Mp: 193–195 °C.
1H NMR (400 MHz, CDCl3) δ (ppm): 7.74–7.76(m, 1H), 7.14–7.17 (m, 1H), 6.95–6.97 (m, 1H), 6.05 (s, 1H), 5.51 (s, 2H), 3.40 (s, 3H).

8-Oxo-5-aza-spiro[2.5]octane-5-carboxylic acid benzyl ester,

str2

1H NMR PREDICT OF TITLE COMPD

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13C NMR PREDICT

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8-Oxo-5-aza-spiro[2.5]octane-5,7-dicarboxylic acid 5 benzyl ester 7 methyl ester
COMPD 5

SYNTHESIS CONSTRUCTION BY WORLDDRUGTRACKER………EXCLUSIVE

 

सुकून उतना ही देना प्रभू, जितने से जिंदगी चल जाये। औकात बस इतनी देना, कि औरों का भला हो जाये।
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09b37-misc2b027LIONEL MY SON
He was only in first standard in school when I was hit by a deadly one in a million spine stroke called acute transverse mylitis, it made me 90% paralysed and bound to a wheel chair, Now I keep him as my source of inspiration and helping millions, thanks to millions of my readers who keep me going and help me to keep my son happy
सुकून उतना ही देना प्रभू, जितने से
जिंदगी चल जाये।
औकात बस इतनी देना,
कि औरों का भला हो जाये।

 

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7-allyl-6-hydroxy-indan-1-one…Mom will teach you NMR

Figure US08242291-20120814-C00009

Thermal Claisen rearrangement on 6-allyloxy-indan-1-one,  (III) to obtain 7-allyl-6-hydroxy-indan-1-one, (IV):

  • Formula: C12H12O2
  • Molecular Weight: 188.22200
Synonyms:

http://www.google.com/patents/US8242291
EXAMPLE 2

This example refers to reaction b of the process of the invention.
20 kg of the intermediate of formula (III) prepared as described in example 1 are suspended in 50 l of Dowtherm A under nitrogen flow. In an inert atmosphere, it is heated to approximately 200° C. for approximately 5 hours. Upon completion of the reaction (TLC) a clear red-brown solution is obtained, without the formation of black pitch. The reaction mixture is cooled slowly to 25° C. (a partial precipitation is observed). 100 l (5 volumes) of cyclohexane are added and it is cooled to between 0 and 5° C. for one hour. It is filtered by washing with cyclohexane and dried at reduced pressure and T=45° C. for at least 12 hours. 16.8 kg of yellow solid are obtained which is refluxed in 80 l of toluene in the presence of decolouring carbon. The suspension is filtered, washing it with hot toluene. Part of the solvent is distilled at reduced pressure until the beginning of crystallisation. It is cooled at room temperature and then to between 0 and 5° C. for at least one hour.
The filtered solid is washed with cold toluene and dried at reduced pressure at T=45° C. for at least 12 hours. 15.3 kg of intermediate (IV) are obtained in the form of an almost white solid of quality suitable for continuation of the synthesis.
1H-NMR and mass spectroscopic analyses are performed on part of the product thus obtained, purified by chromatography for analytical purposes (silica gel, 7 parts in volume of heptane—3 parts in volume of ethyl acetate), obtaining the following results:
Electron impact mass: [M+]=188
1H-NMR (500 MHz, CDCl3): δ (ppm)
2.72 ppm, t, J=6 Hz, 2H,  AR C=OCH2 CH2 AR
3.03 ppm, t, J=6 Hz, 2H, AR C=OCH2 CH2 AR
4.03 ppm, d, J=6 Hz, 2H, ARCH2CH=CH2
5.13-5.20, Σd, 2H, ARCH2CH=CH2
5.60 ppm, s, 1H, 0H
5.98-6.10 ppm, m, 1H, CH2CH=CH2
7.13 ppm, d, J=8 Hz, 1H, AR
7.25, d, J=8 Hz, 1H. AR
PREDICT
1H NMRCLICK ON PICTURE

6-hydroxy-7-prop-2-enyl-2,3-dihydroinden-1-one NMR spectra analysis, Chemical CAS NO. 320574-77-4 NMR spectral analysis, 6-hydroxy-7-prop-2-enyl-2,3-dihydroinden-1-one H-NMR spectrum13 C NMR

CLICK ON PICTURE

6-hydroxy-7-prop-2-enyl-2,3-dihydroinden-1-one NMR spectra analysis, Chemical CAS NO. 320574-77-4 NMR spectral analysis, 6-hydroxy-7-prop-2-enyl-2,3-dihydroinden-1-one C-NMR spectrum
6-hydroxy-7-prop-2-enyl-2,3-dihydroinden-1-one

COSY PREDICT

HMBC PREDICT

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COCK SAYS MOM CAN TEACH YOU NMR

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