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Organic Synteses vol 70 - Meyers A.I.

Meyers A.I. , Boecman R.K. Organic Synteses vol 70 - John Wiley & Sons, 1992. - 163 p.
ISBN 0-471-57743
Download (direct link): organicsynthesesvol701992.pdf
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1. Department of Chemistry, University of Texas at Austin, Austin, TX 78712.
2. Procedure of Kambe and Yasuda: Kambe, S.; Yasuda, H. Bull. Chem. Soc. Jpn. 1968, 41, 1444.
3. Procedure of Tindall: Tindall, J. B. Ind. Eng. Chem. 1941, 33, 65.
4. Procedure of Barton and Zard: Barton, D. H. R.; Zard, S. Z. J. Chem. Soc., Chem. Commun. 1985, 1098.
5. Ono, N.; Maruyama, K. Chem. Lett. 1988, 1511.
6. Fischer, H.; Guggemos, H.; Schäfer, A. Ann. Chem. 1939, 540, 30.
7. "The Porphyrins”; Dolphin, D., Ed.; Academic Press: New York, 1978-1979; Vols. I-VI I.
8. (a) Lindsey, J. S.; Hsu, H. C.; Schreiman, I. C. Tetrahedron Lett. 1986, 27, 4969; (b) Lindsey, J. B.; Schreiman, I. C.; Hsu, H. C.; Kearney, P. C.; Marguerettaz, A. M. J. Org. Chem. 1987, 52, 827; (c) Wagner, R. W.; Lawrence,
D. S.; Lindsey, J. S. Tetrahedron Lett. 1987, 28, 3069.
9. (a) Eisner, U.; Lichtarowicz, A.; Linstead, R. P. J. Chem. Soc. 1957, 733; (b) Eisner, U.; Linstead, R. P.; Parkes, E. A.; Stephen, E. J. Chem. Soc. 1956, 1655.
10. Whitlock, H. W.; Hanauer, R. J. Org. Chem. 1968, 33, 2169.
11. Paine, J. B., Ill; Kirshner, W. B.; Moskowitz, D. W.; Dolphin, D. J. Org. Chem. 1976, 41, 3857.
12. Wang, C.-B.; Chang, C. K. Synthesis, 1979, 548.
13. Inhoffen, H. H.; Fuhrhop, J. H.; Voight, H.; Brockmann, H., Jr. Ann. Chem. 1966, 695, 133.
14. (a) Cheng, D. O.; LeGoff, E. Tetrahedron Lett. 1977,1469; b) LeGoff, E.; Cheng, D. O., In "Porphyrin Chemistry Advances"; F. R. Longo, Ed.; Ann Arbor Science Publishers, 1979; pp. 153-156.
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15. Callot, H. J.; Louati, A.; Gross, M. Bull. Soc. Chim. Fr. 1983, 317; Callot, H. J.; Louati, A.; Gross, M. Angew. Chem., Inter. Ed. Engl. 1982, 21, 285.
16. Treibs, A.; Haberle, N. Justus Liebigs Ann. Chem. 1968, 718, 183.
17. Alternatively, the ethyl 3,4-diethylpyrrole-2-carboxylate may be carried on directly to give octaethylporphyrin,5 although the yields reported (ca. 40%) are not quite as good as those obtained by the present procedure. Similarly, this substance or the 3,4-diethylpyrrole produced by the present procedure could conceivably serve as the basis for an an improved synthesis via a Mannich base-type approach such as that outlined in refs. 9 -12.
18. The procedure reported here appears to be quite general. We have, for example, used it to prepare a p-substituted tetrakis-fused cyclohexylporphyrin (1,2,3,4,8,9,10,11,15,16,17,18,22, 23,24,25-hexadecahydro-29H,31 H-tetra-benzo[BGLQ]porphine) in 51% overall yield starting from 1-nitrocyclohexene.
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Appendix
Chemical Abstracts Nomenclature (Collective Index Number); (Registry Number)
3.4-Diethylpyrrole: Pyrrole, 3,4-diethyl- (8,9); (16200-52-5)
2,3,7,8,12,13,17,18-Octaethylporphyrin: Porphine, 2,3,7,8,12,13,17,18-octaethyl- (8);
21 H,23H-Porphine, 2,3,7,8,12,13,17,18-octaethyl- (9); (2683-82-1)
4-Nitro-3-hexanol: 3-Hexanol, 3-nitro- (8,9); (5342-71-2)
Propionaldehyde (8); Propanal (9); (123-38-6)
1-Nitropropane: Propane, 1-nitro- (8,9); (108-03-2)
4-Acetoxy-3-nitrohexane: 3-Hexanol, 4-nitro-, acetate (9); (3750-83-2)
Acetic anhydride (8); Acetic acid anhydride (9); (108-24-7)
Ethyl 3,4-diethylpyrrole-2-carboxylate: 1 H-Pyrrole-2-carboxylic acid,
3.4-diethyl-, ethyl ester (11); (97336-41-9)
Ethyl isocyanoacetate: Acetic acid, isocyano-, ethyl ester (8,9); (2999-46-4)
1,8-Diazabicyclo[5.4.0]undec-7-ene: Pyrimido[1,2-a]azepine, 2,3,4,6,7,8,9,10-octahydro- (8,9); (6674-22-2)
Formaldehyde (8,9); (50-00-0)
p-Toluenesulfonic acid (8); Benzenesulfonic acid, 4-methyl- (9); (6192-52-5) Trichloromethyl chloroformate: Formic acid, chloro-, trichloromethyl ester (8); Carbonochloridic acid, trichloromethyl ester (9); (503-38-8)
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PREPARATION AND DIELS-ALDER REACTION OF A REACTIVE, ELECTRON-DEFICIENT HETEROCYCLIC AZADIENE: DIMETHYL 1,2,4,5-TETRAZINE-3.6-DICARBOXYLATE. 1,2-DIAZINE AND PYRROLE INTRODUCTION
1,2,4,5-Tetrazine-3,6-dicarboxylic acid, dimethyl ester)
A. 2 N2CHC02C2H5
F.
NaOH
C.
E.
Zn
h2o
C02Na
1
n^nh
HN^N
C02Na
1
D. 3
CH3COOH
PhNU
T NH
dioxane 25 °C
C02CH3
C02CH3
B.
HCI
h2o
nitrous gases CH2CI2
C02CH3
C02CH3
5
C02H
1
n^nh
HN^N
C02H
2
co2ch3
N^N
co2ch3
4
Submitted by Dale L. Boger, James S. Panek, and Mona Patel.1 Checked by Richard Hutchings and Albert I. Meyers.
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1. Procedure2
A. Disodium dihydro-1,2,4,5-tetrazine-3,6-dicarboxylate. A 2-L, three-necked, round-bottomed flask is equipped with an overhead stirrer, thermometer, and a 500-mL addition funnel. Sodium hydroxide (320 g, 8 mol) and 500 mL of water are added. Ethyl diazoacetate (200 g, 1.75 mol, Note 1) is placed in the addition funnel and added dropwise to the stirred sodium hydroxide solution so as to maintain the temperature of the reaction mixture between 60°C and 80°C (approximately 1.5 hr, Note 2). After the reaction slurry is cooled to room temperature, it is poured into 2 L of 95% ethanol, mixed well, and the liquid is decanted. This washing procedure is repeated five times using 1.5 L of 95% ethanol each time. The precipitate is collected by filtration using a Buchner funnel, the collected solid is washed with 1 L of absolute ethanol and 1 L of ether, and dried (12 hr) in the air to afford 160-184 g (85-97%) of disodium dihydro-
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