Books
in black and white
Main menu
Home About us Share a book
Books
Biology Business Chemistry Computers Culture Economics Fiction Games Guide History Management Mathematical Medicine Mental Fitnes Physics Psychology Scince Sport Technics
Ads

Organic syntheses vol 58 - Sheppard W.A.

Sheppard W.A., Buchi G.H. Organic syntheses vol 58 - Wiley, 1978. - 123 p.
Download (direct link): organicsynthesesvol581978.pdf
Previous << 1 .. 53 54 55 56 57 58 < 59 > 60 61 62 63 64 65 .. 93 >> Next

6. The checkers prepared diethyl fumarate by the sulfuric acid-catalyzed esterification of fumaric acid.7 Diethyl fumarate obtained from Aldrich Chemical Company, Inc., contained dimethyl fumarate as a contaminant.
7. The submitters allowed the reaction to proceed for 24 hours after monitoring by gas chromatography (1.83 m. x 0.64 cm., 10%
166
ORGANIC SYNTHESES—VOL. 58
SE-30/60-80 mesh Chromosorb W, 150°) indicated that the disappearance of diethyl fumarate was not complete after 5.5 hours. The submitters made no attempt to optimize the reaction time. The checkers found the reaction to be complete after 7 hours at 135-145°.
8. The checkers distilled cyclohexene 2 after 7 hours’ reaction time using a Biichi Kugelrohr apparatus to obtain 9.9-10.0 g. (95-96%) of cyclohexene 2.
9. Cyclohexene 2 has the following spectral properties: infrared (liquid film) cm 1730, 1670; proton magnetic resonance: (carbon tetrachloride) 8 (multiplicity, number of protons, assignments, coupling constant J in Hz.): 0.16 [singlet, 9, Si(CH3)3], 1.17 (triplet, 6, CH3, J= 7), 2.00-3.16 (multiplet, 6, ring CH), 4.07 (quartet, 4, ÎCH2, J = 7), 4.70 (broad singlet, 1, olefinic CH).
3. Discussion
The first reference to 2-trimethylsilyloxy-l,3-butadiene (1) was a report2 of its reaction with tetracyanoethylene by Cazeau and Frainnet without mention of any experimental details. Later, Conia3 reported its synthesis in 50% yield with only a reference made to the usual House procedure4 for silyl enol ethers. The diene 1 has also been prepared using lithium diisopropylamide as base and chlorotrimethylsilane in tetrahydrofuran-ether (1:1) in yields up to 65%, but on a smaller scale.5
TABLE I
Preparation of Trimethylsilyloxycyclohexenes
ÑÎÑÍç H H 60
ñî2ñí3 H H 46
co2ch3 H CO ,CH, 71
co2c2H5 H co2c2h5 77
co2c2h5 CO,C2H5 H 39
2-TRIMETHYLSILYLOXY-l,3-BUTADIENE AS A REACTIVE DIENE 167
Butadienes substituted with alkoxy groups in the 2-position, e.g.,
2-ethoxy-1,3-butadiene,6 have been prepared from methyl vinyl ketone, but they required several conversions and a tedious spinning-band distillation to purify the product. This slight modification of the House procedure has been used to conveniently prepare 2-trimethylsilyloxy-l,3-butadiene from the readily available methyl vinyl ketone. This one-step procedure has provided large amounts of a new and reactive diene for Diels-Alder reactions, as illustrated in Table I.
1. Contribution No. 3759 from the Department of Chemistry, University of California, Los Angeles, California 90024.
2. P. Cazeau and E. Frainnet, Bull. Soc. Chim. Fr., 1658 (1972).
3. C. Girard, P. Amice, J. P. Barnier, and J. M. Conia, Tetrahedron Lett., 3329 (1974).
4. H. O. House, L. J. Czuba, M. Gall, and H. D. Olmstead, J. Org. Chem., 34, 2324 (1969).
5. Ì. E. Jung and C. A. McCombs, Tetrahedron Lett., 2935 (1976).
6. (a) H. B. Dykstra, J. Amer. Chem. Soc., 57, 2255 (1935); (b) N. A. Milas, E. Sakel, J. T. Plati, J. T. Rivers, J. K. Gladding, F. X. Grossi, Z. Weiss, M. A. Campbell, and H. F. Wright, J. Amer. Chem. Soc., 70,1597 (1948).
Appendix Chemical Abstracts Nomenclature (Collective Index Number; Registry Numbers)
2-Trimethylsilyloxy-1,3-butadiene: Silane, trimethyl[( 1 -methylene-
2-propenyl)oxy]- (8,9); (38053-91-7)
Methyl vinyl ketone: 3-Buten-2-one (8,9); (78-94-4)
Formamide, N,JV-dimethyl- (8,9); (68-12-2)
Silane, chlorotrimethyl- (8,9); (75-77-4)
Triethylamine (8); Ethanamine, iV,JV-diethyl- (9); (121-44-8) Diethyl rrans-4-trimethylsilyloxy-4-cyclohexene-l,2-dicarboxylate:
4-Cyclohexene-l,2-dicarboxylic acid, 4-(trimethylsilyloxy)-, diethyl ester (8,9); (-)
Diethyl fumarate: Fumaric acid, diethyl ester (8); 2-Butenedioic acid (jE)-, diethyl ester (9); (623-91-6)
Disiloxane, hexamethyl- (8,9); (107-46-0)
Fumaric acid (8); 2-Butenedioic acid (E)-(9); (110-17-8)
Dimethyl fumarate: Fumaric acid, dimethyl ester (8); 2-Butenedioic acid (E)- dimethyl ester (9); (624-49-7)
168
ORGANIC SYNTHESES—VOL. 58
Tetracyanoethylene: Ethenetetracarbonitrile (8,9); (670-54-2) Lithium diisopropylamide: Diisopropylamine, lithium salt (8); 2-propanamine, N-(l-methylethyl)-, lithium salt (9); (4111-54-0)
1,3-Butadiene, 2-ethoxy- (8,9); (4747-05-1)
CHEMICAL HAZARD WARNING
Benzene has been identified as a carcinogen. OSHA has issued emergency standards (5/77) on its use. All procedures involving benzene should be carried out in a well-ventilated hood, and glove protection is required.
For an OSHA list of carcinogens see Organic Syntheses, 56, 128 (1977). The following compounds have been added to the OSHA list of carcinogens:
* Asbestos Benzene
*Coal tar volatiles—coke oven emissions Vinyl chloride
The following have also been identified as strong carcinogens:
Benz(a)pyrene
2,4-Diaminotoluene Dimethylcarbamoyl chloride 1,1-Dimethylhydrazine (and salts)
Dimethyl sulfate Hexamethylphosphoramide Hydrazine (and salts)
N- (2-Hydroxyethyl)ethyleneimine Methylhydrazine (and salts)
2 -Nitronaphthalene Nitrosoainines Propane sultone Propyleneimine
Previous << 1 .. 53 54 55 56 57 58 < 59 > 60 61 62 63 64 65 .. 93 >> Next