[10061-02-6]  · C3H4Cl2  · 1,3-Dichloropropene  · (MW 110.97) (Z)


(bifunctional alkylating agent)

Alternate Name: 1,3-dichloropropylene.

Physical Data: (E) isomer: bp 112 °C; d204 1.224 g cm-3. (Z) isomer: bp 104.3 °C; d204 1.217 g cm-3.

Solubility: sol ethers, hydrocarbons; slightly sol H2O.

Form Supplied in: available as a mixture of (E) and (Z) isomers.

Handling, Storage, and Precautions: flammable liquid; suspect carcinogen. Handle in a fume hood.

Bifunctional Alkylating Agent.

1,3-Dichloropropene can be functionalized at each terminus by either nucleophiles or electrophiles. Most nucleophiles react with this reagent, as well as other 1,3-dihalopropenes, in an SN2 substitution reaction to yield terminal vinyl halides that are unreactive towards further substitution.1 Bis-substitutions with thiolate,2a selenate,2a or formate2c anions are effected under strongly basic conditions, leading to the useful propenone synthons 1,3-bis(phenylthio)- or 1,3-bis(phenylseleno)propene.2a,b Functionalized copper-zinc reagents, RCu(CN)ZnX, add to 1,3-dichloropropene with a high degree of SN2 selectivity (>98%) to afford bis-functionalized alkenes in good to excellent yields with good stereoselectivity for formation of the (E) isomer (eq 1).3

Under Arbuzov conditions a 1,3-dienyl phosphonate results from reaction of 1,3-dichloropropene with triethyl phosphite.6

Terminal bis-trimethylsilylation of 1,3-dichloropropenes can be effected by metalation with Lithium Diisopropylamide, with in situ trapping by Chlorotrimethylsilane in THF/ether mixtures at -75 °C (eq 2).4

A simple synthesis of 1,3-butadienes in moderate yields and excellent stereoselectivity (trans:cis > 95:5) is accomplished by reaction of aldehydes or ketones with 1,3-dichloropropene and Zinc powder in an aqueous medium (eq 3).5

Homoallylic alcohols result from addition to aldehydes that is mediated by Samarium(II) Iodide (eq 4).7

Vinylcyclopropanes are obtained in moderate yields by reaction of 1,3-dichloropropenes with a,b-unsaturated esters in the presence of Copper-t-Butyl Isocyanide complexes in benzene at 80 °C (eq 5).8

1. (a) Julia, M.; Blasioli, C. BSF(2) 1976, 1941. (b) Larcheveque, M.; Valette, G.; Cuvigny, Th. T 1979, 35, 1745. (c) Savignac, P.; Breque, A.; Mathey, F.; Varlet, J.-M.; Collignon, N. SC 1979, 9, 287.
2. (a) Reich, H. J.; Clark, M. C.; Willis, W. W. JOC 1982, 47, 1618. (b) Corey, E. J.; Erickson, B. W.; Noyori, R. JACS 1971, 93, 1724. (c) Zahalka, H. A.; Sasson, Y. S 1986, 763.
3. Chen, H. G.; Gage, J. L.; Barrett, S. D.; Knochel, P. TL 1990, 31, 1829.
4. Shimizu, N.; Shibata, F.; Tsuno, Y. BCJ 1987, 60, 777.
5. Chan, T.-H.; Li, C.-J. OM 1990, 9, 2649.
6. Petrzilka, M.; Grayson, J. I. S 1981, 753.
7. Souppe, J.; Danon, L.; Namy, J. L.; Kagan, H. B. JOM 1983, 250, 227.
8. Ito, I.; Yonezawa, K.; Saegusa, T. JOC 1974, 39, 1763.

Thomas R. Verhoeven

Merck Research Laboratories, Rahway, NJ, USA

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