Chloromethyl acetophenone

A soln. of 2,2-bis(chloromethyl)acetophenone in acetonitrile added dropwise during 0.5 hr. to N-cyclohex-l-enylpyrrolidine, triethylamine, and acetonitrile, stirring continued 1 hr., the solvent removed, first at atmospheric pressure and finally in vacuo, water added to the resulting immonium salt, and stirred 12 hrs. at room temp. -> 3-benzoylbicyclo[3,3.1]nonan-9-one. Y 81%. F. e. s. H. Stetter, K. D. Ramsch, and K. Elfert, A. 1974, 1322 bicyclo[4.n.l]enones cf. W. C. Still, Synthesis 1976, 453 ring closure with 3-chlor-2-enamines cf. Synth. Meth. 31, 838. 

The scope and limitations for transfer hydrogenation employing either the iron porphyrin system or the combination of iron compound/terpy/PPhs are listed in Table 8. In most cases, the FeCVterpy/PPhs system displays a higher activity. Except for chloromethyl- and cyclopropyl-acetophenone, the desired products were obtained in good to excellent yields. It should be noted that a ring opened product was not observed when cyclopropyl acetophenone was employed. Hence, a radical-type reduction pathway was excluded and a hydride mechanism appeared to be reasonable. 

Benzophenone, directed reaction with acetaldehyde, 50, 68 Benzoylacetone, from acetophenone and acetic anhydride, 51, 93 BENZYL CHLOROMETHYL ETHER, 52,16... 

Seyferth ef al." generated chlorocarbene from /i-butyllithium and methylene chloride in the presence of triphenylphosphine to produce triphenylphosphine chloromethyl-enc, which reacts with acetophenone to give a mixture of W.v- and rran.v-l-chloro-2-phenyl-l-prupene (2). 

Halo-substituted acetophenones such as m-bromo- [74] or p-chloroacetophe-none [46] were reduced with borane in high enantioselectivity in the presence of oxazaborolidines 4b and 47, respectively. Other important halogen-containing ketones are chloromethyl or bromomethyl ketones. Oxazaborolidine reduction of co-chloro- or co-bromoacetophenone gives enantio-enriched halohydrins that can be converted into chiral oxiranes [20]. Martens found that the sulfur-containing oxazaborolidine catalysts 60 show high enantioselectivity in this kind of reduction [44, 86, 87]. Enantiopure halohydrins were obtained as shown in Scheme 8. 

Chlorination, acenaphthene, 69 acetophenone, 71 acetyl-p-toluidine, 72 anthranilic acid, 8 p-chlorotoluene in side chain, 74 8-ethylisothiuronium sulfate, 142 2-methylnaphthalene, 79 succinimide, 86 with NaClOs and HC1, 72 with sulfuryl chloride, 8 Chloromethylation, ethylbenzene, 146 p-xylene, 129 thiophene, 80... 

Chloro- acetophenone Phenacyl Chloride Omega-Chloro- acetophenone Alpha-Chloro- acetophenone Phenyl Chloromethyl Ketone Tear Gas... 

Beilstein Handbook Reference) Acetophenone, 2-chloro- AI3-52322 BRN 0507950 Caswell No. 179C CCRIS 2370 Chemical mace Chloroacetophenone a-Chloroacetophenone 1-Chloroacetophenone 2-Chloro-1-phenylethanone 2-Chloroacetophenone Chloromethyl phenyl ketone CN CN (lacrimator) EINECS 208-531-1 EPA Pesticide Chemical Code 018001 Ethanone, 2-chloro-1-phenyl- HSDB 972 Mace (lacrimator) NCI-C55107 NSC 41666 ra-Chloroacetophenone Phenacyl chloride Phenacylchloride Phenylchloromethylketone UN1697. Pharmaceubcal intermediate. A lachrymator, is the primary component of Mace, a riot-control gas. Plates, mp = 56.5° bp = 247° d n 1,324 insoluble in H2O soluble in MezCO, petroleum ether, very soluble in EtOH, EtzO, C6H6, CS2 LDso (rat ori) = 127 mg/kg. Janssen Chimica Lancaster Synthesis Co. Penta Mfg. 

Observations from both Nierenstein and Robinson have enabled the understanding of this reaction. It is also accepted that excess diazomethane at lower temperatures leads to diazoketones because hydrogen chloride liberated gets consumed by its preferential reaction with excess diazomethane to form methyl chloride 5. This explains why hydrogen chloride gas added through an external source to a solution of diazoketone can drive the Nierenstein to completion. Further evidence to support this theory was offered by McPhee and Klingsberg in the procedure for the synthesis of benzyl chloromethyl ketone from phenylacetyl chloride, by which the diazoketone is separately treated with hydrogen chloride at 0 °C and also by Bhatt et al. in their synthesis of a-chloromethyl-3,4,5-triacetoxy acetophenone in which diazoketone is the key intermediate. ... 

While acetophenones are typically resistant to chloromethylation due to the electron-withdrawing ability of the carbonyl, some highly substituted acetophenones have been known to undergo this reaction. In the case of 14, treatment with HCl and paraformaldehyde results in the production of 15 in high yield. 

Also obtained by reaction of zinc powder on 3,5-bis(chloromethyl)-2-hydroxy-acetophenone in aqueous acetic acid (8%) [2551]. 

CH2SO2CH3 Obtained by reaction of 3 -chloromethyl-4 -hydroxy-acetophenone with magnesium methylsulfmate in refluxing aqueous methanol for 18 h (52%) [2544]. 

Preparation from 3-chloromethyl-2-hydroxy-5-methyl-acetophenone (b.p. 110-116°) [2494] by reaction with methanol in the presence of concentrated hydrochloric acid and iron powder at reflux for 3.5. 5 h (82%) [3262], (49%) [2494]. 

Obtained by reaction of chloromethyl methyl ether with 2,3,4,6-tetrahydroxy-acetophenone in ethanol in the presence of sodium ethoxide under nitrogen, first at 0°, then at 40 (13%) [2882]. 

Obtained by treatment of 2,4-dihydroxy-3-methyl-acetophenone with chloromethyl methyl sulfide in the presence of KOH/K COj mixture in boiling 2-butanone [4274],... 

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