4- Cyclohexenyl methyl ketone

Kerosene, purified, 84, 7 Ketene, 21, 13, 64 KeTBNE DIETHYLACETAl, 83, 45 Ketene, diethyl eetal, 83, 4S Ketene diuer, 81, 4, 64 Ketene lamp, 81, 65 Keto add, 80, 2 a-KETOGLDTASlC ACID, 86, 42 Ketone, 1-cyclohexenyl methyl, 39, I... 

Cyclohexenyloxy)- -ethylester El5/1,206 (Keton + R-CHN2) E19b, 1118 (Carben + Keton) (6-Methyl-l-cyclohexenyl-oxy)- -methylester E19b, 1119 (Carben + Keton)... 

Piperidin 1-[(1-Cyclohexenyl )-methyl-amino]- E15/1, 751 (Keton + RjN —NH —R) Pyridin l-Methyl-3-(l-methyl-2-piperidinyl)-l,4,5,6-tetrahydro-E15/1, 655 (Dehydr.) Spiro(5.6]dodecan 7-Hydrazono-V/la, 255... 

Perhaps the most striking difference between conjugated and nonconjugated dienes is that conjugated dienes undergo an addition reaction with alkenes to yield substituted cyclohexene products. For example, 1,3-butadiene and 3-buten-2-one give 3-cyclohexenyl methyl ketone. 

Kl=acetophenone,K2=n-propyl pyruvate (CPl3C0C02-n-Pr),K3=i-butyl levulinate (CH3COCH2CH2C02- -Bu),K4=f-BuCOCH3,K5=3-MeOPhCOCH3,K6=2-py-ridyl methyl ketone, K7=l-tetralone, K8=l-acetylnaphthalene,K9=2-acetylnaphthalene,K10=ethyl levulinate,Kll=2-octanone,K12=2-phenylcyclohexanone, K13=3-pyridyl methyl ketone, K14=Me2HSiOCH2COCH3,K15=Me2HSiOCH2COPh,K16=l-cyclohexenyl methyl ketone, K17=ethyl pyruvate, K18=2,2-dimethyl-acetylacetonate,K19=methyl levulinate, K20=3,3-dimethyl-pentane-2,4-dione, K21=2-nonanone,K22=PhCOCH2Cl. 

Kl=acetophenone, K7=l-tetralone, K8=l-acetylnaphthalene, K9=2-acetylnaphthalene, K16= 1-cyclohexenyl methyl ketone, K23=4-BrPhCOCH3, K24=PhCOEt, K25= -PrCOEt,K26=EtCO-cyclopentyl... 

Acetylation of cyclohexanone affords 2-chloro-2-cyclohexenyl methyl ketone in 82% yield.626... 

Cycloalkenes can also be acylated with aluminum chloride or tin tetrachloride as catalyst 627,628 cycloheptene, acetyl chloride, and aluminum chloride give 70% of 1-cycloheptenyl methyl ketone.629 The yield from cyclohexene and phenylacetyl chloride is, however, below 30% but better yields are obtained with acetyl chloride and zinc chloride (60% of 1-cyclohexenyl methyl ketone630,631) or acetic anhydride and tin tetrachloride.632... 

According to Jones and Sondheimer,47 l-ethynyl-l,4-cyclohexanediol is boiled for 2.5 h in 85 % formic acid, after which the acid is distilled off in a vacuum, and the residue is heated with water for 30 min (to hydrolyse any formic ester). 4-Hydroxy- 1-cyclohexenyl methyl ketone is thus obtained in 62% yield. 

As shown in Scheme 7.14, these metal compounds act as catalysts because these cyclometalation products are highly reactive and react easily with other reagents. The substrates of these reactions are not only aromatic compounds, such as methyl phenyl ketone (Eq. (7.50)) [100,101,103] and phenylimine (Eq. (7.51)) [100,103], but also nonbenzenoid compounds, such as thiophenyl methyl ketone (Eq. (7.52)) [100,101] and cyclohexenyl methyl ketone (Eq. (7.53)) [103]. 

A mixture of 3-cyclohexenyl methyl ketone (prepn. s. 532) and W-4 Raney-Ni in a rocking autoclave pressurized with Hg to 900 p. s. i. g., when the temp, drops after the exothermic saturation of the carbon-carbon double bond is complete hydrogenation continued at 120 and 1500 p. s. i. g. for 1 hr. cyclo-hexylmethylcarbinol. Y 96%. W. K. Johnson, J. Org. Ghem. 24, 864 (1959). 

Under comparable conditions the submitters found that the corresponding dihydropyran derivatives were similarly obtained by the condensation of acrolein with methyl vinyl ether in 80-81% yield, with ethyl vinyl ether (77-85% yield), with w-butyl vinyl ether (82% yield), with ethyl isopropenyl ether (50% yield), and with w-butyl cyclohexenyl ether (40% yield). Other <, /3-un-saturated carbonyl compounds that have thus been condensed with ethyl vinyl ether are crotonaldehyde (87% yield), meth-acrolein (40% yield), a-ethyh/3-n-propylacrolein (54% yield), cinnamaldehyde (60% yield), /3-furylacrolein (85% yield), methyl vinyl ketone (50% yield), benzalacetone (75% yield), and benzal-acetophenone (74% yield). 

Fig. 97. Solvent retained by nitrocellulose films (50/i thickness) after exposure to air at 25°C (Baelz [48]). I—Cyclohexenyl acetate, II—methyl cyclohexanone, III—diacetone alcohol, IV—cyclohexanone, V—cellosolve acetate, VI—amyl acetate-ethyl alcohol I 1, VII—amyl acetate, VIII— methyl cellosolve acetate, IX—amyl acetate-toluene 1 1, X—butyl acetate-ethyl alcohol 1 1, XI—butyl acetate, XII—cellosolve, XIII—methyl-ethyl ketone, XIV—cellosolve-toluene 1 1, XV—methyl cellosolve, XVI—ethyl acetate, XVII—acetone.

Bicyclo 4.1.0]heptan 7-Trimethyl-silylcarbonyl- E17b, 1393 (7-Br/7-SiR3 — 7-H/7-CO—SiR3) Cyclohexan trans-2-Hydroxy-1-(trimethylsilyl-ethinyl)- E19d, 146 (sp-CH - C - Li/Oxiran) Cyclopenten 2-Ethyl-4-methylen-l-trimethylsilyl- E17c, 2251 (Methylen-cyclo propan + In) Ethen l-(l-Cyclohexenyl)- -trimethylsilyloxy- E1S/1, 441 (Keton 4- RjSi—O —S02 —R) Furan 2-Methyl-5-propyl-3-trimethylsilyl- E18, 674 (In-Hydromagnesier./+ R —CN)... 

---