3.4.6- Trimethyl-2-heptene

Einer Umlagerung unterliegt 3-Oxo-2,2,4,4-tetramethyl-7-oxa-bicyclo 4.1.0Jheptan in Ather (450 W llano via L Corex-Filter). 4-Hydroxy-2,2,6-trimethyl-hepten- 5)-saure-lacton und 4-Oxo-2,2,6-trimethyl-he.pten-(5)-al fallen bei 95%igem Umsatz mit 50 bzw. 20% d.Th. an3 ... 

Trimethyl-2-heptene (XIX) is formed by loss of a proton from the ethyl group in XVIII. Neither 3,5,5-trimethyl-3-heptene formed by a correspomding loss of a proton from the methylneopentyl group or... 

Trimethylbutene (Triptene). The polymerization of trimethyl-butene is of interest because rearrangement of the olefin, unless of a very radical nature, can give only the starting material. It was found (Cook et al., 41) that polymerization in the presence of 75% sulfuric resulted in a 91% yield of polymer, 70% of which was 2,2,3,5,5,6,6-heptamethyl-3-heptene. The minor products of the reaction consisted of 3.1% of unreacted triptene, 0.9% of 8- to 10-carbon atom olefins, 3.0% of 10-carbon atom olefins, 9.0% of 11- to 14-carbon atom olefins and 12.0% of residue. The formation of the heptamethylheptene is to be expected on the basis of the carbonium ion mechanism ... 

A scries of a-substituted /J-(2-phenylcthcnyl)-/ -hydroxy ketones, e.g., ( )-5-hydroxy-2,2,4-trimethyl-5,7-diphenyl-6-hepten-3-one, has been investigated340. It is possible to find the most stable conformers of the diastereomeric ketones and to differentiate between them by the identification of a long-range W-coupling between the olefinic and the hydroxy proton (emphasized bonds), which can exist only in the u configuration. 

ANILINE (continued) 4-Methyl-2-heptene 2,4,4-Trimethyl-2-pentene Diisobutene 1-Nonene... 

The hydroformylation of several olefins in the presence of Co2(CO)8 under high carbon monoxide pressure is reported. (S)-5-Methylheptanal (75%) and (S)-3-ethylhexanal (4.8%) were products from (- -)(S)-4-methyl-2-hexene with optical yields of 94 and 72%, respectively. The main products from ( -)(8)-2,2,5-trimethyl-3-heptene were (S)-3-ethyl-6,6-di-methylheptanal (56.6%) and (R)-4,7,7-trimethyloctanal (41.2%) obtained with optical yields of 74 and 62%, respectively. (R)(S)-3-Ethyl-6,6-dimethylheptanal (3.5% ) and (R)(S)-4,7,7-trimethyloctanal (93.5%) were formed from (R)(S)-3,6,6-trimethyl-l-heptene. (+/S)-l-Phenyl-3-methyl-1-pentene, under oxo conditions, was almost completely hydrogenated to (- -)(S)-l-phenyl-3-methylpentane with 100% optical yield. 3-(Methyl-d3)-l-butene-4-d3 gave 4-(methyl-d3)pentarwl-5-d3 (92%), 2-methyl-3-(methyl-d3)-butanal-4-d3 (3.7%), 3-(methyl-d3)pentanal-2-d2,3-d1 (4.3%) with practically 100% retention of deuterium. The reaction mechanism is discussed on the basis of these results. 

To demonstrate that optically active aldehydes from formylation of the methyl groups of optically active olefins can be obtained as main reaction products with good optical yields, we have studied the hydroformylation of ( + )(S)-2,2,5-trimethyl-3-heptene. None of the methyl groups of the tertiary butyl group were carbonylated. Primarily the reaction product was from carbonylation of the other two methyl groups present in the molecule (Table 1). (S)-3-Ethyl-6,6-dimethylheptanal... 

S)-l-Phenyl-3-methyl-l-pentene, initially synthesized to extend the data obtained with (+)(S)-2,2,5-trimethyl-3-heptene, under usual oxo conditions is almost completely hydrogenated with an optical yield of practically 100% while the hydroformylation products are barely detectable. 

The above ester (91 grams) was pyrolized at 510°C in a stream of nitrogen and gave 3,6,6-trimethyl-l-heptene (30 grams, bp 146°C nD25 1.4144). 

R) (S)-3,6,6-Trimethyl-1-heptene. (R)(S)-3,6,6-Trimethyl-l-hept-ene has been hydroformylated in exactly the same conditions adopted for the hydroformylation of its isomer 2,2,5-trimethyl-3-heptene. The separation and identification of the reaction products have been made using the technique previously described. The results are reported in Table I. 

Bieyclo 2.2.1 hepten 2-Lithium-l, 7,7-trimethyl - El9d, 244 (Hydrazon En Li)... 

Bicyclo[2.2.1]hepten 5-(2,2-Dieth-oxy-ethenyl)- E15/2, 1680 [ -CH(OR)2 + R-CHO] Bntan l,3-Dioxo-l-(2,6,6-trimethyl-1 -cyclohexenyl)-(9-Hydroxy- -damascon) El9b, 1261 (Hydroxy — carben - Keton) Cyclohexan... 

C,3H260 (Continuation) 4( >Hepten 2-Hydroxy-6-methy -4-pentyl- Vl/la, 2, 1481 Hexan 4-tert.-Butyl-5-oxo-2,2,4-trimethyl- VII/2a, 577... 

SYNS ISOMETHEPTENE 6-METHYLAMINO-2-METHYLHEPTENE METHYLISOOCTENYLAMINE 2-METHYL-6-METHYLAMINO-2-HEPTENE METHYL-OCTENYLAADNE OCTANIL OCTTN OCTINUM OCTON N-l,5-TRIMETHYL-4-HEXENYLAMINE... 

C10H20 2,4,6-trimethyl-3-heptene, isomer 123434-07-1 439.96 38.146 2 21046 C10H2002 6-methyl-2-heptyl acetate 67952-57-2 460.15 40.069 1,2... 

C8H16 3-methyl-trans-2-heptene 22768-20-3 160.38 15.368 2 14986 C8H16 2,4,4-trimethyl-2-pentene 107-40-4 166.84 6.794 1... 

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