Synthesis of dl-3,3,4-Trimethylcyclopentanone

Baumgarten, Henry E.; Gleason, Donald C.

doi:10.1021/jo50005a002

Cited by 11 publications

(5 citation statements)

References 17 publications

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“…Another method for the removal of such halogens is thermal dehydrohalogena- tion of the chloro ester (144). Thus, the chloro ester obtained on chlorination with hydrogen chloride and ethanol of the thionyl chloride scission product of -carbethoxy-d, ß, y-trimethyl-Y-valerolactone was thermally dehydrohalogenated to the unsaturated ester corresponding to ß,ß, -trimethyladipic acid (60).…”

Section: (D) Reactions With Unsaturated Compoundsmentioning

confidence: 99%

“…A more direct route to the unsaturated ester, at least with some chloro esters, has been found in simple alkaline hydrolysis (60).…”

Section: (D) Reactions With Unsaturated Compoundsmentioning

confidence: 99%

“…Diethyl carbonate also condenses with other esters possessing a-hydrogen atoms. Monosubstituted malonic esters result from the condensations, in yields of 25 to 60 per cent (708). The reaction is performed with equimolar proportions of the ester and sodium ethoxide with excess diethyl carbonate, while the ethyl alcohol formed in the reaction is continuously removed by distillation.…”

Section: Introductionmentioning

confidence: 99%

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Syntheses Of Alkylated Alkanedioic Acids

Diaper¹,

KUKSIS²

1959

Chem. Rev.

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example of such a synthesis is the conversion of 2-pentenal, through a Reformatsky condensation with ethyl -bromopropionate and oxalation of the unsaturated product, eventually to 2,6-dimethylsuberic acid (401).It has been shown that formates and oxalates may function as carbonyl components in a Reformatsky synthesis. Ethyl -bromoisobutyrate reacts with ethyl oxalate (569) and with ethyl formate (82), giving hydroxy esters which could be converted to 2,2-dimethylsuccinic and 2,2,4,4-tetramethyIglutaric acids, respectively.The application of the Reformatsky reaction to nitriles (154) leads to the formation of ketones in a manner comparable with the Grignard reaction and is a convenient method for the synthesis of /3-keto esters.By varying the nature of the carbonyl compounds and the halo esters employed, many alkylated dicarboxylic acids have been prepared with the help of this reaction, yet the possible products may be of only a few types. Branching is confined to the a-and ß-positions at one or both ends of the chain, and while the -position may bear one, two, or no alkyl groups, the /3-position cannot bear more than one side chain.Theoretically, in all of the above cases the ester groups of the final products may be converted into aldehyde or keto groups through the acyl chlorides and dialkyl metals (142).A repetition of the Reformatsky process would lengthen the chain with or without further branching at the new points of junction of carbon chains (629).

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Section: (D) Reactions With Unsaturated Compoundsmentioning

confidence: 99%

“…A more direct route to the unsaturated ester, at least with some chloro esters, has been found in simple alkaline hydrolysis (60).…”

Section: (D) Reactions With Unsaturated Compoundsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Syntheses Of Alkylated Alkanedioic Acids

Diaper¹,

KUKSIS²

1959

Chem. Rev.

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“…Apparently the reduction step is essentially stereospecific leading to only one arrangement of the methyl groups (probably cis) on the cyclohexane ring. This communication reports our first attempt to prepare the cis-trans isomers of X through a modification and extension of a procedure used previously (12) in this laboratory for the synthesis of 3,3,4-trimethylcyclopentanone. The sequence followed is outlined on the flow sheet.…”

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confidence: 99%

“…At first an attempt wras made to follow closely the earlier work (12) by preparing e-carbethoxy-ß, y-dimethyl-S-caprolactone (II) from the Reformatsky reaction between methyl or ethyl y-acetylvalerate (I, R = CH3 or C2HS) and ethyl bromoacetate. However, the yield of II was at best only 18%, so this sequence was abandoned.…”

mentioning

confidence: 99%