Butane, 2, 2, 3-trimethyl

Fig. 4.24 Heat of immersion of a carbon (prepared by pyrolysis of Saran Polymer A) in different liquids at 300 K. The liquids for points 1-6 were (I) methanol (2) benzene (3) n-hexane (4) 3-methyl benzene (5) 2,2-dimethyl butane (6) 2,2,4-trimethyl pentane. The abscissae represent the molar volumes of the liquids. (Redrawn from the original diagram of Barton, Beswick and Harrison. " )...

S-Butyryl thiocholine iodide [(2-butyrylmercaptoethyl)trimethyl ammonium iodide] [1866-16-6] M 317.2, m 173", 173-176". Recrystd from propan-l-ol and dried in vacuo store in the dark under N2. The bromide has m 150° (from Me2CO) or m 140-143° (from butan-l-ol). [Gillis Chem and Ind (London) 111 1957 Hansen Acta Chem Scand 11 537 1957.]... 

Sodium, with l-bromo-3-chloro-cyclobutane to give bicyclo [l.l.O]butane, 51, 55 Sodium amalgam, 50, 50, 51 Sodium amide, with 2,4-pentane-dione and diphenyliodonium chloride to give l-phenyl-2, 4-pentanedione, 51, 128 Sodium azide, 50, 107 with mixed carboxylic-carbonic anhydrides, 51, 49 Sodium borohydride, reduction of erythro-3-methanesulfony-loxy-2-butyl cyclobutanecar-boxylate, 51, 12 reduction of 2-(1-phenylcyclo-pentyl)-4,4,6-trimethyl-5,6-dihydro-1,3(4H)-oxazine to 2-(1-phenylcyclopentyl)-4,4, 6-trimethyltetrahydro-l,3-oxazine, 51, 25 Sodium cyanoborohydride, used... 

Use the structure-reactivity relationship approach to calculate the rate constants for the reactions of OH with the following compounds and calculate the percentage difference from the recommended values in Table 6.2 (a) ethane, (b) n-butane, (c) 2-methylpen-tane, (d) 2,2-dimethylpentane, (e) 2,2,3-trimethyl-butane, (f) n-nonane, (g) n-decane. 

A modification of this method utilizes the direct conversion of l,2-bis(trimethyl-siloxy)cyclobutene in one step to 2,2-disubstituted cyclopentane-1,3-diones. For example, 2-ethyl-2-methylcyclopentane-l,3-dione (3) was obtained in 91% yield from 1.2-bis(trimethyl-siloxy)cyclobutene and butan-2-one 2,2-dimethylpropane-l,3-diyl acetal.41 Further examples... 

Methanol can be converted to hydrocarbons over acidic catalysts. However, with the exception of some zeolites, most catalysts deactivate rapidly. The first observation of hydrocarbon formation from methanol in molten ZnCl2 was reported in 1880, when decomposition of methanol was described to yield hexamethylbenzene and methane.414 Significant amounts of light hydrocarbons, mostly isobutane, were formed when methanol or dimethyl ether reacted over ZnCl2 under superatmo-spheric pressure.415 More recently, bulk zinc bromide and zinc iodide were found to convert methanol to gasoline range (C4-C13) fraction (mainly 2,2,3-trimethyl-butane) at 200°C with excellent yield (>99%).416... 

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. 

When either an alcohol or an amine function is present in the alkene, the possibility for lactone or lactam formation exists. Cobalt or rhodium catalysts convert 2,2-dimethyl-3-buten-l-ol to 2,3,3-trimethyl- y-butyrolactone, with minor amounts of the 8-lactone being formed (equation 51).2 In this case, isomerization of the double bond is not possible. The reaction of allyl alcohols catalyzed by cobalt or rhodium is carried out under reaction conditions that are severe, so isomerization to propanal occurs rapidly. Running the reaction in acetonitrile provides a 60% yield of lactone, while a rhodium carbonyl catalyst in the presence of an amine gives butane-1,4-diol in 60-70% (equation 52).8 A mild method of converting allyl and homoallyl alcohols to lactones utilizes the palladium chloride/copper chloride catalyst system (Table 6).79,82 83... 

If chloral (239) is treated with dimethyl-TMS-amine (187), l-(trimethylsiloxy)-l-dimethylamino-2,2,2-trichloro-ethane (244) is obtained via -elimination this yields dimethylformamide (245)l64 TMS-azide (14) forms with n-butanal (240) 1-azido-1-trimethyl-siloxy-butane (24d)165 [see section El]. 

Abbreviations ACMP = o-anisylcyclohexylmethylphospine DIOP =2,3-0-isopropylidene-2,3-dihydroxyl-l, 4-bis(diphenylphosphino)butane NMDPP = neomenthyldiphenylphos-phine MDPP = menthyldiphenylphosphine CAMPHOS = 1,2,2-trimethyl-l, 3-bis(diphenyl-phosphinomethyl)cyclopentane. cData from unpublished research of the New Hampshire Group. 

Photolysis of an alkyl azidoacetate in the presence of 1-methyl- or 1,3,3-trimethyl-cyclopropenes may be explained in terms of an addition of ethoxycarbonylnitrene to the double bond to produce a 2-azabicyclo[1.1.0]butane, but this rearranges under the reaction conditions to the azadiene, although only in low yield 214,215 ... 

Ausgehend von Phosphorsaure-difluorid-dimethylamid wird mit l,3-Bis-[methylami-no]-butan/Triethylamin (2 Mol) bei 20° in Benzol 2-Fluor-l,3,4-trimethyl-1,3,2-diaza-phosphorinan-2-oxid (38% Isomerengemisch) erhalten388 ... 

Cyclopropanes have also been obtained by reaction of enamines with a-chloro electrophilic alkenes. After Michael addition the chlorine undergoes nucleophilic displacement by the regenerated enamine or enolate anion260,261 (Scheme 112). Bicy-clo[ 1.1.0] butanes may be obtained by cycloaddition of trimethyl ethylenetricarboxylate followed by a base catalysed displacement of the amine moiety262 (Scheme 113). 

Cd represents a double-bonded C atom, Ct a triple-bonded C atom, and Cb a C atom in a benzene ring. Values in parentheses are to be used when corrections for gauche configurations are made. The correction applies to each such configuration. Thus 2-methyl butane has one gauche correction, 2,3-dimcthyl butane has two, and 2,2,3-trimethyl pentane has five. 

Diisopropyl-nitro- XI/2, i 11 Dipropyl-nitro- XI/2, 111 Trimethyl- -(3-hydroxy-propanoyli-min) E16a, 1044 (N-Alkylier.) Butan 2-Nitramino-3,3-dimethyl-IV/ld, 365... 

Bicyclo[1.1.0 butan 1,2,2-Trimethyl-E19b, 430 (C,H-Insertion) Bicyclo[2.2. l heptan... 

Triaza-tricycloJ5.1.1.02,4]nonan 3,5-Dioxo-l,4,7-trimethyl- E17e, 57 (subst.-Bicyc]o[1.l.0]butan + Succinimid)... 

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