Butyl formal

Synonyms Amyl aldehyde butyl formal pentanal valeric aldehyde... 

Hill and Carothers (4) investigated the acetal interchange reaction with di-n-butyl formal and glycols (Equation 4). When n was 3 or 4, cyclic formals were the principal products. Fentamethylene glycol (n = 5) gave a sirupy liquid polymer. The reaction with decamethylene gly-... 

From Di-m-butyl Formal. When 2-butyne-l,4-diol and di-n-butyl formal were allowed to react as described above, in the presence of a catalytic amount of p-toluenesulfonic acid at temperatures up to 190° C., nearly two equivalents of n-butyl alcohol distilled off. The product was a mushy, light brown solid of molecular weight 475, as determined cryoscopically in benzene. 

SYNS AMYL ALDEHYDE BUTYL FORMAL PENTANAL n-PENTANAL VALERAL VALERIANIC ALDEHYDE VALERIC ACID ALDEHYDE VALERIC ALDEHYDE VALERYLALDEHYDE... 

BUTYL FORMAL (110-62-3) Forms explosive mixture with air (flash point 54°F/12°C). Violent reaction with strong oxidizers, strong acids, bromines, ketones. Incompatible with caustics, ammonia, amines. 

Beilstein Handbook Reference) AI3-16105 Amyl aldehyde BRN 1516304 Butyl formal CCRIS 3220 EINECS 203-784-4 FEMA Number 3098 HSDB 851 NSC 35404 Pentanal n-Pentanal Pentyl aldehyde UN2058 Valeral Valeraldehyde n-Valeraldehyde Valerianic aldehyde Valeric acid aldehyde Valeric aldehyde n-Valeric aldehyde Valetyl aldehyde Valerylaldehyde. Liquid mp = -91.5° bpn 103° d = 0.8095 Xm = 178,182,184 nm (gas) slightly soluble in H2O, soluble in EtOH, EtzO. 

Butyl formal, butyl ether, and polysulfide blend Carboxyl terminated polybutadiene and epoxy blend... 

Fig. 2, Representative bend specimens after testing at 76°K (a) butyl formal, butyl ether, and polysulfide blend (b) fluorosilicone (c) polysulfide (d) silicone (e) polyurethane (f) epoxy (g) epoxy-silicone and (h) carboxyl terminated polybutadiene and epoxy blend. 

Butyl-5-ethyltetrahydro-2H-pyran-2-one. See Ethyl butyl valerolactone Butyl formal. See n-Valeraldehyde Butyl formate... 

CAS 110-62-3 EINECS/ELINCS 203-784-4 UN 2058 (DOT) FEMA 3098 Synonyms Aldehyde C-5 Amylaldehyde Butyl formal Pentaldehyde Pentanal n-Pentanal Valeral Valeraldehyde Valerianic aldehyde Valeric acid aldehyde Valeric aldehyde Valerylaldehyde Empirical C5H10O Formula CH3(CH2)3CHO Properties Colorless liq. sol. in alcohol, ether, propylene glycol, oils si. sol. in water m.w. 86.13 dens. 0.81 (20/4 C) m.p -92 C b.p. 103.4 C flash pt. 4 C ref. index 1.3882... 

The formals of tertiaiy alcohols are not readily produced. Conant, Webb, and Mendum obtained tei-tiary butyl formal as a by-product in the formation of tertiary butyl carbinol when tertiaiy butyl magnesium chbride w s reacted ritli anhydrous formaldehyde. This formal is recovered unchanged by steam distillation from 80 per cent sulfuric acid, but is hydrolyzed by heating with an equal Aveight of 95 per cent ethanol containing 2 cc of concentrated hydi-ochloric acid. 

Cycloadditioiis in which 1,2-dithietes acted formally as dienes are among the most typieal reaetions of 1,2-dithietes. Tire dithiete 144 is highly reaetive and eapable of reaetions even with simple alkenes and alkynes (60JA1515 61JA3434,61JA3438).Tlius, 144 reaeted with aeetylene to form 191 and 192 with the initial formation of 193, and with tetramethylethylene to give 194. Other [4 + 2] eyeloadditions of 144 involved those with ethylene, cyelohexene, fra s-stilbene, ethyl vinyl ether, butyl vinyl sulfide, 3-hexyne, and DMAD. 

For example /-butyl phenyl ether with aluminium chloride forms para-t-butyl phenol155. Often the de-alkylated phenol is also formed in considerable quantity. The reaction formally resembles the Fries and Claisen rearrangements. Like the Fries rearrangement the question of inter- or intramolecularity has not been settled, although may experiments based on cross-over studies156, the use of optically active ethers157 and comparison with product distribution from Friedel-Crafts alkylation of phenols158 have been carried out with this purpose in view. 

Transformations through 1,2-addition to a formal PN double bond within the delocalized rc-electron system have been reported for the benzo-l,3,2-diazaphospholes 5 which are readily produced by thermally induced depolymerization of tetramers 6 [13] (Scheme 2). The monomers react further with mono- or difunctional acyl chlorides to give 2-chloro-l,3,2-diazaphospholenes with exocyclic amide functionalities at one nitrogen atom [34], Similar reactions of 6 with methyl triflate were found to proceed even at room temperature to give l-methyl-3-alkyl-benzo-l,3,2-diazaphospholenium triflates [35, 36], The reported butyl halide elimination from NHP precursor 13 to generate 1,3,2-diazaphosphole 14 upon heating to 250°C and the subsequent amine addition to furnish 15 (Scheme 5) illustrates another example of the reversibility of addition-elimination reactions [37],... 

The intramolecular formal [3+3] cycloaddition reaction of l- [l-phenyl-2-(4-oxobut-2-enyloxy)ethyl]amino cyclo-hexen-3-one at 150°C in the presence of piperidinium acetate afforded /ra 3--l,4a-77-l-phenyl-l,2,4,4a,7,8,9,10-octahydro[l,4]oxazino[4,3- ]quinolin-7-one <2002JA10435>. At 85°C, the 6-(l-piperidnyl)-l,2,4,4a,5,6,7,8,9,10-dec-ahydro derivative formed, which could be converted into the l,2,4,4a,7,8,9,10-octahydro derivative by heating at 150 °C. Cyclization of iV-[(2-butyl-2-oxoethoxy)acetyl]-3,4-dimethoxyphenylethylamine on the action of TFA gave llb-butyl-1,3,4,6,7,1 lb-hexahydro[l,4]oxazino[3,4- ]isoquinolin-4-one <1997JOC2080>. 

The common by-products obtained in the transition-metal catalyzed reactions are the formal carbene dimers, diethyl maleate and diethyl fumarate. In accordance with the assumption that they owe their formation to the competition of olefin and excess diazo ester for an intermediate metal carbene, they can be widely suppressed by keeping the actual concentration of diazo compound as low as possible. Usually, one attempts to verify this condition by slow addition of the diazo compound to an excess (usually five- to tenfold) of olefin. This means that the addition rate will be crucial for the yields of cyclopropanes and carbene dimers. For example, Rh6(CO)16-catalyzed cyclopropanation of -butyl vinyl ether with ethyl diazoacetate proceeds in 69% yield when EDA is added during 30 minutes, but it increases to 87 % for a 6 h period. For styrene, the same differences were observed 65). 

Anthracyclinone synthesis. Wulf and Xu1 have reported a high-yield formal synthesis of 11-deoxydaunomycinone (5) in which the first step is a benzannelation of the chromium carbene 1 with the acetylene 2 to provide the naphthol 3, which is not isolated but treated with TFA to induce cleavage of the /-butyl ester and to... 

Similarly, the benzannulated enyne-allenes 172 and 173 were prepared from the propargylic acetates 171 by cuprate addition or by Pd-catalyzed addition of arylzinc chloride (Scheme 20.35) [49]. The presence of a butyl group and a p-anisyl group at the allenic terminus of 173a and 173b permits competition between a formal ene reaction and a formal Diels-Alder reaction leading to 174 and 175, respectively. 

An immediate reaction takes place between 178 or 179 and 3,5-di-tert-butyl-l,2-benzoquinone to lead to the dioxagermole 189, the formal adduct of the germylene (ArO)2Ge with the quinone. A single electron mechanism, supported by an ESR study and depicted in Scheme 37, was postulated to account for the formation of 189.132... 

Radical cyclization of polyfunctional 5-hexenyl halides mediated by Et2Zn and catalyzed by nickel or palladium salts has been demonstrated to produce stereoselectively polyfunctional 5-membered carbo- and heterocycles [56, 57]. Based on this strategy a formal synthesis of methylenolactocin (11) was achieved (Scheme 20). The acetal 130, readily being built up by asymmetric alkylation of aldehyde 127 followed by reaction with butyl vinyl ether and NBS, served as the key intermediate for the construction of the lactone ring. Nickel(II)-catalyzed carbometallation was initiated with diethylzinc to yield exclusively the frans-disubstituted lactol 132, which could be oxidized directly by air to 134. Final oxidation under more forcing conditions then yielded the lactone (-)-75 as a known intermediate in the synthesis of (-)-methylenolactocin (11) [47aj. 

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