Methyl-1-aminobutane

Eleven and five-tenths grams (0.50 gram atom) of sodium is added in small portions to a stirred solution of 0.15 g. of powdered ferric nitrate in 300 ml. of liquid ammonia. (Hood.) The reaction mixture is cooled in a solid carbon dioxide-ethanol bath during this and subsequent operations. After the blue color of liquid ammonia solution is discharged (15-20 minutes after addition of the sodium), the temperature of the reaction mixture is adjusted to —50° and 53 g. (0.50 mole) of isoamyl chloride is added at the rate of 30-40 drops per minute. Stirring is continued for 1 hour after completion of the addition. The excess ammonia is then allowed to evaporate slowly, and the residue is hydrolyzed by the dropwise addition of excess water. Twenty grams of sodium hydroxide is then added, and the mixture is extracted with ether. Distillation of the ether followed by fractionation of the residual liquid gives a 40% yield of 3-methyl-l-aminobutane with a 10% recovery of alkyl chloride. The amine boils at 95°. 

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An enzyme that catalyzes the fonnation of 4-N-methyl-aminobutanal from A -methylputrescine has been isolated from several sources. The enzyme that forms the A -methyl-A -pyrrolinium salt (3), N-methylputrescine oxidase, has been isolated from tobacco roots (Leete, 1980, 1990). 

The next step, the methylation of putrescine, already belongs to the secondary metabolism and is catalyzed by the first pathway-specific enzyme, putrescine A-methyltransferase (PMT) discovered in tobacco roots (Mizusaki et al. 1971). Its product, A-methylputrescine, represents the direct precursor of 4-methyl-aminobutanal, as was shown by a cell free preparation of tobacco roots. The oxidative deamination of the diamine is catalyzed by A-methylputrescine oxidase, an enzyme of ahigh substrate specificity (Mizusaki etal. 1972). 4-Methy laminobutanal is cyclized spontaneously forming the A-methyl-A -pyrrolinium cation (present as a salt) (Leete 1967). An alternative route has been proposed for the biosynthesis... 

SCHEME 1. Conformational map of the RcRn and RcSn diastereomers of /V-ethyl-iV-methyl-2-aminobutane (EMAB). Interconversions among conformers within dashed boxes are fast on the NMR time scale at 104 K. Those between dashed boxes occur via rotations about the methine carbon-nitrogen bond with barriers which are DNMR-visible. The interconversion between the solid boxes occurs via nitrogen inversion (disstereomeric interconversion). The values in parentheses are MM2-80 results. Reprinted with permission from Reference 71. Copyright (1988) American Chemical Society... 

Fermenting baker s yeast transformed 2-butanone oxime containing 44% excess of the ( )-isomer into optically active (R)-2-aminobutane in 58% enantiomeric excess. The chiral amine was also obtained in 24% e.e. from the oxime acetate but the oxime methyl ether gave a racemic product (equation 2)16. 

Very recently (51), nonequivalence has been found in a variety of additional monobasic solutes whose configurational analysis was thought earlier to lie outside the scope of the CSA technique. 2-Butanol, for example, when dissolved in benzene saturated with TFAE, shows nonequivalence in both methyl resonances. A variety of other chiral and prochiral compounds such as 2-propanol, methyl 2-propyl sulfide, 2-aminobutane, and 2-methyl-1-butanol show nonequivalence for their enantiotopic methyl groups under these conditions. The magnitudes of nonequivalence in these instances are small (0.02-0.03 ppm) but, as illustrated in Figure 4 for enriched 2-butanol,... 

But the name currently in vogue for this two-ring systemis 1,3-benzodioxole. As a prefix it becomes 1,3-benzodioxol-5-yl-something, and so J would be called l-(l,3-benzodioxol-5-yl)-2-aminobutane. This is the source of the code name BDB. And the N-methyl homologue, the alpha-ethyl analogue of MDMA, is named MBDB, or METHYL-J, and is with its own separate entry in this footnote. 

O-H-O bonds are stronger than N-H - N bonds, which explains the order of the last two compounds. No hydrogen bonding is possible in the first two compounds, but C-O bonds are polar, giving the ether a higher boiling point than the alkane. The actual boiling points are pentane, 36°C methyl propyl ether, 39°C 1-aminobutane, 78°C and 1-butanol, 118°C. 

Among these bioactive molecules, SMA derivatives have held an important place ever since Fessenden showed equivalent biological activities of the chlorohydrates of 3-methyl-3-phenyl-2-aminobutane, a sympathomimetic amine, and 1-dimethylphenysilyl-aminoethane, the silicon analog.477 Both the enantiomers of this SMA have been synthesized 478... 

The first committed step in TA and nicotine biosynthesis is catalyzed by putrescine JV-methyltransferase (PMT) (Fig.7.4).82 A PMT cDNA isolated from tobacco showed extensive homology to spermidine synthase from mammalian and bacterial sources.83 A-Methylputrescine is oxidatively deaminated to 4-aminobutanal, which undergoes spontaneous cyclization to form the reactive A-methyl-A1-pyrrolinium cation. Although the enzymes involved are unknown, the A-methyl-A1-pyrrolinium cation is thought to condense either with acetoacetic acid to yield hygrine as a precursor to the tropane ring, or with nicotinic acid to form nicotine. 

The final hydrogenolysis step leading to the required a-arylalk-anamine also yields lV-methyl-2-aminobutan-l-ol (2) which can be recovered and distilled in view of recycling via its transformation into the hydrazine (4). 

The oxidation of some aliphatic amines is a good route to aliphatic nitro compounds. tert-Butylamine is oxidized in 83% yield to 2-methyl-2-nitropropane by potassium permanganate in water at 45 °C for 8 h and at 55 °C for 8 h [738, 892], Under similar conditions, 4-amino-2,2,4-tri-methylpentane is converted into 4-nitro-2,2,4-trimethylpentane in 69-82% yields [859]. Refluxing 3a-acetoxy-20a-amino-5p-pregnane with a chloroform solution of m-chloroperoxybenzoic acid for 40 min furnishes 3a-acetoxy-20a-nitro-5p-pregnane in 66% yield [379]. 2-Aminobutane is converted into 2-nitrobutane by peroxyacetic acid [253] or dimeth yldioxirane [277] (equation 498). 

A reinvestigation of the geometry of the four optically active forms of 4-methyl-cyclophosphamide, prepared from (+)- and (->3-aminobutan-l-ol, has demonstrated the necessity for corrections to previous stereochemical assignments. ... 

AB AI3-35093 2-Aminobutane Butafume 2-Butanamine Butylamine (RS)-sec-Butylamine 2-Butylamine Caswell No. 125 CCRIS 4757 Deccotane EINECS 237-732-7 EPA Pesticide Chemical Code 004214 Frucote HSDB 6312 NSC 8030 Propylamine, 1-methyl Tutahe. Used agriculturally as a fungistat. Liquid mp = -104 bp = 63 d = 0.724 soluble in H2O, EtOH, LDso (rat orl) = 380 mg/kg. DowEtanco Ltd. Pennwalt Corp. 

In contrast, reaction of diethyl propionylphosphonate with lithium bis-(trimethylsilyl)amide (LiHMDS) at -78 °C gave the expected enolate as evidenced by its highly diastereoselective condensation with benzaldehyde, leading to the formation of 3-hydroxy-2-methyl-3-phenylpropionic acid (equation 91) " . An attempt was made to develop this concept to enantioselective aldol condensation. However, condensation of a cyclic chiral propionylphosphonamidate (31), synthesized from ( S)-A-isopropyl-4-aminobutan-2-ol, with benzaldehyde yielded 3-hydroxy-2-methyl-3-phenylpropionic acid in disappointingly low 47% e.e. (equation 92)... 

A mixture of 50 grams of a-dl-1,2-diphenyl-2-hydroxy-3-methyl-4-dimethylaminobutane hydrochloride, 50 grams of propionic anhydride and 50 cc of pyridine was refluxed for about 5 hours. The reaction mixture was cooled to 50°C and ethyl ether was added to the point of incipient precipitation. The hydrochloride salt of reaction precipitated upon cooling and was removed by filtration and washed with anhydrous ether. On recrystallization from a mixture of methanol and ethyl acetate, a-dl-1,2-diphenyl-2-propionoxy-3-methyl-4-dimethyl-aminobutane hydrochloride melted at 170°-171°C. 

ARIADNE itself, reduced not with LAH or AH (which would give the primary amine), but rather with sodium borohydride and borane dimethylsulfide. The product, 1-(2,5-dimethoxy-4-methylphenyl)-N-hydroxy-2-aminobutane hydrochloride, was a white crystalline material. The TOM analogue got as far as the nitrostyrene. This was made from 2-methoxy-4-methyl-5-(methylthio)benzaldehyde (see under the 5-TOM recipe for its preparation) and nitropropane in acetic acid, and gave bright yellow crystals. The true pseudo-analogue is the 2,4,6-trimethoxy material based on TMA-6, which is the "real" pseudo-TMA-2. The nitrostyrene from 2,4,6-trimethoxybenzaldehyde and nitropropane crystallized from MeOH/CH3CN as fine yellow crystals, and this was reduced with AH in cold THF to 1-(2,4,6-trimethoxyphenyl)-2-aminobutane which was a bright, white powder. 

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