Pyrrolidine 2-propyl

Methyl 6,8-dideoxy-6-(l-methyl-trans-4-propyl-L-pyrrolidin-2-ylcarbonylamino)-l-thio-D-erythro-D-galacto-octopyranoside... 

The first step involves the preparation of 1 -(3-isobutoxy-2-chloro)propyl pyrrolidine as an intermediate. 345 ml of thionyl chloride dissolved in 345 ml of chloroform are added, drop by drop, to 275 g of 1 -(3-isobutoxy-2-hydroxy)propyl pyrrolidine dissolved in 350 ml of chloroform, while maintaining the temperature at approximately 45°C. The reaction mixture is heated to reflux until gas is no longer evolved. The chloroform and the excess of thionyl chloride are removed under reduced pressure. The residue is poured on to 400 g of crushed ice. The reaction mixture is rendered alkaline with soda and the resulting mixture is extracted twice with 250 ml of diethyl ether. The combined ethereal extracts are dried over anhydrous sodium sulfate. After evaporation of the solvent the residue is distilled under reduced pressure. 220 g of product are obtained having the following properties boiling point = 96°C/3 mm, n074 = 1.4575. 

Hydroxy-butandisaure-propyl- —> 3-Hydroxy-l-propyl-pyrrolidin -, 88,65% d.Th. ... 

Cyclische a-Amino-ketone erleiden bei der Elektroreduktion eine Strukturverande-rung l-Methyl-2-athyl-3-oxo-piperidin wandelt sich in 30%iger Schwefelsaure haupt-sachlich in 1 -Methyl-2-propyl-pyrrolidin um (an Cd bei 60°, 41% d.Th.). Daneben entste-hen an anderen Kathoden zusatzlich Methyl-heptyl-amin bzw. an Kupfer l-Methyl-2-pro-pyl-4,5-dihydro-pyrrol1 ... 

In the presence of samarium(II) iodide, A-(2-iodobenzyl)dialkylamines 347 react with electrophiles at an a-carbon atom to yield deiodinated products by way of intermediate samarium compounds 348. Thus TV-(2-iodobenzyl)diethylamine and pentan-3-one afford the hydroxy amine 349 and 7V-(2-iodobenzyl)pyrrolidine and propyl isocyanate give the amide 350390. 

Secondary aliphatic amines, such as diethylamine, pyrrolidine or piperidine, react with the electron-poor nitrate ester 2-(trifluoromethyl)-2-propyl nitrate (369) under neutral conditions to afford the corresponding W-nitro derivatives 370412. 

FDMR has also been used to detect the transient radical cations formed from secondary amines by pulse radiolysis. As mentioned earlier this technique has been used to study a variety of systems such as the radical cation of triethylamine. The radical cations of diethylamine, n-propyl amine and f-butylamine, have also been studied25. The results have shown that the FDMR signal is enhanced with increasing alkyl substitution of the amine as in the pyrrolidines (18) and the piperidines (19)25. 

Als Base dient hierbei ein doppelter OberschuB an Amin. Die Produkte (z.B. Bis-[l,l-diethyl-propinyl]-amitv, 48%) konnen, je nach Bedingungen, zu sterisch stark gehinderten primaren Aminen (z. B. H2/Pt02/Ethanol, 300 kPa 3-Amino-3-ethy -pentan 90%), sekundaren Aminen (z.B. H2/Raney-Ni/Ethanol, 420kPa Bis-[1, l-diethyl-propyl]-amin 72%) Oder cyclischen Aminen (z.B. Hj/Pd-C/Ethanol, Normaldruck, 0° 2,2,5,5-Tetra-ethyl-3,4-dimethyl-2,5-dihydro-pyrrol, 48% neben 2,2,5,5-Tetraethy -4-methyl-3-methylen-pyrrolidin 15%) hydriert werden. 

Die Reduktion von Amiden und Lactamen zu Aminen kann mit einer N-Alkylierung verbunden werden, indem man zunachst die Reduktion mit Lithium-alanat in Tetrahy-drofuran durchfiihrt und das Reaktionsgemisch dann mit einem geeigneten Alkyl-halo-genid behandelt, wie hier fur die Herstellung von I-Propyl-pyrrolidin formuliert3. 

Die Reduktion von N-(2-Dialkylamino-ethyl)- und N-(3-Dialkylamino-propyl)-succinimi-den mit Lithium-alanat liefert l-(2-Dialkylamino-ethyl)- bzw. 1 -(3-Dialkylamino-propyl)-pyrrolidine (s. Bd. XI/1, S. 586). Dagegen verlauft die Reduktion von N-(Ani-lino-methyl)-succinimiden mit Natrium-boranat in Dimethyl-sulfoxid unter C-N-Spal-tung und Bildung von N-Methyl-anilinen4 ... 

O eOCHj Li [A1H4]/Ethcr Ruckil. 10 min 2-( 2-Hydroxy-propyl)-/-methyI-pyrrolidin [4 Diastereoisomere Hygrolin (2 Isomcre) + Pseudo-hygrolin (2 Isomcre)] 81 6... 

Hydrazones prepared from (S)- l-amino-2-(methoxymethyl)pyrrolidine (242) and acyclic ketones have been shown to undergo deprotonation and alkylation with almost complete asymmetric induction at the a-center (79AG(E)397). The ant alarm pheromone, (+)-(5)-4-methyl-3-heptanone (245), was prepared from the metallated hydrazone of diethyl ketone (243) by alkylation with n-propyl iodide and subsequent cleavage of the crude product via its JV-methyl iodide with acid (Scheme 52). The optical purity of the product was >99%. 

H). C,8H34N206S. the first lincosaminide antibiotic to which a structure was assigned, is defined chemically as methyl 6,8-dideoxy-6-(l-methyl-fro/M-4-propyl-L-pyrrolidin-2-ylcarbonylamino)-l-thio-D-erythro-L>-gal-actu-octopyranoside. Both lincomycin and the semisynthetic clindamycin (I, R = H, R = Cl), CisH ClNjOsS, are widely used in clinical practice. The trivial name of the sugar fragment of this antibiotic, methyl a-thiolincosaminide, has lent itself to the other members of this family, whether produced as secondary metabolites of soil microorganisms or derived semisynthetically by chemical modification. 

Loss of ethene from 67 leads to the enamine 68 which loses either a propyl radical (m/z 56) or, more easily, a methyl radical probably after pyrrolidine ring formation (cf 19 in Scheme 12) (Scheme 37). 

A solution of the Step 7 product (0.16 mmol) and 1-hydroxybenzotriazole hydrate (0.16 mmol) in CH2C12 was cooled to 0°C, then stirred 30 minutes, and treated sequentially with pyrrolidine (0.16 mmol), 3-ethyl-3 -(dimethylamino)propyl-carbodiimide hydrochloride (0.16 mmol), and 60 pi triethylamine. Stirring was continued for additional 30 minutes at 0°C and 2 days at ambient temperature. The mixture was then partitioned between 1.5 ml water and 20 ml EtOAc and combined organic extracts washed with 1.5 ml brine, dried with Na2S04, and concentrated. 

Preparation of (3R,4S)-3-aminomethyl-4,5-dimethyl-hexanoic acid 1-butyl ester and [4/ -[4/ (S )]]-4-(l,2-dimethyl-propyl)-pyrrolidin-2-one... 

Pyrrolidin 2-(l-Hydroxy-propyl)-l-propyl- E21e, 5280 (5-NRC1 - en Cyclisier.)... 

Pyrrolidin l-Anilino-2-methyl- E16a, 635 (R2NH 4- R-NH-O- ) Pyrrolo[l,2-a]pyrazin 6-Methyl-l-propyl-3,4-dihydro- E6a, 678 [2-Acyl — 5-CH3 — furan + H2N-(CH2)2-NH2] Pyrrolo l,2-b pyridazin 2,7-Diethyl-3,4-dihydro- E6a, 593 (3,6,9-Undecantrion 4- N2H4)... 

SYN CYCLOPROPANECARBOXYLIC ACID, 3-(2,2-DICHLOROETHENYL)-2,2-DIMETHYL-, CYANO(3-PHENOXYPHENYL) METHYL ESTER, MIXED WITH ACETIC ACID ANHYDRIDE, 5-((2-(2-BUTOXYETHOXY) ETHOXY) METHYL)-6-PROPYL-l,3-BENZODIOXOLE, DIMETHYLBENZENE AND 1-METHYL 2-PYRROLIDIN ONE... 

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