Amines from amine ethers

The Sommelet procedure2 yields a mixture of aldehyde and amines. Acidification removes the amines from the ether extract. 

Ethylene derivatives from amines Ethers from phenols... 

Amino-4 -chlorobiphenyl [135-68-2] M 203.5, m 132-133°, 134°, pK st Crystallise the amine from petroleum ether, EtOH or aqueous EtOH. The acetyl derivative has m 245° from EtOH. [Dewar James J Chem Soc 4270 1958, Gelmo Chem Ber 39 4176 1906, Beilstein 12 H 1319,12II757,12IV 3269.]... 

In a 500 ml. flask, fitted with a reflux condenser, place 53 g. of 1-chloro-methylnaphthalene (Section IV.23), 84 g, of hexamethylenetetramine and 250 ml. of 1 1 acetic acid [CAUTION 1-Chloromethylnaphtha-lene and, to a lesser degree, a-naphthaldehyde have lachrymatory and vesicant properties adequate precautions should therefore be taken to avoid contact with these substances.] Heat the mixture under reflux for 2 hours it becomes homogeneous after about 15 minutes and then an oil commences to separate. Add 100 ml. of concentrated hydrochloric acid and reflux for a further 15 minutes this will hydrolyse any SchifiF s bases which may be formed from amine and aldehyde present and will also convert any amines into the ether-insoluble hydrochlorides. Cool, and extract the mixture with 150 ml. of ether. Wash the ether layer with three 50 ml. portions of water, then cautiously with 50 ml. of 10 per cent, sodium carbonate solution, followed by 50 ml. of water. Dry the ethereal solution with anhydrous magnesium sulphate, remove the ether by distillation on a steam bath, and distil the residue under reduced pressure. Collect the a-naphthaldehyde at 160-162718 mm. the yield is 38 g. 

Reduction of a nitro compound to a primary amine. In a 50 ml. round-bottomed or conical flask fitted with a reflux condenser, place 1 g. of the nitro compound and 2 g. of granulated tin. Measure out 10 ml. of concentrated hydrochloric acid and add it in three equal portions to the mixtiue shake thoroughly after each addition. When the vigorous reaction subsides, heat under reflux on a water bath until the nitro compound has completely reacted (20-30 minutes). Shake the reaction mixture from time to time if the nitro compound appears to be very insoluble, add 5 ml. of alcohol. Cool the reaction mixture, and add 20-40 per cent, sodium hydroxide solution imtil the precipitate of tin hydroxide dissolves. Extract the resulting amine from the cooled solution with ether, and remove the ether by distillation. Examine the residue with regard to its solubility in 5 per cent, hydrochloric acid and its reaction with acetyl chloride or benzene-sulphonyl chloride. 

The addition of N-bromosuccinimide (1.1equiv) to a dichlo-romethane solution containing the alkene (1 equiv) and cyana-mide (4 equiv). The solution was maintained at room temperature (3 days) and then washed with water, dried, and concentrated in vacuo. Treatment of the bromocyanamide [intermediate] with 1% palladium on charcoal in methanol (1h) led to reduction of the for-madine. Addition of base to the reaction mixture (50% aqueous KOH, reflux 6h) followed by extraction with ether gave monoamine. (Yield is 48-64% final amine from alkenes analogous to safrole)... 

Their basicity provides a means by which amines may be separated from neutral organic compounds A mixture containing an amine is dissolved m diethyl ether and shaken with dilute hydrochloric acid to convert the amine to an ammonium salt The ammonium salt being ionic dissolves m the aqueous phase which is separated from the ether layer Adding sodium hydroxide to the aqueous layer converts the ammonium salt back to the free amine which is then removed from the aqueous phase by extraction with a fresh portion of ether... 

PF3 forms complexes with amines, ethers, and other bases as well as F , with which phosphoms becomes six-coordinate. Dry phosphoms pentafluoride does not attack glass. The yellow crystalline phosphoms pentabromide forms from the reaction of PBr and excess bromine. 

Propylene oxide has found use in the preparation of polyether polyols from recycled poly(ethylene terephthalate) (264), haUde removal from amine salts via halohydrin formation (265), preparation of flame retardants (266), alkoxylation of amines (267,268), modification of catalysts (269), and preparation of cellulose ethers (270,271). 

Zirconium tetrachloride is instantly hydrolyzed in water to zirconium oxide dichloride octahydrate [13520-92-8]. Zirconium tetrachloride exchanges chlorine for 0x0 bonds in the reaction with hydroxylic ligands, forming alkoxides from alcohols (see Alkoxides, METAl). Zirconium tetrachloride combines with many Lewis bases such as dimethyl sulfoxide, phosphoms oxychloride and amines including ammonia, ethers, and ketones. The zirconium organometalLic compounds ate all derived from zirconium tetrachloride. 

Other synthetic routes to pyrazinones and quinoxalinones are from the halo compounds, by dealkylation of ethers (8lJCS(Pl)3111> or by diazotization of the corresponding amines, but since the halo derivatives are normally derived from the hydroxy compounds, and the amines from the halo derivatives, direct synthesis seems to represent the most practical approach. 

The classical structures of pyrrole, furan and thiophene (31) suggest that these compounds might show chemical reactions similar to those of amines, ethers and thioethers (32) respectively. On this basis, the initial attack of the electrophile would be expected to take place at the heteroatom and lead to products such as quaternary ammonium and oxonium salts, sulfoxides and sulfones. Products of this type from the heteroaromatic compounds under consideration are relatively rare. 

Phenylpftenanttirldlne (3).3 Amine hydrochloride 1 (2.72 g, 9 28 mmol) in EtOH (75 mL) was treated with 0 926 N cold solution of KCXI. Colorless crystals appear The mixture was shaken lor 30 mtn in ice, water was added and the product was filtered and dryed (PaOs) to afford 2.7 g of 2 (100%), rnp 102°C (hexane) 2 (2 0 g, 6 6 mmol) in anh pyndine (20 mL) was treated with an excess of NaOCHa (exothermc) Alter 20 h the solvent was removed In vacuum, the residua triturated with EtaO and the extract treated with dry HCI to obtain the hydrochlonda of 3, mp 107-108°C (from petroleum ether), mp 95-100° (Irom water) Olphenylmethyieneanlllna (5). To a suspension of lead tetraacetate (4.9 g, fO mmol) in PhH (100 mL) under Na was added a solution of tnphenyhnethylamine 4 (2 6 g, 10 mmol) in PhH (100 mL) dropwise under stirring The mixture was refluxed for 1 h, cooled, filtered, washed and the solvent evaporated The residue was crystallized from EtOH to give 2 2 g of 5 (85%), mp 111-112°C. 

C. Thiete 1,1-dioxide. A sample of 3-chlorothietane l,l-d1ox1de (8.0 g, 0.057 mol) Is dissolved In dry toluene (300 ml) (Note 7) In a 500-mL, twonecked, round-bottomed flask equipped with a reflux condenser, magnetic stirrer, heating mantle (or silicone oil bath), and thermometer. The reaction Is heated to 60° C and tri ethyl amine (28.7 g, 0.28 mol, 39,5 ml) Is added through the condenser. The reaction mixture Is stirred for 4 hr and triethyl-amine hydrochloride is removed by filtration and washed with toluene (100 mL), Toluene is removed on a rotary evaporator and the residue is recrystallized from diethyl ether-ethanol (Note 8) to give a white solid (4.5-4.8 g, 75-81 ) mp 49-50°C (llt mp 52-54°C). 

Tri-n-octylamine [1116-76-3] M 353.7, b 164-168 /0.7mm, 365-367 /760mm, d 0.813, n 1.450, pK 10.65. It was converted to the amine hydrochloride etherate which was recrystd four times from diethyl ether at -30° (see below). Neutralisation of this salt regenerated the free amine. [Wilson and Wogman J Phys Chem 66 1552 1962.] Distd at l-2mm pressure. 

The epoxidised polybutadiene resins available to date are more viscous than the diglycidyl ethers except where volatile diluents are employed. They are less reactive with amines but have a similar reactivity with acid anhydride hardeners. Cured resins have heat distortion temperatures substantially higher than the conventional amine-cured diglycidyl ether resins. A casting made from an epoxidised polybutadiene hardened with maleic anhydride and cured for two hours at 50°C plus three hours at 155°C plus 24 hours at 200°C gave a heat... 

Similar behavior can be observed even in the case of substituted quinuclideines 170). Neostrychnine (68) serves as an example of more complex compounds which show spectra differing from those of other enamines. The ultraviolet spectrum of this compound exhibits no batho-chromic shift and its basicity is considerably decreased 159,171,172) (pK in methylcellosolve at 20° is 3.8, whereas the analogous saturated compound has a pK under the same conditions of 7.45, and a compound with the double bond further removed, strychnine, has a pK of 7.37). As another example, the ultraviolet spectrum of trimethyl conkurchine (69) shows the same absorption maxima as a saturated tertiary amine (A in ether, about 213 m/i). 

A solution of 24.6 g of o-allyl-epoxypropoxybenzene dissolved in 250 ml of absolute ethanol saturated with ammonia was placed in an autoclave and heated on a steam-bath for 2 hours. The alcohol was then removed by distillation and the residue was redissolved in a mixture of methanol and ethylacetate. Hydrogen chloride gas was introduced into the solution. The hydrochloride salt was then precipitated by the addition of ether to yield 11.4 g of product. Five grams of the amine-hydrochloride thus formed were dissolved in 50 ml of methanol and 9 ml of acetone. The resulting solution was cooled to about 0°C. At this temperature 5 g of sodium borohydride were added over a period of 1 hour. Another 2.2 ml of acetone and O.B g of sodium borohydride were added and the solution was kept at room temperature for 1 hour, after which 150 ml of water were added to the solution. The solution was then extracted with three 100-ml portions of ether which were combined, dried over potassium carbonate, and evaporated. The free base was then recrystallized from petrol ether (boiling range 40°-60°C) to yield 2.7 g of material having a melting point of 57°C. 

After cooling, the solution was diluted with 1.5 liters of water and subjected to three extractions with ether. The amine was extracted from the ethereal solution with 2 N HCI and liberated therefrom by the addition of solid NaOH (while cooling). The alkaline solution was extracted with ether and the ethereal solution was dried with soiid NaOH. Distii-lation resulted in 10.6 grams (70% of the theory) of 1-aminoadamantane which, after sublimation, melted at 180° to 192°C (seal capillary). It is converted to the hydrochloride. 

The reaction mixture then is extracted with ether, the excess amine is removed from the ethereal solution under reduced pressure and the ether then removed by evaporation to give 3-tert-butylamino-2-oxopropanol. 

As well as the disubstituted C2-symmelrie pyrrolidines E and F, the monosubstituted (f> )-2-(mcthoxymethyl)pyrrolidine G can be used as chiral auxiliary for the diastereoselecti ve addition of organomctallic reagents to a-oxo amides16. As with the phenylglyoxylic acid derivatives derived from amines E and F. methyllithium or methylmagnesium bromide in diethyl ether preferentially attack the (,S)-mms-conformer 11 (R = ( 6H5), leading to predominant formation of the (2 S)-diastercomer by Re-side attack. 

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