Kost, A. N. published the artcileAcrylonitrile as a starting material for synthesis of amino nitriles and polyamines, SDS of cas: 10517-44-9, the publication is Uchenye Zapiski Moskov. Gosudarst. Univ. im. M. V. Lomonosova (1950), 39-97, database is CAplus.
cf. C.A. 41, 1609h; 42, 3722g. Dissertation at the University (1946) with complete exptl. details and bibliography of 169 references. A laboratory preparation of CH2:CHCN (I) was developed as follows. To a hot saturated solution of 100 g. SnCl2 was added 30 g. Zn dust with stirring and, after completion of reaction, the mixture was allowed to stand 2 hrs., decanted, washed with 10% AcOH, let stand overnight with 60 ml. 80-90% AcOH, filtered, washed with H2O until neutral, and washed with EtOH and Et2O, giving 30-35 g. Sn dust. All traces of Zn must be removed for good results with this catalyst. Heating 50 g. HOCH2CH2CN with 5 g. of the above Sn dust in a distillation apparatus with chilled receiver so that vapor temperature is below 110¡ã yields a 2-layer distillate; the upper layer after drying with CaCl2 yields up to 90% I. If com. ethylene oxide is used in the preparation of the cyanohydrin, the product may be contaminated with MeCH:CHCN, H2O, and NH3; it is purified by 5-10 min. treatment with P2O5 and distillation (b758 78¡ã). Refluxing the cyanohydrin with silica gel, activated C, MgSO4, Fe oxides, pieces of sheet Fe, Al foil, and Al2O3 gave but 0-30% yields of I. Passage of the cyanohydrin over Al2O3 at 200-20¡ã gave but 18-20% I. To 950 ml. aqueous NH4OH (saturated in the cold) was added 95 g. I dropwise with cooling over 2 hrs. so that the mixture remained homogeneous; after 30 min. at room temperature, distillation gave 30% H2NCH2CH2CN, b14 77-8¡ã, b23 89¡ã, nD20 1.4390, d20 0.9584, which polymerized in several days in a sealed ampul even in darkness. Distillation of the higher-boiling residue gave 47% HN(CH2CH2CN)2, b14 177-9¡ã, b22 209-11¡ã, nD20 1.4630, d20 1.0196; HCl salt, m. 147-8¡ã (from MeOH); N-Bz derivative, m. 112¡ã (from MeOH). The free amine generated by addition of 50% aqueous Me2NH to solid NaOH was fed into 106 g. I with ice cooling over 6-8 hrs., and the mixture distilled after 2 hrs. at room temperature yielding 80-1% Me2NCH2CH2CN, b750 171¡ã, nD20 1.4283, d20 0.8705; picrate, m. 151¡ã; HCl salt, m. 199¡ã (from MeOH). A mixture of 40 g. Et2NH and 26.5 g. I gave a slight heat evolution after 5-10 min.; refluxed on a steam bath 2 hrs. (yellow color) and distilled, it yielded 89-95% Et2NCH2CH2CN, b20 86-9¡ã. If the heating is done in sealed tubes 6-8 hrs. no yellow color is formed and the yield is nearly 100%; the pure product b2 65¡ã, b9 76¡ã, b20 87¡ã, b45 112¡ã, b755 197.3¡ã (corr.), d20 0.8761, nD20 1.4380; HCl salt, m. 120¡ã; picrate, m. 85¡ã. This (3.1 g.) refluxed 4 hrs. with 4. g. 25% NaOH and evaporated gave the amorphous Na salt of the corresponding acid; refluxing 6.3 g. of the nitrile with 11 g. concentrated HCl, cooling, filtering, and evaporating repeatedly in vacuo gave an amorphous mass, which was freed in aqueous solution of Cl ion by Ag2CO3, the Ag ion removed with H2S, and the filtrate evaporated, yielding 60% Et2NCH2CH2CO2H, m. 70-5¡ã. The best reaction conditions for piperidine and I are as follows: Piperidine (17 g.) and 11.1 g. I mixed with cooling in an ampul (cooled until the heat evolution stopped in 15-20 min.) and heated 4 hrs. on a steam bath, then let stand overnight, gave 96-7% (CH2)5NCH2CH2CN, b18 114-15¡ã; some 22% is formed by refluxing 5 g. piperidine with 5 g. HOCH2CH2CN 3 hrs. at 120-50¡ã; if Sn dust is added the yield is 52.5%. An extensive study showed that the reaction of I with PhNHEt is best carried out by heating in an ampul 100 hrs. on steam bath in the presence of 3% Ac2O and a little hydroquinone, when 65-70% PhEtNCH2CH2CN, b8 158¡ã, b11 164-5¡ã, nD20 1.5503, d20 1.0260, is obtained; HCl salt, hygroscopic solid; picrate, oil; the free base couples with diazotized sulfanilic acid even in acid medium and the coupling product, isolated as the Na salt, is a green solid, giving a brown color in acid solution Coupling with diazotized p-O2NC6H4NH2 gave a brown product, C17H17O2N5, while tetrazotized benzidine reacts only slowly in acidified solution, yielding a red-violet solution which turns yellow in neutral or basic solution; the free azo derivative is soluble in organic solvents. Hydrolysis of PhEtNCH2CH2CN is very slow with H2O at 100¡ã in a sealed tube; concentrated HCl at room temperature acts slowly and incompletely even in 48 hrs., while heating at 110-20¡ã leads to loss of PhNHEt; heating with 30-40% H2SO4 gives an impure product. Alk. hydrolysis gives low yields of the corresponding acid. Refluxing 14 g. PhEtNCH2CH2CN and 20 g. KOH in 20 ml. H2O and 70 ml. EtOH 15 hrs., acidifying with HCl, and repeatedly extracting with iso-BuOH, adding Et2O to the extract gave 33.1% PhEtNCH2CO2H.HCl, a high-melting solid, giving a brown color with FeCl3. This couples even in acid solution with diazotized sulfanilic acid, yielding a red azo derivative; p-O2NC6H4N2Cl also couples in acid medium, giving a red azo derivative PhEtNCH2CH2CN (4.5 g.) added slowly to 15 ml. concentrated H2SO4, and the mixture let stand 40 hrs., then diluted with H2O (50 ml.), neutralized with concentrated NH4OH, and let stand overnight giving a precipitate of PhEtNCH2CH2CONH2, 68.5-76.5%, m. 55-8¡ã (crude), m. 67¡ã (from MeOH). I (35 g.) added to 20 g. dry (CH2NH2)2 dropwise with cooling at 15-20¡ã over 2 hrs. the mixture shaken 2 hrs. at room temperature and let stand overnight in a stoppered flask gave 39.8% H2NCH2CH2NHCH2CH2CN, b1.5 101¡ã, nD20 1.4727, d20 0.9912 (with MeZnI at room temperature only the primary amino group reacts, while at 100¡ã all active H can be determined) (the picrate and styphnate are oils, while HCl salt is a viscous mass), and 59.8% (CH2NHCH2CH2CN)2, b1.5 174¡ã, b3.5 191¡ã, nD20 1.4793, d20 1.0256 [picrate and styphnate, oils; HCl salt, m. 184-7¡ã (decomposition)]. The structure of the latter appears confirmed by the improbability of reaction of I with a cyanoethylated group, and further by the reaction with MeZnI which indicates 1.94 active H atoms/mole at 100¡ã and 0.5 at room temperature Me2NCH2CH2CN treated with MeI in C6H6 with cooling gave the methiodide, m. 153¡ã (from MeOH); EtI at room temperature yielded the ethiodide, m. 128.5¡ã (from MeOH); EtBr at 60¡ã yielded the ethobromide, m. 157¡ã (from Et2O-MeOH); PrBr and CH2:CHCH2Cl at 80¡ã yielded the corresponding quaternary salts, m. 189¡ã (from Et2O-MeOH), and 185-7¡ã (from MeOH), resp. Et2NCH2CH2CN with MeI at room temperature gave the methiodide, m. 152¡ã (from MeOH), while EtI at 60¡ã gave the ethiodide, m. 168¡ã (from MeOH). (CH2)5NCH2CH2CN with MeI at 100¡ã gave the methiodide, m. 152¡ã (from MeOH), while EtI reacted slowly at 100¡ã yielding the ethiodide, m. 160-1¡ã (from MeOH). Reduction of H2NCH2CH2CN with BuOH-Na gave variable yields when com. Na was used, because of traces of K (Dzirkal, C.A. 36, 2255.6); a 2% K-Na alloy gave high yields comparable to those obtained with pure Na. In the best procedure 30 g. of this alloy was rapidly treated with 14 g. H2NCH2CH2CN in 450 ml. BuOH, and despite vigorous reaction the mixture was immediately heated in an oil bath at 140-50¡ã, cooled after 35-40 min., diluted with 130-50 ml. cold H2O, steam-distilled 4-6 hrs. into the calculated amount of aqueous HCl, and the distillate evaporated, yielding 81% CH2(CH2NH2)2.2HCl, m. 242¡ã (from EtOH). Similar reduction of Me2NCH2CH2CN gave 52-6% Me2NCH2CH2 CH2NH2, b128-30 70-80¡ã (crude), b20 44-5¡ã, b748 133¡ã, nD20 1.4415, d20 0.8272; di-HCl salt, m. 184¡ã (from MeOH); picrate, C17H20N8O14, m. 211¡ã (from H2O). The higher-boiling material yielded a little 3,3′-bis(dimethylamino)dipropylamine, b20 128-31¡ã, nD20 1.4531 (HCl salt, hygroscopic solid; tripicrate, m. 200¡ã; chloroplatinate, 2C10H25N3.3H2PtCl6, soluble in H2O, insoluble in aqueous EtOH). Reduction of Et2NCH2CH2CN with NaBuOH gave 38-63% diamine; a 2% K-Na alloy gave good consistent 60-70% yields; pure Et2NCH2CH2CH2NH2, b12 61-2¡ã, b70 85-7¡ã, b80 99-100¡ã, b755 168-70¡ã, nD20 1.4435, gave 2 active H with MeZnI at room temperature and at 100¡ã; picrate, m. 190.5¡ã (from MeOH); Bz derivative, oil. Refluxing this amine with an equimolar amount of oleic acid 2 hrs., adding a little amine, heating another hr., concentrating, and evaporating with C6H6 gave a product that formed extremely stable organic-aqueous emulsions. The higher-boiling fractions from the above reduction gave a little bis(diethylamino) dipropylamine, b12 148-50¡ã (picrate, m. 152¡ã), also obtained if the reduction is run with pure Na. Reduction of (CH2)5NCH2CH2CN with 2% K-Na in BuOH gave 57% 1-(3-aminopropyl)piperidine, b4 65-6¡ã, b9 79-81¡ã, nD20 1.4729. COCl2 with ROH gave the ClCO2R: R =Et, b752 92-4¡ã; Pr, b742 114-16¡ã, nD20 1.4036; iso-Pr, b745 101-2¡ã, nD20 1.3996, d20 1.0777; Bu, b16 40-7¡ã, b756 138¡ã, nD20 1.4128, d20 1.0513. COCl2 with ROH in MePh in the presence of 5-8% quinoline gave the following ClCO2R: iso-Bu, b750 123-7¡ã; iso-Am, b754 150-1¡ã, nD20 1.4176, d20 1.0490; C8H17, b5 86.5¡ã, b10 96-7¡ã, b15 107¡ã, nD20 1.4330, d20 0.9841; cyclohexyl, b25 80-5¡ã, nD25 1.4628; 1-menthyl, b5 96¡ã, b11 108-9¡ã, nD20 1.4712; PhCH2, b7 85-7¡ã; with an equimolar amount of quinoline were obtained: sec-Bu, 72%, b23 30-1¡ã, b748 121-4¡ã, nD20 1.4490; 1-methyl-2-cyclohexyl, b30 101.5¡ã, nD20 1.4560; Ph, b7 64¡ã, nD20 1.5162. The diamines (0.025 mole) in Et2O were treated with 0.025 mole powd. potash, then 1.5-2 ml. H2O, and RO2CCl in Et2O was added with cooling; the usual treatment gave the desired urethan derivatives: Me2NCH2CH2CH2NHCO2Et, 55.8%, b16 137-7¡ã, nD20 1.4480, d20 0.9653; l-menthyl ester, 51.8%, b1 164.5¡ã, nD20 1.4706, d20 0.9557, m. 45¡ã; Et2NCH2CH2CH2NHCO2Et, 66.7%, b7 130¡ã, nD20 1.4503; iso-Pr ester, 53.2%, b1.5 122-3¡ã, nD30 1.4452, nD20 1.4493, d20 0.9367; sec-Bu ester, 42.5%, b5 132¡ã, nD20 1.4513, d20 0.9334; C8H17 ester, 63.3%, b2 181.5-2¡ã, nD30 1.4528, nD20 1.4577, d20 0.9168; cyclohexyl ester, 46.5%, b1.5 165-7¡ã, nD30 1.4725, nD20 1.4752, d20 0.9765; 2-methylcyclohexyl ester, 81.5%, b2 177¡ã, nD30 1.4693, nD20 1.4723, d20 0.9679; l-menthyl ester, 88.2%, b3 173¡ã, nD20 1.4719, d20 0.9482, m. 31¡ã; Ph ester, 33.6%, b3 196-201¡ã, nD20 1.4770; PhCH2 ester, 24%, b3 132-5¡ã, nD20 1.5030. C5H5NCH2CH2CH2NHCO2Et, 78.3%, b9 150-3¡ã, nD20 1.4742, d20 1.0070; Pr ester, 70.4%, b18 187-8¡ã, nD20 1.4735, d20 0.9935; iso-Pr ester, 62.8%, b8 155-8¡ã, nD20 1.4706, d20 0.9878; Bu ester, 62.8%, b3 146¡ã, b5 167-8¡ã, nD20 1.4730, d20 0.9788; iso-Bu ester, 53.5%, b2 136.5-7¡ã, nD20 1.4710, d20 0.9813; iso-Am ester, 66.2%, b2 159.5¡ã, nD20 1.4712, d20 0.9749; C8H17 ester, 63.7%, b9 212-13¡ã, nD20 1.4720, d20 0.9550.
Uchenye Zapiski Moskov. Gosudarst. Univ. im. M. V. Lomonosova published new progress about 10517-44-9. 10517-44-9 belongs to catalysis-chemistry, auxiliary class Salt,Amine,Aliphatic hydrocarbon chain, name is Propane-1,3-diamine dihydrochloride, and the molecular formula is C3H12Cl2N2, SDS of cas: 10517-44-9.
Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia