О-этилизомочевина

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возможно ли получить из диэтилсульфата и мочевины, О-этилизомочевину? ведь известно, что при взаимодействии диметилсульфата с мочевиной большим выходом получается О-метилизомочевина.
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Непонятно, по другому делали

Tertiary oxonium salts. II. Meerwein, Hans; Battenberg, Ernst; Gold, Heinrich; Pfeil, Emanuel; Willfang, Georg. Journal fuer Praktische Chemie 1939, 154 83-156.

Abstract

cf. C. A. 31, 1760.9. Addn. of 14 g. of ClCH2CH.O.CH2 (I) to 19 g. BF3.Et2O in 50 cc. ether at a rate such that the ether constantly boils, followed by stirring for 2 hrs., gives 100% of (Et3O).BF4 (II), m. 92°; similarly 6.4 g. BF3.Pr2O in 40 cc. Pr2O, treated with 4.6 g. I, gives 30% of tripropyloxonium borofluoride, m. 73-4° (decompn.). SbCl5 (75 g.), added to 100 cc. Me2O with cooling in Et2OCO2, followed by slow addn. of 11.6 g. I, gives 95.5% of trimethyloxonium hexachloroantimoniate (III), (Me3O).SbCl6, m. 158° (decompn.), which is stable for months in a closed vessel. Evapn. of the mother liquor from III gives 48.1 g. of a brown oil; to show that this contains ClCH2(MeOCH2)CHOSbCl4 (IV), it was decompd. with Rochelle salt and KOH (the soln. being kept neutral to litmus), giving 8.7 g. of g-chloropropylene glycol Me ether (V), b. 170-4°; SbCl5 and Et2O, followed by I, give 95% of the Et analog (VI) of III, m. 135-7° (decompn.); it is considerably more sol. than III in org. solvents; heating causes decompn. with formation of EtCl; 109 g. of VI with 30% aq. alkali gives 16.9 g. Et2O, 6.5 g. EtOH and 3.6 g. EtCl; the filtrate from VI gives the Et analog of IV, red-brown, m. 91°; aq. alkali give 82.5% of the Et analog of V, b. 178-84°. SbCl5, Et2O and (C2H4)2O give 79% of (Et3O).SbCl6, m. 132°; the mother liquor yields EtOCH2CH2OSbCl4. AlCl3, Et2O and I give 82% of triethyloxonium tetrachloroaluminate, (Et3O).AlCl4, m. 72° (decompn.); the ether filtrate contains 86.4% of the Al chloroalcoholate of g-chloropropenyl glycol Et ether, m. 114-15°; 5 g. of the salt gives 2.6 g. of ClCH2CH(OH)CH2OEt, b13 71-3°; heating the salt gives EtCl and AlCl3.Et2O; decompn. of 19 g. of the salt with 2 N NaOH gives 0.5 g. EtOH, EtCl and Et2O; with H2O alone 16 g. of the salt gives 4 g. EtCl and 3.5 g. Et2O. FeCl3.Et2O and I give 100% of trimethyloxonium tetrachloroferriate, (Et3O).FeCl4, m. 74° (decompn.); the filtrate gives 89% of the ferric chloroalcoholate of ClCH2CH(OH)CH2OEt, yellow, m. 103-5°; decompn.
with H2O gives 82% of EtOH. BF3.Me2O (1.7 moles) and 1 mole MeF, allowed to stand 3 months in a sealed tube, give 38% of (Me3O).BF4, m. 148° (decompn.) (previously reported 124.5°); careful heating gives the 2 components. BF3.Et2O and MeF, after standing 4 months, give 52% of methyldiethyloxonium borofluoride, m. 99-100° (decompn.). BF3.Me2O and PrF give (Me3O).BF4 and not the expected (PrMe2O).BF4. SbCl5.Et2O (1 mole) and 7 moles EtCl, allowed to stand 14 days at room temp., give a small yield of VI. Neg. results were obtained in attempting to add MeCl or EtCl to the etherates of AlCl3, FeCl3, BCl3 or SnCl4; SbCl5.Et2O does not add ClCH2OMe, PhCH2Cl or AcCl; ClCH2OMe is decompd. into HCHO and MeCl; PhCH2Cl gives a resin with loss of HCl; AcCl is transformed into AcOEt and EtCl. If the reaction of SbCl5.Et2O and I, including the filtration and washing, is carried out at the temp. of Et2O-CO2, there results 98.5% of the internal salt ClCH2CH(CH2O+Et)OS-bl5 (VII), decomps. 58°; it is not pptd. by ether from solns. in org. solvents; decompn. with alk. Rochelle salt soln. gives 90% of EtOH and 96.3% of the Et analog of V, b15 74.5-5.5°; the latter on shaking with 0.1N NaOH loses HCl and yields glycide ether; decompn. of VII with H2O also did not yield EtCl. Slowly heating VII to 90° gives 85% of EtCl and the Et analog of IV. Similarly SbCl5.Et2O and (C2H4)2O give 97.5% of the salt Et2O+CH2CH2OS-bCl5 (VIII), decomps. 58°. On standing at room temp. VII and VIII decomp. into EtCl and the SbCl4 compds.; in 20 hrs. the m. p. of VIII decreases from 58 to 23°; VII shows the same change in 10 hrs.; after 18 hrs. VII loses 16.2% EtCl, whereas VIII gives 6.5% EtCl in 24 hrs.; after 70 hrs. the reaction is practically complete in each case. VII and SbCl5.Et2O in Et2O at room temp. give 100% of VI and 97.5% of the Et analog of IV; VIII gives 100% of VI and 87% of the SbCl4 compd. of HOCH2CH2OEt, m. 107°.
BF3.Me2O in Me2O, cooled with Et2O-CO2 and treated with I, gives 81.3% of the salt (ClCH2CH(CH2O+Me2)OB-F3, with 1 mol. Me2O, m. 75-80° (decompn.); it is very unstable and decomps. in 2-3 hrs. to a yellow-brown oil with liberation of BF3. BF3.Et2O reacts similarly but on warming to room temp. the ppt. from 57.7 g. BF3.Et2O and 44.4 g. of I reacts with the Et2O which adheres to it to give 7.1 g. EtF, 7 g. Et2O, 31.5 g. BF3.Et2O, 26.5 g. ClCH2CH(OEt)CH2OEt (b14 72-3°, d423 1.017), 1.2 g. of ClCH2CH(OBF2)CH2OEt, b14 80-90° and 4.9 g. [ClCH2CH(CH2OEt)O]3B (IX), b0.05 145-50°. If the inner oxonium salt from 50 g. BF3.Et2O and 35 g. I is treated with BF3.Et2O at the temp. of Et2O-CO2 there results 61 g. (91%) of II and 40.2 g. of IX. It is probable that SnCl4.Et2O forms an inner oxonium salt with I but it is so unstable that it cannot be isolated; on standing for some time the soln. contg. 26.1 g. of SnCl4 gives 8.6-9.6 g. of the SnCl3 compd. (X) of (ClCH2)2CHOH (XI), which may be isolated by extg. the SnCl4.Et2O with CCl4 and may be crystd. from C2H4Cl2; on decompn. with Rochelle salt and NaHCO3 61 g. X gives 14.4 g. XI. BF3.C5H5N (XII) and (C2H4)2O in C5H5N with ice cooling give 100% of the salt C5H5N+OCH2CH2OB-F3 (XIII), m. 131-2°; it is hydrolyzed by H2O; with aq. NaI.HgI2 XIII gives yellow needles, m. 39°, of the salt (HOCH2CH2NC5H5)HgI3 and with NaCl.HgCl2 (HOCH2CH2NC5H5)Cl.6HgCl2. XII and I in C5H5N give 62.8% of the salt ClCH2CH(OB-F3)CH2N+C5H5, which, recrystd. from SO2 by addn. of PhNO2, m. 164-5°. BF3.NMe3 and (C2H4)2O, heated and shaken in a sealed tube at 40-5° for 2 hrs. and at 60-70° for 2 hrs., give 100% of the salt Me3N+CH2CH2OB-F3, m. 296-8° after pptn. from MeNO2 by PhNO2. BeCl2 (8 g.) in 80 cc. ether forms an oil which reacts with 9.3 g. I to give 97.5% of the Be chloroalcoholate of (ClCH2)2CHOH, with 1 mole Et2O, m. 114-15°. BeCl2.Et2O and (C2H4)2O give 96% of the Be chloroalcoholate of ClCH2CH2OH, with 1 mole of Et2O, m. 199-200°. BiCl3 and I in ether or C6H6 give 100% of the compd.
(ClCH2)2CHOBiCl2, m. 145-50°. Cryst. compds. were not obtained from I and the etherates of ZnCl2, SbCl3, BCl3, TiCl4 and AlBr3. That (Et3O).BF4, (Me3O).BF4, (Et3O)SbCl6 and (Et3S)BF4 are salts is shown by their elec. cond. in SO2 (data given for various dilns.). The equiv. cond. of (Et3O)OH at 20° is 187, 192 and 197 for v 10, 100 and 400. (Et3O).BF4 (9.5 g.) and 5.8 g. Me2O in 30 cc. CH2Cl2, on standing 5 days, give 92% of (Me3O).BF4. VI (5.4 g.) and (CH2)4O (1.5 cc.) give 6.2 g. of ethyltetramethyleneoxonium hexachloroantimoniate, [Et.O(CH2)4]. SbCl6 (XIV), m. 132° (decompn.); decompn. of 46 g. of the salt with 200 cc. 2 N NaOH with stirring for 5 hrs. gives 0.8 g. of (CH2)4O and EtOH, 2.8 g. of EtO(CH2)4OH, b19.5 87°, d419 0.9073 and 3.2 g. of the ether EtO(CH2)4O(CH2)4OEt, b18.5 140°. VI and (CH2CHMe)2O at room temp. for a few hrs. give the a,a-di-Me deriv. of XIV, m. 142° (decompn.). IV and (CH2)5O give 52% of ethylpentamethyleneoxonium borofluoride, very hygroscopic, m. 45°. VI and (CH2)5O in 2 hrs. give 92% of ethylpentamethyleneoxonium hexachloroantimoniate, m. 154-5° (decompn.); dioxane gives the compd. [O(CH2CH2)2O.Et].SbCl6, m. 156° (decompn.). Solid (Me3O).BF4 added to 10% of H2AuCl6 gives trimethyloxonium chloroaurate, (Me3O).AuCl4, yellow, m. 133° (decompn.); Et analog, yellow, m. 92° (decompn.); ethylpentamethylene analog, yellow powder. Triethyloxonium chloroplatinate, decomps. above 120°; it is stable only for a short time. II and a soln. of 1 cc. SbCl5 in 50 cc. of a satd. NaCl soln. give (Et3O)SbCl6; SnCl4 in NaCl give triethyloxonium hexachlorostannate, needles, which slowly decomp. at room temp. into SnCl4.Et2O and EtCl; at 45° the decompn. is complete in 5 min. II and BiI3.NaI in ice-cold H2O give the compd. (Et3O).Bi2I7, dark red, which slowly decomps. with liberation of EtI; working at low temps. a salt with the composition (Et3O)BiI4, brick-red, can be obtained which in the dry state splits off EtI and Et2O, giving (Et3O).Bi2I7; BiCl3 in concd. NaCl gives the compd.
(Et3O).Bi2Cl7, m. 84° (decompn.). II and NaI.HgI2 give the compd. (Et3O).HgI3, yellow, which is completely decompd. in 24 hrs. at room temp. and much more quickly at 50-60°; this compd. ppts. from 2 l. of a soln. contg. 0.1 g. II. HgCl2 in NaCl gives the very unstable salt, (Et3O).HgCl3. II and an acidified soln. of Na4Fe(CN)6 give the pale yellow-green salt (Et3O)2.H2Fe(CN)6.2H2O, which is stable for only a short time. Et2SO (8.3 g.) and 13.5 g. II give diethyloxyethylsulfonium borofluoride, (Et2SOEt).BF4, which decomps. quickly in the air; VI gives the very unstable (Et2SOEt).SbCl6, m. 159° (decompn.); it begins to decomp. within 1 hr. Me3NO and II in CH2Cl2 give (Me3NOEt).BF4, which is very hygroscopic; VI gives (Me3NOEt).SbCl6. II and CO(NH2)2, mixed in the dry state, soon liquefy, forming [(H2N)2COEt]BF4, which forms a picrate, m. 184-5° (decompn.); alkali decomps. the salt, giving O-ethylisourea. II and AcNH2 give the compd. [MeC(:NH)OEt]BF4, very hygroscopic. (Et3O).AlCl4 and PhCN, on standing 14 days, give PhCN.AlCl3, m. 96-8°, and PhCCl:NEt, identified as PhCONHEt, m. 70-1°. Similar results were obtained with p-MeOC6H4CN, PhCH2CONH2 and PhCH:CHCONH2.