Jutz, Christian published the artcileUnsaturated aldehydes and ketones. I. Preparation of unsaturated aldehydes by a method involving the Vilsmeier reaction, SDS of cas: 16909-09-4, the publication is Chemische Berichte (1958), 850-61, database is CAplus.
cf. Vilsmeier, Chemiker-Ztg. 75, 133(1951). MeNPh(CH:CH)nCHO (I) (n = 1), b0.8 144-5¡ã, m. 48-9¡ã (Et2O), was prepared from PhNHMe and CHú·CCHO (prepared from CHú·CCH2OH by oxidation with CrO3 in H2O; cf. Huber, Dissertation, Munich, 1953). I (n = 2), properties not given [cf. Zincke and W¨¹rker, Ann. 338, 109(1905)] was formed by treating pyridine in the presence of PhNHMe with BrCN, and treating the resulting 1-methylanilino-1,3-pentadien-5-al methylanil bromide [cf. K?nig, J. Prakt Chem. 69, 134(1904)] (details not given). To I (n = 1) (0.1 mole) and 0.115 mole PhNMe2 in 50 cc. absolute CHCl3 or tetrahydrofuran below 0¡ã were added gradually 16 g. POCl3, giving a mixture of salts of p-dimethylaminocinnamaldehyde methylanil, dark green, partially crystalline sirup, the separation of which was increased by adding petr. ether, and keeping at 20¡ã overnight. The upper phase was decanted and the sirup (II) extracted several times with petr. ether, taken up in 100 cc. MeOH and treated dropwise with 10% aqueous Na2CO3 until alk. The separated oil was steam distilled briefly to remove PhNHMe without loss of the partially volatile product. The cooled still residue was extracted with four 50-cc. portions of CHCl3 giving 12-14 g. p-Me2NC6H4CH:CHCHO (III), yellow leaflets, m. 141¡ã (K?nig, et al., C.A. 23, 381). An aliquot of II in MeOH with aqueous NaClO4 gave p-dimethylaminocinnamaldehyde methylanil perchlorate (IV), C18H21N2ClO4, dark violet crystals, or bluish-green crystals with metallic luster, m. 158-9¡ã (Me2CO-Et2O, or MeOH-Et2O). IV was also formed by warming III and PhNHMe at 50¡ã with the min. amount 2N HCl and adding NaClO4. Formed similarly to III, from 8 g. each of I (n = 1), PhNEt2, and POCl3 was 8.6 g. p-Et2NC6H4CH:CHCHO, yellow, m. 73-4¡ã (MeOH). Equimolar amounts of PhNMeCHO, POCl3, and PhNMe2 caused a separation of intermediate salts, from which was formed p-dimethylaminobenzaldehyde methylanil perchlorate, C16H19N2ClO4, pale yellow, m. 179-80¡ã(Me2CO or MeOH-Et2O), also formed from PhNMe2 and Me2NC6H4CHO in acid with HClO4. Similarly, primary aromatic amines reacted with p-Me2NC6H4CHO in aqueous acid solutions and then with NaClO4 to form the corresponding anil perchlorates of the following: p-dimethylaminobenzaldehyde, C15H17N2ClO4, orange, m. 230-1¡ã (decomposition) (Me2CO-Et2O); p-dimethylaminocinnamaldehyde, C17H19N2ClO4, violet, m. 190¡ã (decomposition) (MeOH-Et2O). I (n = 2) (9.4 g.) and 7 g. PhNMe2 in tetrahydrofuran at -20¡ã with 9 g. POCl3 and 5 g. PhNMe2 treated as in the case of III gave, after a fully-described purification, 2 g. p-Me2NC6H4(CH:CH)2CHO, golden yellow, m. 156-7¡ã (sublimation in high vacuum followed by ligroine), whose methylanil perchlorate, blue violet with metallic luster, m. 205¡ã (decomposition) (Me2CO-Et2O). To 4 g. I (n = 1) and 5.6 g. 1-phenyl-1-(p-dimethylaminophenyl)ethylene in 25 cc. absolute C6H6, cooled, was added 10 cc. Ac2O, shaken, and then treated dropwise with 2.5 g. anhydrous ZnCl2 in 10 cc. AcOH, giving a violet-blue Zn complex salt. After removing the excess Ac2O, AcOH, and C6H6 in vacuo, the residue dissolved in 200 cc. 25% MeOH was treated with 1 g. PhNHMe in 2N HCl, warmed to 50¡ã, filtered, and saturated NaClO4 added to the filtrate, giving 9.3 g. 1-phenyl-1-(p-dimethylaminophenyl)-1,3-pentadien-5-al methylanil perchlorate (V), moss-green leaflets, m. 214-15¡ã (decomposition). V in CHCl3 shaken with 20% aqueous Na2CO3 and filtered, the CHCl3 separated, and the aqueous phase re?xtd. with CHCl3; the combined extracts gave about 94% (crude) 1-phenyl-1-(p-dimethylaminophenyl)-1,3-pentadien-5-al, orange, m. 119.5-20.5¡ã (ligroine). I (n = 1) (0.1 mole) and 0.115 mole m-C6H4(OMe)2 in CHCl3, stirred and cooled below 0¡ã were treated with 16 g. POCl3 in 20 cc. CHCl3, warmed gradually to 35¡ã, stirred and treated with 200 cc. ligroine which caused the separation of 2 phases; the lower one was washed repeatedly with petr. ether, dissolved in 150 cc. CHCl3, and washed successively with H2O, 2N HCl, H2O, 10% Na2CO3, and H2O, dried and evaporated giving 17-17.5 g. 2,4-dimethoxycinnamaldehyde (VI), m. 99.5-100¡ã (C6H14 or aqueous MeOH); semicarbazone, m. 198-201¡ã (decomposition) (EtOH). VI oxidized in alc. NaOH with Ag2O gave 2,4-(MeO)2C6H3CH:CHCO2H, m. 186-7¡ã. 1-Tetrahydroquinolinyl-1-propen-3-al (9.4 g.) and 10 g. CH2(CO2H)2 in 60 cc. glacial AcOH, treated with 15 cc. Ac2O and 2 g. ZnCl2 in 5 cc. AcOH turned from brown to blue and evolved CO2 slowly; after 24 hrs. 50 cc. MeOH was added, the mixture warmed to 50¡ã and poured into 1 l. 2% NaClO4 solution, giving, on cooling a mixture of perchlorates, which was dried and extracted in a Soxhlet with 200 cc. Me2CO. The extract treated with 70 cc. C6H6 gave 6 g. 1,7-bis(1-tetrahydroquinolinyl)heptamethine monoperchlorate, C25H27N2ClO4, long needles with blue metallic surface luster, m. 168¡ã (decomposition) (Me2CO). The thimble residue, insoluble in Me2CO, yielded 3 g. 1,3-bis(1-tetrahydroquinolinyl)trimethine monoperchlorate (properties not given). VII in CHCl3 shaken with aqueous K2CO3 gave 1-tetrahydroquinolinyl-1,3,5-heptatrien-7-al, m. 149-50¡ã (C6H14) (cf. Dieterle and Riester, C.A. 31, 49117). 1-Methylanilino-1-propen-3-al (8 g.) treated as in the preparation of VII gave an incompletely separated mixture (IX) of the methylanil perchlorates of 1-methylanilino-1,3,5-heptatrien-7-al and 1-methylanilino-1-propen-3-al (IXa). IX sintered 155¡ã, m. 163-4¡ã, and contained about 65-70% IXa (gaged from anal. data). Pure IXa, m. 166¡ã (decomposition), was prepared from I, PhNHMe and NaClO4, in acid solution IX (4 g.) in 50 cc. CHCl3, shaken with aqueous K2CO3, the aqueous phase extracted with CHCl3, and the combined organic extracts washed with H2O and Na2CO3, dried and evaporated gave 0.7-0.9 g. 1-methylanilino-1,3,5-heptatrien-7-al, orange-brown, m. 120-1¡ã (decomposition) (after extraction with ligroine, b. 60-80¡ã, discarding these extracts and then extracting with ligroine b. 80-120¡ã). p-Me2NC6H4CHO (3 g.) and 3 g. PhNMe2 in 20 cc. CHCl3 was added dropwise to 3.5 g. POCl3 in 10 cc. CHCl3 at 0¡ã; after standing at 20¡ã and warming to 35¡ã, 100 cc. petr. ether were added and the resulting sirup (X) washed repeatedly with petr. ether. X, in little cold EtOH with aqueous NaClO4 yielded 5.5-6.5 g. 4,4′-bis(dimethylamino)benzhydrol perchlorate, metallic blue leaflets, m. 161-3¡ã (decomposition) (varying with rate of heating) (Me2CO-Et2O).
Chemische Berichte published new progress about 16909-09-4. 16909-09-4 belongs to catalysis-chemistry, auxiliary class Alkenyl,Carboxylic acid,Benzene,Ether, name is (E)-3-(2,4-Dimethoxyphenyl)acrylic acid, and the molecular formula is C11H12O4, SDS of cas: 16909-09-4.
Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia