Julia, Marc; Julia, Sylvestre; Bemont, Bernard published the artcile< Cyclopropane acids>, HPLC of Formula: 90940-40-2, the main research area is .
γ-Chloroesters, easily prepared from γ-lactones, were cyclized to cyclopropanecarboxylic esters in good yield by strong bases. Substituted derivatives had the trans configuration, presumably owing to isomerization (during the reaction) of any cis isomer present. BzCH2CH2CO2H (178 g.) in 200 ml. warm 20% NaOH was reduced with 30 g. KBH4 (added in small portions) to give 90% PhCH.CH2.CH2.C(O).O (I). The same procedure also gave the p-MeO, p-Cl (m. 50°), p-Me, and p-Br (m. 83°) derivatives of I, and BzCMe2CH2CO2H (II) and BzCH2CMe2CO2H gave the corresponding lactones, m. 56-7° (III), and 48°, resp. The chloroesters were prepared by two methods. A: a solution of 10 g. I in 58 cc. EtOH was saturated with dry HCl, kept 48 hrs., evaporated, poured onto ice, and the mixture saturated with NaCl, extracted with Et2O, and distilled to give 66% PhCHClCH2CH2CO2Et (IV), b0.1 115°, decomposed on repeated distillation B: 216 g. SOCl2 was added to 96 g. I in 144 g. C6H6, the mixture boiled 3 hrs., cooled, and slowly added to 480 cc. alc. HCl; removal of solvent and distillation gave 97% IV. The following substituted Et 4-chlorobutyrates were prepared similarly [substituents, b.p. (mm.), method, and % yield given): 4-Me, 78° (10), A, 55, B, 89; 4,4-di-Me, -, B, used without purification; 4-(p-MeOC6H4), – (not distilled), A, 96 (B failed); 4-(p-ClC6H4), 125-6° (0.05), A, 75, B, 95; 4-(p-MeC6H4), 108-10° (0.05), A, 87, B, 82; 4-(p-BrC6H4), 128-9° (0.05), A, 91, B, 90; 4,3,3-PhMe2, 145° (5), B, 60. To 15 g. IV was added 40 cc. 1.7N tert-AmONa in C6H6. The solution warmed, became red, and a precipitate formed. After 30 hrs., the mixture was boiled 5 hrs., cooled, quenched in H2O, extracted with Et2O and distilled, b0.2 101-40°. The distillate was shaken with 2.8% aqueous KMnO4 to a permanent color, the MnO2 removed and washed with H2O and Et2O, and the combined extracts distilled to give 77% trans-PhCH.CH2.CHCO2Et (V), b0.2 105-6°, m. 38-9°, hydrolyzed by KOH-MeOH to the trans-acid (VI), m. 90°, whose anilide (VII) m. 145°. IV was also cyclized by NaNH2 in liquid NH3 (67% yield), MeONa in MeOH (45% yield of VI), PhCMe2ONa in C6H6 (61% VI), tert-BuOK in tert-BuOH (64% VI), PhCMe2OK in PhCMe2OH at 100° (64% VI), and alc. NaOEt (58% VI). The cis isomer of VI (Burger, CA 42, 6755f) was esterified with CH2N2, the ester boiled 4 hrs. with tert-AmONa in C6H6 and hydrolyzed to give 73% VI. Similarly, tert-BuONa and EtONa gave 47 and 20% VI, resp. The anilide of cis-VI (VIII) m. 146-7°; a mixture of VII and VIII m. 120°. The following Et cyclopropanecarboxylates and derivatives were prepared similarly [substituents, b.p. (mm.), cyclizing agent, and % yield given]: none, 95-7° (330) (n22D 1.4242), tert-AmONa, 45 (PhCMe2ONa, 47) (acid b26 89-90%, n20D 1.4391; S-benzylthiuronium salt m. 151°); 2-Me, 65-70° (14), tert-AmONa, 50 (acid b10 92°, n21D 1.4384; anilide m. 110°); 2,2-Me2, 90° (15) (n19D 1.4280), tert-AmONa, 50 (acid b143 140°, n20D 1.4390; amide m. 172-3°); 2-(p-MeOC6H4), 124-6° (0.05) (m. 78-9°), tert-AmONa, 84 (acid m. 112-13°; anilide m. 171°); 2-(p-MeC6H4), 108° (0.6) (m. 28°), tert-AmONa, 61 (acid m. 119°; anilide m. 161°); 2-(p-BrC6H4), 130° (0.8) (m. 32°), tert-AmONa (acid m. 122°; anilide m. 175°); 2,3,3-PhMe2 (IX), 110-20° (5) (n19D 1.5040), by cyclizing the chloroester from III with NaCPh3, 10.3 (acid m. 100-1°) [also prepared (18%) from Me2C.CHPh.CH2.C(O).O (X) with SOCl2 and then tert-AmONa]. To 4.5 g. V in 120 cc. Et2O, 1 g. LiAlH4 was added in small portions with cooling, the mixture kept 4 hrs., boiled 12 hrs., and hydrolyzed (first with moist Et2O and then with H2O added dropwise); extraction, alk. hydrolysis of unchanged V, further extraction, and distillation gave 66% trans-PhCH.CH2.CHCH2OH, b3 125°, n25D 1.5412; phenylurethan m. 88-9°; 3,5-dinitrobenzoate m. 126-7°. Similarly, IX (cis-trans mixture) was reduced to the carbinol isomer mixture, b0.05 101-2°, n17D 1.5316; phenylurethan m. 122°; 3,5-dinitrobenzoate m. 114°. In an attempt to prepare II, PhCOCBrMe2 and NaCH(CO2Et)2 in boiling alc. gave (instead of II) 92% PhCOCMe:CH2, b0.5 85-90°; 2,4-dinitrophenylhydrazone m. 228°; semicarbazone m. 186-7°. The same reagents in HCONMe2 heated 3 hrs. at 100° and the product distilled and crystallized from Et2O-petr. ether gave 61% PhC:C(CO2Et).CO2.CMe2 (XI), b0.25 147-9°, m. 75-6°, λ 270 mμ (log ε 3.78), and from the mother liquors 3% PhC:C(CO2H).CO2.CMe2 (XII), m. 165° (also obtained from XI and KOH-MeOH), and a trace of II, m. 85°. XII (5 g.) in 50 cc. alc. was reduced with 0.5 g. 10% Pd-C and 16 kg./sq. cm. H, and the saturated lactone-acid decarboxylated at 120° in vacuo and distilled to give 68% X, b0.5 140°, m. 93-4°.
Bulletin de la Societe Chimique de France published new progress about UV and visible spectra. 90940-40-2 belongs to class chlorides-buliding-blocks, and the molecular formula is C10H9ClO2, HPLC of Formula: 90940-40-2.
Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics