+++ синтез 2-х соединений

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Frather
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+++ синтез 2-х соединений

Сообщение Frather » Сб ноя 19, 2011 10:20 pm

Уважаемые коллеги, помогите пожалуйста найти способы синтеза следующих 2-х соединений

1. Diethyl 2-formylsuccinate CAS: 5472-38-8

2.


Заранее благодарю!!
Последний раз редактировалось Frather Вс ноя 20, 2011 12:18 am, всего редактировалось 1 раз.

Arkadii_Tarasevych
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Re: синтез 2-х соединений

Сообщение Arkadii_Tarasevych » Сб ноя 19, 2011 11:26 pm

Синтез первого:

1. Preparation of dihydropyrrolopyrimidinone derivatives for use as MARK inhibitors By Haidle, Andrew; Stanton, Matthew; Altman, Michael; Konrad, Kaleen; Zabierek, Anna; Katz, Jason; Jewell, James From PCT Int. Appl. (2009), WO 2009152027 A1 20091217. Language: English, Database: CAPLUS
Title compds. I [R1 = (un)substituted alkyl, Ph, or pyridyl; R2 = (un)substituted Ph, 3-pyridinyl, or 4-pyrazolyl; R3 = Me; or R1 and R3 together with the carbon to which they are attached form (un)substituted 1-indanyl or dihydrobenzofuran-3-yl], and their pharmaceutically acceptable salts, are prepd. and disclosed as microtubule affinity regulating kinase (MARK) inhibitors. Thus, e.g., II was prepd. by formylation of 4-aminostyrene with Et formate followed by coupling with 5,5-dimethyl-7-[(1S)-1-methylpropyl]-2-(methylsulfonyl)-5,7-dihydro-6H-pyrrolo[2,3-d]pyrimidin-6-one (prepn. given), oxidn., reductive amination with 1-methoxy-N-methylpropan-2-amine. Select I were evaluated in MARK inhibition assays (data given).
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2. PLP Catabolism: Identification of the 2-(Acetamidomethylene)succinate Hydrolase Gene in Mesorhizobium loti MAFF303099 By Mukherjee, Tathagata; Hilmey, David G.; Begley, Tadhg P. From Biochemistry (2008), 47(23), 6233-6241. Language: English, Database: CAPLUS
The function of the mlr6787 gene from Mesorhizobium loti MAFF303099 has been identified. This gene encodes 2-(acetamidomethylene)succinate hydrolase, an enzyme involved in the catabolism of pyridoxal 5'-phosphate (vitamin B6). This enzyme was overexpressed in Escherichia coli, purified to homogeneity, and characterized. 2-(Acetamidomethylene)succinate hydrolase catalyzes the hydrolysis of 2-(acetamidomethylene)succinate to yield succinic semialdehyde, acetic acid, carbon dioxide, and ammonia. The kcat and Km for this reaction were 0.6 s-1 and 143 μM, resp. The enzyme was shown to utilize the E isomer of 2-(acetamidomethylene)succinate.
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3. The complete stereochemistry of the enzymatic dehydration of 4-hydroxybutyryl coenzyme A to crotonyl coenzyme A By Friedrich, Peter; Darley, Daniel J.; Golding, Bernard T.; Buckel, Wolfgang From Angewandte Chemie, International Edition (2008), 47(17), 3254-3257. Language: English, Database: CAPLUS
The stereospecific action of the microbial enzyme 4-hydroxybutyryl-Co-A dehydratase on the three prochiral centers of its substrate 4-hydroxybutyryl-Co-A can now be described as antielimination of the 2Re and 3 Si hydrogen atoms with retention of configuration during the substitution of the hydroxy group by a hydrogen atom. The results confirm the relationship of the dehydratase to acyl-Co-A dehydrogenases and the view that the Fe4S4 cluster acts as a Lewis acid.
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4. Design and synthesis of 7H-pyrrolo[2,3-d]pyrimidines as focal adhesion kinase inhibitors. Part 1 By Choi, Ha-Soon; Wang, Zhicheng; Richmond, Wendy; He, Xiaohui; Yang, Kunyong; Jiang, Tao; Sim, Taebo; Karanewsky, Donald; Gu, Xiang-Ju; Zhou, Vicki; et alFrom Bioorganic & Medicinal Chemistry Letters (2006), 16(8), 2173-2176. Language: English, Database: CAPLUS
(amino)(aryl)pyrrolo[2,3-d]pyrimidines such as I and II and pyridopyrimidines such as III are prepd. as inhibitors of focal adhesion kinase (FAK). The structure-activity relationships for pyrrolopyrimidines are detd.; electron-donating arylamino substituents at the 2-position and pyridinyl substituents at the 9-position lead to moderately active FAK inhibitors, while oxo-substituted analogs have reduced activities. I, II, and III inhibit FAK with IC50 values of 0.1 μM, 0.1 μM, and 0.2 μM, resp., comparable to the initial lead compd. IV (IC50 = 0.1 μM).
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5. Imidazo[1,2-c]pyrimidinylacetic acid derivatives, their preparation, pharmaceutical compositions and use as CRTH2 antagonists By Ly, Tai-Wei; Yoshino, Takashi; Takekawa, Yuki; Shintani, Takuya; Sugimoto, Hiromi; Bacon, Kevin B.; Urbahns, Klaus From PCT Int. Appl. (2005), WO 2005073234 A2 20050811. Language: English, Database: CAPLUS
The invention relates to a group of imidazo[1,2-c]pyrimidinylacetic acid derivs. I and salts thereof which are antagonists of CRTH2 (G-protein-coupled chemoattractant receptor, expressed on Th2 cells). In compds. I, R1 is acyl, alkenoyl, alkylsulfonyl, alkyl, alkenyl, alkylaminocarbonyl, or alkoxycarbonyl; R2 is H or C1-6 alkyl; R3 is H, halo, C1-6 alkyl optionally substituted with up to three halogens, C1-6 alkoxy optionally substituted with up to three halogens, or tertiary amino; and R4 is H or C1-6 alkyl. The invention also relates to the prepn. of I, pharmaceutical compns. contg. I with one or more pharmaceutically acceptable excipients, as well as to the use of the compns. for the treatment of disorders or diseases assocd. with CRTH2 activity. 4-Nitrophenylacetonitrile underwent addn. of ammonia, followed by cyclocondensation with tri-Et 1,1,2-ethanetricarboxylate to give pyrimidineacetate II. Chlorination of II, substitution with aminoacetaldehyde di-Me acetal, and heterocyclization resulted in the formation of imidazopyrimidineacetate III. Redn. of the nitro group of III followed by amidation with 4-(trifluoromethyl)benzoic acid deriv. and ester hydrolysis gave imidazo[1,2-c]pyrimidineacetic acid IV. The compds. of the invention were found to have antagonistic activity to CRTH2, and two of them had IC50 values below 10 nM and compd. IV expressed IC50 between 10 nM and 100 nM.
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6. The total synthesis of racemic teucvin and 12-epi-teucvin By Liu, Hsing-Jang; Zhu, Jia-Liang; Chen, I-Chia; Jankowska, Renata; Han, Yongxin; Shia, Kak-Shan From Angewandte Chemie, International Edition (2003), 42(16), 1851-1853. Language: English, Database: CAPLUS
The total syntheses of racemic teucvin (I) and 12-epi-teucvin (II) have been reported. The synthetic challenges presented by the title compds. have been successfully met by employing an intermol. Diels-Alder approach that is rather efficient in terms of stereo- and regiochem. control.
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7. Preparation of pyrimidine-containing carboxylic acid esters having insecticidal and acaricidal activities By McDonald, Edward; Salmon, Roger; Whittle, Alan John; Hutchings, Michael Gordon From Eur. Pat. Appl. (1988), EP 295839 A2 19881221. Language: English, Database: CAPLUS
The title compds. [I; R1 = C1-6 alkyl, C2-8 alkenyl, C2-6 alkynyl, C1-4 haloalkyl, C2-8 haloalkenyl, C3-6 cycloalkyl optionally substituted by ≥1 C1-4 alkyl or halo; R2 = C1-8 alkyl, C1-4 haloalkyl, C1-6 alkoxy, halo, C3-6 cycloalkyl optionally substituted by ≥1 C1-4 alkyl or halo, Ph optionally substituted by ≥1 C1-4 alkyl, C1-4 haloalkyl, or C1-4 alkoxy; R3 = H, halo; R4 = residue of an alc. of formula R4-OH which forms an insecticidal ester when combined with chrysanthemic acid, permethrin, or cyhalothrin acid; X = O, S], useful as insecticides or acaricides, were prepd. To a stirred soln. of 0.1 (RS)-2-[2-(1,1-dimethylethyl)pyrimidin-5-yl]-3,3-dimethylbutanoic acid, 0.089 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl alc., and 0.002 g 4-dimethylaminopyridine in CH2Cl2, 0.084 g DCC was added and the mixt. was stirred 18 h to give 0.09 g 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl (RS)-2-[2-(1,1-dimethylethyl)pyrimidin-5-yl]-3,3-dimethylbutanoate (II). II at 500 ppm gave 50-79% mortality against Blattella germanica and 80-100% mortality against 9 addnl. pest species, e.g. Tetranychus urticae, Nephotettix cinticeps, and Diabrotica balteata. An emulsifiable conc. compn. contg. Synperonic OP10 3.0, calcium dodecylbenzenesulfonate 2.0, and Aromasol H 94.0 wt. % was prepd.
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8. Formylsuccinic Ester and its Relation to Aconic Acid By Wislicenus, Wilhelm; Boklen, Emil; Reuthe, Felix From Justus Liebigs Annalen der Chemie (1909), 363, 340-70. Language: Unavailable, Database: CAPLUS
Formyl-succinic ester, CO2EtCH2C(:CHOH)CO Et, is prepd. by the action of Na on succinic ester and formic ester, in excess, in dry Et2O. Yield, 60-70%. Oil, b15 137°. Copper salt, (C6H13O5) Cu, green needles, m. 132-3°. Nickel salt, (C9H13O5)2Ni, green needles, m. 219-20°. Phenylisocyanate deriv., C16H19O6N, small prisms, m. 103-4°. Benzoyl deriv., C16H18O6, long needles, m. 57-8°. p-Nitrobenzoyl deriv., C16H17O8N, needles, m. 104°. The ester heated in a tube with H2O at 120-30° is split into β-aldehydopropionic acid, EtOH and CO, giving a convenient method of prepg. β-aldehyde acids. Yield 80%. Phenylhydrazide of the phenylhydrazone m. 188-9°. One mol. PhNH.NH2 converts the ester into a phenylhydrazine deriv. of a pyridazine, C13H14O3N, pale yellow leaves, m. 111-2°. Sapon. yields an acid, C11H10O3N2, small prisms, m. 178-9°. Yield 50%. Oxidn. with KMnO4 gives C11H8O3N2, microscopic crystals, m. 180-1°. Silver salt, C11H7O3N2Ag, yellow powder. Two mol. PhNHNH2 converts the ester into a pyrazolone deriv., C17H16O2N4, microscopic crystals, m. 192-4°. p-Toluidine yields the di-Et ester of p-toluido-γ-itaconic acid, C16H21O4N, colorless, m. 115-6°. The formyl ester reduces to itamalic ester. PCl5 acts energetically, forming chloritaconic ester, CO2Et:C(:CHCl)CH2CO2Et, liq. of fruity odor, b20 125°. Chloritaconic acid, C5H5O4Cl, granular crystals, m. 150-1°. Stable in boiling H2O. Monomethyl ester, C6H7O4Cl, rhombohedrons, m. 74-5°. Formylsuccinic ester eliminates EtOH and some CO. Aconic acid could not be isolated from the residue. Aconic acid, chlorinated in abs. EtOH yields formylsuccinic ester. Yield 80%. Formylsuccinic di-Me ester, b12 112-5°. Cu salt, (C7H9O5)2Cu.H2O, green needles, m. 133-5°; also (C7H9O5)2Cu, greenish yellow, m. 144-5°. Basic methylate, C3H12O6Cu, blue prisms, m. 193-4°. One mol. PhNHNH2 converts the di-Me ester into a yellow cryst. body, C12H12O3N2, m. 133-4°. Two mol. gives same product as the Et ester. Aniline gives anilidoitaconic dimethylester, C13H15O4N, microscopic needles, m. 91-3°.
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Arkadii_Tarasevych
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Re: синтез 2-х соединений

Сообщение Arkadii_Tarasevych » Сб ноя 19, 2011 11:38 pm

По поводу второго, скайфайндер ничего не выдаёт. Но если проводить поиск по подобным структурам, есть аналогичный циклический ацеталь, похожие циклические кетали, всё производные 2-замещённой янтарной кислоты. Думаю, найдёте, что Вам нужно:

1. Addition to electron deficient olefins of α-oxy carbon-centered radicals, generated from cyclic ethers and acetals by the reaction with alkylperoxy-λ3-iodane By Sueda, Takuya; Takeuchi, Yasunori; Suefuji, Takashi; Ochiai, Masahito From Molecules (2005), 10(1), 195-200. Language: English, Database: CAPLUS
Thermal decompn. of 1-tert-butylperoxy-1,2-benziodoxol-3(1H)-one in cyclic ethers and acetals at 50 °C generated a-oxy carbon-centered radicals, which underwent an addn. reaction with vinyl sulfones and unsatd. esters.
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2. Addition of aldehydes and their equivalents to electron-deficient alkenes using N-hydroxyphthalimide (NHPI) as a polarity-reversal catalyst By Tsujimoto, Shinya; Sakaguchi, Satoshi; Ishii, Yasutaka From Tetrahedron Letters (2003), 44(30), 5601-5604. Language: English, Database: CAPLUS
Radical addn. of aldehydes and masked aldehydes like 1,3-dioxolanes to electron-deficient alkenes was achieved by the use of catalytic amts. of BPO and N-hydroxyphthalimide (NHPI) as a polarity-reversal catalyst under mild conditions. Three-component radical coupling of 1,3-dioxolanes, maleates, and alkenes was performed in the presence of BPO and NHPI under similar conditions.
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3. Preparation of ketones from aldehydes and olefins By Ishii, Yasutaka; Nakano, Tatsuya From Jpn. Kokai Tokkyo Koho (2002), JP 2002338514 A 20021127. Language: Japanese, Database: CAPLUS
Ketones are prepd. by addn. reaction of aldehydes or their acetals with olefins in the presence of cyclic imides having groups I (X = O, OR; R = H, protective group). Reaction of pentanal with 1-octene in C6H6 in the presence of N-hydroxyphthalimide and benzoyl peroxide at 80° for 12 h gave 55% 5-tridecanone.
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4. Oxygen promoted addition of 1,3-dioxolane to electron-deficient alkenes By Watanabe, Yoshihisa; Tsuji, Yasushi; Takeuchi, Ryo From Bulletin of the Chemical Society of Japan (1983), 56(5), 1428-30. Language: English, Database: CAPLUS
1,3-Dioxolane reacted with electron-deficient alkenes, such as di-Et maleate, maleic anhydride, di-Et fumarate and fumaronitrile, in O or air to give 1:1 adducts in good to excellent yields. The presence of O promoted the reaction. The reaction appears to be characteristic of 1,3-dioxolane. CH2(OMe)2 and CH2(OEt)2 did not react with di-Et maleate under the same conditions.
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5. Syntheses of bile pigments. XI. Total synthesis and elucidation of the relative configuration of two epimeric methanol adducts of phycocyanobilin dimethyl ester By Gossauer, Albert; Hinze, Ralf Peter; Kutschan, Reinhard From Chemische Berichte (1981), 114(1), 132-46. Language: German, Database: CAPLUS
On treatment of phycocyanobilin di-Me ester [(±)-I] with boiling MeOH, one mol. of I was reversibly added at the ethylidene group of the chromophore to give only 2 of the 4 possible diastereomeric adducts, which were also obtained, along with I, on methanolysis of the protein moiety of C-phycocyanine after esterification of the methanolic exts. The structure and relative configurations of both MeOH adducts were elucidated by stereospecific total syntheses from the corresponding monothioimides of known relative configurations. In order to det. the latter, all 4 racemic stereoisomers of II were prepd.
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6. Succinic acid esters substituted with cyclic ethers By Mistr, Adolf; Krejci, Frantisek From Czech. (1977), CS 167781 B1 19760528. Language: Czech, Database: CAPLUS
A mixt. of dialkyl maleate and cyclic ether was irradiated from a 60Co source 15 h at 50° under N to give 52-81% RO2CCH2CHR1CO2R (R = Me, Et; R1 = tetrahydrofuryl, dioxolanyl, tetrahydropyranyl, 1,4-dioxanyl).
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7. Synthesis of some 4-aminoalkyl-5-methyl-3-isoxazolols structurally related to muscimol and γ-aminobutyric acid (GABA) By Hjeds, Hans; Krogsgaard-Larsen, Povl From Acta Chemica Scandinavica, Series B: Organic Chemistry and Biochemistry (1976), B30(6), 567-73. Language: English, Database: CAPLUS
The zwitterions I (R = H, Me) were prepd. from O2NCHMeCH2OH in 6 steps via alkylation of EtO2CCH2COMe with EtO2CNHCHRCH2Cl and H2NOH treatment of the pyrrolinecarboxylate II, whereas the zwitterions III were obtained by eluting a soln. of the isoxazolylmethylamine hydrobromides IV, obtained by treating the amine hydrochloride V with HBr-HOAc, through Amberlite IRA 400 (OH).
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8. Addition of cyclic ethers and acetals to maleic acid derivatives By Krejci, F.; Pichler, J. From Scripta Facultatis Scientiarum Naturalium Universitatis Purkynianae Brunensis (1974), 4(9), 71-80. Language: English, Database: CAPLUS
Tetrahydrofuran, tetrahydropyran, and dioxolane underwent addns. with maleic anhydride and Et and Me maleate initiated by uv light, uv light and MeCOPh, and gamma irradn. Thus, a mixt. of tetrahydrofuran and maleic anhydride was exposed to gamma irradn. from 60Co for 7 hrs to give 65% tetrahydro-2-furylsuccinic anhydride, which was hydrolyzed to the acid.
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9. Carbene reactions. IV. Addition of dimethoxycarbene to carbon-carbon multiple bonds By Hoffmann, Reinhard W.; Lilienblum, Werner; Dittrich, Brigitte From Chemische Berichte (1974), 107(10), 3395-407. Language: German, Database: CAPLUS
Dimethoxycarbene (I) added to di-Et fumarate to give the cyclopropane II. Addn. to styrene derivs. gave also 3,3-dimethoxycyclopropanes. The addn. of I to MeO2CC≡-CCO2Me, PhC≡CH, and Ph2C:CO gave the furan III, PhCH:-CHCOC≡CPh, and the dioxolane IV, resp.
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10. Synthesis of pyridoxine. II. The preparation of pyrrole derivatives By Murakami, Masuo; Takahashi, Kozo; Matsumoto, Jan; Tamazawa, Kazuharu; Murase, Kiyoshi; Iwamoto, Hidenori; Iwanami, Masaru From Bulletin of the Chemical Society of Japan (1968), 41(3), 628-33. Language: English, Database: CAPLUS
A new method for the synthesis of 2-acetyl-3,4-bis(ethoxycarbonyl)pyrrole and its derivs. by the Diels-Alder reaction is described, and the reaction mechanism of their formation is discussed.
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11. Photoalkylation of cyclic acetals By Rosenthal, I.; Elad, Dov From Journal of Organic Chemistry (1968), 33(2), 805-11. Language: English, Database: CAPLUS
The acetone-, acetophenone-, and benzophenone-initiated photochem. addn. of olefins to 1,3-dioxolane and 1,3,5-trioxane is described. The addn. of terminal olefins to 1,3-dioxolane leads to 2-alkyl-1,3-dioxolanes (I) (1:1 adducts) as the major products in yields of up to 50%; with di-Et maleate, di-Et (1,3-dioxolan-2-yl)syccinate may be obtained in yields of up to 90%. The corresponding reaction with 1,3,5-trioxane leads to 2-alkyl-1,3,5-trioxanes (II) in yields of up to 25% with terminal olefins and 84% with di-Et maleate. 31 references.
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12. Cyclic acetal telomers By Patrick, Tracy M., Jr. No Corporate Source data available (1954), US 2684373 19540720. Language: Unavailable, Database: CAPLUS
In the presence of a suitable promoter, telomeric polymers are formed by reaction between 1,3-dioxolane (I), 1,3-dioxane, or derivs. of these acetals (substituted in the 2-, 4-, and (or) 5-position with alkyl groups contg. 1-6 C atoms) with esters of di- or tribasic unsatd. acids; the latter must contain 4-6 C atoms and a C2H4 group conjugated with 1 or more CO groups. The products are useful as lubricants, softeners for synthetic rubber, antifoam agents, and wax additives. The reaction is promoted by ultraviolet light or a peroxide. Thus I 64.5, di-Et maleate 50.1, and Bz2O2 0.5 g. were refluxed 16.5 hrs. at 80-100° to give 30.1 g. of a viscous polymer, nD25 1.4732, as well as a colorless viscous liquid identified as di-Et 2-(1,3-dioxolanyl)succinate, b1 120-5°, nD25 1.4457, d2525 1.1426, in 25% yield.
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13. Stabilization of keto compounds by acetalization By Kuhn, Martin From Journal fuer Praktische Chemie (Leipzig) (1940), 156, 103-49. Language: Unavailable, Database: CAPLUS
The stabilization of keto compds. through acetal formation has been studied as a method for prepg. compds. which, because of their capacity to form peroxides easily, might serve as catalysts in polymerization processes. Cyclic acetals and ketals are formed by heating the keto compds. with a glycol and an acid catalyst (such as PhSO3H, H2SO4) in C6H6 or C2HCl3 and distg. off the H2O of reaction. Cyclic ketals with 5- and 6-membered rings have been formed from all keto acids, whether the CO group is α, β, γ or δ to the CO2H group; these ketals are appreciably attacked by dil. HCl only above 50° and are completely resistant to alk. sapon.; they also distil without decompn. The many ramifications of the AcCH2CO2Et synthesis make it probable that a large no. of derivs. can be prepd. which would have widely different solvent properties. Ketal formation does not occur when a double bond is in the α, β-position to the CO group, as in benzylidene- or furfurylideneacetoacetates. That Ac2CHCO2Et and PhAcCHCN do not react is explained by the presence of the α,β-double bond in the enol form. AcCEt2CO2Et also does not react. The formation of cyclic ketals from keto acids causes the stabilization of those keto compds. which otherwise are easily transformed into cyclic compds. or undergo condensation in other ways. Cyclohexanone (I) (49 g.), 48 g. C3H5(OH)3 and 0.1 g. PhSO3H in 100 cc. C6H6, boiled 2 hrs. (9 cc. H2O distils), give 64% of the hydroxypropylene ketal (II), (CH2)5C.O.CH2.CH(CH2OH).O or (CH2)5C.O.CH2.CH(OH).CH2.O, b15, 133-5°, d413 1.1237; short irradiation with ultraviolet light causes strong peroxide formation. Boiling 27 g. II, 25 g. ClCH2CO2H and 10 drops H2SO4 in C6H6 gives 97.5% of the chloroacetate (III) of II, b15 170-4°, d412 1.2278; III and Et2NCH2CH2OH in 3 cc. EtOH give the diethylaminoethoxyacetate, m. 196° (decompn.); III also reacts with Et2NH to give a basic ester. Camphor (25 g.) and 20 g. HOCH2CH(OH)CH2Cl (IV) give 56% of the 1-chloro-2,3-propylene ketal, b17 146°, d415 1.1141. PhAc and IV with H2SO4 in PhMe give 55% of the 1-chloro-2,3-propylene ketal, b15 138-40°, d418 1.1712. BzCH2Cl and (CH2OH)2 with PhSO3H in PhMe give 95% of the ethylene ketal (V), b15 144-6°, m. 67°; boiling with EtOH-NaOH for several hrs. does not split off the Cl; heating with AcCHNaCO2Et or with MeOCH2CH2OCH2CH2ONa in PhMe gives unchanged V. With a MeOH soln. contg. 3.2% H2SO4 and 20% H2O, BzCH2Cl was produced as follows: 1 hr. at 83° 100%; 2 hrs. at 65° 96%; 1, 4 and 12 hrs. at 50° 25, 63 and 100%, resp. BzCHCl2 does not react with (CH2OH)2; neg. results were also obtained with benzylideneacetone, furfurylideneacetone and benzylideneacetophenone. BzCH2Br gives 92% of the ethylene ketal, b11 142°, m. 60-1°; it shows some decompn. on standing in the light; there is no reaction with EtONa after 10 hrs. at 70°; acid cleavage as above is 89, 99 and 100% after 1, 2 and 3 hrs. at 50°; the ketal reacts with Mg to form a Grignard reagent. The product from 1 atom of Br and 1 mole of Me2CO yields with (CH2OH)2 60% of the ethylene ketal of bromoacetone, b16 76-8°, d418 1.3223, and 5% of the same deriv. of dibromoacetone, b16 113°, d414 1.8929. ClCH2Ac yields 93% of the ethylene ketal, b18 62-4°, d413 1.1835, and (ClCH2)2CO gives 85% of the ethylene ketal, b12 105°, d412 1.3568. Vinyl Me ketone (VI) and (CH2OH)2 do not yield the ketal but a compd., b18 145-6°, which is probably a mixt. of (CH2OCH2CH2Ac)2 and the corresponding ketal. ClCH2CH2Ac (VII) (prepd. from 100 g. VI and HCl in C6H6) with (CH2OH)2 gives 98 g. of a compd. (VIII), b30 50-70°, which contains 10.2% Cl (calcd. for ketal of VII, 23.6%); the Cl cannot be completely removed by KOH; 95 g. VIII, treated with 20.5 g. pulverized KOH, the mixt. dild. with 50 cc. H2O and heated 1 hr. on the water bath, treated with 25 cc. 30% NaOH and again heated 1 hr., gives 50 g. of a product b20 75-80° and contg. 18.8% Cl; thus this is not a method for the prepn. of the ethylene ketal of VI. BzCH2CH2Cl and (CH2OH)2 give only a polymerization product. Glucose (18 g.) and 22 g. of I in C6H6-BuOH with PhSO3H give 28 g. of the compd. b0.5 193-5°. Phenylglucosazone (IX) (18 g.) and 20 g. I with 0.6 g. PhSO3H give 32 g. of a dark brown resin with 8.5% N, which appears to be a condensation product with about 80% of the IX; IX gives a diacetone condensation product as a dark brown resin. In the prepn. of acetals of NH2 ketones the base is dissolved in HCl, the soln. evapd. and the salt dried by boiling with C6H6; such salts react with glycols in the presence of H2SO4 or PhSO3H to yield ketals. However, it was not possible to react these salts with monovalent alcs. (EtOH, BuOH, AmOH or octyl alc.) in C6H6, xylene or decalin; the use of orthosilicic esters was also without effect. Whereas the di-Me and di-Et acetals of these ketones are hydrolyzed by EtOHHCl or by small amts. of NH4Cl or ZnCl2, the cyclic acetals are stable under these conditions. Et2N(CH2)3Ac.HCl (X) (31.4 g. of ketone), 15 g. (CH2OH)2 and 0.5 cc. H2SO4 in C6H6 give in 1 hr. 3.6 cc. H2O and yield, 85% of the ethylene ketal, Et2N(CH2)3CMe.O.CH2.CH2.O, b15 116°, d418 0.9253; X and C3H5(OH)3, give the hydroxypropylene ketal, b15 163, d418 0.9931; the Bz deriv. is a thick oil. Et2N(CH2)2Ac (XI) gives 70% of the ethylene ketal, b13 93-4°, b760, 208°, d418 0.9438; it does not give a condensation product with PhNH2; dodecyl bromide gives the salt C22H46O2NBr, a bright brown waxy mass, sol. in EtOH and C6H6; it is an emulsifying agent for oils. XI yields 60% of the 1,3-butylene ketal, b13 112-13°, d418 0.9391. The H2SO4 salt of XI and C3H5(OH)3 give 40% of the hydroxypropylene ketal, b12 145-50°, d417 1.0228. The condensation product of cyclohexylethylamine with HCHO and Me2CO β-(cyclohexylethylamino)ethyl Me ketone) and (CH2OH)2 with a trace of PhSO3H in C6H6 give the ethylene ketal, b14 166°. 2-(Cyclohexylmethylaminomethyl)cyclohexanone (prepd. by condensation of 2 moles of I, 2 moles of HCHO and 1 mole of cyclohexylamine-HCl) and 2 moles of (CH2OH)2 give 50% of the ethylene ketal, b14 190-2°, b1 160-2°, d418 1.0375. The base (CH2:CHCOCH2CH2)2NC6H11 (prepd. from 37 g. cyclohexylamine-H2SO4, 35 g. vinyl Me ketone and 15 g. paraformaldehyde in 30 g. AcOH) does not react with (CH2OH)2. Dropwise addn. of 53.2 g. vinyl Me ketone to 75 g. cyclohexylamine in 50 cc. C6H6, the soln. shaken with dil. HCl, the HCl soln. evapd. to dryness and treated with 50 g. of (CH2OH)2 and 0.2 g. of PhSO3H in C6H6, give 64 g. (40%) of the ethylene ketal of β-cyclohexylaminoethyl Me ketone, light yellow, b18 162-3°, d418 0.9962; the Bz deriv. is an oily liquid. The condensation product from 45 g. EtNH2 and 98 g. mesityl oxide (2 days at room temp.), transformed into the HCl salt and reacted with 65 g. of (CH2OH)2 and 0.2 g. PhSO3H, gives 20 g. (11.7%) of the ethylene ketal of diacetone.ovrddot.ethylamine, yellow, b14 84-6°, d418 0.9796. Diacetoneamine does not react with (CH2OH)2. BzCH2Cl (15.45 g.) and 23.7 g. of a dimethylalkylamine (the alkyl being an aliphatic residue with 10-20 C atoms) with 2 cc. H2O, warmed slowly until the melt is sol. in H2O, freed from H2O by C6H6 and reacted with C3H5(OH)3 and PhSO3H, give 46.5 g. of a quaternary chloride (XII), a light brown, oily product, which gives a clear sq. soln. with strong foaming tendency; this soln. is an emulsifying agent for oils; NaOH ppts. from the aq. soln. of XII the NH4 base as a thick oil, sol. in C6H6. AcCH2CO2Et (XIII) (32.5 g.) and 39 g. of EtOH with 0.1 g. PhSO3H in 200 cc. C6H6, refluxed 5 hrs., give unchanged XIII; likewise, 2 mols. BuOH and ClCH2CH2OH with 1 mol. XIII in PhMe contg. H2SO4 give unchanged XIII. The ethylene ketal of XIII is hydrolyzed by 5 N aq.-alc. NaOH; the free acid is very sol. in H2O; re.ovrddot.esterification with EtOH and H2SO4 in C6H6 gives 46% of the ketal; the 1,3-butylene ketal behaves similarly. XIII does not yield a ketal with HO(CH2)4OH-i. e., a 7-membered ring is not formed. XIII with C3H5(OH)3 and PhSO3H in C6H6 yields 69.5% of the hydroxypropylene ketal, b14 145°, d419 1.1559, and IV gives 81% of the 1-chloro-2,3-propylene ketal (XIV), b13 132°, d419 1.1968. Warming 22.2 g. XIV with 3 g. Na in 40 cc. MeOH for 0.5 hr. gives 83% of the 1,2-Δ2,3-propylene ketal (XV), b13 118-20°, which contained a small amt. of Cl. XIV and PhONa in MeOH give 48% of 1-phenoxy-2,3-propylene ketal (XVI), b11 198°, and 42% of XV. Hydrolysis of XVI with 5 N aq.-alc. NaOH gives an oily acid, re.ovrddot.esterified with EtOH and PhSO3H to XVI. Iso.ovrddot.octylphenol and Na in PhMe with XIV give a nearly quant. yield of the 1-p-iso.ovrddot.octylphenoxy-2,3-propylene ketal, a bright yellow-brown thick oil; the alk. soln. foams strongly and emulsifies oils. CO(CH2CO2Et)2 (20.2 g.), 10 g. (CH2OH)2 and 5 drops of H2SO4 in C6H6 give 45% of the ethylene ketal, b25 162-4°, d418 1.1453. AcCH(CH2Ph)CO2Et yields 95% of the ethylene. ketal, b11 178-9°, d413 1.1016. Et dodecylacetoacetate, b0.5 168-70° (74% yield), and (CH2OH)2 give 80% of the ethylene ketal, b0.5 184-6°; the free acid m. 63°. Di-Et α-acetylglutarate gives 62% of the ethylene ketal, b24 180-2°, d419 1.0950; the Me Et ester yields 31% of the ethylene ketal, b15 168-70°, d415 1.1315, and 68% of the 1-chloro-2,3-propylene ketal, b17 209-10°, d415 1.1956. The following ethylene ketals were also prepd.: Et γ-acetylbutyrate, b17 135-6°, d418 1.0468, 82%; Et levulinate, b15 110-12°, d419 1.0570, 66%; Et pyruvate, b15 80-1°, d418 1.2380, 70%; Bu phenylformylacetate, b20 212-14°, d418 1.0876; Et phenylformylacetate, b15 172-4°, d419 1.1355. Et phenacylacetoacetate, BzCH2CHAcCO2Et and (CO2H)2 give the bisethylene ketal (XVII), b0.5 174-8°, m. 62-4°; hydrolysis with N NaOH gives the free acid, m. 150-1°. The fraction from the prepn. of XVII which b0.5 140-70° gives on hydrolysis with NaOH 2-phenyl-5-methylfuran-3-carboxylic acid, m. 179-81° (Paal, Ber. 17, 2764(1884)). The condensation of AcCHNaCO2Et and 2-chlorocyclohexanone in PhMe (heating 1 hr. on the water bath) with (CH2OH)2 and PhSO3H in PhMe give 30.4% of Et 2-methyl-4,5,6,7-tetrahydrocoumarone-3-carboxylate, b13 143-4°, d418 1.0998; the free acid m. 161°. CH2(CHAcCO2Et)2 gives 54.5% of the bisethylene ketal, b20 214-18°, d418 1.1557. The reaction product of CHNa(CO2Et)2 and vinyl Me ketone in C6H6, washed with dil. HCl and reacted with (CH2OH)2 and PhSO3H, gives 71.5% of the ethylene ketal of di-Et β-acetylethylmalonate, b14 162-4°, d419 1.0955. Prepd. similarly, the ethylene ketal of Me β-acetylethylcyanoacetate, b14 168-70°, d418 1.1440, results in 28% yield. EtO2CCHAcCH2CO2Et gives 60% of the ethylene ketal, b14 162°, d420 1.1234.

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Re: синтез 2-х соединений

Сообщение Frather » Вс ноя 20, 2011 12:18 am

Спасибо Arkadii_Tarasevych :up:

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