EFFECTS OF ETHYLENE GLYCOL AND KOH IN THE FORMATION OF 2-METHOXY-4-PROPYLPHENOL ON EUGENOL ISOMERIZATION REACTION

Formation reaction mechanism of  2-methoxy-4-propylphenol on eugenol isomerization that involved protic hydrogen originated from ethylene glycol as a solvent has been done. To check this reaction mechanism, the effect of amounts of ethylene glycol as a solvent and KOH as a reagent on the quantity of 2-methoxy-4-propylphenol as a product has been carried out. The reaction product was analyzed by GC and GC-MS. Quantity of 2-methoxy-4-propylphenol as a product increased if ratio of quantity of ethylene glycol as solvent to quantity of KOH as reagent became larger. The result showed that formation process of 2-methoxy-4-propylphenol involved the protic hydrogen of solvent. The existence of cis-isoeugenol as an initiator compound in forming 2-methoxy-4-propylphenol indicated that the reaction mechanism followed the steps (1) cis-isoeugenolic ion gave Cb with negative charge at prophenyl group through resonance (2) a negative charge Cb then attacked a protic H atom in the solvent, and (3) hydride ion will attack Cb to form 2-methoxy-4-propylphenolic ion .   Keywords: 2-methoxy-4-propylphenol, ethyleneglycol - KOH

Karakterisasi Dan Aktivitas Katalitik Berbagai Variasi Komposisi Katalis Ni Dan Znbr2 Dalam γ-Al2o3 Untuk Isomerisasi Dan Hidrogenasi (R)-(+)-sitronelal

Pengaruh sifat dan karakter berbagai variasi komposisi katalis Ni dan ZnBr2 yang terimpregnasi dalam γ-Al2O3 terhadap aktivitas dan selektivitasnya untuk reaksi isomerisasi dan hidrogenasi (R)-(+)-Sitronelal telah dilakukan. Dalam penelitian ini, terdapat tiga jenis variasi komposisi Ni dan ZnBr2 dalam γ-Al2O3, yaitu: A1=Ni/ZnBr2/γ-Al2O3 (3:2), A2=Ni/ZnBr2/γ-Al2O3 (1:1) dan A3=Ni/ZnBr2/γ-Al2O3 (2:3). Katalis dikarakterisasi menggunakan X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area, dan SEM-EELS. Luas area permukaan spesifik dan porositasnya ditentukan berdasarkan adsorption-desorption gas nitrogen pada 77 K. Distribusi dan volume pori ditentukan dengan desorption isotherm pada P/Po ≥ 0,3. Hasil yang didapat menunjukkan bahwa terdapat hubungan antara karakter dan sifat katalis dengan aktivitas katalitiknya terhadap produk isomerisasi dan hidrogenasi (R)-(+)-Sitronelal. Uji aktivitas dilakukan dalam sebuah reaktor mini dengan 0,5 g katalis dan 3 mL (R)-(+)-Sitronelal menggunakan atmosfir gas N2 dan/atau H2 dalam waktu 5 dan 24 jam masing-masing pada suhu 90 dan 120 °C. Komposisi katalis, pemilihan jenis atmosfir gas dan suhu sangat berpengaruh terhadap aktivitas dan selektivitas pembentukan produk isomerisasi dan hidrogenasi. Konversi (R)-(+)-Sitronelal tertinggi ditunjukkan oleh katalis A3=Ni/ZnBr2/γ-Al2O3 (2:3) dengan kondisi reaksi selama 5 jam (4 jam N2 + 1 jam H2) pada suhu 90 °C dan 24 jam (4 jam N2 + 20 jam H2) pada suhu 120 °C. The influence of catalyst properties and characteristics of Ni and ZnBr2 catalysts impregnated in γ-Al2O3 on the activity and selectivity of (R)-(+)-Citronellal isomerisation and hydrogenation has been done. In this study, there were three sets of Ni and ZnBr2 in γ-Al2O3 with various composition, they were A1=Ni/ZnBr2/γ-Al2O3 (3:2), A2=Ni/ZnBr2/γ-Al2O3 (1:1), A3=Ni/ZnBr2/γ-Al2O3 (2:3). The catalysts were characterized using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area and SEM-EELS. The catalysts spesific surface area and porosity determined by adsorption-desorption of dinitrogen at 77 K. Pore distribution and volume were determined by the desorption isotherm at P/Po ≥ 0.3. The result showed that there was correlation between the catalyst characteristics and catalytic activity to (R)-(+)-Citronellal isomerisation and hydrogenation product. The activity test were performed in a mini fixed bed reactor with 0.5 g of catalyst and 3 mL of (R)-(+)-Citronellal using N2 and/or H2 gas atmosphere in 5 and 24 hours at each temperature 90 and 120 oC. The catalyst composition of the choice of gas atmosphere and temperature greatly influenced the activity as well as the selectivity of isomerisation and hydrogenation product formation. The highest conversion was achieved for A3=Ni/ZnBr2/γ-Al2O3 (2:3) with complete conversion of (R)-(+)-Citronellal were obtained when it was running in 5 hours (4 hours N2 + 1 hour H2) at 90 oC and 24 hours (4 hours N2 + 20 hour H2) at 120 oC

STUDY OF REACTION PATHWAY AND KINETIC OF ESTRAGOLE ISOMERIZATION TO CIS-ANETHOLE AND TRANS-ANETHOLE

Estragole isomerization in basic condition resulted cis- and trans-anethole. Hence, there were two reaction pathway of estragole isomerization i.e. parallel and consecutive. The reaction pathway gave information about reaction mechanism. Estragole isomerization was carried out in various kind and volume of solvent, base ratios, and at various time and temperature. The products were analyzed by GC-MS, and FTIR. The result showed that the estragole isomerization pathway in ethanol and ethylene glycol was parallel. The mechanism of estragole isomerization proceed through carbanion intermediate with Eatotal of 178,6238 J/mol .Keywords: estragole, cis-anethole, trans-anethole, isomerization pathway

PARALLEL REACTION ON CATALYTIC HYDROGENATION REACTION OF CIS-ISOEUGENOL INTO 2-METHOXY-4-PROPYLPHENOL

Catalytic hydrogenation of eugenol (Mr 164) and isoeugenol (Mr 164) by using synthetic catalyst Ni/-Al2O3 had been carried out. Eugenol transformation into 2-methoxy-4-propylphenol (Mr 166) as a main product could be achieved in 100% and no conversion reaction of eugenol into isoeugenol. If the raw material was 96% trans-isoeugenol or 61% cis-isoeugenol then the product was 67% or 92% of 2-methoxy-4-propylphenol. On the catalytic hydrogenation of trans-isoeugenol into 2-methoxy-4-propylphenol there was no parallel reaction of trans-isoeugenol into cis-isoeugenol. Conversely, catalytic reaction of cis-isoeugenol into 2-methoxy-4-propylphenol always followed by conversion reaction of cis-isoeugenol into trans-isoeugenol. Transformation of cis-isoeugenol into 2-methoxy-4-propylphenol below 200 oC was equilibrium reaction and above 200 oC was an irreversible reaction.   Keywords: Catalytic hydrogenation, cis-isoeugeno

Isolation and Identification of Volatile Components in Teme by Simultaneous Distillation-Extraction Method by Modified Extraction Method = Isolasi dan Identifikasi Komponen Volatil Tempe dengan Metoda Distilasi-...

An isolation and identification of volatile components in tempe for 2, 5 and 8 days fermentation by simultaneous distillation-extraction method was carried out. Simultaneous distilallation-extraction apparatus was modified by Muchalal from the basic Likens-Nickerson\u27s design. Steam distillation and benzena as an extraction solvent was used in this system. The isolation was continuosly carried out for 3 hours which maximum water temperature in the Liebig condenser was 8°C. The extract was concentrated by freeze concentration method, and the volatile components were analyzed and identified by combinied gas chromatography-mass spectrophotometry (GC-MS). The Muchalal\u27s simultaneous distillation extraction apparatus have some disadvantage in cold finger condenser, and it\u27s extractor did not have condenser. At least 47, 13 and 5 volatile components was found in 2, 5 and 8 days fermentation, respectively. The volatile components in the 2 days fermentation were nonalal, a-pinene, 2,4-decadienal, 5-phenyldecane, 5- phenylundecane, 4-phenylundecane, 5-phenyldodecane, 4-phenyldodecane, 3-phenyldodecane, 2-phenyldodecane, 5-phenyltridecane, and caryophyllenein the 5 days fermentation were nonalal, caryophyllene, 4-phenylundecane, 5-phenyldodecane, 4-phenyldodecane, 3- phenyldodecane, 2-phenyldodecaneand in the 8 days fermentation were ethenyl butanoic, 2- methyl-3-(methylethenyl)ciclohexyl etanoic and 3,7-dimethyl-5-octenyl etanoic. Keywords: Tempe, Muchalal\u27s simultaneous distillation-extraction apparatu

A Study Of The Synthesis Of Veratryl Cyanide Required As An Intermediate For The Preparation Of C-9154 Antibiotic Derivative From Vanilin = Studi Tentang Sintesis Veratril SianidaSebagai Senyawa Antara Dalam Pembuatan...

ABSTRACT The synthesis of veratryl cyanide (1-(3,4-dimethoxy phenyl acetonitril] required as an intermediate for the preparation of C-9154 antibiotic derivative was carried out. The starting material used was vanilin, while the reaction steps consisted of (1) methylation of vanilin, (2) reduction of veratraldehyde, (3) synthesis of veratryl bromide, and (4) treatment of this bromide with KCN. The analysis of the products was carried out using IR, 1H NMR and GC-MS spectrophotometers. The methylation of vanilin was conducted using dimethylsulfate and NaOH at 100oC for 2 hours to give 79.3% yield of veratraldehyde. The reduction of veratraldehyde with LiBH4 in ethanol - THE mixture (1:1 v/v) at reflux for 4 hours afforded veratryl alcohol in 85.3% yield. This veratryl alcohol was treated with red phosphorous and Br2 in CCI4 at 60oC for 2 hours to give 1-(2-bromo-4,5-dimethoxy)-phenyl bromomethane in 67.4% yield, instead of the desired veratryl bromide (I -3,4-dimethoxy)-phenyl bromomethane]. This benzyl bromide derivative was then treated with KCN in the presence of tween 80 as a phase catalyst transsfer in benzene-water solvent system at reflux for 2 hours to yield 1-(2-bromo-4,5- dimethoxy)phenyl acetonitril in 58.5%. Keywords: Vanilin, veratryl cyanide, C-9154 antibiotic derivativ

The Stereotchemistry Effect of Eugenol, C/S-Isoeugenol and Trans-Isoeugenol on Their Catalytic Hidrogenation = Pengaruh Stereokimia Molekul Eugenol, cis-Isoeugenol, dan trans-Isoeugenol Pada Reaksi Hidrogenasi Katalitik.

The stereochemistry effect of eugenol, cis-isoeugenol and trans-isoeugenol on their catalytic hydrogenation by Ni/y-Al203 catalyst was investigated. In this investigation, the catalyst is prepared by impregnation of Nickel into solid of y-Al203 in methanol as a solvent. The calcination process, which is followed by reduction, is performed on Muchalal reactor at 400 °C. After that, the catalytic hydrogenation is carried out under hydrogen gas atmosphere by mixing 10 mL sample and 0.5 g Ni/y-Al203 catalyst at 200°C for 3 hours. The stereochemistry effect of reactants is evaluated by computer modelling using PM3 semiempirical methods. The mass spectrum of catalytic hydrogenation product from those compounds shows a molecular ion at Ink 164, which proves the existence of 2 âmethoxy-4-propylphenol. The eugenol gives the highest conversion (99%), followed by cis-isoeugenol (81%) and trans-isoeugenol (67%). It was found that there is a correlation between the stereochemistry of those compounds and catalytic reactivity. Keywords: stereochemistry effects, 2-methoxy-4-propylpheno

Ibuprofen salt production and its application in tablet dosage form

Ibuprofen is an anti-inflammatory drug and is practically insoluble in water. The low melting point and the poor flowability of ibuprofen can lead to process difficulty in tablets production. The purpose of this research was to make the sodium salt form of ibuprofen which has better solubility in water.Sodium ibuprofen salt was prepared by reacting the ibuprofen and sodium hydroxide, then characterized using TG/DTA, DSC, spectrophotometer UV-VIS, spectrophotometer IR, X-ray diffraction, and SEM. Tablets were prepared by wet granulation method.The characterization result showed that sodium ibuprofen result of the synthesis was dehydrate form with melting point of 199.9 °C. Granules of sodium ibuprofen result of the synthesis had better flowability and bigger density than ibuprofen granules. The physical characterization of the tablet showed that the formula of sodium ibuprofen resulted from the. Sodium ibuprofen showed the higher release rate than ibuprofen so can give quicker onset of action.Key words: sodium ibuprofen, ibuprofen, dissolution

CYCLISATION-ACETYLATION KINETICOF (R)-(+)-CITRONELLAL BY Zn2+-NATURAL ZEOLITE AS SOLID SOLVENT CATALYST

ABSTRACT Kinetic in cyc/isation-acetylation of (R)-(+)-citronellal with acetic anhydride was investigated over Zn2+_ Natural zeolite (Zn2+-Natzeo)as a catalyst. (R)-(+)-citronellalhas been isolated from citronella oil by fractional distillation under reducing pressure. Enantiose/ectivecapillary GC on a Supelco/3-DEX225 column has been used for analysis the enantiomers ratio of citronellal. Catalyst Zn2+-Natzeo has prepared through acid activation of natural zeolite from Malang using HF 1% and HCI 6 M, followed by ion-exchange with 3 M NH4CIand calcination at 450 °C for 1 h under nitrogen to obtainedH-natural zeolite (H-Natzeo). H-Natzeo was modifiedto Zn2+-Natzeoby ion exchange with 0.1 M ZnC/2" Cyclisation-acetylation reaction was carried out by heating (R)-(+)-citronellal (CIT), acetic anhydride (AA), and 1 g catalyst in glass batch reactor with vigorous stirring at 80°C. Molar ratio CIT/AA that used, i.e. 0.250.51.01.2and 1.5.As the reaction proceeded, 1 mL sample was taken off at 10203060120180min and extractedusing n-hexane for every molar ratio. Structure analysis of product was conducted by GC-MS. Kinetic of the cyclisation-acetylation reaction was analyzed according to the Langmuir-Hinshelwood mechanism. Increasing molar ratio of CIT/AA will decrease the isopulegyl acetate (lPA) and neo-isopulegyl acetate (NIPA) formation. Rate constant of cyclisation-acetylation reaction catalyzed by Zn2+-Natzeo was 30.964-47.619 mmol(min. g catrf at 80°C, 30 min and the ratio adsorption equilibrium constant Kcr,lKAA was 7.09. Keywords: Cyclisation-acetylation,(R)-(+)-citronellal,Zn2+-naturalzeolite, kineti