Aldehyde

In this review paper, information about carbonyl compounds, methods of synthesis, reactions, properties,
stability, using as catalysis in various reactions in most of organic reactions, reactivity, types of carbonyl compounds, aldehydes, ketones.

The Perkin reaction is an organic reaction which is used for synthesis of α, β-unsaturated aromatic acid by the condensation of an aromatic aldehyde and an acid anhydride, in the presence of an alkali salt of the acid. The alkali salt acts as a base catalyst and other bases can be used instead.

Introduction. The aims of this study were to determine
the effects of different natural plant extracts used as an
alternative of Sulphur dioxide on wine aroma compounds.
Materials and methods. The wine production was done
according to the accepted conventional method of red wines
(Cabernet Sauvignon). The experimental design was
achieved by using different plant extracts (grape pomace,
rosemary, black blueberry) at different concentrations. As
the first control group was used wine samples processed
without natural extracts and Sulphur dioxide treatments and
as the second group was used wines produced with 25mg/L
Sulphur dioxide addition.
Results and discussion. The highest total amount of
volatile compounds was achieved by applying blueberry
extract and grape pomace extract. The combined application
of Sulphur dioxide and blueberry extract increased the wine
volatile complexity. The best results related to higher
alcohols synthesis and their accumulation in wines was
obtained by using Sulphur dioxide (25 mg/L) and plant
extracts (0.3 mL). The terpenes were dominated by geraniol.
The highest value was obtained in sample treated with grape
pomace.
The ester fraction was represented by 9 identified
compounds. The highest total ester content (169.13 mg/L)
was found in sample obtained with combined treatment of
25 mg/L Sulphur dioxide and rosemary extract 0.3 mL. The
other three variants of rosemary treatments demonstrated
quantitatively close ester content. In samples containing
grape pomace extract was found the lowest total ester
content compared to all others. From this group, only sample
including25 mg/L Sulphur dioxide and grape pomace extract
0.3 mL (40.62 mg/L) was distinguished. Methyl alcohol was
found in all tested wines. The methyl alcohol levels were
very low and not pose a risk to the consumer.
Conclusions. The study demonstrated the possibilities of
optimization of Sulphur dioxide by using natural plant
extracts.

Carbonyl compounds are an important component of atmospheric chemistry with the potential to form secondary pollutants (in gaseous and/or particulate forms). For their analysis, derivatization by pentafluorophenyl hydrazine has been applied in gas chromatography (GC) or high performance liquid chromatography (HPLC). Because of the need for an appropriate solvent, we have evaluated the relative derivatization performance of five solvents (methanol, pentane, hexane, dichloromethane, and water) for GC analysis. Six light and common (C 1 –C 5) aldehydes (i.e., formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, i-valeraldehyde, and valeraldehyde) out of a large member of carbonyl compounds were selected in this research. Anomalously large response was observed for the formaldehyde-hydrazone prepared in methanol and water, while that of acetaldehyde-hydrazone was reduced for pentane (by ~89%) relative to the others. If we exclude these biased cases, their response factors were in the order of: methanol N pentane N hexane N dichloromethane N water. This ordering was seen consistently in their relative recovery: methanol N pentane N dichloromethane ≈ hexane N water. The method detection limits (ng) of the aldehyde-hydrazone (as aldehyde mass) in each solvent were in the order: 1.0 (hexane) b 1.2 (dichloromethane) b 1.6 (methanol) b 2.5 (pentane) b 4.0 (water). As such, evidence suggests that solvent should be selected carefully to optimize the GC-based quantitation of aldehyde-pentafluorophenyl-hydrazones.

The objective of this study was to determine the aromatic profile of red wines obtained from Rubin, Storgozia, Bouquet, Trapezitsa,
Kaylashky Rubin and Pinot Noir varieties from the region of Central Northern Bulgaria. First five varieties are hybrids selected in the
Institute of Viticulture and Enology (IVE). Pinot Noir was used for control. GC-FID study for determination of the aromatic profile of
red wines from proposed varieties was conducted. Twenty four volatile compounds were identified: 9 esters, 8 higher alcohols, 1
aldehyde, 5 terpene alcohols. The presence of methyl alcohol in all wines were found. Its concentrations were normal for red wines. The
highest total content of volatile compounds was found in the wine from Kailashky Rubin variety (693.97 mg.dm-3
). The ester fraction
was dominated by ethyl acetate. The highest total ester content was found in the wine from Pinot Noir variety (204.08 mg.dm-3
). It was
followed by the wine from Bouquet variety (195.75 mg.dm-3
). Acetaldehyde was the major established aldehyde. It was found in the
largest quantity in the wine from Trapezitsa variety (87.44 mg.dm-3
). 2-methyl-1-butanol (active amyl alcohol) and 3-methyl-1-butanol
(isoamyl alcohol) were found in the highest content from the higher alcohols fraction. The highest total content of higher alcohols was
found in the wine from Rubin variety (379.38 mg.dm-3
). Five terpene alcohols were identified in the wines. Geraniol was presented in all
examined wines. An extensive aromatic characterization by gas chromatographic analysis of red wines obtained from grapevine
varieties selected in the Republic of Bulgaria was carried out. The research proves that the red wines obtained in the conditions of
Central Northern Bulgaria were characterized by a complex aromatic composition due to the presence of different esters, higher alcohols
and terpenes.

Leather manufacturing involves a number of unit processes, out of which tanning is the most important in so far as it converts the putrescible hides/skins into non-putrescible leather. In this study, glutaraldehyde has been exploited as a means to reduce the use of basic chromium sulfate for the production of quality shoe upper crust leather. The paper consists in studying the physical properties of aldehyde-tanned leather and chrome-tanned leather. The aim is to find out the possibility of replacing the wet-blue leather, containing Cr(III) salts, with the glutaraldehyde-tanned wet-white leather. The physical properties of the aldehyde-tanned leather were evaluated, analyzed and compared with the conventional chrome-tanned shoe upper crust leather. Statistical analysis illustrated that the tensile strength, the percentage of elongation, stitch tear strength, Baumann tear strength and grain crack strength of the leather was 211±1 kg/cm 2 , 38±0.5 %, 89±0.11 kg/cm, 63±0.4 kg/cm and 23...

The aromatic profile of three different grape brandies was examined by GC-FID. The standard solution (purity> 99.0%) based on which volatile aromatic compounds of brandies were identified includes: acetaldehyde, ethyl acetate, methanol, isopropyl acetate, 1-propanol, 2-butanol, propyl acetate, 2-methyl propanol, isobutanol, 1-butanol, isobutyl acetate, ethyl butyrate, butyl acetate, 2-methyl-1-butanol, 3-methyl-1-butanol, ethylisovalerate, 1-pentanol, phenyl acetate, 1-hexanol, ethyl hexanoate, hexyl acetate, 1-heptanol, linalool oxide, phenyl acetate, ethyl caprylate, α-terpineol, nerol, β-citronellol, geraniol. As an internal standard 1-octanol was used. Seventeen volatile aromatic compounds have been identified. The highest total content of volatile compounds was established in grape brandy 2 (481.16 mg/dm 3). From the aldehydes group in all distillates the presence of acetaldehyde was found. The highest concentration of this compound was found in grape brandy 1 (113.73 mg/dm 3). The ester composition was diverse, with domination of ethyl acetate. The highest content of esters was found in grape brandy 2 (293.65 mg/dm 3). The total concentration of higher alcohols in brandies was low. 1-hexanol was found in all brandies tested. The presence of this compound indicates poor maturation of the grape raw material used. The highest terpenic content was found in grape brandy 1 (0.23 mg/dm 3). The brandies have been found to contain methyl alcohol. This is an indicator of their authenticity.

Carbohydrate and derived products –an overview find the properties types of carbohydrates and the presence of carbohydrate containing crude drugs details. Some of the examples of derived products like Indian gum, Isabgol, agar, tragacanth, and honey

The BP Deepwater Horizon oil spill was detrimental to the prosperity of marine and wildlife habitats, as well as the fishing and tourism industry in the surrounding region. Oil spills can also indirectly affect the economies of countries outside the region, specifically through the spread of toxins harmful to aquatic life. A reversed-phase high-performance liquid chromatographic method (HPLC) with UV detection is developed and validated for the quantitative determination of pollutants in surface oil exposed to sunlight. Octanal, hexanal, and propionaldehyde are the three waste products targeted in this study. These aldehydes have specific negative impacts on marine wildlife, such as long term cardiotoxicity in fish and liver dysfunction in mammals. Because aldehydes and ketones are considered a waste product in aquatic environments, this long-term study was conducted to identify and quantify the formation of aldehydes in emulsified crude oil and seawater by high-performance liquid chromatography (HPLC) and solar simulation. Oil samples collected from BP’s Surrogate Macondo Well were irradiated by solar simulator over six, twelve, and eighteen hour periods. The aqueous solution from beneath the oil was then pulled, derivatized with dinitrophenylhydrazine (DNPH), and analyzed by HPLC with UV detection to be compared to the standard chromatograms generated for propionaldehyde, octanal, and hexanal. Chromatogram results from the eighteen hour irradiated BP Surrogate oil indicated that aldehydes were present after exposure to sunlight, and within the range of the aldehyde standards used based on their carbon chains. The procedure developed in this research will allow EPA and bioremediation organizations to identify toxins forming as photoproducts in an oil spill, and treat affected marine ecosystems accordingly.

Gas chromatographic study (GC-FID) for determination of the influence of maceration and addition of
flavoring enzyme on the aromatic profile of red wines from Central Northern Bulgaria was conducted. The wines
were obtained from selected clones (Gamza 52-9-4, Gamza 52-9-5 and Pamid 5/76) and varieties (Kaylashky
rubin, Trapezitsa). Nineteen volatile compounds have been identified. Of these, 5 higher alcohols, 9 esters and 4
terpene alcohols affected the aroma of the wines. Methyl alcohol has been found in wines. Its concentrations were
normal for red wines. The highest total concentration of volatile compounds was found in the Gamza clone 52-9-
5 control (363.10 mg/dm3). Gamza 52-9-4 clone, Kaylashky rubin and Trapezitsa varieties have been observed to
increase the content of higher alcohols after addition of flavoring enzyme, while in the wines from Gamza 52-9-5
clone and Pamid 5/76 clone, the trend was reversed. The ester composition of the experimental samples was
diverse. Increased ester content, after the addition of flavoring enzyme was found in Gamza 52-9-4 clone,
Kaylashky rubin and Trapezitsa variety. In Gamza 52-9-5 and Pamid 5/76, the trend was reversed. The dominant
ester was ethyl acetate. The highest content of terpene alcohols was observed in the wine from the control variant
of clone Pamid 52-9-4 (0.69 mg/dm3).

Aims: Formaldehyde and acetaldehyde associated with alcohol consumption are both carcinogenic to humans (WHO IARC group 1 carcinogens). While several surveys exist on occurrence and exposure of the two aldehydes in alcoholic beverages from Europe and the Americas, we aimed to study domestic products of Asian countries.

Methods: Alcohol products from Asian countries (China, Korea, Japan and Thailand), including traditionally fermented beverages (sake, rice wine) as well as distilled spirits, were collected (n = 54) and chemically analyzed for alcohol quality.

Findings: In 9 of 39 samples (23%) analyzed for formaldehyde, its concentration was higher than the WHO IPCS tolerable concentration of 2.6 mg/L. Three samples contained more than 10 mg/L with a maximum concentration of 14.6 mg/L. In 15 of 54 samples (28%) analyzed for acetaldehyde, the concentration exceeded 50 g/hL of pure alcohol (pa). The maximum concentration of acetaldehyde was 127 g/hL pa. The incidence of the aldehydes, especially of formaldehyde, in the Asian sample was considerably higher than what was found in surveys of European-style alcoholic beverages.

Conclusions: While acetaldehyde is a natural constituent of alcoholic beverages and is also produced during ethanol metabolism in humans, the presence of formaldehyde is unusual and raises questions about its origin. A likely explanation is that it is used as a disinfectant during production—a questionable practice, not only because of the resultant residues in the beverages, but also because of the risks to production workers of occupational exposure. Detailed exposure assessment using larger samples is needed to characterize the risk arising from the aldehydes for the alcohol-drinking population.

Ferrocene is one of the most widely established compounds in the chemical literature, and it is frequently used as a starting material in both organometallic and organic chemistry transformations. 1 This sandwich-type compound consists of an iron(II) atom bonded in an   fashion to two cyclopentadienide rings (Cp). Redox cycling between the Fe 2+ /Fe 3+ states is both chemically and electrochemically reversible. 2 Certainly this final point is one main reason why ferrocene has been so popular as a redox reporter in supramolecular structures. 3 The Cp rings are aromatic and hence it is possible to perform typical electrophilic substitution reactions on one or both of the rings. 4 Selective reactions on a single Cp ring to introduce two disparate functional groups (e.g. PPh 2 , dihydrooxazole) is also possible. 5 For this latter case the ferrocene subunit is used as a planar chiral ligand for asymmetric catalysis applications. 6 For each ring to incorporate a different functional group can be complex, often requiring selective BuLi reactions at low temperatures. 7 A long reaction time and a convoluted purification method is possible starting from 1,1′-ferrocenedicarboxaldehyde. 8 A very mild and fast method to achieve a similar outcome would appear to be appealing, provided the two functional groups are useful for further reactions. 9 It turned out that, as part of our research effort into producing ferrocene-based porphyrin and borondipyrromethene (Bodipy) compounds, we discovered such a simple procedure. The oxidation of ferrocenecarboxaldehyde using aqueous KMnO 4 in acetone is well documented to produce the corresponding carboxylic acid. 10 Repeating the literature method afforded ferrocenecarboxylic acid in reasonable yield. However, we found that the same procedure applied to 1,1′-ferrocenedicarboxyaldehyde in acetone or acetonitrile did not produce the corresponding dicarboxylic acid (Scheme 1). The 1 H NMR spectrum for the major product isolated from the acetonitrile reaction showed different resonances for the two Cp rings, confirming the product to be unsymmetrical. Furthermore, two downfield resonances at  193.21 and 170.77 for the 13 C{ 1 H} NMR spectrum were consistent with the presence of aldehyde and carboxylic acid groups. The mass spectrum showed a peak at m/z 259, and a broad peak at ca. 2939 cm 1 in the FT-IR spectrum confirmed production of a carboxylic acid group. The combined evidence verified the product to be compound 1, in which one aldehyde was oxidized but the other remained untouched. Hence, under these conditions the ferrocene is desymmetrized since it contains two different functional groups. The overall yield for 1 is 49% after a fast and chromatography-free work up, providing material pure enough for further synthetic reactions. A similar reaction performed using an acetone/H 2 O mixture (ca. 1:1) did not afford a product with a 1 H NMR spectrum consistent with compound 1. Instead, additional resonances were observed in the olefinic region ( = 7.35 and 6.30, J = 16.2 Hz), a methyl resonance ( = 2.25) and a downfield resonance ( = 197.51) in the 13 C NMR spectrum, which is consistent with the existence of a CH 3 CO group (see Supporting Information). 11 The mass spectrum showed a peak at m/z 299, and once again the FT-IR spectrum corroborated the presence of a carboxylic acid (2934 cm 1). 12 The spectroscopic data are fully consistent with compound 2 with a trans double bond. We speculate that oxidation of one aldehyde to the carboxylic acid activates the other carbonyl in 1 to a condensation reaction with the acetone present in solution. Presumably for ferrocenecarboxaldehyde the reaction of the aldehyde with acetone is too slow to compete with oxidation. Rather surprisingly, compounds 1 and 2 could not be found in the literature using popular search tools (i.e., Scifinder, Reaxys). The closest analogue to 2 is the structural isomer (C 15 H 14 FeO 3) in which one ring has a formyl and the other the (E)--(methoxycarbonyl)ethenyl subunit. 8 This material was produced by a controlled Wittig reaction with 1,1′-ferrocenedicarboxaldehyde, yielding a mixture of compounds which had to be separated by chromatography. Again for compound 1 the structural analogue (C 12 H 10 FeO 3) has both the formyl and carboxylic acid substituted on the same Cp ring. 13 Scheme 1. Reagents and Conditions: (i) KMnO 4 , CH 3 CN/H 2 O, 0 °C; (ii) KMnO 4 , acetone/H 2 O, 0 °C. Scheme 2. Reagents and Conditions: (i) 2-acetylpyridine, aq. NaOH/NH 4 OH, dark; (ii) (a) diethyl malonate, NaOEt, EtOH; (b) H 2 O, H + .

The BP Deepwater Horizon oil spill was detrimental to the prosperity of marine and wildlife habitats, as well as the fishing and tourism industry in the surrounding region. Oil spills can also indirectly affect the economies of countries outside the region, specifically through the spread of toxins harmful to aquatic life. A reversed-phase high-performance liquid chromatographic method (HPLC) with UV detection is developed and validated for the quantitative determination of pollutants in surface oil exposed to sunlight. Octanal, hexanal, and propionaldehyde are the three waste products targeted in this study. These aldehydes have specific negative impacts on marine wildlife, such as long term cardiotoxicity in fish and liver dysfunction in mammals. Because aldehydes and ketones are considered a waste product in aquatic environments, this long-term study was conducted to identify and quantify the formation of aldehydes in emulsified crude oil and seawater by high-performance liquid chromatography (HPLC) and solar simulation. Oil samples collected from BP’s Surrogate Macondo Well were irradiated by solar simulator over six, twelve, and eighteen hour periods. The aqueous solution from beneath the oil was then pulled, derivatized with dinitrophenylhydrazine (DNPH), and analyzed by HPLC with UV detection to be compared to the standard chromatograms generated for propionaldehyde, octanal, and hexanal. Chromatogram results from the eighteen hour irradiated BP Surrogate oil indicated that aldehydes were present after exposure to sunlight, and within the range of the aldehyde standards used based on their carbon chains. The procedure developed in this research will allow EPA and bioremediation organizations to identify toxins forming as photoproducts in an oil spill, and treat affected marine ecosystems accordingly.