Mole Of Formaldehyde Research Articles

Circular Design and Functionalized Upcycling of Waste Commodity Polystyrene via C-H Activation Using Microwave-Assisted Multicomponent Synthesis.

The inefficient reuse and recycling of plastics-and the current surge of medical and take-out food packaging use during the pandemic-have exacerbated the environmental burden. This impels the development of alternative recycling/upcycling methods to pivot toward circularity. We report the use of the Mannich three-component coupling reaction for the modification of polystyrene (PS) recovered with a 99.1% yield from waste food containers to form functionalized nitrogen and oxygen-rich PS derivatives. A series of functionalized PS with increasing moles of formaldehyde (F) and morpholine (M) (0.5 × 10-2, 1.0 × 10-2, and 2.0 × 10-2 mol) was achieved using a sol-gel-derived Fe-TiO2 catalyst in a solvent-free, microwave-assisted synthesis. Modified polymers were characterized with viscometry, 1H NMR, 13CNMR (DEPT) FTIR, XPS, UV, and TGA. Functionalization scaled with an increasing ratio, validating the 3CR approach. Further functionalization was constrained by a competing oxidative degradation; however, the varying hydrogen bond density due to nitrogen and oxygen-rich species at higher ratios was shown to compensate for molecular weight loss. The integration of the N-cyclic quaternary ammonium cations exhibited the potential of functionalized polymers for ion-exchange membrane applications.

Use of LC-MS/MS and Stable Isotopes to Differentiate Hydroxymethyl and Methyl DNA Adducts from Formaldehyde and Nitrosodimethylamine

Formaldehyde is a known human and animal carcinogen that forms DNA adducts, and causes mutations. While there is widespread exposure to formaldehyde in the environment, formaldehyde is also an essential biochemical in all living cells. The presence of both endogenous and exogenous sources of formaldehyde makes it difficult to develop exposure-specific DNA biomarkers. Furthermore, chemicals such as nitrosodimethylamine form one mole of formaldehyde for every mole of methylating agent, raising questions about potential cocarcinogenesis. Formaldehyde-induced hydroxymethyl DNA adducts are not stable and need to be reduced to stable methyl adducts for detection, which adds another layer of complexity to identifying the origins of these adducts. In this study, highly sensitive mass spectrometry methods and isotope labeled compounds were used to differentiate between endogenous and exogenous hydroxymethyl and methyl DNA adducts. We demonstrate that N(2)-hydroxymethyl-dG is the primary DNA adduct formed in cells following formaldehyde exposure. In addition, we show that alkylating agents induce methyl adducts at N(2)-dG and N(6)-dA positions, which are identical to the reduced forms of hydroxymethyl adducts arising from formaldehyde. The use of highly sensitive LC-MS/MS and isotope labeled compounds for exposure solves these challenges and provides mechanistic insights on the formation and role of these DNA adducts.

A study on the kinetics of condensation reaction of phenol‐modified cardanol–formaldehyde resin

AbstractPhenol‐modified cardanol–formaldehyde novolac resins have been synthesized using equal proportions of phenol and cardanol. To this mixture of phenol and cardanol, 0.6 and 0.8 mol of formaldehyde were added separately, under acidic conditions, at five different temperatures ranging between 80 and 120°C with an interval of 10°C. This was carried out for a maximum period of 6 h. The free formaldehyde and free phenol contents were determined at regular time intervals to check the completion of the reaction. The synthesized novolacs have been studied by infrared spectroscopic analysis (FT‐IR). The reaction between cardanol, phenol, and formaldehyde was found to follow a second‐order rate kinetics. The overall rate constant (k) increased with the increase of temperature. Based on the value of rate constants, various other parameters such as activation energy (Ea), change in enthalpy (Δ H) and entropy (Δ S), and free energy change (Δ G) of the reaction were also evaluated. It was found that the condensation reaction of phenol and cardanol with formaldehyde was nonspontaneous and irreversible. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 380–389, 2010

New melamine–formaldehyde–ketone resins. VI. Preparation of filled molding compositions and compression‐molding materials from reactive solvents based on cyclohexanone

AbstractThe conditions and a method of preparing new molding compositions and filled compression‐molding materials from melamine–formaldehyde–cyclohexanone resins are described. The resins were obtained from melamine solutions in a reactive solvent prepared by the reaction of 1 mol of cyclohexanone with 7 mol of formaldehyde. The fillers were wood powder and sulfite cellulose. The thermal properties of the samples prepared from the compositions were studied with dynamic thermal analysis, thermogravimetry, and differential scanning calorimetry analysis. Selected mechanical properties [Brinell hardness, unnotched impact strength (Charpy method), and bending strength] of the cured resins were also measured. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Studies on the oxygen atom transfer reactions of peroxomonosulfate: Catalytic effect of hemiacetal

The reaction of peroxomonosulfate (PMS) with glycolic acid (GLYCA), an alpha hydroxy acid, in the presence of Ni(II) ions and formaldehyde was studied in the pH range 4.05–5.89 and at 31°C and 38°C. When formaldehyde and Ni(II) ions concentrations are ∼5.0 × 10−4 M to 10.0 × 10−4 M, the reaction is second order in PMS concentration. The rate is catalyzed by formaldehyde, and the observed rate equation is (−d[PMS])/dt = (k′2[HCHO][Ni(II)][PMS]2)/{[H+](1+K2[GLYCA])}. The number of PMS decomposed for each mole of formaldehyde (turnover number) is 5–10, and the major reaction product is oxygen gas. The first step of the reaction mechanism is the formation of hemiacetal by the interaction of HCHO with the hydroxyl group of nickel glycolate. The peroxomonosulfate intermediate of the Ni-hemiacetal reacts with another molecule of PMS in the rate-limiting step to give the product. This reaction is similar to the thermal decomposition of PMS catalyzed by Ni(II) ions. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 642–649, 2009

Sevoflurane Breakdown Produces Flammable Concentrations of Hydrogen

Fires, explosions, and extreme heat production may occur when sevoflurane reacts with desiccated barium hydroxide lime. The identity of the flammable gas has not previously been published, although carbon monoxide, methanol, formaldehyde, and methyl formate have been identified in low quantities. The authors reacted sevoflurane with excess desiccated barium hydroxide lime or soda lime at 55 degrees, 100 degrees, 200 degrees, 300 degrees, and 400 degrees C. Formaldehyde, methanol, sodium formate, and hexafluoroisopropanol were reacted with barium hydroxide lime at 300 degrees or 400 degrees C. The authors measured hydrogen production by gas chromatography with a thermal conductivity detector and calculated the molar yield of hydrogen produced. Up to 3 moles of hydrogen were produced per mole of sevoflurane degraded. Each mole of formaldehyde produced up to 2 moles of hydrogen at 400 degrees C. Formate and hexafluoroisopropanol produced up to 1 mole of hydrogen each at 400 degrees C. More than 2 moles of hydrogen were produced by methanol at 400 degrees C. Soda lime and barium hydroxide lime produced similar amounts of hydrogen from sevoflurane above 200 degrees C, but barium hydroxide lime produced more than soda lime at lower temperatures. The temperature above which large amounts of hydrogen were produced seemed to be 300 degrees C. Up to 3 moles of hydrogen are produced by the chemical reaction of sevoflurane with heated, desiccated absorbent. The high yield, ease of ignition, and low tissue solubility of hydrogen make it the most likely fuel in anesthesia machine fires due to the reaction of sevoflurane with desiccated absorbent.

Formaldehyde-Releasing Prodrugs in Combination With Adriamycin Can Overcome Cellular Drug Resistance

The anticancer drug Adriamycin is widely used in cancer chemotherapy and is classified as a topoisomerase II inhibitor. However, in the presence of formaldehyde, Adriamycin also forms high levels of DNA adducts. In this study, a new series of butyric acid and formaldehyde-releasing drugs related to AN9 (pivaloyloxymethyl butyrate) was assessed for their ability to facilitate Adriamycin-DNA adduct formation in Adriamycin-sensitive and -resistant cell lines (HL60 and HL60/MX2; MES-SA and MES-SA/Dx5). Drugs that released two molar equivalents of formaldehyde per mole of prodrug were superior in their ability to enhance adduct formation compared to those that released one molar equivalent. Adduct formation (as assessed by binding of radiolabeled Adriamycin to genomic DNA) was always lower in the resistant cell lines compared to the sensitive cell lines. However, in growth inhibition experiments, prodrug combinations were able to overcome Adriamycin resistance to varying degrees, and the combination of Adriamycin with selected prodrugs that release two moles of formaldehyde totally overcame resistance in HL60/MX2 cells. These HL60-derived cells express altered levels of topoisomerase II and also express a mutant form of the enzyme. Combinations of Adriamycin with selected prodrugs that release one or two moles of formaldehyde partially overcame P-glycoprotein-mediated resistance in MES-SA/Dx5 cells. Formaldehyde-releasing prodrugs (as single agents) overcame both forms of resistance in the two resistant cell lines, demonstrating that they were not substrates of these resistance mechanisms. Collectively, these results suggest that changing the mechanism via which Adriamycin exerts its anticancer effect by dramatically increasing adduct levels (requiring coadministration of formaldehyde-releasing prodrugs) may be a useful means of cancer treatment, as well as for overcoming Adriamycin-induced resistance.

Synthesis of Variously 9,9‐Dialkylated Octahydropyrimido[3,4‐a]‐s‐triazines with Potential Antifungal Activity.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Solubilization of nitrogen‐containing heterocyclic compounds in reactive solvents

AbstractA reactive solvent was obtained by reacting 1 mol of cyclohexanone with 5 mol of formaldehyde. The structure of the solvent was studied by using 1H‐NMR and IR spectroscopy. It was used for solubilization of melamine and other heterocyclic compounds containing NH groups, such as adenine, carbazole, cytozine, guanine, thymine, and uracyl, as well as isocyanuric, barbituric, and uric acids. The solubilization involved the reaction of formaldehyde (liberated at an elevated temperature) with amino groups of the compound. Melamine was the compound with the best solubility in the reactive solvent. Preliminary attempts of curing the solutions have also been made. The oligomers cured at 120°C in the presence of acidic catalysts. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2650–2659, 2002

Synthesis of variously 9,9-dialkylated octahydropyrimido [3,4- a]- s-triazines with potential antifungal activity

9,9-Dialkyloctahydropyrimido[3,4- a]- s-triazines were synthesized by iminodimethylation reaction between a 5,5-dialkyl-6-aminopyrimidine-2,4(3 H,5 H)-dione, a substituted aniline and two moles of formaldehyde. The synthesis of 5,5-dialkyl-6-aminopyrimidinedione consisted of the condensation of urea with ethyl 2,2-dialkylcyanoacetates. 18 Octahydropyrimido[3,4- a]- s-triazines were synthesized and compounds resulting from a supplementary aminomethylation were also obtained. Most of these compounds were tested for antifungal activity in vitro. Only 9,9-dibutyl-6,8-dioxo-3(2-chlorophenyl)2,3,4,5,6,7,8,9-octahydropyrimido[3,4- a]- s-triazine showed some activity against Microsporum canis.

Synthesis of New Phosphines and P-Heterocycles from Phosphonates Containing Allyl Group

Addition of phenylphosphine to allylphosphonate followed by reduction of the resulting diphosphonate gives a new branched phosphine, bis(3-phosphinopropyl)phenylphosphine. Its reaction with paraform and p-toluidine yields oligomeric 3-[3-(propylenophenylphosphino)propyl]-1,5-di-p-tolyl-1,5,3,7-diazadiphosphacyclooctane. Diethyl (5-allyl-2-ethoxybenzyl)phosphonate was obtained. Its reduction gives unsaturated (5-allyl-2-ethoxybenzyl)phosphine. This product adds two moles of formaldehyde to give bis(hydroxymethyl)(5-allyl-2-ethoxybenzyl)phosphine. The reaction of this compound with p-toluidine yielded, depending on the conditions, the corresponding bis(aminomethyl)phosphine, 1,3,5-diazaphosphorinane, and 1,5,3,7-diazadiphosphacyclooctane, and also their derivatives containing allyl substituents.

Chemical Structures of (+)-Catechin-Formaldehyde Reaction Products (Stiasny Precipitates) Under Strong Acid Conditions: Part 1. Solid-State 13C-NMR Analysis

Summary To determine more accurately the amount of polyflavanoids in tannin extracts from radiata pine bark, which react with formaldehyde, it is important to elucidate chemical structures of (﹢)-catechin-formaldehyde reaction products (Stiasny precipitates). The Stiasny value of 106.4% for (﹢)-catechin was obtained from the reaction with formaldehyde under strong acid conditions. This value is almost identical to the value calculated from the Stiasny precipitates, which were formed in the ratio of two molecules of (﹢)-catechin to three molecules of formaldehyde. The solid-state 13C NMR spectrum was measured to elucidate the structures of the Stiasny precipitates, and analysed on the basis of the chemical shifts of (﹢)-catechin. The NMR results indicate that C-6 and C-8 in the A-ring are bonded by methylene bridges to form polymers, and also form methylene bridges with C2′, C5′ or C6′ in the B-ring of a catechin unit. Consequently, the reaction products of (﹢)-catechin-formaldehyde under strong acid conditions (Stiasny precipitates) are (﹢)-catechin-polymers, which consist of two moles of (﹢)-catechin and three moles of formaldehyde. The methylene bridges are formed mostly between A-rings, and less frequently, between A- and B-rings and between B-rings of the catechin units.

A Study of the Acid Lability and Acute Toxicity of Dimethoxymethane in Rats

The pH stability and acute oral toxicity of dimethoxymethane (DMM) in rats were studied. In in vitro studies, DMM was found to be stable in artificial gastric juice at pH 2.5 and above but readily hydrolyzed at pH 2 and below, with 1 mole of DMM producing approximately 1 mole of formaldehyde and 2 moles of methanol. DMM incubated in sealed, excised stomachs appeared to equilibrate with the external incubation fluid over a 24-hour period without significant hydrolysis. In the toxicity study, three groups of female rats ( n = 5) were administered, by gavage, phosphate-buffered saline (control), DMM (31 mmoles/kg body weight [bw]/day), or methanol (MeOH) (30 mmoles/kg bw/day), respectively, for 3 consecutive days and then sacrificed on day 5. Transient ataxia lasting about 30 minutes was observed in animals following DMM administration. Increased urine volume was observed in the DMM group at the end of days 4 and 5. Markedly elevated level of formic acid was present in the urine of the MeOH group at days 1, 2, and 3, but not in the DMM group. Urinary ascorbic acid levels were increased in the DMM group on days 1, 2 and 3, and returned to baseline level at days 4 and 5. Microscopic examination detected no abnormal histological changes in the liver and kidneys of MeOH-or DMM-treated animals. No treatment effects were observed on the following endpoints: organ weights (liver, heart, thymus, kidneys), serum corticosterone, serum chemistry profile, hematology, hepatic phase 1 and phase 2 mixed-function oxidase activities, hepatic and serum thiobarbituric acid, hepatic glutathione, urinary protein, and urinary N-acetylglucosaminidase activity. These observations suggested that hydrolysis of DMM in the stomach required a gastric acidity below pH 2.5. At higher pH, intact DMM readily penetrated the stomach and therefore likely reached the circulation and other body tissues. There was no significant hydrolysis of orally administered DMM, and the acute effects were limited to transient ataxia and biochemical responses in the liver.

1H NMR Spectroscopic Studies of the Stability of an Oxazolidine Condensation Product

Condensation of (–)-norephedrine with excess formaldehyde under mild conditions leads to formation of the 2:1 condensation product N,N′-methylenebis(4-methyl-5-phenyl)oxazolidine compared with the reaction with 1 mol of formaldehyde, which leads to 4-methyl-5-phenyloxazolidine. 1H and 13C NMR spectroscopy was used to monitor the stability of this compound and its decomposition products. The 2:1 condensation product is found to be stable in CDC13 but breaks down rapidly in CD3OD to yield a 50:50 mixture of 4-methyl-5-phenyloxazolidine and 3-hydroxymethyl-4-methyl-5-phenyloxazolidine. Upon addition of D2O to this equimolar mixture, the latter compound decomposes to norephedrine and formaldehyde, whereas the former compound is stable. © 1997 by John Wiley & Sons, Ltd.

ワラ類の化学パルプ化 （ＩＩ） 稲ワラ・ソーダ蒸解黒液リグニンから分散剤の調製

Soda lignin from rice straw was sulfomethylated, and the dispersion ability of sulfomethylated lignin was compared with that of commercial softwood lignosulfonate. The results are summarized as follows : (1) Black liquor from soda cooking of rice straw was adjusted to pH 8.2 with aq. sulfurous acid. Same mole of formaldehyde as sodium sulfite formed in black liquor was added, and then dissolved lignin was directly sulfomethylated (SML I). Sulfomethylated black liquor was separated by gel filtration method (SML II : 0.18 S/C6-C3).(2) SML I shows the similar standard dispersion number (SDN), regardless of max. temperature of soda cooking and reaction time of sulfomethylation.SDN of sulfomethylated liquor including SWL I, however, is inferior to that of lignosulfonate. This may be due to the low content of sulfonic acid group and low purity of SML I. In order to utilize straw soda lignin as dispersant, it is necessary to isolate soda lignin from black liquor and to sulfomethylate the isolated soda lignin.(3) The setting time of mortar with SML II show the relatively similar results to that of commercial lignosulfonate. SML I, however, requires a long period of the setting time. The utilization of SML I as the dispersant is impractical in mortar manufacture.(4) The dispersion effect with SML II was compared by the use of various types of additives. Among seventeen additives tested here, citric acid, gluconic acid, glucuronic acid and K, H-glucarate show the excellent SDN. Very high SDN shown by K, H-glucarate is worth noting.

Development of Methylal Synthesis by Reactive Distillation.

The world’s first technology for the commercial production of methylal is the reactive distillation method. Its application to a new formaldehyde process has also been investigated. Whereas the oxidation of methanol yields one mole of water per mole of formaldehyde, methylal oxidation produces only one mole of water for every three moles of formaldehyde. Thus, the output by methylal oxidation is more than 70% formaldehyde compared with 55% by methanol oxidation.For this purpose, basic research on methylal synthesis was conducted and the world’s first commercial production of methylal using reactive distillation was accomplished. Using this methylal, the world’s first methylal oxidation technology for manufacturing highly concentrated aqueous formaldehyde was established.This highly concentrated aqueous formaldehyde is then fed to an acetal homopolyrner and copolymer plant having a combined capacity of 35,000 tons/year.

Development of a new advanced process for manufacturing polyacetal resins. Part I. Development of a new process for manufacturing highly concentrated aqueous formaldehyde solution by methylal oxidation

AbstractA new technology for the production of highly concentrated aqueous formaldehyde was developed by oxidizing methylal. Whereas the oxidation of methanol yields 1 mol of water per 1 mol of formaldehyde, methylal oxidation produces only 1 mol of water for every 3 mol of formaldehyde. Thus, the output from methylal oxidation is more than 70% formaldehyde compared with 55% from methanol oxidation. For this purpose, basic research for methylal synthesis was tried and the world's first commercial production of methylal was accomplished. Using this methylal, the world's first technology of methylal oxidation for manufacturing highly concentrated aqueous formaldehyde was established by development of a new methylal oxidation catalyst composed of iron, molybdenum, and a third component. This highly concentrated aqueous formaldehyde is then fed to the acetal homopolymer and copolymer plant whose combined capacity is 35,000 tons/years. © 1993 John Wiley & Sons, Inc.

Development of an advanced process for manufacturing trioxane ethylene oxide copolymer

An advanced process for manufacturing trioxane ethylene oxide copolymer has been developed. First, a new technology for production of highly concentrated aqueous formaldehyde was developed by oxidizing methylal. Whereas oxidation of methanol yields 1 mol of water per mole of formaldehyde, methylal oxidation produces only 1 mol of water for every 3 mol of formaldehyde. Thus the output from methylal oxidation is more than 70% formaldehyde, compared with 55% from methanol. The relatively high formaldehyde concentration enhances formation of trioxane. Purified trioxane is copolymerized with ethylene oxide in the presence of an end-capping agent such as methylal producing an end-capped polymer with high thermal stability. Two new intermediates in the initiation reaction of the copolymerization, 1,3,5,7-tetraoxacyclononane (TOCN) and 1,3,5,7,10- pentaoxacyclododecane(POCD) were isolated and a new initiation mechanism was proposed. A commercial plant employing this process with a capacity of 15 000 tons/year is operating well.

3,5-ジアセチル-1,4-ジヒドロ-2,6-ジメチルピリジンのポーラログラフィーとそのホルムアルデヒド定量への応用

3, 5-Diacetyl-1, 4-dihydro-2, 6-dimethylpyridine (DDL), prepared by the condensation of 1 mol of formaldehyde with 2 mol of acetylacetone in the presence of ammonia and applied to a colorimetric determination of formaldehyde, was studied by polarography. It was found that the direct current and square wave polarograms and the cyclic voltammograms of DDL at pH 2 and 10 showed irreversible reduction waves. DDL was easily oxidized to colorless 3, 5-diacetyl-2, 6-dimethylpyridine in acidic solutions by exposure to daylight and air, but stable in basic solutions. Thus, DDL solution should be made to be basic by adding tetraethylammonium hydroxide immediately after the reaction of formaldehyde with acetylacetone in the presence of ammonium acetate. Formaldehyde can be easily determined by the polarography of the alkaline DDL solution.

1,3,-Dioxolane, An Alternative to Formalin as a Standard for Formaldehyde

Four potential primary standards for formaldehyde were evaluated as replacements for the formalin usually used with colorimetric reagents in analyzing textiles for form aldehyde. Of the four—sodium formaldehyde bisulfite, hexamethylenetetramine, tet raoxane, and 1,3,—dioxolane—only 1,3,-dioxolane yielded the stoichiometric amount of formaldehyde under relatively mild conditions of hydrolysis. 1,3,-Dioxolane can be hydrolyzed in 6N HCl for four hours to produce one mole of formaldehyde per mole of 1,3,-dioxolane. Stabilities of standard formaldehyde solutions from 1,3,-diox olane were compared with those from formalin, and there is a discussion of 1,3, dioxolane-based formaldehyde solutions used to prepare calibration curves of several colorimetric reagents for formaldehyde.