The Photochemical Reaction between Chlorine and Formaldehyde. The Preparation of Formyl Chloride

Krauskopf, Konrad B.; Rollefson, G. K.

doi:10.1021/ja01327a006

Cited by 23 publications

(16 citation statements)

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“…The first 0 insertion with methylene bromide should yield formyl bromide, but formyl halides are exceedingly unstable at room temperature. They react in water by alpha elimination to produce carbon monoxide [22], which is detected. Fig.…”

Section: H-cci (Hocci3) O=cc12mentioning

confidence: 99%

BIODEHALOGENATION: RAPID OXIDATIVE METABOLISM OF MONO- AND POLYHALOMETHANES BY METHYLOSINUS TRICHOSPORIUM OB-3b

Bartnicki¹,

Castro²

1994

Environ Toxicol Chem

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Resting cells of Methylosinus trichosporium OB-3b grown in the absence of copper salts rapidly oxidize mono-and polyhalomethanes. The order of reactivity of the series is CH,X > CH2X2 2 CHX, (X = CI, Br). Based on halide ion release, the half-life for methyl bromide and methyl chloride is 9.4 min with a cell density of 0.1 g/ml. The dihalomethanes and bromoform react at the same rate and half as rapidly as the methyl halides. Chloroform is converted to carbon dioxide at one-fourth the methyl halide rate (t,,, = 38 min). No isotope effect was observed with either deuteromethylene chloride or deuterochloroform (CD,C12, CDCI,). In all cases, the dehalogenation chemically follows an oxygen insertion into the C-H bond, and the final product is carbon dioxide (HCO;). All reactions are inhibited by acetylene, establishing methane monooxygenase as the responsible enzyme. Incubations with I3CHCl3, l3CH,Brz, and I3CH3Br and nuclear magnetic resonance (NMR) analysis of reaction mixtures showed the first hydrolytically stable products from CHCI, (HCO;) and CH,Br, (CO), but neither formaldehyde nor formate could be detected as intermediates with methyl bromide by this method. The oxidative destruction of halomethanes by this methylotroph is rapid and not very sensitive to structure.

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Section: H-cci (Hocci3) O=cc12mentioning

confidence: 99%

BIODEHALOGENATION: RAPID OXIDATIVE METABOLISM OF MONO- AND POLYHALOMETHANES BY METHYLOSINUS TRICHOSPORIUM OB-3b

Bartnicki¹,

Castro²

1994

Environ Toxicol Chem

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“…Although these species have not yet been detected, the non-chlorinated cumulenene ketone species-formaldehyde (H 2 CO), ketene (H 2 C=C=O), propadienone (H 2 C=C=C=O), and their corresponding radicals post hydrogen cleavage (HC n O)-have been detected in the atmosphere 38,39 and interstellar clouds [40][41][42] . The dehalogenated radicals of these species have also been discovered in laboratory settings with some also observed in the ISM, suggesting that reactions similar to those of formyl chloride are certainly possible in similar conditions 43,44 . These cumulene neutrals and radicals are bathed in a chlorine environment, which may eventually lead to the formation of chlorinated cumulenones via HC n O + Cl 2 → ClHC n O + Cl.…”

Section: Introductionmentioning

confidence: 75%

Highly-Excited State Properties of Cumulenone Chlorides in the Vacuum-Ultraviolet

Nguyen¹,

Peters²,

Fortenberry³

2020

Preprint

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Recent observations of chloromethane in interstellar environments suggest that other organohalogens, which are known to be critically important in Earth s atmosphere, may also be of significance beyond our own terrestrial veil. This raises the question of how such molecules behave under extreme conditions such as when exposed to vacuum ultraviolet (VUV) radiation. VUV photons promote molecules to highly excited states that fragment in non-statistical patterns controlled by the initial femtosecond dynamics. A detailed understanding of VUV-driven photochemistry in complex organic molecules that consist of more than one functional group is a particularly challenging task. This quantum chemical analysis reports the electronic states and ionization potentials up to the VUV range (6 -11 eV) of the chlorine-substituted cumulenone series molecules. The valence and Rydberg properties of lone-pair terminated, π-conjugated systems are explored for their potential resonance with lone pairs from elsewhere in the system. The carbon chain elongation within the family ClHC n O, where n=1-4, influences the electronic excitations, associated wavefunctions, and ionization potentials of the molecules. The predicted geometries and ionization potentials are in good agreement with the available experimental photoelectron spectra for formyl chloride and chloroketene, n=1-2. Furthermore, comparison between the regular cumulenone species and the corresponding chlorinated derivatives exhibit similar behaviors especially for n=3, where the allene backbone in propadienone chloride is severely bent. Most notably for the excited states is that the Rydberg character becomes more dominant as the energy increases, with some retaining valence characters.

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“…a From initial rate and reactant pressures. 6 From initial rate of a first-order rate plot. c From integrated firstor second-order rate plot.…”

Section: 37mentioning

confidence: 99%

“…The rate coefficients kz, ka, and k4 were larger for the trans-DCE than the cts-DCE, and for each isomer they were larger in N2 than in 0 2 buffered reactions. The ozonolysis can be explained in terms of the mechanism (6) Rz f 0 3 Rz03 (7) Rz03 + Rz r %OX (8) (9) ROz + Rz R30z R403 + 0 3 -2RO + 2RO2…”

mentioning

confidence: 99%

ChemInform Abstract: GAS‐PHASE OZONOLYSIS OF CIS‐ AND TRANS‐DICHLOROETHYLENE

Blume

Hisatsune

Heicklen

1976

Chemischer Informationsdienst

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Dichloroethylene (DCE), either czs or trans, was reacted with 0 3 at 23°C in both NZ and 0 2 buffered mixtures. Both reactant consumption and product formation were monitored by infrared spectroscopy and, in some cases, 0 3 consumption was monitored by ultraviolet absorption. For thoroughly dried mixtures, the initial products were only HCClO and Oz, but geometrical isomerization also occurred. The stoichiometry of the overall reaction always wasThe HCClO was unstable and disappeared slowly in a first-order reaction which was, at least in part, heterogeneous. The products were CO and HC1 so that the stoichiometric reaction was (2) In the NZ buffered reaction, inhibition occurred as the reaction progressed and 0 2 was produced. From the reactant and product decay curves, the following rate behavior was established:The rate was always faster in NZ than in 0 2 .The rate law was complex. rate = kz [DCE] [OX] rate = k3 [DCElZ[03] high [DCE] low [DCE]

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The Photochemical Reaction between Chlorine and Formaldehyde. The Preparation of Formyl Chloride

Cited by 23 publications

References 0 publications

BIODEHALOGENATION: RAPID OXIDATIVE METABOLISM OF MONO- AND POLYHALOMETHANES BY METHYLOSINUS TRICHOSPORIUM OB-3b

BIODEHALOGENATION: RAPID OXIDATIVE METABOLISM OF MONO- AND POLYHALOMETHANES BY METHYLOSINUS TRICHOSPORIUM OB-3b

Highly-Excited State Properties of Cumulenone Chlorides in the Vacuum-Ultraviolet

ChemInform Abstract: GAS‐PHASE OZONOLYSIS OF CIS‐ AND TRANS‐DICHLOROETHYLENE

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