A Synthesis of Unsymmetrical Dimethyl Hydrazine Using Lithium Aluminum Hydride

Schueler, F. W.; Hanna, Calvin

doi:10.1021/ja01154a537

Cited by 24 publications

(6 citation statements)

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“…Catalytic hydrogenation was of interest for industrial purposes, and Pd/C, Pt/C, and Rh/C all yield the corresponding hydrazines, although the yield of 27 is strongly dependent on reaction conditions and the identity of 1 . , The yield of 27 by catalytic hydrogenation is improved by the inclusion of a salt (e.g., NH 4 OAc, CaCl 2 ) in the reaction mixture . Hydride reduction using LAH generally provides fair to good yields of 1,1-dialkyl or 1,1-alkylaryl 27 , ,− but diarylnitrosamines are easily over-reduced to give the parent amine and ammonia unless the reaction conditions are carefully controlled . Reduction of 1 can be effected with sodium metal in either absolute ethanol or ethanol in liquid ammonia, but the yield is lower than with LAH for many substrates .…”

Section: Reactions Of Nitrosamines In the Ground Statementioning

confidence: 99%

An Organic Chemist’s Guide to N-Nitrosamines: Their Structure, Reactivity, and Role as Contaminants

2021

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N-Nitrosamines are a class of compounds notorious both for the potent carcinogenicity of many of its members and for their widespread occurrence throughout the human environment, from air and water to our diets and drugs. Considerable effort has been dedicated to understanding Nnitrosamines as contaminants, and methods for their prevention, remediation, and detection are ongoing challenges. Understanding the chemistry of N-nitrosamines will be key to addressing these challenges. To facilitate such understanding, we focus in this Perspective on the structure, reactivity, and synthetic applications of N-nitrosamines with an emphasis on alkyl N-nitrosamines. The role of Nnitrosamines as water contaminants and the methods for their detection are also discussed.N-Nitrosamines (or simply "nitrosamines") are a class of compounds sharing the general structure 1 (Chart 1), where

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Section: Reactions Of Nitrosamines In the Ground Statementioning

confidence: 99%

An Organic Chemist’s Guide to N-Nitrosamines: Their Structure, Reactivity, and Role as Contaminants

2021

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“…We therefore explored the potential of the ocSERS strategy to detect NDMA. Briefly, as shown in Figure 6b, NDMA was reduced to UDMH using lithium aluminum hydride (LiAlH 4 ), 60 followed by measurement by the ocSERS assay. Figure 6c,d shows that a Raman signal of C�N−N stretching at 1536 cm −1 was observed, and the peak intensity exhibited a dose-dependent manner with a linear relationship (R 2 = 0.9839).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Orthogonal Chemical Reporter Strategy Enables Sensitive and Specific SERS Detection of Hydrazine Derivatives

Zhou

Chen

et al. 2022

ACS Appl. Mater. Interfaces

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Hydrazine and its derivatives are well-known environmental hazards and biological carcinogens; therefore, there is a great need for a powerful workflow solution for protecting the public from unexpected exposure to toxic contaminants. Recently, functional surface-enhanced Raman scattering (SERS) exhibits enormous benefits in sensing trace biochemical substances due to its fingerprint-like identification of individual molecules, making it an ideal method for detecting and quantifying hydrazine. Herein, for the first time, we integrated the orthogonal chemical reporter strategy with SERS to build an intelligent hydrazine detection platform (orthogonal chemical SERS, ocSERS), in which 4-mercaptobenzaldehyde was incorporated on a nanoimprinted gold nanopillar array, which acted as an orthogonal coupling partner of hydrazine to form Raman active benzaldehyde hydrazone, allowing for sensitively detecting hydrazine with a detection limit of 10–13 M in complex circumstances. Particularly, ocSERS could effectively identify the carcinogen N-nitrosodimethylamine (NDMA) after its reduction to dimethylhydrazine (UDMH), enabling ultrasensitive detection of UDMH (10–13 M). Importantly, ocSERS could not only monitor elevated levels of NDMA in ranitidine due to improper storage but also quantify NDMA in urine and blood after oral administration of NDMA-containing drugs, thereby preventing NDMA overexposure. Therefore, ocSERS represents the first click SERS sensor and may open up a new analytical field.

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“…It seems that LiA1H4 reacts with N-nitroso compounds such as N-nitrosodiphenylamine to give a moderate yield of diphenylamine (16) while the same secondary amine is produced almost quantitatively when N-nitrosodiphenylamine reacts with NaBH2S3.…”

Section: N-nitrosodiphenylaminementioning

confidence: 99%

Reactions of NaBH₂S₃ with some typical organic nitrogen compounds

Brindle¹,

Liard²,

Berube³

1976

Can. J. Chem.

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The following substrates react with sulfurated sodium borohydride, NaBH2S3, to give the corresponding products as shown by the formulas in parentheses: azobenzene [Formula: see text], azoxybenzene [Formula: see text], phenyl isocyanate (C6H5NH2, C6H5NHCH3), N-nitrosodiphenylamine ((C6H5)2NH, (C6H5)2NNH2), diphenylcarbamyl chloride ((C6H5)2NH), phenyl isothiocyanate (C6H5NH2), benzyl carbamate (C6H5CH2OH), benzyl N-phenylcarbamate (C6H5CH2OH, C6H5NH2, C6H5CH2SH), benzyl nitrite (C6H5CH2OH), benzyl nitrate (C6H5CH2OH), benzyl thiocyanate (C6H5CH2S2CH2C6H5), and pyridine-1-oxide (C5H5N). Benzotriazole, pyridine, phthalimide, and N,N′-diphenylurea were found to be stable towards NaBH2S3.The advantage of sulfurated sodium borohydride, NaBH2S3, over sodium borohydride, NaBH4, as a reducing agent was also proven when it was found that most of the above substrates were inert toward NaBH4 except for the following organic nitrogen compounds which reacted with NaBH4 to give the products indicated in parentheses: N-nitrosodiphenylamine ((C6H5)2NH), diphenylcarbamyl chloride ((C6H5)2NCH3), phenyl isothiocyanate (C6H5NHCH3), benzyl N-phenylcarbamate (C6H5CH2OH, C6H5NHCH3), and benzyl thiocyanate (C6H5CH2-S2CH2C6H5).

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A Synthesis of Unsymmetrical Dimethyl Hydrazine Using Lithium Aluminum Hydride

Cited by 24 publications

References 0 publications

An Organic Chemist’s Guide to N-Nitrosamines: Their Structure, Reactivity, and Role as Contaminants

An Organic Chemist’s Guide to N-Nitrosamines: Their Structure, Reactivity, and Role as Contaminants

Orthogonal Chemical Reporter Strategy Enables Sensitive and Specific SERS Detection of Hydrazine Derivatives

Reactions of NaBH₂S₃ with some typical organic nitrogen compounds

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A Synthesis of Unsymmetrical Dimethyl Hydrazine Using Lithium Aluminum Hydride

Cited by 24 publications

References 0 publications

An Organic Chemist’s Guide to N-Nitrosamines: Their Structure, Reactivity, and Role as Contaminants

An Organic Chemist’s Guide to N-Nitrosamines: Their Structure, Reactivity, and Role as Contaminants

Orthogonal Chemical Reporter Strategy Enables Sensitive and Specific SERS Detection of Hydrazine Derivatives

Reactions of NaBH2S3 with some typical organic nitrogen compounds

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Reactions of NaBH₂S₃ with some typical organic nitrogen compounds