Can primary amine be produced using Grignard reagent?

I found a way to produce Secondary Alkyl Amines using Grignard Reagent.  
  

[![Grignard to R-NH-R1](https://i.stack.imgur.com/n6IYz.jpg)](https://i.stack.imgur.com/n6IYz.jpg)  
(source: [wiley.com](https://chemistry-europe.onlinelibrary.wiley.com/cms/asset/0c9c09d6-2ed1-4884-8823-e6d57a8a835a/slct201601464-toc-0001-m.jpg))  

  



But I want to know if I can use $\ce{HNO2}$ instead of $\ce{R-NO2}$ here to obtain $\ce{R^1-NH2}$ [say, $\ce{H-NH-R^1}$] or is there any other way to produce Primary Amines ($\ce{R-NH2}$) using Grignard Reagent ($\ce{R-Mg-X}$)?




Grignard reagents, in addition to being nucleophiles, are strong bases. Attempting to react a Grignard $\ce{RMgX}$ with nitrous acid is simply going to result in protonation of the Grignard to give $\ce{R-H}$ and magnesium nitrite.


Primary amines can be prepared from Grignard by reaction with 1,3-dioxolan-2-one *O*-sulfonyloxime.


[![enter image description here](https://i.stack.imgur.com/cS9RK.png)](https://i.stack.imgur.com/cS9RK.png)


**Ref**: Synthesis of Primary Amines by the Electrophilic Amination of Grignard Reagents with 1,3-Dioxolan-2-one O-Sulfonyloxime
Mitsuru Kitamura, Takahiro Suga, Shunsuke Chiba, and Koichi Narasaka
Organic Letters **2004** 6 (24), 4619-4621 DOI: [10.1021/ol0479951](https://pubs.acs.org/doi/10.1021/ol0479951)


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Yes indeed. Primary amines can be made using Grignard reagent. The first reported instances of such reaction was found during the 1930s where they used mono/dihaloamines and reacted with Grignard reagent to form primary amine, secondary amine and other side products like ammonia and mixed magnesium halide reaction (Ref.1a).


$$\ce{RMgX + NH2Cl -> RNH2 + MgXCl + (other side products)}$$
$$\ce{RMgX + NH2Cl -> RCl + MgXNH2 (side reaction)}$$


When dihaloamines is used, the yields are not that promising (Ref.1b):



> 
> Dibromoamine reacts with Grignard reagents to produce primary amines, secondary amines, ammonia, and nitrogen. The percentage yields of these products if Grignard reagent used is *n*-butyl magnesium chloride are ***n*-butylamine 7.8 per cent**, di-n-butylamine 2.2 per cent, ammonia 79.0 per cent, nitrogen 5.9 per cent;
> 
> 
> 


There are tons of other electrophilic aminating agent beside one mentioned in Waylander's answer. Some examples being 4,4′-Bis(trifluoromethyl)benzophenone O-sulfonyloximes (Ref.2a), 2-Imidazolidinone O-sulfonyloxime (Ref. 2b). You can find tons of other reaction which uses Grignard agent to produce amines. (Ref. 3)


**References**


1. The formation of primary amines from Grignard reagent by George H. Coleman and Charles B. Yager:
	* From Monochloroamine (1929 paper) DOI: [10.1021/ja01377a029](https://pubs.acs.org/doi/pdf/10.1021/ja01377a029)
	* From Dibromoanime (1933 paper) Link: <https://scholarworks.uni.edu/pias/vol40/iss1/53/>
2. Preparation of Primary Amines from Grignard reagents by Koichi et.al.
	* by the Alkylation of O-Sulfonyloximes of Benzophenone Derivatives(1999 paper) DOI: [10.1246/bcsj.72.1869](https://www.journal.csj.jp/doi/abs/10.1246/bcsj.72.1869)
	* with 2-Imidazolidinone O-Sulfonyloxime (2003 paper) DOI: [10.1246/bcsj.76.1063](https://www.journal.csj.jp/doi/abs/10.1246/bcsj.76.1063?src=recsys)
3. Synthesis of amines by the electrophilic amination of organomagnesium, -zinc, -copper, and -lithium reagents by Tahir Daşkapan, DOI: [10.3998/ark.5550190.0012.520](https://www.arkat-usa.org/get-file/38801/)


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