ISSN 1070-3632, Russian Journal of General Chemistry, 2021, Vol. 91, No. 3, pp. 305–347. © Pleiades Publishing, Ltd.

, 2021.
Russian Text © The Author(s), 2021, published in Zhurnal Obshchei Khimii, 2021, Vol. 91, No. 3, pp. 331–375.

REVIEW

Catalytic N-Alkylation of Anilines

A. R. Bayguzinaa,* and R. I. Khusnutdinova
a Institute of Petrochemistry and Catalysis of the Russian Academy of Sciences, Ufa, 450075 Russia
*e-mail: [email protected]

Received December 9, 2020; revised February 9, 2021; accepted February 15, 2021

Abstract—The review summarizes data on modern approaches to N-alkylation of anilines using metal complex
and heterogeneous catalysts based on palladium, platinum, rhodium, nickel, iron, copper, gold supported on various
materials, as well as zeolites, metal oxides (titanium, iron, copper, and aluminum). The N-alkylation reactions of
anilines with alkyl halides, alcohols, dimethyl carbonate, aldehydes, as well as with CO2/H2 and alkylation with
alternative reagents are considered.
Keywords: aniline, N-methylaniline, N-alkylation, homogeneous and heterogeneous catalysts
DOI: 10.1134/S1070363221030014

1. Introduction 305
2. N-alkylation of anilines with alkyl halides 306
3. Alkylation of anilines with alcohols 307
4. N-methylation of anilines with dimethyl carbonate 329
5. Reductive N-methylation of anilines with formaldehyde 331
6. N-methylation of anilines with CO2/H 334
7. Unusual reactions of N-alkylation of anilines 336
8. Summary 340

1. INTRODUCTION N-alkyl-substituted anilines are valuable intermediates,

Arylamines are an important class of organic which are used in the production of plastics, explosives,
compounds that are widely used in production of photoreagents, pesticides, stabilizers, dyes, drugs,
medicines, dyes, explosives, jet and rocket fuels and polymers, and solvents [2–4].
stabilizers, photographic materials, etc. In the oil Considering the practical importance of N-mono-
refining industry, aromatic amines are used in producing and N,N-dialkylanilines, the development of efficient
ashless antioxidant and antiknock additives, as well as methods for their catalytic synthesis is an urgent task of
additives for fuels, oils, polymers and latexes. Of the modern organic chemistry. Achievements and successes
arylamines, N-methylaniline is of the greatest interest in the N-alkylation of anilines are partially reported in
for the production of gasoline as an antiknock additive. monographs and reviews [4–23]. A literature review
In addition, N-methylaniline is used as a raw material for shows, that the number of works on the N-alkylation
the synthesis of dyes, polymers, herbicides, as a solvent, of anilines using heterogeneous and metal complex
medicines, and pyroxylin powder stabilizers. Nitration catalysts is expanding every year, which prompted us
of N-methylaniline with a nitrating mixture provides to try to summarize the data on new advances in this
tetryl, a high explosive for blasting caps and intermediate area. The attraction of metal complex catalysts and their
detonators. impregnated forms is due to the fact that they are used
N,N-Dimethylaniline is used for producing polyester to solve the problem of lowering the temperature down
resins, dyes (malachite green, methylene blue), explosives, to room temperature, involving functionally substituted
and as value reagent in organic synthesis [1]. Other anilines and complex alcohols in the reaction, and

305
306 BAYGUZINA, KHUSNUTDINOV

Scheme 1.
zeolite
ArNH2 + Br Ar N + Ar N
PhH, 50qC, 5 h H
mono- di-
Ar = p-NO2C6H4

zeolite, yield (%), mono-/di- ratio: NaY, 15%, 24 : 1; KY, 79%, 19 : 1; CsY,
3.6%, 100 : 1; NaX, 25%, 4.9 : 1; KX, 14%, 5.2 : 1.
Scheme 2.
catalyst
PhNH2 + n-BuI PhNHBu + PhNBu2
PhH, boiling, 14 h
mono- di-
catalyst, yield (%), mono-/di- ratio: KX, 67%, 97 : 1; NaY, 58%, 120 : 1.
Scheme 3.
20 wt % HT5,
EtOH (aq.)
Br
ArNH2 + o
Ar N
30 C, 45 min 3 h
10 mmol 22 mmol

Ar = Ph, 4-MeC6H4, 4-ClC6H4, 4-BrC6H4, 4-FC6H4, 4-MeOC6H4, 4-NO2C6H4,

4-AcC6H4, 4-HOC6H4 (4480%); 2-CF3C6H4 (10%).

increasing the selectivity of the process with respect to 2. N-ALKYLATION OF ANILINES

mono- and dialkylanilines. This is especially important WITH ALKYL HALIDES
for N-methyl- and N,N-dimethylanilines, which have Zeolites X and Y are effective catalysts for the
close boiling points (195.6 and 194°C), and their isolation selective mono-N-alkylation of primary arylamines with
in an individual form from a mixture is very difficult. alkyl halides (Scheme 1) [27–30].
The review highlights the latest advances in catalytic N-Alkylation of aniline with alkyl halides RX (R =
N-alkylation of anilines with use of various zeolites, Me, Et, Bn; X = Cl, Br, I) in acetonitrile has been reported
Al2O3 and metal complexes (Pd, Ru, Ir, Mn, Fe, Co, in [31]. The catalyst was CsF-promoted Celite zeolite.
Ni, and Cu). In addition, the reaction mechanisms were Zeolites KX and NaY catalyze the N-alkylation of
discussed. aniline with BuI (Scheme 2) [28]. The reaction proceeded
Alkylation is one of the most important reactions that by boiling in benzene for 14 h. The yield of a mixture of
is widely used in industry for the production of a wide mono- and dibutylanilines was 58–67%, depending on
range of chemicals [24, 25]. N-Alkylation (methylation) the nature of the zeolite.
of arylamines is a complex process from the catalytic The selective N-alkylation of aniline with benzyl and
point of view, since aromatic amines are much less active allyl bromides under the action of the Al2O3–K2O catalyst
than aliphatic ones in the N-alkylation reaction [26]. (prepared by mixing Al2O3 with KNO3) in acetonitrile
According to the literature, the methods for the at 30°C has been reported in [32]. The yields of N,N-
preparation of N-alkyl-substituted anilines can be divided dibenzyl- and N,N-diallylanilines were 72 (in 7 h) and
into six groups: N-alkylation of anilines with alkyl halides, 85% (in 1 h), respectively. The catalyst retained high
alcohols, dimethyl carbonate, reductive N-methylation activity when reused.
with formaldehyde, CO2/H2, and unusual reactions of Magnesium-aluminum hydrotalcites (HT5, Mg/Al =
N-alkylation of anilines under the action of heterogeneous 53) promote di-N-alkylation of aniline and its derivatives
and homogeneous metal complex catalysts. with allyl bromide in aqueous ethanol under mild
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 CATALYTIC N-ALKYLATION OF ANILINES 307

Scheme 4.

Scheme 5.

Scheme 6.
N N
0.1 equiv. ɋX,0.2 equiv. L-3
HN N
Ar1NH2 + Ar2X Ar1NHAr2
Ph
3 equiv. K2CO3+22°&K N
1.5 equiv. O
H
L-3

Ar1 3K0H2C6H122C6H0H20HC6H3; ,

Ar2 3K0H2C6H+22CC6H122C6H (75– ; %U$U2 0HC6H (70%).

conditions (Scheme 3). Hydrotalcites can be easily under mild conditions in air and tolerated a wide range
regenerated and reused [33]. of functional groups (Scheme 6) [36].
As is known, the carbon–halogen bond in aryl halides 3. N-ALKYLATION OF ANILINES
is stronger than in alkyl halides. Examples of the use of WITH ALCOHOLS
zeolites for the N-arylation of anilines with ArX are few.
Alcohols are more convenient alkylating agents than
This problem was solved using metal complex catalysts.
alkyl halides because they are cheaper and less toxic. The
Thus, air and moisture resistant Ni(II)(σ-aryl) complexes
[Ni]-1 stabilized with N-heterocyclic carbene ligands L-1 alkylation of amines with alcohols gives rise to water as
were used for alkylation of anilines with aryl chlorides a by-product instead of amine salts, recycling of which
under mild conditions (Scheme 4) [34]. can be problematic. The production of methylamines from
The rhodium complex Rh(cod)BF 4 [Rh]-1 in ammonia and methanol is based on N-alkylation with metha-
combination with the N-heterocyclic carbene ligand nol. In this way, the world produces ~500 000 tons/year
L-2 showed high catalytic activity in the N-arylation of of methylamine, dimethylamine and trimethylamine.
substituted anilines with bromobenzene (Scheme 5) [35]. The reaction is poorly selective, requiring the separation
The catalytic system CuI–prolinamide L-3 was used of these three products. Another class of halogen-free
for the N-arylation of aliphatic and aromatic amines with N-alkylating agents are epoxides. In particular, ethylene
aryl halides in aqueous media. The reaction took place epoxide is used in the production of ethanolamines.
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308 BAYGUZINA, KHUSNUTDINOV

Scheme 7.
[Cu], H2
PhNH2 + MeOH PhNHMe
o
180250 C, 1.0 MPa

CH3OH = CH2O + H2

CH2O + C6H5NH2 = PhN=CH 2 + H2O

PhN=CH 2 + H2 = PhNHCH3

PhNHCH3 + CH 3OH = PhNH(CH3)2 + H2O

Advances in the N-alkylation of aniline with alcohols the zeolite acidic sites (stage 1), then the methyl group is
using solid acid catalysts such as zeolites, metal oxides coordinated with the oxygen atom (stage 2). Next, a six-
and their modified forms have been discussed in detail membered transition state is formed (stage 3), favorable
in the review [37]. The nature, elemental composition, for the release of water (stage 4) due to abstraction of the
and structural features of these catalysts indeed play zeolite proton and the OH group from methanol [41]. In
an important role in monitoring the conversion of the stage 5, aniline attacks the methyl group to form a new
substrates and the selectivity of N-alkylation of anilines six-membered complex. The latter decomposes (stage 7)
with alcohols [37, 38]. with the release of the target N-methylaniline and the
The main industrial method for producing N-methyl- protonated zeolite, which continues the cycle. The
aniline is the vapor-phase catalytic alkylation of aniline formation of N,N-dimethylaniline proceeds in a similar
with methanol in the presence of a copper-containing way.
hydrogenation-dehydrogenation catalyst under hydrogen Garces and co-workers [42] reported the synthesis of
atmosphere. In the Russian Federation, this process has N,N-dimethylaniline by reacting aniline with methanol
been implemented in 1996 at JSC Volzhsky Orgsintez (1 : 3) under the action of types X (RHO-zeolite) and L
(Volzhsky). The mechanism of the process can be (S zeolite, K-LTL) zeolites at 400°C. The yield of N,N-
represented by Scheme 7. dimethylaniline was 95%.
The disadvantage of this method is the low selectivity N-Alkylation of aniline with methanol can be catalyzed
for N-methylaniline (usually below 90%), in addition, the with γ-alumina [43]. Selectivity of the reaction depends
catalysts used quickly lose activity and require frequent on temperature: its increase promotes the formation of
regeneration. N,N-dimethylaniline (2–3%) is formed as N,N-dimethylaniline (Scheme 9).
a by-product [39]. The N-methylation of aniline with methanol in the
Authors [40] showed that mesoporous molecular gas phase in the presence of γ-Al2O3 at a temperature of
sieves Al-MCM-41 with a Si/Al modulus from 15 to 300–400°С has been reported in [44].
40 can be used for the N-methylation of aniline with Liquid-phase N-methylation of aniline with methanol
methanol. The reaction led to the formation of a mixture is usually carried out in the presence of mineral acids, of
of N-methylaniline and N,N-dimethylaniline in a ratio which sulfuric and hydrochloric acids are most often used.
of (3–4) : 1. The reaction is carried out in autoclaves under a pressure
In [41], Al2O3-mordenite was used as a catalyst for of over 3 MPa and at a temperature of 180–220°C [45, 46].
the N-methylation of amines, in particular aniline. The There is data on the use of a broad range of
process was carried out in a fixed bed reactor at 270°C, heterogeneous transition metals catalysts in the alkylation
10 bar and a methanol–amine ratio of 4 : 1. Under of aniline and its derivatives with alcohols: Pt/C [47]; Pd/C
these conditions, the selectivity with respect to N,N- [48], Pd/TiO2 [49, 50], PdZn/Al2O3 [51], Pd/AlO(OH)
dimethylaniline was 57% with an aniline conversion of [52], Pd/Fe2O3 [53]; NiO/θ-Al2O3 [54], Ni/γ-Al2O3 [54],
64%. NiCuFeOx [55], Ni@ [56]; Fe3O4 [57], Fe3O4/FeO [58],
A plausible reaction mechanism is presented in Scheme Fe(ClO4)3/SiO2 [59]; Ag/Al2O3 [60], Ag/Al2O3–Ga2O3
8. The process begins with the coordination of methanol at [61], Ag6Mo10O33 [62], Ag/Al2O3–FeCl3∙6H2O [63],
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 CATALYTIC N-ALKYLATION OF ANILINES 309

Scheme 8.

Scheme 9.
J-Al2O3
PhNH2 + MeOH PhNHMe + PhNMe2
gas phase
1:3

200ɨɋ conversion 45% 90% 10%

320ɨɋ conversion 99.5% 5% 85%

Scheme 10.
1 mol % Pt/C
RC6H4NH2 + MeOH RC6H4NHMe
o
0.1 equiv. NaOH, 140 ɋh
1 mmol 8192%
10 mmol

R = H, 4-Me, 4-But, 4-MeO, 4-F, 4-Cl.

Ag/GO (graphene oxide) [64]; Аu/TiO2 [65–67]; Cu/SiO2 can be assumed that the key stage of the process is the
[68], CuO–Cr2O3–Al2O3 [39], СuО–ZnO–Al2O3–CaO dehydrogenation of alcohol with the formation of an
[69], Сu-Mo/TiO2 [70], Cu0.5Zn0.5Fe2O4 [71], hydrotalcite aldehyde. Platinum on carbon is an active catalyst for the
(CuAl-HT) [72], Cu(OH)2–Al(OH)3 [73] (Table 1). The methylation of anilines with methanol. Thus, selective
list of used transition metals is not random, they all have N-monomethylation of aniline and substituted anilines
dehydrogenating and hydrogenating properties, and it with methanol was carried out using Pt nanoparticles
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310 BAYGUZINA, KHUSNUTDINOV

Table 1. Catalytic N-alkylation of anilines with alcohols

Catalytic
N-alkyla-
tion of Additional XC6H4NHR or
ROH Catalyst Т, °С Time, h Base References
anilines conditions XC6H4NR2 (yield, %)
with
alcohols
H MeOH Pd/C 150 12 NaOMe – C6H5NHMe (92) [74]
4-Me ′′ ′′ ′′ ′′ ′′ – 4-MeC6H4NHMe (91) ′′
3-Me ′′ ′′ ′′ ′′ ′′ – 3-MeC6H4NHMe (90) ′′
2-Me ′′ ′′ ′′ 16 ′′ – 2-MeC6H4NHMe (90) ′′
4-Et ′′ ′′ ′′ 12 ′′ – 4-EtC6H4NHMe (90) ′′
4-Pri ′′ ′′ ′′ ′′ ′′ – 4-PriC6H4NHMe (91) ′′
2-Pri ′′ ′′ ′′ 18 ′′ – 2-PriC6H4NHMe (91) ′′
4-MeO ′′ ′′ ′′ ′′ ′′ – 4-MeOC6H4NHMe (92) ′′
2-MeO ′′ ′′ ′′ ′′ ′′ – 2-MeOC6H4NHMe (92) ′′
4-F ′′ ′′ ′′ 12 ′′ – 4-FC6H4NHMe (84) ′′
4-Cl ′′ ′′ ′′ ′′ ′′ – 4-ClC6H4NHMe (70) ′′
4-Br ′′ ′′ ′′ ′′ ′′ – 4-BrC6H4NHMe (58) ′′
H ′′ Pd/C 130 ′′ t-BuOK – C6H5NHMe (95) [75]
4-MeO ′′ ′′ ′′ ′′ ′′ – 4-MeOC6H4NHMe (96) ′′
4-Me ′′ ′′ ′′ ′′ ′′ – 4-MeC6H4NHMe (98) ′′
H BnOH Pd/C Reflux 24 HCO2Na – C6H5NHBn (74) [48]
4-MeO ′′ ′′ ′′ ′′ ′′ – 4-MeOC6H5NHBn (88) ′′
H MeOH ′′ ′′ ′′ ′′ – C6H5NHMe (63) ′′
′′ PrnOH ′′ ′′ ′′ ′′ – C6H5NHPrn (67) ′′
′′ BnOH PdZn/Al2O3 110 0.5 - 1 atm Ar C6H5NHBn (99) [51]
′′ CyOH ′′ ′′ 8 ′′ ′′ C6H5NHCy (84) ′′
′′ OctnOH ′′ ′′ 6 ′′ ′′ C6H5NHOct (91) ′′
′′ BnOH Pd/AlO(OH) 90 20 ′′ 1 atm H2 C6H5NHBn (84) [52]
′′ OctnOH Pd/Fe2O3 150 24 ′′ – C6H5NHOct (86) [53]
′′ ′′ ′′ 170 18 ′′ – C6H5NOct2 (95) ′′
′′ EtOH Pd/TiO2 25 3 ′′ UV irradiation C6H5NHEt (95) [50]
′′ BunOH ′′ ′′ 4 ′′ ′′ C6H5NHBu (91) ′′
′′ BnOH ′′ ′′ 6 ′′ ′′ C6H5NHBn (92) ′′
3-Me ′′ ′′ ′′ 12 ′′ ′′ 3-MeC6H4NHBn (97) ′′
4-Me ′′ ′′ ′′ 14 ′′ ′′ 4-MeC6H4NHBn (82) ′′
4-Cl ′′ ′′ ′′ 12 ′′ ′′ 4-ClC6H4NHBn (82) ′′
2-Cl ′′ ′′ ′′ ′′ ′′ ′′ 2-ClC6H4NHBn (95) ′′
4-MeO ′′ ′′ ′′ 16 ′′ ′′ 4-MeOC6H4NHBn (82) ′′
3-MeO ′′ ′′ ′′ 12 ′′ ′′ 3-MeOC6H4NHBn (96) ′′
H MeOH Pt/C 140 15 NaOH – C6H5NHMe (92) [47]
4-Me ′′ ′′ ′′ ′′ ′′ – 4-MeC6H4NHMe (91) ′′
4-But ′′ ′′ ′′ ′′ ′′ – 4-ButC6H4NHMe (90) ′′
4-MeO ′′ ′′ ′′ ′′ ′′ – 4-MeOC6H4NHBn (96) ′′
4-F ′′ ′′ ′′ ′′ ′′ – 4-FC6H4NHMe (88) ′′
4-Сl ′′ ′′ ′′ ′′ ′′ – 4-ClC6H4NHMe (81) ′′
H OctnOH NiO/θ-Al2O3 144 3 – – C6H5NHOctn (99) [54]
′′ ′′ Ni/γ-Al2O3 ′′ ′′ ′′ – C6H5NHOctn (60) ′′
′′ EtOH NiO/θ-Al2O3 ′′ 24 ′′ – C6H5NHEt (87) ′′

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 CATALYTIC N-ALKYLATION OF ANILINES 311

Table 1. (Contd.)
Catalytic
N-alkyla-
tion of Additional XC6H4NHR or
ROH Catalyst Т, °С Time, h Base References
anilines conditions XC6H4NR2 (yield, %)
with
alcohols
′′ BnOH NiO/θ-Al2O3 ′′ 5 ′′ – C6H5NHBn (99) [54]
′′ CyOH ′′ 130 24 ′′ – C6H5NHCy (94) ′′
′′ ′′ NiCuFeOx 144 ′′ – Sealed tube C6H5NHCy (98) [55]
′′ BnOH ′′ ′′ ′′ ′′ ′′ C6H5NHBn (94) ′′
4-Me MeOH ′′ ′′ ′′ ′′ ′′ 4-MeC6H4NHMe (89) ′′
H BnOH Ni@a 183- 6 – – C6H5NHBn (76) [56]
184
′′ HexnOH Ni@a Reflux ′′ ′′ – C6H5NHHexn (87) ′′
′′ BnOH Fe3O4 90 2 t-BuOK – C6H5NHBn (88) [57]
4-MeO ′′ ′′ ′′ ′′ ′′ – 4-MeOC6H4NHBn (84) ′′
H ′′ Fe3O4/FeO 40 0.5 t-BuOK – C6H5NHBn (95) [58]
′′ Ph2CHOH Fe(ClO4)3/SiO2 85 6 – – C6H5NHCHPh2 (92) [59]
H MeOH CuO–Cr2O3– 240 1.4 h–1 ′′ Flow reactor C6H5NHMe (97%) [39]
Al2O3
H BunOH Cu/SiO2 280 0.4 h–1 ′′ ′′ C6H5NHBun (96%) [68]
H EtOH СuО–ZnO– 230 0.4 g/h ′′ Flow reactor/ C6H5NHEt (84.5) [69]
Al2O3–CaO H2
H MeOH Сu–Mo/TiO2 25 21 ′′ UV irradiation C6H5NMe2 (46) [70]
–1
H ′′ Cu0.5Zn05Fe2O4 300 3.58 h ′′ Flow reactor C6H5NHMe (59) [71]
4-MeO ′′ Cu0.5Zn0.5Fe2O4 ′′ ′′ ′′ ′′ 4-MeOC6H4NHBn (34) ′′
H BnOH CuAl–HTb 160 9 K2CO3 – C6H5NHBn (91) [72]
4-MeO ′′ ′′ ′′ ′′ ′′ – 4-MeOC6H4NHBn (97) ′′
H ′′ Ag/Al2O3 120 1 Cs2CO3 – C6H5NHBn (99) [60]
′′ ′′ Ag/Al2O3– 110 26 NaH – C6H5NHBn (82) [61]
Ga2O3
′′ DecnOH Ag6Mo10O33 160 20 t-BuOK – C6H5NHDecn (84) [62]
′′ BnOH ′′ ′′ 12 ′′ – C6H5NHBn (93) ′′
′′ ′′ Ag/GOc 100 12 Cs2CO3 – C6H5NHBn (99) [64]
′′ ′′ Ag/Al2O3– 144 24 – – C6H5NHBn (94) [63]
FeCl3∙6H2O
′′ ′′ Аu/TiO2 110 14 – 5 atm N2 C6H5NHBn (92) [67]
′′ MeOH ′′ 20 4 – UV irradiation C6H5NMe2 (61) [66]
′′ EtOH ′′ ′′ ′′ ′′ ′′ C6H5NHEt (74) ′′
′′ PrnOH ′′ ′′ ′′ ′′ ′′ C6H5NHPrn (89) ′′
′′ BunOH ′′ ′′ ′′ ′′ ′′ C6H5NHBun (87) ′′
a
Ni@ – nickel nanoparticles;
b CuAl-HT – hydrotalcite;
c GO – graphene oxide.

supported on activated carbon (Pt/C) in the presence A plausible reaction mechanism was proposed, which
of a NaOH base [47]. The yields of the corresponding is shown in Scheme 11. First, methanol is dehydrated
N-methylanilines were 81–92% (Scheme 10). The Pt/C with the release of formaldehyde and two hydrogen
catalyst retains high selectivity when reused. atoms fixed on the Pt surface. For the reaction to proceed
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312 BAYGUZINA, KHUSNUTDINOV

Scheme 11.

PhNH2 + CH3OH PhNHCH3

Pt
1 3

PtH2
CH2
H 2
N
O
H PhNH2

Scheme 12.

NHR NH2 NR2

0.42 mol % Pd/Fe2O3 0.42 mol % Pd/Fe2O3
+ ROH
o o
150 C, 24 h 170 C, 18 h
1:3
n
n n
R = Oct (86%), Dec (80%). R = Octn (95%), Dec (85%).

Scheme 13.

successfully, the presence of NaOH is necessary, which selectivity and tolerance to functional groups in anilines
promotes the dehydrogenation of methanol through and alcohols, which made it possible to use a wide range
deprotonation. In a number of works, NaOMe, ButOK, of substrates (Table 1). The problem of selectivity is
NaHCO3, K3PO4, Cs2CO3 were used as a base instead especially acute for the preparation of N-methyl- and
of NaOH. In the next step, CH2O reacts with an amine N,N-dimethylanilines, which have close boiling points
to give an imine (step 2). At the final step, imine 1 is (195.6 and 194°C), and their separation is very difficult.
hydrogenated to form N-methylaniline. As is known, Palladium-based catalysts Pd/C, Pd/AlO(OH),
the condensation of formaldehyde with primary amines Pd/Zn/Al2O3, and Pd/Fe2O3 are active in the alkylation
with the formation of imine 1 proceeds easily. The kinetic of anilines with alcohols in a wide temperature range of
results in combination with the density functional theory 90–170°C (Table 1). Thus, in the presence of Pd/Fe2O3
(DFT) calculations indicate that the high efficiency catalyst, an increase in temperature to 170°C leads to
of Pt/C catalyst is due to the moderate strength of the di-N-alkylation of aniline with 1-octanol and 1-decanol
platinum–hydrogen bond [47]. even with shorter heating (Scheme 12) [53].
Transition metals catalysts for the alkylation of It is known that the Pd/TiO2 catalyst under UV
anilines with alcohols have three important advantages irradiation (λ > 300 nm) promotes the N-monoalkylation
over acids and zeolites: the possibility of carrying out the of aniline and its derivatives with alcohols (ethanol,
reaction at a lower temperature, the ability to control the n-butanol, and benzyl alcohol) under mild conditions at
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 CATALYTIC N-ALKYLATION OF ANILINES 313

Scheme 14.
NH2 NHR NR2
Au/TiO 2
+ ROH +
hȞ, 4 h

R = Me (mono-/di- ratio = 5.5 : 60.7%), Et (74.4 : 8.9%), Prn (89.1 : 2.4%),

Bun (87.8 : 0%), Hexn (52.5 : 0%).

Scheme 15.
NH2 NHCH2C6H4R2
0.04 ɝFe3O4/FeO
R1 + R2C6H4CH2OH R1
40oC, 0.51 h, 1.5 mL H2O

R2 = H, R1 = H (95%), 4-MeO (91%), 4-Ac (39%), 3-NO2 (82%), 4-NO2 (61%), 4-Br (81%), 4-Cl (69%),
4-F (39%); R1 = H, R2 = 4-Me (91%), 4-MeO (94%), 4-Cl (92%), 4-NO2 (78%), 2-NO2 (70%).

Scheme 16.

Ni@ or Co@
PhNH2 + ROH o
PhNHR + PhNR2
160183 C
n n
Ni@: R = Bn (mono-/di- ratio = 46.6 : 44%), Oct (38.5 : 15.5%), Hex (87 : 3.5%);
Co@: R = Bn (36 : 15%).

25°C [50]. Under these conditions, the corresponding proceeded in moderate yields, 58 and 60% respectively
N-methylanilines were obtained in quantitative yield (40°C, 3 h).
(Scheme 13). Under similar conditions (Pd/TiO2, hν, The authors [56] carried out the alkylation of aniline
15–20 h), methanol reacted with aniline to give N,N- with alcohols using as a catalyst cobalt and nickel
dimethylaniline in 81% yield [49]. nanoparticles with a size of less than 20 nm, capable of
UV irradiation also activates the Au/TiO2 catalyst. forming a homogeneous colloidal solution. It was found
Photocatalytic N-alkylation of aniline with aliphatic that both secondary and tertiary amines were formed
primary alcohols in the presence of Au/TiO 2 took during the reaction (Scheme 16). The reaction took
place under mild conditions (50°C, 4 h) [66]. In the place at an elevated temperature (≥150°C). Therefore, in
laboratory, this method is suitable only for high-boiling
case of methanol, the major reaction product was
alcohols and amines.
N,N-dimethylaniline. Ethanol, n-propanol, n-butanol,
n-hexanol provided monoalkyl derivatives (Scheme 14). A special place among the catalysts for the N-alkylation
of anilines is occupied by cyclopentadienyl carbonyl
A very active catalyst for the N-alkylation of anilines
iron complexes (Knölker’s complexes) [Fe]-1–[Fe]-6
with benzyl alcohol and its derivatives are Fe 3O 4 (Scheme 17) [57, 76–83]. They belong to a unique class
nanoparticles prepared from Fe2+ and Fe3+ salts under of complexes, one of the ligands of which is directly
the influence of an external magnetic field (EMF). The involved into the catalytic process at the stage of hydrogen
reaction proceeded at 40°С for 0.5–1 h (Scheme 15). The transfer, which makes it unnecessary to use an additional
separation of the catalyst and the reaction products was reagent – bases, which, by deprotonation, promote
carried out using an external magnet, thus recovering the dehydrogenation of alcohols with the formation
more than 95% of the catalyst. The catalyst retains its of aldehydes. However, in the absence of bases, it is
activity in 4 repeated runs [58]. A similar reaction of necessary to increase concentration of complexes [Fe]-1–
aniline with aliphatic alcohols (methanol and ethanol) [Fe]-6 up to 10 mol %. At lower concentrations, bases
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314 BAYGUZINA, KHUSNUTDINOV

Scheme 17.

Ph C6H4CF3-p SiMe3

O O O

H -p Fe SiMe3
Fe
Ph Fe C6 4CF3
OC CO OC CO OC CO
CO CO CO
[Fe]-1 [76, 78] [Fe]-2 [78] [Fe]-3 [77, 80, 81]

C6H4OMe-p Ph Ph
N Ph

O O O
N Ph
H Ph Ph
Fe C6 4OMe-p Fe Fe
OC CO OC CO
OC CO CO
CO CO
[Fe]-4 [82, 83] [Fe]-5 [82, 83] [Fe]-6 [76]

Scheme 18.

(for example, CsOH [82], K2CO3 [83] or ButOK [57]) imine. The [Fe]-7 complex serves as a donor of two
were used to achieve high yields of the target products. hydrogen atoms (Scheme 19).
Knölker complexes are tolerant to most functional For the successful N-alkylation of aniline and its
groups both in the substituted anilines and alcohols, derivatives with methanol (Scheme 20), which is
which makes it possible to introduce a wider range of hardly dehydrogenated in the presence of the Knölker
these substrates into the reactions. Thus, the N-alkylation complex [Fe]-5, special conditions are required: the
of anilines with alcohols catalyzed by the iron complex
presence of a base (CsOH) and hydrogen. According
[Fe]-3 (Scheme 18) has been reported in [81].
to DFT calculations, molecular hydrogen acts not only
Scheme 19 shows a presumable reaction mechanism.
as a reducing agent, but also as a reagent for shifting
At the first stage, trimethylamine oxide attacks the [Fe]-3
thermodynamic equilibrium [82].
complex, leading to the release of a vacancy in the [Fe]-3
complex. At the next stage, alcohol 2 is dehydrogenated to According to [77], silver fluoride has a promoting
aldehyde 3, and the cyclopentadienone ligand serves as an effect in relation to the Knölker complex [Fe]-3. In the
acceptor of one hydrogen atom. Further, the condensation presence of the [Fe]-3–AgF system, it was possible to
of the aldehyde with the amine occurs to form imine 4. carry out the N-alkylation of aniline and its derivatives
The process is completed by the hydrogenation of the with secondary alcohols (Scheme 21).
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 CATALYTIC N-ALKYLATION OF ANILINES 315

Scheme 19.
SiMe3 SiMe3
OH
Me3NO
O O
CO R1 R2
2
Fe SiMe3 Fe SiMe3
OC CO OC O
CO CO
[Fe]-3 [Fe]-3a R1 R2 SiMe3
3
LA
LA R3 OH
N R3NH2
NHR3
Fe SiMe3
R1 R2 OC H
R1 R2 CO
4
5 [Fe]-7

Scheme 20.
NH2 NHMe
2 mol % [Fe]-5, 10 mol % CsOH
R + MeOH R
110 oC, 16 h

R = H, 4-MeO, 4-Me, 4-Br, 3-Br, 2,5-(CF3)2 (9499%); R = 4-I, 4-CN (87%).

Scheme 21.
H
10 mol % [Fe]-3 N R3
NH2 OH 40 mol % AgF
R1 + R1
R2
R2 R3 o
toluene, 110 C, 24 h
5 equiv. 2697%
i i n
R1 = H, 4-MeO, 2-MeO, 3-MeO, 4-Cl; R 2 = Me, Et; R3 = Hexn, Me, Pr , Pr CH2, Pent , Ph,
4- MeOC6H4; R2R3 = (CH2) (CyOH).

The presence of bases is not required when using the 1,2,4-trimethylbenzene (1,2,4-TMB) medium. The yield
iron hydride complex [Fe]-8 as a catalyst for N-alkylation of N-benzylaniline was 85% (Scheme 24).
(Scheme 22) [84]. The synthesis of N-methyl- and N,N-dimethyl-
High activity in the N-alkylation of aniline and substituted anilines by reacting aniline with methanol in
its derivatives with secondary alcohols shows iron the presence of a FeCl3·6H2O catalyst in a CCl4 medium
perchlorate supported on silica gel Fe(ClO4)3/SiO2 has been reported in [86]. So, at 140°С after 4 h (CCl4–
(Scheme 23) [59]. MeOH, 1 : 2), the reaction resulted in the formation
According to [85], iron bromide catalyzes the of N-methyl- and N,N-dimethylanilines in equimolar
N-alkylation of aniline with benzyl alcohol in the amounts. After 8 h, N,N-dimethylaniline was the major
presence of a ligand L-4, DL-pyroglutamic acid, in a product (Scheme 25).
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316 BAYGUZINA, KHUSNUTDINOV

Scheme 22.

Scheme 23.
R2 R2 H
H R4
NH2 R4 N
Fe(ClO4)3/SiO2
+ HO R3 R3
CHCl3, ', 2.56 h
R1 H R1
85–92%
R1 = H, Br, NO2, Cl, CN, MeO; R2 = H, NO2; R3 = Me, Ph; R4 = Me, Ph, 4-ClC6H4.

Scheme 24.

Scheme 25.
CCl4–MeOH (1 : 2)
PhNHMe + PhNMe2
140°C, 4 h
FeCl3Â6H2O 33% 37%
PhNH2

CCl4–MeOH (1 : 4) +
PhNMe2
140°C, 8 (16) h NMe2 NMe2
92% (47%) 6% (45%)

Scheme 26.
[Fe]
MeOH + CCl4 MeOCl HCHO (1)
–CHCl 3 –HCl

MeOH + HCl MeCl + H2O (2)

The reaction proceeded in the absence of a base with In the case of 1,4-butane- and 1,5-pentanediols, the
the obligatory presence of CCl4; therefore, the authors reaction also did not stop at the N-alkylation stage, but
believe that methyl chloride acts as an alkylating agent
in the studied reaction, the formation of which can be ended with the formation of N-arylpyrrolidines and
represented by Scheme 26. N-arylpiperidines [87, 88].
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 CATALYTIC N-ALKYLATION OF ANILINES 317

Scheme 27.

Me
NHC3H5 Co(acac)2–P(CH2CH2PPh2)3
F
BAr 4 N
N PPri2
N N [Co]-2 [91] Co PCy2
Cy2P Co Cl
HN N NH CH2SiMe3 i
Pri2P Co PPri2 N PPr 2
Cp*CoI2 - PCy3 [Co]-4 [89] Me
Cl Cl
[Co]-5 [93]
[Co]-1 [90] [Co]-3 [92]

Scheme 28.

Scheme 29.

In a series of works [89–93], cobalt complexes [Co]-1– generated by dissociation of [Co]-3 complex. The key
[Co]-5 (Scheme 27) were used as catalysts for the stage of the process is the deprotonation of alcohol, and
N-alkylation of aniline and its derivatives with alcohols. the deprotonating agent is not the base, but aniline itself
An effective and selective catalyst for the N-alkylation (stage 2). At the same time, a cobalt alkoxy complex
of anilines with aliphatic and benzyl alcohols is [Co]-1 [Co]-3.2 is formed, which, by releasing acetophenone
complex, in the presence of which the reaction proceeds (stage 3), is converted into a hydride complex
under mild conditions (80°C, 20–24 h), and the yields of [Co]-3.3. The coordination unsaturated hydride complex
the corresponding N-alkyl- and N-benzylanilines reach [Co]-3.3 is stabilized by PCy3 (step 4), then takes part in
90% (Scheme 28) [90]. the hydrogenation of the imine (step 6), which is formed
The [Cp*Co(PCy)3I2] complex [Co]-3 showed high by the reaction of acetophenone with aniline (step 5).
activity in the N-alkylation of aniline and its derivatives The process ends with the transfer of a proton from
with secondary alcohols (Scheme 29) [92]. A probable PhNH3+I– to [Co]-3.5 complex with the formation of
reaction mechanism is shown in Scheme 30. According the final product PhCH(Me)NHPh and the regeneration
to quantum-chemical calculations, the catalytically active of aniline (stage 7). It should be noted that PCy3 takes
intermediate is [Cp*CoI2] complex. The complex is easily part in the stabilization of not only the hydride complex
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 91 No. 3 2021
318 BAYGUZINA, KHUSNUTDINOV

Scheme 30.

>ɋS &R 3&\3)I] +I í

ɋS &R 3&\3)I2
[Co]-3
>ɋS &R,2]2
í3&\ 3 3&\3
VWHS
OH
1+3K ɋS &R,2
3K1+2 + 3K1+2 + 3K
[Co]-3.1
3K VWHS VWHS
3K1+3+I í
3K1+3+I í

&S &S
VWHS
&R &R
1+3K O
I 1 3K 3K1+2 I O
H
[Co]-3.5 3K íH 2O 3K
3K 3K
[Co]-3.2
í3&\3 3&\3 EK\GULGHHOLPLQDWLRQ

LQVHUWLRQ í3&\3 3&\3

&S &S
VWHS VWHS
&R I &R
I H &S
&\33 1
[Co]-3.3 &R I
3K &\33 O
í3&\3 3&\3
[Co]-3.7 VWHS 3K
&S
[Co]-3.6
&R I
&\33 H
[Co]-3.4

[Co]-3.3, but also [Co]-3.2 and [Co]-3.5 complexes (in most active complex was [Co]-5, in the presence of which
this case, [Co]-3.6 and [Co]-3.7 are formed, creating it was possible to involve a wide range of substituted
conditions for the reaction as a whole). anilines and primary alcohols in the N-alkylation reaction
For the efficient N-alkylation of both aromatic and (Scheme 32) [93].
aliphatic amines with alcohols, we used the cobalt
Surprisingly, manganese complex showed high
complex [Co]-4 containing a pincer ligand PNP in the
coordination sphere (Scheme 31) [89]. activity in the reaction of N-alkylation of anilines
Co(II) complexes [Co]-5–[Co]-8 stabilized by the with alcohols. For the N-alkylation of aniline and its
N,N′-bis(diisopropylphosphino)-N,N′-dimethyl-1,3- derivatives with alcohols, four types of manganese
diaminobenzene ligand (PCP) proved to be effective complexes [Mn]-1–[Mn]-4 with various pincer ligands
catalysts for N-alkylation of anilines with alcohols. The were used (Scheme 33) [94–99].
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 CATALYTIC N-ALKYLATION OF ANILINES 319

Scheme 31.
NH2 2 mol % [Co]-4 NHMe
R1 + R2CH 2OH 4 A MS, toluene, R1
', 48 h

1.2 equiv. 80–95%

i
R1 = H, 2-MeO, 4-Cl; R2 = Ph, 4-FC6H4, Pr .

Scheme 32.

Me Me Me
Me
N N N
N PPri2 PPri2 PPri2
PPri2
Cl
Co Cl Co Me Co CH2SiMe3
Co Cl
i
N PPr 2
i
N PPr 2
i
i
N PPr 2 N PPr 2
Me Me Me
Me

[Co]-5 [Co]-6 [Co]-7 [Co]-8

NH2 NHMe
2 mol % [Co]-5, 1.3 equiv. ButOK
R1 + R2CH2OH ɨ R1
toluene, 80 ɋ16 h

72–91%

R1 = H, 4-Me, 4-MeO; R2 = Ph, 4-ClC6H4, 4-Me2NC6H4, Me2CHCH2CH2, PhCH=CHCH2.

Scheme 33.
Ph

N N OC Br CO
PPri2 N.. HN Br PPri2
Br HN N NH Mn .N
..
. .. . Mn
N Mn CO .. ..
Pr2iP Mn PPri2 N CO N
CO CO
PPri OC CO Br P
2
Pri2

[Mn]-1 [94–96] [Mn]-2 [98] [Mn]-3 [99] [Mn]-4 [94–96]

The indicated complexes [Mn]-1–[Mn]-4 are active in the reaction completion at the stage of imine 7 formation
the N-alkylation of anilines with alcohols in the obligatory (Scheme 34) [98].
presence of bases such as ButOK [94–99], KH [97], or
Authors [98] found that the starting catalytically active
ButONa [98]. Structure and nature of the catalyst has a
intermediate is the manganese hydride complex [Mn]-5,
decisive influence on the reaction outcome. In particular,
the alkylation of aniline and its derivatives with alcohols which reacts with ButOK or ButONa to form complexes
in the presence of the [Mn]-2 complex in the presence of [Mn]-6 and [Mn]-7. It turned out that the potassium
ButOK afforded secondary amines 6 as the main reaction complex [Mn]-6 reacts with N-benzylideneaniline 40 times
products, while replacing ButOK with ButONa resulted in faster than the complex with sodium [Mn]-7, which can
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320 BAYGUZINA, KHUSNUTDINOV

Scheme 34.

Scheme 35.

Scheme 36.

explain the difference in the behavior of ButOK and Under relatively mild conditions (80°C, 24 h), aniline
ButONa in the studied reaction (Scheme 35). and its derivatives can be N-alkylated with alcohols under
The complex of manganese [Mn]-3 with a carbene the action of a manganese complex [Mn]-4 containing
ligand showed a uniquely high activity in the N-alkylation a tridentant PNP ligand in the coordination sphere
of anilines with aliphatic alcohols, benzyl alcohol and its (Scheme 37) [94].
derivatives; the reaction takes place at room temperature The N-alkylation of aniline with benzyl alcohol and
(Scheme 36) [99]. its derivatives in the presence of K2CO3 is catalyzed
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 CATALYTIC N-ALKYLATION OF ANILINES 321

Scheme 37.

Scheme 38.

NH2 NHCH2R2
1020 mol % MnO2
R1 + R2CH2OH R1
1020 mol % K2CO3, air, 135oC, 24 h

1.0 mmol 1.2 mmol 8498%

R1 = H, 4-Me, 3-Me, 4-EtO, 4-Cl, 3-Cl, 2-Cl; R2 = Ph, 4-MeOC6H4, 4-MeC6H4.

Scheme 39.

manganese dioxide (Scheme 38). The reaction takes aniline and its derivatives, the activity and selectivity of
place in air, but its preparative value is low, since MnO2 which depend on the valence state of ruthenium and the
and K2CO3 are solids, which creates great difficulties for nature of the ligand environment (Scheme 39) [101–110].
scaling [100]. For the reaction to proceed successfully, the presence of
In a series of works, ruthenium complexes [Ru]-1– such bases as ButOK [101, 102, 110, 111], ButOLi [107],
[Ru]-13 were used as catalysts for the N-alkylation of K2CO3 [109], NaOMe [112], Na [113], which apparently
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322 BAYGUZINA, KHUSNUTDINOV

Scheme 40.

Scheme 41.

take part in the dehydrogenation of alcohols with the this complex ranges from 600 to 3100, which makes it
formation of aldehydes by deprotonation. possible to successfully carry out the reaction at a low
The most active catalyst for the N-alkylation of aniline, concentration (0.02 mol %).
4-chloroaniline and m-toluidine with aliphatic alcohols Another ruthenium complex [Ru]-13 with the NNN-
(EtOH, BunOH, HexnOH) and aromatic alcohols is the pincer ligand, which contains 1,10-phenanthroline
ruthenium complex [Ru(cod)Cl2]n [Ru]-1 in combination and 2-hydroxypyridine fragments in the molecule
with 1,3,5-triaza-7-phosphoadamantane ligand L-5. In the (Scheme 42) [116], has a uniquely high efficiency (TON
presence of the indicated catalytic system, the reaction 42840) in the N-alkylation of anilines. In addition,
proceeds at 55°С for 12–36 h (Scheme 40) [114]. complex [Ru]-13 is resistant to air and moisture.
Most of the ruthenium complexes facilitate the The iridium complexes [Ir]-1–[Ir]-14 (Scheme 43) are
N-alkylation of anilines with alcohols in the temperature effective and rather versatile catalysts for the N-alkylation
range of 80–120°C. Despite the considerable reaction of aniline and its derivatives with alcohols.
time (12–36 h), the N-alkylation of anilines proceeds It should be noted that most of these catalysts are
with selective formation of monoalkyl derivatives. To active in the N-alkylation of anilines in the presence of
obtain dialkyl derivatives, more rigid conditions are bases such as NaOH, KOH, ButOK, NaOMe, NaHCO3,
required. Thus, N-dialkylation of aniline with ethanol, K2CO3, K3PO4, and Cs2CO3.
n-propanol, n-butanol in the presence of [RuCl2(PPh3)3] In a number of works, the N-alkylation of anilines with
[Ru]-4 occurs at 180°C for 5 h. The yield of N,N-diethyl-, alcohols in the presence of Ir-containing catalysts was
N,N-dipropyl- and N,N-dibutylaniline was 74, 88, and studied using methanol as an example. In particular, the
79%, respectively [115]. complexes [Ir]-5 [121], [Ir]-6 [122], [Ir]-7 [123], [Ir]-11
A very active and versatile catalyst for the N-alkylation [126], and [Ir]-13 [128] promote selective formation of
of aniline and its derivatives with alcohols is the monomethylanilines with a yield of up to 96%. In this
ruthenium complex [Ru]-12 with a pincer-type ligand case, the product yields depend on the nature and position
(Scheme 41) [113]. The turnover number (TON) of of the functional groups in the starting anilines.
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 CATALYTIC N-ALKYLATION OF ANILINES 323

Scheme 42.

NH2 NHR2
0.2 mol % [Ru-13]
R1 + R2OH R1
25 mol % ButOK, dioxane, 110°C, 16 h

R2 = Bn, R1 = H (87%), 4-Me (58%), 3-Cl (78%), 4-MeO (79%), 4-Cl (85%), 4-Br (82%), 2,4-(MeO)2 (76%);
R1 = H, R2 = 4-MeOC H CH2 (77%), 4-MeC6H4CH2 (71%), 4-ClC6H4CH2 (81%), 4-BrC6H4CH2 (71%),
furfuryl (67%), 2 -thienyl-CH2 (66%), Bun (51%), CH2Cy (69%), 1-CH2- naphthyl (83%).

NH2 NHMe
1mol % [Ru-13]
R + MeOH R
0.5 mmol NaOMe, 110oC, 24 h

R = H (84%), 3-Cl (81%), 4-MeO (79%), 4-Br (74%).

Scheme 43.

N-Monomethylation of aromatic anilines with The iridium complex [Ir]-9, obtained by the reaction
methanol is catalyzed with the iridium complex of [Ir]-1 with the P,N-ligand L-6 Py2NPPri2, turned out
[Cp*IrCl2]2 [Ir]-6 in the presence of NaOH (Scheme 44) to be an effective catalyst for the selective N-alkylation
[122, 130]. of anilines with benzyl alcohol. The reaction proceeded
According to [121], iridium complexes [Ir]-5 facilitate under mild conditions (70°C, 24 h) to form the
three types of transformations: methanol dehydrogenation corresponding N-benzylanilines in a yield of up to 97%
with the formation of formaldehyde, CH2O condensation (Scheme 46) [117, 131].
with aniline, and imine hydrogenation (Scheme 45). The The versatile catalyst for the N-alkylation of anilines
role of the base, which is used in a stoichiometric amount, is the iridium complex [IrCp*I2]2, which allows the
is to deprotonate methanol. N-alkylation of aniline and its 4-methyl-, 4-methoxy-,
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324 BAYGUZINA, KHUSNUTDINOV

Scheme 44.

Scheme 45.

NH2 NHMe
5 mol % [Ir]-5
R + MeOH R
0.13 mmol KOH,
120oC, 5 h, MW
0.13 mmol 7196%

R = 4-MeO (95%), 4-Br (95%), 4-NO2 (60%), 4-CF3 (14%), 4-NH2 (54%), 2-Me (29%), 2,6-Me2 (1%).

Scheme 46.
NH2 NHBn
0.05–2 mol % [Ir(cod)Cl]2 [Ir ]-1, Py2NPPri L-6
R + BnOH R
1.1 equiv. ButOK, 0.2 mL diglyme, 70ɨɋ, 24 h

<98%
R = H, 4-MeO, 4-Cl, 3,5-Me2, 3,5-Cl2, 2-Ph, 2-Cl.

Scheme 47.

Scheme 48.
0.2 mol % [Ir]-12
PhNH2 + ROH PhNHR
autoclave

R = Bn (90%, 150oC, 2.5 h), Et (100%, 80oC, 2 h), But (0%, 150oC, 2 h).

4-chloro-, 4-bromo-, 4-carbomethoxy-, and 4-cyano and secondary alcohols was also catalyzed by the
derivatives with a range of primary and secondary [Cp*IrCl2]2 complex [Ir]-6 in the presence of NaHCO3
alcohols (Scheme 47) [119]. [133].
In [132], the [Cp*IrCl2]2 (5 mol %) complex [Ir]-6 The N-alkylation of aniline with alcohols was carried
with the addition of K2CO3 (5 mol %) was used for out under a multifunctional heterogeneous catalyst
the N-alkylation of aniline with benzyl alcohol. The [Ir]-12, which is an metal organic framework based on
benzylaniline yield (110°C, 17 h) was 88%. The Ir–Zr. This catalyst was effective for the synthesis of
N-alkylation of aniline and its derivatives with primary various N-substituted anilines in air in the absence of a
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 CATALYTIC N-ALKYLATION OF ANILINES 325

Scheme 49.

Scheme 50.

NH2 1 mol % [Ir]-11 NHMe

R + MeOH R
0.30.5 equiv. Cs2CO3, 120ɨɋ, 12 h

8291%

R = 2-F, 3-Cl, 4-Br, 4-CN, 4-CO2Me, 3-MeO.

Scheme 51.

Scheme 52.

base (Scheme 48). The catalyst was removed and reused In [126], for the N-methylation of anilines with
without significant loss of activity [127]. methanol, it was proposed to use the iridium complex
A very active catalyst for the monomethylation of [Ir]-11 with 2,2′-dibenzimidazole ligand, which takes
functionally substituted anilines is an iridium complex part in the transfer of hydrogen from methanol to the
[Ir]-13 with a heterocyclic carbene ligand (NHC-Ir). It is
noteworthy that the NHC-Ir catalyst is the solid and can imine [Ir]-15 (Scheme 50). Another function of the base
be easily recovered and used more than 20 times without is noteworthy: it reacts with the complex, freeing up the
loss of activity and selectivity (Scheme 49) [128]. coordination site for iridium (Scheme 51).
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326 BAYGUZINA, KHUSNUTDINOV

Scheme 53.

NH2 0.1 mol % Ir NCs

NHMe
R + MeOH R
0.5 mmol Cs2CO3, 150ɨɋ, 24 h

R = H (78%), 4-Me (80%), 4-Cl (87%).

Scheme 54.
5 mol % [IrCl(cod)2] [Ir]-1, 1 mol % [Ir]-14,
2 mol % PyN(Me)PPh2 L-7 50 mol % NaHCO3
PhNHBn PhNH2 + BnOH PhNHBn
MS, toluene, 110°C, 45 h
0.010.5 mol % ButOK,
36% toluene (1 mL), 110°C, 24 h 98%

Scheme 55.

H
NH2 NHR PPri2
0.1 mol % [Os]-2
+ ROH N Os CO
200oC, 30 h
PriP X
2

R = Me (60%), Et (36%), Penti (45%), Bn (37%). [Os]-1: X = Cl; [Os]-2: X = H

Selective N-monomethylation of aniline with methanol the N-alkylation of anilines with alcohols, which differ
is catalyzed by the iridium nanocatalyst Ir@YSMCNs significantly in activity. Thus, the osmium complexes
(iridium nanoparticles encapsulated in mesoporous [Os]-1 and [Os]-2 showed low activity in the N-alkylation
carbon nanospheres) (Scheme 52) [134]. The catalyst is of anilines with alcohols. The reaction took place
stable and does not lose activity with repeated use. under rigid conditions (200°C, 30 h). Despite this, the
For the methylation of anilines with methanol, yields of N-alkyl(benzyl)anilines did not exceed 60%
iridium nanoclusters (1–1.5 nm in size) stabilized with (Scheme 55) [138].
dimethylformamide were used. The TON for the indicated
Copper(II) acetate (1 mol %) promoted the N-alkylation
catalyst is 310 (Scheme 53) [135].
of aniline with benzyl alcohol at 130°C for 48 h. The yield
N-Monoalkylation of arylamines with benzyl of N-benzylaniline was 99%. The reaction proceeded in
alcohol is catalyzed by the iridium-containing complex
the presence of 100 mol % of ButOK in dioxane [139,
[IrCl(cod)2] [Ir]-1 activated with the P,i-ligand. The yield
140].
of N-benzylaniline was 36% [136]. In [129], an iridium
complex [Ir]-14 with a carbene ligand was used for the The synthesis of N-alkyl- and N,N-dialkylanilines
N-alkylation of aniline with alcohols. High yields of was carried out by the reaction of aniline and substituted
reaction products were observed only for benzyl alcohol. anilines with primary and secondary alcohols under the
For the reaction to proceed successfully, 50 mol % of action of CuCl2·2H2O and CuBr2 in the presence of a
NaHCO3 base is required (Scheme 54). CCl4 promoter (Scheme 56) [141]. The detection of
In [137], N-methylaniline was alkylated with benzyl hydrogen chloride (which was formed by the hydrolysis
alcohol in the presence of 15 mol % of AgOTf and of CCl4) by mercurometric titration suggests that HCl
15 mol % of [IrCl2Cp*(NHC)] (110°C, 7 h). As a result, reacts with copper salts to give the Gustavson type
N-benzylmethylaniline was formed in a quantitative yield. complexes [CuBr 2 ·HCl] and [CuCl 2 ·HCl], which
There are some examples of the use of complexes promote N -alkylation of aniline with methanol to form
of copper, palladium, samarium, osmium, and gold in N,N-dimethylaniline.
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 CATALYTIC N-ALKYLATION OF ANILINES 327

Scheme 56.

Scheme 57.

Scheme 58.

NH2 1 mol % PdCl2, 1 mol % L-8 NHBn

O
+ BnOH
t
20 mol % LiOH, PBu PBut
3 equiv. 100ɨɋ, 24 h
Xantphos(But)
L-8

Xantphos(But) = 4,5-bis(di-tert-butylphosphino)-9,9-dimethylxanthene.

In [142], the N-alkylation of aniline and its derivatives the action of this complex, a broad range of substituted
with various alcohols was carried out under the action of anilines was easily alkylated at low concentrations of
palladium(II) acetate (Scheme 57). the catalyst (up to 0.5 mol %) and a base (Cs2CO3, up to
The SiO2-supported PdCl2–[Xantphos(But)] (L-8) 5 mol %) (Scheme 59) [145].
complex showed high efficiency in the N-alkylation According to [144], the N-alkylation of aromatic
of aniline with benzyl alcohol (Scheme 58). In the amines with benzyl alcohol and its derivatives is catalyzed
N-alkylation of amines for the first cycle, the TON for with the rhenium hydride complex [Re]-2 (Scheme 60).
the indicated complex was 46 000. The catalyst can be
reused up to 4 times without any noticeable change in Samarium iodide SmI2 (3 mol %) was successfully
characteristics [143]. used for the N-alkylation of anilines with benzyl
alcohol and its derivatives under microwave irradiation
The authors [144, 145] reported the successful use
(Scheme 61) [146].
of rhenium complexes for the N-alkylation of anilines
with alcohols. Thus, the selective mono-N-methylation High selectivity in the N-benzylation of aniline and its
of anilines with methanol catalyzes the rhenium complex derivatives with BnOH (100°C, 48 h) was characteristic
[Re]-1 containing a tridentate diphosphinoamino ligand in of the Au/Ag-containing catalytic system PhAuCl/AgOTf
the coordination sphere in the presence of a base. Under (Scheme 62) [147].
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328 BAYGUZINA, KHUSNUTDINOV

Scheme 59.

Scheme 60.

Scheme 61.
NH2
3 mol % SmI2
NHR2
1
R
+ R2OH R1
1 equiv. ButOK, toluene, MW, 140°C, 1 h
1.5 equiv.
6883%

R1 = H, 2,5-Me2, 4-F, 4-MeO, 4-Br; R2 = Bn, 4-MeC6H4CH2, 4-MeOC6H4CH2, 2,4-Cl2C6H3CH2.

Scheme 62.

NH2 PhPAuCl/AgOTf (10%) NHBn

R + BnOH R
ButOCl, 1,4-dioxane, 100ɨɋ, 48 h

7290%

R = 4-Me, 2-Me, 4-MeO, 4-CF3O, 3-Cl, 4-Cl, Br.

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 CATALYTIC N-ALKYLATION OF ANILINES 329

Scheme 63.
R
Ni(OAc)2·4H2OEt3N
+ CCl4 + RCH2CH2OH +
135145oC, 8 h R R
NH2 N N
conversion 4060%
2629% 1424%
R = H, Me, Et.

Scheme 64.

The formation of N-alkylanilines was observed in at moderate temperatures is much lower than that of alkyl
the reaction of aniline with aliphatic alcohols in a CCl4 halides or dimethyl sulfate.
medium under the action of a nickel-containing catalyst Another problem associated with the use of dimethyl
Ni(OAc)2·4H2O–Et3N (Scheme 63) [148]. carbonate is that reactions with its participation can proceed
4. N-METHYLATION OF ANILINES in two directions: methylation and carboxymethylation,
WITH DIMETHYL CARBONATE which is the reason for the low selectivity of the
Recently, the need to create environmentally friendly reaction with respect to N-methyl derivatives [152,
chemical technologies has aroused great interest in 153]. Therefore, selective catalysts are required for the
dimethyl carbonate as a safe and green methylating agent N-alkylation reaction of dimethyl carbonate and other
[8, 9, 149–151]. organic carbonates with anilines [154].
One of the problems that limits the use of dialkyl In [150, 155–157], zeolites X and Y were used as a
carbonates and, in particular, dimethyl carbonate as catalyst for the N-alkylation of anilines with dimethyl
alkylating agents is that their use must be combined with carbonate. The selectivity of mono-N-methylation was
active catalysts, since the reactivity of organic carbonates 92–98% with aniline conversion of up to 93%. The
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330 BAYGUZINA, KHUSNUTDINOV

Scheme 65.

reactions were carried out both in a flow reactor and under macro-, and mesoporous FeHY-mmm zeolite to obtain
batch conditions [Scheme 64, (1)]. N-monomethylanilines (Scheme 65).
Commercially available faujasite NaY catalyzes the Mesoporous aluminosilicates MCM-41 containing
N-alkylation of primary arylamines (p-XC6H4NH2, X = Lewis acid sites (Zn2+, Sn4+, Ti4+, and Zr4+) introduced
H, Cl, NO2) with symmetrical and non-symmetrical by ion exchange were tested for the methylation of
dialkyl carbonates [R 1 OCOOR 2 , R 1 = Me, R 2 = 2,4-diaminotoluene with dimethyl carbonate [163].
MeO(CH2)2O(CH2)2; R1 = R2 = Et; R1 = R2 = Bn; R1 = The reaction proceeded with the selective formation
R2 = All; R1 = Et, R2 = MeO(CH2)2O(CH2)2] with of the N-monomethyl derivative. These catalysts are
high selectivity (90–97%) for mono-N-alkylanilines more active than NaY zeolite. It is believed that the
[Scheme 64, (2), (3)], due to the combined molecular increased efficiency of these catalysts is due to the strong
sieve effect and acid-base properties of zeolite [151]. acidic properties of metal ions in comparison with Na+
According to [158, 159], in the presence of faujasite [163–165].
NaY dimethyl carbonate behaves as a chemoselective The selective N-monomethylation of aniline with
N-methylating agent with respect to functionalized dimethyl carbonate is facilitated by calcined Mg–Al
anilines, such as aminophenols, aminobenzyl alcohols, hydrotalcites (Mg/Al = 3) [166].
aminobenzoic acids, and aminobenzamides. The
reaction proceeds with the exclusive formation of N-Methylation of aniline with dimethyl carbonate in
N-methylanilines with a selectivity of up to 99% in supercritical CO2 in the presence of γ-Al2O3 proceeded
the absence of side processes of O-methylation or stepwise with the formation of N-methylaniline, and then
N-/O-methoxycarbonylation. Dimethyl carbonate, which N,N-dimethylaniline in quantitative yield. The reaction
usually promotes methylation only at >120°C, is activated was carried out by passing a mixture of aniline with
by the NaY zeolite catalyst at 90°C. the reactions with dimethyl carbonate (1 : 1) through a layer of γ-Al2O3 at
aminobenzoic acids proceeded at a higher temperature a rate of 0.2 mL/min and CO2 at a rate of 1.0 mL/min at
(≥130°C) [Scheme 64, (4)] [160]. a pressure in the system of 100 bar [167, 168].
Active catalysts for the N-methylation of aniline with In [169], N-methylation of anilines with dimethyl
dimethyl carbonate are zeolites without binder HY-BS, carbonate in the presence of ZrOCl2·8H2O was carried out.
NaY-BS, and KNaY-BS. Thus, the reaction of aniline with Dimethyl carbonate, which reacts with anilines at elevated
dimethyl carbonate (1 : 4) at 150°С for 1 h in the presence temperatures (>120°C), in the presence of zirconium
of an acid catalyst 0.94HY-BS leads to the formation of oxychloride methylates anilines at 90°C under aerobic
N-methylaniline and N,N-dimethylaniline in 88 and 5% conditions. The selectivity for N-monomethylaniline was
yields, respectively [161]. In [162], selective methylation 50–100% with an aniline conversion of 40–85%. The
of aniline and its derivatives with dimethyl carbonate was catalytic activity of ZrOCl2·8H2O remains unchanged
carried out under the action of iron-containing micro-, after at least 8 repeated runs.
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 CATALYTIC N-ALKYLATION OF ANILINES 331

Scheme 66.
0.2 mol % Ru(acac)2, 3 mol % L-9, NHMe
NH2 5 mol % additive
NMe2
+ MeOCO2Me +
Ɍ+) P/ +2 (6 MPa), 150°C, 18 h

0.05 mmol 16 equiv. 348% 995%

additive = CH3CO2H,CF3CO2H, MeSO3H, ɪ-TsOH, HOTf, HNTf2, LiNTf2, LiCl; solvent = dioxane,
ɌHF, PenttOH, Bu n2O; L-9 = 1,1,1-tri(diphenylphosphinomethyl)ethane (Triphos).

Scheme 67.

According to [165], the selective and active catalysts in In [171, 172], a probable mechanism of the
the N-methylation of arylamines with dimethyl carbonate N-methylation of aniline with dimethyl carbonate has
are aluminum salts with terephthalic acid, as well iron been presented (Scheme 68).
and copper salts with benzene-1,3,5-tricarboxylic Dimethyl carbonate was successfully used for the
acids. In this case, the main direction of the reaction is N-alkylation of N-methylanilines under the action of the
N-methylation, which prevails over carbamoylation. platinum complex [Pt]-1 (Scheme 69) [173].
Metal organic frameworks (MOF), which are solid 5. REDUCTIVE N-METHYLATION OF ANILINES
materials with infinitely long crystalline structures WITH FORMALDEHYDE
formed by crosslinking organic ligands and metal ions or The literature describes methods for the preparation
clusters through coordination bonds, actively catalyze the of N-alkylylanilines by reductive N-alkylation of
N-methylation of anilines using dimethyl carbonate [165]. aniline and its derivatives with aldehydes, in particular
There are several examples of the use of MOF formaldehyde. Thus, reductive N-methylation of amines
catalysts for the methylation of aniline and its derivatives with formaldehyde in the presence of Pd/C (2 mol %)
and calcium hydride as a hydrogen donor (60 mol %)
with dimethyl carbonate [170, 171]. Thus, methylation of
was performed in toluene at 60°С within 16 h [174].
aniline with dimethyl carbonate catalyzed by a ruthenium
The aniline conversion was 84%, and the ratio of
complex in a hydrogen atmosphere as a reducing agent
N-monomethylaniline to N,N-dimethylaniline was 85:15.
proceeds at an elevated temperature (150°С, 18 h)
However, the use of expensive CaH2 as a reducing agent,
and leads to the formation of N-methyl- and N,N- which is insoluble in aniline, significantly reduces the
dimethylanilines with a yield of up to 95% (Scheme 66) attractiveness of this method for practical application.
[171].
The complex [RuCl 2 (p-cymene)] 2 [Ru]-3 in
The iron complex [Fe]-9, containing in the coordination combination with Ph2SiH2 is very effective for reductive
sphere an N-heterocyclic carbene ligand L-10 [IMes = N-alkylation of aniline with aldehydes to obtain secondary
1,3-bis(2,4,6-trimethyliphenyl)imidazol-2-ylidene] amines in good yield. The reaction takes place under mild
promotes N-methylation of the secondary amines with conditions (20°C, 4 h) with high chemoselectivity. The
dimethyl carbonate in the presence of a hydrogen donor catalyst [Ru]-3 is tolerant to a wide range of functional
PhSiH3 (Scheme 67) [170]. groups in the both substrates (Me, Ph, NO2, CO2Me,
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332 BAYGUZINA, KHUSNUTDINOV

Scheme 68.
O
PhNH2 cat N
+
O O H2
Ph

O
H2

O O
+ PhNH2 H
MeOH N
H2O Ph

H2 H2O
O
H
N O H+, H2 + PhNH2 H
Ph H O N O
O PhNH2
MeOH
Ph
H

H+, H2
+ PhNH2 H H
N N
Ph R
MeOH O PhNH2

Scheme 69.

Scheme 70.

NH2 O 2 mol % [RuCl2(p-cymene)]2 [Ru]-3, NHCH2R2

1.5 equiv. Ph2SiH2
R1 + R1
R2 H CH2Cl2, MS 4 A, 20oC, 4 h

1.1 equiv. 7086%

R1 = H, 4-Me, 4-Br, 2-F; R2 = 4-NO2C6H4, Ph, 4-MeC6H4, But, 4-MeO2CC6H4.

F, Cl, Br, OMe) [175]. Under similar conditions, in the formaldehyde and HCO2NH4 leads to N-methylaniline
presence of [Ru]-3, N-methylanilines are easily alkylated in 45% yield (Scheme 71).
(Scheme 70). N-Monomethylation of anilines with paraformaldehyde
An example of N-alkylation of anilines with aldehydes and molecular hydrogen (0.5 MPa) catalyzes CuAlOx
in the presence of Pd/C in the presence ammonium [177]. The yield of N-methylaniline was 89% (120°С,
formate as a source of hydrogen has been reported 9 h). A similar reaction of aniline and m-aminophenol with
in [176]. In particular, the reaction of aniline with paraformaldehyde in the presence of Raney nickel (6 wt %)
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 CATALYTIC N-ALKYLATION OF ANILINES 333

Scheme 71.
NH2 NHCH2R2
0.1 equiv. Pd/C, 10 equiv. HCO2NH4
R1 + R2CHO
PriOH/H2O (10 : 1), 10–60 min

45100%

R1 = H, 2-Me, 3-Me, 4-Me, 2-MeO, 3-MeO, 4-MeO, 4-F, 4-CF3, 4-CO2H, 4-CO2Et, 4-OH;
R2 = H, Me, Et, Prn, Pri, But, CH2CHMe2, Pentn, c-Pent, Cy, CH2CH2Ph, Ph, 4-MeC6H4, 4-MeOC6H4, Bun.

Scheme 72.

Br
N CO
NH2 NHR2
o
(1) EtOH, 100 C, 24 h Mn
R1 2 R1 HN CO
+ R CHO (2) 2 mol % [Mn]-8, 5 mol % ButOK,, P
H2 (5 MPa), 50100°C, 1848 h Ph2 CO
7298% [Mn]-8

R1 = Ph, 4-MeOC6H4,4-MeC6H4, 4-IC6H4; R2 = Bn, 2-MeC6H4CH2, 4-MeOC6H4CH2, 3-FC6H4CH2.

Scheme 73.

NH2 O NH
1 mol % [Ir]-17
+ R2
R2
R1 o
H2 (0.5 ɆPɚ), toluene, MS 4A, 35 C, 1224 h
R1

R1 = H, R2 = 4-MeOC6H4 (92%, ee 91%), Pentn (83%, ee 92%), n-Pr (91%, ee 92%);

R1 = Cl, R2 = Ph (86%, ee 87%).

Ar1
SO2Ar
Ph
N Cp* O
Ir OH
X= P
N X O
Ph H2 O
[Ir]-17
Ar1
Ar = 2,3,4,5,6-(Me)5C6 Ar = 2,4,6-(Pri)3C6H2

in a stream of hydrogen (1.7 MPa) proceeds under more initial stage of the process is the condensation of anilines
rigid conditions (180°C, 8 h) [178]. The yield of N,N- with aldehydes with the formation of imines, which are
dimethylaniline and N,N-dimethyl-3-hydroxyaniline was reduced by hydrogen to an amine.
65 and 21%, respectively. According to [180], the reaction of aniline with
In [179], the N-alkylation of substituted anilines was benzaldehyde and a 2,6-dimethyl-3,5-dicarboethoxyhyd-
carried out using aldehydes and molecular hydrogen ropyridine as a hydrogen donor in the presence of
in the presence of a manganese pyridinylphosphine Ph3PAuCl–AgOTf leads to the formation of N-benzyl-
complex as a catalyst (Scheme 72). It is obvious that the aniline in 95% yield.
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334 BAYGUZINA, KHUSNUTDINOV

Scheme 74.
CO2 + H2
PdGa/TiO2

NH HCOO N H H2
N

Scheme 75.
NH2 NMe2
2 mol % Re/TiO2
R + CO2 + H2 R
200oC, 2436 h
1 MPa 5 MPa
7898%

R = H, 4-Me, 4-MeO, 3-Me.

Scheme 76.
1 mol % [Ru(acac)] [Ru]-14,
NH2 NHMe
2 mol % triphos L-9, 1.5 mol % MSA
R + CO2 + H2 R
Ɍ+)°C, 5 h
2 MPa 6 MPa H2O

R = H (35%), 4-MeO (90%), 4-Me (69%), 4-F (39%), 4-Cl (15%), 4-Br (13%).

PPh2
NH2 2.5 mol % [Ru]-15, NMe2 Ph2P
5 mol % HNTf2 Ru
R + CO2 + H2 R P
Ɍ+)°C, 10–24 h
Ph2
2 MPa 6 MPa
8494%
[Ru(triphos)(tmm)]
R = H, 4-Cl, 3-CF3-4-Me, 4-F, 2,4,6-Me3.
[Ru]-15

The iridium complex [Ir]-17 in the presence of chiral Pd, Ru, Rh, Cu, Re and Au [10, 11, 22, 182–186]. Thus,
phosphoric acid 5 catalyzes the reductive N-alkylation the Pd/CuZrOx cluster catalyzes the N-methylation of
of a wide range of anilines with complex ketones and aniline with CO2 (1 MPa) and molecular hydrogen
hydrogen to form optically active amines (Scheme 73) (2.5 MPa) in an octane medium at 150°C for 30 h. The
[181]. yield of monomethylaniline was 75% [187].
6. N-METHYLATION OF ANILINES
PdGa/TiO2 is an effective catalyst for the direct
WITH CO2 AND HYDROGEN
methylation of N-methylaniline with CO2/H2 to N,N-di-
The development of new synthetic approaches to methylaniline (Scheme 74). The conversion of aniline
utilize carbon dioxide is one of the most important tasks
(180°C, 5 MPa H2, 5 MPa CO2, 10 h) was 98%, while
of chemists. In recent years, studies have been actively
the selectivity for N,N-dimethylaniline was 94% [188].
carried out in the reductive N-methylation of amines, in
particular aniline and its derivatives, using carbon dioxide TiO2-Supported rhenium catalyzes the N-methylation
and molecular hydrogen (or its donors) in the presence of anilines with CO2 and H2 under rigid conditions for a
of heterogeneous and metal complex catalysts based on long time (Scheme 75) [189].
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 CATALYTIC N-ALKYLATION OF ANILINES 335

Scheme 77.
H
N 2 mol % [RuCl2(DMSO)4] [Ru]-16, NR2Me
R2 4 mol % BuPAd2 L-12, PhSiH3 (4 equiv. to aniline)
R1 + CO2 R1
toluene, 100oC, 1036 h

0.5 mmol 3 MPa 7197%

R1 = H, 4-Cl, 2-CF3, 4-CN, 2,6-Pri2; R2 = Bn, Me, Ph, Allyl.

Scheme 78.

Scheme 79.

NHMe 2 mol % [RuCl2(DMSO)4] [Ru]-16, NMe2

4 mol % BuPAd2 L-12, PhSiH3 (4 equiv. to amine)
+ CO2
toluene, 100oC
NH NMe2
0.05 mmol 63%

The authors [190] synthesized N-monomethylaniline The reductive methylation of anilines and methyl-
(21%) and N,N-dimethylaniline (65%) under the action of anilines with CO2 (100°C, 10 h) was carried out in
Au/Al2O3 (0.5 mol %) using CO2 (2 MPa) as a precursor the presence of Ru-containing metal complex catalyst
of the methyl group and molecular hydrogen (6 MPa). [Ru]-16 using phenylsilane as a hydrogen donor
The reaction took place in hexane at 140°С for 7 h. (Scheme 77) [183].
Ruthenium complexes Ru(acac)3 [Ru]-14 Reductive N-methylation of primary and secondary
in the presence of triphos ligand L-9 [184] and aromatic and aliphatic amines with CO2 and phenylsilane
[Ru(triphos)(tmm)] [Ru]-15 are effective catalysts for is also catalyzed by Rh(I) complex [Rh]-2 containing a
the N-methylation of anilines with CO2/H2 (Scheme 76) pyrimidine-based carbene ligand (NHC). The reaction
[185]. Thus, in [184], N-methylation of anilines was is ambiguous due to the formation of formyl derivatives
carried out using CO2 and H2 in the presence of the 9, 10 along with methyl derivatives [191]. With an
Ru(acac) 3–triphos (L-9) catalytic system and acid increase in the concentration of PhSiH3 to 8 equiv. it
additives or LiCl. The reaction took place under rigid is possible to increase the selectivity of the reaction
conditions (140°C, 5 h) at a hydrogen and CO2 pressure with respect to monomethyl derivatives 7 for aniline,
of 6 and 2 MPa. The ruthenium complex [Ru(triphos) 2,4,6-trimethylaniline and 4-methoxyaniline to 99% by
(tmm)] [Ru]-15 under similar conditions promotes di-N- reducing the content of N-formylanilines 9 and 10 to 0%
methylation of anilines and its derivatives [185]. (Scheme 78).
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336 BAYGUZINA, KHUSNUTDINOV

Scheme 80.

Scheme 81.

Ru
HCO2H CO2 + H2

PhNHMe

Ru

H2O HCO2 or H2 CO2 + H2O

O H
Ru
Me Me Me CH3
N H N H N
Ru
Ph Ph Ph
HCO2H

The catalytic system RuCl 2 (dmso) 4 [Ru]-16– decomposition of HCOOH catalyzed by the rhodium
BuPAd2 L-12 facilitates the exhaustive methylation of complex [Ru]-17 with the formation of CO2 and H2,
N-methyl-o-phenylenediamine with carbon dioxide and formylation, and hydrogen transfer (Scheme 81).
phenylsilane as a hydrogenating agent (Scheme 79) [183]. The known method of N-alkylation of aniline and
7. UNUSUAL REACTIONS its derivatives with carboxylic acids. In particular, the
OF N-ALKYLATION OF ANILINES N-alkylation of anilines using RCOOH and phenylsilane
Methods for the preparation of N-alkylanilines by as a reducing agent is catalyzed the iron carbonyl complex
alkylation of aniline with orthoformate, acetonitrile, and Fe2(CO)9 (Scheme 82) [193].
also transamination are known in the literature. A method Scheme 83 shows a plausible reaction mechanism,
was developed for the N-methylation of anilines using according to which the formation of N-alkyl derivatives
formic acid and hydrogen in the presence of ruthenium(II) occurs via two routes. The first route starts with acid
catalyst [Ru]-17 (Scheme 80) [192]. amidation. The process completes with the reduction of
In this work, a probable reaction mechanism was the amide with PhSiH3. The second route involves the
proposed, according to which the formation of the reduction of the acid to an aldehyde, which reacts with
NCH3 group occurs in several stages, including the an amine to give a Schiff base. It can be assumed that the
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 CATALYTIC N-ALKYLATION OF ANILINES 337

Scheme 82.

NH2 NMe2
5 mol % Fe2(CO)9
R + HCO2H 3 mmol PhSiH3,
R
100oC, 12 h, toluene
0.5 mmol 1.5 mmol

R = H (70%), 4-F (28%), 4-Cl (57%), 4-Br (50%), 4-Me (53%).

NHR2 NR2Me
5 mol % Fe2(CO)9
R1 + HCO2H R1
1.5 mmol PhSiH3 ,
100oC, 1 h, toluene
0.5 mmol 0.75 mmol

R2 = Me, R1 = H (92%), 4-Me (89%), 4-MeO (90%), 4-F (88%), 4-Cl (94%), 2-MeO2C (8.4%);
R1 = H, R2 = Et (81%), Pri (61%), Bn (66%), Allyl (83%), CH2CH2OH (64%).

Scheme 83.
R1NH2 + RCOOH
rout I +H2O
rout II
PhSiH3
O
H2O O PhH2SiO
1 OSiH2Ph
R HN1
R R NH2 +
R H R
ɚɦɢɞ H

+H2O
PhSiH3 reduction
H2O

R1HN R R1N R
reduction
Schiff base

Scheme 84.
NHR2 5 mol % Cu(OAc)2, 3 equiv. PhSiH3 NR2Me
R1 + HCO2H R1
80oC, 8 h, Bu2O
1.5 equiv.

R2 = Me, R1 = 4-MeO (92%), 4-Cl (87%), 4-NO2 (0%); R1 = H, R2 = Bn (86%), CH2CH2OH (81%).

main role of Fe2(CO)9 is to catalyze the steps of reduction (Scheme 85). The reaction takes place under mild
of amide, acid, and Schiff base. conditions (20–60°C, 18 h) [195].
Reductive methylation of secondary amines with Finely dispersed metallic platinum supported on
formic acid and phenylsilane is catalyzed copper(II) activated carbon catalyzes the N-methylation of aniline,
acetate (Scheme 84) [194]. its derivatives, and N-alkylanilines with formic acid in the
A method was developed for the N-methylation of presence of the reducing agent PhSiH3 (Scheme 86) [196].
anilines under the action of platinum catalysts [Pt]-1 In [197], N-methylaniline was obtained by a two-
using formic acid and silanes as a reducing agent step method: in the first step, aniline reacts with
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338 BAYGUZINA, KHUSNUTDINOV

Scheme 85.
NHR2 [Pt(CH2=CHSiMe2)2O] [Pt]-1/dppp (1 : 1)
NMe2
1
R + HCO2H PhSiH3, 20°C, 18 h, Bun2O
1
R

R2 = H, R1 = H, 4-F, 4-Cl, 4-Br, 4-SMe, 3-Cl, 2-Cl, 2,5-Me2, 2,5-Pri2, 2-Ph (86-99%); R2 = Me,
R1 = 4-MeO, 3-MeO, 4-CO2Me, 2-CF3 (71–94%). dppp = 1,3 -bis(diphenylphosphino)propane.

Scheme 86.
NH2 0.3 mol % Pt/C, 5 equiv. PhSiH3
NMe2
R + HCOH2 R
toluene, 80oC, 15 h

0.3 mmol 3 equiv.

R = 4-Cl (96%), 2,4,6-Me3 (36%), 2-SMe (96%), 4-MeO (95%).

Me
H N
N 2 0.1 mol % Pt/C, 2.5 equiv. PhSiH3 R2
R + HCO2H 1
R1 R
toluene , 80oC, 15 h

0.3 mmol 2 equiv.

R1 = H, R2 = Et (76%), Pri (64%), Ph (72%), CH2CH2OH (86%), CH2CH2CN (55%); R2 = Me, R1 =

4-Me (80%), 3-Me (69%), 3-Cl (93%), 4-CO2Et (91%), 4-NO2 (61%), 4-Br (79%), 4-MeO (74%).

Scheme 87.
OEt NaBH3(OAc)
MCM-41-SO3H
Ar NH2 + HC(OEt)3 Ar N CH Ar NHMe
3h Ɍ+)K
8 93%

Scheme 88.

NH2 NHR2
5 mol % cat
+ HPO(OR2)2
MW, 120oC, 2030 min
R1 R1
1 : 0.6

R1 = Me, R2 = Et, cat = CuCl2 (17%), FeCl3 (5%), InCl3 (50% + 10% dialkylamine ), ZnCl2 (20%),
Cu(OTf)2 (59%), In(OTf)3 (87%), Zn(OTf)2 (44% + 20% dialkylamine); cat = In(OTf)3,
R1 = H, Me, MeO, Cl, Br, I, CN, NO2, R2 = Me, Et, Prn (6191%)

triethylorthoformate under the action of mesoporous In [198], selective mono-N-alkylation of aniline and
zeolite MCM-41-SO3H to form an intermediate ethyl- its derivatives was carried out using dialkyl phosphites
N-phenylformimidate 8, which is reduced in the second under the action of copper, iron, zinc, and indium
step with NaBH3(OAc) (Scheme 87). compounds (Scheme 88). The reaction selectivity for
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 91 No. 3 2021
 CATALYTIC N-ALKYLATION OF ANILINES 339

Scheme 89.

PhNHR In(OTf)3 PhNHR

O OH OH
R
H P O O P H HO P H
R
O O O
R
In(OTf)3
..
.. PhNH2
PhNH2

Scheme 90.

Scheme 91.
8 mol % Pd/C (10 wt %)
ArNH2 + RNH2 ArNHR
MW (170oC, <21 atm.), 1.5 h THF
2 equiv.

Ar = Ph, R = Hexn (92%), Pri (72%), PhCH2CH2 (36%); Ar = 2,4-Me2C6H3, R = 2-Bu (86%);
Ar = 4-MeOC6H4, R = Cy (79%); R = Bun, Ar = 2-MeOC6H4 (79%), 2-OH (67%), 4-CO2Me (34%).

Scheme 92.

mono-N-alkylaniline is greatly enhanced by replacing A similar reaction involving 2-propyl-, 2-butyl- and
conventional heating with microwave radiation. Scheme 1-hexylamines with aniline and its derivatives is catalyzed
89 shows a plausible reaction mechanism. by palladium on carbon. The catalyst can be reused at
Another method for the synthesis of N-alkyl- and N,N- least three times (Scheme 91) [200].
dialkylanilines is based on the transamination reaction. The catalytic system, consisting of the four-nuclear
Thus, selective N-alkylation of aniline and its derivatives complex Ru–H [Ru]-18 with the catechol ligand
with primary and secondary amines catalyzed by the L-12, catalyzes the reaction of n-hexylamine and
cobalt complex [Co]-4 was performed to obtain a broad 3,4,6-trimethoxybenzylamine with 4-chloro- and
range of secondary amines (Scheme 90) [199]. 4-methoxyanilines (Scheme 92) [201].
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 91 No. 3 2021
340 BAYGUZINA, KHUSNUTDINOV

Scheme 93.
1.5 mol % Pd/C
R1C6H4NH2 + NR23 R1C6H4NHR2
MW, 175oC, 1.5 h, toluene
2 mmol 3 mmol

R1 = H, R2 = Prn (92%), Bun (93%), Hexn (95%), Bn (41%); R1 = 4-Me, R2 = Pr (94%),

Oct (96%); R2 = Pr, R1 = 3-CF3 (57%), 2-F (31%), 4-F (40%), 2-But (66%), 3-Me (91%),
2-Me (92%); R2 = Hex, R1 = 2-Me (94%), 2-MeO (95%).

Scheme 94.
10% Pd/C, H2
PhNH2 + MeCN PhNHEt + PhNEt2
MeOH (1 mL), 24 h
8992% 211%

Scheme 95.
5 mol % [Cu]
ArX + RNH2 ArNHR
H2O, 100oC, 12–48 h 5699%

X = Cl, Br, I; Ar = Ph, 4-ClC6H4, 3- ClC6H4, 2-ClC6H4, 4-BrC6H4, 4-HO2CC6H4,

2-HO2CC6H4, 4-NO2C6H4, 3-NO2C6H4, 2-NO2C6H4, 4-MeC6H4, 2-MeOC6H4,
4-CNC6H4, 4-AcC6H4; R = H, Me, Et, Bun, Cy.

The synthesis of N-alkylanilines was performed by the aryl halides, alcohols, dimethyl carbonate, aldehydes,
reaction of anilines with tertiary amines under the action and CO2/H have much in common, including common
of a heterogeneous Pd-containing catalyst (Scheme 93) advantages and disadvantages. A serious disadvantage of
[202]. The reaction took place in toluene with microwave the N-alkylation of aniline and its derivatives with alkyl
heating (175°С, 1.5 h). halides under the action of zeolites, as well as complexes
The authors [203] developed a method for producing of Ni, Rh and Cu, is the formation of by-products (HCl,
N-ethylaniline using acetonitrile (an alkylating agent) HBr, HI) and the need for their recycling. Dimethyl
and hydrogen. The reaction was catalyzed by Pd/C and carbonate as an N-methylating agent in relation to anilines
Rh/C (20°C). The yields of N-ethylaniline and N,N- has so far found limited application due to its high cost
diethylaniline were 89–100 and 0–11%, respectively and the need to carry out the reaction at a temperature
(Scheme 94). The disadvantage of this method is the above its boiling point. N-Methylation of anilines using
long reaction time and the use of expensive Pd/C and formaldehyde and a hydrogen donor or CO2/H2 requires
Rh/C catalysts. special equipment, which also limits their practical
N-Alkylanilines can be obtained by the reaction of application both in laboratory and in industry.
aryl halides with methylamine in the presence of copper The synthesis of N-alkyl-, N,N-dialkylanilines using
powder (5 mol %) at 100°С for 12–48 h. The yield of alcohols as alkylating agents is of the greatest preparative
N-alkylanilines was 56–99% (Scheme 95) [204]. The and industrial interest due to the formation of water as a
authors failed to synthesize diphenylamine from aniline by-product. Therefore, it is not surprising that in recent
and bromobenzene under similar conditions. years great success has been achieved in the N-alkylation
of anilines and its derivatives with alcohols under the
8. SUMMARY
action of metal complex catalysts based on compounds
Analyzing the data presented, one can conclude the and complexes of Cu, Ti, Fe, Ni, Co, Mn, Au, Ru, Ir, Pd,
methods for the synthesis of N-alkyl-substituted anilines and Os. The complexes of the indicated transition metals
based on the reactions of N-alkylation of anilines with are tolerant to the main functional groups in anilines
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 91 No. 3 2021
 CATALYTIC N-ALKYLATION OF ANILINES 341

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