Synthesis of Nitrogen Heterocarbaldehydes

Chapter-I

SYNTHESIS OF NITROGEN HETEROCARBALDEHYDES

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1.1 INTRODUCTION
There are various methods; like Reimer-Tiemann reaction, Gattermann
reaction, Gattermann-Koch reaction, Vilsmeier-Haac reaction, Duff reaction; used for
the direct formylation of an aromatic nucleus. However, in terms of ease and safety of
operations, the Reimer-Tiemann reaction is often the most advantageous route
preferred in chemical synthesis. The Reimer-Tiemann reaction owes its names to two
young German chemists, Karl Reimer and Ferdinand Tiemann. They isolated and
identified hydroxy arylaldehydes 2, 3 as the principal products of an aromatic
compound phenol 1 and chloroform in alkaline medium.1,2,3,4
OH OH OH
i) +
CHO OHC
1 2 3
o
Scheme 1. Reagent and conditions: i) aq. NaOH, CHCl3, 55 C, 3 hr.

Nitrogen heterocarbaldehydes have great deal of importance because of their use as a

starting material in organic and pharmaceutical industry and versatile intermediate in
the synthesis of biologically active chalcones, chalconeimines, flavones, flavanones,
flavonols, Schiff bases and coumarins. Further chalcones are used for the synthesis of
large number of pyrazolines, phenylpyrazolines, pyrimidines, isoxazoles, 1,5-
benzothiazepines, and 1,5-benzodiazepines. Hence synthesis of nitrogen
heterocarbaldehydes (25a-i) is undertaken.

1.2 REVIEW OF LITERATURE

Nitrogen heterocarbaldehydes were prepared from corresponding aromatic
nucleus by Reimer-Tiemann reaction; method is well documented in literature.5,6,7.
Subhash M. Lonkar et al.8 have reported the preparation of 5-chloro-2-hydroxy
benzaldehyde 5 by Modified operation in Reimer-Tiemann reaction of 4-chlorophenol
4 with chloroform in aqueous alkali.

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 Synthesis of Nitrogen Heterocarbaldehydes

OH OH
i)

Cl Cl CHO
4 5
o
Scheme 2. Reagent and conditions: i) aq. NaOH, CHCl3, 55 C, 3 hr.

Pattekhan et al.9 have reported the formation of 2,4-dihydroxy benzaldehyde 6 and 2-

hydroxy-4-methoxy benzaldehyde 7 from the resorcinol by Reimer-Tiemann reaction
in the presence of β-cyclodextrin catalyst.

HO OH MeO OH

and
CHO CHO
6 7

Xu Hong Zhao et al.10 reported the preparation of o and p- hydroxy benzaldehyde

o
through the Reimer-Tiemann reaction. The reaction was best conducted at 44-55 C
and mixture of sodium hydroxide, phenol and chloroform in the molar ratio 3:2:1.
Zine Babasaheb S. et al.11 have reported the synthesis of 1H-indole-3-carbaldehyde 9
from indole 8 by Vilsmeier- Haack formylation reaction.
CHO
i)

N N
H H
8 9
o
Scheme 3. Reagent and conditions: i) DMF, POCl3, 0-35 C

Hirao K. et al.12 have reported the photo reaction of phenol with chloroform in the
presence of diethyl amine to form salicylaldehyde.
Asghar Davood et al.13 have reported the synthesis of 2-methyl-4(5)-carboxaldehyde
11 by oxidation of 2-methyl-4(5)-hydroxy methyl imidazole 10 in presence of
activated MnO2 in acetonitrile.
HOH2C OHC
N N
i)

N CH3 N CH3
H H
10 11
Scheme 4. Reagent and conditions: i) MnO2, CH3CN, Reflux, 24 hr

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 Synthesis of Nitrogen Heterocarbaldehydes

Deshpande et al.14 have reported synthesis of β-hydroxy-α-naphthaldehyde 12 from β-

naphthol by Reimer-Tiemann reaction.

CHO
OH

12

Ding et al.15 have synthesized 4-hydroxy benzaldehyde from phenol by Reimer-

Tiemann reaction using β-cyclodextrin as a catalyst. Kalechits et al.16 have
synthesized 2-hydroxy-1-napthaldehyde by Reimer-Tiemann reaction under condition
of heterogeneous catalysis. Castillo et al.17 have showed a theoretical study on the
molecular mechanism for the normal Reimer-Tiemann reaction.
Vibhute et al.18 have studied iodination of 2’-hydroxy-5’6-benzochalcones by using
iodine and iodic acid. Pawar et al.19 have synthesized iodo-vanillin from vanillin by
using iodine and iodic acid. Corello et al.20 have carried out iodination of hydroxy
acetophenones using iodine and aqueous sodium carbonate solution.

1.2.1 DIFFERENT METHODS FOR THE SYNTHESIS OF HETERO

CARBALALDEHYDES
Number of synthetic methods have been well documented in the literature for
arylaldehydes. The direct introduction of aldehyde group into an aromatic nucleus is
possible with Gattermann21, Gattermann-Koch22, Vilsmeier23, Duff24 and Reimer-
Tiemann reaction. Only the Gattermann and Duff reactions are applicable to phenols.
Since in the Gattermann reactions the entering aldehyde group usually occupies the
para position to the hydroxy group and the Duff reaction fails with the polyhydric
phenols and phenols carrying electron donating substituents. Vilsmeier reaction gives
very poor yields. The Reimer-Tiemann reaction is the only method for the direct
formylation where CHO get entered to the ortho and para positions to hydroxy group.
1] By Reimer-Tiemann Reaction:
By Reimer-Tiemann reaction phenol 13 is converted into an aromatic hydroxy
aldehydes 14, 15 by warming with chloroform in aqueous alkaline medium.25, 26, 27, 28

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 Synthesis of Nitrogen Heterocarbaldehydes

OH OH
CHO OH
i)
+
OHC
13 14 15
o
Scheme 5. Reagent and conditions: i) aq. NaOH, CHCl3, 55 C, 3 hr.

2] Reimer-Tiemann Reaction with Photoreaction:

Hirao et al.29 have reported a photoreaction for the synthesis of aromatic
aldehydes like salicylaldehydes 17 and 4-hydroxy benzaldehydes 18 from phenol 16
with chloroform in presence of diethyl amine.
OH OH
CHO OH
i)
+
OHC
16 17 18

Scheme 6. Reagent and conditions: i) CHCl3,(C2H5)2NH, hν, 5 hr.

3] Reimer-Tiemann Reaction using β–Cyclodextrin Catalyst:

Divakar and co-workers30 have reported the synthesis of 2,4-dihydroxy
benzaldehydes 20 and 2-hydroxy-4-methoxy benzaldehydes 21 from resorcinol 19
using β–cyclodextrin catalyst (β–CD) by Reimer-Tiemann reaction.
CHO CHO
OH OH
HO OH
i)
+

OH OCH3
19
20 21

Scheme 7. Reagent and conditions: i) CHCl3, NaOH, β–cyclodextrin

4] Reimer-Tiemann Reaction using Phase Transfer Catalyst:

Yoel Sasson et al.31 have reported the effect of phase transfer catalyst on the
Reimer-Tiemann reaction. Tertiary amines have considerable effect on the process of
Reimer-Tiemann reaction. Quaternary ammonium salts, on the other hand were found
inactive as phase transfer catalyst in the Reimer-Tiemann reaction.

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 Synthesis of Nitrogen Heterocarbaldehydes

5] By Vilsmeier-Haac formylation reaction:

Hemant Badwaik and co-workers32 have reported the synthesis of 2-
chloroquinoline-3-carbaldehyde 23 from acetanilide 22 by Vilsmeier- Haac
formylation reaction.
NHCOCH 3 CHO
i)

N Cl
22 23
Scheme 8. Reagent and conditions: i) DMF, POCl3, 80-90 OC, 14-16 hr.

1.3 PRESENT WORK AND METHOD

The chemistry of nitrogen heterocarbaldehydes has great deal of importance
because of their use as a starting material in organic and pharmaceutical industry.
Chalcones, chalconeimines, flavones, flavanones, flavonols, Schiff bases and
coumarins are used for the synthesis of large number of heterocycles such as
pyrazolines, phenylpyrazolines, pyrimidines, 1,5-benzothiazepines, 2-azetidinones, 4-
thiazolidinones etc as their utility lies in the usefulness of synthons.
According to the review of literature, the most convenient method for the
synthesis for nitrogen heterocarbaldehydes is Reimer-Tiemann reaction. We have
synthesized some nitrogen heterocarbaldehydes by doing modified operation in
Reimer-Tiemann reaction. Further nitrogen heterocarbaldehydes were used for the
synthesis of chalcones.
LITERATURE METHOD FOR THE SYNTHESIS OF ARYLALDEHYDES BY
REIMER-TIEMANN REACTION
Arylaldehydes are prepared from the corresponding phenols by Reimer-
Tiemann reaction. The method is given in the literature33,34, is heating phenol, sodium
o
hydroxide dissolved in water and chloroform at 60-70 C for 2 hours. Unreacted
chloroform is removed by steam distillation. Reaction mixture on acidification by
dilute hydrochloric acid and further ortho isomer separated from para isomer by
steam distillation. This method involves twice steam distillation, which is time
consuming, expensive and yield of ortho isomer is low (20-35%) reported.
In the present investigation, we decided to investigate a simple inexpensive
and convenient procedure for the preparation of benzimidazole-2-carbaldehyde from
benzimidazole by Modified operation in Reimer-Tiemann reaction.

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SYNTHESIS OF BENZIMIDAZOLE-2-CARBALDEHYDE BY MODIFIED

OPERATION IN REIMER-TIEMANN REACTION
Synthesis of benzimidazole-2-carbaldehyde 25c was made from the
benzimidazole 24c by modified Reimer-Tiemann reaction in solvent water: ethyl
alcohol [90:10 v/v] instead of water for dissolving sodium hydroxide. After
completion of the heating reaction as above, the reaction mixture is cooled at 15-20
O
C for one hour. Solid separates out. Separated solid filtered on Buchner funnel and
washed with ethyl alcohol 2-3 times. Further the obtained solid was dissolved in
minimum amount of water and acidified with very dilute hydrochloric acid. A solid
product, benzimidazole-2-carbaldehyde, separates out in the pure form in 55-62%
yield. Unreacted benzimidazole goes into the filtrate.
This modified method implemented for the synthesis of nitrogen
heterocarbaldehydes has following advantages over normal Reimer-Tiemann reaction.
1. The procedure is very simple.
2. The isolation of product is very easy and gets 100% pure product, no need of
further purification.
3. Steam distillation is avoided.
4. Time as well as heat energy can be saved.

N i) N

N N CHO
H H
24a-i 25a-i
Scheme 9. Reagent and conditions: i) NaOH in [H2O: EtOH], CHCl3, 55-60 OC, 1 hr.

1.3.1 RESULT AND DISCUSSION

Synthesis of nitrogen heterocarbaldehyde was made from corresponding
heterocycles by remodel Reimer-Tiemann reaction in solvent water : ethyl alcohol
[90:10 v/v] instead of water dissolving hydroxide. After completion of the heating of
o
the reaction as above reaction mixture was cooled at 15-20 C for one hour, solid
separates out. Separated solid was filtered and washed with proper solvent for 2-3
times. Further solid was dissolved in minimum amount of water and resulting solution
was acidified with very little amount of dilute acid. Nine heterocarbaldehydes, 25a-i
were prepared by this procedure. The structure of the products was confirmed by IR,

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 Synthesis of Nitrogen Heterocarbaldehydes

1
H NMR, Mass and by comparing their melting points with those of samples prepared
by known literature value. The remodel procedure for synthesis of
heterocarbaldehydes has remarkable advantages such as, the procedure is very simple,
isolation of products is very easy and gets 100% pure product, no need of further
purification, steam distillation is avoided, time as well as heat energy can be saved
and obtained excellent yields. All the physical data of synthesized nitrogen
heterocarbaldehydes, 25a-i is shown in Table 1.

1.4 EXPERIMENTAL
1) By modified operation in Reimer-Tiemann Reaction:
Synthesis of Benzimidazole-2-carbaldehyde: 25c
Benzimidazole 24c [0.1 mol, 11.8gm] sodium hydroxide [7.8 gm in 29 ml
water and 12 ml ethyl alcohol v/v] was taken in 500 ml three naked round bottom
flask. The flask was mounted over mercury sealed mechanical stirrer, fitted with
reflux condenser and separating funnel. Then the flask was heated on water bath up to
60 OC. Chloroform [0.25 mol, 20.07 ml] taken in a separating funnel was added
within 45 minutes slowly in a way that refluxing continue. After completion of the
addition of chloroform, reaction mixture was heated further for 1 hour at 55-60 OC
and then cooled to 15-20 OC for 1 hour. Solid separates out. Separated solid was
filtered on Buchner funnel, washed with ethyl alcohol. Solid was transferred in beaker
and dissolved in minimum amount of water and acidified with little amount of very
dilute hydrochloric acid. The product separates out 25c. Separated solid was
recrystallized from 95% absolute ethyl alcohol.
All other nitrogen heterocarbaldehydes 25a-i were prepared by the same
method (Scheme 9) and their physical data listed in (Table 1).

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 Synthesis of Nitrogen Heterocarbaldehydes

Table 1
Physical data of Nitrogen Heterocarbaldehydes
M.P.
Sr. Substrate Products Yield (OC)
No. (24a-i) (25a-i) (%) Lit. Found

O
H

1 N 62 193-195 193
H
24a N
H
25a

O
H
CH3
2 N 58 200-201 205
H CH3
24b N
H
25b

N
N O
3 51 224 219
N
H N H
24c H
25c
O

H
4 54 210 207
N
N
OH
24d OH 25d
Cl
Cl O

H
5 58 -- 176
Cl N
Cl N
OH
24e OH 25e

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Br
Br O

H
6 55 -- 189
Br N Br N

OH 24f OH 25f

I I O

H
7 52 -- 194
I N I N
OH 24g OH 25g

N O

H
N N
8 H 60 174-177 171
N
24h H
25h
O
N
H
N CH3 N
9 H 58 165 162
24i N CH3
H
25i

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 Synthesis of Nitrogen Heterocarbaldehydes

1.5 SPECTRAL ANALYSIS

IR spectra of compounds in KBR were recorded on FTIR Bruker; model
Alpha T-spectrophotometer with software OPUS (Vmax in cm-1). 1H NMR spectra
were recorded in DMSO on NMR instrument; model Bruker 300 MH Z with software
Top Spin using TMS as an internal standard (chemical shifts given in δ ppm). The
mass spectra (MS) were recorded on Pexciex Mass spectrophotometer, model API
2000 with software Analyst 1.4.2.
IR Spectra:
The IR spectra of nitrogen heterocarbaldehydes showed characteristic band at
near region 1700 cm-1 due to >C=O stretching vibrations. The aldehydic (C-H)
stretching vibrations showed band at near region 2700 cm-1. All the nitrogen
heterocarbaldehydes showed absorption in the region 3163-3423 cm-1 due to (N-H) of
indole or imidazole ring. A broad peak near at 3400 cm-1 is observed due to phenolic
–OH at p-position while for ortho -OH the distinctive band is not observed, it might
be due to hydrogen bonding. These assignments are in agreement with those observed
by research groups.
1
H NMR spectra:
1
H NMR spectra of synthesized nitrogen heterocarbaldehydes were studied in
DMSO showed characteristic singlet signals near δ 9-10 due to aldehydic (-CHO)
proton and at δ 8.4-11 due (-NH) protons of indole or imidazole ring respectively.
Phenolic 2’ OH protons appeared as singlet near at δ 12.5 while for 4’ OH, the singlet
near δ 8.5 is observed and aromatic protons appear as multiplet around δ 7.0. For
compounds containing aromatic methoxy groups, the singlet near at δ 2.3 was
observed. These findings are in agreement with those observed by several research
groups.
Mass spectra:
The mass spectra for the nitrogen heterocarbaldehydes exhibited correct
molecular ion peaks for its molecular weight.

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1H-Indole-3-carbaldehyde: (1-A): 25a

IR (KBr) v cm-1 = 3423, 2932, 2739, 1707.
1
H NMR (δ) = 12.17 (s,-NH), 9.96 (s, 1H,-CHO), 8.31 (s, 1H, Ar-H), 8.14-8.12 (d,
1H, Ar-H), 7.55-7.52 (d, 1H, Ar-H), 7.30-7.21 (m, 2H, Ar-H).
Mass (m/z) = 145[M+H]+

1H-Benzimidazole-2-carbaldehyde: (3-A): 25c

IR (KBr) v cm-1 = 3418, 2620, 1770, 1643, 1563.
1
H NMR (δ) = 9.77 (s, 1H, -CHO), 8.44 (s, -NH), 8.38 (d, 1H, Ar-H), 7.80 (d, 1H,
Ar-H), 7.64-7.61 (m, 1H, Ar-H), 7.25-7.22 (m, 1H, Ar-H).
Mass (m/z) = 147 [M+H]+

1H-Imidazole-4-carbaldehyde: (8-A): 25h

IR (KBr) v cm-1 = 3123, 2928, 2731, 1759, 1668, 1561.
1
H NMR (δ) = 9.76 (s, 1H, -CHO), 13.00 (s, -NH), 8.01 (s, 1H, Ar-H), 7.94 (s, 1H,
Ar-H).
Mass (m/z) = 95 [M+H]+

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Fig.1.0 IR Spectra of Compound (1-A) : 25a

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Fig.1.1 H NMR Spectra of Compound (1-A) : 25a

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Fig.1.1.1 H NMR Spectra of Compound (1-A) : 25a

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Fig.1.2 Mass Spectra of Compound (1-A) : 25a

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Fig.1.2.1 Mass Spectra of Compound (1-A) : 25a

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Fig.1.3 IR Spectra of Compound (3-A) : 25c

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Fig.1.4 H NMR Spectra of Compound (3-A) : 25c

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Fig.1.4.1 H NMR Spectra of Compound (3-A) : 25c

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Fig.1.5 Mass Spectra of Compound (3-A) : 25c

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Fig.1.5.1 Mass Spectra of Compound (3-A) : 25c

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Fig.1.6 IR Spectra of Compound (8-A) : 25h

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Fig.1.7 H NMR Spectra of Compound (8-A) : 25h

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Fig.1.7.1 H NMR Spectra of Compound (8-A) : 25h

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 Synthesis of Nitrogen Heterocarbaldehydes

Fig.1.8 Mass Spectra of Compound (8-A) : 25h

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Fig.1.8.1 Mass Spectra of Compound (8-A) : 25h

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 Synthesis of Nitrogen Heterocarbaldehydes

1.6 References:
1. Reimer K., Ber, 1876, 9, 423.
2. Reimer K., Tiemann F., Ber, 1876, 9, 824.
3. Reimer K., Tiemann F., Ber, 1876, 9, 1268.
4. Reimer K., Tiemann F., Ber, 1876, 9, 1285.
5. Vogel’s Text Book of Practical Organic Chemistry, 4th ed.; Longman Publisher,
England, 1978.
6. Vogel’s Text Book of Practical Organic Chemistry, 5th ed.; Dorling Kindersley
Publisher, India, 2008.
7. Blatt, A.H., Organic Synthesis, Collective vol. III, 1955, 3, 463.
8. Lonkar S. M., Vibhute Y. B., Sayyed M. A., Basser M. A., Mendeleev
Communication., 2007, 17, 51.
9. Pattekhan H.H. Divakar S.J., Molecular catalysis; A chemical, 2001, 169 (1-2),
185.
10. Xu. Hong Zhao.; Xi-shan Cao.; Long;Yu Wei-min.; Hwaxue Yu Nianhe, Biangi
Weiyuahui (Chinese), 2003, 5, 264.
11. Zine Babasaheb S., Ph.D. Thesis, ‘Synthesis and characterization of biologically
important newer aryl heterocyclic compounds’, submitted to Dr. B. A. M.
University, Aurangabad (India), 2017, 26.
12. Hirao K.; Ikegocone M.; Younemistu Y. Tetrahedron Lett., 1974, 30(15), 2301.
13. Asghar Davood, Eskandar Alipour, Abbas S; Turk J. Chem., 2008, 32, 389.
14. Deshpande P.H.; Vikran, 1963, 7, 15.
15. Ding, Guohua, Zang, Guangyu, Guilin Gongxueyuan Xuebao, (Chinese), 2001, 24
(4), 392.
16. Kalechits G. V., Osinovskii A. J., Matveenko Yu., Opkhovik V. K.; Russian J.
Applied Chemistry, 2002, 75 (6), 962.
17. Castillo R., Modine V., Andres.; J. Chem. Phy. Lett., 2000, 318, (1-3), 270.
18. Vibhute Y.B., [Link] Chem. Soc., 1976, 33, 736.
19. Pawar R.P., Ph.D. Thesis submitted to S. R. T. M. University, Nanded, 1998.
20. Corello M., Piscopes E., Abigenta E.; Anna Chem, (Rome), 1960, 50, 883.
21. Turce W. E., Organic reactions, 1957, 9, 37.
22. Crounse N. N., Organic reactions, 1949, 5, 290.

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 Synthesis of Nitrogen Heterocarbaldehydes

23. Fieser I. F., Hart well J. L., Jones J. E., Wood J. H., Bost R. W.; Organic synthesis
coll., 1955, 3, 98.
24. Ferguson L. N., Chem Revs., 1946, 38, 229.
25. Reimer K., Ber, 1876, 9, 423.
26. Reimer K., Tiemann F., Ber, 1876, 9, 824.
27. Reimer K., Tiemann F., Ber, 1876, 9, 1268.
28. Reimer K., Tiemann F., Ber, 1876, 9, 1285.
29. Hirao K.; Ikegocone M.; Younemistu Y., Tetrahedron Lett., 1974, 30(15), 2301.
30. Pattekhan H.H. Divakar S.J., Molecular catalysis; A chemical, 2001, 169(1-2),
185.
31. Yoel Sasson, Minda Yonovich, Tetrahedron Lett., 1979, 20 (9), 3753.
32. Hemant Badwaik, S. Venkataraman, Deepa Thakur, Minu Vinod, J. Raamamurthy
and Kiran Deshmukh; Asian J. Research Chem.; June,2011; 4(6), 893.
33. Vogel’s Text Book of Practical Organic Chemistry, 4 th ed.; Longman Publisher,
England, 1978.
34. Blatt, A.H., Organic Synthesis, Collective vol. III, 1955, 3, 463.

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