A Convenient Synthesis of 3-Butenylamine

Full text of DOI:10.1080/00304948.2018.1537743

Organic Preparations and Procedures International
The New Journal for Organic Synthesis
ISSN: 0030-4948 (Print) 1945-5453 (Online) Journal homepage: https://www.tandfonline.com/loi/uopp20
A Convenient Synthesis of 3-Butenylamine
David A. Johnson & Gordon W. Gribble
To cite this article: David A. Johnson & Gordon W. Gribble (2018) A Convenient Synthesis
of 3-Butenylamine, Organic Preparations and Procedures International, 50:6, 575-577, DOI:
10.1080/00304948.2018.1537743
To link to this article: https://doi.org/10.1080/00304948.2018.1537743
Published online: 08 Feb 2019.
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Organic Preparations and Procedures International, 50:575–577, 2018
2018 Taylor & Francis Group, LLC
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ISSN: 0030-4948 print / 1945-5453 online
DOI: 10.1080/00304948.2018.1537743
OPPI BRIEF
A Convenient Synthesis of 3-Butenylamine
David A. Johnson and Gordon W. Gribble
Department of Chemistry, Dartmouth College, Hanover, NH 03755, USA
In connection with a project in our laboratory we required an efficient, safe, and scal-
able synthesis of 3-butenylamine (4-amino-1-butene) (1). Although such homoallylic
1
2
amines are well known, syntheses of the parent 3-butenylamine are sparse. Galand
reported the hydrogenation of allyl cyanide with zinc-copper couple to give 1 in
3
unspecified yield. Roberts described a three-step sequence to give 1 via benzenesulfo-
nation of 3-butenyl alcohol (allylcarbinol), displacement of benzenesulfonate with azide
ion, and reduction of the azide with lithium aluminum hydride to give 1 in 61.5% from
3
4
the benzenesulfonate. Both Roberts and later Brown noted that lithium aluminum
hydride reduction of 3-butenonitrile (allyl cyanide) was unsatisfactory, perhaps due to
5
the acidity of the a-hydrogens of the nitrile. Brown nicely circumvented this obstacle
by employing the less basic aluminum hydride, and was able to reduce 3-butenonitrile
to 1 in 55% yield. However, we were only able to obtain 1 in 8–12% yield using alumi-
6
num hydride. Courtois reported the synthesis of 1 in 40% yield via the reaction of allyl
aluminum bromide with (methoxymethyl)-N,N-bis(trimethylsilyl) amine.
Contrary to these reduction protocols for accessing 1, we envisaged a direct amina-
7
tion strategy making use of the venerable Gabriel amine synthesis in combination with
8
a Mitsunobu reaction. Our successful synthesis of 1 using this methodology is shown
in Scheme 1. Thus, reaction of commercially available 3-butenyl alcohol (2) with phtha-
limide (3), triphenylphosphine, and diethyl azodicarboxylate (DEAD) gave the expected
phthalimide 4 in 85% yield. Cleavage of 4 with hydrazine yielded 3-butenylamine (1)
in 54% yield following distillation.
In conclusion, we report a simple, convenient, and potentially scalable preparation
of 3-butenylamine in two steps that avoids the use of air-sensitive hydride and alumi-
num reagents and possibly explosive azide intermediates.
Experimental Section
General
Melting points were determined in open capillaries with either a Mel-Temp Laboratory
Devices apparatus or a Buchi 510 apparatus and are uncorrected. The elemental analysis
Received April 9, 2018; in final form July 19, 2018.
Address correspondence to Gordon W. Gribble, Department of Chemistry, Dartmouth College,
Hanover, NH 03755. E-mail: gordon.w.gribble@dartmouth.edu
575

5
76
Gribble and Johnson
Scheme 1
was performed by Atlantic Microlabs, Atlanta, GA. Infrared spectra were recorded on a
1
3
1
Perkin-Elmer 599 instrument. C NMR and 300 MHz H NMR spectra were recorded
on a Varian XL-300 multinuclear Fourier transform NMR. Mass spectra were obtained
on a Finnigan 4023 GC/MS system. Flash chromatography was carried out using
Silicycle ultra pure silica gel 60A (230-400 mesh). Tetrahydrofuran (THF) was distilled
from Na/benzophenone.
N-(3-Butenyl)phthalimide (4)
To a solution of 3-buten-1-ol (2) (2.00 g, 0.0277 mol; Fluka), phthalimide (3) (4.08 g,
0
.0277 mol), and triphenylphosphine (7.27 g, 0.0277 mol) in THF (65 mL) was added
dropwise over 15 min a solution of diethyl azodicarboxylate (4.82 g, 0.0277 mol) in
ꢀ
THF (10 mL) with ice bath cooling to maintain the reaction temperature at 20–25 C.
The resulting solution was stirred at room temperature for 40 h and then concentrated in
vacuo. Flash chromatography with ether-hexane (1:4) furnished 4.75 g (85%) of 4 as
ꢀ
analytically pure, colorless needles: mp 53–54.5 C; IR (KBr) 3950 (m), 2940 (m),
1
775 (s), 1695 (vs), 1620 (s), 1435 (s), 1400 (s), 1365 (s), 1340 (s), 1300 (m), 1260
ꢁ
1 1
(m), 1180 (m), 1060 (s), 970 (m), 940 (s), 870 (m), 805 (m), 720 (s) cm ; H NMR
(
CDCl ) d 8.00–7.50 (m, 4H), 6.20–5.30 (m, 1H), 5.26–4.83 (m, 2H), 3.78 (t, J ¼ 7 Hz,
3
1
3
2
1
1
H), 2.46 (q, J ¼ J ¼ 7 Hz, 2H); C NMR (CDCl ) d 168.0, 134.3, 133.6, 131.8,
1
2
3
þ
22.9, 117.2, 37.0, 32.6; MS m/e (relative intensity) 201 (M , 6), 161 (10), 160 (100),
33 (8), 105 (10), 104 (14), 85 (6), 83 (6), 77 (32), 76 (26), 75 (8), 71 (11), 69 (11), 57
(35), 56 (14), 55 (20), 51 (15), 50 (21).
Anal. Calcd for C H NO : C, 71.62; H, 5.51; N, 6.96. Found: C, 71.59; H, 5.53;
1
2
11
2
N, 6.92.

3-Butenylamine
577
3
-Butenylamine (1)
A solution of 4 (2.00 g, 9.94 mmol) in 95% EtOH (10 mL) was treated with 85% hydra-
zine hydrate (0.78 g, 0.016 mol) and stirred overnight at room temperature. The result-
ing suspension was treated with 10% aqueous HCl (10 mL) and the precipitated
material was filtered off and washed with H O (2 x 5 mL). The combined filtrate and
2
washings were concentrated to a small volume, filtered again, and then diluted with
H O (15 mL) and extracted with ether (2 x 25 mL). The aqueous acid layer was basified
2
with 50% aqueous NaOH and extracted with ether (3 x 25 mL). The combined ethereal
extracts were dried (K CO ) and distilled at atmospheric pressure through a Vigreux
2
3
ꢀ
5
ꢀ
column (10 cm) to give 0.58 g (54%) of amine 1 (bp 75–77 C), (lit. bp 76–77 C); IR
(
1
neat) 3370 (s), 3300 (s), 3085 (m), 2980 (s), 2935 (s), 2880 (s), 1640 (m), 1435 (m),
ꢁ
1 1
060 (m), 990 (m), 910 (m) cm ; H NMR (CDCl ) d 6.15–5.40 (m, 1H), 5.23–4.80
3
(m, 2H), 2.85–2.60 (m, 2H), 2.40–2.00 (m, 2H), 1.36 (s, 2H).
Acknowledgment
We gratefully acknowledge support from Dartmouth College.
ORCID
Gordon W. Gribble
http://orcid.org/0000-0002-7573-0927
References
1
2
3
4
5
6
7
8
. C. O. Puentes and V. Kouznetsov, J. Heterocycl. Chem., 39, 595 (2002).
. E. Galand, Bull. Soc. Chim. Belg., 39, 529 (1930).
. E. Renk and J. D. Roberts, J. Am. Chem. Soc., 83, 878 (1961).
. H. C. Brown and M. K. Unni, J. Am. Chem. Soc., 90, 2902 (1968).
. N. M. Yoon and H. C. Brown, J. Am. Chem. Soc., 90, 2927 (1968).
. G. Courtois, D. Mesnard, B. Dugue, and L. Miginiac, Bull. Soc. Chim. Fr., 93 (1987).
. M. S. Gibson and R. W. Bradshaw, Angew. Chem. Internat. Edit., 7, 919 (1968).
. O. Mitsunobu, M. Wada, and T. Sano, J. Am. Chem. Soc., 94, 679 (1972).