JASTEE, Vol.

1, Issue 1 Bommarito: ID of a Cyclopentyl Nitrite Inhalant

Christopher R. Bommarito1
Identification of a Cyclopentyl Nitrite Inhalant

ABSTRACT: A submission of an acidic yellow liquid was found to consist of cyclopentyl

nitrite, an alkyl nitrite compound that has not appeared in forensic literature. As no
commercial standards were available, a comparison standard was synthesized.
Thirteen commercial alkyl nitrite products were purchased and examined and each was
found to contain butyl nitrite, regardless of commercial content labeling.

KEYWORDS: Cyclopentyl Nitrite, Cyclopentyl Nitrate, Cyclopentanol, Butyl Nitrite,

Poppers

Amyl and Butyl Nitrite inhalants, produced by reacting sodium nitrite with amyl or
butyl alcohol, are vasodilators that are inhaled to enhance sexual pleasure. Nitrite
inhalants also cause vasodilatation, with brief hypotension, dizziness, and flushing,
followed by reflex tachycardia (1). These products, known as “Poppers”, are typically
sold in specialty shops as over-the-counter products labeled as head cleaners or air
fresheners.
An unmarked brown glass vial was seized in a traffic stop of an erratic driver. The
vial contained a clear, yellow tinted acidic (pH 1-2) liquid that had a strong solvent odor.
A vapor phase infrared spectrum (Figure 1) revealed the liquid to consist of a non-
aromatic nitrite compound, but inconsistent with the commonly encountered amyl and
butyl nitrite and the uncommon but previously reported cyclohexyl nitritei. Capillary
gas chromatography-mass spectrometry of the liquid indicated a cyclopentanol moiety.

Materials and Methods

Vapor phase infrared spectra were collected by placing a drop of liquid in a gas cell
(International Crystal Laboratories 8-054 equipped with KBr windows) and examined via
a Fourier transform infrared spectrometer (Perkin Elmer Spectrum One with mid-range
MCT detector).
Gas chromatography-mass spectrometry data were obtained by drawing a 10 ul
sample of the container headspace in a gas-tight Hamilton syringe and injecting into a
Thermo-Finnigan Trace Gas Chromatograph-Mass Spectrometer (EI), equipped with a
15M x 0.25mm ID DB-5 column with a 0.25mm film thickness. The initial oven

1Michigan State Police Forensic Science Division, 7320 N. Canal Road, Lansing, MI 48913

Received 01 Oct. 2009; and in revised form 30 Dec. 2009; accepted 08 Jan. 2010

Page 8
JASTEE, Vol. 1, Issue 1 Bommarito: ID of a Cyclopentyl Nitrite Inhalant

temperature was 40° C, held for 5 minutes and ramped to 200° C at a rate of 25° C per
minute.
Ion chromatography was performed by diluting the samples in analytical grade water
(NERL Diagnostics 9800-1) and the anions separated on a Dionex DX-120 Ion
Chromatograph, equipped with an AS9-HC (Dionex 4 x 250mm) column. A laboratory
prepared 9mM sodium carbonate eluent mobile phase was used with a flow rate of 1.2
ml/min. under isocratic conditions.

Results
Gas Chromatography-Mass Spectrometry of the questioned liquid headspace showed
the presence of three major peaks at 1.18, 1.37 and 2.37 minutes (Figure 1).

RT: 0.43 - 8.23

1.19 NL:
100 1.33E6
TIC MS q
90 sample
headspace
80 _07083114
2455
70
Relative Abundance

60

50

40

30 1.35

20

10 0.48
1.52 1.78 2.39 2.46 3.50 3.72 4.26 4.55 5.09 5.34 5.89 6.14 6.44 7.03 7.96 8.03
0
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0
Time (min)

FIG 1- Gas chromatogram of questioned liquid headspace

The compound eluting at 1.19 minutes had a 41 base peak and major ions at 55, 57,
67, 69 and 84 (Figure 2). A search of the instrument’s NIST library identified the
compound as “Cyclopentanol, nitrate, Formula C5H9NO3, CAS #21823-29-0”. An
internet search for this compound and CAS number did not reveal any information.
The compound eluting at 1.37 minutes had a 57 base peak with major ions at 44, 67
and a molecular ion of 86. This component was identified using a reference standard as
cyclopentanol (Figure 3).
The compound eluting at 2.37 minutes also displayed a 57 base peak and major ions
at 44, 67 and a molecular ion of 86. This compound was identified using the NIST
reference library as 2-pentanol, distinguished from cyclopentanol based on ion ratios.

Page 9
JASTEE, Vol. 1, Issue 1 Bommarito: ID of a Cyclopentyl Nitrite Inhalant

q sample headspace_070831142455 #132 RT: 1.19 AV: 1 SB: 1 1.09 NL: 3.34E5
T: {0,0} + c EI det=230.00 Full ms [ 35.00-500.00]
41
100

95

90

85

80

75
69
70

65

60
Relative Abundance

55

50

45

40

35
55 57 67
30

25 43
39
20

15

10
38 65
44 53 70
5
45 51 58 63
71 78 82 84 83 90 98 102 111 114 125 127 131 139 143 147 154 158 164 167 178 188 191 195 198
0
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200
m/z

FIG. 2- Mass spectrum of the case sample’s peak eluting at 1.19 min. This peak is
consistent with cyclopentyl nitrite.

q sample headspace_070831142455 #153 RT: 1.35 AV: 1 SB: 1 1.64 NL: 1.31E5
T: {0,0} + c EI det=230.00 Full ms [ 35.00-500.00]
57
100

90

80

70
Relative Abundance

60

50

40
44
30

20
41 58
10 39 67 68
45 56
59 71 86 88 97 104 109 120 124 130 141 153 160 169 173 179 188 196 200
0
40 60 80 100 120 140 160 180 200
m/z

FIG. 3- Mass spectrum of the case sample’s peak eluting at 1.35 min. This peak is
consistent with cyclopentanol.

It was suspected by the author that the compound identified by the NIST library as
“Cyclopentanol, nitrate” was actually cyclopentyl nitrite. The structure of cyclopentyl
nitrate appears unstable and it was surmised that the compound would be reduced in
solution to the nitrite of the compound (Figure 4). Neither cyclopentyl nitrate nor

Page 10
JASTEE, Vol. 1, Issue 1 Bommarito: ID of a Cyclopentyl Nitrite Inhalant

cyclopentyl nitrite had been reported in the forensic literature nor do either have a
commercially available analytical standard.

FIG. 4- Reduction of Cyclopentyl Nitrate to Cyclopentyl Nitrite

An attempt to manufacture a cyclopentyl nitrite standard was made by reacting

cyclopentanol (99%, Alfa Aesar, Heysham, England) with potassium nitrite (ACS, Fisher
Scientific, Fair Lawn, NJ) in con. sulfuric acid (ACS, Fisher Scientific, Fair Lawn, NJ) No
visible reaction occurred and FTIR and GC-MS examination of the product indicated no
detectable cyclopentyl nitrite was produced. The cyclopentanol was then reacted with
ammonium nitrate (ACS, Mallinckrodt, St. Louis, MO) in con. sulfuric acid. This resulted
in a sustained exothermic reaction resulting in a yellow liquid with a pH of 1-2, similar
to the questioned liquid in the case. Vapor phase IR spectra and headspace GC-MS
data were obtained under the same conditions as the questioned liquid and confirmed
the compounds produced in the reaction were consistent with the known liquid (Figures
5, 6, 7).

RT: 0.42 - 8.21

1.18 NL:
100 5.48E5
TIC MS K
90 cyclo prep
std_07083
80 1143400

70 1.37
Relative Abundance

60

50 0.47

40

30 2.37
0.56
20

10 0.67 1.54 1.82 2.50 3.18 3.39 3.92 4.20 4.68 5.10 5.19 6.00 6.49 6.65 7.03 7.58 8.19

0
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0
Time (min)

FIG. 5- Gas chromatogram of headspace of liquid produced from cyclopentanol,

ammonium nitrate and sulfuric acid.

Page 11
JASTEE, Vol. 1, Issue 1 Bommarito: ID of a Cyclopentyl Nitrite Inhalant

K cyclo prep std_070831143400 #129 RT: 1.18 AV: 1 SB: 1 2.04 NL: 1.49E5
T: {0,0} + c EI det=230.00 Full ms [ 35.00-500.00]
41
100

90

80

70
Relative Abundance

60
69
50

40

30 55 57
43 67
39
20

10 65
44 53 70
59 71 84 83 94 105 111 114 121 128 138 142 148 153 163 170 176 180 195 200
0
40 60 80 100 120 140 160 180 200
m/z

FIG. 6-Mass spectrum of the laboratory prepared sample peak eluting at 1.18 min.
This peak is consistent with cyclopentyl nitrite.2

FIG. 7-Vapor phase infrared spectrum of prepared cyclopentyl nitrite standard

(top/black), questioned sample (middle/blue) and butyl nitrite (bottom/red).2

2 Figure titles corrected following errata published in JASTEE 6-3.

Page 12
JASTEE, Vol. 1, Issue 1 Bommarito: ID of a Cyclopentyl Nitrite Inhalant

To determine if the reaction product was cyclopentyl nitrite or cyclopentyl

nitrate, ion chromatography was performed. The retention times of the reacted liquid
were compared to that of a standard anion mixture (Dionex #56933) and found to
consist primarily of nitrite with a trace amount of nitrate present. This finding was
sufficient along with the FTIR and GC-MS analytical data to confirm both the standard
synthesized from cyclopentanol, ammonium nitrate and sulfuric acid and the questioned
sample as containing cyclopentyl nitrite. Three commercial alkyl nitrite products (Blue
Boy, Jungle Juice and Crypt Tonight) were also examined by this method and also found
to show the presence of nitrite anions.
In an attempt to locate a commercial product containing cyclopentyl nitrite, thirteen
commercial “Popper” samples were purchased and analyzed via gas phase FTIR and GC-
MS in the same manner as described above. The results are listed in Table 1.

Product Name Label Content Compounds Detected

Jungle Juice Plus Room
Odorizer
Crypt Tonight Head Cleaner
PowR PeleT Video Head
Cleaner
Mr. Chaps Leather Cleaner
Amsterdam Poppers
Can Opener Cleaner
Jim Diamond’s 24k Cleaner
Zap! Cleaner
Purple Video Head Cleaner
Nitro Supra Liquid Aroma
Blue Boy Liquid Incense
Pig Sweat Polish Remover
Ecstasy Pop
TABLE 1- Results of commercial alkyl nitrite analysis. All products contained butyl
nitrate, regardless of label content.
Isopentyl Nitrite Butyl Nitrite, Butyl
Alcohol
85% isobutyl alcohol, 5%HCl, 5% H2O, 5% Butyl Nitrite, Butyl
Other Alcohol
85% isobutyl alcohol, 5%HCl, 5% H2O, 5% Butyl Nitrite, Butyl
Other Alcohol
85% isobutyl alcohol, 5%HCl, 5% H2O, 5% Butyl Nitrite, Butyl
Other Alcohol
Alkyl Nitrate Butyl Nitrite, Butyl
Alcohol
Anaerobic Stabilizer Resin Butyl Nitrite, Butyl
Alcohol
Anaerobic Stabilizer Resin Butyl Nitrite, Butyl
Alcohol
Anaerobic Stabilizer Resin Butyl Nitrite, Butyl
Alcohol
Cyclohexyl Nitrite Butyl Nitrite, Butyl
Alcohol
Does not contain Alkyl Nitrites Butyl Nitrite, Butyl
Alcohol
Isobutyl Nitrite Butyl Nitrite, Butyl
Alcohol
None Butyl Nitrite, Butyl
Alcohol
None Butyl Nitrite, Butyl
Alcohol

Page 13
JASTEE, Vol. 1, Issue 1 Bommarito: ID of a Cyclopentyl Nitrite Inhalant

All the commercial products examined were found to contain butyl nitrite and butyl
alcohol. This was regardless of the commercial labeling which indicated that the
products contained various ingredients, including isopentyl nitrite, cyclohexyl nitrite and
other substances. One labeled product, “Nitro Supra” indicated that the product “does
not contain alkyl nitrites”, yet upon examination, butyl nitrite was also found in this
product. None of the products examined showed the presence of cyclopentyl nitrite.

Discussion
It appears that while butyl nitrite is the most commonly sold over-the-counter nitrite
inhalant, manufacturers/distributors of many of these products may use a number of
alkyl nitrate compounds and not appropriately label the packaging. It was not
determined whether cyclopentyl nitrite inhalant that was encountered in this case was
clandestinely produced or used as an ingredient of a commercial nitrite inhalant. If it
was a commercial product, it may have not been labeled as containing this material.

References

(1) Dearmore, I., Cyclohexyl Nitrite Encounter, J Forensic Sci 1999; 44(1):197-204

(2) Porter, RS, et al., The Merck Manual Online, Merck & Co., Retrieved on 8-12-08.,
http://www.merck.com/mmpe/sec15/ch198/ch198m.html#sec15-ch198-ch198m-400

Page 14