SOME INFORMATIONS ABOUT „NOVICHOK“-AGENTS

AND THE „FOLIANT“-PROGRAMM

(by: fritz)

The “Foliant”-program started at 1973-1976 an had the aim to develop new CWs.
Also effort was made to produce the agents covert and with precursors which were not related
with CWs 8and so to avoid detection by international inspectors) The results were the
“novichok”-agents and their unitary forms.
This program was revealed in 1992 by two chemists (Lev Fedorov and Vil Mirzayanov) who
were involved in this program.
SUBSTANCES:

“Substance 33”
(also: “Soviet V-gas; binary form has no established name, Mirzayanov calls it:
“novichok-#”)
• analog of VX, was produced in the USSR instead of VX
• produced in the ”Khimpron” Cheboksary Production Association (former names:
production facility no.3, Chuvash Production association; Khimpron imeni Leninsiy
Komsomol) at Vovocheboksark (near Cheboksary) in the Chuvash republic, upper Volga
region (“novichok-#” was produced at the same site as “novichok 7”)
• could not be detected by U.S. CW-detectors
• may have been used (or set free through incomplete burning of Iraqi CW) in the first gulf-
war and may so perhaps be the reason for the “gulf-war-syndrome”
• in the early 1980s 15000t were produced

“novichok”-agents
(binary agents)
• described as: “a new toxic agent...an injury with it is practically incurable...those who
were once affected with this toxic agent have remained disabled for the rest of their lives”
• it may even be ten (five to eight times) times stronger than VX
• Binary versions consist e.g. from Acetonitril and an organic phosphate compound
(pesticide precursor) an other version needs only the addition of alcohol to form the agent.

“novichok-7”
• similar volatility as soman but is ten times more effective
• produced in the “Volsk 12” facility [former name: Volsk affiliate of GosNIIoKhT
(=Russian Scientific Research Institute of Organic Chemistry an Technology)]
in Shikhany in the Saratov-oblast; this facility was not mentioned under the 1989
Wyoming WOU Mirzayanov later alleged the production of CW at this site

“A-230”
• officially approved by the soviet army in1988
• created in the FOLIANT-program
• was produced at the same site as “novichok 7”

“A-232”
(binary form: “novichok-5”)
• created in the FOLIANT-program
• made from industrial and agricultural chemicals that are not toxic and that never have
been used for poison gas
• as toxic (five to eight times stronger) as VX; as resistant to treatment as Soman; more
difficult to detect and easier to produce than VX
• was produced at the same site as “novichok 7” ( both: “A-232” and “novichok-5”)
• never received soviet approval

“A-234”
ethyl analog of “A-232”

_______________________________
these informations were taken from:
• The UK GulfWeb: Novichok, Svoviet Chemical Warfare Agents Novichok and substance 33
• Publications of the center for Security Policy: No. 97-D 19
• Russia’s toxic threat (Source??)
• Dr. Lev A. Fedorov: Chemical weapons in Russia: History, Ecology, Politics
• Jonathan B. Tucker: Converting former Soviet CW-plants

Some additional sources which I unfortunately could not verify:

• The Baltimore Sun; Oct. 18, 1992; Will Englund: Russia still doing work on Chemical arms
• The Baltimore Sun; Sept. 16, 1992, will Englund: Ex-Soviet Scientist Says Gorbachev´s regime Created
New Nerve Gas In ´91
• Moscow News weekly; No. 39, 1992; Lev Fedorov and Vil Mirzayanov: A Poisoned Policy
• Wall Street Journal; May 25, 1994; Vil Mirzayanov: article name:???

ADDITIONS to Samosa´s paper:

• Ken (Kenneth) Alibek is definitively not an alias of Vil Mirzayanov.

Ken Alibek (original name: Kanatjan Alibekov) was born in Kazachstan and worked for
“Biopreparat” a secret soviet establishment for the research of BW. (interesting book:
BIOHAZARD The chilling True story of the Largest Biological Weapons Program in the
World- Told from Inside by the Man Who ran It; by Ken Alibek and Stephan Handelman)
• Novichok-formulas:
I looked up the CA and found the following:

I)
CAS-RN 26102-97-6:
[[(2-chloroethoxy)fluorohydroxyphosphinyl]oxy]carbonimidic chloride fluoride
C3H4Cl2F2NO3P
Mentioned in:
CAS:
77: 100370d; 113761g
78: 136375u

II)
CAS-RN 26102-98-7:
[[(2-chloro-1-methylethoxy)fluorohydroxy-phosphinyl]oxy]carbonimidic chloride
fluoride
C4H6Cl2F2NO3P
Mentioned in:
CAS:
77: 113761g

III)
CAS-RN 26102-99-8
[[(2-chloro-1-methylpropoxy)fluorohydroxy-phosphinyl]oxy]carbonimidic chloride
fluoride
C5H8Cl2F2NO3P
Mentioned in:
CAS:
77: 100370d; 113761g
78: 136375u

of course I read the mentioned articles and will give you a summary of the contents:

CCl2FNO reacts with P(OPh)3 (in Et2O under N-atm.) to give:

Cl
F
Ph
O N
O
P O
Cl
O Ph
Ph

Similar adducts
R
R

O
O
P
O
Cl F
N Cl

F
 were formed with fluorinated Phospholanes
R

P
F R
O
(R= H or Me)

These compounds were stable under subzero temperatures but on being warmed
underwent a conversion to:
R R
O

Cl O P O F

F N

Cl

according to this information I will consider the first formula given on Samosa´s
document to be the one with R= H.

Also in his document two articles are mentioned in the Journal of General Chemistry (rus:
Zhurnal Obshchei Khimii)
These are not exactly about the “novichok”-agents but about similar compounds.
1) phosphorylated alkanoyl chloride oximes from trialkyl phosphites and the
corresponding 1,1-dichloro-1-nitrosoalkanes (Allen-Reaktion):
R
R O
O R Cl
R1 O P O R1
O
P O
+ N - RCl N
R O Cl O
R
Cl

2) O-methylchloroformimido-O-ethylmethylphophonate
R2 O
R R2 O R2 O
O
O P O R
X N
+
+ P O + O P O + R2 Cl
- O N
O R2 O R2 O R2
R1 R2
R1 R2

The above mentioned “Allen-Reaktion is described in an article in the journal of the

American Chemical Society (79, (1975), 3071).
It speaks about the reaction of alkyl esters of trivalent phosphorous with α -halonitro-
compounds to give oxime esters of pentavalent phosphorous:
 R2 O
R R2 O R2 O
O
O P O R
X N
+
+ P O + O P O + R2 Cl
- O N
O R2 O R2 O R2
R1 R2
R1 R2

In which a redox-reaction between the nitro-compound and the phosphite takes place to
produce a nitroso-compound and phosphate.

The ease in which this reaction takes place increases with the number of α -halogen-
atoms and bromine-compounds are more active than chlorine-compounds. Nitromethane
does not react. The oxime-esteres were obtained in yields of 32-63%.