Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
2002-09-18
2003-04-29
Barts, Samuel (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C548S371700, C548S561000
Reexamination Certificate
active
06555711
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to an &agr;-amino-N-allylamidino nitrobenzene compound and process for its preparation.
BACKGROUND OF THE INVENTION
The photographic art employs couplers to provide colored dyes in image reproductions. The couplers react imagewise with color developer to produce the desire reproduction. One of the couplers useful for this purpose is a pyrazolo[1,5-b][1,2,4]triazole compound that has found utility for forming a magenta dye in the usual system employing subtractive primaries.
Such couplers and methods of making them were originally disclosed in U.S. Pat. No. 4,621,046. Other methods have been disclosed in U.S. Pat. Nos. 4,705,863 and 6,020,498. The latter patent suggests the use of certain N-alkylamidino nitrobenzene derivatives for synthesizing intermediates in the process. It is desirable, however to provide alternative processes for preparing the desired compounds, especially processes that can provide improved yields.
SUMMARY OF THE INVENTION
The invention provides a process comprising reacting an N-allylimino nitrobenzene compound with a diaminodinucleophile to form an &agr;-amino-N-allylamidino nitrobenzene compound and also provides the compound itself as a composition of matter.
The invention provides a useful process for synthesizing useful compounds employing allyl groups. Embodiments of the invention can provide improved yields compared to prior art processes.
DETAILED DESCRIPTION OF THE INVENTION
The invention is summarized above. The process of the invention is generally shown in reaction scheme 3 in the following scheme.
In reaction 3, an N-allylimino nitrobenzene compound is reacted with a diaminodinucleophile to form an &agr;-amino-N-allylamidino nitrobenzene compound. Suitably, the reaction is carried out in the presence of a solvent that is inert under the reaction conditions. Useful solvents may be selected from the group consisting of C
1
to C
8
aliphatic alcohols, chlorinated or unchlorinated aromatic hydrocarbons such as toluene, the xylenes, monochlorobenzene or dichlorobenzenes, chlorinated or unchlorinated aliphatic hydrocarbons, ethers such as tetrahydrofuran, and esters such as ethyl acetate or isopropyl acetate. Preference is given to using alcohols, in particular isopropyl alcohol. In particular the reaction may be carried out using a mixture of toluene and isopropyl alcohol where the 3-tert-butyl-5-aminopyrazole in an isopropyl alcohol solution is added to a toluene solution of the amidine.
The reaction is exothermic and conveniently carried out at a temperature ranging from −10° C. to +30° C. and desirably from 0 to 15° C.
The reaction is carried out with the diaminodinucleophile being present in stoichiometric quantity or in excess compared to the &agr;-amino-N-allylamidino nitrobenzene compound, with an excess of up to 0.5 mols/mol and a range of 1 to 1.25 mols/mol preferred. The compound is one having at least two nucleophilic nitrogen atoms and may include a ring compound such as an 3-tert-butyl-5-aminopyrazole.
Reaction 3 is typically described using the above captioned equation and the following limitations:
Z and X may independently be halogen, alkoxy, aryloxy, alkylthio, arylthio or heterocyclic groups;
R
1
, R
2
, and R
3
may independently be hydrogen, halogen, alkoxy, aryloxy, alkylthio, arylthio, (cyclo-)alkyl, alkenyl, alkynyl, silyl or heterocyclic groups; provided that R
1
, R
2
, and R
3
may also be contained within a carbocyclic or heterocyclic aromatic or non-aromatic ring system;
R
4
and R
5
may independently be hydrogen, halogen, alkoxy, aryloxy, alkylthio, arylthio, alkyl, alkenyl, alkynyl, silyl or heterocyclic groups; provided that R
4
and R
5
may also be contained within a carbocyclic or heterocyclic aromatic or non-aromatic ring system; and
Y is a leaving group such as hydroxy, halogen, alkoxy, aryloxy, acetoxy, siloxy, mesylate or tosylate. The preferred leaving groups are mesylate or tosylate.
The reaction may be represented by the following reaction 3
wherein
Z and X are independently selected from halogen, alkoxy, aryloxy, alklthio, arylthio and heterocyclic akyl groups and n is 0 to 4;
R
1
, R
2
, R
3
are independently selected from H, halogen, alkoxy, aryloxy, alkylthio, arylthio, alkyl, saturated or unsaturated cyclohydrocarbyl, heterocylic, aroyl, alkenyl, alkynyl, and silyl groups, provided that R
1
, R
2
, R
3
may also be contained within a ring system; and
R
4
and R
5
are independently selected from H, halogen alkoxy, aryloxy, alkylthio, arylthio, alkyl, saturated or unsaturated cyclohydrocarbyl, hetereocylic, aromatic, aryl, alkenyl, alkynyl, silyl, provided that R
4
and R
5
may also be contained within a ring system.
The starting amide can be prepared using known methods, for example where the amine can be reacted with an acyl halide, an anhydride, an ester, or direct coupling with a carboxylic acid. (Woodcock, D. J. in Patai
The Chemistry of the Amino Group
; Wiley: N.Y., 1968, p. 440.)
In order to carry out step 2, use is generally made of a chlorinating agent such as, in particular, thionyl chloride (SOCl
2
), phosphorus pentachloride (PCl
5
), phosphorus oxychloride (POCl
3
), phosgene (COCl
2
), or oxalyl chloride (COCl)
2
, or one of their mixtures as more fully described in:
SOCl
2
Lawson, A.; Miles, D. H. ; J Chem Soc [JCSOA9] 1959, 2865.
POCL
3
Harris, R. L. N.; Synthesis [SYNTBF] 1980 (10), 841.
PCl
5
Madronero, R.; Vega, S.; Synthesis [SYNTBF] 1987 (7), 628.
(COCl)
2
Fujisawa, T.; Mori, T.; Sato, T.; Tetrahedron Lett [TELEAY] 1982, 23 (48), 5059.
Preference is given to using thionyl chloride. The chlorinating agent is employed in stoichiometric quantity or in excess. For reasons of economy, the quantity of chlorinating agent is preferably from 1 to 1.25 mol per mol of amide. The reaction can be carried out without solvent, with the chlorinating agent then serving as the solvent, or in the presence of a solvent or a mixture of solvents which are inert under the reaction conditions and which are selected from chlorinated or unchlorinated aromatic hydrocarbons such as toluene, the xylenes, monochlorobenzene or the dichlorobenzenes, or chlorinated or unchlorinated aliphatic hydrocarbons such as ethane or dichloromethane. Toluene is very suitable.
The temperature of this reaction is generally between 25° C. and the reflux temperature of the solvent. When toluene is the chosen solvent and the chlorinating agent is thionyl chloride, the temperature is, in particular, between 70° C. and 110° C.
Catalysts such as N,N-dialkylated amides, in particular dialkylated formamides whose alkyl groups possess from 1 to 8 carbon atoms, such as N,N-dimethylformamide and, more especially, N,N-dibutylformamimde, can be added in order to accelerate the reaction. In general, the chlorination lasts between 2 and 15 hours. Once the reaction has finished, it is not necessary to isolate the chloroimine that is formed from the reaction medium.
General conditions for forming the oxime are described in the following literature:
C. G. McCarty, “
Chemistry of the Carbon
-
Nitrogen Double Bond
” Ed. S. Patai, Interscience, New York (1970), pp 408-439;
J. A. Gautier, M. Miocque and C. C. Farnoux, “The Chemistry of Amidines and Imidates”, Ed. S. Patai, Interscience, New York, (1975) pp 313-314.
Steps 5 and 6 are ring closure reactions and are more fully described in U.S. Pat. No. 4,705,863.
Unless otherwise specifically stated, use of the term “group”, “substituted” or “substituent” means any group or radical other than hydrogen. Additionally, when reference is made in this application to a compound or group that contains a substitutable hydrogen, it is also intended to encompass not only the unsubstituted form, but also its form further substituted with any substituent group or groups as herein mentioned, so long as the substituent does not destroy properties necessary for the intended utility. Suitably, a substituent group may be halogen or may be bonded to the remainder of the molcule by an atom of
Niger Robert J.
Vreeland William B.
Barts Samuel
Eastman Kodak Company
Kluegel Arthur E.
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