Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2000-04-04
2001-01-30
Ramsuer, Robert W. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C549S023000, C549S057000
Reexamination Certificate
active
06180797
ABSTRACT:
BACKGROUND OF THE INVENTION
Thiochroman and dihydrobenzothiophene herbicidal agents and methods of their preparation are described in U.S. Pat. No. 5,506,194, U.S. Pat. No. 5,607,898 and WO 97/08164 among other publications. The 6-(arylcarbonyl)thiochroman and 5-(arylcarbonyl)dihydrobenzothiophene derivatives are effective herbicidal agents at low rates of application and demonstrate selective control of noxious weeds in the presence of important economic crops such as corn and rice.
A common route to prepare these useful herbicidal agents entails the dehalogenation of an 8-halo-6-carbethoxythiochroman or 7-halo-5-carbethoxydihydrobenzothiophene intermediate compound. Heretofore, methods to dehalogenate said intermediate compound required high pressure hydrogenation techniques. Further, product yield and quality may be less than satisfactory. The importance of the dehalogenated 6-carbethoxythiochroman and 5-carbethoxydihydrobenzothiophene intermediates, particularly as key intermediates in the manufacture of herbicidal arylcarbonylthiochroman and arylcarbonyldihydro-benzothiophene agents, creates a significant need in the art for alternative and effective processes for their preparation.
SUMMARY OF THE INVENTION
The present invention provides a safe efficient process for the preparation of a compound of formula I
wherein
R and R
1
are each independently H or C
1
-C
4
alkyl;
R
2
and R
3
are each independently H, C
1
-C
4
alkyl or R
2
and R
3
may be taken together with the atom to which they are attached to form a group C═NOR
9
or C═O;
R
4
, R
5
, R
6
, R
7
, R
8
and R
9
are each independently H or C
1
-C
4
alkyl; and
m is 0 or 1
which process comprises reacting a compound of formula II
wherein Hal is Cl, Br or I and R, R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, R
7
, R
8
and m are as described hereinabove with a catalytic amount of Pd/C and at least two molar equivalents of ammonium formate in the presence of a polar solvent optionally at an elevated temperature.
DETAILED DESCRIPTION OF THE INVENTION
Compounds of formula I are important key intermediates in the manufacture of thiochroman and dihydrobenzothiophene herbicidal agents. Methods to prepare the formula I intermediates commonly require high pressure hydrogenation procedures which may give less than satisfactory product yield and quality. Surprisingly, it has now been found that compounds of formula I may be readily and efficiently prepared from their halo precursors at atmospheric pressure using a transition metal catalyst and ammonium formate as a hydrogen source in the presence of a polar solvent, optionally at an elevated temperature. Advantageously, the product formula I compounds are obtained in good yield and high quality. The reaction is shown in flow diagram I.
Polar solvents suitable for use in the process of the invention include alkanols, carboxylic acids or mixtures thereof, preferably methanol, ethanol or a mixture thereof.
Transition metal catalysts suitable for use in the inventive process include those transition metals commonly used in catalytic hydrogenation procedures such as Pt, Pd, Ni, Rh and similar conventional transition metals, preferably Pd. A catalytic amount designates that amount of catalyst required to facilitate the reaction and may range from an equimolar amount to a trace amount, preferably about 5 mole % to 20 mole %.
Suitable reaction temperatures useful in the inventive process may range from ambient temperatures to the reflux temperature of the solvent or solvent mixture. In general, increased reaction temperature leads to increased reaction rate and drives the reaction to completion. However, excessively high temperatures may be detrimental and are not required. Preferable reaction temperatures are about 25° C.-200° C., more preferably about 50° C.-150° C.
Stoichiometrically, the inventive process requires at least 2 molar equivalents of ammonium formate in order to go to completion, however excess amounts of ammonium formate may be employed without detrimental effect.
Therefore, in accordance with the process of the invention, a compound of formula II, preferably wherein Hal is chlorine, is admixed with a polar solvent, preferably an alkanol, acetic acid or a mixture thereof, treated with at least 2 molar equivalents of ammonium formate, preferably 3 to 5 molar equivalents, and a catalytic amount of a transition metal catalyst, preferably Pd on carbon (Pd/C) at temperatures ranging from ambient temperatures to the reflux temperature of the solvent, preferably about 25° C.-200° C., more preferably about 50° C-150° C., to obtain the desired formula I compound.
Compounds of formula II preferred for use in the inventive process include those compounds of formula II wherein Hal is Cl; m is 1; and R
2
and R
3
are taken together with the atom to which they are attached to represent C═NOR
9
. Another group of formula II compounds preferred for use in the inventive process are those compounds wherein Hal is Cl; m is 0; and R
2
and R
3
are each independently C
1
-C
4
alkyl.
Thiochroman and dihydrobenzothiophene herbicidal agents may be prepared from compounds of formula II via the inventive process to form the intermediate compound of formula I; when R is C
1
-C
4
alkyl, hydrolyzing the formula I compound to the corresponding carboxylic acid of formula III; and reacting the formula III acid with an hydroxypyrazolyl compound of formula IV to obtain the arylcarbonyl compound of formula V, optionally reacting the formula V compound with a sulfonyl chloride of formula VI to obtain the arylcarbonyl compound of formula VII. The formula V and formula VII arylcarbonylthiochromans and dihydrobenzothiophenes are potent herbicidal agents. The reaction sequence is shown in flow diagram II wherein R
10
is C
1
-C
4
alkyl; R
11
is H or C
1
-C
4
alkyl; and R
12
is C
1
-C
6
alkyl or phenyl optionally substituted with one to three halogen, NO
2
, C
1
-C
4
alkyl, or C
1
-C
4
alkoxy groups.
The herbicidal agents of formula V and formula VII and their preparation from compounds of formula I are described in U.S. Pat. Nos. 5,506,194 and 5,607,898. The hydrolysis and sulfonation steps described above may be accomplished using conventional methods. The coupling of the hydroxypyrazole compound of formula IV and the subsequent rearrangement to the desired compound of formula V may be performed using standard methods such as those described in U.S. Pat. No. 5,506,194 and U.S. Pat. No. 5,607,898, i.e. in the presence of a base and a dehydrating agent.
For a more clear understanding of the invention, the following examples are set forth below. These examples are merely illustrative and are not understood to limit the scope of underlying principles of the invention in any way. Indeed, various modifications of the invention, in addition to those shown and described herein, will become apparent to those skilled in the art from the following examples and the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.
The terms
1
HNMR and
13
CNMR designate proton and carbon 13 nuclear magnetic resonance, respectively. The term IR designates infrared spectroscopy. HPLC designates high performance liquid chromatography.
REFERENCES:
patent: 5506194 (1996-04-01), Nasuno et al.
patent: 5607898 (1997-03-01), Nakumura et al.
patent: WO 97/08164 (1997-03-01), None
Anwer, M.K. and Spatola, A.F., Tetrahedron Letters, 26 (11), pp. 1391-1384 (1985).
American Cyanamid Co.
Hogan Jr. John W.
Maurer Barbara V.
Ramsuer Robert W.
LandOfFree
Process for the dehalogenation of thiochroman and... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Process for the dehalogenation of thiochroman and..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for the dehalogenation of thiochroman and... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2464975