Claims
- 1. A Diels-Alder Adduct of a dihydro-nitrogen heterocyclic phosphoramidate of the formula ##STR21## with a dienophile where ##STR22## represents a 1,2-dihydro-2-R-pyridinyl or lower alkyl substituted 1,2-dihydro-2-R-pyridinyl, R and R.sub.1 are lower alkyl or phenyl and X is O or S, said dienophile being of the formula
- Ch.sub.2 = cha, where A represents CHO, CO.sub.2 H, CO.sub.2 CH.sub.3, CO.sub.2 C.sub.2 H.sub.5, COCl, COCH.sub.3, COC.sub.6 H.sub.5, CN, NO.sub.2, C.sub.6 H.sub.5, CH.sub.2 OH, CH.sub.2 Z, CH.sub.2 NH.sub.2, CH.sub.2 CN, CH.sub.2 CO.sub.2 H, CH.sub.2 NCS, OCOCH.sub.3, SC.sub.6 H.sub.4 CH.sub.3, Z or H,
- C.sub.6 h.sub.5 ch = cha, where A represents CHO, CO.sub.2 H, CO.sub.2 CH.sub.3, CO.sub.2 C.sub.2 H.sub.5, COCH.sub.3, COC.sub.6 H.sub.5,
- Ch.sub.2 = ca.sub.2, where A represents CO.sub.2 C.sub.2 H.sub.5, CN, COCH.sub.3, Z,
- Ach = cha, where A represents CO.sub.2 H, COCl, CO.sub.2 CH.sub.3, CO.sub.2 C.sub.2 H.sub.5, COCH.sub.3, COC.sub.6 H.sub.5, Z, Quinone,
- Ac .tbd. ca, where A represents CO.sub.2 H, CO.sub.2 CH.sub.3, CO.sub.2 C.sub.2 H.sub.5,COC.sub.6 H.sub.5, C.sub.6 H.sub.5, H,
- and where Z represents halogen, or said dienophile is crotonaldehyde, dibenzalacetone, 1-cyclopentene-3-one, 1-cyclohexene-3-one, crotonic acid, crotonyl chloride, 3,4-dihydro-1-naphthoic acid, coumarin, beta-naphthol (as keto tautomer), cyclopentadiene, 1,3-cyclohexadiene, acenaphthylene, 4-vinyl-1-cyclohexene, 1-methyl-1-cyclopentene, dicyclopentadiene, maleic anhydride, or N-phenyl maleimide, and where said Diels-Alder Adduct is characterized by having the following structure in the adduct ##STR23## the carbons C.sub.1 and C.sub.2 being carbons of an unsaturated carbon to carbon bond of said dienophile and the atoms of the 6 membered ring of said structure containing nitrogen and the indicated double bond being the atoms of the 1,2-dihydropyridine group and the free valences of said structure being attached to atoms of said Diels-Alder Adduct.
- 2. The compound of claim 1 where ##STR24## and where R is phenyl, R.sub.1 is ethyl and X is O.
- 3. The compound of claim 1 where ##STR25## and where R is butyl, R.sub.1 is methyl and X is S.
- 4. The compound of claim 1 where ##STR26## and where R is methyl, R.sub.1 is ethyl and X is O.
- 5. The compound of claim 1 where ##STR27## and where R is butyl, R.sub.1 is ethyl and X is O.
- 6. The compound of claim 1 where ##STR28## and where R is butyl, R.sub.1 is methyl and X is S.
- 7. The compound of claim 1 where ##STR29## and where R is methyl, R.sub.1 is isopropyl and X is O.
- 8. The compound of claim 1 where ##STR30## and where R is phenyl, R.sub.1 is ethyl and X is O.
- 9. The Diels-Alder Adduct of claim 1 where the phosphoramidate is ##STR31## and the dienophile is maleic anhydride, the adduct having the structure ##STR32##
- 10. The Diels-Alder Adduct of claim 1 wherein the phosphoramidate is ##STR33## and the dienophile is N-phenyl maleimide, the adduct having the structure ##STR34##
Parent Case Info
This application is a Division of Ser. No. 210,106 filed Dec. 20, 1971, now U.S. Pat. No. 3,821,232. su
This invention relates to dihydro-nitrogen heterocyclic phosphoramidates characterized by the formula ##STR3## where R is a substituted group and R.sub.1 is an alcohol moiety, where R and R.sub.1 are alkyl, aryl, cycloalkyl, alkaryl, aralkyl, etc., X is oxygen or sulfur, and the circle represents a cyclic structure which may be a sole cyclic structure or attached to other cyclic groups. Representative compounds include ##STR4## where R and R.sub.1 are lower alkyl, aryl, etc. These dihydro-nitrogen heterocyclic phosphoramidates may also be termed dihydro-nitrogen-N-phosphonates and thiophosphonates.
These compounds are prepared by reacting nitrogen heterocyclics in a hydrocarbon metal or Grignard type reaction for example, according to the following reactions ##STR5##
These products have a wide variety of uses including their use as corrosion inhibitors, biocides, etc. Derivatives of these products can also be prepared, such as the Diels-Alder Adduct, etc.
Any nitrogen heterocyclic capable of being activated so as to react with a phosphochloridate can be reacted. These include heterocyclics having one or more rings where at least one ring has a nitrogen heterocyclic group and the other rings are carbocyclic or heterocyclic, i.e.; they may contain oxygen or other non-carbon elements in the ring, etc.
They may be illustrated by the formula ##STR6## where the R's, which may or may not be the same, are hydrogen or a substituted group, for example, alkyl, cycloalkyl, aryl, aralkyl, alkoxy, halo, etc. The R's may also be further substituted provided the substituted groups do not interfere with the reaction.
An R group may also be joined to an adjacent group so as to form a ring provided ortho and/or para positions are available for substitution, for example in the following aromatic type ring systems: ##STR7##
The above ring systems may also be substituted. The adjacent rings may also contain heterocyclic groups for example oxygen, nitrogen, etc., and/or may contain rings having less than six molecules in the ring for example a 5 member ring.
In certain instances more than one nitrogen heterocyclic ring may be capable of reacting with the phosphochloridate so that substitution may occur in more than one ring.
Representative examples of heterocyclic reactants include pyridines and benzo- and dibenzo- derivatives of pyridine, for example, pyridine, alkylated pyridines such as 2-picoline, 3-picoline, 4-picoline, etc., 2,4-lutidine, 2,6-lutidine, 2,3-lutidine, etc., collidines, etc., quinoline and alkylated quinolines, etc., isoquinolines, and alkylated isoquinolines, etc., phenanthridines, and substituted phenanthridines, etc., acridines and substituted acridines, etc.
By means of the present reaction, the chloridate moiety of a phosphite group is added to the nitrogen atoms in the form of the phosphite ester to form an amide ##STR8##
The phosphorus reactant in this reaction is a diester acid halide of a phosphoric or thio-phosphoric acid, ##STR9## The X can be oxygen or sulfur, for example ##STR10## R can be alkyl, cycloalkyl, aralkyl, aryl, etc., such as methyl, ethyl, propyl, cyclohexyl, phenyl, etc.
The reaction is preferrably carried out in an inert solvent such as hexane, benzene, tetrahydrofuran, dioxane, etc., at temperatures from -70.degree. to +100.degree. C., but preferably from -20.degree. to +20.degree. C.
The organometallic reagent can be any alkali metal alkyl or aryl derivative such as butyl lithium, methyl lithium, phenyl lithium, or a Grignard reagent such as methyl magnesium chloride, phenyl magnesium bromide, etc.
The preparation of the dihydro-nitrogen heterocyclic phosphoramidate can be carried out in two ways both of which involve two steps. The nitrogen heterocyclic compound can be reacted with the organometallic reagent to form an intermediate which is then reacted with the phosphorus reagent. The second method involves reaction of the heterocyclic compound with the phosphorus reagent followed by treatment with the organometallic reagent. Although in some cases it is possible to form the dihydro-nitrogen heterocyclic phosphoramidates by mixing all three reagents it is usually preferred to use either of the two step-wise reaction procedures.
US Referenced Citations (1)
| Number |
Name |
Date |
Kind |
|
3821232 |
Redmore |
Jun 1974 |
|
Divisions (1)
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Number |
Date |
Country |
| Parent |
210106 |
Dec 1971 |
|
Patent Grant
3998833
