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Justia Patents US Patent for Herbicidal 5-amino-3-oxo-4-(3-substituted-phenyl)-4-pyrroline and derivatives thereof Patent (Patent # 4,643,762)
Herbicidal 5-amino-3-oxo-4-(3-substituted-phenyl)-4-pyrroline and derivatives thereof
Aug 27, 1984 - Chevron Research Company
5-Amino-3-oxo-4-(substituted-phenyl)-4-pyrroline and derivatives thereof. The compounds generally exhibit both pre-emergence and post-emergence phytotoxicity and are useful as herbicides and also plant growth regulating agents at low dosages.
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This invention relates to 5-amino-3-oxo-4-(substituted-phenyl)-4-pyrroline derivatives and to the use of such compounds as herbicides and plant growth regulators.
U.S. Pat. No. 3,577,433 is directed to a process for preparing a very broad genus of compounds having the formula: ##STR1## wherein R.sup.1 is a hydrocarbon group, such as alkyl, cycloalkyl, aryl, arylalkyl, alkaryl, optionally substituted with groups that are free of reactive hydrogen or (R.sup.1).sub.2 N can form a heterocycle, R is as defined for R.sup.1 or is -NR.sup.1 R.sup.1 ; and R.sup.2 and R.sup.4 are independently hydrogen, alkyl, aryl, cyclocalkyl, aralkyl, alkaryl, and the like. The compounds are described as useful as hydrogen halide acceptors and catalysts.
Tetrahedron, Vol. 25, 5721-32 (1969); CA:v 72:43329t discloses 1,4-diphenyl-3-oxo-5-dimethylaminopyrroline as part of an academic discussion. J. Organic Chemistry Vol. 41, pp. 390-2, discloses 1-ethyl-2-(2-carboxyphenyl)-3-oxo-4-phenyl-pyrroline in an academic paper. Based on Chem. Abstracts Vol. 92:41753r, Russian patent document SU No. 687070 discloses 1,4-diphenyl-3-oxo-5-aminopyrroline and the corresponding 2-methyl, ethyl and phenyl derivatives thereof and Chem. Abstracts Vol. 89:163331 describes a paper by Dopov. of the Akad. Nauk. Ukr. RSR, in Ser. B. Geol., Khim. Biol Nauk, Vol. (7), pp. 619-21 as disclosing 1,4-diphenyl-2,2-dimethyl-3-oxo-4-aminopyrroline. Japanese patent document No. 69/5222 (1969)--Chem. Abstracts Vol. 70:115004S discloses 1-methyl-3-oxo-4-phenyl-5-aminopyrroline as a pharmaceutical.
Chemiker-Zeitung 104 (1980) No. 10, Pages 302-303, is an academic paper disclosing the ring closure of 1-(dimethylamino)-2,4-diphenyl-1-buten-3,4-dione to yield 5-dimethylamino-2,4-diphenyl-2,3-dihydrofuran. British Pat. No. 1,521,092, discloses certain 3-phenyl-5-substituted-4(1H)-pyrid-ones or -thiones as herbicides. Japanese Patent Application No. 13,710/69 (Chemical Abstracts 71:61195e) discloses 5-amino-3-oxo-4-(phenyl or 4-chlorophenyl)-2,3-dihydrofurans. Japanese Pat. No. 19090 (Chemical Abstracts 69P10352e) discloses certain 2,3-dihydrothiophenes as pharmaceuticals. Helvetica Chemica Acta, Volume 66, Pages 362-378 (1983) discloses 5-N-cyclopropyl-4-phenyl-2-methoxycarbonylmethylene-3-furanone as part of an academic chemical synthesis discussion.
In my prior application, Ser. Nos. 505,169; 594,497; and 607,610 filed June 17, 1983, now abandoned; Mar. 29, 1984, now U.S. Pat. No. 4,537,673; and May 9, 1984; now abandoned, respectively, I disclosed certain herbicidally active derivatives of 5-amino-3-oxo-4-substituted phenyl-2,3-dihydrofuran. In my application Ser. No. 623,805, filed June 23, 1984, now U.S. Pat. No. 596,595, I disclosed certain herbicidally active 5-amino-3-oxo-4-substituted phenyl2,3-dihydrothiophene derivatives.
The present invention provides compounds having both pre-emergence and post-emergence herbicidal activity. The compounds have very good pre-emergence activity against a broad spectrum of both broad-leaf weeds and grassy weeds. At lower application rates the compounds also exhibit plant growth regulating properties.
The compounds of the present invention can be represented by the following formula: ##STR2## wherein R is hydrogen, lower alkyl, lower alkenyl, fluoroalkyl having 1 through 4 carbon atoms and 1 through 3 fluoro atoms; fluoroalkenyl having 2 through 4 carbon atoms and 1 through 3 fluoro atoms; phenyl, naphth-1-yl; 4-fluorophenyl; 2,6-difluorophenyl; benzyl; naphth-1-ylmethylene; 2-halobenzyl; 2-lower alkylbenzyl; 3-halobenzyl; 3-lower alkylbenzyl; or substituted phenyl having the formula: ##STR3## wherein one or two of X.sup.1, X.sup.2 or X.sup.3 is lower alkyl, lower alkoxy, halo, nitro, or haloalkyl having 1 through 3 carbon atoms and 1 through 3 halo atoms independently selected from the group of fluoro, chloro, bromo or iodo; and the other(s) is hydrogen;
R.sup.1, R.sup.2 and R.sup.3 are independently hydrogen, methyl or ethyl, with the proviso that if one of R.sup.1, R.sup.2 or R.sup.3 is ethyl, then the other two are each hydrogen;
X is hydrogen, lower alkyl, lower alkoxy, halo, or trifluoromethyl and can be at any available position on the phenyl ring; and
Y is alkyl, having 3 or 4 carbon atoms; alkoxy, having 3 or 4 carbon atoms; alkylthio having 3 or 4 carbon atoms; halo, haloalkoxy having 1 through 3 carbon atoms and 1 through 3 halo atoms; haloalkylthio, having 1 through 3 carbon atoms and 1 through 3 halo atoms; or haloalkyl having 1 through 3 carbon atoms and 1 through 3 halo atoms.
The invention also comprises compatible salts of the compound of Formula (I).
The compounds of Formula (I) exist as keto .revreaction. enol isomers and also have an asymmetric carbon atom and can also exist as optical isomers. In some instances the compounds also exist as geometric isomers. The above Formula I is intended to encompass the respective isomers as well as mixtures thereof and the respective isomers as well as mixtures thereof are encompassed within the invention.
It has also been discovered that the presence of a 3-trifluoromethyl substituent on the 4-phenyl group of the compounds of the present invention generally very substantially enhances herbicidal activity.
In a further aspect the invention provides a herbicidal composition comprising a compatible carrier and a herbicidally effective amount of the compounds of Formula (I), or compatible salts thereof, or mixtures thereof.
The present invention also provides a method for preventing or controlling the growth of unwanted vegetation, which comprises treating the growth medium and/or the foliage of such vegetation with a herbicidally effective amount of the compound(s) of Formula (I) and/or compatible salts thereof.
In another aspect, the present invention provides a plant growth regulating composition comprising a compatible carrier and a plant growth regulating amount of the compound of Formula (I), compatible salts of Formula (I), or mixtures thereof, effective to alter the normal growth pattern of said plants.
The present invention also provides a method for regulating plant growth which comprises treating the growth medium and/or the foliage of such vegetation with a plant growth regulating effective amount of the compound(s) of Formula (I) and/or compatible salts thereof, effective to alter the normal growth pattern of said plants.
The present invention also provides chemical intermediates and processes for preparing the compounds of Formula (I).
The invention will be further described hereinbelow.
FURTHER DESCRIPTION OF THE INVENTION AND THE PREFERRED EMBODIMENTS
Illustrations of typical compounds of Formula (I) of the present invention can be had by reference to Examples 3-6 set forth hereinbelow. In terms of substituents, the preferred compounds are those wherein R is lower alkyl, aryl or substituted aryl, more preferably methyl, phenyl or substituted phenyl, and especially phenyl, monomethylphenyl or monohalophenyl, more preferably, phenyl, 2-methylphenyl, 2-halophenyl, and especially 2-fluorophenyl. Preferably two of R.sup.1, R.sup.2 and R.sup.3 are hydrogen and the other is methyl or hydrogen, ethyl or n-propyl, and more preferably R.sup.1 and R.sup.2 are hydrogen and R.sup.3 is methyl. Preferably, X is hydrogen and Y is trifluoromethyl or halo, especially trifluoromethyl. Also, generally when R is substituted phenyl, it is preferred in terms of herbicidal activity that the substitution is at the ortho or meta position.
The compounds of Formula (I) wherein R.sup.1 and R.sup.2 are each hydrogen can be prepared via the following schematically represented process: ##STR4## wherein R, R.sup.3 and X and Y are as defined hereinabove; and R.sup.4 is lower alkyl, aryl (e.g. phenyl) or arylalkylene (e.g. benzyl).
This process can be conveniently effected by contacting Compound (A) with Compound (B), and a strong base (e.g. sodium methoxide, sodium ethoxide), preferably in an inert organic solvent.
Typically, this process is conducted at temperatures in the range of about from 0.degree. C. to 100.degree. C., preferably 75.degree. C. to 85.degree. C. for about from 5 to 36 hours, preferably 18 to 24 hours, using about from 1.0 to 10.0, preferably 1.0 to 1.2 moles of Compound (A) per mole of Compound (B). Suitable inert organic solvents which can be used include, for example, lower alkanols (e.g. methanol, ethanol, propanol, etc.); tetrahydrofuran; dimethoxyethane; dioxane; and the like, and compatible mixtures thereof.
Suitable strong bases which can be used include, for example, alkali metal alkanolates, for example, sodium methoxide, sodium ethoxide, potassium ethoxide, sodium hydride, potassium hydride, and the like. The strong base should preferably be one which does not yield water as a by-product in this reaction system.
Suitable inert solvents which can be used include, for example, lower alkanols (for example, methanol, ethanol, and propanol) tetrahydrofuran, dimethoxyethane, dioxane, and the like, and compatible mixtures thereof. Conveniently, the alkali metal alkanolate is prepared in situ by reacting an alkali metal with excess alkanol which in turn serves as solvent for the above reaction.
The starting materials of Formulas (B) are generally known materials and can be prepared by known procedures, or obvious modifications thereof (i.e., substitution of appropriate starting materials). The preparation of Compound (B) is for example described in Org. Syn. Coll., Volume 1, 107 (1941).
The compounds of formula A can be prepared by esterification of the corresponding amino acids. The compounds of Formula (A), wherein R is phenyl or substituted phenyl, can also be prepared via the procedures described in the J. Organic Chemistry, Vol. 29, p. 2764 (1964) or by obvious modifications thereof (e.g. substitution of appropriate reactants and solvents, etc.). Also, more generally, the compounds of Formula A can be prepared via the following schematically represented process: ##STR5## wherein M is a cation, preferably an alkali metal cation; X.sup.3 is a mineral acid anion (e.g., chloride), R.sup.5 is lower alkyl, and R and R.sup.3 are as defined hereinabove.
In the first step of this process an aldehyde having the appropriate R group is contacted with a cyanide salt (preferably in alkali metal cyanide, e.g. potassium cyanide) and a monoamine having the desired R.sup.3 group, preferably in an inert organic solvent.
Typically, this reaction is conducted at temperatures in the range of about from 20.degree. C. to 100.degree. C. for about from 1 to 10 hours using about from 1.0 to 5.0 mole equivalents of cyanide salt and 1.0 to 5.0 mole of amine per mole of aldehyde. Suitable solvents which can be used include, for example, aqueous lower alkanol (e.g., ethanol) solutions.
In the next step the previous product is converted to a carboxy acid salt via reaction with a mineral acid, e.g. hydrochloric acid. This process is typically conducted at temperatures in the range of about from 90.degree. C. to 110.degree. C. for about from 24 to 36 hours using at least a mole equivalent amount of mineral acid.
In the next step the acid salt is neutralized via treatment with a base to yield the carboxy ionic intermediate. This can be conveniently effected via treatment with sodium hydroxide. This intermediate can in turn be esterified to compound A using any suitable esterification procedure, such as, for example, via reaction with an alkanol in the presence of an acid catalyst, or as described by A. I. Vogel, "Practical Organic Chemistry", 3rd Ed. Page 1000 (1956).
The compounds of Formula A are preferably prepared via the precedure described by W. C. Lo in commonly assigned U.S. application Ser. No. 644,594, filed on even date herewith, and hereby incorporated by reference. This process can be represented by the following overall reaction equation. ##STR6## wherein R, R.sup.3 and R.sup.4 are as defined hereinabove and M.sup..crclbar. is an anion, preferably a halide.
This process can be conveniently effected by contacting Compound B' with an ammonium salt having the appropriate R.sup.3 group as part of its ammonium cation. Preferably, this process is conducted as a phase transfer reaction in the presence of water, and a water immiscible inert organic solvent and a phase transfer agent. Preferably, the reaction is also conducted in the presence of a weak base, for example, sodium bicarbonate. The weak base serves to liberate low concentrations of methylamine for reaction with the bromoesters (B').
This process is typically conducted at temperatures in the range of about from 0.degree. C. to 100.degree. C., preferably, 40.degree. C. to 45.degree. C., for about from 1 to 60 hours, preferably 18 to 48 hours using about from 1 to 10 moles, preferably 3 to 4 moles of the ammonium salt and 1 to 10 moles, preferably 5 to 6 moles of sodium bicarbonate and 0.05 to 1 moles, preferably 0.05 to 0.1 of benzyltriethylammonium chloride ammonium salt per mole of compound (B').
Suitable inert organic solvents which can be used include, for example, methylene chloride, chloroform, 1,2-dichloroethane, trichloroethane, toluene, and the like.
Suitable phase transfer agents which can be used are reagents and compatible salts thereof which transfer hydrophilic ions into liquid lipophilic organic mediums and include benzyl triethylammonium chloride, methyltrioctylammonium chloride and the like. In place of sodium bicarbonate, the following reagents could be used; potassium bicarbonate, lithium bicarbonate, sodium hydrogen phosphate, potassium hydrogen phosphate and the like.
The compounds of Formula (B') wherein R is hydrogen, lower alkyl, lower alkenyl, fluoroalkyl, fluoroalkenyl, benzyl, naphth-1-ylmethene or substituted benzyl can be conveniently prepared via the general procedure described in "Organic Synthesis", Vol. 4, p. 608 (1963) using the appropriate starting materials and solvents.
The compounds of Formula (B') wherein R is aryl or a substituted aryl can be conveniently prepared via bromination: ##STR7## wherein R.sup.3 and R.sup.4 are as defined hereinabove and R' is aryl or substituted aryl.
The bromination step can be conveniently effected by treating compound (C) with N-bromosuccinimide, in the presence of a suitable catalyst and preferably in an inert organic solvent.
Typically this bromination is conducted at temperatures in the range of about from 0.degree. C. to 100.degree. C., preferably 75.degree. C. to 77.degree. C. for about from 1 to 10 hours, preferably using about 1 to 2 moles, preferably 1 to 1.1 moles, N-bromosuccinimide and about 0 to 1, preferably 0.05 to 0.1 mole of catalyst per mole of compound C. Suitable catalysts which can be used include, for example, dibenzoyl peroxide, di-t-butylperoxide, azobisisobutyronitrile, and the like. Suitable solvents which can be used include, for example, carbon tetrachloride, chlorobenzene, 1,2-dichloroethane, tetrachloroethylene, methylene chloride, and the like and compatible mixtures thereof.
The starting materials of Formula (C) are generally known compounds and can be prepared by known procedures or obvious modifications thereof (e.g., substitution of appropriate starting materials, solvents, etc.). Note, for example, Org. Syn. Coll., Volume 1, p. 270 (1941).
The compound of Formula (I) wherein one or both of R.sup.1 and R.sup.2 are lower alkyl or lower alkenyl can be prepared by alkylation (or alkenylation) of the amino group: ##STR8## wherein R, R.sup.3, X and Y are as defined hereinabove; R.sup.5 is methyl or ethyl; R.sup.6 is hydrogen, methyl or ethyl; and R.sup.5 Z' is an alkylation agent.
This process can be effected by contacting Compound (I') with a suitable alkylation agent capable of alkylating primary or secondary amino groups.
For example, this can be effected by contacting Compound (I') with methyl or ethyl iodide, preferably in an inert organic solvent and preferably in the presence of a scavenger base. Typically, this process is conducted at temperatures in the range of about from 0.degree. C. to 100.degree. C., preferably 20.degree. C. to 45.degree. C. for about from 1 to 72, preferably 2.0 to 18.0 hours. Where it is desired to alkylate only one of the external amino hydrogens, then typically about from 1.0 to 1.1 moles of R.sup.3 I reactant is used per mole of Compound (I'). Where it is desired to alkylate both amino hydrogens, then typically about from 1.9 to 4 moles of R.sup.5 I are used per mole of Compound (I'). Also variation in the amino substituents can be effected by first alkylating only one of the two amino hydrogens and then alkylating the second amino hydrogen with an alkylating agent having a different R.sup.3 alkyl or alkenyl group. Suitable inert organic solvents which can be used, include, for example, liquid halogenated alkanes; for example, methylene chloride, carbon tetrachloride, dichloroethane; tetrahydrofuran and the like. Suitable scavenger bases include, for example, the bases described hereinabove with respect to the reaction of Compound (A) with Compound (B).
The compounds of Formula (I") wherein one of R.sup.5 or R.sup.6 is methyl or ethyl can be advantageously prepared using dialkyl sulfate as the alkylating agent. This can be conveniently effected by contacting the compound of Formula (I") with the desired lower alkyl sulfates in the presence of a strong base and preferably in an inert organic solvent in the presence of a phase transfer agent. Typically, this process is conducted at temperatures in the range of about from 0.degree. C. to 100.degree. C., preferably 20.degree. C. to 45.degree. C., using about from 1.0 to 4.0 moles of dialkyl sulfate per mole of Compound (I'). An excess, typically about 2.5 mole of base is used. Preferably, this process is also conducted in an inert organic solvent such as, for example, methylene chloride, carbon tetrachloride, dichloroethane, tetrahydrofuran, and the like.
Suitable strong bases which can be used include, for example, sodium hydroxide, potassium hydroxide, sodium ethoxide, sodium carbonate, potassium carbonate, and the like. Suitable phase transfer agents are agents which transfer hydrophilic ions into a lipophilic organic medium and include, for example, benzyl triethylammonium chloride, tetra-n-butylammonium chloride, methyltrioctylammonium chloride, and the like.
The compatible salts of Formula (I) can be prepared by conventional procedures by treating the compound of Formula (I) with a suitable strong base such as, for example, n-butyllithium, sodium hydride, potassium hydride, and the like, having the desired cation, by conventional procedures. Additional variations in the salt cation can also be effected via ion exchange with an ion exchange resin having the desired cation.
General Process Conditions
In the above-described processes, it is generally preferable to separate the respective products before proceeding with the next step in the reaction sequence, except where described as an in situ step or unless otherwise expressly stated. These products can be recovered from their respective reaction product mixtures by any suitable separation and purification procedure, such as, for example, recrystallization and chromatography. Suitable separation and purification procedures are, for example, illustrated in the Examples set forth hereinbelow.
Generally, the reactions described above are conducted as liquid phase reaction and hence pressure is generally not significant except as it affects temperature (boiling point) where reactions are conducted at reflux. Therefore, these reactions are generally conducted at pressures of about from 300 to 3,000 mm of mercury and conveniently are conducted at about atmospheric or ambient pressure.
It should also be appreciated that where typical or preferred process conditions (e.g., reaction temperatures, times, mole ratios of reactants, solvents, etc.) have been given, that other process conditions could also be used. Optimum reaction conditions (e.g., temperature, reaction time, mol ratios, solvents, etc.) may vary with the particular reagents or organic solvents used but can be determined by routine optimization procedures.
Where optical isomer mixtures are obtained, the respective optical isomers can be obtained by conventional resolution procedures. Geometric isomers can be separated by conventional separation procedures which depend upon differences in physical properties between the geometric isomers.
As used herein the following terms have the following meanings unless expressly stated to the contrary:
The term "lower alkyl" refers to both straight- and branched-chain alkyl groups having a total of from 1 through 6, preferably 1 through 4, carbon atoms and includes primary, secondary and tertiary alkyl groups. Typical lower alkyls include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl.
The term "lower alkenyl" refers to alkenyl groups having 2 through 6, preferably 2 through 4, carbon atoms and includes, for example, vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-methylprop-1-enyl and the like.
The term "halo" refers to the group of fluoro, chloro, bromo and iodo.
The term "aryl" refers to aryl groups having 6 through 10 carbon atoms and includes, for example, phenyl, naphthyl, indenyl, and the like.
The term "arylalkylene" refers to the group ArR.sup.5 - wherein Ar is aryl and R.sup.5 is alkylene having 1 through 3 carbon atoms and includes both straight-chained and branched-chained alkylenes, for example, methylene, ethyl, 1-methylethyl, and propyl.
The term "3-oxo-4-pyrroline" refers to the group having the formula: ##STR9##
The term "compatible salts" refers to salts which do not significantly alter the herbicidal properties of the parent compound. Suitable salts include cation salts such as, for example, the cation salts of lithium, sodium, potassium, alkali earth metals, ammonia, quaternary ammonium salts, and the like.
The term "room temperature" or "ambient temperature" refers to about 20.degree. C. to 25.degree. C.
The compounds of Formula (I) exhibit very good pre-emergence herbicidal activity and to a lesser extent also exhibit post-emergence herbicidal activity.
Generally, for post-emergent applications, the herbicidal compounds are applied directly to the foliage or other plant parts. For pre-emergence applications, the herbicidal compounds are applied to the growth medium, or prospective growth medium, for the plant. The optimum amount of the herbicidal compound or composition will vary with the particular plant species, and the extent of plant growth, if any, and the particular part of the plant which is contacted and the extent of contact. The optimum dosage can also vary with the general location, or environment (e.g., sheltered areas such as greenhouses compared to exposed areas such as fields), and type and degree of control desired. Generally, for both pre- and post-emergent control, the present compounds are applied at rates of about from 0.02 to 60 kg/ha, preferably about from 0.02 to 10 kg/ha.
Also, although in theory the compounds can be applied undiluted, in actual practice they are generally applied as a composition or formulation comprising an effective amount of the compound(s) and an acceptable carrier. An acceptable or compatible carrier (agriculturally acceptable carrier) is one which does not significantly adversely affect the desired biological effect achieved by the active compounds, save to dilute it. Typically, the composition contains about from 0.05% to 95% by weight of the compound of Formula (I) or mixtures thereof. Concentrates can also be made having high concentrations designed for dilution prior to application. The carrier can be a solid, liquid, or aerosol. The actual compositions can take the form of granules, powders, dusts, solutions, emulsions, slurries, aerosols, and the like.
Suitable solid carriers which can be used include, for example, natural clays (such as kaolin, attapulgite, montmorillonite, etc.), talcs, pyrophyllite, diatomaceous silica, synthetic fine silica, calcium aluminosilicate, tricalcium phosphate, and the like. Also, organic materials, such as, for example, walnut shell flour, cotton-seed hulls, wheat flour, wood flour, wood bark flour, and the like can also be used as carriers. Suitable liquid diluents which can be used include, for example, water, organic solvents (e.g., hydrocarbons such as benzene, toluene, dimethylsulfoxide, kerosene, diesel fuel, fuel oil, petroleum naphtha, etc.), and the like. Suitable aerosol carriers which can be used include conventional aerosol carriers such as halogenated alkanes, etc.
The composition can also contain various promoters and surface-active agents which enhance the rate of transport of the active compound into the plant tissue such as, for example, organic solvents, wetting agents and oils, and in the case of compositions designed for pre-emergence application agents which reduce the leachability of the compound or otherwise enhance soil stability.
The composition can also contain various compatible adjuvants, stabilizers, conditioners, insecticides, fungicides, and if desired, other herbicidally active compounds.
At reduced dosages the compounds of the present invention also exhibit plant growth regulating activity and can be used to alter the normal growth pattern of green plants.
The compounds of Formula (I) can be applied as plant growth regulators in pure form, but more pragmatically, as in the case of herbicidal application, are applied in combination with a carrier. The same types of carriers as set forth hereinabove with respect to the herbicidal compositions can also be used. Depending on the desired application, the plant growth regulating composition can also contain, or be applied in combination with other compatible ingredients such as desiccants, defoliants, surface-active agents, adjuvants, fungicides, and insecticides. Typically, the plant growth regulating composition will contain a total of about from 0.005% to 90% by weight of the compound(s) of Formula (I) depending on whether the composition is intended to be applied directly or diluted first.
A further understanding of the invention can be had in the following non-limiting Preparation and Examples. Wherein, unless expressly stated to the contrary, all temperatures and temperature ranges refer to the Centigrade or Celsius system and the term "ambient" or "room temperature" refers to about 20.degree. C. to 25.degree. C. The term "percent" or "%" refers to weight percent and the term "mole" or "moles" refers to gram moles. The term "equivalent" refers to a quantity of reagent equal in moles, to the moles of the preceding or succeeding reactant recited in that example in terms of finite moles or finite weight or volume. Where given, proton-magnetic resonance spectrum (p.m.r. or n.m.r.) were determined at 60 mHz, signals are assigned as singlets (s), broad singlets (bs), doublets (d), double doublets (dd), triplets (t), double triplets (dt), quartets (q), and multiplets (m); and cps refers to cycles per second. Also where necessary examples are repeated to provide additional starting material for subsequent examples.
EXAMPLES EXAMPLE 1 Methyl Bromo-Phenylacetate
This example illustrates the W. Lo process [U.S. application Ser. No. 644,594, filed on even date herewith] for preparing the title compound.
In this example, a mixture containing 5.93 g of N-bromosuccinimide, 5.0 g of methyl phenylacetate; and a catalytic amount (about 0.1 g) of benzoyl peroxide in 0 ml of methylene chloride was warmed to reflux and then refluxed for about four hours. The mixture was then cooled to about 0.degree. C. and filtered. The filtrate was concentrated by evaporation under vacuum affording 7.1 g of the title compound as an oil.
EXAMPLE 2 Methyl Methylamino-phenylacetate
This example illustrates the W. Lo method [U.S. application Ser No. 644,594), filed on even date herewith) for preparing the title compound.
In this example a mixture containing 30.7 g of methyl bromo-phenylacetate, 36.2 g of methyl ammonium chloride (i.e. CH.sub.3 NH.sub.3 Cl); 3.0 g of benzyltriethylammonium chloride and 67.5 g of sodium bicarbonate in about 300 ml of methylene chloride (and about 25 ml of water) was warmed to reflux and refluxed for about 18 hours. The mixture was then cooled and washed three times with water, dried over magnesium sulfate and concentrated by vacuum evaporation affording 17.1 g of the title compound as an oil.
Similarly, by following the same procedure but respectively using ethylammonium chloride in place of methylammonium chloride, methyl ethylamino-phenylacetate can be prepared.
Similarly, by following the same procedure but replacing methyl bromo-phenylacetate with methyl 2-bromopropionate; methyl 2-bromo-3-butenate; methyl 2-bromo-3-fluoropropionate; methyl bromo-(3-trifluoromethylphenyl)acetate; methyl bromo-(2-bromophenyl)acetate; methyl bromo-benzylacetate; methyl bromo-(3-nitrophenyl)acetate; and methyl bromo 1-naphthylacetate, the corresponding aminomethylamino and ethylamino esters can also be prepared. (The bromoesters can be prepared by applying the procedure of Example 1 hereinabove or the appropriate procedure described in A. I. Vogel "Practical Organic Chemistry", 3rd Ed., p. 429 (1956) or the procedure described in "Organic Synthesis", Vol. 4, p. 608 (1963) to the appropriate starting materials and in some instances are commercially available.
EXAMPLE 3 1-Methyl-2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-4-pyrroline
In this example, sodium ethoxide was prepared by mixing 3.0 g of metallic sodium with 100 ml of absolute ethanol. After the evolution of hydrogen stopped, a mixture containing 16.0 g of (3-trifluoromethylphenyl)-acetonitrile and 17.1 g of methyl methylamino-phenylacetate was added dropwise to the sodium ethoxide-ethanol mixture. The resulting mixture was then refluxed overnight (about 16 hours) and then cooled to room temperature. The mixture was then added to 300 ml of water and extracted with diethyl ether. The ethyl ether extract was filtered to remove precipitate. The filtrate was concentrated by evaporation affording a solid. This solid was then triturated in ethyl ether. The ethyl ether was then removed from the solid. The solid was washed several times with ethyl ether and then dried overnight affording 6.2 g of the title compound.
Similarly, by applying the above procedure but using the corresponding (substituted phenyl) acetonitrile in place of (3-trifluoromethylphenyl)acetonitrile, the following compounds can be prepared:
1-methyl-2-phenyl-3-oxo-4-(5-chloro-3-trifluoromethylphenyl)-5-amino-4-pyrr oline;
1-methyl-2-phenyl-3-oxo-4-(2-bromo-3-trifluoromethylphenyl)-5-amino-4-pyrro line;
1-methyl-2-phenyl-3-oxo-4-(6-fluoro-3-trifluoromethylphenyl)-5-amino-4-pyrr oline;
1-methyl-2-phenyl-3-oxo-4-(4-methyl-3-trifluoromethylphenyl)-5-amino-4-pyrr oline;
1-methyl-2-phenyl-3-oxo-4-(5-methoxy-3-trifluoromethylphenyl)-5-amino-4-pyr roline;
1-methyl-2-phenyl-3-oxo-4-(6-nitro-3-trifluoromethylphenyl)-5-amino-4-pyrro line;
1-methyl-2-phenyl-3-oxo-4-(3,5-di-trifluoromethylphenyl)-5-amino-4-pyrrolin e;
1-methyl-2-(3-nitrophenyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-4-pyrr oline;
1-methyl-2-benzyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-4-pyrroline;
1-methyl-2-(naphth-1-yl)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-4-pyrrol ine;
1-methyl-2-(2-bromo-5-nitrophenyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-amin o-4-pyrroline;
1-methyl-2-(naphth-1-ylmethylene)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino -4-pyrroline;
1-methyl-2-(2-fluorophenyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-4-pyr roline;
1-methyl-2-phenyl-3-oxo-4-(2-chloro-3-propylphenyl)-5-amino-4-pyrroline;
1-methyl-2-phenyl-3-oxo-4-(4-ethyl-3-butoxyphenyl)-5-5-amino-4-pyrroline;1- methyl-2-phenyl-3-oxo-4-(5-methoxy-3-chlorophenyl)-5-amino-4-pyrroline;
1-methyl-2-phenyl-3-oxo-4-(5-pentyl-3-chlorophenyl)-5-amino-4-pyrroline;
1-methyl-2-phenyl-3-oxo-4-(3,5-dipropoxyphenyl)-5-amino-4-pyrroline;
1-methyl-2-(3-nitrophenyl)-3-oxo-4-(3-bromophenyl)-5amino-4-pyrroline;
1-methyl-2-benzyl-3-oxo-3-(2-chloro-3-fluorophenyl)-5amino-4-pyrroline;
1-methyl-2-(naphth-1-yl)-3-oxo-4-(3-bromo-2-ethylphenyl)-5-amino-4-pyrrolin e;
1-methyl-2-(naphth-1-yl)-3-oxo-4-(3,4-dibutylphenyl)-5-amino-4-pyrroline;
1-methyl-2-(naphth-1-ylmethylene)-3-oxo-4-(2,3-difluorophenyl)-5-amino-4-py rroline;
1-methyl-2-(3-fluorobenzyl)-3-oxo-4-(3-iodo-4-methylphenyl)-5-amino-4-pyrro line;
1-methyl-2-phenyl-3-oxo-4-(3-chlorophenyl)-5-amino-4pyrroline;
1-methyl-2-phenyl-3-oxo-4-(3-propylphenyl)-5-amino-4pyrroline;
1-methyl-2-phenyl-3-oxo-4-[3-(2,2-dichloroethylthio)phenyl]-5-amino-4-pyrro line;
1-methyl-2-phenyl-3-oxo-4-(3-trifluoromethoxyphenyl)-5-amino-4-pyrroline;
1-methyl-2-phenyl-3-oxo-4-(3-bromophenyl)-5-amino-4pyrroline;
-methyl-2-phenyl-3-oxo-4-(3-iodophenyl)-5-amino-4pyrroline;
1-methyl-2-phenyl-3-oxo-4-(3-fluoromethylthiophenyl)-amino-4-pyrroline;
1-methyl-2-phenyl-3-oxo-4-[3-(2,3,3-trifluoropropoxy)phenyl]-5-amino-4-pyrr oline;
1-methyl-2-phenyl-3-oxo-4-(3-fluorophenyl)-5-amino-4yrroline; and
1-methyl-2-methyl-3-oxo-4-(3-isopropyl)-5amino-4-pyrroline.
Similarly, by respectively using methyl ethylamino-phenylacetate and amino-phenylacetate in place of methyl methylamino-phenylacetate, the corresponding 1-ethyl homologs and 1-desmethyl homologs of the above compounds can be made, for example, 1-ethyl-2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-4-pyrroline and 2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)5-amino-4-pyrroline.
EXAMPLE 4 1-methyl-2-phenyl-3-oxo-4-(-3-trifluoromethylphenyl)-5-methylamino-4-pyrrol ine
In this example, 4.1 g of 1-methyl-2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-4-pyrroline, was added to 100 ml of methylene chloride containing 1.0 g of sodium hydroxide, dissolved in 4.0 ml of water, and 0.28 g of benzyltriethylammonium chloride at room temperature. Dimethyl sulfate (1.17 ml) dissolved in 20 ml of methylene chloride was admixed dropwise to the aforementioned mixture at room temperature. After the addition was complete, another 0.28 g of benzyltriethylammonium was added and the mixture was stirred at room temperature for 18 hours. At the end of this time, a white precipitate was collected from the mixture by filtration. This solid was stirred with 50 ml of 1N aqueous hydrochloric acid for two hours after which it was collected with suction filtration and washed with aqueous sodium bicarbonate solution followed by water. The solid was dried affording 1.0 g of the title compound as a white powder.
Similarly, by applying the same procedure using the corresponding 5-amino derivatives as starting materials (which in turn can be prepared by applying the procedures of Examples 1-3 hereinabove using the appropriate starting materials), the corresponding 5-methylamino homologs thereof can be prepared, for example:
2-phenyl-3-oxo-4-(5-chloro-3-trifluoromethylphenyl)-5-methylamino-4-pyrroli ne;
2-phenyl-3-oxo-4-(2-bromo-3-trifluoromethylphenyl)-5-5-methylamino-4-pyrrol ine;
2-phenyl-3-oxo-4-(6-fluoro--3-trifluoromethylphenyl)-5-methylamino-4-pyrrol ine;
2-phenyl-3-oxo-4-(4-methyl-3-trifluoromethylphenyl)-5-methylamino-4-pyrroli ne;
2-phenyl-3-oxo-4-(5-methoxy-3-trifluoromethylphenyl)-5-methylamino-4-pyrrol ine;
2-phenyl-3-oxo-4-(6-propyl-3-trifluoromethylphenyl)-5-methylamino-4-pyrroli ne;
2-phenyl-3-oxo-4-(3,5-di-trifluoromethylphenyl)-5-methylamino-4-pyrroline;
2-(3-nitrophenyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-4-pyrroli ne;
2-benzyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-4-pyrroline;
2-(naphth-1-yl)-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-4-pyrroline ;
2-(2-bromo-5-nitrophenyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-4 -pyrroline;
2-(naphth-1-ylmethylene)-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-4- pyrroline;
2-(2-fluorophenyl)-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-4-pyrrol ine; and
2-phenyl-3-oxo-4-(2-chloro-3-propylphenyl)-5-methylamino-4-pyrroline;
2-phenyl-3-oxo-4-(4-ethyl-3-butoxyphenyl)-5-methylamino-4-pyrroline;
2-phenyl-3-oxo-4-(5-methoxy-3-chlorophenyl)-5-methylamino-4-pyrroline;
2-phenyl-3-oxo-4-(5-hexyl-3-chlorophenyl)-5-methylamino-4-pyrroline;
2-phenyl-3-oxo-4-(3,5-dipropoxyphenyl)-5-methylamino-4-pyrroline;
2-(3-nitrophenyl)-3-oxo-4-(3-bromophenyl)-5-methylamino-4-pyrroline;
2-benzyl-3-oxo-4-(2-chloro-3-fluorophenyl)-5-methylamino-4-pyrroline;
2-(naphth-1-yl)-3-oxo-4-(3-bromo-2-ethylphenyl)-5-methylamino-4-pyrroline;
2-(fluoromethyl)-3-oxo-4-(3,4-dibutylphenyl)-5-methylamino-4-pyrroline;
2-(2-naphth-1-ylmethylene)-3-oxo-4-(2,3-difluorophenyl)-5-methylamino-4-pyr roline;
2-(3-fluorobenzyl)-3-oxo-4-(3-iodo-4-methylphenyl)-5-methylamino-4-pyrrolin e;
2-phenyl-3-oxo-4-(3-chlorophenyl)-5-methylamino-4-pyrroline;
2-phenyl-3-oxo-4-(3-propylphenyl)-5-methylaminopyrroline;
2-phenyl-3-oxo-4-[3(2,2-dichloroethylthio)phenyl]-5-methylamino-pyrroline;
2-phenyl-3-oxo-4-(3-trifluoromethoxy)-5-methylaminopyrroline;
2-phenyl-3-oxo-4-(3-bromophenyl)-5-methylaminopyrroline;
2-phenyl-3-oxo-4-(3-iodophenyl)-5-methylaminopyrroline;
2-phenyl-3-oxo-4-(3-fluoromethylthiophenyl)-5-methylamino-pyrroline;
2-(2-phenyl)-3-oxo-4-[3-(2,3,3-trifluoropropoxy)phenyl]-5-methylamino-pyrro line;
2-phenyl-3-oxo-4-(3-fluorophenyl)-5-methylaminopyrroline;
2-phenyl-3-oxo-4-(3-isopropylphenyl)-5-methylaminopyrroline;
1-methyl-2-methyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-4-pyrroli ne;
1-ethyl-2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-4-pyrrolin e;
1,2-dimethyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-4-pyrroline;
1-ethyl-2-fluoromethyl-3-oxo-4-(3-bromophenyl)-5-amino-4-pyrroline;
1-methyl-2-(3-trifluoromethylphenyl)-3-oxo-4-(5-chloro-3-trifluoromethylphe nyl)-3-oxo-5-methylamino-4-pyrroline;
2-(2-bromophenyl)-3-oxo-4-(3-butylphenyl)-5-methylamino-4-pyrroline;
1-ethyl-2-benzyl-3-oxo-4-(3-butoxyphenyl)-5-amino-4-pyrroline;
1-methyl-2-(3-t-butyl)-3-oxo-4-(2-chloro-3-methylphenyl)-5-methylamino-4-py rroline; and
2-(naphth-1-yl)-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-4-pyrroline .
Similarly, by approximately doubling the amount of dimethylsulfate and increasing the reaction time and/or temperature, the corresponding 5-dimethylamino homologs thereof can be prepared.
EXAMPLE 5 Lithium salt of 2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-4-pyrroline
The lithium salts of the present invention can be prepared by the following procedure.
5.6 ml of 1.6 M n-butyllithium in hexane is added dropwise to a stirred solution containing 2.86 g of 2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-amino-4-pyrroline in 25 ml of tetrahydrofuran at -30.degree. C. The resulting mixture is stirred for 20 minutes and then concentrated in vacuo to afford the title compound.
Similarly, by following the same procedure, the corresponding lithium salts of the compounds of Examples 2-5 can also be prepared.
The compounds listed in Table A hereinbelow were prepared using the appropriate starting materials and procedures described in the Examples hereinabove.
TABLE A
##STR10##
Carbon Hydrogen
R.sup.1
R   Calc.
Calc.
Melting Point .degree.C.
1  H H   H     .phi.**
2  H H   CH.sub.3
.phi.
207-209*
3  H CH.sub.3
CH.sub.3
4  H H   CH.sub.2 CH.sub.3
2-Cl.phi.
2-F.phi.
10 H CH.sub.3
H CH.sub.3
CH.sub.2 CH.sub.3
* = Decomposition
.phi.** = Phenyl, for example, 2Cl.phi. = 2-chlorophenyl
C-1 = Comparison Compound:
1-ethyl-2-phenyl-3-oxo-4-(3-trifluoromethylphenyl)-5-methylamino-4-pyrrol
In this example, the compounds of Table A were respectively tested using the procedures described hereinbelow for pre-emergent and post-emergent activity against a variety of grasses and broad-leaf plants including one grain crop and one broad-leaf crop. The compounds tested are identified by compound number in Table A hereinabove.
Pre-Emergent Herbicide Test
Pre-emergence herbicidal activity was determined in the following manner.
Test solutions of the respective compounds were prepared as follows:
355.5 mg of test compound was dissolved in 15 ml of acetone. 2 ml of acetone containing 110 mg of a non-ionic surfactant was added to the solution. 12 ml of this stock solution was then added to 47.7 ml of water which contained the same nonionic surfactant at a concentration of 625 mg/L.
Seeds of the test vegetation were planted in a pot of soil and the test solution was sprayed uniformly onto the soil surface at a dose of 27.5 micrograms/cm.sup.2. The pot was watered and placed in a greenhouse. The pot was watered intermittently and observed for seedling emergence, health of emerging seedlings, etc., for a 3-week period. At the end of this period, the herbicidal effectiveness of the compound was rated based on the physiological observations. A 0-to-100 scale was used, 0 representing no phytotoxicity, 100 representing complete kill. The results of these tests are summarized in Table 1.
Post-Emergent Herbicidal Test
The test compound was formulated in the same manner as described above for the pre-emergent test. This formulation was uniformly sprayed on 2 similar pots containing plants 2 to 3 inches tall (except wild oats, soybean and watergrass which were 3 to 4 inches tall) (approximately 15 to 25 plants per pot) at a dose of 27.5 microgram/cm.sup.2. After the plants had dried, they were placed in a greenhouse and then watered intermittently at their bases as needed. The plants were observed periodically for phytotoxic effects and physiological and morphological responses to the treatment. After 3 weeks, the herbicidal effectiveness of the compound was rated based on these observations. A 0-to-100 scale was used, 0 representing no phytotoxicity, 100 representing complete kill. The results of these tests are summarized in Table 2.
Pre-Emergence Herbicidal Activity
Application Rate: 27.5 micrograms/cm.sup.2, unless otherwise noted
Broad-Leaf Plants     Grasses
% Phytotoxicity       % Phytotoxicity
No.   Lambsquarter
Pigweed
1      80    100  100  65   100   60    60    40
2      98     98   98  70   100   100   100   70
3     100    100  100  40    90   90    80    30
4      50     0    75   0    0    30     0     0
5     100    100  100  95   100   100   100   98
6     100     95  100  30    98   98    98    70
7      0      0    0    0    0     0     0     0
8      20     30   50   0    0     0     0     0
9     100    100  100  100  100   100   100   100
10    100    100  100  80    95   95    60    20
C-1    0      0    0    0     0    0     0     0
Post-Emergence Herbicidal Activity
1      0     33    0    0   0     0     0     0
2     30     30   50   50   30    0     0     0
3     30     40   30   30   0     0     0     0
4      0      0    0    0   0     0     0     0
10    30     50   50   50   20    20    0     0
C-1    0      0    0    0   0     0     0     0
As can be seen from the above Table 1, the compounds of the invention generally exhibit a broad spectrum of excellent pre-emergence phytotoxic activity and especially so Compounds Nos. 2, 5, 6, 9, and 10. Also, as shown by Table 2 a number of the compounds also exhibit modest post-emergence phytotoxic activity against broadleaf plants. Compound No. 7 failed to exhibit preemergence activity in this test but exhibited modest post-emergence phytotoxicity against broad-leaf plants. Also, it can be seen that Comparison Compound C-1 was wholly inactive in this test even though it is a methyl homolog of the Compound No. 3, of the present invention, which exhibited very good pre-emergence herbicidal activity.
Obviously, many modifications and variations of the invention described hereinabove and below can be made without departing from the essence and scope thereof.
1. A compound having the formula: ##STR11## wherein R is phenyl or monosubstituted phenyl having the formula: ##STR12## wherein one of X.sup.1 or X.sup.2 is lower alkyl, lower alkoxy, halo, nitro, or haloalkyl having 1 through 3 carbon atoms and 1 through 3 halo atoms independently selected from the group of fluoro, chloro, bromo or iodo; and the other is hydrogen; and
R.sup.1, R.sup.2 and R.sup.3 are independently hydrogen, methyl, or ethyl with the proviso that if one of R.sup.1, R.sup.2 or R.sup.3 is ethyl, then the other two are each hydrogen;
2. The compound of claim 1 wherein R.sup.1, R.sup.2 and R.sup.3 are independently hydrogen or methyl.
3. The compound of claim 2 wherein one of R.sup.1 or R.sup.2 is hydrogen.
4. The compound of claim 3 wherein R is phenyl or halophenyl or trifluoromethylphenyl or alkylphenyl.
5. The compound of claim 4 wherein R is phenyl, 2-halophenyl, or 2-methylphenyl.
6. The compound of claim 3 wherein R is phenyl, 2-halophenyl or 2-lower alkylphenyl.
7. The compound of claim 6 wherein R.sup.1, R.sup.2 and R.sup.3 are hydrogen.
8. The compound of claim 3 wherein R is phenyl, monofluorophenyl, monochlorophenyl, or monomethylphenyl.
9. The compound of claim 8 wherein R is phenyl and R.sup.1, R.sup.2 and R.sup.3 are hydrogen.
10. The compound of claim 3 wherein two of R.sup.1, R.sup.2 and R.sup.3 are hydrogen and the other is hydrogen or methyl.
11. The compound of claim 10 wherein R is monofluorophenyl.
12. The compound of claim 10 wherein R is phenyl.
13. The compound of claim 10 wherein R is 2-fluorophenyl.
14. The compound of claim 13 wherein R.sup.2 and R.sup.3 are each hydrogen.
15. The compound of claim 13 wherein R.sup.1 is hydrogen.
16. A herbicidal composition comprising a herbicidally effective amount of the compound of claim 1, or mixtures of such compounds, and a compatible carrier.
17. A herbicidal composition comprising a pre-emergent herbicidally effective amount of the compound of claim 1, or mixtures thereof, and a compatible carrier.
18. A method for destroying plants which comprises applying a herbicidally effective amount of the compound of claim 1, or mixtures thereof, to the foliage or growth medium of said plants or their seeds.
19. A method for destroying plants which comprises applying a pre-emergent herbicidally effective amount of the compound of claim 1, or mixtures thereof, to the growth medium of said plants or their seeds.
3020288 February 1962 Wragg et al.
3510495 May 1970 Beck
3577433 May 1971 Fuks et al.
4013445 March 22, 1977 Bellus et al.
4132713 January 2, 1979 Broadhurst
44-5222 March 1969 JPX
687070 September 1979 SUX
Chem. Abs. 92:41753r. J. Org. Chem., vol. 41, No. 2 (1976) pp. 390-392. Tetrahedron v. 23 (1967), pp. 4395-4407.
Filed: Aug 27, 1984
Date of Patent: Feb 17, 1987
Assignee: Chevron Research Company (San Francisco, CA)
Inventor: Carl E. Ward (San Jose, CA)
Primary Examiner: Glennon H. Hollrah
Assistant Examiner: D. B. Springer
Attorneys: S. R. LaPaglia, R. C. Gaffney, L. S. Squires
Current U.S. Class: 71/95; Chalcogen Attached Directly To The Five-membered Hetero Ring By Nonionic Bonding (e.g., 3-pyrrolidinols, Etc.) (548/541); 71/76
International Classification: A01N 4336; C07D20736;


Here is the starting sketch of the concept.
It quickly evolved into a vest format to ease up the complication of trying to fit everything in the suspender format.
I went a little overboard on the construction process by making a silicone sleeved , heat-shrink sealed, 10 LED unit that joined together with a connector. While this left me with a lot of versatility, it took way to long to construct.
You can see the overly involved construction process in these videos.
The final assembly ended up super durable, as it traveled well to Vegas stuffed in a carry-on (the TSA was very curious about it), was stepped on, and had beer spilled on it during a concert.
The original intent of making it sample colors and add this into the animations was scrapped, as I was having some difficulty in figuring out how to integrate a sampled color into the LED animations that I was using within the time constraints I had. This is definitely something I am interested in figuring out in the future.
The final direction I went in was a series of animations that drove through 4 sets of parallel neopixel strips, with a push button cycling through the different animations.
The biggest leaning I found from the field was the brightness. It was WAY too bright to use during a concert. This was adjusted down to 40% following night one, but found that was still not enough. I made a scrambled attempt to integrate a potentiometer into the circuit to control the brightness, but may have been too intoxicated to pull this off.


text:
Andrzej Bemer (; died ca. 1626) was a 17th-century sculptor and architect, active in Poland and in Silesia, probably of German or Czech ancestry. Born in Breslau, early in his career he moved to Lesser Poland. There he authored or co-authored numerous churches and chapels. Among them are the Bernardine Church, the Chapel of Boim family (attributed) and the town hall's tower, all located in Lwów (modern Lviv, Ukraine).

Polish sculptors
Polish male sculptors
Architects from Wrocław
Architects from Lviv
Year of birth missing
Year of death missing
17th-century deaths

redpajama_set_name: RedPajamaWikipedia


text:
package com.kodekutters.gpsd4scala.core

import com.kodekutters.gpsd4scala.protocol._
import play.api.libs.json._

/**
  * Author: Ringo Wathelet
  * Date: 18/04/13
  * Version: 1
  */

/**
  * parse the (json) ByteString received from the gpsd server into Report objects
  */
class GpsdParser {

  /**
    * parse the input ByteString which may contain multiple json objects,
    * into a corresponding list of Report objects
    *
    * @param data the input ByteString to parse, this is split on new line "\\r?\\n"
    *             to extract possible multiple json objects
    * @return an optional list of Report objects corresponding to the input json objects
    */
  def parse(data: akka.util.ByteString): Option[List[Report]] = {
    try {
      // split the data string on a new line, in case it has multiple json objects
      val lines = data.utf8String.trim.split("\\r?\\n")
      val results = lines collect { case line => parseOne(line.trim) }
      Some(results.flatten.toList)
    } catch {
      case _: Throwable => None
    }
  }

  /**
    * parse a string assumed to represent only one json Report object
    * @param line the string to parse
    * @return a Report object
    */
  def parseOne(line: String): Option[Report] = {
    try {
      val jsMsg = Json.parse(line)
      val clazz = (jsMsg \ "class").getOrElse(JsString(""))
      clazz match {
        case JsString("GST") => Json.fromJson[GST](jsMsg).asOpt
        case JsString("TPV") => Json.fromJson[TPV](jsMsg).asOpt
        case JsString("ATT") => Json.fromJson[ATT](jsMsg).asOpt
        case JsString("DEVICE") => Json.fromJson[Device](jsMsg).asOpt
        case JsString("DEVICES") => Json.fromJson[Devices](jsMsg).asOpt
        case JsString("SKY") => Json.fromJson[SKY](jsMsg).asOpt
        case JsString("VERSION") => Json.fromJson[Version](jsMsg).asOpt
        case JsString("WATCH") => Json.fromJson[Watch](jsMsg).asOpt
        case JsString("POLL") => Json.fromJson[Poll](jsMsg).asOpt
        case JsString("PPS") => Json.fromJson[PPS](jsMsg).asOpt
        case JsString("ERROR") => Json.fromJson[Error](jsMsg).asOpt
        //        case JsString("ALMANAC") => Json.fromJson[ALMANACObject](jsMsg).asOpt
        //        case JsString("EPHEM1") => Json.fromJson[EPHEM1Object](jsMsg).asOpt
        //        case JsString("EPHEM2") => Json.fromJson[EPHEM2Object](jsMsg).asOpt
        //        case JsString("EPHEM3") => Json.fromJson[EPHEM3Object](jsMsg).asOpt
        //        case JsString("ERD") => Json.fromJson[ERDObject](jsMsg).asOpt
        //        case JsString("HEALTH") => Json.fromJson[HEALTHObject](jsMsg).asOpt
        //        case JsString("HEALTH2") => Json.fromJson[HEALTH2Object](jsMsg).asOpt
        //        case JsString("IONO") => Json.fromJson[IONOObject](jsMsg).asOpt
        //        case JsString("SUBFRAME") => Json.fromJson[SUBFRAMEObject](jsMsg).asOpt
        case _ => None
      }
    } catch {
      case _: Throwable => None
    }
  }

}

redpajama_set_name: RedPajamaGithub


text:
Speakers to explore indigenous research approaches
The spring 2015 Engaged Cornell Speaker Series on indigenous approaches to research will bring three service-learning scholars, educators and practitioners to Cornell to discuss a diverse range of perspectives through dialogues and workshops for faculty, students, staff and community members.
The series, founded to advance the Cornell community's knowledge, skills and understanding of community-engaged learning and research, is a collaboration among the Public Service Center, Engaged Learning + Research and the Office of Academic Diversity Initiatives.
Karim-Aly Kassam, international professor of environmental and indigenous studies in the Department of Natural Resources and American Indian Program at Cornell, will speak on "How Do We Teach Students to Speak Truth to Power Thoughtfully and With Humility and Grace? Engendering a New Generation of Public Intellectuals," Friday, Feb. 6, noon to 1:30 p.m. in Room 423 of the ILR Conference Center.
Kassam's international research focuses on the complex connectivity of human and environmental relations, addressing indigenous ways of knowing, food sovereignty, sustainable livelihoods and climate change. Kassam investigates the relationship between biological and cultural diversity to expand the foundations of the notion of pluralism. Recently, Kassam has undertaken research in Central Asia on livelihood security, ecological foundations of pluralism, adaptation to climate change and health sovereignty through the use of medicinal plants.
In his talk, Kassam will draw on human ecological research undertaken among indigenous communities in the circumpolar Arctic, the Northern Forest and the Pamir Mountains of Afghanistan and Tajikistan, and he will suggest key pedagogical principles that facilitate public scholarship.
"Public scholarship cannot be an occasional activity undertaken by the professor but must be integrated into teaching pedagogy and applied research methods; thereby, illustrating to undergraduate and graduate students alike that it is the cornerstone of intellectual life in democratic society," Kassam said.
Virginia Kennedy, M.A. '09, Ph.D. '13, executive director of the Otsego Land Trust, will speak on "Living Conservation Values: Re-Connecting to the Lands and Waters That Sustain Us," Friday, March 13, noon to 2 p.m. in 102 Mann Library.
Kennedy studied English and American Indian studies at Cornell, where her research focused on environmental ethics. Through Cornell's American Indian Program, she has traveled to Native and non-Native communities around the U.S. to explore different cultural approaches to protecting land and water.
"No human being can live without healthy land, clean water and the diversity of life that thrives on this planet," said Kennedy. "Taking care of what takes care of us makes practical sense, and maybe more than that for me, morally and spiritually, it's just the right thing to do."
Alvin W. Yeo will speak on "Engaged Learning in ICT [information and communications technology] for Development in Malaysian Borneo: Reflections and Lessons Learnt Employing a Systemic, Holistic, Interdisciplinary and Participatory (SHIP) Approach," Friday, April 24, from noon to 2 p.m. in Room 423 Mann Library.
Yeo is director of the Institute of Social Informatics and Technological Innovations (ISITI) and is a professor of Information Systems at the Faculty of Computer Science and Information Technology in UNIMAS, Malaysian Borneo. He works in the field of information and communications technologies for rural development and has been involved in more than 40 research and development projects to bring about socio-economic development in Malaysia.
Yeo will explore using information and communication technologies for development as well as his experiences with ISITI and UNIMAS, and the SHIP approach in developing engaged learning with the indigenous communities.

redpajama_set_name: RedPajamaCommonCrawl


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Over the past 24 years, Madrigal Chorale has proudly awarded nearly $70,000 of scholarship monies to aspiring and talented young vocalists in the Southeast Michigan area. This year, Madrigal Chorale continues its commitment to vocal music by inviting high school choirs to compete for awards and participate in a unique Choral Invitational Festival on Sunday, March 24, 2019.
All Class B, C or D high school choral groups in Macomb, Oakland and Wayne counties are invited to apply and compete for prize money. Applicants will submit an application and recording that will be judged. The top three choral groups will be selected to win a $1,000 prize each and participate in the Choral Invitational Festival on March 24.
Eligible groups must submit their application and recording for judging by January 11, 2019. Finalists will be notified by February 1, 2019 regarding their participation in the Celebration Concert. Please note that participation in the March 24 event is required in order to receive any award.
Complete details and an application form are attached.
Congratulations to our 2019 prize winners, Canton Preparatory High School Chamber Choir, Detroit School of Arts Madrigal Ladies.


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The Chicagoland Cooperator's Condo, HOA & Co-op Expo Wednesday November 14th-A Day of Learning, Networking & Shopping
By The Chicagoland Cooperator Staff 2012 September
At last, it's that time of year again! After its blockbuster debut last year, The Chicagoland Cooperator's annual Condo, HOA & Co-op Expo is returning to the Navy Pier Convention Center in Chicago on Wednesday, November 14, 2012 from 10 a.m. to 5 p.m. With 200 exhibitors, countless product demos, free advice booths, and full roster of educational seminars, it's literally a one-stop, custom-built marketplace for new vendors, products and ideas.
The Expo is a must-attend event for the Chicagoland area's condo board members, property managers, real estate professionals and unit owners. (check www.chicagocondoexpo.com for more information!)
One Day, One Place – Endless Solutions
The Chicagoland Expo is the largest expo in the state entirely dedicated to connecting condo, HOA, and co-op managers, board members, and residents with the professionals and service providers their communities need on a regular basis.
Yale Robbins Publications LLC, The Chicagoland Cooperator's parent company and producer of the Expo, has been sponsoring successful, hugely popular trade events for the condo, co-op, and HOA community in New York, New Jersey, New England, and Florida for years. The New York show is over two decades old and going strong, and YR-produced expos in the other markets have established themselves as must-see events for residential community decision-makers, including board members, property managers, and involved owners.
"The express purpose of the Chicagoland Expo is to help attendees make useful, productive connections, gain valuable information, and network with their peers," says company president Yale Robbins. So if you're a decision-maker for a condo, homeowners association, or co-op community—or even if you just call one home—and you have a pressing legal issue or an important project waiting in the wings, you owe it to yourself and your community to drop by the Expo and experience what it has to offer. It would take months to meet with the same number of vendors and professionals a typical Expo attendee will interact with in one afternoon on the show floor.
The scale of the Chicago show is certainly impressive—however, "It's not just the sheer number of exhibitors that sets this event apart," says executive vice president Henry Robbins. "It's the quality of the vendors and service providers we've assembled. We're here to connect decision-makers from residential communities throughout the region with key players in the market."
It's About Education
In addition to the scores of exhibitors, another huge draw is the Chicagoland Expo's full slate of free educational seminars. Geared to help anyone involved—or even just interested—in the administration of a residential building or homeowners association, the 2012 seminar panels will provide in-depth discussion of the legal, administrative, management, and financial concerns pertinent to the region's HOA managers, board members, and residents.
This year will feature management pros from Associa and Caruso Management, consulting and reserve study experts from Strategic Inspections, representatives from DRF/Nicor, The Chicagoland Cooperator, and more. Last year's seminars drew standing-room-only audiences, so make sure to arrive early and claim your spot! All presentations are free for all attendees, and conclude with a Q&A segment to allow audience members to get direct feedback from panelists.
But Wait...There's More!
In addition to networking and education opportunities, the Chicagoland Condo, HOA & Co-op Expo will feature free advice booths staffed by professionals from a broad array of industries, waiting to answer any and all HOA- and building-related questions face-to-face. If you have questions about your association's finances, policies, or day-to-day management, you can stop by one of the booths for answers from leading legal, management, maintenance and financial professionals. How's that for instant gratification?
And if all that isn't enough, the Expo will also feature dozens of raffles and giveaways throughout the day—including the Grand Prize Reserve Fund giveaway, courtesy of The Chicagoland Cooperator and Yale Robbins Publications LLC. One attendee at the show will be drawn at random to win a $2,500 contribution to their building or association's reserve fund. The winner will be drawn after registration has closed, and a check for the winnings will be made payable to the winner's association, care of their management company. Only board members qualify to enter the reserve fund drawing, and attendance at the Expo is required for eligibility. For complete details on how to enter the reserve fund drawing, visit the Expo website, www.chicagocondoexpo.com
So stay tuned to The Chicagoland Cooperator for updates and new additions to the Expo's exhibitor and seminar roster, and be sure to visit us at Navy Pier in Chicago on Wednesday, November 14. For more information on who is exhibiting at the show, to sign up as an exhibitor, or to register for this exciting event, go to www.ChicagoCondoExpo.com.


Social media gurus make social media management sound so darn difficult. Why? Maybe it's because they have social media management services to sell you, or they could be in the wrong business.
But here's what the gurus don't want you to know: The toughest part about social media management is simply getting started.
That's it. Social media management isn't overly tricky – once you have your checklists mastered.
All you need is about 90 minutes up-front to set up your social media checklists. After that, you only need 15 minutes per day to maintain that system. You've got this.
Before we move into your social media management checklist, let me clarify that social media management is NOT social media growth.
There's a lot more to social media marketing than managing your channels.
One primary misconception is lumping social media management together with social media growth. They are two very different activities.
Social Media Growth = focusing on growth by using social media growth tactics.
When I say you can manage your social channels in 15 minutes a day, this does not mean you'll get more followers. Know the difference between management and growth.
Now that we've clarified management and growth, let's discover how to set up that 15-minute social media checklist. This is the fun part.
The "be everywhere" strategy only works for brands with resources and dedicated manpower. For the rest of us, choose only two or three channels for your social media management checklist.
I recommend using a social media audit to identify these channels, as this ensures you're not going by your gut, but for those of you want to skip that step, choose the channels you want to focus on.
This is the step where most businesses feel overwhelmed – from all the options, how do you pick the best social media marketing tools for you? Which ones are worth the cost? Which ones can you get for free?
My mantra is to K.I.S.S. (keep it simple stupid). Pick a tool that can do many functions, and you can cover your social media management bases without breaking the bank or wasting time.
These are the functions you need to manage your social media channels – and here are the applications I use in my own social media marketing process.
What does it cost me to manage my social channels each month? A whopping $49.
Insider tip: You could use Buffer's Power Scheduling tool to *almost* replace CoSchedule ReQueue, but, I like the convenience of ReQueue because I also use CoSchedule as my editorial calendar.
You can use my social media management go-tos, or research options on G2 Crowd to find tools that fit your specific needs. Go get these set up before moving on to the next step.
You identified your most important social channels, you've set up your social media management tools. Now, it's time to create your social media checklists for those channels.
The key with checklists is that they are subject to change based on interactivity and the focus of each social channel. I like to create checklists that I can "check off" within my project management system to ensure I don't miss a step.
Whether you adhere to a checklist or take a more open-ended approach is up to you. For those of you linear thinkers, checklists take the stress and guesswork out of the process. For those of you creative thinkers, you might want to glance at your checklists for inspiration, rather than use them as a template.
Treat it like a game. How many meaningful engagements can you have in under 15 minutes?
Start with responding to inbound engagements (people talking to you) and then outbound engagements (you reaching out to other people.) You never want to miss a meaningful engagement from someone who mentions you.
There's no social media management God looking over your shoulder to be sure you make it through every item on your checklist – no need to stress. Get what you can done and save the rest for your next social media check-in.
You might not need to check every channel every day – you could even spend 15 minutes on Twitter on Monday and then 15 minutes on LinkedIn on Tuesday. Figure out what works best for you and have fun with it.
You've been using your social media management checklists for a full week. Congrats.
Spend five or ten minutes reviewing your checklists to pinpoint which activities are most meaningful and generate results.
Use the 80/20 principle to determine which social media activities to put at the top of your social media management checklists. Stop other activities altogether or move them to the bottom of your checklist.
This weekly check-in is critical to increasing your social media management efficiency. After several weeks, you can either manage your channels on auto-pilot or outsource the task altogether.
Social media isn't rocket science. By implementing a system to manage your social channels, you'll no longer feel overwhelmed or wonder what you should do each time you log in.
Social media can empower you to better connect and cultivate the right relationships. All you need to do is cut the fluff.
Mindi Rosser is a social media strategist for hire, who specializes in helping brands, businesses and people look great online. As a digital native, she has spent nearly a decade working with B2B and B2C companies on developing and implementing strategic marketing programs. She consults for The Conversion Company, an online marketing firm helping B2B companies and executives use social media to drive dramatic business results. Connect with Mindi on LinkedIn or tweet her (@mindirrosser) to chat about all things B2B marketing, social selling, employee advocacy and social media. You can also follow her social marketing strategy blog at http://www.mindirosser.com.


The African Packaging & Label Indaba offers detailed insight into the trends and developments in the South African packaging and labelling market. The event is primarily geared at education, and will focus on the main packaging and label segments of flexible packaging, glass, corrugated, metal, rigid plastics, PSA, IML, shrink and wrap around. An impressive host of international speakers from the UK, Dubai and Israel will offer their unique perspective on the South African packaging industry. The event will be held on 5 and 6 October at the Forum in Bryanston, Johannesburg.
Be sure not to miss engaging topics and talks from industry leaders from across the value chain.
Packaging and economics – where are the pockets of excellence?
Regulation and packaging accountability – who bears the brunt?
Stand out, become unique. A global drive towards digital added value.
Day one will include an interactive networking and cocktail function which will be held at Cafe del Sol in Bryanston.
R4 500 per delegate – for two days!
R2 500 for one day.
Special IPSA, PACSA, PIFSA, Plastics SA member fee – R4 300 per delegate – for two days.


First cook from a new book! From Root and Leaf by Rich Harris I started with Flatbreads with Creamed Feta and Sticky Aubergines.
I am a big fan of Rich's recipes. Some time back I was looking for inspiration to start cooking some more interesting dishes on the BBQ and I found his book "Fire and Smoke". The great thing about this book is that there are loads of recipes for cooking on the BBQ and they are all totally different to what you see in the usual BBQ cookbooks.
Recently I was seeking inspiration again and I bought a lot of books all at once. I had a quick look through them all but Rich's second book "Root and Leaf" really caught my attention. There were so many recipes in there that I was just desperate to cook that I decided to work my way through the book until I had cooked a lot of them. One of the great things about the book is that the recipes aren't meat replacement dishes where the meat is just replaced with veg but instead each recipe is a standalone dish showcasing the veg as the star. Loads of dishes and recipes from all around the world and most of them can be cooked on the BBQ if you want to. I am struggling for time lately so I did cook some of them inside just to save time, I have written them all up though and each one could be cooked on the BBQ if you wanted.
Strong white bread flour, yeast, water, olive oil, sea salt, sugar and semolina all mixed in the kitchenaid with the dough hook in for 10 minutes then left it to rest for an hour before splitting the dough out.
Whilst the dough was rising I made the carrot topping: White wine vinegar, water, sugar, yellow mustard seeds, carrots and salt.
The sticky Aubergine topping was made by frying cubed aubergine then mixing in sherry vinegar, brown sugar and cumin seeds.
Lastly I blitzed feta, cream cheese and double cream together to make the creamed feta topping.
I cooked these in the Ooni Pro. Fired up with a couple of fistfuls of Resilient Woodlands Mixed Hardwood and lit with a few flamers underneath. Once the charcoal was lit I added some chunks of Beech to take the temperature up to about 500c.
Last time I split the dough into 8 but the first one was a bit small this time so I did 4 larger ones after that. They didn't take long to cook at that temperature!
First flatbread: Brushed with a garlic and sumac infused oil then topped with creamed feta and the carrot dressing before adding zaatar, sumac and olive oil on top.
Time for an aubergine one: The same sumac and garlic infused oil, then the creamed feta followed by the aubergine topping. Zaatar, sumac and olive oil on top at the end.
I really enjoyed these, what a great first cook from a new book! The flatbreads worked really well, putting them in a plastic freezer bag once cooked kept them warm and soft. The creamed feta topping was so tasty and worked well with both the carrot and aubergine dressings. Out of the two I think the aubergine one was my favourite, really good!
Pretty simple cook and you could do most of the prep the night before to make it quick and easy on the day.
Notes: No major changes, great dish.


I haven't been able to find a way to explode music on Symphony Pro. I find it invaluable to be able to compose to a single staff and then explode it to separate staves. This is really a time saver when writing Sax Solis or tutti passages. Any chance this will become a feature? Or is it and I am missing out on the way to do it?
This isn't a possibility yet, but is on our roadmap for this Spring/Summer. For now, we recommend MusicXML to export & interchange scores between software that supports this nonetheless convenient feature. Thanks for the feedback!


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Q: Get the math symbols from textbox and insert into database asp.net c# I am having textbox in a form. Users filling the form along with mathematical symbols but it is converting to some other character while storing to database(SQL). It should store the symbols, Can you tell me how do fix this issue?

A: Question column in your table should be able to store unicode characters, try change the type to nvarchar
create table test (
question nvarchar(10)
)

insert into test(question) values(N'√25 = 5')

A: The way your symbols are stored depend on the encoding of the SQL database. You need to select an encoding which can handle math symbols like Unicode (https://en.wikipedia.org/wiki/Mathematical_operators_and_symbols_in_Unicode)

redpajama_set_name: RedPajamaStackExchange


For the longest time, it was a decrepit stables building in an infamous, crime-ridden park that neighbors were afraid to enter, alongside a creek that stank every time rains washed sewage into it.
Then neighborhood activists led by Carole Williams-Green capped a 10-year organizing effort by converting the stables building into the Cobbs Creek Environmental Education Center in 2001, with classrooms for academic programming and meeting space for residents.
Fairmount Park increased cleanup efforts in the Cobbs Creek park and developed programming to bring neighbors into the park, including a 5k race, now in its fourth year. (Full disclosure: I served on the board of the center from 2008 to 2010.) The Philadelphia Water Department has made Cobbs Creek a model neighborhood in its efforts to reduce pollution from stormwater runoff.
But something was missing. "[It was] such an amazing facility and a little slice of habitat in the city, but it wasn't a visitor center," says artist Josh Robeson, who taught a summer educational program there in 2009 with Tony Croasdale, now Visitor Services Manager at the Center.
"I wanted CCCEEC to have a space like Pennypack, Heinz and Schuylkill Center," Croasdale says. On June 6, the Center opened the Carole Williams Green Exhibits Room, funded by the Philadelphia Water Department as part of its Green Cities, Clean Waters initiative, which aims to improve Philadelphia's waterways by better managing stormwater runoff.
Visitors at the exhibit can read about the history of the watershed and the challenges it faces today, and then experiment with stormwater runoff on the 15-foot stream table in the center of the room. A "green wall" watered by rain captured from the center's roof presents one solution.
Urban kids can enjoy nature as well as anyone else, but an introduction helps. Paintings by Robeson, guidebooks and iPads with nature apps are a start, but binoculars positioned for children to point out the window at the bird feeders offer connections.
The exhibit's local wildlife diorama features male and female wood ducks, carved by Philadelphia sculptor Peter Morgan, and appear to float on the surface of Cobbs Creek. A snapping turtle lurks beneath them. But this diorama differs from the rest in that it features a large combined sewer outflow pipe.
This is Cobbs Creek, after all, a ribbon of natural beauty weaving through an urban landscape of rowhomes and asphalt streets. We can go there to enjoy the wood ducks and other wildlife—over 100 species of birds have been documented in the park, according to Croasdale—but we can't ignore what washes into the creek from the city to either side.


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A Consolidation of Bureaucracy
Lewiston Daily Sun, January 22, 1931
The late 1920s and early 1930s were a time of great expansion for the newly dubbed Pownal State School – enrollment went from 271 in 1919 to 780 in 1932. This growth was spurred by a continuation of the fears of people with developmental disabilities being bad influences on society, but also, as the Great Depression began, from a sense that families and communities did not have the resources to care for those with disabilities and that an institution would be the most efficient option.
Alongside the growth of centralized institutional care for people with disabilities, the early 30s brought a parallel consolidation of governmental administration under the executive branch, beginning in 1931 with "An Act relating to the Administration of the State", which created several new administrative departments, including the Department of Health and Welfare – in which the Bureau of Institutional Service would take responsibility for the oversight of all the state-run institutions in Maine, including being tasked "to license and supervise all institutions and agencies operating within the state for the care and treatment of defectives, dependents, and delinquents".
Governor Gardiner claimed that such a reorganization would lead to a "more competent, energetic administration", but the bill had its detractors in the Legislature, who saw such a move towards consolidation as government overreach.
Lewiston Daily Sun, May 15, 1931
"The danger, therefore, which is threatened by the consolidation of departments and the appointment of commissioners and bureau of chiefs is placing too much money and political power in the hands of a few individuals. Another danger, as I see it in the bill, is that the authority conferred upon these administrative boards and bureau chiefs is an unlimited authority. The jurisdiction to deal with particular subjects involving the conduct of individuals is conferred in terms which are so indefinite that we will have to resort to the courts for a construction of the limitation of authority and power granted in this bill." – Representative Farris of Augusta, March 31, 1931
The plan also had its support:
"Mr. Speaker and members of the Eighty-fifth Legislature: I am well aware that the lassiez-faire policy in government prevails in certain quarters. The bill which we have before us under discussion is nothing but a simplification of the fiscal program of our beloved State of Maine It has not been drafted under cover. The Cole Committee, in 1921, recommended these changes. This bill has been worked upon for six months, and by some of the ablest people of the State of Maine, and I for one am willing to accept their judgment as to the constitutionality of the law." Representative Briggs of Caribou, March 31, 1931
In the end, the bill passed, and the Department of Health and Welfare was created.
1931 Public Law, Chapter 216, An Act Relating to the Administration of the State
In 1933, another law was passed establishing the organization and duties of the Department of Health and Welfare, and giving it much power over the institutions in Maine.
1933 Public Law Ch. 1 – An Act to Revise the Health and Welfare Laws


In today's Wall Street Journal I review the off-Broadway premiere of Tracy Letts' Mary Page Marlowe. Here's an excerpt.
Tracy Letts is one of this country's foremost writers, a playwright who is unafraid to explore the private lives of Americans of all kinds, from the sleazy trailer trash of "Killer Joe" to the freshly divorced misanthrope at the heart of "Linda Vista." He is also a character actor of near-unique range who fills his plays with complex, richly nuanced roles. Yet nothing he had previously done prepared audiences for "Mary Page Marlowe," first performed by the Steppenwolf Theatre Company in 2016, in which he used six different women (and a doll) to portray a seemingly ordinary Ohio accountant whose life is a scrapbook of what it means to be a woman in America. I called it "the most purely beautiful play that Mr. Letts has given us" in my review of the Chicago premiere, and now that it has reached New York in a new staging of identical merit, it looks—if possible—even more impressive.
Mr. Letts' 90-minute play, which is set between 1946 and 2015, is structured in a way that requires detailed explanation on paper. The six actors who play the title role (Blair Brown, Emma Geer, Mia Sinclair Jenness, Tatiana Maslany, Kellie Overbey, and Susan Pourfar) appear in ten of the 11 vignette-like scenes in which Mary Page is seen as a baby and at 12, 19, 27, 36, 40, 44, 50, 59, 63 and 69. Some scenes take place at key moments in her life—we see her in the hospital not long after she learns that she is going to die—while others appear at first glance to have been picked at random. Moreover, the scenes are not arranged chronologically but in an order of the author's own devising….
If this elaborate description makes "Mary Page Marlowe" sound like an avant-garde exercise in fractured narrative, be assured that it doesn't play that way. It unfolds simply and intelligibly, proceeding according to a dramatic logic that makes total sense to the eye and ear. What we see before us is a woman who gradually comes to understand, however haltingly and imperfectly, who and what she is….


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Johann Heinrich Ramberg
German artist
Johann Heinrich (a.k.a.John Henry) Ramberg (22 July 1763 – 6 July 1840) was a German painter and printmaker.Ramberg was born at Hanover to a father who fostered his artistic talent.
He first showed his talent by drawings of scenes in the Harz Mountains.These became known to George III, King of Great Britain, his sovereign, since he was also Elector of Hanover.
In 1781 he was introduced to George III and made "many humorous sketches and caricatures" for him.George induced Ramberg to go to London, where he provided support.
Ramberg may have been a student of Joshua Reynolds and Francesco Bartolozzi; in November 1781, he studied with Benjamin West at the Royal Academy Schools.
In 1782 he began exhibiting at the Royal Academy and in 1784 he was awarded a silver medal for his life drawing.
In 1784 Ramberg drew the exhibition itself, showing Reynolds and the Prince of Wales, as well as several other pieces.According to the Oxford Dictionary of National Biography, "[t]hese works are of interest to historians for their record of exhibitions in the Great Room of the Royal Academy in the late eighteenth century." In 1788, Ramberg visited the Netherlands, Germany, and Italy, and then returned to Hanover in 1792, where he was appointed electoral court painter.
While court painter he periodically took on students, including John Fischer.He painted the curtain the court theater in Hanover in 1789.
He met the German author Goethe in 1790–91 and painted Alexander Crossing the Granicus as a decoration for Carlton House.
He was also a book illustrator, participating in John Boydell's Shakespeare Gallery, for example, and Thomas Macklin's Poets' Gallery.He painted portraits of members of the British royal family: the princesses Mary, Elizabeth, and Sophia.
He illustrated German almanacs and pocketbooks for over 20 years, but according to the Oxford Dictionary of National Biography "his best illustrations are those which he himself etched for the narrative cycles Reineke Fuchs and Tyll Eulenspiegel, both published in 1826".
He became one of the most well known illustrators in Germany.He did the drawings for a deluxe edition of Wieland's works.
Ramberg died at Hanover and was buried in the Gartenkirchhof.
Heinrich Jacob Aldenrath
Friedrich August von Klinkowström


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Q: Why do i have to put name for each object in FireBase data structure? Lets take a look at google example for simple array
 "chats": {
    "one": {
      "title": "Historical Tech Pioneers",
      "lastMessage": "ghopper: Relay malfunction found. Cause: moth.",
      "timestamp": 1459361875666
    },
    "two": { ... },
    "three": { ... }
  },

My question is why do we have to put name for each chat ? if i want to add another object i need to know which are the existing keys and create new one for which reason ? i just want a list of chats in this example and the names one two three means nothing to me...
why cant i put a list of objects with no name under chats ?

A: "chats": {
    "one": {
      "title": "Historical Tech Pioneers",
      "lastMessage": "ghopper: Relay malfunction found. Cause: moth.",
       "timestamp": 1459361875666
},
"two": { ... },
"three": { ... }
},

Instead of one, two and three, you can use random ids using the push() method in android, so you will have something like this:-
   "chats": {
     "id_1": {
      "title": "Historical Tech Pioneers",
      "lastMessage": "ghopper: Relay malfunction found. Cause: moth.",
      "timestamp": 1459361875666
   },
     "id_2": { ... },
     "id_3": { ... }
     },

You can retrieve the key like this:-
String mGroupId = mGroupRef.push().getKey();

You can think of the ids as primary key


The need for a Six Sigma project comes from a business problem or an opportunity. This one-day course is based on the Define Phase of the DMAIC framework and is the second of six courses designed to prepare individuals to conduct continuous improvement work in their organizations. The purpose of this course is to help students familiarize themselves with the expectations, tools, concepts, and deliverables of the Six Sigma Define Phase. Within this phase, students will understand the importance of the business problem or opportunity as it relates to process improvement and Six Sigma. Students will also explore other aspects of the Define Phase such as stakeholder identification, customer requirements gathering and analysis, and required elements to create a Six Sigma project plan.
Develop a voice of customer (VOC) plan.


Summary: Develop and publish public course description intended for prospective learners.
Not linked to the course assignment but productive first step towards developing a design blueprint.
Note: Learners from OERu partners will be able to reuse the course description for the OERu website.
For inspiration and ideas, explore the web pages for the institutions linked below to read a large variety of course descriptions. Are there any writing styles that you prefer?
Creating the "Course description" subpage from your course planning page in the wiki.
Drafting the text for your course description and publishing this in the wiki.
By completing this challenge you will have content suitable for publishing on an "About" page for your course website.


The Monterey Police Department says the remains belong to Jennifer Lynn Morris, a woman who was reported missing on January 25, 1983. Morris' vehicle was located at the Del Monte Shopping Center shortly after her disappearance.
The remains were located between southbound Highway 1 and the Del Monte Shopping Center.
Morris' parents, who originally reported her missing, are now deceased. Morris is survived by two brothers.
The Monterey Police Department is asking anyone with information in connection with Morris' disappearance and death to contact their confidential tip line at 831-646-3840 or Detective Mike Bruno at 831-646-3812.


ICANN participates in NLNOG RING, a project that helps network operators cooperate to help diagnose and fix network problems.
For network operators, a point of view outside their own network is essential. It lets them see what others see. NLNOG RING allows instant access to specific queries from many points or just one point on the Internet.
Each RING server host provides access to a machine on their network with a static IPv4 and IPv6 address and an unfiltered view of the Internet. Other participants in the RING are can use that machine in combination with others in the RING to help identify, understand, and resolve network problems.
There are currently almost 350 networks participating in the RING, offering other network operators view of the Internet from almost 50 countries. ICANN is proud to participate and host RING servers in its east and west coast data centers.