N-Phenyl benzenecarbohydrazonoyl chloride IA was reported to cause severe dermatitis in human [14Rothe A. Contact dermatitis from N-(a-chlorobenzylidene) phenylhydrazines Contact Dermatitis Chem Abstr 1988 108 162843c 1988; 18: 16-9.]. Out of 6 people, five-chemistry students were affected following a single contact. The clinical picture of the dermatitis was characterized by a biphasic course. Circumscribed slight lesions, developing usually within one day in directly affected areas were followed after 4 to 12 days by generalized widespread erythema and edema with papules and vesicles [14Rothe A. Contact dermatitis from N-(a-chlorobenzylidene) phenylhydrazines Contact Dermatitis Chem Abstr 1988 108 162843c 1988; 18: 16-9.].

IA, Ar-C(Cl)=NNHAr', Ar = Ar' =C6H5

N-phenyl 4-methylbenzenecarbohydrazonoyl chloride IB was the first candidate of hydrazonoyl halides that proved effective against gastrointestinal nematodes and cestodes of ovines following a single oral dose of 30-50 mg/kg [15Kaugars G. Insecticidal acaricidal and anthelmintic benzoyl chloride phenylhydrazone derivatives Fr Demande, 2,103,533, May19, 1972; Chem Abstr 1973; 78: 29473c.-19Folz S D, Pax RA, Klei TR, et al. Development of a novel in vitro equine anthelmintic assay J Vet Pharmacol Ther 1988 11 177-182 Chem Abstr 1988; 109: 85599u.]. The sheep developed mild diarrhea and anorexia 10 days after treatment which lasted for 2-4 days, after which the sheep acquired their normal health. No ill signs were observed one week after treatment. N-(4-Chlorophenyl) 4-methoxybenzene-carbohydrazonoyl chloride IC has also been found to be an effective potent anthelmintic compound [20Perronnet J, Girault P, Grandadam JA. Anthelmintic N-(a-chloro-4'-methoxybenzylidene)-4-chlorophenylhydrazine FrDemade 275,566 Nov 30 1973 Chem Abstr 1974; 80: 70550e.].

IB 4-MeC₆H₄C(Cl)=NNHC₆H₅

IC 4-MeOC₆H₄C(Cl)=NNHC₆H₄Cl-4

In attempt to elucidate the relationship between structure and anthelmintic activity (SAR), Rector and coworkers [21Rector DL, Folz SD, Conklin RD, Nowakowski LH, Kaugars G. Structure-activity relationships in a broad-spectrum anthelmintic series.Acid chloride phenylhydraones. 1.Arylsubstitu-tions and chloride variations J Med Chem 1981; 24: 532-8.] prepared a series of thirty substituted N-phenyl benzenecarbohydrazonoyl chlorides I and evaluated their activity against three mouse helminths, Syphacia obvelata, Nematospiroides dubius and Hymenolepis nana. The dosage used was the highest dose (up to 7.5 mg / mouse / day) which did not elicit toxic effects on the mouse. The structural features required to give the superior anthelmintic activity in the series studied are meta- and/or para- halogen, alkoxy, alkyl, or alkylthio substituent(s) in the acid ring moiety. This is because any compound with an o-substituent in the acid ring residue was found to lack activity. Except for the N-(p-chlorophenyl), any substituent in the N-ring residue gave compounds with little or no activity. Multiple substitution in either ring decreases the activity. Also, the reported data revealed that there did not appear to be the detrimental ortho effect operating in the N-ring substitution as was apparent in the acid ring case.

The anthelmintic activity of other series of N-aryl and N-alkyl benzenecarbohydrazonoyl bromides IB (X= Br) and their chloride IB' (X = Cl) analogs were tested on mice infected with the nematode Nippostrongylus braziliensis [22Molodykh Zh V, Lisenkova AN, Buzykin BI, KitaevYu P. Athelmintic activity of some hydrazones Khim Farm Zh 1977 11 81-83 Chem Abstr 1977; 86: 165070m., 23Wing KD. Anthemintic N-alkyl-N,N'-diacylhydrazines: nonsteroidal ecdysone agonists S 524,333 Jun 13 1995 Chem Abstr 1995; 123: 313108e.]. The most active compound was N-(2-bromo-4-nitrophenyl) benzenecarbohdrazonoyl bromide IBc and the least active was N-(4-methylphenylsulfonyl) benzenecarbohydrazonoyl chloride IBd.

IBc C₆H₅C(Br)=NNHC₆H₃Br(NO2)-2,4

IBd C₆H₅C(Br)=NNHSO₂C₆H₃Me-4

Other derivatives such as N-phenyl 4-methylthiobenzene-carbohydrazonoyl chloride IB and its N-(4-methylthio) benzenecarbohydrazonoyl chloride IC as well as N-(2,4-dibro-mophenyl) 4-methylthiobenzenecarbohydrazonoyl chloride ID were reported to be useful anthelmintics [24Kaugars G. Alkylthiobenzoic acid phenylhydrazides U S Patnt 414,932 Mar 29 1977 Chem Abstr 1977; 87: 5665b.].

IB-D ArC(Cl)=NNHAr'

Ar / Ar': B, 4-MeSC₆H₄ / Ph; C, Ph / 4-MeSC₆H₄;

D, 4-MeSC₆H₄ / 2,4-Br₂C₆H₃

Also, N-phenyl derivatives of 4-methyl-, 4-nitro- and pentafluoro- benzenecarbohydrazonoyl chlorides as well as N-(2,4-dibromophenyl) benzenecarbohydrazonoyl chloride and N-(2,4,6-trichlorophenyl) 4-chlorobenzenecarbohydra-zonoyl chloride were reported to be useful anthelmintics [25Kaugars G, Germich EG. Benzoyl chloride phenylhydrazones against insects and mites US Patnt 417,540 Apr 12 1977 Chem Abstr 1977; 87: 22800.].

IB-D Ar-C(X)=NNHAr'

Ar / Ar': IB, C₆H₅ / 2,4-Br₂C₆H₃;

ICa, 4-MeC₆H₄ / Ph; ICb, 4-O₂NC₆H₄ / C₆H₅;

ICc, C₆F₅ / C₆H₅;

ID, 4-ClC₆H₄ / 2,4,6-Cl₃C₆H₂

Moon et al.[26Moon MW, Kaugars G. Pyruvyl chloride phenylhydrazone anthemintic US Patnt 3 32,662 Jan 13 1976 Chem Abstr 1976; 84: 16001q.] synthesized a few N-aryl 2-oxopro-panehydrazonoyl chlorides VI in search of new anthelmintics. The results showed that N-(2,4-dichlorophenyl) derivative VIa (250 mg/Kg orally) was effective in sheep and N-(2-chloro-4-nitrophenyl) derivative VIb (30 mg/Kg orally) was effective in dogs.

VI CH₃COC(Cl)=NNHAr

Ar: a, 2,4-Cl₂C₆H₃; b, 2-Cl,4-O₂NC₆H₃

Some N-aryl C-heteroarylmethanehydrazonoyl chlorides IV were also reported to be useful as anthelmintics [27Kaugars G. Halogen substituted pyridinealdehyde phenylhydrazones US Patnt 399,111, Oct 17 1972 Chem Abstr 1976; 84: 116001q., 28Kaugars G. Thiophenecarbonyl chloride phenylhydrazones US Patnt 309,703 May 07 1974 Chem Abstr 1976; 84: 116001q.].

IV Het-C(Cl)=NNHAr

Het: A, 2-furyl; B, 5-Br-2-(5-Br-furyl); C, 2-thienyl;

G, 3-pyridyl, M, 2-Cl-(pyrid-3-yl)

Ar: a, Ph; b, 2,4,6-Cl₃C₆H₂

Several N-aryl benzenecarbohydrazonoyl chlorides I were reported active against anthropod pests and worms [29Kaugars G. Antianthropodal formulation U S Patnt 379,542 Apr 22 1975 Chem Abstr 1975; 83: 9553d.]. For example, N-(4-methylthiophenyl) benzenecarbohydrazonoyl chloride IB, N-phenyl 4-methylthiobenzenecar-bohydrazonoyl chloride ICa and its N-(2,4-dibromophenyl) analog ID [30Kaugars G. Alkylthio benzoyl chloride phenylhydrazones US Patnt 331,318 Jan 06 1976 Chem Abstr 1976; 84: 121494g.] and N-phenyl 3-trifluromethylbenzocar-bohydrazonoyl bromide ICb [31Kaugars G. a a a -Trifluoro-m-toluoyl chloride phenylhydrazone Ger Ofen 234,574 Jul 13 1972 Chem Abstr 1972; 76: 72258g.] were found useful for control of anthropodal pests such as insects, spiders, ticks and mites.

IB, Ph-C(Cl)=NNH C₆H₄-SMe-4

ICa, 4-MeSC₆H₄-C(Cl)=NNHPh

ICb, 3-F₃CC₆H₄-C(Cl)=NNHPh

ID, 4-MeSC₆H₄-C(Cl)=NNH C₆H₃Br₂-2,4

A series of N-aryl 2-aryl-2-oxo-ethanehydrazonoyl bromides VII were tested as antiviral agents. The results showed that all compounds investigated succeeded to reduce the number of local lesions induced by tomato mosaic virus on detached Datura metel leaves [32Habib HM. The antiviral effect of some substituted a -keto hydrazidoyl chlorides Egypt J Microbiol 1987 22 129-142 Chem Abstr 1989; 110: 111581z.]. The order of activity was found to be Y/X: 4-Br / H = H / 4-Cl > H / 4-Me = 4-Me /H > H / 4-NO₂. Analysis of the results obtained revealed that the activity of the studied compounds is more than that found for N-(4-nitrophenyl) benzenecarbohydrazonoyl bromide I. This result was considered to indicate that the presence of the 2-oxo group enhances the antiviral activity [32Habib HM. The antiviral effect of some substituted a -keto hydrazidoyl chlorides Egypt J Microbiol 1987 22 129-142 Chem Abstr 1989; 110: 111581z.].

VII YC₆H₄-CO-C(Br)=NNHC₆H₄X

Y/X: a, 4-Br / H; b, H / 4-Cl; c, H / 4-Me; d, 4-Me /H; e, H / 4-NO₂

Twenty seven hydrazonoyl halides of types I, III and VI were examined for their toxicity, fungicidal, fungistatic and bactericidal activities. The fungicidal activity was found to depend on the acid residue R [33Molodykh ZhV, Buzykin BI, Kudrina MA, Sysoeva L. Antimicrobial activity of some arylhydrazones of acyl halides and arylhydrazides of carboxylic acids Khim Farm Zh 1980 14 33-42 Chem Abstr 1980; 93: 94943e.]. The toxicity of the studied halides I, III and VI in warm blooded animals decrease in the order of substituents H > 4-NO₂ > 4-Cl > 4-Br > 2- or 3-NO₂ [33Molodykh ZhV, Buzykin BI, Kudrina MA, Sysoeva L. Antimicrobial activity of some arylhydrazones of acyl halides and arylhydrazides of carboxylic acids Khim Farm Zh 1980 14 33-42 Chem Abstr 1980; 93: 94943e., 34Buzykin BI, Sysova LP, Molodykh ZhV, Kudrina MA, Neklesova ID, Kitaev Yu P. Acetyl chloride 4-bromophenyl- hydrazone possessing fungicidal and bactericidal properties USS 68610 Mar 07 1981 Chem Abstr 1981; 95: 42395z.].

I, YC₆H₄-C(X)=NNHC₆H₃R'R"-2,4

Y = H, 4-Br, 4-F, 4-Cl, 3-O₂N, 4-O₂N; X = Cl, Br

III, R-C(X)=NNHC₆H₃R'R"-2,4

R: Me, Et, Pr; X: Cl, Br

VI, MeCO-C(Cl)=NNHC₆H₃R'R"-2,4

R' = H, Br, O₂N; R" = H, Br, Cl, O₂N, H₂NSO₂

Dubenko et al. [35Dubenko RG, Granin EF, Konysheva VD, Gorbenko EF, Bazavova MI, Pel'kis PS. Fungicidal properties of arylhydazones of glyoxalic acid substituted derivatives Fiziol Akt Veshchestva 1981 13 33-37 Chem Abstr 1982; 96: 99275k.] reported that some N-aryl derivatives of, 2-oxo-2-phenylethanehydrazonoyl chlorides VII, 2-amino-2-oxoethanehydrazonoyl chlorides IX and cyanomethanehydrazonoyl chlorides XIII showed activity against wheat stem rust, phytophora infection of tomatoes and cucumber powdery mildew. Both systemic and contact activities were reported. Activities of these compounds were correlated with their structure.

VII PhCO-C(Cl)=NNHC₆H₄X

IX ArNHCO-C(Cl)=NNHC₆H₄X

XIII NC-C(Cl)=NNHC₆H₄X

X: a, H; b, Cl; c, Br; d, I; e, O₂N; f, AcNHSO₂; g, EtOCO

Also some N-aryl 2-oxopropanehydrazonoylchlorides VI were reported to be useful fungicides [36Draber W, Buechel KH, Hammann I, Frohberger PE. Pyruvamide 1-(phenylhydrazones) Ger Ofen 233,997 Oct 05 1972 Chem Abstr 1973; 78: 15844n.].

VI, CH₃COC(Cl)=NNHAr; Ar = RR'C₆H₃,

R = H, 2-Cl, 2-Me, 3-F₃C

R' = H, 2-, 3-, 4-Cl, 5-F₃C, 6-Me, 4-O₂N

Kukota et al. [37Kukota SN, Borisenko VP, Bodnar VN, Zhuravskaya NI, Lozinskii MO. Synthsis and phytotoxicity of arylhydrazones of substituted pyruvic and a,ß-dioxobutyric acids Fiziol Akt Veshchestva 1978 10 32-36 Chem Abstr 1979; 90: 6212a.] tested fifteen N-(4-substituted phenyl) 3-bromo-2-oxopropanehydrazonoyl bromides VI and their 3-pyridinio bromide analogs IV as plant growth regulators at 0.01, 0.001 and 0.0001 %. The N-(4-methylphenyl)-, N-(4-chlorophenyl)- and N-(4-nitrophenyl)- derivatives depressed the growth of roots, stalks and leaves of lettuce and Oats.

VI, BrCH₂COC(Cl)=NNHC₆H₄X

IV, [C₅H₅N⁺-C(Cl)=NNH C₆H₄X] Br^-

X = 4-Me, 4-Cl, 4-O₂N

Kaugars and his coworkers [27Kaugars G. Halogen substituted pyridinealdehyde phenylhydrazones US Patnt 399,111, Oct 17 1972 Chem Abstr 1976; 84: 116001q., 28Kaugars G. Thiophenecarbonyl chloride phenylhydrazones US Patnt 309,703 May 07 1974 Chem Abstr 1976; 84: 116001q.] prepared two series of N-aryl hetarylcarbohydrazonoyl chlorides IV and indicated that they are primarily useful as herbicides.

IV, Het-C(Cl)=NNHAr

Het: A, 2-furyl, B, 2-(5-Br-furyl), C, 2-thienyl, D, 2-picolinyl,

E, nicotinyl, F, 4-pyridinyl

Ar = XC₆H_5-n; X: a, H, b, 2,4,6-Cl₃

N-(2,4-Dichlorophenyl) propanehydrazonoyl chloride IIIa and its N-(2,4,6-trichlorophenyl) analog IIIb were reported to have, at 1Ib/acre, postemergence contact herbicidal activity against bread leaf weeds, and to a lesser degree against grasses [38Moon M W, Friedman A R, Steinhards A. Herbicidal activityof phenylhydrazones and related azo compounds J Agric Food Chem 1972 20 1187-1190 Chem Abstr 1973; 78: 39208j.]. Some other N-aryl (C₂-₄)alkane-hydrazonoyl chlorides IIIA were reported to be useful herbicides [39Kaugars G. Combating insects and mites using alkanoyl chloride phenylhydrazones U S Patnt 345,215, Jul 10 1973 Chem Abstr 1973; 79: 78412m.].

CH₃CH₂-C(Cl)=NNHAr

III, Ar: a, 2,4-Cl₂C₆H₃; b, 2,4,6-Cl₃C₆H₂

IIIA, R-C(Cl)=NNHC₆H_5-nX_n

R = C₂-₄; X = H, 4-Cl, 2,4-Cl₂, 4-Me

Also a series of N-aryl cyanomethanehdrazonoyl chlorides XIII was prepared and tested on lettuce and Oat cultured on agar [40Karabanov Yu V, Gershkovich A A, Lozinskii M O, Borisenko V P, Samolyuk L. Herbicidal activity of 1-halo-1-cyano-3-aryl-2,3-diaza-1-propenes Fiziol Akt Veshchestva 1974 6, 64-67 Chem Abstr 1975; 82: 165760d.]. Of these hydrazonoyl chlorides only N-(4-nitrophenyl)- and N-(2,4-dichlorophenyl)- derivatives XIIIa and XIIIb were reported to be the most effective herbicides, decreasing germination and inhibiting growth to the highest extent. Both compounds acted as herbicides at 0.0001% [40Karabanov Yu V, Gershkovich A A, Lozinskii M O, Borisenko V P, Samolyuk L. Herbicidal activity of 1-halo-1-cyano-3-aryl-2,3-diaza-1-propenes Fiziol Akt Veshchestva 1974 6, 64-67 Chem Abstr 1975; 82: 165760d.]. N-(4-methylphenyl) cyanomethanehydrazonoyl chloride XIIIc at 0.0001% was reported to stimulate lettuce stem growth to the highest extent [40Karabanov Yu V, Gershkovich A A, Lozinskii M O, Borisenko V P, Samolyuk L. Herbicidal activity of 1-halo-1-cyano-3-aryl-2,3-diaza-1-propenes Fiziol Akt Veshchestva 1974 6, 64-67 Chem Abstr 1975; 82: 165760d.].

XIII, NC-C(Cl)=NNHAr

Ar: a, 4-O₂NC₆H₂; b, 2,4-Cl₂C₆H₃; c, 4-MeC₆H₄

Twelve N-aryl alkanehydrazonoyl chlorides IIIA were also prepared and found useful as herbicides (e.g., against crabgrass, wild oats, yellow foxtail) [41Kaugars G. Weed control with substituted phenylhydrazones U S Patnt 3 70,505, Mar 11 1975 Chem Abstr 1975; 83: 78891z.]. N-(4-Chloro-phenyl) 2,2-dimethylpropanehydrazonoyl chloride IIIB was reported to exhibit the highest activity against crabgrass, wild oats and yellow foxtail [41Kaugars G. Weed control with substituted phenylhydrazones U S Patnt 3 70,505, Mar 11 1975 Chem Abstr 1975; 83: 78891z.].

IIIA, R-CX)=NNHAr, R = Et, Pr, Me₂CH, Me₃C

IIIB, (CH₃)₃C-C(Cl)=NNHC₆H₄Cl-4

Some other derivatives of N-Phenyl benzenecarbohydrazonoyl chloride I were prepared as useful herbicides [42Andree R, Luerssen K, Santel H J, et al. Preparation of benzhydrazidoyl halides as acaricides, insecticides and herbicides Ger OffenDE 400,591, Jul 15 1993; Chem Abstr 1993; 119: 133475f.]

I, XC₆H₄-C(Cl)=NNHC₆H₄Cl-2

X: alkyl, alkoxy, alkenyl, halo, CN, O₂N

Strinadkin et al. [43Strinadkin P S, Buzykin B I, Gazetdinova N G, Sysoeva L P, Kitaev Yu P. Antisarcoptic activity of arylhydrazones of chloro(bromo)carboxylic acid anhydrides Fiziol Akt Veshchestva 1981765-67 Chem Abstr 1985; 103: 208842d.] reported that of the twenty derivatives of N-aryl substituted benzenecarbohydrazonoyl-, eth-anehydrazonoyl-, 3-pyridinecarbohydrazonoyl-, 4-pyridine-carbohydrazonoyl- and 2-oxopropane-hydrazonoyl halides I-VI, respectively N-(2-nitrophenyl) benzene-carbohydra-zonoyl chloride was the most effective as antisarcoptic. A single application (5-10 ml 0.05%) of such a chloride or 0.5% of N-(2,4-dibromophenyl) benzenecarbohydrazonoyl bromide I to rabbit's ears eradicated psoroptosis within 10 days.

I Ar-C(Cl)=NNHAr'

III CH₃-C(Cl)=NNHAr

IV Het-C(Cl)=NNHAr

VI CH₃CO-C(Cl)=NNHAr

Het: F, 4-Pyridyl G, 3-Pyridyl

Also, Buzykin et al. [44Buzykin B I, Strinadkin P S, Zabolotnyi K F, et al. Antisarcoptic activity and allergenic properties of arylhydrazones of acylhalogeniddes Fizio Akt Veshchestva 1990 22 20-24 Chem Abstr 1991; 115: 177380t.] studied the antisarcoptic activity of twenty one hydrazonoyl halides of types I, III and X against Psoroptos Cuniculi and reported that the activity of I increases with increasing electron donating properties of the substituent in the Ar’ group, 4-MeO > 4-Cl > 4-Br > 3-NO₂ > 4-NO₂ > 2-NO₂. They found that one application of 0.05% of a 13.6% compositon emulsion of N-phenyl benzenecarbohydrazonoyl chloride Ia to rabbit ears 100% eradicated psoroptosis. LD₅₀ of hydrazonoyl halides studied for mice was 0.4-13.5 ml/kg vc. a 0.5-10.9M LC₅₀ for P. Cuniculi. Both N-(2-nitrophenyl) benzenecarbohydrazonoyl chloride Iband N-phenyl 4-bromobenzenecarbohydrazonoyl chloride Ic were strongly allergenic to rabbits.

I, Ar-C(Cl)=NNHAr'

Ar' = XC₆H₄; X = 4-MeO, 4-Cl, 4-Br, 3-NO₂, 4-NO₂, 2-NO₂

III, HC(Cl)=NNHAr'

X, (RO)₂PO-C(Cl)=NNHAr'

N-Phenyl 4-methylthiobenzenecarbohydrazonoyl chloride Ia, N-(4-methylthiophenyl) benzenecarbohydrazonoyl chloride Ib and N-(2,4-dibromophenyl) 4-methylthioben-zenecarbohydrazonoyl chloride Ic [24Kaugars G. Alkylthiobenzoic acid phenylhydrazides U S Patnt 414,932 Mar 29 1977 Chem Abstr 1977; 87: 5665b., 25Kaugars G, Germich EG. Benzoyl chloride phenylhydrazones against insects and mites US Patnt 417,540 Apr 12 1977 Chem Abstr 1977; 87: 22800., 45Hatzinikolis E N, Koutepas N G. Evaluation of acaricides against Tetranychus urticae koch (Acarina, Tetranychidae) Nea Agrotike Epiteor 1977 31 49-51 Chem Abstr 1977; 87: 48889v.] and N-(4-chlorophenyl) 3,3-dimethyl-2-oxopropanehydrazonoyl chloride VI [41Kaugars G. Weed control with substituted phenylhydrazones U S Patnt 3 70,505, Mar 11 1975 Chem Abstr 1975; 83: 78891z.] were reported to be useful as acaricides and miticides.

I Ar-C(Cl)=NNHAr'

VI Me₃CCOC(Cl)=NNHC₆H₄Cl-4

Ar / Ar': a, H/ 4-MeSC₆H₄; b, 4-MeSC₆H₄ / H;

c, 4-MeSC₆H₄/2,4-Br₂C₆H₃

Kaugars et al. [46Kaugars G, Germich E G. Benzoyl chloride phenylhydrazones as pesticides Ger Ofen 126 366 Jan 15 1970 Chem Abstr 1970; 72: 100323n., 47Kaugars G, Gemrich E G, Rizzo V L. Miticidal activity of benzoyl chloride phenylhydrazones J Agric Food Chem197321 647-650 Chem Abstr 1973; 79: 112347f.] screened seventy N-aryl benzenecarbohydrazonoyl chlorides I for miticidal activity and repellency, using the two-spotted spider miet. They reported that such activities depend to a large extent on the nature, position and number of substituents in either or both aromatic rings, the highest activity was shown by N-(2-chlorophenyl) derivatives of 4-chloro- and 4-bromo-benzenecarbohyd-razonoyl chlorides Ia,b and N-(3-trifluoromethyl) benzenecarbohydrazonoyl chloride Ic. Replacement of the hydrazone NH by N(CH₃) decreased the activity [48Moon MW. The chlorination of aldehyde and ketone phenylhydrazones J Org Chem 1972; 37: 383-5.].

I Ar-C(Cl)=NNHAr'

Ar / Ar': a, 4-ClC₆H₄ / 2-ClC₆H₄H; b, 4-BrC₆H₄/ 2-ClC₆H₄; c, C₆H₅ / 3-F₃CC₆H₄

Kaugers and Germrich [15Kaugars G. Insecticidal acaricidal and anthelmintic benzoyl chloride phenylhydrazone derivatives Fr Demande, 2,103,533, May19, 1972; Chem Abstr 1973; 78: 29473c., 49Kaugars G, Germich E G. Insecticidal and miticidal benzoyl chloride phenylhydrazones Ger Ofen 109,868 Oct 16 1969 Chem Abstr 1970; 72: 54978e.] indicated that N-aryl benzene-carbohydrazonoyl chlorides I are highly active as miticides. One of these compounds, namely N-(2,4,6-trichlorophenyl) benzenecarbohydrazonoyl chloride IB, has been extensively field tested and has been assigned the trade mark Banomite. The latter was reported to decrease significantly Texas citrus mite (Euteranychus banksi) eggs and adults [50Dean H A. Citrus mite control with certain acaricides J Rio Grande Val Hortic Soc 1974 28 122-130 Chem Abstr 1975; 83: 159083q.]. Other derivatives of benzenecarbohydrazonoyl chloride having methylthio group in either the C-phenyl or the N-phenyl groups were reported to be useful as acaricides [25Kaugars G, Germich EG. Benzoyl chloride phenylhydrazones against insects and mites US Patnt 417,540 Apr 12 1977 Chem Abstr 1977; 87: 22800.].

IB Ph-C(Cl)=NNHC₆H₂Cl₃-2,4,6

Several other N-aryl alkanehydrazonoyl chlorides III were also reported to be useful as acaricides [39Kaugars G. Combating insects and mites using alkanoyl chloride phenylhydrazones U S Patnt 345,215, Jul 10 1973 Chem Abstr 1973; 79: 78412m., 51Boesch R. Phenylhydrazone derivatives Ger Ofen 226,783, Dec 13 1973 Chem Abstr 1974; 80: 70518a.].

III RC(Cl):NNHAr

R = Me, Et, n-Pr, i-Pr, t-Bu

Ar = 2,4-Cl₂C₆H₃; 4-Cl,2-NO₂C₆H₃, 2,4,6-Cl₃C₆H₂

Also, N-phenyl methylthio-substituted benzenecarbohydrazonoyl chlorides IA,B were useful as acaricides [24Kaugars G. Alkylthiobenzoic acid phenylhydrazides U S Patnt 414,932 Mar 29 1977 Chem Abstr 1977; 87: 5665b., 52Kaugars G. Methylthio derivatives of benzoyl chloride phenylhydrazone Ger Ofen,134,482, Jan 27 1972; Chem Abstr 1972; 76: 112931e.].

IA,B RC₆H₄C(Cl):NNHC₆H₄R’

R/R’: 4-MeS / H, 4-Cl,2-MeS / H, H / 4-MeS, 4-MeS / 2,4-Br₂

N-(2,4,6-Trichlorophenyl) benzenecarbohydrazonoyl chloride IB (banamite) was found more toxic (LC₅₀ 12 ppm) to the two spotted spider mite (Tetranychus urticae) than were nine of its potenrial metabolites. It inhibited rat liver monoamine oxidase at medium inhibitory concentrations (I₅₀) of 4.7 x 10^-5, 1.2 10^-4 > 1.0 x10^-3 and 1.4 x 10^-3 M, respectively. Compounds relatively nontoxic to mites were usually ineffective monoamine oxidase inhibitors [53Knowles CO, Aziz SA. Toxicity of benzoyl chloride (2,4,6-trichlorophenyl)hydrazone (Banamite) and potential metabolites to twospotted spider mites and potency as inhibitors of rat liver monoamine oxidase Bull Environ Contam Toxicol 1974 12 158-160 Chem Abstr 1975; 82: 12245q.].

IB, Ph-C(Cl)=NNHC₆H₂Cl₃-2,4,6

In another report [54Moon M W, Gemrich II E, Kaugers G G. Acaricidal activity of thioketal adducts of pyruvoyl chloride phenylhydrazone and related compounds J Agric Food Chem 1972 20 888-891 Chem Abstr 1972; 77: 9772n.], it was indicated that the acaricidal activity of the dithioketal of N-(2,4-dichlorophenyl) 2-oxopropanehydrazonoyl chlorides IVA against the 2-spotted spider mite (Tetranychus urticae) on lima bean plants depended on R group, and was in the descending order R: Me, Et, Ph, H and C₅H₁₁, that is the most active compound thus being the chloride IVAa. The thioketal IVAa was reported to be much more active than the corresponding ketal IVBa. Of the series IV, the most active halides were those having 3-F3C, 4-Brsubstituents in the N-aryl group.

Emmel et al. [55Emmel L, Henbach G. Acaricidal phenylhydrazones of dicarbonyl compounds Ger Ofen 217,761, Nov 04 1971 Chem Abstr 1972; 76: 33935f., 56Emmel L, Henbach G. Acaricidal phenylhydrazones of dicarbonyl compounds Ger Ofen 217,762 Apr 14 1971 Chem Abstr 1972; 76: 45971c.] prepared nineteen derivatives of ethyl N-arylhydrazonochloroacetates VIIIA and their methyl analogs VIIIB and used against red spiders on beans and apple trees. Also, N-(2,4-dibromophenyl) benzenehydrazonoyl bromide I was reported to be effective gave 100% control of houseflies in 48 h [57Noguchi T, Asada M, Ando M, Matsuda K, and Uchiyama Y. Insecticide-acaricide composition of the hydrazine series Japan at 702,326 Jan 24 1973 Chem Abstr 1974; 80: 11233f.].

VIII ROCOC(Cl):NNHC₆H₄X

I PhC(Br)=NNHC₆H₃Br₂-2,4

R: A, Et; B, Me

X: H, 3-F₃CO, 3-FCH₂-CF₂-O, 3-Cl₂CH-CF₂-O, 2-Me-4-Cl₂CH-CF₂-O

N-Phenyl and N-(2,4,6-trichlorophenyl) derivatives of 2-furyl-, 2-thienyl, 2- or 3-pyridyl- and 2-chloro-4-pyridyl- carbohydrazonoyl chlorides IV were also proved to have acaricidal activity [58Kaugars G. Pesticidal heterocyclic phenylhydrazone derivatives Ger Ofen 2 1972; 77: 5337q.].

IV Het-C(Cl)=NNHAr

Het: A, 2-furyl; B, 5-Br-2-furyl; C, 2-thienyl; G, 3-pyridyl;

H, 2-pyridyl; I, 2-Cl-4-pyridyl;

Ar: Ph, 2,4,6-Cl₃C₆H₂

Also, eighteen N-aryl 2-oxopropanehydrazonoyl chlorides VI were prepared and found useful acaricides [36Draber W, Buechel KH, Hammann I, Frohberger PE. Pyruvamide 1-(phenylhydrazones) Ger Ofen 233,997 Oct 05 1972 Chem Abstr 1973; 78: 15844n.].

VI, CH₃COC(Cl)=NNHC₆H₃RR'

R = H, 2-Cl, 2-Me, 2-Et R' = H, Me, Et

N-(4-Fluorophenyl) 2-chlorobenzenecarbohydrazonoyl chloride IC was prepared and reported to control totally Plutella maculipennis larvae on cabbage leaves when 0.01% concentration of it was used [42Andree R, Luerssen K, Santel H J, et al. Preparation of benzhydrazidoyl halides as acaricides, insecticides and herbicides Ger OffenDE 400,591, Jul 15 1993; Chem Abstr 1993; 119: 133475f.].

IC, 4-F-R_nC₆H_4-nC(Cl)=NNHC₆H₅

R = alkyl, alkoxy, alkenyl, halo, CN, O₂N; n = 0, 1-4

Also, thirty four alkanehydrazonoyl chlorides III, IV, IB and V were found useful as acaricides and insecticides [27Kaugars G. Halogen substituted pyridinealdehyde phenylhydrazones US Patnt 399,111, Oct 17 1972 Chem Abstr 1976; 84: 116001q., 28Kaugars G. Thiophenecarbonyl chloride phenylhydrazones US Patnt 309,703 May 07 1974 Chem Abstr 1976; 84: 116001q., 59Boesch R. Alkanoyl chlororide phenylhydrazones Ger Ofen 226,872 Dec 06 1973 Chem Abstr 1974; 80: 59659b.-64Draber W. a-Chloro- a -formylcarbonyl phenylhydrazones Ger Ofen 245,881 Mar 23 1972 Chem Abstr 1972; 77: 5147c.].

III, R-C(Cl)=NNHAr

R = CEmmel_1-7 alkyl; Ar = 2-Cl-4-R”-5-R’C₆H₂: R’ = C_1-4 alkoxy, CH₂=CHCH₂O, HC=CCH₂O, or Cl, R” = Cl, Me or HC=CCH₂O

IV, Het-C(Cl)=NNHAr;

Het: A, 2-furyl, B, 5-Bromo-2-furyl; C, 2-thienyl, D, picolinyl, E, nicotinyl; I, 2-Cl-4-pyridyl;

Ar: Ph, 2,4,6-Cl₃C₆H₂

IB, PhC(Cl)=NNHC₆H₂Cl₃-2,4,6

V, OCH-C(Cl)=NNHC₆H₃Cl₂-3,4

N-Aryl 2-oxoethanehydrazonoyl chlorides V and their ketal and thioketal derivatives IV were reported to have strong pesticidal effects [65Draber W, Buechel K H, Hammann I, Unterstenhoefer G. Pesticidal glyoxyloyl chloride 1[(substituted phenyl)hydrazones] S Africa 9 0368, Jan 06 1970 Chem Abstr 1970; 73: 45130r.].

Kaugars et al. [46Kaugars G, Germich E G. Benzoyl chloride phenylhydrazones as pesticides Ger Ofen 126 366 Jan 15 1970 Chem Abstr 1970; 72: 100323n., 66Kaugars G, Germich E G. Benzoyl chloride phenylhydrazones as pesticides Ger Ofen 126,366, Jan 15 1970 Chem Abstr 1970; 72: 100323n.]reported that various substituted N-phenyl benzenecarbohydrazonoyl chlorides I have pesticidal properties.

I, Ar-C(Cl)=NNHAr'

N-Phenyl 3-trifluoromethylbenzenecarbohydrazonoyl chloride IAa was found by Kaugars et al. to be useful pesticide for controlling arthropods [31Kaugars G. a a a -Trifluoro-m-toluoyl chloride phenylhydrazone Ger Ofen 234,574 Jul 13 1972 Chem Abstr 1972; 76: 72258g.]. In addition, it was reported that N-phenyl 4-methylthiobenzenecarbohydrazonoyl chloride IAb and N-(4-methylthiophenyl) benzenecarbohydrazonoyl chloride IBa are useful for control of arthropodal pests such as insects, spiders, ticks and mites [63Hamed MS, Knowles CO. Penetration of pesticides into the bulb mite Rhizoglyphus echinopus Exp Appl Acarol19897 201-218 Chem Abstr 1989; 111: 169352n.].

IAa, 3-CF₃C₆H₄-C(Cl)=NNHPh

IAb, 4-MeSC₆H₄-C(Cl)=NNHPh

IBa, Ph-C(Cl)=NNHC₆H₄SMe-4

Eighteen N-aryl 2-oxopropanehydrazonoyl chlorides VI were prepared and reported to be useful insecticides [36Draber W, Buechel KH, Hammann I, Frohberger PE. Pyruvamide 1-(phenylhydrazones) Ger Ofen 233,997 Oct 05 1972 Chem Abstr 1973; 78: 15844n.].

VI, MeCO-C(Cl)=NNHC₆H₃RR'

R: H, 2-Cl, 2-Me, 3-F₃C

R': H, Me, Et

N-Phenyl and N-(2,4,6-trichlorophenyl) derivatives of 2-furan-, 2-thiophene-, 2-pyridine-, 3-pyridine- and 2-chloro-4-pyridine- carbohydrazonoyl chorides IV were found useful as insecticides because of their insect metamorphosis-inhibiting activity [27Kaugars G. Halogen substituted pyridinealdehyde phenylhydrazones US Patnt 399,111, Oct 17 1972 Chem Abstr 1976; 84: 116001q., 58Kaugars G. Pesticidal heterocyclic phenylhydrazone derivatives Ger Ofen 2 1972; 77: 5337q., 59Boesch R. Alkanoyl chlororide phenylhydrazones Ger Ofen 226,872 Dec 06 1973 Chem Abstr 1974; 80: 59659b.]. Tests on cabbage looper and three other insects were given.

IV Het-C(Cl)=NNHAr

Het: A, 2-furyl; C, 2-thienyl; G, 3-pyridyl; I, 2-Cl-4-pyridyl

Ar: Ph, 2,4,6-Cl₃C₆H₂

N-Phenyl 2-substituted-propanehydrazonoyl chlorides of type IIIA and IIIB were also reported to be useful as insecticides because of their insect metamorphosis-inhibiting activity [41Kaugars G. Weed control with substituted phenylhydrazones U S Patnt 3 70,505, Mar 11 1975 Chem Abstr 1975; 83: 78891z., 67Moore JE. Insecticidal phenylhydrazone sulfides US Patent932,660 Jan 13 1976 Chem Abstr 1976; 84: 135317p.].

IIIA, Me-CH(SR)-C(Cl)=NNHPh

R = Me, Et, i-Pr, t-Bu, 4-ClC₆H₄

IIIB, R'C(Cl)=NNHAr

R': Et, Pr, Bu, i-Pr, t-Bu

Ar = XC₆H₄; X: H, 2-Me, 4-O₂N, 4-Cl, 2,4-Cl₂, 2,4,6-Cl₃

In addition, substituted N-phenyl benzenecarbohydrazonoyl halides I and N-aryl (C_2-4)-alkanehydrazonoyl chlorides III were reported to be useful as insecticides and miticides [25Kaugars G, Germich EG. Benzoyl chloride phenylhydrazones against insects and mites US Patnt 417,540 Apr 12 1977 Chem Abstr 1977; 87: 22800., 39Kaugars G. Combating insects and mites using alkanoyl chloride phenylhydrazones U S Patnt 345,215, Jul 10 1973 Chem Abstr 1973; 79: 78412m., 46Kaugars G, Germich E G. Benzoyl chloride phenylhydrazones as pesticides Ger Ofen 126 366 Jan 15 1970 Chem Abstr 1970; 72: 100323n., 49Kaugars G, Germich E G. Insecticidal and miticidal benzoyl chloride phenylhydrazones Ger Ofen 109,868 Oct 16 1969 Chem Abstr 1970; 72: 54978e., 66Kaugars G, Germich E G. Benzoyl chloride phenylhydrazones as pesticides Ger Ofen 126,366, Jan 15 1970 Chem Abstr 1970; 72: 100323n.]. For example N-(2,4-dibromophenyl) benzenecarbohydrazonoyl bromide 1 gave 100% control of houseflies in 48 h.

I, XC₆H₄-C(Cl)=NNHC₆H₄Y

X: H, 3-, 4-Me, 4-F, 2-, 3-, 4-Cl, 4-Br, 4-I, 2-Me, 4-i-Pr, 2,4-Cl₂, 3,4-Cl₂, 2,6-Cl₂, 2,4-Cl(NO₂), 3,4-Me(NO₂), 3,4-Me₂, 2,5-Me₂, 3,5-Me₂, F₅

Y: 2,4-Br₂, 2,5-Cl₂. 2-Me, 4-Cl, 4-O2N,

III, R-C(Cl)=NNHAr

R = C_nH_n-1, n = 2,3,4

Furthermore, ketal, thioketal and dithioketal derivatives of N-aryl 2-oxopropanehydrazonoyl chlorides IVJ-L were reported to be useful insecticides for European red mites and double-spotted spider mites [65Draber W, Buechel K H, Hammann I, Unterstenhoefer G. Pesticidal glyoxyloyl chloride 1[(substituted phenyl)hydrazones] S Africa 9 0368, Jan 06 1970 Chem Abstr 1970; 73: 45130r., 68Moon MW. Insecticidal glyoxyloyl halide phenylhydrazones Ger Ofen 256,058 Jun 22 1972 Chem Abstr 1972; 77: 126648a.].

N-Phenyl and N-(4-methylthiophenyl) derivatives of benzenecarbohydrazonoyl chloride and its 2- and 4-methylthio analogs I were also reported to be useful as insecticides and acaricides [15Kaugars G. Insecticidal acaricidal and anthelmintic benzoyl chloride phenylhydrazone derivatives Fr Demande, 2,103,533, May19, 1972; Chem Abstr 1973; 78: 29473c., 24Kaugars G. Alkylthiobenzoic acid phenylhydrazides U S Patnt 414,932 Mar 29 1977 Chem Abstr 1977; 87: 5665b., 42Andree R, Luerssen K, Santel H J, et al. Preparation of benzhydrazidoyl halides as acaricides, insecticides and herbicides Ger OffenDE 400,591, Jul 15 1993; Chem Abstr 1993; 119: 133475f., 52Kaugars G. Methylthio derivatives of benzoyl chloride phenylhydrazone Ger Ofen,134,482, Jan 27 1972; Chem Abstr 1972; 76: 112931e.].

I, Ar-C(Cl)=NNHAr'

Ar = Ph, 2-MeSC₆H₄, 4-MeSC₆H₄

Ar' = Ph, 4-MeSC₆H₄

Kaugars prepared a series of N-aryl C-heteroaryl-methanehydrazonoyl chlorides IV and found that such halides are useful as insecticides [28Kaugars G. Thiophenecarbonyl chloride phenylhydrazones US Patnt 309,703 May 07 1974 Chem Abstr 1976; 84: 116001q., 60Kaugars G. Chloro substituted furfural phenylhydrazone US Patnt 321,261 Jun 28 1974 Chem Abstr 1976; 84: 116001q.].

IV, Het-C(Cl)=NNHC₆H_5-nCl_n

Het: A, 2-furyl, C, 2-thienyl, D, 2-pyridyl, G, 3-pyridyl, I, 4-pyridyl n = 1, 2, 3

Also, N-(2,4-dibromophenyl) benzenecarbohydrazonoyl bromide Ie was reported to be effective as insecticide as it gave 100% control of house flies in 48 hr [57Noguchi T, Asada M, Ando M, Matsuda K, and Uchiyama Y. Insecticide-acaricide composition of the hydrazine series Japan at 702,326 Jan 24 1973 Chem Abstr 1974; 80: 11233f.].

I, Ph-C(Br)=NNHC₆H₃Br₂-2,4

In another report, it was indicated that the ketal derivatives of N-aryl 2-oxoethanehydrazonoyl chloride IV are effective insecticide [69Draber W, Buechel KH, Hammann I, Unterstenhofer G. Pesticidal a-halo-a-formyl carbonyl phenylhydrazones US Patent 366112Jan 18 1972 Chem Abstr 1972; 76: 140166c.].

Also, N-(4-chlorophenyl) 2,2-dimethylpropanehydrazonoyl chloride III was found useful as insecticide against housefly, cotton weevil and Mexaican beanbeetle [41Kaugars G. Weed control with substituted phenylhydrazones U S Patnt 3 70,505, Mar 11 1975 Chem Abstr 1975; 83: 78891z.].

III (CH₃)₃C-C(Cl)=NNHC₆H₄Cl-4

Also, several N-(2,4,6-trichlorophenyl) 2-alkylthioalkane-hydrazonoyl chlorides III were found to be useful as insecticides having morphogenic hormonal mimetic activity [70Moore JE. Insecticidal bisphenylhydrazone sulfides US Patnt 367,450 Feb 18 1975 Chem Abstr Chem Abstr 1975; 82: 139754k.-72Moore JE. Insecticidal bisphenylhydrazone sulfides S Patt 3n56,505 May 11 1976 Chem Abstr 1976; 85: 46220e.]. The bis-hydrazonoyl chlorides X1 were reported to have insecticidal activity against cabbage looper and alfafa weevil larvae [39Kaugars G. Combating insects and mites using alkanoyl chloride phenylhydrazones U S Patnt 345,215, Jul 10 1973 Chem Abstr 1973; 79: 78412m.].

The bis-hydrazonoyl chloride XII was reported to be useful insecticide for fertilizers [73Waheed A. Dow Chemical Co..4-\dichloro-N-[chloro-(2.4dichlorophenyl) methylene]benzenecarbohydrazonoyl chloride Jpn Kokai Tokkyo Koho 8098148 July 25 1980 Chem Abstr 1981; 94: 30332t.].

Kaugars [41Kaugars G. Weed control with substituted phenylhydrazones U S Patnt 3 70,505, Mar 11 1975 Chem Abstr 1975; 83: 78891z.] indicated that tweleve N-aryl (C_3-5)alkane hydrazonoyl chlorides III are useful as miticides, insecticides against housefly, cotton ball weevi, mexican bean beetle and as herbicides against crabgrass, wild oats and yellow foxtail.

III, R-C(Cl)=NNHAr; R = C_nH_n-1, n = 3,4, 5

In addition, Moon [74Moon MW. Controlling weeds with 1'-formyl-1'-halobenzenea- zomethanes U S Patnt 330,642, Aug 20 1974 Chem Abstr 1975; 82: 39582j.] prepared a series of 1'-formyl-4'-halobenzeneazamethanes VI and indicated that they are useful as weed controlling agents.

VI, RCOCR'(X)-N=N-Ar;

R = Lower alkyl, cycloalkyl, cycloalkoxy, haloalkyl, haloalkoxy

R' = Lower alkyl, cycloalkyl, Ph

X = Br, Cl

The hydrazonoyl chlorides VII, IX and XIII showed also activity against wheat stem rust, phytophora infection of tomatoes and cucumber powdery mildew [34Buzykin BI, Sysova LP, Molodykh ZhV, Kudrina MA, Neklesova ID, Kitaev Yu P. Acetyl chloride 4-bromophenyl- hydrazone possessing fungicidal and bactericidal properties USS 68610 Mar 07 1981 Chem Abstr 1981; 95: 42395z.].

VII, PhCO-C(Cl)=NNHAr IX, H₂NCO-C(Cl)=NNHAr

XIII, NC -C(Cl)=NNHAr

In addition, the hydrazonoyl bromides VI were tested as plant growth regulators. They depressed the growth of roots, stalks and leaves of lettuce and oats [37Kukota SN, Borisenko VP, Bodnar VN, Zhuravskaya NI, Lozinskii MO. Synthsis and phytotoxicity of arylhydrazones of substituted pyruvic and a,ß-dioxobutyric acids Fiziol Akt Veshchestva 1978 10 32-36 Chem Abstr 1979; 90: 6212a.].

VI BrCH₂COC(Br)=NNHC₆H₄X

X = 4-Me, 4-Cl, 4-NO₂

N-(2,4,6-Trichlorophenyl) benzenecarbohydrazonoyl chloride (banamite) IB was reported to be more toxic (LC₅₀ 12 ppm) to the twospotted spider mite (Tetranychus urticae) and it inhibits rat liver manoamine oxidase at median inhibitory concentrations [53Knowles CO, Aziz SA. Toxicity of benzoyl chloride (2,4,6-trichlorophenyl)hydrazone (Banamite) and potential metabolites to twospotted spider mites and potency as inhibitors of rat liver monoamine oxidase Bull Environ Contam Toxicol 1974 12 158-160 Chem Abstr 1975; 82: 12245q.]. Compounds relatively nontoxic to the mites were usually ineffective monoamine oxidase inhibtors

IB PhC(Cl)=NNHC₆H₂Cl₃-2,4,6