CA1072967A - Thiophenes useful in the control of certain arthropods - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Substituted thiophenes of the following formula, some of which are new compounds, are useful in controlling certain arthropods, particularly mites and insects:

where X is alkyl, halogen, nitro, haloalkyl, alkoxy, alkylthio or aryl;
a is 0, 1 or 2;
Y is hydrogen, halogen, nitro, aryl, arylthio or arylsulfono;
and Z is hydrogen, or aryl.
E.g., 2,3,5-triphenylthiophene is highly effective in controlling mites.

Description

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This lnvention relates to a method o~ controlling certain arthropods, using certain substituted thiophenes, as well as compositions and new chemical compounds use-; ful in such method.
Arthropods which are controlled by the method of the invention include acarids, particularly plant-feeding mltes and mites and tickswhich a~flict man and Qnlmals, as well as in~ect pests.
- Plant-feeding mites produce enormous losses to agrlcultural corps in a world plagued by constant shortages food. Crops such as alfalfa, apples, corn, cotton, grapes, oranges, potatoes, sorghum, peanuts and many others may be completely devastated by these tiny pests.
In addition, ~arlous spocies have become so special-lized in structure and h~blt that they must subslst on the bodles of man and animals. Feu domestlcated or wild animals are immune to their attack. Mites are expert at tormenting thelr host. There 18 probably no creature in exl~tence uhich can cause more torment for its size than a "chigger" can by burrowing beneath the skin of man.
Other species such as ltch and mange mites cause seriou~ skin diseases in animals such as dogs, cats, - rabbits, horses, cattle and plgs.
Ticks and some species of mites suck the blood of man and animals. Besides the lrritation involved, a multitude of anlmal dlseases may be transmitted by this method o~ food procurement. Dread dlseases such as Rocky ~; Mountain spotted fe~er~ relapsln~ fever and tularemia are trans~ltted by the bites oP ticks.
During the last thirty years, numerous chemlcals ,~ .

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have been utllized in protecting both msn and mQn's food ~nd flber against in~ury from mites and tlck~, as well as insects. There is a continuing need ior novel, effective and sare chemicals to accompllsh thl~ task.
In accordance with the lnvention it has now been found that certain substituted thiophenes are useful in the control of arthropods. me substituted thiophenes employed in the control of arthropods in the method of the lnvention are those of the formula ., z X~ Y

where X is alkyl, halogen, nitro, haloalkyl, alkoxy, alkylthio or aryl;
a i8 O, 1 or 2;

Y is hydrogen, halogen, nltro, aryl, arylthio or aryl~ulfono;

and Z i8 hydrogen, or aryl.

-~ Certaln co~pounds wlthin the foregoing formNla are belleved to be new chemicals, namely 2-(~-methyl-thl:ophengl) thiophene, 2-(o-biphenylyl)thiophene, 2-(3,4-xylyl)thiophene, and the compounds in which Y is nitro, arylthio or arylsulfono Compounds UBefUl in the inven~ion may be prepared by varlous methods. Thus, 2-sub~tltuted thiophenes may be .. :

- ~ lt~Z967 :

prepared by an anhydrous verslon (C. M. Camaggi, R.
Leardlnl, M. Tiecco and A. Tundo, J. Chem. Soc., B 1683 [1970]) of the Gomberg-Bachmann free radical arylation reactlon (M. Gomberg and W. E. Bachmann, J. A. Chem.
Soc., 46, 2339 rl924])- n-Butyl nitrite may be used as the diazotizing reagent and a 20 to 25-fold exce6s of thiophene may ~erve both as solvent as diluent to reduce the extent of disubstltution. Free radical arylation o~
thiophenes proceeds about 95% ln the alpha-position. The i 10 distilled or recrystalllzed arylthiophenes are generally ~ -greater than 98% pure. Reaction times are 3-7 days at room temperature and ylelds are mainly ln the upper half of the 20-50% range.
Similarly, phenylthio-sub~tltuted arylthlophenes may be prepared by a Frledel-Crafts substltution uslng benzensulfenyl chloride as the electrophlllc reagent (T. FuJisawa, T. Kobori, N. Ohtsuka and G. Tsuchihashi, Tetr. Letters, No. 49, 5071 [1968]).
A preferred sub-class of chemicals employed in the method of the invention, especially as miticldes, are those o~ the above formula ln which X is alkyl having 1 to 3 carbon atoms, halogen (e.g. chlorine, bromine, fluorine), nitro, haloalkyl having 1 to 3 carbon atoms, alkoxy having 1 to 3 carbon atoms, alkylthio having 1 to 3 carbon atoms, or phenyl; a is O, 1 or 2; Y i~ hydrogen, halogen, nitro, phenyl, phenylthio or phenylsulfono; and Z i8 hydrogen or phenyl. New chemical~ within the foregoing ~ub-class are

2-(p-methylthiophenyl)thiophene, 2-(o-biphenylyl)thiophene, 2-(3~4-xylyl)thiophene, and compounds in whlch Y is nitro, phenylthio or phenylsulfono.

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_~_ AB representative chemicals u~eful in the inven-tion there may be mentioned by way of non-limiting example ~uch compounds as:
2-(3-nitrophenyl)-5-phenylthiophene 2-(4-nitrophenyl)-5-phenylthiophene 2-(3-chlorophenylthio)-5-phenylthiophene 2-(4-chlorophenylthio)-5-phenylthiophene 2-(4-anisyl)-5-phenylthlophene 2-(4-nitrophenylthlo)-5-phenylthiophene 2-(1-naphthyl)-5-phenylthiophene 2-(2-naphthyl)-5-phenylthlophene 2-(1-anthryl)-5-phenylthiophene 2-(9-phenanthryl)-5-phenylthiophene 2-(3-nltrophenyl)-5-(~tolyl)thicphene 2-(p-bromophenyl)-3,5-diphenylthlophene 2-(m-nltrophenyl)-5-(phenylthlo)thiophene 2-(~-ethoxyphenyl)-5-(3-chlorophenylthio)thiophene 2-(4-anisyl)-5-(~-butylphenylthio)thiophene

3,5-diphenyl-2-(o-propylphenyl)thiophene 2-(1-naphthyl)-5-(m-nitrophenyl-)thiophene . 5-(~-chlorophenyl)-2-(2-naphthyl)-3-phenylthiophene 2~ anthryl)-5-(~-trichloromethylphenyl)thiophene 2-(4-chlorophenylthio)-5~-tolyl)thiophene 2-(p-biphenylyl)-5-(p-tolyl)thiophene 2-(3-nitrophenyl)-5-phenylthio-thiophene 2-(4-nitrophenyl)-5-phenylthiothlophene 2-(3-methylthiophenyl)-5-phenylthiothiophene 2-(4-methylthiophenyl)-5-phenylthiophene 2-(2-anisyl)-5-phenylthiothiophene 2-(3-chlorophenyl)-5-phenylthiothlophene ,:

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2~ naphthyl)-5-phenylthiothlophene - 2-(2-naphthyl)-5-phenylthlothiophene 2-(1-anthryl)-5-phenylthiothiophene 2-(9-phenanthryl)-5-phenylthiothiophene 5 2-(3-nitrophenyl)-5-(~-tolythio)thiophene .2-(4-nitr~phenyl)-5-(p-chlorophenylthio)thlophene 2-(3-nltrophenylthio)-3,5-diphenylthlophene 3~5-diphenyl-2(~-tolylthio)thlophone 2-(4-anlsyl)-3,5-diphenylthioph~ne 2-(2-naphthyl)-4-phenyl-5-phenylthiothlophene 2-(4-ani~yl)-5-phenylsul~onylthlophone 2-phenylQulronyl-5-(3,4-xylyl)thiophene 2-(4-chlorophenyl)-5-phenylsulfonylthiophene 2-(~-methoxyphenylsul~onyl)-5-phenylthiophene 2-(~-chlorophenyl~ulfonyl3-3,5-diphenylthiopheno 2-phenyl-5-(p-tolylsulfonyl)thiophene 1 2-(l-naphthyl)-4-phenylthiopheno ¦ 2-(2-naphthyl)-4-phenylthiophene 2-(1-anthryl)-4-phenlthiophene 2-(9-phenanthryl)-4-phenylthiophene 2-chloro-3-(4-nitrophenyl)-5-(p-tolyl)thiophene 2-(4-nitrophenylthio)-3,5-diphenylthiophene 2~bromo-3,5-bi~(p-propyloxyphenyl)thlophene : 2-(p-tert-butylphenylthio)-5-(~-chlorophenyl)thiophene ~: 25 2-(4-nitrophenylthio)-5-(3,5-xylyl)thlophene ~ 2-(4-chlorophenylthlo)-5-(3,4-methylenedioxylphenyl) :~ thiophene ,, .
:ij 4~ naphthyl)-2-(~-trifluoromethylphenyl)thiophene 2-(o-ethylthiophenyl)-5-(4-nitrophenylthlo)thiophene 2-(p-biphenylyl)-5-(4-chloropphenylthio)thiophene ; 2-(2-nitrophenylthio)-3,5-diphenylthiophene 2-(~-trifluoromethylphenyl)-3,5-diphenylthiophene , ~ - -., ; ~ ' . .

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2~ chlorophenylthio)-3,5-diphenylthiophene 2-(m-chlorophenylthio)-3,5-diphenylthiophene 2-(p~methoxyphenylthio)-3,5-diphenylthiophene 2-(m-trifluoromethylphenyl)-3,5-dlphenylthiophene 2,4-diphenyl-5-(1-naphthyl)thiophene 2~4-dipheny1-5-(2-naphthyl)thiophene 5-(1-anthryl)-2,4-diphenylthlophene 2,4-diphenyl-5-(3-phenanthryl)thiophene 3,5-bis(~-chlor~phenyl)-2-phenylthiothiophene 2-phenylthio-3,5-bis-(~-tolyl)thlophene 3,5-bis(~-bromophenyl)-2-phanylthiothiophene 3,5-dl ~-anl~yl-2-phenylthlothlophene 3,5-di p-anisyl-2-(~-chlorophen~lthlo)thiophene 2-(~-chlorophenylthio)~,5-dlphenylthiophene 2-(m-chlorophenylthlo)-3,5-dlphenylthiophene The inventlon i8 Fræticed by applylng to a locus, sub-~ect to attach by certain arthropods, viz., acardis or in-sects, an effective amount, viz., an acarlcidal or insectlcidal amount~ of a chemical of the kind de~cribed. Frequently the locus is either palnt li~e, for example such crops as al~alfa, apples, corn, cotton, grapes, oranges, portatoes, sorghum, peanuts, etc., or animal llie, including m~n. The chemicals may be applied alone or with a carrier, which may enhance the e~fectiveness of the active agent or facili-tate handling, to loci to be protected against m~es or the like, for example as du~ts when admlxed with or ab-sorbed on powdered solid carriers, such as the ~arious m~neral silicates, e.g., mica, talc, pyrophillite and clays, or as liquids or ~prays when in a liquid carrier, as in solution in a 6uitable solvent, such as acetone, benzene or kerosene, or dlsper3ed ln a ~ultable non~olvent medlum, rOr example, water. In protectlng plant~ (the term lncludlng plant parts) whlch are subJect to attack by these pests, the chemical~ o~ the pre~ent lnvention are prererably applled as aqueou~ emulslons contalnlng a ~urrace-actlve dl3persing agent, whlch msy be an anlonic, nonlonic or cationlc sur~ace-actlve agent.
Such surface-~ctive agents are well known and refer-ence is made to Canad~an Patent No. 512,908 for detailed examples of the same. The chemicals of the lnvention may be mixed with such surrace-active dlsperalng agents, with or without an organlc solvent, as acarlcldal concentrates for subsequent addltion Or ~ater to make aqueous suspenslons Or the chemicals Or the desired concentratlon. The chemlcals o~ the ln-ventlon may be admlxed with powdered solld carrlers, such as mineral sllicates, together wlth a surrace-actlve dlsperslng agent 80 that a wettable powder may be obtalned, whlch may be applled dlrectly to locl to be protected agalnst mltes or the llke, or whlch may be shaken up wlth water to rorm a ~uspenslon o~ the chem-m~cal (and powdered solld carrlér) ln water for appll-oatlon ln that ~orm. m e chemlcal~ o~ the pre~ent lnven-tion may be applled to locl to be protected agalnst mltes or ln~ect~ by the aero~ol m~thod. Solution~ ~or the serosol treatment may be prepared by dls~olvlng the ~hemical dlrectly ~n the aerosol carrler which i~ llquid under presQure but whlch 1~ a ga~ at ordinary temperature (e.g., 20 C.) and atmospherlc pres3ure, or the aerosol solution may be prepared by ~irst dis301ving the chemlcal .

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in a less Yolatile solvent and then admixlng such solu-tlon wlth the highly volatile liquid aerosol carrier.
The chemicAls may be used admlxed with carriers that are active of themselves, for example, other lnsect~cides, acaricides, fungicides, or bactericides.
Practical formulations ordlnarily contain from 1 to 95% active ingredient. Spray dilution~ mag range ~rom a ~ew parts per million to undiluted concentrate applied by ultra low volume techniques. The concentra-tion of chemical per acre would vary depending upon many factors, but normally range from 0.1 to lO pounds.
In one aspect, the in~ention ls directed to new ; compositlons useful in the control of certain arthropods, comprising the described substituted thiophene chemical, ; 15 in acarlcidally or insectlcidally e~fective amount, in combinatlon wlth a carrier therefor.
` The following examples will serve to illustrate I the practice of the invention in more detall.
, Example 1 2-(p-Methylthiophenyl)thiophene In a 4-l. Erlenmeyer flask were placed 69.5 g.
(0.400 mole) 4-(methylthio)anillne hydrochlorlde, 500 ml.
of thiophene and 40.5 g of triethylamlne. The mixture was stirred 10 minutes at room ~e~perature~ Thiophene I (2000 ml., total 31.8 moles) and 65 ml. (0.58 mole) of 1 25 n-butyl nitrite were added. The mlxture wa~ then ætirred at room temperature (23C.) ~or 14 days.
The reaction mix*ure was divided into two equal portions, each of which was wa~hed with three 500-ml. -p~rtions of water. The organic residues were then con-centr~ted by evaporation of unreacted thiophene. The concentrated residue was then di~tllled at reduced `~ :
. .
. . . - . : . .

` 1(~7~367 ~g_ pressure to glve 19 g. (23~) of 2-(p-methylthlophenyl)-thlophene, b.p. 135-146 (0.1 mm), a yellow solld melt-lng at 108-110.
Anal. Calc'd for CllHloS2: C, 64-o4; H, 4-89-Found: C, 64.44; H, 4.82 Example 2 2-(o-Blphe~ylyl)thlophene In a 4-1. Erlenmeyer ~lask were placed 100 g.
(0.600 mole) o~ P~alz and Bauer o-aminoblphenyl, m.p.
49-51, 3000 ml. (38.2 moles) of thiophene and 90 ml.
i 10 (0.80 mole) of n-butyl nltrlte. The mlxture was thoroùghly stlrred and then allowed to stand at room temperature ~or elght days. Unreacted thiophene was removed by distlllatlon. Tho resldue was di~tllled at reduced pre~ure to glve 49.4 g. (34.8~) of 2-(o-blphenylyl)-thlophene b.p. 138-155 (0.1 mm.), ND 1.6465.

Example 3 2-Phenyl-5-(phenylthlo)thio~hene In a 500 ml. rlask were placed 36.9 g. (0.23 mole) Or 2-phenylthlophene, 200 ml. Or reagent carbon tetra-chlorlde, 36.9 g. (0.26 mole) of benzenesulrenyl chlorlde ! 20 and 0.2 6. 0~ iron powder. The reaction mixture was allowed to stand rour days at room temperature. Dlstil-latlon Or the carbon tetrachlorlde gave a crystalllne re~idue which was recrystalllzed ~irst ~rom ethanol-ethyl acetate (9:1) and then ~rom ethyl acetate-pentane (1:9) to glve 10.6 g. (17%) o~ 2-phenyl-5-(phenylthlo)thiophene, , m.p. 72.5-74.5.
Anal. Calc'd for C16H12S~: C, 71.60; H, 4.51; S, 23.90.
Found: C, 70.98; H, 4.47; S, 23.61 The ln~rared spectrum showed the pre~ence Or both the phenyl and the phenylthio group by the ab~orption maxima at 761 cm and 744 ¢m 1.

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Example 4 2~Phenyl-5-(phenylsulfonyl)thiophene A solution of 2.68 g. (10 mmoles) of 2-phenyl 5-(phenylthlo)thiophene in 30 ml. of acetic acld was treated with 4 ml. (40 mmoles) of 30% hydrogen peroxide and allowed to stand 16 hours. Filtration separated a first crop of 1.70 g. Chilllng the filtrate to 4 and refiltration gave a ~econd crop of 0.33 g., m.p. 115-116.5. The total yield of 2.03 g. i3 68% of the theoretlcal for 2-phenyl-5-(phenyl~ulfonyl)thiophene.
Anal- Calc'd for C16H122S2 C~ 63-97; H~ 4-03 S, 21.36.
Found: C, 64.02; H, 3.93; S, 20.52.
The presence of a sulfone group, rather than two sulfoxide groups, in the product is demonstrated by the two strong infrared absorptlon maxima at 1320 cm (S-0 symmetrlcal vibration) and 1150 am (S-0 asymmetrical vibratlon) characterl~tic of the sulfone group. The fact that oxidation occurred at the phenylthio sulfur, ln pre-ference to the thiophene ring sulfur, is ~hown by the proton magnetic resonance spectrum. This spectrum show3 two ortho proton~ of a phenylsulfonyl group at 7.97-8.17 ~ and ten other protons farther upfield (7.19-7.67 ~ ).

Example 5 2-Phenylthio-5-p-tolylthiophene Into 500 ml. of reagent carbon tetrachloride ; were added 61 g. (0.35 mole) of 2-p-tolyl~hiophene, 41 ml. (51 g., 0.35 mole) of benzenesulfenyl chloride and 0.05 g. of powdered lron. The reactlon mixture was allowed to ~tand four days at room temperature after which the carbon tetrachloride wa~ diskilled off and the ~ 96'~

45-gram residue washed with a mixture Or 80 ml, ot` et;ller and 250 ml. of petroleum ether, Recrystallization Or the washed solld from 300 ml. of ethanol gave 28 g. (29(~) of 2-phenylthio-5-~-tolylthiophene, m.p. 85-86, Anal. Calc'd for Clj~l4S2: C, 72.30; H, 5,00, S, 22,71 Found: C, 72,53; H, 4,97; S, 22,02, The structure is confirmed by the proton magnetic resonance spectrum which shows a ratio of 3 aliphatic protons (as methyl groups, 2,34 ~) to 11 aromatic protons (7,11-7.49 S).
Exam~le 6 2-(p-Isopropylphenyl)-5-(phenylthio)thiophene Into 150 ml, of reagent carbon tetrachloride were added 29 g. (0,143 mole) 2-(~-isopropylphenyl)thiophene, 17 ml. (21 g " 0.145 mole) of benzenesulfenyl chloride and 0.05 g, of iron powder. At the end of four days a vapor phase chromatogram of the reaction mixture showed the presence of diphenyl disulfide, unreacted 2-(~-iso-propylphenyl)thiophene and the desired product. An additicnal 4 ml. (5 g., 0.035 mole) of benzenesulfenyl chloride and 0.05 g. of lron powder was added and the mixture allowed to stand another four days at room temperature. Evaporation of the carbon tetrachloride gave a residue which was twice recrystallized from 250-ml.
portions of petroleum ether. There was obtained 16 g.
(36~) of 2-(_-isopropylphe-nyl)-5-(phenylthio)thiophene, m,p. 61-63~, . - . . .
. .

1~'7296'7 Anal, Calc'd for ClgHlgS2: C, 73.50; H, 5.85; S, 20.65.
Found: C, 73.22; H, 5.75; S, 20,59 Example 7 2-(m-Chloro~hen~ 5-(phenylthio)thiphene A mixture of 89 g, (o.46 mole) of 2-(m-chlorophenyl)-thiophene, 400 ml. of reagent carbon tetrachloride, 54 ml, (67 g., o.46 mole) of benzenesulfenyl chlorlde and 0.05 g, of lron powder was allowd to stand for four days at room temperature, A ~urther 12 ml, (15 g,, O,10 mole) o~
benzenesulfenyl chloride and 0,05 g. of lron powder were 1 10 added. After four days the carbon tetrachloride was removed by dlstillatlon, The residue was distllled at reduced pressure to give 30 g, (22%) of 2-(m-chlorophenyl)-chlorophenyl)-5-(phenylthio)thiophene, b,p, 200-205 (0,15 mm,), Anal, Calc~d. for C16HllClS2: C, 63,46; H, 3,66; Cl, 11.71; S, 21,18, Found: C, 63,20; H, 3,65; Cl, 12,04; S, 21',37 '' Example 8 2-Phenylthio-5-(m-trifluoromethylphenyl)thiophene A mixture of 29,7 g, (0,13 mole) of 2-(m-trif~uoro_ methylphenyl)thiophene, 200 ml. of reagent carbon tetra-chloride, 15.5 ml. (18,8 g. 0.13 mole3 of benzenesulfenyl chloride and 0,05 g. of lron powder was allowed to stand

4 days at room temperature, The reaction mixture was found by vapor phase chromat~graphy to contain approximately equal amounts o~ 2-(m-trifluoromethylphenyl)thiophene, diphenyl disulfide and the de~lred di~ubstituted thiophene.
An additional 12~7 ml, (0.11 mole) of benzenesulfenyl ~ chloride and 0,05 g, of iron powder were added, The mlx~ure ; wa~ stirred 2 hours at room temperature and then 1 hour at reflux, The carbon tetrachloride ~olvent was removed by distillation, The residue was dlstilled at reduced pressure . : ,, ~ . -: .
,, - . . ~ . - .. . , . . :
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- to glve 17 g. (39%) of 2-phenylthlo-5-(m-trlfluoromethyl-phenyl)thlophene b.p. 172-210 (0.04 mm.), n21 = 1.6329-1,6330.
Anal. Calc'd. for C17HllF3S2: C, 60.70; H, 3.30;
S, 19.06.
Found: C, 59.39; H, 3.35; S, 18.73 The low value found for carbon probably arises from the difficulty in quantitatlvely convertlng the carbon of the trifluoromethyl group to carbon dloxide under the combustl~n analysis conditions.
2-(3,4-Xylyl)thlophene ~ ~olutlon of 182 g. (1.50 moles) o~ 3,4-dimethylanlline, m.p. 49-51, in 3000 ml. (38 moles) of thiophene WA8 treated with 226 ml. (2.00 moles) of n-butyl n~trite. me solution was allowed to ~tand at room temperature ~or one week. Unreacted thlophene was removed by distillation with a steam bath. The residue - wa~ distllled at reduced pressure to glve 75 g. (27%) of 2-(3,4-xylyl~thlophene, b.p. 107-122 (o.o8 mm.). Vapor phase chromatography showed the presence of about 2% of I the xylldine starting material, re ved by washing f~rst with two 100-ml. portions of 10% hydrochloric acid followed by two 150-ml. portions of distilled water, Anal. Calc~d for C12H12S: C, 76.55; H, 6.43, S, 17.03.
Found: C, 76.11; H, 6.51; S, 15.26.
Example 10 2-Phenylth~5-(3,4-xylyl~thiophene A mixture of 37 g. (0.197 mole) of 2-(3,4-xylyl)-thiophene, 200 ml, of reagent carbon tetrachloride, 29 ml.
(36 g., 0.249 mole) of benzenesulfenyl chloride and 0.05 g.
.
of iron powder wa6 allowed to ~tand two days at room .. _ . .. . . .. ...... , .. . _ .. . . . . . . .

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lt)~Z967 temperature. A vapor phase chromatogram of the mixture showed that all the 2-(3,4-xylyl)thiophene had been con-sumed. The carbon tetrachloride was removed by distilla-tion and the residue recrystallized from ethanol to give a first crop of 17 g, (29%) of 2-phenylthio-5-(3,4-xylyl)-thiophene, m,p, 77-78~, Anal, Calc'd for ClgH16$2: C, 72,93; H, 5.
Found: C, 73,17; H, 5,33; S, 22,18, me proton magnetic resonance spectrum showed a ratio of six methyl protons (2,26 6) to ten aromatic protons (7.06-7,33 ~), Example 11 2-Nitro-3,5-diphenylthio~hene A solution of 2,04 g, (0,010 mole) of 2,4-diphenyl-thiophene in 150 ml, of acetic anhydride was cooled to 5 and treated with 2,4 g. (0,010 mole) of cupric acetate during five minutes, The temperature of the reaction mixture was held at 10-15 for one hour, me mlxture was allowed to warm to 28 during the next hour, then poured onto 120 g, of crushed ice and diluted to 1 liter, The mixture was extracted with three 25-ml, portions of chloroform, The combined extracts were freed of chloro-form by evaporation, The residue was recrystallized from ethanol to give 1,5 g, (53%) of 2-nitro-3,5-diphenyl-thiophene, m,p, 100-104.
Anal, Calc'd ~or C16HllN02S: C, 68.31; H, 3,94, N, 4.98, S, 11,40, Found: C, 67,63; H, 3,69; N, 5,14; S, 10~96, The proton magnetic resonance spectrum showed a ratio of ten aromatic protons (7,41-7,82 ~) to one thiophene proton (7,21 ~), ~6 Exam~le 12 3,5-Diphenyl-2-(~henylthio ? thlo~hene A solution of 17.7 g. (75 mmoles) of 2,4-diphenyl-thiophene in 300 ml. of carbon tetrachloride was treated w~th 8.7 ml. 10.8 g. (75 mmoles) of benzenesulfenyl chlor-ide and allowed to stand for one week. The solvent was removed by evaporation. The residue was washed with ether to obtain 14 g. of crude product which was re-crystallized from ethyl acetate. There was obtained 10.5 g. (41~) of 3,5-diphenyl-2-(phenylthio)thiophene, m.p. 96-97.
Anal. Calc'd for C2 ~ 16S2 C, 76.70; H, 4.68; S, 18.61.
Found: C, 76.70; H, 4.56; S, 18.27.
Example 13 2-(p-Bromophenyl)-5-(m-nitrophenyethio)thiophene To a solution of 21.2 g. (0.112 mole) of m-nitro-benzenesulfenyl chloride in 160 ml of carbon tetrachloride were added 24.5g. tO.103 mole) of 2-(~-bromophenyl)thiophene and 0.1g, of lron powder. me reaction mixture was allowed to stand one week at room temperature. Evaporatlon of the solvent and recrystallization of the residue from 140 ml of ethyl acetate gave 17.6g. (4~ ) of 2-(~-bromophenyl)-5-(m-nitrophenylthio)thiophene, m.p. 120-122.
Anal. Calc'd for C16H10BrN02S2: C, 48.99; H, 2.57;
Br, 20.37; N, 3.59; S, 16.35.
Found: C, 48.87; H, 2.54; Br, 20.50; N, 3.95; S, 16.04.
Example 14 2~ nisyl-5-(phenylthio)thiophene A solution of 34g. (0.179 mole) of 2-p-anisyl-thiophene ~n 500 ml of carbon tetrachloride was treated ~lth 23 ml ~28.5g., 0~197 mole) of benzenesulfenyl chloride and 0.lg. of iron powder. The mlxture was allowed to ~tand at room temperature for eight dayæ.

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The mixture was filtered to remove a small amount o~
solid. The filtrate wa~ evaporated to give 67g. of crude solld product. Recrystallization from 220 ml o~
ethyl acetate gave 15.4g. (29~) of 2-p-anisyl-5-(phenylthlo)thlophene, m p. 92-93:
Anal. Calc~d for C17H140S2 : C, 68.42; H, 4 73;
S, 21.49 Found: C, 69.09; H, 4.73; S, ?0.93.
Exam~le 15 2-(~-Chlorophenylthlo)-5-~henylthlophene A solutlon of 40 g. (0.250 mole) of 2-phenyl-thiophene ln 200 ml of carbon tetrachloride wa~ treated at room temperature with 45g. (0.252 mole) of ~-chloro-benzenesulfenyl chloride. Iron powder (O.lg.) was added and the reaction mixture was allowed to stand for seven days at room temperature. Flltratlon remo~ed a ~mall amount of insoluble material. Evaporation of the fil-trate ga~e a residue o~ 79.8g. of crude product, m.p.
85-ô7. Recrystallization of the residue from 400 ml of absolute ethanol gave 40g. (53~) of Z-(p-chlorophenylthio)-

5-phenylthiophene, m.p. 101-103.
Anal. Calc'd for C16~11ClS2 : C, 63.46; H, 3.66;
Cl, 11.71; S, 21.18.
Found: C, 63.65; H, 3.79; C1, 11.55; S, 20.52.
Example 16 Mite Contact Test Cotton, GossyPium hirsutum L. - variety Stoneville-213, in the second primary leaf stage, grown in twelve ounce cups under greenhouse conditlons at 70-75F, was used in this test. One plant (two primary leave~) in one pot was used for each replicate; two replicates were used for each 3~ chemical tested. A one-inch diameter circle of tree .

96~

tanglefoot, a sticky, non-toxic preparation, was used to confine the mites to the upper leaf surfaces. Approximate-ly twenty-five adult two-spotted splder mites (~ 3~
urticae) were transferred to each test plant 24 hours prior to treatment Test compounds were prepared for spraying at 1000 ppm (parts per million) concentration by dlssolving them in a 8mall amount of acetone and adding a suitable wetting agent. Typically, o.6 grams of chemical were dissolved (or suspended) in 10 ml of acetone, two drops of Triton-X100 (trademark; octylphenoxy polyethoxy ethanol with 9-10 mole percent of polyethylene oxide) wetting agent were added and thi~ wa~ suspended ln 100 ml of water to make a 6000 ppm suspenslon An aliquot was then further diluted with di~-tllled water to 1000 ppm concentration of chemical.
The infested plants were sprayed with the dis-persions UBing a small spray atomizer to thoroughly drench the ~oliage. The plants were returned to the greenhouse where they were held for 8iX days. After this period the plants were examined for adult live mites remalning on the leaves. On an estimation basis and in comparison with the number of living mites on the check plants, the percent control was determlned.
Data for the mite contact test are shown in Table I, ; 25 wherein chemicals 1 to 14 correspond to the compounds pre-pared in Example 1 to 14, respectively. Chemicals 16 to 24 are ldenti~ied as follows:
16 ! 2-phenylthiophene 17. 2,5-dlphenylthiophene 18. 2-(~-isopropylphenyl)th~ophene ' ' ' ' ~' ~ ' ' ' 9~

19. 2-(m-chlorophenyl)thiophene 20. 2-(p-methoxyphenyl)thiophene 21, 2~ nitrophenyl)thiophene 22. 2,4-diphenylthlophene 23. 2-bromo-3,5-diphenylthiophene 24. 2,3,5-triphenylthiophene.
In a slmilar test the known chemical 2,5-bis(phenyl-thio)-thiphene (T. FuJisaw~ et al., cited abo~e), whlch is outside the general formula given above, displayed miticidal actlvity, but was phytotoxic as evidenced by puckering of new growth The known chemlcal 3,4-diphenylthiophene (H. J. ~acker and W. Stevens, Rec. trav chim., 59~ 423 [1940]), which is outside the general formula given above, sho~ed no miticidal activlty, The known miticlde 2~ t-butylphenoxy)cyclohexyl-2-propynyl sulflte (Omite; trade-mark) was used at 80 ppm and 16 ppm for mite control comparisons in a similar test; the LD95 for this chemical rAnges ~rom 20 to lOOppm depending on environmental factors . such as light intensity, temperature and humitlty, I

~ .

; ' .

~ - ~

Z~

Table I
Mit e Contact Te st Chemical% Control

6 98

7 100

8 100

9 98 .
.

~ ~0~7Z~6 .

Example 7 Mlte One-Day Re~ldual Test Cotton, Gos~yplum hir~utum L., variety Stone-~ille-213~ in the second primary leaf stage, grown in twelve ounce cups under greenhouse conditions at 70-75C, was used`inthis test.
One plant (two primary lea~es) in one pot was used for each replicate; two replicates ~ere used for each concentration of chemical te6ted.
Test compounds were prepared by disaolvlng 50 I 10 mg5 of chemlcal in one ml of acetone, addlng one drop of Emulfor 719, a commercial surface-acti~e dispersing agent (trademark; polyoxyethylatod vegetable oil) and suspended in 50 ml Or water for a concentration of 1000 ppm (parta per million). Aliquots were further diluted with dis-tllled water to the concentration to~ted.
The plants were sprayed with the di3persions of the chemlcal~, uaing a small apray atomizer to thoroughly dr~nch the foliage.
One day following treatment Q circle of tree tangle-foot was placed on the upper surfaces of the ; treated lea~es and adult mites were tranaferred into this confinement, Count6 of theae mitea were made im-mediately following tranafer and agaln aix days later.
Abbott's formula was uaed to compensate for check . ,~.
~ 25 mortality. The adJuated percent control waa obtained ; by the following expre~sion, wherein A i8 the ad~usted control, C ls the ~ live mitea on check plants and T
ia the % llve mites on treated plant~:
. ~ ..
.~ .

~' - , .
''., ' - A = C-T X 100 Data from the mite one-day residual test are shown in Table II, wherein the test ChemicQls have the numbers previously assigned, Table II

Mite One Day Residual Test Control Chemical PPM PPM PPM

_ 75 11 . 100 100 94 . 21 100 100 85 12 10~ 100 74 .

" .

_ ample 18 Mosquito Larvae Test Chemicals are prepared by dis~olving 30 mg of the chemical in 10 ml of aceto~e. Dilutions are made with w~ter to 10 ppm and 1 ppm. Two 25 ml allquots at each rate are placed ln test tubes to whlch are added

10 to 25 forth instar lar~ae of the yellow fever mo~quito, Aedes aegypti.
The tubes are held at 20C in darkness for 72 hours. At the end of thls perlod the percent control is determlned.
Performance of mono, di and tri ~ub~tltuted thio-phenes i~ shown in Table III, wherein the test chemicals ; are a5 pre~lously numbered.

, zg6i7 Table III

Mosguito Lar~rae Te~t % Control Chemical p pp . ,, .

Z!~6'~

SUPPLEMENTARY DISCLOSURE

As chemicals of particular interest useful in the invention there may be ~entioned:
2-~- chlorophenyl-3,5-diphenylthiophene 2,3-di(~-tolyl)-5-phenylthiophene 2,3,5-tri(~-tolyl~thiophene 2~3-di-(~-chlorophenyl)-5-phenylthiophene 2,3-dl~-chlorophenyl)-5-~-tolylthiophene 2,3-diphenyl-5-p-ethylphenylthiophene 2,3,5-tri(~-anlsyl)thiophene 2,3-diphenyl-5-(3,4-dimethylphenyl)thiophene 2,3-di(~-bromophenyl)-5-~-tolylthiophene 2,3-diphenyl-5-~-ethoxyphenylthiophene 2~5-diphenyl-3-m-tolylthiophene 2,5-diphenyl-3-p-anisylthiophene 2,5-diphenyl-3-(3,4-dimethylphenyl)thiophene 2~3-(3,4-dimethoxyphenyl)-5-phenylthiophene : ,.
2,5-diphenyl-3-~-bromophenylthiophene 2,5-diphenyl-3-p-fluorophenylthiophene 2~5-diphenyl-3-~-nitrophenylthiophene 2,3-diphenyl-5-m-nitrophenylthibphene 2,5-diphenyl-3-m-trifluoromethylphenylthiophene 2~3-dipheny1-5-(3,4~5-tr~methoxyphenyl)thiophene 2,3-diphenyl-5-m-trifluoromethylphenylthiophene ., .
2-p-tolyl-3,5-di(~-bromophenyl)thiophene 2,5-diphenyl-3-~-ethoxyphenylthiophene 2,3-diphenyl-5-m-methoxyphenylthiophene 2,3-bis(~-tolyl)-5-phenylthiophene 2,5-diphenyl-3-(3,4-dimethylphenyl)thiophene 2,5-dlpheny3.-3-~-ethoxyphenylthiophene ~ -~4-~ 3~j~7 2,3-bis(2-chlorophenyl)-5-phenylthiophene 2~5-diphenyl-3-o-tolylthiophene 2-m-nitrophenyl-3-~-methoxyphenyl-5-p-tolylthiGphene 2,3-bis(~-methoxyphenyl)-5-m-tolythiophene 2,3-diphenyl-5-(3,4-dimethoxyphenyl)thiophene 2,3-diphenyl-5-(2,3,4-trichlorophenyl)thiophene ?,3-diPhenyl-5-(2~4-d~nethoxyphenyl)thiophene 5-(3,4-dimethoxyphenyl)-2,3-diphenylthiophene 3,5-diphenyl-2-(~-cyclohexylphenylthio)thiophene 3,5-diphenyl-2-(~-phenylphenylthio~thiophene 2,5-diphenyl-3-(~-cyclopentylphenyl)thlophene 2,5-diphenyl-3-(~-phenylphenyl)thiophene 3,5-diphenyl-2-(~-~luorophenyl)thiophene .
2-~-chlorophenyl-3,5-diphenylthiophene 15 . 2,3,5-tri(~-anisyl)thiophene 2,3-diphenyl-5-(3,4-dimethylphenyl)thiophene 2~3-di(p-bromophenyl)-5-~-tolylthiophene 2,3-d~phenyl-5-m-nitrophenylthiophene 2,3-diphenyl-5-(3,4,5-trimethoxyphenyl)thiophene 2~3-diphenyl-5-m-trifluoromethylphenylthiophene 2-~-tolyl-3,5-di(p-bromophenyl)thiophene 2-fluoro-3,5-diphenylthiophene 2-chloro-3,5-diphenylthiophene 253-bls(p-isopropylphenyl)-5-phenylthiophene ~ ' "

.

iO'~96~

The following preparations illustrate additional compounds.
Compound 25,2,3-Diphenyl-S-p-tolylthiophene In a l-liter stainless steel autoclave equipped with stirrer were placed 71 g (0.217 mole) of 1,2-diphenyl-4-p-tolylbutane-1,4-dione, 100 ml. of xylene, and 45 g (0.101 mole) of phosphorus pentasulfide. The autoclave was sealed, chilled in a Dry Ice-acetone bath, and charged with 120 g (3.52 moles) of hydrogen sulfide. The autoclave was then heated at 160-190C (920-1130 psig) for 225 minutes. The autoclave was cooled to room temperature and the hydrogen sulfide vented into an aqueous sodium hydroxide solution. The ~ residue in the autoclave was stirred with 150 ml of absolute ; ethanol. The slurry thus formed wasfiltered. The residue was dried to give 35.4 g (50.0%) of crude 2,3-diphenyl-5-_-tolylthiophene, m.p. 110-112C. Recrystallization from 190 ml of toluene and 625 ml of ethanol gave 30.1 g (42.5%) of pure 2,3-diphenyl-5-~-tolylthiophene, m.p. 114-116C.
Anal. Calcd. for C23H18S: C, 84-62; H~ 5.56;
S, 9.82. Found: C, 84.56; H, 5.69; S, 9.79.
Compound 26. 2,3-Diphenyl-5-p-chlorophenylthiophene In a l-liter stainless steel autoclave equipped with stirrer were placed 76.9 g (0.220 mole) of 1,2-diphenyl 4-p-chlorophenylbutane-1,4-dione, 100 ml of xylene and 45 g (0.101 mole) of phosphorus pentasulfide The autoclave was cooled with a Dry Ice-acetone bath and ~ charged with 120 g (3.52 moles) of hydrogen sulfide. The I autoclave was heated with stirring for 200 minutes at 155-178C (1000-1200 psig). The autoclave was cooled and ; , , l~t~29~

the hydrogen sulfide allowed to escape into a sodium hydroxide solution. The residue was stirred with 150 ml of absolute ethanol. Filtration and drying gave a crude product of 61.2 g (80.2~) m.p. 115-117. Recrystallization from 190 ml of toluene and 625 ml of ethanol gave 47.2g (61.9~) of pure 2,3-diphenyl-5-p-chlorophenylthiophene, m.p.
121-122C.
Anal. Calcd. for C22H15ClS, C, 76-18; H~ 4-36;
Cl, 10.22. Found: C, 75.96; H, 4.38; Cl, 10.29 Compound 27. 2,3-Di-~-anisyl-5-p-tolylthiophene ! In a l-liter stainless steel autoclave equipped with stirrer were placed 40.6 g (0.105 mole) of 1,2-di-~-anisyl-4-_-tolylbutene-1,4-dione, 100 ml of xylene and 25 g (0.056 mole) of phosphorus pentasulfide. The vessel was chilled with a Dry Ice-acetone bath and charged with 130 g (3.81 moles) of hydrogen sulfide. The autoclave was then heated with stirring for 215 minutes at 158-165C
(1250-1360 psig). After cooling the vessel, the hydrogen sulfide was allowed to vent into a sodium hydroxide solu-tion. The residue was treated with 150 ml of absolute ethanol to destroy unreacted phosphorus pentasulfide.
After removal of the ethanol there remained 70.5 g of crude product. Recrystallization from ethanol-dioxane (70:30) gave 20 g (49.3%) of pure 2,3-di- -anisyl-5-_-tolylthiophene, m.p. 99-102C. and a second crop of 6.5 g (16.0%) m.p. 92-96C.
Anal. Calcd. for C25H22O2S: C, 77.69; H, 5.74;
S, 8.30. Found: C, 77.15; H, 6.00; S, 8.16.

Compound 2~. 2,3-Di-_-anisyl-5-p-chlorophenylthiophene In a l-liter stainless steel autoclave equipped ll~7Z967 with stirrer were placed 54.5 g (0.133 mole) of 1,2-di _-anisyl-4-_-chlorophenylbutane-1,4-dione, 100 ml of xylene and 30 g (0.0675 mole) of phosphorus pentasulfide. The autoclave was cooled with a Dry Ice-acetone bath and 130 g (3.81 moles) of hydrogen sulfide was distilled into the autoclave. The vessel was stirred and heated for three hours at 162-168QC (1220-1290 psig). After cooling to room temperature the hydrogen sulfide was vented into an aqueous sodium hydroxide solution. Treatment with 150 ml of absolute ethanol to remove unreacted phosphorus penta-sulfide gave 77 g of crude product. Recrystallization from 400 ml of absolute ethanol gave 45 g (83.1%) of pure 2,3-di-~-anisyl-5-_-chlorophenylthiophene, m.p. 125-` 128C.
Anal. Calcd. for C24HlgC1O2S: C, 70.84; H, 4-71-Found: C, 69.81; H, 4.91.
Compound 29. 2,3-Diphenyl-5-m-anisylthiophene In a l-liter stainless steel autoclave equipped with stirrer were placed 51.6 g (0.150 mole) of 1,2-diphenyl-4-_-anisylbutane-1,4-dione, 100 ml of xylene ', and 30 g (0.0675 mole) of phosphorus pentasulfide. The ' I autoclave was cooled in Dry Ice and charged with 130 g (3.81 moles) of hydrogen sulfide. The mixture was then heated and stirred 235 minutes at 154-177C (1120-1320 psig). The vessel was cooled to room temperature. The hydrogen sulfide was vented into a sodium hydroxide solution. The residue was treated with 150 ml of absolute ethanol to destroy excess phosphorus sulfides. Washing the product with another 330 ml of ethanol gave 32 g (62.3%) of crude product. Recrystallization from 50 ml ~:, ., .

, - 28 -i , ,: - ~- , ' : ~ ' ' . ' - ' ~ : ' ~ qzg6~
.

of toluene and 150 ml of ethanol gave 19.8 g (38.5~) of pure 2,3-diphenyl-5-m-anisoylthiophene, m.p. 100-102C.
Anal. Calcd. for C23H18OS: C, 80-66; H, 5.30;
S, 9.36. Found: C, 80.41; H, 5.06; S, 9.35.
Compound 30. 2,3-Diphenyl-5~-~-bromothiophene A mixture of 31.4 g (0.080 mole) of 1,2-diphenyl-4-~-bromophenylbutane-1,4-dione, 100 ml of xylene, 16 g (0.036 mole) of phosphorus pentasulfide and 125 g (3.67 mole) of hydrogen sulfide was heated in a l-liter stainless 1,0 steel autoclave with stirring for four hours at 156-176C.
(1140-1320 psig). The reactor was cooled to room tem-perature and the hydrogen sulfide was led into a sodium hydroxide solution. Treatment of the residue with 150 ml of absolute ethanol gave 18.5 g (59.1%) of crude solid, m.p. 135-137. Recrystallization from 20 ml of dioxane and 60 ml of absolute ethanol gave 16.5 g (52.7%) of pure 2,3-diphenyl-5-_-bromothiophene.

Anal. Calcd. for C H BrS: C, 67.52; H, 3.86;

Br, 20.42; S, 8.19. Found: C, 67.60; H, 3.86;
Br, 20.70; S, 7.96.

I Compound 31. 2,3-Diphenyl-5-_-fluorophenylthiophene -- .
; A mixture 49.8 g (0.15 mole) of 1,2-diphenyl-4-_-fluorophenylbutane-1,4-dione, 100 ml of xylene, 30 g (0.0675 mole) of phosphorus pentasulfide and 130 g (3.81 moles) of hydrogen sulfide was heated and stirred in a 1-liter stainless steel autoclave for 4 hours at 157-185C.
(620-1145 psig). After cooling the vessel to 20~C and venting the hydrogen sulfide into a sodium hydroxide solution, the residue was stirred with 150 ml of absolute ethanol.

Filtration gave 31.5 g (63.6~) of crude product, m.p. 108-, . . , . ~ . . - .
,. . . - - . : : -. , . . . , . :
.. .. . , . , . . , . .. -- l~qZ96'~

110C. Recrystallization from 30 ml of dioxane and 90 ml of ethanol gave 24 g of pure 2,3-diphenyl-5-_-fluoro-phenylthiophene, m.p. 111-113C.
Anal- Calcd- for C22H15FS C, 79.97; H~ 4-58;
S, 9.70. Found: C, 79.89; H, 4.46; S, 9.73.
Compound 32. 2,3-Diphenyl-5~-o-chlorophenylthiophene A l-liter stainless steel stirred autoclave was charged with 33 g (0.0946 mole) of 1,2-diphenyl-4-o-chlorophenylbutane-1,4-dione, 100 ml. of xylene, 20 g of phosphor~s pentasulfide and 125 g of hydrogen sulfide.
The autoclave was then heated at 160-187C for three hours.
The autoclave was cooled and vented. The residue was washed with ethanol and filtered off to give 17 g (51.8%) of crude product, m.p. 103-107C. Recrystallization from 20 ml of dioxane and 40 ml of ethanol gave 10.5 g (32%) of pure product, m.p. 117-118C.
Anal. Calcd. for C22H15ClS: C, 76-18; H~ 4-36;
` Cl, 10.22; S, 9.24. Found: C, 75.47; H, 4.24;
! Cl 10.23; S, 9.27.
Compound 33. 2,3-Diphenyl-5-(3,4-dichlorophenyl)thiophene In a l-liter stainless steel autoclave equipped with electrically-driven stirrer were placed 38.3 g (0.100 mole) of 1,2-diphenyl-4-(3,4-dichlorophenyl)butane-1,4-dione, 100 ml of xylene, 20 g of phosphorus penta-sulfide and 140 g of hydrogen sulfide. The reactor was heated for three hours at 160-164C. The crude product ~, remaining after cooling and venting the reactor was stirred with ethanol. Filtration gave 30.5 g (80%) of solid m.p.
101-103C. Recrystallization from 30 ml of dioxanP and 60 ml of ethanol gave 22.5 g (59%) of pure product, m.p.

.1 .

, ,: .

i~7Z96 106.2-107.8C.
Anal- Calcd- for C22H14C12S C~ 69-30; H~ 3-70;
Cl, 18.59; S, 8.41. Found: C, 69.51, H, 3.71;
Cl, 18.46; S, 8.18.
Compound 34. 2,3-Diphenyl-5~-_-methoxyphenylthiophene -In a l-liter steel autoclave fitted with a mechani-cal stirrer, a thermometer and a pressure gauge were placed 32 g (0.09 mole) of 1,2-diphenyl-4-_-methoxyphenylbutane-1,4-dione, 100 ml of xylene, 20 g (0.045 mole) of phos-phorus pentasulfide and 130 g of hydrogen sulfide. The mixture was stirred and heated 3 hours at 157-162C (1190-1220 psig). The vessel was cooled and the hydrogen sulfide vented into an aqueous sodium hydroxide trap. The semisolid residue was stirred with 150 ml of absolute ethanol. Fil-tration gave 23 g (72%) of crude product, m.p. 130-132C. and a second crop of 3.7 g (11.6%) m.p. 124-126C. The two crops were combined and recrystallized from 30 ml of a mixture of dioxane and 60 ml of absolute ethanol to give 22 g (69%) of pure product m.p. 133-134C.
Anal. Calcd. for C23H18OS: C, 80.67; H, 5.30;

S, 9.36. Found: C, 80.12; H, 5.31; S, 9.26.
Compound 35. 2,3-Diphenyl-5-(3-Fluoro-4-methoxyphenyl)thiophene In a l-liter autoclave were placed 30 g (82.8 mmoles) of 1,2-diphenyl-4-(3-fluoro-methoxyphenyl)butane-1,4-dione, 100 ml of xylene, 18.4 g (41.4 mmoles) of phosphorus penta-sulfide and 130 g of hydrogen sulfide. The vessel was heated 205 minutes at 155-163C (1145-1235 psig.). The reactor was cooled and the hydrogen sulfide vented into a solution of 200 g of sodium hydroxide in 2 1 of water.
The semisolid residue was stirred with 150 ml of absolute . ~ .

l~Z967 ethanol. Filtration gave a first crop of 14.7 g (49.3%) m.p. 122-125C. Chilling the filtrate and refiltration gave a second crop of 10.5 g (35.2%), m.p. 118-122C. The two crops were combined and recrystallized from a mixture of 30 ml of dioxane and 70 ml of absolute ethanol to give 21.5 g (72.0%) of colorless plates, m.p. 123-125C.
Anal. Calcd. for C23H17FOS: C, 76-64; H~ 4-75;
S, 8.90. Found: C, 76.51; H, 4.68; S, Compound 36. 2,3-Diphenyl-5-~-t-butylphenylthiophene A l-liter stirred autoclave was charged with 55.6 g tO.150 mole) of 1,2-diphenyl-4-p-t-butylphenylbutane-1,4-dione, 100 ml of xylene, 33.3 g (0.075 mole) of phosphorus pentasulfide and 130 g of hydrogen sulfide. The mixture was stirred and heated at 160-166C. for 3 hours. The reactor was cooled and vented. The residue was stirred with 150 ml of absolute ethanol. Filtration gave a first crop of 18 g (32.6%) m.p. 108-112C. Chilling the filtrate and refilter-ing gave a second crop of 24 g (43.4%) m.p. 102-105C. The two crops were combined for recrystallization from a mixture of 50 ml of dioxane and 100 ml of absolute ethanol. The pure product (31.3 g., 56.6%) had a m.p. of 117-119C.
Anal. Calcd. for C26H24S: C, 84.74; H, 6.56;
S. 8.70. Found: C, 85.26; H, 6.55; S, 8.39.

.
.

1~7Zg6~

Compound 37 - 2,3-Bis(_-methoxyphenyl)-5:-_-methylphenylthiophene . . ~
A l-licer stainless steel autoclave equipped with mechanical stirrer was charged with 18.5 g of 1,2-bis(_-methoxyphenyl)-4-_-methylphenyl-1,4-butane-dione, 100 ml of xylen~, 10.6 g of phosphorus penta-sulfide and 120 g of hydrogen sulfide. The mixture was stirred and heated at 160-165C for 2.9 hrs. The vessel was cooled, the hydrogen sulfide was vented and the residue stirred with 150 ml of ethanol to destroy unreacted phosphorus pentasulfide. Filtration and evaporation of solvent left 2,3-bis(p-methoxyphenyl)-5-_-methylphenylthiophene as a light yellow viscous oil.

. .

.

1~7~6~

Compound 38 - 2,3-Diphenyl-5-(3,4-dimethoxyphenyl)thiophene In a l--liter stainless steel autoclave fitted with mechanical stirrer were placed 37.4 g of 1,2-diphenyl-4-(3,4-dimethoxyphenyl)butane-1,4-dione, 100 ml of xylene, 22.2 g of phosphorus pentasulfide and 120 g of hydrogen sulfide.
The mixture was stirred and heated at 162 for 3.25 hrs. The reactor was cooled to 10C. The hydrogen sulfide was vented and the residue was stirred with 150 ml of ethanol; filtra-tion and evaporation gave a residue of 2,3-diphenyl-5-(3,4-dimethoxyphenyl)thiophene as a viscous tan oil.
Compound 39 - 2,3-Diphenyl-5-(3,4,5-trimethoxyphenyl)thiophene !

In a l-liter stirred stainless steel autoclave were placed 40.4 g 1,2-diphenyl-4-(3, 4,5-trimethoxyphenyl)-butane-1,4-dione, 100 ml of xylene, 22.2 g of phosphorus pentasulfide and 128 g of hydrogen sulfide. The reaction mixture was heated with stirring for 3 hours at 160-168C
(1210-1250 psig. pressure). The reactor was cooled to 10C and the hydrogen sulfide was released. The residue was stirred with 150 ml of ethanol to decompose unreacted phosphorus pentasulfide. Filtration and evaporation gave 38.8 g (96.4~) of 2,3-diphenyl-5-(3,4,5-trimethoxyphenyl)-thiophene.

. . ~ .

~'7296'~

Compound 40 - 2,3-Diphenyl-5-(2,4-dimethoxyphenyl ? thiophene In a 1-1 stainless steel autoclave were placed 56.2 g (0.150 mole) of 1,2-diphenyl-4-(2,4-dimethoxyphenyl)-- butane 1,4-dione, 100 ml of xylene, 33.3g (0.075 mole) of phosphorus pentasulfide and 120g of hydrogen sulfide.
The contents of the autoclave were stirred at 160-162C
(1040-1080 psig.) for three hours. The autoclave was then cooled and the remaining hydrogen sulfide was vented into a trap of aqueous sodium hydroxide. The residue was stirred with 150 ml~of absolute ethanol to destroy excess phosphorus pentasulfide. Chilling to -78C and fil~ration gave 27.6 g (49.4%) of cured product, m.p. 107-110C. Re-crystallization from 30 ml of dioxane and 60 ml of ethanol gave 17.3 g (31~) of pure 2,3-diphenyl-5-(2,4-dimethoxyphenyl)thio-phene, m.p. 112-114C.
Anal. Calcd. for C24H20O2S: C, 77.39; H, 5.41;
S, 8.61. Found: C, 77.01; H, 5.59; S, 9.46.
Compound 41 - 2,3-Diphenyl-5-(~-cyclopentylphenyl)thiophene A l-liter stainless steel stirred autoclave was charged with 55 g (0.144 mole) of 1,2-diphenyl-4-p-cyclopentylphenylbutane-1,4-dione, 100 ml of xylene 33 g (0.074 mole) of phosphorus pentasulfide and lOOg of hydrogen sulfide. The autoclave and contents were heated with stirring at 160-170C. (960-1030 psig) for three hours. The vessel was cooled and vented to re-lease hydrogen sulfide into a trap of sodium hydroxide solution. The residue was stirred with 150 ml of ethanol ~ .

; - - 35 -' .

, .. . . . .
. .

iV~2~7 to decompose excess phosphorus pentasulfide. Chilling to -78C gave 47.5g (86.8%) of nearly pure product m.p.
149-150C. Recrystallization from 75 ml dioxane and 150 ml ethanol gave pure 2,3-diphenyl-5-(_-cyclopentyl-phenyl)thiophene, m.p. 149.5-150.5C.
Anal. Calcd. for C27H24S: C, 85-22; H~ 6-36;
S, 8.43. Found: C, 85.40; H, 6.14; S, 8.00.
Compound 42 - 2-_-Fluorophenyl-3,5-diphenylthiophene In a 2-1 three-necked flask fitted with reflux condenser, dropping funnel and mechanical stirrer were placed 6.lg (0.25g-atom) of magnesium and 200 ml of ether. From the dropping funnel was added a solution of 36.2g (0.25 mole) of _-fluorobenzyl chloride in 100 ml of ether while the contents of the flask were stirred vigorously. The addition was completed in one hour. The mixture was stirred another thirty minutes and then treated with a solution of 50g (0.238 mole) of 3-phenylpropio-phenone in 250 ml of diethyl ether and 100 ml of tetra-hydrofuran. The addition required one hour. The mix-ture was heated at reflux on a steam bath for another hour; then it was cooled and poured onto 1 kg of ice and 40 ml of concentrated hydrochloric acid. The hydrolysis mixture was extracted with one 300-ml and two 100-ml portions of chloroform. The extracts were combined, ; washed with 200 ml of water and evaporated down to give 78g of crude 1-_-fluorophenyl-2,4-diphenylbutanol-2 which was heated for four hours at reflux with 20 ml of concentrated sulfuric acid and 80 ml of water. The organic phase was separated and washed with two 200 ml ~U~2g~

portions of distilled water. The second wash was neutral.
The organic phase was dried in a rotary evaporator to give 77g of crude 1-_-fluorophenyl-2,4-diphenylbutene-1.
A 15-g (0.05 mole) aliquot of this triarylbutene was mixed with 4.8g (0.15g-atom) of sulfur and 3 drops of 1,5-diazabicyclo [4.3.0] non-5-ene and heated at 220-230C for 22 hours. The reaction mixture was transferred to a sublimation apparatus and heated at 100C (0.02 mm Hgj to give 2.9 g of yellow needles. Recrystallization from dioxane-ethanol gave pure 2-_-fluorophenyl-3,5-diphenylthiophene as almost colorless needles, m.p. 118-119C.
Anal. Calcd. for C H FS: C, 79.97; H, 4.58.

Found: C, 80.18; H, 4.31.
The infrared spectrum of the recrystallized product showed peaks at 695 and 746 cm 1 (monosubstituted benzene ring) and at 790 and 845 cm 1 (m-disub-stituted benzene ring).

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Example 19 This example illustrates a citrus rust mite test.
Grapefruit trees, of the variety Thompson Pink, were treated in this test conducted at Sanford, Florida. The trees were naturally infested with a population of the citrus rust mite, Phyllocoptruta oleivora, which is a pest that feeds on both foliage and fruit of citrus trees. Four replicate trees were treated with each chemical rate. Sprays were applied at 100 lbs. pressure with a spray gun which was used to drench the foliage. In the counting procedure, twenty-five leaves were sampled on each tree, 100 leaves per treatment. A one-square-inch area of each leaf was examined with a hand lense. A density index number was recorded for each leaf examined as follows - 0 = no mites, 1=1-2 mites, 2=3-6 mites, 3= 7 or more mites. These index numbers were then totalled and divided by the number of leaves to provide an average density rating.
The percent reduction of citrus rust mite density over the untreated checks was then calculated by adaptation of Abbott's formula.
Density Rating % Reduction = Check - Treated Density rating of check X 100 Counts were made at intervals after treatment, as indicated in the Tables IV, V and VI.
The results on Table IV indicate that the com-pounds of this invention compare most favorably with a widely used commercial product where the long range con-trol of citrus rust mites is concerned. Tables V and VI
provide evidence that additional compounds of this inven-tion are most suitable for the control of citrus rust mites.

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Percent Reduction of Citrus Rust Mite Density Over the Untreated Check . ~

Rate Days Post- Treat~ nt Compound PPM 13 35 50 100 96.7 79 75 ZO

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TABLE VI*
Percent Reduction of Citrus Rust Mite Density Over the Untreated Check Compound Rate 10 Days Post-Treatment PPM

* 10 leaves counted/rep. Each Rep. equalled a 12-inch branch tip isolated with Tanglefoot.

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Example 20 A mite contact test is carried out according to the procedure of Example 16 (two-spotted spider mites on cotton), using the compounds shown in Table VII, at a con-centration of 1000 and 500 ppm, with the results shown in said table.

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TABLE VII

Mite Contact Test % Control Compound PPM PPM

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Accordingly, in a broader aspect o~ the inven-tlon the substituted thiophenes e~ployed are those of the formula A

whereln A, Y and æ may be the same or different and are as follows:
A is phenyl, naphthyl, or substituted phenyl carrying one or more substituents, said substituents being ~luorine, chlorine, bromine, nitro, alkyl having 1 to 5 carbon atoms, cycloalkyl having 5 or 6 carbon atoms, phenyl, alkoxy having 1 to 3 carbon atoms, alkyl-thio having 1 to 3 carbon atoms, alkylenedioxy having 1 or 2 carbon atoms or halomethyl having 1 to 3 halogen atoms selected from ~luorine, chlorine and bromine;
Y has the mean~ngs of A and additionally is hydrogen, fluorine, chlorine, bromine, nitro, phenyl-thio, phenylsu7fono, or phenylthio substituted with one or more of the substitutents fluorine, chlorine, bro~ine, nitro, alkyl having 1 to 5 carbon atoms, cycloalkyl hav-ing 5 or 6 carbon atoms, alkoxy having 1 to 3 carbon atoms or halomethyl having 1 to 3 halogen atoms selected from ~luorine, chlor~ne and bromine; and .

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Z is hydrogen, phenyl or phenyl having one or more substituents, said substituents being fluorine, chlorine, bromine, nitro, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 3 carbon atoms and halo-methyl having 1 to 3 halogen atoms selected from fluorine, chlorine and bromine.
In another aspect of the method of the invention there is employed a substituted thiophene of the fore-going formula wherein:
A is phenyl, phenyl substituted with fluorine, chlorine, alkyl having 1 to 4 carbon atoms, phenyl, methoxy, methylthio, trifluoromethyl and nitro; Y is hydrogen, bromine, phenyl, phenylthio and substituted phenyl and phenylthio having substituents selected from chlorine and methoxy; and Z is hydrogen, phenyl and phenyl substituted with fluorine, chlorine and methoxy.

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Certain compounds within the above formula are new, namely those wherein:
A is phenyl, naphthyl or phenyl substituted with one or more radicals selected from fluorine, chlorine, bromine, nitro, alkyl having 1 to 5 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, phenyl, alkoxy having 1 to 3 carbon atoms, alkylenedioxy having 1 to 2 carbon atoms, alkylthio having 1 to 3 carbon atoms, and halomethyl carrying 1 to 3 atoms selected from fluorine, bromine and chlorine, provided that when Y and Z are hydrogen A is not phenyl substituted with halogen, nitro, alkyl, and alkoxy, and when Y is hydrogen, halogen and phenyl and Z is hydrogen or phenyl A is not phenyl, alkaryl or naphthyl;
Y is hydrogen, fluorine, chlorine, bromine, phenyl, naphthyl, phenylthio, substituted phenyl or substituted phenylthio having one or more substituents, said substituents being fluorine, chlorine, bromine, nitro, alkyl having 1 to 5 carbon atoms, cycloalkyl having 5 or 6 carbon atoms, phenyl, alkoxy having 1 to 3 carbon atoms, alkylthio having 1 to 3 carbon atoms, alkylenedioxy having 1 or 2 carbon atoms, or halomethyl having 1 to 3 halogen atoms wherein the halogen is fluorine, chlorine or bromine; and Z is hydrogen, phenyl or substituted phenyl having one or more substituents, said substituents being fluorine, chlorine, bromine, nitro, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 3 carbon atoms, or halomethyl having 1 to 3 halogen atoms wherein the halogen is fluorine, chlorine or bromine.

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Of the foregoing new compounds, a preferred class is represented by those wherein A is phenyl or phenyl substituted with fluorine, chlorine, bromine, alkyl having 1 to 5 carbon atoms, cyclopentyl, phenyl, trifluoromethyl, methoxy and methylthio; Y is hydrogen, phenyl, phenylthio, substituted phenyl and phenylthio groups substituted with chlorine, nitro and methoxy, and Z is hydrogen, phenyl or phenyl substituted with fluorine, chlorine and methoxy.

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Also of interest are compounds wherein Y and/or Z of the above formula represent such substituents as polycyclic aryl groups having more than lO carbon atoms, or phenylsulfonyl (unsubstituted or substituted with such moieties as halogen, alkyl, alkoxy, nitro, and the like), as well as compounds wherein Z has the m~an-ings halogen such as fluorine and chlorine, phenyl carrying substituents such as cycloalkyl, alkylenedioxy, or wherein Z may be naphthyl, phenylthio and substituted phenylthio.
m e invention is remarkable for its ability I to control the citrus rust mite on oranges, grapefruit _d s1mllar crops.

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Claims (55)

What is claimed is:

1. A substituted thiophene of the formula wherein a, X, Y and Z have one of the following sets of values:

2. The substitited thiophene of claim 1 which is 2-(methylthiophenyl)thiophene.

3. The substituted thiophene of claim 1 which is 2-(o-biphenylyl)thiophene.

4. The substituted thiophene of claim 1 which is 2-phenyl-5-(phenylthio)thiophene.

5. The substituted thiophene of claim 1 which is 2-pheny1-5-(phenylsulfonyl)thiophene.

6. The substituted thiophene of claim 1 which is 2-phenylthio-5-p-tolylthiophene.

7. The substituted thiophene of claim 1 which is 2-(p-isopropylphenyl)-5-(phenylthio)thiophene.

8. The substituted thlophene of claim 1 which is 2-(m-chlorophenyl)-5-(phenylthio)thiophene.

9. The substituted thiophene of claim 1 which is 2-phenylthio-5-(m-trifluoromethylphenyl)thiophene.

10. The substituted thiophene of claim 1 which is 2-(3,4-xylyl)thiophene.

11. The substituted thiophene of claim 1 which is 2-phenylthio-5-(3,4-xylyl)thiophene.

12. The substituted thiophene of claim 1 which is 3,5-dipheny1-2-(phenylthio)thiophene.

13. The substituted thiophene of claim 1 which 3 2-(p-bromophenyl)-5-(m-nitrophenylthio)thiophene.

14. The substituted thiophene of claim 1 which is 2-p-anisyl-5-(phenylthio)thiophene.

15. The substituted thiophene of claim 1 which is 2-(p-chlorophenylthio)-5-phenylthiophene.

16. A method of controlling acarid or insect pests comprising contacting the acarid or insect with an acaricidal or insecticidal amount of a sub-stituted thiophene as in claim 1.

17. The method of claim 16 in which the pests which are contacted with the substituted thiophene are mites located on plant life.

18. The methold of claim 17 in which the sub-stituted thiophene is 2-(p-methylthlophenyl)thiophene.

19. The method of claim 17 in which the sub-stituted thiophene is 2-(o-biphenylyl)thiophene.

20. The method of claim 17 in which the sub-stituted thiophene is 2-pheny1-5-(phenylthio)thiophene.

21. The method of claim 17 in which the sub-stituted thiophene is 2-phenyl-5-(phenylsulfonyl)thiophene.

22. The method of claim 17 in which the substituted thiophene is 2-phenylthio-5-p-tolylthiophene.

23. The method of claim 17 in which the sub-stituted thiophene is 2-(p-isopropylphenyl)-5-(phenylthio)-thiophene.

24. The method of claim 17 in which the sub-stituted thiophene is 2-(m-chlorophenyl)-5-(phenylthio)-thiophene.

25. The method of claim 17 in which the substituted thiophene is 2-phenylthio-5-(m-trifluoromethylphenyl)-thiophene.

26. The method of claim 17 in which the sub-stituted thiophene is 2-(3,4-xylyl)thiophene.

27. The method of claim 17 in which the sub-stituted thiophene is 2-phenylthio-5-(3,4-xylyl)thio-phene.

28. The method of claim 17 in which the sub-stituted thiophene is 3,5-diphenyl-2-(phenylthio)thio-phene.

29. The method of claim 17 in which the sub-stituted thiophene is 2-(p-bromophenyl)-5-(m-nitro-phenylthio)thiophene.

30. The method of claim 17 in which the sub-stituted thiophene is 2-p-anisyl-5-(phenylthio)thiophene.

31. The method of claim 17 in which the sub-stituted thiophene is 2-(p-chlorophenylthio)-5-phenyl-thiophene.

CLAIMS SUPPORTED BY SUPPLEMENTARY DISCLOSURE

32. A substituted thiophene of the formula wherein A, Y and Z may be the same or different and are as follows:
A is phenyl, naphthyl or phenyl substituted with one or more radicals selected from fluorine, chlorine, bromine, nitro, alkyl having 1 to 5 carbon atoms, cyclo-alkyl having 5 to 6 carbon atoms, phenyl, alkoxy having 1 to 3 carbon atoms, alkylenedioxy having 1 to 2 carbon atoms, alkylthio having 1 to 3 carbon atoms, and halo-methyl carrying 1 to 3 atoms selected from fluorine, bro-mine and chlorine, provided that when Y and Z are hydro-gen A is not phenyl substituted with halogen, nitro, alkyl, or alkoxy, and when Y is hydrogen, halogen or phenyl and Z
is hydrogen or phenyl A is not phenyl, alkylphenyl or naph-thyl;
Y is hydrogen, fluorine, chlorine, bromine, phenyl, naphthyl, phenylthio, phenylsulfone,substituted phenyl substituted phenylthio having one or more substituents, said substituents being fluorine, chlorine, bromine,nitro, alkyl having 1 to 5 carbon atoms, cycloalkyl having 5 or 6 carbon atoms, phenyl, alkoxy having 1 to 3 carbon atoms, alkylthio having 1 to 3 carbon atoms, alkylenedioxy having 1 or 2 carbon atoms, or halomethyl having 1 to 3 halogen atoms wherein the halogen is fluorine, chlorine or bromine;and Z is hydrogen, phenyl or substituted phenyl having one or more substituents, said substituents being fluorine, chlorine, bromine, nitro, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 3 carbon atoms, or halomethyl having 1 to 3 halogen atoms wherein the halogen is fluorine, chlorine or bromine.

33. The substituted thiophene of claim 32 where-in A is phenyl or phenyl substituted with fluorine, chlorine, bromine, alkyl having 1 to 5 carbon atoms, cyclopentyl, phenyl, trifluoromethyl, methoxy or methylthio; Y is hydro-gen, phenyl, phenylthio, substituted phenyl or substitued with chlorine, nitro or methoxy; and Z is hydro-gen, phenyl or phenyl substituted with fluorine, chlorine or methoxy.

34. The substituted thiophene of claim 32 which is 5-p-butylphenyl-2,3-diphenylthiophene.

35. The substituted thiophene of claim 32 which is 5-m-methoxyphenyl-2,3-diphenylthiophene.

36. The substituted thiophene of claim 32 which is 5-p-methoxyphenyl-2,3-diphenylthiophene.

37. The substituted thiophene of claim 32 which is 5-p-fluoropheny1-2,3-diphenylthiophene.

38. The substituted thiophene of claim 32 which is 5-(3-fluoro-4-methoxyphenyl)-2,3-diphenylthiophene.

39. The substituted thiophene of claim 32 which is 5-o-chloropheny1-2,3-diphenylthiophene.

40. The substituted thiophene of claim 32 which is 5-p-chlorophenyl-2,3-diphenylthiophene.

41. The substituted thiophene of claim 32 which is 2,3-bis(p-methoxyphenyl)-5-p-tolylthiophene.

42. The substituted thiophene of claim 32 which is 5-(2,4-dimethoxyphenyl)-2,3-diphenylthiophene.

43. A method of controlling acarid or insect pests comprising contacting the acarid or insect pests with an acaricidal or insecticidal amount of a substituted thiophene as in claim 32.

44. The method of claim 43 wherein A is phenyl or phenyl substituted wlth fluorine, chlorine, bromine, alkyl having 1 to 5 carbon atoms, cyclopentyl, phenyl, trifluoromethyl, methoxy or methylthio; Y is phenyl, phenylthio, substituted phenyl or phenylthio substituted with chlorine, nitro or methoxy, and Z is hydrogen, phenyl or phenyl substituted with fluorine, chlorine or methoxy.

45. The method of claim 43 wherein the pests which contacted with the substituted thiophene are mites located on plant life.

46. The method of claim 43 in which the substituted thiophene is 5-p-butylphenyl-2,3-diphenylthiophene.

47. The method of claim 45 in which the substituted thiophene is 5-m-methoxyphenyl-2,3-diphenylthiophene.

48. The method of claim 45 in which the substituted thiophene is 5-p-methoxypheny1-2,3-diphenylthiophene.

49. The method of claim 45 in which the substituted thiophene is 5-p-fluoropheny1-2,3-diphenylthiophene.

50. The method of claim 45 in which the substituted thiophene is 5-(3-fluoro-4-methoxypheny1)-2,3-diphenylthio-phene.

51. The method of claim 45 in which the substituted thiophene is 5-o-chloropheny1-2,3-diphenylthiophene.

52. The method of claim 45 in which the substituted thlophene is 5-p-chloropheny1-2,3-diphenylthiophene.

53. The method of claim 52 in which the mites are citrus rust mites.

54. The method of claim 45 in which the substituted thiophene is 2,3-bis(p-methoxypheny1)-5-p-tolylthiophene.

55. The method of claim 45 in which the substituted thiophene is 5-(2,4-dimethoxyphenyl)-2,3-diphenylthiophene.