GB1598096A - Insect repellent compounds - Google Patents

Insect repellent compounds Download PDF

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GB1598096A
GB1598096A GB20816/80A GB2081680A GB1598096A GB 1598096 A GB1598096 A GB 1598096A GB 20816/80 A GB20816/80 A GB 20816/80A GB 2081680 A GB2081680 A GB 2081680A GB 1598096 A GB1598096 A GB 1598096A
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azaspiro
urea
alkyl
double bond
group
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Rohm and Haas Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/20—Spiro-condensed ring systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/08—Amines; Quaternary ammonium compounds containing oxygen or sulfur
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/75—Reactions with formaldehyde
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/28—Saturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings
    • C07C47/36—Saturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/54—Spiro-condensed
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
    • C07D211/12—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with only hydrogen atoms attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
    • C07D211/16—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with acylated ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/34—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/70—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
    • C07D295/215—Radicals derived from nitrogen analogues of carbonic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/26—Radicals substituted by doubly bound oxygen or sulfur atoms or by two such atoms singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/30—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/10—Spiro-condensed systems

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental Sciences (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Catching Or Destruction (AREA)

Description

PATENT SPECIFICATION (II 1) 1 598 096
( 21) Application No 20816/80 ( 22) Filed 12 Dec 1977 ( 62) Divided out of No1598095 1 ( 31) Convention Application No 751932 ( 32) Filed 17 Dec 1976 ( 31) Convention Application No 839159 ( 32) Filed 3 Oct 1977 in À ( 33) United States of America (US) ( 44) Complete Specification published 16 Sept 1981 ( 51) INT CL 3 C 07 D 211/00 AOIN 43/00 C 07 D 207/02 405/04 C 07 C 47/32 121/46 C 07 D 317/14 (C 07 D 405/04 211/00 309/00) ( 52) Index at acceptance C 2 C 1175 1177 1178 1179 1200 1342 1492 1531 1532 1672 200 211 215 220 221 223 225 226 227 22 X 22 Y 246 247 248 250 251 253 257 25 Y 27 X 280 281 28 X 290 29 X 29 Y 304 305 30 Y 313 316 31 Y 326 335 339 342 34 Y 350 360 361 362 364 366 368 36 Y 37 X 43 X 485 492 509 50 Y 579 584 594 623 624 628 62 X 62 Y 652 656 658 65 X 662 676 678 67 X 69 Y 73 Y 770 776 77 Y 805 80 Y AA BF BG KF KK MB MD NS TC WH WL ZB ZL ZM ( 54) NOVEL INSECT REPELLENT COMPOUNDS ( 71) We, ROHM AND HAAS COMPANY, a Corporation organized under the laws of the State of Delaware, United States of America, of Independence Mall West, Philadelphia, Pennsylvania 19105, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly 5
described in and by the following statement:-
This invention is concerned with a novel class of insect repellent compounds.
The search for insect repellents which have a combination of excellent repellency, high residual activity and essentially no toxicity is a continuing one due to recognition of the possible toxicity to animals or humans of many known 10 insecticides Since long lasting repellents avoid these problems with insecticides and provide essentially the same results, compounds having these effects are in great demand.
In accordance with the present invention, there are provided insect repelling compounds of the formula 15 (x) R 1 | nz (CH 2)n RV 2/\ C 1 3 (C 2)n N-R where R 1 is H, alkyl or alkenyl, R 2 is H, alkyl, cycloalkyl, alkoxycarbonyl or aralkyl, but may also be mononuclear aryl when R' is alkyl or alkenyl, or 20 R 1 and R 2 together represent a straight or branched chain alkylene or alkenylene group, or an alkyleneoxyalkylene group, or an alkylene group containing a hydroxy or alkoxy substituent, X is alkyl, alkoxy, alkoxycarbonylalkyl or cyano, R 3 is alkyl or -C(=Y)NR 4 R 5 where Y is O or S, R 4 is H and R 5 is alkyl, 25 cycloalkyl, other than nortricyclyl, alkenyl, alkoxycarbonyl or alkoxycarbonylalkyl or R 4 and R 5 together represent an alkylene group, mis 0, I or 2, n is I or 2, n' is 1 or 2, 30 with the provisos i) that the heterocyclic ring shown in the formula may contain a single double bond, in which case R 3 will be absent when the double bond is a carbonnitrogen double bond, but excluding compounds containing a carbonnitrogen double bond and where N and n' are both I and R' and R 2 are joined to form, together with the attached carbon atom, a 5,5dimethylcyclopentyl radical; ii) that when the ring shown in the formula is saturated then either X is alkoxycarbonylalkyl and m is I or 2 or R 3 is a -C(=Y)NR 4 R 5 group; 5 iii) that when R' and R 2 are both hydrogen R 3 is a -C(=Y)NR 4 R 5 group:
iv) that when R 4 and R 5 jointly represent alkylene then at least one of R' and R 2 is other than hydrogen or m is 1 or 2.
Also provided are acid addition and quaternary ammonium salts of the above compounds 10 In the case of compounds of Formula I modified in that the heterocyclic ring shown in Formula I contains a double bond, one of R', R 2 and R 3 will be absent and/or at least one of the -CH 2 groups shown will lack a hydrogen atom.
Acid addition salts and quaternary ammonium salts may be formed from organic or inorganic acids such as citric acid or hydrochloric acid or quaternizing 15 agents such as alkyl halides, alkyl sulfates or aryl sulfonates, e g methyl chloride, ethyl iodide or p-toluene sulfonate The above salts may be prepared by methods well known in the art.
When, in Formula I, R' is alkyl it may, for example, be (C 1-C,)alkyl such as methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 20 nonyl When R' is alkenyl, it may, for example, be (C 2-C,)alkenyl such as allyl.
When R 2 is alkyl, it may be any of those alkyl groups listed above for R' When R 2 is cycloalkyl, this group may contain from 4 to 6 nuclear carbon atoms such as cyclobutyl, cyclopentyl and cyclohexyl When R 2 is alkoxycarbonyl it may contain from 2-6 carbon atoms as in ethoxycarbonyl When R 2 is aralkyl it may, for 25 example, be benzyl or benzyl substituted in the ring with (C,-Cs)alkyl When R 2 is mononuclear aryl, it may typically be phenyl or phenyl substituted with (C 1Cs)alkyl.
When R' and R 2 are joined they may, together with the carbon atom to which they are attached, form a heterocyclic group of from 5 to 11 nuclear carbon atoms, 30 the rings of these groups being optionally bridged by an alkylene group Examples of such groups are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclohexenyl, cycloheptenyl, cyclononenyl, bicyclo ( 2 2 1)heptyl (norbornyl), 5-norborn-2-yl and tetrahydropyranyl When R' and R 2 are joined to form a ring which is substituted, the substituent(s) may, for example, be one or 35 more hydroxy, (C,-Cs)alkoxy or (C,-Cs)alkyl groups.
When R 3 is alkyl, it may contain from I to 5 carbon atoms such as methyl, ethyl, propyl, butyl or pentyl When R 3 is the group -C(=Y)NR 4 Rs and R 4 is hydrogen, R 5 may, for example, be (C,-Cs)alkyl, (C 4 C 6)cycloalkyl, (C 2Cs)alkenyl or alkoxycarbonyl of up to 60 carbon atoms such as methoxycarbonyl 40 and ethoxycarbonyl When R 4 and R 5 are joined together, they may form, together with the nitrogen atom to which they are attached, a 5 to 7 membered saturated heterocyclic ring e g pyrrolidinyl, piperidyl and homopiperidyl X may, for example, be (C,-Cs)alkyl such as methyl, ethyl, propyl, butyl and pentyl; (C,Cs)alkoxy atoms such as methoxy, ethoxy, propoxy, butoxy and pentoxy; or 45 alkoxycarbonylalkyl containing up to 12 carbon atoms, for example, methoxycarbonylmethyl or butoxycarbonylethyl.
A sub-class of compounds useful in the invention is made up of compounds of Formula I above, wherein, in Formula I, R' is hydrogen, alkyl or alkenyl: R 2 is hydrogen, alkyl or cycloalkyl; or R' and R 2 are joined and form, together with the 50 carbon atom to which they are attached, a cycloalkyl or cyclo(alkoxyalkyl) residue or a cycloalkylalkyl residue bridged with a methylene group; R 3 is alkyl or the group -C(=Y)NR 4 R 5 wherein Y is O or S and (a) R 4 is hydrogen and Rs is alkyl, alkenyl or alkoxycarbonyl or (b) R 4 and Rs are joined and form, together with the nitrogen atom to which they are attached, a saturated heterocyclic group; X is 55 alkyl, alkoxy, alkoxycarbonylalkyl or cyano, m is 0 or an integer of I or 2 and N and n' are integers of I or 2.
Another sub-class of compounds are those as just defined but in which the heterocyclic ring shown in Formula I contains a double bond, there being excluded from this sub-class compounds wherein, in the ring shown in Formula I, there is a 60 carbon-nitrogen double bond, N and n' are both 1 and R' and R 2 are joined to form, together with the attached carbon atom, a 5,5-dimethylcyclopentyl residue A third sub-class of compounds are those belonging to the two sub-classes just described but in which R 2 is hydrogen and R 3 is the group -CON Halkyl and n' is 1.
The most preferred compounds are of the formula 65 1,598,096 1 O R 1 R 2(X')m' (CH) R Ru > | / ( IA)n R RR R 9 N -C-N-s R wherein (a) R 7 is hydrogen and R 8 is (C 1-C 5)alkyl or (C 3-C,1) alkoxycarbonylalkyl or (b) R 7 and R 8 are joined to form an alkylene group which together with the nitrogen atom to which it is attached forms a 5 or 6membered ring: X' is (C,-C 5)alkyl or (C 3-C 1,)alkoxycarbonylalkyl; R 9, RI , R 1 ' and R 12 are 5 either hydrogen (except when R 7 and R 8 are joined, in which case at least one of R 9, R' , R"' and R 12 is other than hydrogen, or m' is 1 or 2) or, the two members in one of the pairs R 9/R'0 and R"/R 12 are joined and form, together with the carbon atom to which they are attached form a cycloalkyl ring of 5 to 11 nuclear atoms, N is 1 or 2 and m' is 0, 1 or 2, and compounds of Formula IA modified in that the 10 heterocyclic ring shown contains a single double bond, the group C(=O)NR 7 R 8 being absent when that double bond is a carbon-nitrogen double bond.
When, in Formula IA, R 8 is alkyl, it is typically (C,-C 5)alkyl such as methyl, ethyl, propyl, butyl or pentyl When R 8 is alkoxycarbonylalkyl it may, for example, be methoxycarbonylmethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl or 15 butoxycarbonylethyl When R 7 and RI are joined, they can form, together with the nitrogen atom to which they are attached, a saturated heterocyclic ring such as pyrrolidyl or piperidyl Especially preferred are those compounds wherein R 7 and R 8, together with the nitrogen atom to which they are attached, form a pyrrolidinyl and piperidinyl residue and N is 1 These compounds exhibit particularly good 20 insect repellent and residual action.
Particularly preferred compounds are: 2 azaspiro l 5 5 l undec 7 enylcarboethoxymethyl urea ( 2 (ethoxycarbonyl methylcarbamoyl) 2azaspiro l 5 51 undec 7 ene); 2 azaspiro l 5 5 l undec 7enylpentamethylene urea ( 2 (N,N pentamethylene carbamoyl) 2 25 azaspiro l 5 5 lundec 7 ene); 2 azaspiro l 5 5 lundec 7 enyl N,N tetramethylene urea ( 2 (N,N tetramethylenecarbamoyl) 2 azaspiro l 5 5 l undec 7 ene); 2 azaspiro l 5 5 l undecyltetramethylene urea ( 2 (N,N tetramethylenecarbamoyl) 2 azaspiro l 5 5 l undecane); ethyl alpha ( 2 methyl 2 azaspiro l 5 5 lundec 7 ene)acetate; 2 azaspiro l 10 5 l 30 hexadec 1 ene; 2 azaspiro l 5 5 lundeca 1,7 diene; 2 azaspiro l 7.5 ltridec I ene; 2 azaspiro l 5 5 lundec 1 ene; N N butyl N' 3,3 diethylpentamethylene urea; 2 azaspiro l 5 5 l undec 7 enylallyl urea ( 2 (allylcarbamoyl) 2 azaspiro l 5 5 lundec 7 ene); ethyl a ( 2 N butyl 2 azaspiro l 5 5 lundec 7 ene)acetate; 2,6 dimethylpiperidyl 35 N butyl urea (N (n butylcarbamoyl) 2,6 dimethylpiperidine); 2,6dimethylpiperidyl N carbo N butoxymethyl urea (N (n butoxycarbonylmethylcarbamoyl) 2,6 dimethylpiperidine; and 3 azaspiro l 5.5 l undecyltetramethylene urea ( 3 (N,N tetramethylenecarbamoyl) 3 azaspiro l 5 5 lundecane 40 The compounds concerned in this invention are prepared in a variety of ways depending upon the size of the ring or the substituent desired Compounds such as those having the formula:
I (X)m (C R H (CH) i n R 2 XCH = N A wherein R', R 2, X, m and N are as defined above and are prepared by treating a 45 compound of the formula:
X \,,(CH 2)n N HCN R 2/ \ O >g 2 B 1,598,096 with an alkali metal hydride such as lithium aluminum hydride Any solvent which is inert or substantially inert to the reactants may be employed e g ethers such as diethylether and tetrahydrofuran The reaction may be conducted at a temperature in the range of from 0 to 100 C for a period of from 15 minutes to 5 hours; however, the reaction is generally initiated at room temperature and then brought to the reflux temperature of the particular solvent employed.
The preparation of compounds according to this invention and which have an R 3 substituent is illustrated by the following reaction scheme.
(x) a m C R 5 NNCO or y R 4 R NCC 1 (X) R>K RI m (CH 2)n (VH 2)n' (C H D Raney Nickel (H 2) R 2A The reaction with an isocyanate (R 5 N=C=O) is generally conducted at a temperature in the range of from 0 to 50 C in a suitably inert solvent such as benzene.
The reaction with the carbamoyl halide or thiocarbamoyl halide y 11 (R 4 R 5 NCCI), 1,598,096 wherein R 4, Rs and Y are as defined above, is generally conducted at a temperature in the range of from O C to room temperature in a suitably inert solvent such as benzene.
The hydrogenation of products A and E in the above reaction scheme with Raney nickel is carried out in a hydrogenator at 40 to 50 psi of hydrogen using a suitable solvent such as methanol or ethanol.
The products identified as B in the following reaction scheme can be employed in the preparation of the products identified as A in the foregoing reaction scheme The products identified as B also have insect repellent activity and are prepared as follows:
R 1 when n= 1 R 2 ' TSC 12/Na CNW R CH 2 OH /' "C /(CH 2)n CN B k.
F HOCH 2 CH 20 H/TSOH' when n= 2 HOCH 2 CH 2 OH/TSOH' R % / CH 2 CH 2 CN R 2/ CHO G CH 2 =CHCN Sodium Hydroxide Dioxane R 1 CH 2 OH R 2 2 CHO R CHO ( HCHO Sodium Hydroxide Methanol R 1 R/ CHO R 2 H 1 = Toluenesulfonic acid.
2 = Toluenesulfonyl chloride.
Product F in the immediately foregoing reaction scheme is treated with ptoluenesulfonyl chloride (TSCI) at a temperature in the range of from O C to room temperature with O C being the preferred temperature using pyridine as the solvent The ethylene acetal radical is introduced in the molecule by treating the correspondingly substituted aldehyde product (G and H) with ethylene glycol containing p-toluenesulfonic acid (TSOH) as a catalyst Solvents which may be employed include benzene and toluene The reaction is generally conducted at the reflux temperature of the particular solvent employed.
The preparation of those compounds, wherein X is alkyl, alkoxycarbonylalkyl 1,598,096 s N 6 1,598,096 6 or cyano, R 3 is alkyl and there is no internal ring double bond, is accomplished by methods well-known to those skilled in the art and is illustrated below.
R < ( 2 n J 12 R 2 (CH)n 1 R 3 I R 1 (CH 2)n 2 X 1 + 2 R (CH 2 n; N R I Na O Na CN Dialkyl Alkyl 4 4 malonate (X) R 1 < (CH 23 n R 2 (CH 2)n N R 3 The compounds concerned in this invention and compositions containing them can be employed in a wide range of amounts and using a wide variety of 5 carriers or diluents such as are conventionally used in the art.
The amount of active compounds employed in the insect repellent compositions can vary from 0 1 to 90 percent based on the weight of the composition and will depend upon the intended use Usually, the compositions will contain between 0 1 to 10 weight percent of one or more of the active compounds 10 and the latter will usually be used in intimate mixture with a carrier.
When it is desired to use the insect repellent composition directly (i e, without further dilution), the amount of the compound present in the composition will usually be from 0 1 to 5 0 percent based on the total weight of the composition.
When it is desired to formulate a concentrated composition, i e, one suitable for 15 dilution prior to end use, the compounds will usually be present in the composition in an amount of from 0 5 to 90 weight percent.
In general, the repellent compositions will contain a carrier and from 0 1 to ', usually 0 1 to 10 %, by weight of one or more of the active compounds concerned in the invention 20 The carrier employed can be any of those conventionally used in insect repellent formulations, particularly those which are in no way harmful to the environment The carrier can be any one of a variety of organic and inorganic liquid, solid, or semi-solid carriers or carrier formulations conventionally used in insect repellent products and can be a mixture of such carriers 25 Examples of organic liquid carriers include liquid aliphatic hydrocarbons such as pentane, hexane, heptane, nonane, decane and their analogs, as well as liquid 1,598 096 aromatic hydrocarbons Examples of other liquid hydrocarbons include oils produced by the distillation of coal and the distillation of various types and grades of petrochemical stocks including kerosene oils which are obtained by fractional distillation of petroleum at between 840 C and 1300 C and which usually have a flash point between 180 C and 321 C 5 Other petroleum oils include those generally referred to in the art as agricultural spray oils which are light and medium spray oils consisting of the middle fractions in the distillation of petroleum and have a viscosity in the range of from about 40 to 85 sec Saybolt at 41 C and are only slightly volatile These oils are usually highly refined and contain only minute amounts of unsaturated compounds 10 as measured by standard sulfonation tests The customary sulfonation range of such oils is between 90 % and 94 % of unsilfonatable residue These oils are paraffin oils and can be emulsified with water and an emulsifier and diluted to lower concentrations and used as sprays Tall oils obtained from sulfate digestion of wood pulp, like paraffin oils, also can be employed 15 In addition to the above-mentioned liquid hydrocarbons, the carrier can contain conventional emulsifying agents e g, a non-ionic surfactant such as an ethylene oxide condensate of octyl phenol or an anionic surfactant such as an alkali metal salt of an alkylbenzenesulfonic acid) Such emulsifiers are used to permit the composition to be dispersed in and diluted with water for end use application 20 When paraffin oils are employed as carriers in the insect repellent compositions, they are usually used in conjunction with an emulsifier, the mixture being diluted with water, immediately prior to the end-use application Other suitable paraffin oils, particularly those used with emulsions, are referred to in the art as heavy paraffin oils and usually have a viscosity greater than 85 sec Saybolt at 25 C.
Other advantageous organic liquid carriers cafn include liquid terpene hydrocarbons and terpene alcohols such as alpha-pinene, dipentene, and terpineol.
Still other liquid carriers include organic solvents such as aliphatic and aromatic alcohols, esters, aldehydes, and ketones Aliphatic monohydric alcohols include 30 methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and t-butyl alcohols Suitable dihydric alcohols include glycols such as ethylene and propylene glycol and the pinacols (alcohols having the empirical formula: C 6 H 12 (OH)2) Suitable polyhydroxy alcohols include glycerol, arabitol, erythritol, and sorbitol Suitable cyclic alcohols include cyclopentyl and cyclohexyl alcohols 35 Conventional aromatic and aliphatic esters, aldehydes and ketones can be employed and are usually used in combination with the above-mentioned alcohols.
Still other liquid carriers including high-boiling petroleum products, such as mineral oil and higher alcohols, such as cetyl alcohol can also be employed.
Additionally, conventional "stabilizers" or "synergizers" such as t-butyl sulfinyl 40 dimethyl dithiocarbamate, can be employed in conjunction with, or as a component of, the carriers used in the compositions of this invention.
Solid carriers which can be used include finely divided organic and inorganic solid materials Suitable finely divided solid inorganic carriers include siliceous minerals such as clay, including bentonite, attapulgite, fuller's earth, diatomaceous 45 earth, kaolin, mica, talc, and finely divided quartz, as well as synthetically prepared by siliceous materials, such as silica aerogels and precipitated and fume silicas.
Examples of finely divided solid organic carrier materials include cellulose, sawdust and synthetic organic polymers.
Examples of semisolid carriers include petroleum jelly and lanolin and 50 mixtures of liquid and solid carriers which provide semi-solid products.
The repellent compositions can be employed as such or can be diluted with suitable liquids or solids to repel, e g from human beings, animal livestock or their environments, common flying and crawling insect pests, such as roaches, moths, house and stable flies, termites, flour beetles, bean beetles, weevils, ticks, chinch 55 bugs, lice, ants, chiggers and mosquitoes The repellent compositions when applied to an insect environment, effectively repel the insects.
Insect pests can be repelled by contacting the surfaces on which the insects may alight or crawl with a liquid, solid or semi-solid composition The contact can be accomplished directly (e g, by atomizing the composition into the air as a liquid 60 or as a dust so that the material will fall on the desired surface) For such uses, there are preferably used dust or spray dispensing devices such as pump-type applicators or aerosol cans charged with an insect repellent composition containing one or more of the repellent compounds concerned in this invention.
By way of further example, insect-infested animals, such as dogs with fleas or 65 1,598,096 poultry with lice, cows with ticks may be treated with the insect repellent compositions by contacting the fur and/or feathers and the lice, fleas and ticks contained therein, thereby ending the insect infestation Also, granaries and silos can be treated with the compositions of this invention, prior to grain storage, to present beetle, weevil, and other insect infestations in the grain to be subsequently 5 stored Food packaging elements or containers including fiber, cardboard or wooden shipping containers or storage bins, flour sacks, and the like, can be treated with the compositions of this invention to prevent insect infestation.
The working examples given immediately below and subsequently in this specification illustrate the preparation of compounds concerned in this invention 10
EXAMPLE 1
2 Azaspiro l 5,51 undec I -ene (Compound I) Step A 1 ( 2 Cyanoethyl) I formylcyclohexane To a stirred solution of cyclohexane-carboxaldehyde ( 100 g: 0 89 mole) and 50 % potassium hydroxide solution ( 10 2 g) is added, dropwise, acrylonitrile ( 50 4 g: 15 0.95 mole) over the course of one hour, maintaining the reaction temperature between 50 -60 C by occasional cooling After all has been added, the mixture is stirred for an additional one hour until the exotherm ceases and then heated to 0-60 C for 30 minutes The product is acidified with dilute hydrochloric acid, taken up into ether, washed with water, dried (Mg SO 4) and distilled to afford 38 %' 20 of colorless I ( 2 cyanoethyl) I formylcyclohexane ( 55 4 g), b p 142 146 C/5 mm.
Step B 1 ( 2 Cyanoethyl) 1 formylcyclohexane Ethylene Acetal A solution containing 1 ( 2 cyanoethyl) I formylcyclohexane ( 55 4 g; 0 34 mole), ethylene glycol ( 27 9 g; 0 45 mole) andp-toluenesulfonic acid (TSA) 100 25 mg) in dry benzene ( 250 ml) is heated under reflux with a Dean Stark tube for 12 hours The solution is cooled, diluted with ether, washed with water and dried.
Removal of the solvent affords 98 % of 1 ( 2 cyanoethyl) I formylcyclohexane ethylene acetal ( 69 4 g) as a colorless mobil liquid.
Step C 2 Azaspiro l 5,5 lundec I ene 30 To a solution of lithium aluminum hydride (LAH) ( 12 g; 0 32 mole) in dry tetrahydrofuran ( 250 ml) is added, dropwise and while stirring, I ( 2cyanoethyl) 1 formylcyclohexane ethylene acetal ( 41 8 g; 0 20 mole) in tetrahydrofuran ( 50 ml) The mixture is heated under reflux for three hours, after which time the solvent is removed under reduced pressure and ether added ( 500 35 ml) The excess hydride is decomposed and the precipitated salts are removed by filtration The filtrate is extracted several times with dilute hydrochloric acid and the acidic extract is allowed to stand at room temperature for one hour The acidic extract is then made strongly alkaline with a dilute sodium hydroxide solution and extracted with ether The ether is dried and distilled under atmospheric pressure 40 and the residual liquid distilled to afford 53 % of 2 azaspiro l 5,51 undec I ene ( 16 g) as a colorless mobil liquid, b p 65 -67 C/0 70 mm.
EXAMPLE 2
2 Azaspiro l 5,4 ldec I ene (Compound 2) Step A -I Formyl 1 hydroxymethylcyclohexane 45 Methanol is added to a suspension of 37 % formaldehyde solution ( 69 ml) and cyclohexanecarboxaldehyde ( 100 g; 0 89 mole) to afford a homogeneous solution.
The mixture is cooled to O C and a sodium hydroxide solution (IN; 67 ml) is added with stirring over the course of 15 minutes The mixture is allowed to warm to room temperature and is stirred at 25 C overnight The solution is then concentrated, 50 diluted with water and extracted with ether The ether extract is dried, evaporated in vacuo and the residual colorless liquid is distilled to afford 51 % of I formyl 1 hydroxymethylcyclohexane ( 65 g), b p 120 0-125 C/0 90 mm.
Step B I Formyl I hydroxymethylcyclohexane Cyclic Ethylene Acetal A solution containing I formyl 1 hydroxymethylcyclohexane ( 65 g; 0 46 55 mole) and ethylene glycol ( 34 1 g; 0 55 mole) in benzene ( 350 ml) containing ptoluenesulfonic acid ( 100 mg) is heated under reflux with continuous separation of water for three hours and then cooled The benzene solution is washed with water, dried over magnesium sulfate and concentrated to afford 90 % of I formyl I hydroxymethylcyclohexane cyclic ethylene acetal ( 77 g) as a colorless liquid 60 1,598,096 Step C 1 Formyl I p toluenesulfonyloxy methylcyclohexane Cyclic Ethylene Acetal A solution containing 1 formyl 1 hydroxymethylcyclohexane cyclic ethylene acetal ( 77 g; 0 41 mole) in anhydrous pyridine ( 300 ml) is cooled to O C and p-toluenesulfonyl chloride (TSCL) ( 95 5 g; 0 50 mole) is added in portions with 5 stirring over 10 minutes The mixture is then stored at O C for two days, followed by dilution with water The separated oil is extracted with ether, washed with water, dried and concentrated to afford 93 % of 1 formyl 1 ptoluenesulfonylmethyl cyclohexane cyclic ethylene acetal ( 130 g) as a colorless oil 10 Step D 1 Cyanomethyl I formylcyclohexane Cyclic Ethylene Acetal A solution of I formyl I p toluene sulfonyloxymethylcyclohexane cyclic ethylene acetal ( 130 g; 0 38 mole) in dimethyl sulfoxide ( 200 ml) is added dropwise to a suspension of sodium cyanide ( 20 6 g; 0 42 mole) in dimethyl sulfoxide ( 300 ml) with stirring under nitrogen at 90 -95 C over a period of 15 15 minutes After the addition is complete, the mixture is maintained at 90 C overnight The dark solution is cooled, diluted with an equal volume of ice water and extracted with ether The ether extract is washed with water, dried and concentrated to afford 60 0 g ( 81 % yield) of 1 cyanomethyl 1 formylcyclohexane cyclic ethylene acetal ( 60 g) as a dark oil 20 Step E 2 Azaspiro l 5,4 ldec 1 ene A solution containing 1 cyanomethyl 1 formylcyclohexane cyclic ethylene acetal ( 60 g; 0 31 mole) in dry tetrahydrofuran ( 50 ml) is added dropwise over 30 minutes to a suspension of lithium aluminum hydride ( 13 3 g; 0 35 mole) in tetrahydrofuran ( 200 ml) with stirring After the addition is complete, the mixture is 25 heated under reflux for one hour, cooled and decomposed with aqueous sodium hydroxide solution after replacing the tetrahydrofuran with ether The resulting ether solution is extracted with a hydrochloric acid solution ( 2 N) The aqueous extract is washed once with ether and allowed to-stand at room temperature for one hour The aqueous solution is made strongly basic and extracted with ether The 30 ether extract is dried and distilled to afford 14 5 g ( 34 % yield) of 2 azaspiro l 5,4 l dec I ene ( 14 5 g) as a colorless mobile liquid, b p 45-47 C/4 5 mm.
The following reaction scheme indicates how compounds identified in Table 1 below may be prepared.
1,598,096 1,598,096 1 Preparation of corrpounds of the formula X CH Cflk O C 2 =W 2 " Catalyst CHC R 2 "" CHO (a) HOCH.
when (b) TS Ce.
n= I (c) Na CN CM CN R O C R 2., N XI HOCH 2 CH 2 OH TSA when n= 2 v X# R " I(CH 2)CHCN Ci H 20 H (a) LAH (b) acid (c) base X# RI (CM 2)n -H 1,598,096 TABLE '1
Comnound No.
S c.
i 5 (CH 2 2)7 -CH 2 C C 2 CH=CHCH 2CM 1 2 -CH-CH=CH-CH-CH 2 -CH(C 3)CH-2 CH HC 2 -(CM 2)6-(CH 2)10-(CH 2)5 -CH CH C(CH)=C(CH) CH 2 -CH CM CH 4 CHCH 2 2 '2 t 2 OH -(CH 2)3 CH(OC 2 H)CH 2_c 23 -25 2 -C -C 3 C CM 2 H 2 H 2 CH 22 CH 2 CH -CH -C 3 X 4-CM 3 n O 1,598,096 TABLE I (cont) Physical Characteristics Compound No B P / C /mm 3 103-105/2 4 85/4 5 75-80/ 85 6 74-75/ 20 7 70-72/ 30 8 127-130/ 10 9 60/ 05 75-77/ 25 11 130-140/ 30 12 130-140/ 55 13 85/ 25 14 40-41/ 35 45-47/ 15 16 35-37/ 15 17 105-108/ 20 18 84-87/ 10 19 72-74/ 20 Picrate M.P / C 186-189 154-155 5 140-144 183-186 177-178 162-164 5 157-158 5 135-137 128-129 5 180-183 115-117 110-112 75-79 147-149 5 Calc.
C H Elemental Analysis Found N C HN 52.93 5 92 13 72 52 81 6 06 13 8 50.79 4 79 14 81 50 59 4 82 14 8 52.31 4 65 14 35 52 03 4 63 14 7 52.04 5 14 14 28 51 78 5 11 14 2 51.77 5 62 14 21 51 82 5 82 14 5 55.99 6 71 12 44 56 30 6 96 12 7 51.77 5 62 14 21 51 91 5 86 14 6 53.20 5 46 13 79 53 13 5 38 13 6 47.12 48.91 50.25 48.91 55.74 53.73 4.75 5.47 5.80 5.47 7.13 4.51 14.66 47 49 4 80 15 0 15.2 49 30 5 68 15 38 14.65 50 17 6 02 14 64 15.21 48 73 5 53 15 52 12.38 54 59 7 13 12 58 13.93 53 81 4 56 13 83 EXAMPLE 3
Ethyl a ( 2 methyl 2 azaspiro l 5 5 lundec 7 ene) Acetate (Compound 21) Step A 2 Methyl 2 azoniaspiro l 5,5 lundeca 1,7 diene Iodide A solution of 2 azaspiro l 5 5 l undeca 1,7 diene ( 14 9 g: O 10 mole) is dissolved in dry benzene ( 150 ml) and methyl iodide ( 21 3 g; 0 15 mole) is added.
The mixture becomes warm and a solid separates The precipitate is filtered, washed with ether and air-dried to afford 27 0 g ( 93 % yield) of 2 methyl 2 azoniaspiro l 5 5 l undeca 1,7 diene iodide, m p 193 -194 C.
Step B Ethyl a ( 2 methyl 2 azaspiro l 5 5 lundec 7 ene)acetate A solution of sodium ethoxide in absolute ethanol ( 100 ml; 0 035 moie) is treated with ethyl malonate (DEM) ( 5 61 g; 0 035 mole) The ethanol is removed under reduced pressure and the resulting sodiomalonic ester is dissolved in dry dimethyl sulfoxide ( 50 ml)2 Methyl 2 azoniaspiro l 5 51 lundeca 1,7 diene iodide ( 8 73 g; 0 03 mole) is added in one portion and the mixture is stirred and heated at 90 -120 C for two hours, cooled, diluted with water and the separated oil is extracted with ether The ether extract is washed with water, dried and concentrated Distillation of the residual liquid yields 4 8 g ( 505, yield) of ethyl a ( 2 methyl 2 azaspiro l 5 5 lundec 7 ene)acetate, b p 108 C/0 40 mm.
By following substantially the procedure of Example 3 and by substituting the appropriate amine and iodide for those recited in Example 3, Compounds 2232 set forth in Table II are obtained.
TABLEII
R 1 R -R 3 2 2 H 5 Analysis Found N c H Calc.
c H Compound No.
Picrate R 3 13 P(OC /mm) mp"C R 2 N 22 -C 2 Hr, -C 2 H, 23 -CH 2 CH 2 CH=CHCH 224 -CH 2 CH 2 CH=CHCH 2-CH 2 CH 2 CH=CHCH 226 -CH 2 CHCH=CHCH,27 -CH 2 CH 2 CH=CHCH,28 -CHCH 2 CH=CHCH 229 -CHCH 2 CH 2 CH 2 C Hr-C 2 H, -CH 5 31 -C 2 H, -CH, 32 -C 2 H, -C 2 Hr, CH 3 C^ C 3 H, CA, C 5 HI, Co H 13 C 7 Hls CH 3 CA;C 3 H, C 4 HO90-93/35 114-115/0 15 118-120/0 15 126-0 15 132-134/0 15 ' 145-147/0 15 152-154/0 15 108-11010 15 75-77/007 101-105/0,45 110/025 127-128 139-141 164-167 133-135 51.06 53.43 54,35 55.163 6.43 6.12 6.34 6.56 11.91 11.33 11.02 10.72 51.24 53.63 53.97 55.25 6.62 6,38 6.32 6.74 12.26 11.54 11.27 11.26 A \ O pc 0 \ O c EXAMPLE 4
Alternative Procedure for Preparing Ethyl a l 2 methyl 2 azaspiro l 5 51 undec 7 enel acetate (Compound 21) To a solution containing ethyl bromoacetate ( 10 g; 0 06 mole) in dimethyl formamide ( 100 ml) is added zinc-copper couple ( 4 3 g) Heating and stirring are 5 initiated and 2 methyl 2 azoniaspiro l 5 51 undeca 1,7 diene iodide ( 8.73 g; 0 03 mole) is added in one portion The temperature of the resulting mixture is maintained at 100 C for 5 hours and cooled to room temperature The solution is diluted with an equal volume of water and treated with excess concentrated ammonium hydroxide Ether extraction, followed by drying over 10 magnesium sulfate and subsequent distillation affords 7 0 g ( 73 % yield) of ethyl a l 2 methyl 2 azaspiro l 5 5 lundec 7 enelacetate, b p 108 C/ 40 mm.
EXAMPLE 5
2 Azaspiro l 5 5 l undecyltetramethylene urea ( 2 (N,N tetramethylenecarbamoyl) 2 azaspiro l 5 51undecane) (Compound 15 35) A solution containing triethylamine ( 24 2 g; 0 24 mole) and pyrrolidine carbamoyl chloride ( 32 7 g; 0 24 mole) in benzene ( 200 ml) is treated dropwise, under ice cooling, with 2 azaspiro l 5 5 l undecane ( 36 72 g; 0 24 mole) After the addition is complete, the mixture is allowed to stir at room temperature for 2 20 hours The precipitated triethylamine hydrochloride is collected by filtration and the filtrate is concentrated and the residual viscous oil is distilled to afford 53 g ( 88 % yield) of 2 azaspiro l 5 5 l undecyltetramethylene urea, b p 132 C/ 30 mm.
EXAMPLE 6 25
2 Azaspiro l 5 51 undec 7 enylpentamethylene Urea ( 2 (N,Npentamethylenecarbamoyl) 2 azaspiro l 5 5 l undec 7 ene) (Compound 36) A solution containing triethylamine ( 101 g; 1 mole) and piperidylcarbamoyl chloride ( 148 g; I mole) in toluene ( 1 0 1) is treated dropwise under ice cooling with 30 2 azaspiro l 5 5 l undec 7 ene ( 151 g; I mole) After the addition is complete, the mixture is allowed to stir at room temperature for 2 hours The precipitated triethylamine hydrochloride is collected by filtration and the filtrate is concentrated and the residual oil is distilled to afford 218 5 g ( 83 % yield) of 2 azaspiro l 5 5 l undec 7 enylpentamethylene urea, b p 150 -155 C/ 55 mm 35 (m.p ( 37 0-39 C).
EXAMPLE 7
2 Azaspiro l 5 5 l undec 7 enylcarboethoxymethyl Urea ( 2 (ethoxycarbonylmethylcarbamoyl) 2 azaspiro l 5 5 l undec 7 ene) (Compound 37) 40 A solution containing 2 azaspiro l 5 5 l undec 7 ene ( 151 g; I mole) in toluene ( 1 0 1) is treated dropwise, under ice cooling, with ethyl isocyanato-acetate ( 129 g; I mole) After the addition is complete, the mixture is removed and the residual liquid distilled to afford 237 g ( 85 % yield) of 2 azaspiro l 5 5 l undec 7 enyl carboethoxymethyl urea, b p 188 -190 C/ 80 mm 45 By following substantially the procedure of Example 9 and by substituting for the ethyl isocyanato-acetate an equivalent equimolar quantity of allyl isocyanate, n-propyl isocyanate and n-nutyl isocyanate, there is obtained, respectively, 2 azaspiro l 5 5 l undec 7 enylallyl urea; (I (allylcarbamoyl) 2 azaspiro l 5 51 undec 7 ene) (Example 7 A Compound 37 A); 2 azaspiro l 5 51 50 undec 7 enylpropyl urea, (I (n propylcarbamoyl) 2 azaspiro l 5 51 undec 7 -ene) (Example 7 B, Compound 37 B); and 2 azaspiro l 5 51 undec 7 enylbutyl urea, m p 46 -49 C (I (n butylcarbamoyl) 2 azaspiro l 5.51 undec 7 ene) (Example 7 C, Compound 37 C).
EXAMPLE 8 55
2 Azaspiro l 5 5 l undec 7 enyltetramethylene Urea ( 2 (N,Ntetramethylenecarbamoyl) 2 azaspiro l 5 51 undec 7 ene (Compound 38) Step A 2 Azaspiro l 5 5 lundec 7 enecarbamoyl Chloride A solution of 2 azaspiro l 5,5 lundec 7 ene ( 13 g; 0 086 mole) ii 60 benzene ( 25 ml) is added dropwise, under ice cooling, to a solution of phosgene ( 9 1,598,096 .,, ' 1,598,096 15 g; 0 09 mole) in benzene ( 100 ml) The solution is stirred at room temperature for I hour and concentrated under reduced pressure Distillation of the residual colorless liquid affords 7 5 g ( 41 % yield) of 2 azaspiro l 5 5 l undec 7 enecarbamoyl chloride, b p 1 10 -113 C/ 50 mm.
Step B 2 Azaspiro l 5 51 undec 7 enyltetramethylene Urea 5 A solution containing 2 azaspiro l 5 5 l undec 7 enecarbamoyl chloride ( 7 5 g: 0 035 mole) and triethylamine ( 3 54 g; 0 035 mole) in benzene ( 50 ml) is treated with pyrrolidine ( 2 49 g; 0 035 mole) at room temperature After 30 minutes, the triethylamine hydrochloride is collected by filtration and the filtrate is distilled to afford 7 8 g ( 90 % yield) of 2 azaspiro l 5 51 l undec 7 ene 10 tetramethylene urea, b p 135 -138 C/ 30 mm.
By following substantially the procedure of Example 7 and by substituting for the 2 azaspiro l 5 5 l undec 7 ene recited therein an equimolar quantity of Compound A in Table III below and by substituting for the ethyl isocyanatoacetate recited therein an equimolar quantity of Compound B in Table III, the 15 following products are obtained:
Compound No compound A 39 3,3-Dietbylpiperidine 3,3-Diethylpiperidine 41 Tetrahydropyridine 42 Tetrahydropyridine 43 Tetrahydropyridine 44 Tetrahydropyridine Tetrahydropyridine 46 2-Methylpiperidine 47 2-Methylpiperidine 48 2-Methylpiperidine Compound B Product Methyl isocyanate n-B utyl isocyanate Methyl isocyanate Ethyl isocyanate n-Propyl isocyanate n-Butyl isocyanate tert-Butyl isocyanate Methyl isocyanate n-Propyl isocyanate n-B utyl isocyanate N-Methyl-N'-3,3-diethylpentamethylene urea, m p 81 o-83 o C (N-(methylcarbamoyl)-3,3diethylpiperidine) N-n-B utyl-N'-3,3-diethylpentamethylene urea (N-(n-butylcarbamoyl)-3,3-diethylpiperidine N-Methyl-N'-tetrahydropyridyl urea, b p 130 o-1350 C/1 5 mm (N-(methylcarbamoyl) tetrahydropyridine) N-Ethyl-N'-tetrahydropyridyl urea, b p 1350-1381 C/1 5 mm (N-(ethylcarbamoyl) tetrahydropyridine) N-n-Propyl-N'-tetrahydropyridyl urea, b p 1250 C/0 5 mm (N-(n-propylcarbamoyl) tetrahydropyridine) N-n-B utyl-N'-tetrahydropyridyl urea, b p 1381 C/0 75 mm (N-(n-butylcarbamoyl) tetrahydropyridine) N-tert-B utyl-N'-tetrahydropyridyl urea, m p 130 401 C (N-(tert-butylearbamoyl) tetrahydropyridine) N-Methyl-N'-2-methylpiperidyl urea, b p 127 o-1300 C/0 5 mm (N-(methylcarbamoyl)-2-methylpiperidine) N-n-Propyl-N'-2-methylpiperidyl urea, b p 12 OC O C/ 5 mm (N-(n-propylcarbamioyl)-2methylpiperidine) N-n-Butyl-N'-2-methylpiperidyl urea, b p 140 '-1420 C/0 5 mm (N-(n-butylcarbamoyl)-2methylpiperidine) t A pc Compound No Compound A 7-ene 2-Methylpiperidine 51 2-Methylpiperidine 52 2-Methylpiperidine 53 2,6-Dimethylpiperidine 54 2,6-Dimethylpiperidine 2,6-Dimethylpiperidine 56 2,6-Dimethylpiperidine 57 2,6-Dimethylpiperidine 58 2-Ethylpiperidine Compound B Allyl isocyanate tert-B utyl isocyanate Allyl isocyanate Ethyl isocyanatoacetate Ethyl isocyanate n-Propyl isocyanate.
n-Butyl isocyanate Ethyl isocyanatoacetate n-B utyl isocyanatoacetate Methyl isocyanate Product 2-Azaspiro l 5 51-u nde c-7enylallyl urea, b p 173 O1750 C/ 11 O mm (N-allylcarbamoyl)-2-azaspiro-t 5 51-undec7-ene) 2-Methylpiperidyl-N'-tertbutyl urea, m p 125 '-127 o C (N-(tert-butylcarbamoyl)-2methylpiperidine) 2-Methylpiperidyl-N'-allyl urea, b.p 1400-142 o C/0 75 mm (N-(allylearbamoyl)-2-methylpiperidine) 1 -( 2-M ethylpiperidyl)-3-carboethoxymethyl urea, b p 155 O1600 C/0 5 mm (N-(ethoxycarbonylmethylcarbamoyl)-2-methylpiperidine) 2,6-Dimethylpiperidyl-N-ethylurea, m p 940-95 CC (N-(ethylcarbamoyl)-2,6dimethylpiperidine) 2,6-Dimethylpiperidyl-N-npropyl urea, m p 7 T O 79 o C N-(n-propylcarbarnoyl)-2,6dimethylpiperidine) 2,6-Dimethylpiperidyl-N-nbutyl urea, (oil) (N-(n-butylcarbamoyl)-2,6dimethylpiperidine) 2 ',6 '-Dimethylpiperidylcarboethoxymethyl urea, (oil) (N-(n-ethoxycarbamoylmethylcarbamoyl)-2,6-dimethylpiperidine) 2,6-Dimethylpiperidyl-Ncarbo n-butoxymethyl urea, (oil) (N-(n-butoxycarbonylmethylcarbamoyl)2,6-dimethylpiperidine) 2-Ethylpiperidyl-N'-methyl urea, b p 15501 C/3 mm (N-(methylcarbamoyl)-2ethylpiperidine) -J L^ \.0 Compoun NoCopound A Compound B Product O 59 2-Ethylpiperidine 2-Ethylpiperidine 61 2-Ethylpiperidine 62 2-Ethylpiperidine 63 2-Ethylpiperidine 64 2-Ethylpiperidine 4-Ethoxycarbonylpiperidine 66 4-Ethoxycarbonylpiperidine 67 4-13 enzylpiperidine 68 4-13 enzylpiperidine Ethyl isocyanate n-Propyl isocyanate n-B utyl isocyanate tert-Butyl isocyanate Allyl isocyanate Ethyl isocyanatoacetate Methyl isocyanate Ethyl isocyanate Methyl isocyanate Ethyl isocyanate 2-Ethylpiperidyl-N'-ethyl urea, b.p 15301-1550 C/3 mm (N-(ethylcarbamoyl)-2-ethylpiperidine) 2-Ethylpiperidyl-N'-n-propyl urea, b p 1501 C/1 75 mm (Nt-(n-propylcarbamoyl)-2ethylpiperidine) 2-Ethylpiperidyl-N'-n-butyl urea, bup 1500-1560 C/1 5 mm (N_(n-uylcarbamoyl)-2ethylpiperidine) 2-Ethylpiperidyl-N'-tert-butyl urea, m p 1 l 3 01 114 'C (N-(tert-butylearbamoyl)-2ethylpiperidine) 2-Ethylpiperidyl-N'-allyl urea, b.p 15501-1570 C/2 mm (N-(allylcarbamoyl)-2ethylpiperidine) I -( 2 '-Ethylpiperidyl-3-carboethoxymethiyl urea, b p 175 O18001 C/1 75 mm (N-(ethoxycarbonylmethylearbamoyl)2-ethylpiperidine 4 '-Carboethoxypiperidyl-N'methyl urea, b p 1751-180 o C/2 mm (N-(methylearbamoyl)-4ethoxycarbonylpiperidine) 4 '-Carboethoxypperidyl-N'ethyl urea, bp 1730-1800 C/1 mm (N-(ethylcarbamoyl)-4ethoxycarbonylpiperidine) 4-Benzylpiperidyl-N'-methyl urea, (oil) (N-(methylcarbamoyl)-4benzylpiperidine) 4 '-B enzylpiperidyl-N'-ethyl urea, (oil) (N-(ethylcarbamoyl)-4benzylpiperidine) \ O b O Compound No, Compound A oCompounNoCopound A Compound B Product 69 4-Benzylpiperidine 4-B enzylpiperidine 71 4-Benzylpiperidine 72 3-Azaspiro-l 5,5 l-undecane 73 3-Azaspiro-l 5,51-undecane 74 3-Azaspiro-15,51-undecane 2-Azaspiro-l 5,51-undec7-ene 76 2-Azaspiro-l 5,5 l-undec7-ene n-Propyl isocyanate n-B utyl isocyanate Ethyl isocyanatoacetate Pyrrolidylcarbarnoylchloride (tetramethylene carbamoylchloride) Allyl isocyanate Ethyl isocyanatoacetate Cyclohexyl isocyanate Homopiperidylcarbamoylchloride (hexamethylene carbamoylchloride) 4 ' Benzylpiperidyl-N'-npropyl urea, (oil) (N-(n-propylcarbamoyl)-4benzylpiperidine) 4 '-B enzylpiperidyl-N'-butyl urea, (oil) (N-(n-butylcarbamoyl)-4benzylpiperidine) 4 '-Benzylpiperidyl-N-carboethoxymethyl urea, m p I l 00-l 120 C (N-(ethoxycarbonylmethylcarbamioyl)4-benzylpiperidine) 3-Azaspiro-15 51-undecyl-tetramethylene urea, b p 16 Oo-1 64 o C 3 mm (N-(N,N-tetramethylenecarbamoyl)-3-azaspiro-l 5 51undecane) 3-Azaspiro-15 51-undecyl-allyl urea, m 64-670 C (N-(allylcarbamoyl)-3-azaspirol 5.51-undecane) 3-Azaspiro-l 5 51-undecyl-carboethoxy urea, m p 89 I-920 C (N-(ethoxycarbonylrnethylcarbamoyl)3-azaspiro-l 5 51-undecane) 2-Azaspiro-15 511-undec-7-enylcyclohexyl-urea, m p 1030-1060 C (N-(cyclohexylcarbamoyl)-2-azatspirol 5.5 l-undec-7-ene) 2-Azaspiro-l 5 51-undec-6-enyl-hexamethylene urea, b p 1590-162 o C 0.5 mm (N-(N,N-hexamethylenecarbamoyl)-2azaspiro-E 55 51-undec-7-ene) U,o ? O W .0 Compound No Compound A The following test description and results given in Table IV below show the efficacy of the compounds concerned in this invention.
Repellency Screen Male albino guinea pigs (Perfection Breeders) are divided into groups of 2 each and placed into individual cages in a rodent battery equipped with an automatic watering system Individual animal body weights ranged from 450 to 600 g Feed and water were provided ad libitum Guinea pigs are prepared for testing by clipping a patch of hair from the back with a size 10 clipper blade This permits a residual amounts of hair to be left on the animal.
Test compounds are formulated as 5 % solutions in acetone A 2 5 ml volume of test solution is applied with a medicine dropper pipette to an area on the animal's back measuring approximately 7 cmx 5 cm This application results in a deposit rate of 3 5 mg/cm 2 Two guinea pigs are treated with each compound The test animal is anesthetized with sodium pentobarbital administered intraperitoneally at the rate of 35 mg/kg and is placed in a cylindrical plastic cage with only the treated portion of the back exposed The masked animal is introduced into an insect cage filled with either starved stable flies or yellow fever mosquitoes Approximately 5001000 insects are used as the challenge The treated guinea pig is exposed to the test insects for a 5-10 minute period initially and at 3 hours post-treatment and then on a daily basis until the repellency activity of the compound terminates The residual repellency activity of a compound is regarded as terminated when three or more test insects fed on the guinea pig during the exposure period.
Compound No.
Protection Time Yellow Fever Stable Fly Mosquito 4 days (D) 0.5 hours (H) 2 D 3 D 3 H 3 H 3 H 4 D 3 H 2 D 3 H ID 3 H 3 D ID 2 D 3 D 4 D ID 3 H 3 H 2 D 2 D 3 D 2 D 17 D 4 D 7 D 8 D NA (not active) 3 D NA 0.5 H 2 D ID 2 D 2 D 7 days (D) 0.5 Hours (H) 8 D 8 D 3 H 3 H 3 H 3 H 3 H 3 H ID ID 3 H 2 D 2 D 3 H 3 H 3 H 3 H 3 H 3 H ID 2 D ID 2 D D 4 D 12 D 8 D 0.5 H 6 D 3 H 2 +D 2 D 0.5 H 0.5 H 3 H 11 1 2 3 4 6 7 8 9 11 17 19 21 22 23 24 26 27 28 29 31 32 36 37 38 39 41 47 48 51 1,598,096 Compound No.
53 54 56 57 58 59 61 62 63 64 66 67 68 69 71 72 73 74 1,598,096 Protection Time Yellow Fever Stable Fly Mosquito 0.5 H NA 8 D 2 D 7 D 0.5 H 0.5 H 3 H 3 H 3 H 2 D 2 D 3 H 3 H NA 0.5 H NA 3 H 3 H 6 D NA 0.5 H 0.5 H 4 D NA 0.5 H 8 D NA 7 D 2 D 2 D 3 D 2 D 3 H 3 H 3 H 3 H 3 H 0.5 H 0.5 H 0.5 H 3 H 3 H 7 D 2 D NA 0.5 H 3 H In conclusion reference should be made to the fact that various systems of nomenclature may be used for the compounds concerned in this invention Thus, the compound of Example 8, Compound 38, may be named 2 azaspiro l 5 5 l undec 7 enyl tetramethylene or 2 (N,N tetramethylenecarbamoyl) 2 azaspiro l 5 5 l undec 7 ene Compound 38 may be represented by the formula:
A method of repelling insect pests from animals, other than humans, using, inter alia, the compounds of this invention is the subject of our copending Patent Application No 51583/77 (Serial No).
In conclusion, and in view of the provisions of Section 9 of the Patents Act
1949, attention is directed to U K Patent Specification No 1,525,584.

Claims (3)

WHAT WE CLAIM IS:-
1.598096 a?
1 A compound of the formula (X) RW m (CH 2)n N 21 3 (CH 2)n N R where R' is H, alkyl or alkenyl, R 2 is H, alkyl, cycloalkyl, alkoxycarbonyl or aralkyl, but may also be mononuclear aryl when R' is alkyl or alkenyl, or R 1 and R 2 together -represent a straight or branched chain alkylene or alkylenylene group, or an alkyleneoxyalkylene group, or an alkylene group containing a hydroxy or alkoxy substituent, 22 L 9 9 X X is alkyl, alkoxy, alkoxycarbonylalkyl or cyano, R 3 is alkyl or -C(=Y)NR 4 R 5 where Y is O or S R 5 is H and Rs is alkvl, cycloalkyl other than nortricyclyl, alkenyl, alkoxycarbonyl or alkoxycarbonylalkyl or R 4 and R 5 together represent an alkylene group, mis 0, 1 or 2, 5 n is 1 or 2, n' is 1 or 2, with the provisos i) that the heterocyclic ring shown in the formula may contain a single double bond, in which case R 3 will be absent when the double bond is a carbon 10 nitrogen double bond, but excluding compounds containing a carbonnitrogen double bond and where N and n' are both 1 and RI and R 2 are joined to form, together with the attached carbon atom, a 5 5dimethylcyclopentyl radical, ii) that when the ring shown in the formula is saturated then either X is 15 alkoxycarbonylalkyl and m is I or 2 or R 3 is a -C(=Y)NR 4 R 5 group; iii) that when RI and R 2 are both hydrogen R 3 is a -C(=Y)NR 4 R 5 group, iv) that when R 4 and R 5 jointly represent alkylene then at least one of RI and R 2 is other than hydrogen or m is I or
2.
2 A compound according to Claim 1, which is of the formula 20 1 R 12 (X' m' (CH) R 10 / 1 \ 2 N R 7 I / 7 (IA) Rt N C-N R 8 where a) R 7 is hydrogen and R 8 is C 1-C 5 alkyl or C 3-C,, alkoxycarbonylalkyl or b) R' and R 8 are joined to form an alkylene group which with the nitrogen atom to which it is attached forms a 5 or 6-membered ring: 25 X' is C,-C 5 alkyl or C 3-C 11 alkoxycarbonylalkyl; R 9, RI 0, R" and R 12 are each hydrogen, except when R 7 and R' are joined, min which case at least one of R 9, RW , R" and R 12 is other than hydrogen or m' is I or 2:
or the two members in one of the pairs R 9/R'0 and R'1/R 12 are joined and, together with the carbon atom to which they are attached, form a cycloalkyl group of 5-11 30 ring carbon atoms; n is I or 2; and m' is 0, 1 or 2.
3 A compound according to Claim 1, which is of the formula IA as defined in Claim 2, modified in that the heterocyclic ring shown in the formula contains a 35 single double bond, the group -C(=O)NR 7 R 8 being absent when that double bond is a carbon-nitrogen double bond.
4 An acid addition salt or a quaternary ammonium salt of a compound as claimed in Claim 1, 2 or
3.
5 2 Azaspiro l 5 5 lundecyltetramethylene urea 40 6 3 Azaspiro l 5 5 l undecyltetramethylene urea.
7 2 Azaspiro l 5 51 undec 7 enylpentamethylene urea.
8 2 Azaspiro l 5 5 l undec 7 enyl carboethoxymethyl urea.
9 2 Azaspiro l 5 5 lundec 7 enyltetramethylene urea.
10 2 Methylpiperidinyl N N butylurea 45 11 2,6 Dimethylpiperidyl N carbo N butoxymethylurea.
12 2 Azaspiro l 5 5 lundec 7 enylallyl urea.
13 An insect repellant composition comprising a compound or salt according to any one of Claims 1-12 in admixture with an inert carrier or diluent.
For the Applicants, D YOUNG & CO, Chartered Patent Agents, 9 Staple Inn, London WCI.
Printed for Her Maiesty's Stationery Office, by the Courier Press, Leamington Spa, 1981 Published by The Patent Office, 25 Southampton Buildings, London, WC 2 A IAY, from which copies may be obtained.
GB20816/80A 1976-12-17 1977-12-12 Insect repellent compounds Expired GB1598096A (en)

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US4515960A (en) * 1982-05-17 1985-05-07 Hoechst Aktiengesellschaft Spiro-2-aza-alkane-3-carbonitriles, their preparation and their use

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US4419360A (en) * 1979-10-31 1983-12-06 Rohm And Haas Company Arthropod repellants
US5286723A (en) * 1988-08-31 1994-02-15 Daiichi Seiyaku Co., Ltd. Spiro compound
CA1336090C (en) * 1988-08-31 1995-06-27 Isao Hayakawa Spiro-substituted cyclic amines of quinolone derivatives
GB9620049D0 (en) * 1996-09-26 1996-11-13 Hayles J R Repellent formulations
AU753691B2 (en) * 1998-06-18 2002-10-24 Novartis Ag Benzazole compounds and their use

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CH367171A (en) * 1958-08-12 1963-02-15 Cilag Chemie Aktiengesellschaf Process for the production of new N, N-pentamethylene ureas
US3418324A (en) * 1961-03-13 1968-12-24 Geschickter Fund Med Res Heterocyclic secondary amines
IL35988A0 (en) * 1970-01-19 1971-03-24 Du Pont Substituted pyrrolidines,their preparation and pharmaceutical compositions containing them
GB1476351A (en) * 1974-04-17 1977-06-10 Wilkinson Sword Ltd Compounds having a physiological cooling effect and compo sitions containing them
JPS5588039A (en) * 1978-12-27 1980-07-03 Olympus Optical Co Ltd One-shaft rotation type program shutter
FR2885403A1 (en) * 2005-05-03 2006-11-10 Saretco Sa GRID BAR AND GRID FOR FIREPLACE WITH SOLIDARITY GRADES

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