CA1116622A

CA1116622A - Iodopropargyl derivatives their use and preparation

Info

Publication number: CA1116622A
Application number: CA000323296A
Authority: CA
Inventors: Yasuhiro Morisawa; Kiyoshi Konishi; Mitsuru Kataoka
Original assignee: Sankyo Co Ltd
Current assignee: Sankyo Co Ltd
Priority date: 1978-03-15
Filing date: 1979-03-13
Publication date: 1982-01-19
Also published as: NO151703C; SE7902291L; GB2016457A; DE2910220A1; FR2465415B1; GB2016457B; SE445344B; NO790865L; DE2910220C2; FR2465415A1; US4259350A; NO151703B

Abstract

ABSTRACT OF THE DISCLOSURE
Iodopropargyl derivatives of formula:
IC === C.CH2.OR
[wherein R represents an alkanoyl group (which may be unsubstituted or have one or more halogen, cyano, substituted or unsubstituted .alpha.-phenoxy or phenyl substituents) an alkenoyl group, (optionally phenyl-substituted), a substituted or unsubstituted alkoxycarbonyl group, a cylcoalkanoyl group, a substituted or unsubstituted benzoyl group, a substituted or unsubstituted phenoxycarbonyl group, a substituted or unsubstituted benzyloxycarbonyl group, a heterocyclic carbonyl group, an alkylsulphonyl group, a substituted or unsubstituted benzenesulphonyl group, a naphthyloxycarbonyl group, an iodopropargyloxycarbonyl group, a subtstituted or unsub-stituted cycloalkoxycarbonyl group, a heterocyclic methoxycarbonyl group, a 3-pyridyloxycarbonyl group (which may be unsubstituted or have one or more halogen substituents) or an alkenyloxycarbonyl group] are, except where R represents an acetyl or an unsubstituted benzoyl group, new compounds and are useful for the preservation of a variety of organic materials, including the protection of these materials against fungal or insect attack. The derivatives may be prepared by reacting 3-hydroxy-1-iodo-1-propyne with a compound of formula RX (in which R is as defined above and X represents a halogen atom) or, where R in the desired compound contains an oxy-carbonyl group, reacting the 3-hydroxy-1-iodo-1-propyne with phos-gene and then reacting the product with an appropriate hydroxy-containing compound.

Description

1~166ZZ

BACK ROUND OF THE INV~NTION
Most organic materials are susceptible, to some degree, to attack by a variety of natural pests, including fungi and in-sects. Susceptible materials include building materials (such as wood) and industrial materials (such as wet pulps, papers, mats, fibres, leathers, adhesives, paints, synthetic resins and, again, wood) the growth of undesirable fungion these materials can lead not only to contamination but also to structural damage. In the past, reasonably effective control of fungi on such materials has been achieved by the application to these materials of a variety of anti-fungal compounds. The compounds most commonly employed for this purpose are organic compounds of heavy metals (e.g.
compounds of lead or tin, particularly tributyltin oxide) or chlori-nated phenols (such as pentachlorophenol). However, these sub-stances are very toxic to humans and other animals and thus not only are they dangerous to handle during application, but they may also give rise to danger during use of the material treated with them. Furthermore, environmental pollution may occur if , inadequate saftey precautions are taken :.

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during treatment of oryanic materials with these anti-fungal agents or during the use or destruction (e.g. by incineration) of the materials treated. Accordingly, although these anti-fungal agents have proven of great value in the past, it is anticipated that their future use will be restricted or even banned.
However, the world's diminishing resources make it ever more vital that materials should be adequately preserved. For example, wood preservation has become of increasing importance in recent years due to increasing world demands upon dwindling forest resources and because of the introduction of new building pro-cesses (e.g. the prefabricated frame process) and high temperature and humidity conditions in many parts of the world. This demand for preservatives for wood and other organic materials has not been met completely by preservatives of the chlorophenol, organo-tin or inorganic adhesive types, since they not only (as explained above) may be poisonous, but they may be inadequately effective, have an offensive smell and contaminate the material being treated, which makes it diffucult to handle the material easily and safely.
There is, therefore, a strong demand for a new anti-fungal and preservative agent for industrial materials which is more effective, easier to handle and safer.
Japanese Patent Application (examined) No. 19077/65 disclose a compound of general formula IC===C.CH2.OP~ (in which ~1 represents a phenyl or benzyl group which is unsubstituted or has one or more substituents, the substituents being on the

- 2 -- ~l66;~;2 aromatic nucleus and selected from halogen atoms, lower alkyl groups, nitro groups, carbamoyl groups, carboxyl groups and carbo-alkoxy groups); these compounds have been proposed for use as in-dustrial anti-fungal agents.
Similar iodopropargyl derivatives are disclosed in Japallese Patent Application (examined) No. 33182/74, these iodo-propargyl derivatives being of formula ArOCH2OCH2C===CI (in which Ar represents a phenyl group, a naphthyl group or a quinolyl group which are unsubstituted or have an alkyl, halogen or nitro sub-stituent). These compounds have been suggested as fungicides.Similar l-iodo-alkyne derivatives are disclosed in Japanese Patent Application (unexamined) No. 31036/75 and suggested for use as fungicides.

3-Benzoyloxy-l-iodo-l-propyne is disclosed in Chemical Abstracts 631718g (1965); however, no potential use or activity is described for this compound. Also, 3-acetoxy-1-iodo-1-propyne has been disclosed but, again, no use or activity is suggested.
After thorough study of a wide variety of compounds, we have now found that 3-benzoyloxy-1-iodo-1-propyne and 3-ace-toxy-l-iodo-l-propyne and a closely related group of novel compounds have excellent anti-fungal activity and, moreover, have preserva-tive and anti-termite activity.

11~662Z

BRIEF SUl!lMARY OF INVENTION
_. __ _ It is, therefore, an object of the invention to pro-vide a series of novel iodoproparg~l derivatives which are valu-able antifungal, preservative and termiticidal agents.
It is a further object of the invention to provide an anitfungal, preservative and termiticidal composition containing one or more iodopropargyl derivatives as the active agent.
It is a still further object of the invention to pro-vide a method of preserving organic materials (particularly wood, leather and paper) against fungal or insect, particularly termite, attack by applying to or incorporating into the material an iodo-propargyl derivative.
The novel iodopropargyl derivatives of the present ; invention are those compounds of general formula (I):
IC===C.CH2.OR (I) in which:
R represents an alkanoyl group having at least 3 carbon atoms, an alkenoyl group, a halogenated alkanoyl group, a cyano-acetyl group, an ~phenoxyalkanoyl group, a substituted ~phenoxy-alkanoyl group, a phenylalkanoyl group, a cinnamoyl group, a ~,1"

:

11~66ZZ

substituted cinnamoyl group, an alkoxycarbonyl group, a substitutedalkoxycarbonyl group, a cycloalkanoyl group, a substituted ben-zoyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a benzyloxycarbonyl group, a substituted benzyloxycarbonyl group, a heterocyclic carbonyl group, an alkylsulphonyl group, a benzenesulphonyl group, a substi.tuted benæenesulphonyl group, a naphthyloxycarbonyl group, an iodopropargyloxycarbonyl group, a cycloalkoxycarbonyl group, a substituted cycloalkoxycarbonyl group, a heterocyclic methoxycarbonyl group, a 3-pyridyloxycarbonyl group, a halo-substituted 3-pyridyloxycarbonyl group or an alkenyl-oxycarbonyl group. ~ .
The invention also provides a method of protecting a degradable organic material from fungal or termite attack, which comprises applying to or admixing with said material an iodopro-pargyl derivative of general formula (Ia):
IC===C.CH2.OR (Ia) wherein:
Rl represents any one of the groups defined for R or an acetyl group or a benzoyl group.
DETAII.ED DESCRIPTION OF INVENTION
In the above definition of the groups R and Rl, where ' `` ~11662;Z:
6.
- a group is optionally substituted, the.substituents are preferably in the cycloalkyl or aromatic ring system, where appropriate, and are preferably selected from: halogen atoms (especially chlorine, bromine and iodine); cyano groups; nitro groups;.
lower alkyl groups (especially methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl); lower alkanoyl groups (especially acetyl); lower alkoxy groups (especially methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and t-butoxy); and lower alkyl or lower alkoxy groups substituted by any of the above substituents.

10In the compounds of formula (I) and (Ia), ~hen R or R1 represents an alkanoyl group, this may be a straight or branched chain group and preferably has from 2 to 18 (3 to 18 in the case of R ) carbon atoms. Examples of such groups include the acetyl, propionyl, butyryl, isobutyryl, pivaloyl, valeryl, isovaleryl, 2-methylbutyryl, hexanoyl, 2-methylvaleryl, 2-ethylbutyryl, heptanoyl, octanoyl, 2-ethylhexanoyl, nonanoyl, decanoyl, undecanoyl, lauryl, myristoyl, palmitoyl, stearoyl or isostearoyl groups.

Where R or R1 represents an alkenoyl group, this may be a straight or branched chain group and preferably has from 3 to 18 carbon atoms. Examples include the acryloyl, methacryloyl, crotonoyl, butenoyl, sorboyl, oleoyl, 10-undecenoyl and linolyl groups.

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llhere R or R1 represents a halogenated alkanoyl group, it may be straight or branched chain and preferably has from 2 to 12 carbon atoms. Preferred halogen substituents are chlorine or bromine and the group will normally have from 1 to 3 such substituents. Examples of such groups include the bromoacetyl, chloroacetyl, dichloroacetyl, trichloroacetyl, 2-bromopropionyl, 3-bromopropionyl, 2-chloropropionyl, 3-chloro-propionyl, 2-bromobutyryl, 4-chlorobutyryl, 2-chlorobutyryl, 3-chlorobutyryl, 2-bromoisobutyryl, 2-bromovaleryl, 2-bromoiso-valeryl, 2-bromohexanoyl, 2~bromooctanoyl and 11-bromoundecanoyl groups.

Where R or R represents an -phenoxyalkanoyl group, this may be unsubstituted or have one or more substituents.
Where the group is substituted, the substituents are preferably on the phenyl moiety and are preferably 1 or 2 halogen atoms.
The alkanoyl moiety preferably has from 2 to 4 carbon atoms.
Examples of such groups include the phenoxyacetyl, 2-phenoxy-propionyl, 2-phenoxybutyryl, o-chlorophenoxyacetyl, m-chlorophen-oxyacetyl, p-chlorophenoxyacetyl, 2,4-dichlorophenoxyacetyl, o-bromophenoxyacetyl and p bromophenoxyacetyl groups.

Where R or R1 represents a phenylalkanoyl group, this is preferably a phenylacetyl or i3-phenylpropionyl group. Where R or R1 represents a cinnamoyl group, this may optionally have one or more substituents, preferably selecteci from halogen atoms, methoxy groups, methyl groups or nitro groups. Examples .. . - ~.

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1~662Z

8.
include the cinnamoyl group itself and the m-bromocinnamoyl, p-chlorocinnamoyl, p-methoxycinnamoyl, p-methylcinnamoyl and o-nitrocinnamoyl groups.

When R or R1 represents an alkoxycarbonyl grGup, this may be a straight or branched chain group and preferably has from 2 to 1~ carbon atoms. Examples o~ such groups include the methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopro-poxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxy-carbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, n-hexyloxy-carbonyl, sec-hexyloxycarbonyl, 2-methylpentyloxycarbonyl, 4-methyl-2-pentyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, 2-ethylhexyloxycarbonyl, n-nonyloxycarbonyl, 3,5,5-trimethyl-hexyloxycarbonyl, n-decyloxycarbonyl and n-dodecyloxycarbonyl groups.

Where R or R1 represents a cycloalkanoyl group, this will normally have a 4, 5 or 6 membered ring and is preferably cyclobutanecarbonyl, cyclopentanecarbonyl or cyclohexanecarbonyl.

R may represent a benzoyl group and both R and R
may represent a substituted benzoyl group. Where the yroup iS substituted, it preferably has one or two substitu~nts and these are preferably halogen atoms, methyl groups, methoxy groups, cyano groups or nitro groups. Where there are two substituerlts, the substituents may be the same or different. Examples of .

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such sroups are benzoyl~itself and the o-chlorobenzoyl, m-chloro-benzoyl, ~-chlorobenzoyl, o-bromobenzoyl, m-bromobenzoyl, p-bromo-benzoyl, m-fluorobenzoyl, p-fluorobenzoyl, o-iodobenzoyl, p-iodo-benzoyl, 2,4-dichlorobenzoyl, 3,4-dichlorobenzoyl, 3,5-dichloro-benzoyl, o-toluoyl, m-toluoyl, p-toluoyl, 2,4-dimethylbenzoyl, 3,4-dimethylbenzoyl, o-methoxybenzoyl, m-methoxybenzoyl, p-methoxy-benzoyl, 2,4-dimethoxybenzoyl, 3,4-dimethoxybenzoyl, m-cyanobenzoyl, p-cyanobenzoyl, m-nitrobenzoyl, p-nitrobenzoyl, 4-chloro-2-methoxy-benzoyl, 2-methyl-3-nitrobenzoyl, 2-methyl-4-nitrobenzoyl and

4-methyl-3-nitrobenzoyl groups.

When R or R1 represents a heterocyclic carbonyl group, the heterocyclic system is preferably one containing one or more nitrogen, oxygen or sulphur atoms, particularly a pyridyl, thenyl or furyl group. Examples of suitable hetero-cyclic carbonyl groups include the nicotinoyl, isonicotinoyl,2-pyridinecarbonyl, 2-thenoyl and 2-furoyl groups.

lIhere R or R1 represents an alkylsulphonyl group, the alkyl is preferably a straight-chain group and it preferably has from 3 to 8 carbon atoms. Examples of suitable groups include the propanesulphonyl, butanesulphonyl, hexanesulphonyl and octanesulphonyl groups.

~ here R or R represents a benzenesulphonyl group, it may be substituted or unsubstituted and there are preferably provided one or two substituents, which may be the same or different . ~ !

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10 .
and are preferably halogen atoms, methyl groups or methoxy groups.
Examples of suitable ben~enesulphonyl groups include benzene-sulphonyl itself, p-chlorobenzenes~llphonyl, p-bromobenzenesulphonyl, p-fluorobenzenesulphonyl, 2,5-dichlorobenzenesulphonyl, p-toluene-sulphonyl and p-methoxybenzenesulphonyl groups.

~ hen R or Rl represents a substituted phenoxycarbonyl group, it preferably has from 1 to 3 substituents, which may be the same or different, and which are preferably halogen atoms, straight or branched chain alkyl groups (preferably having from 1 to 4 carbon atoms), methoxy groups, nitro groups or acetyl groups. Examples include o-bromophenoxycarbonyl, m-bromophenoxy carbonyl, p-bromophenoxycarbonyl, o-chlorophenoxycarbonyl, m-chloro-phenoxycarbonyl, p-chlorophenoxycarbonyl, o-fluorophenoxycarbonyl, m-fluorophenoxycarbonyl, p-fluorophenoxycarbonyl, 2,3-dichloro-phenoxycarbonyl, 2,4-dichlorophenoxycarbonyl, 2,5-dichlorophenoxy-carbonyl, 2,6-dichlorophenoxycarbonyl, 3,4-dichlorophenoxycarbonyl, 3,5-dichlorophenoxycarbonyl, 2,3,5-trichlorophenoxycarbonyl, 2,4,5-trichlorophenoxycarbonyl, 2,4,6-trichlorophenoxycarbonyl, o-methyl-phenoxycarbonyl, m-methylphenoxycarbonyl, p-methylphenoxy-carbonyl, 2,3-dimethylphenoxycarbonyl, 2,4-dimethylphenoxycarbonyl, 2,5-dimethylphenoxycarbonyl, 2,6-dimethylphenoxycarbonyl, 334-dimethyl-phenoxycarbonyl, 2,3,5-trimethylphenoxycarbonyl, o-ethylphenoxy-carbonyl, m-ethylphenoxycarbonyl, p-ethylphenoxycarbonyl, o-propyl . ;' ;' ~

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~66Z2 11.
phenoxycarbonyl, p-propylphenoxycarbonyl, 4-sec-butylphenoxycarbonyl, 4-t-butylphenoxycarbonyl, o-methoxyphenoxycarbonyl, m-methoxy-phenoxycarbonyl, p-methoxyphenoxycarbonyl, 4-chloro-2-methylphenoxycar-bonyl, 4-chloro-3-methylphenoxycarbonyl, o-nitrophenoxycarbonyl, m-nitrophenoxycarbonyl, p-nitrophenoxycarbonyl, 2,4-dinitrophenoxycar-L~onyl, o-acetylphenoxycarbonyl, m-acetylphenoxycarbonyl, p-acetyl-phenoxycarbonyl, 3-methyl-4-nitrophenoxycarbonyl, or 4-methyl-2-nitro-phenoxycarbonyl groups.

Where R or R1 represents a naphthyloxycarbonyl group, this may be a 1- or 2- naphthyloxycarbonyl group.

Where R or R1 represents a substituted benzyloxycarbonyl group, there are preferably 1 or 2 substituents, which may be the same or different, and these are preferably selected from halogen atoms, methyl groups, methoxy groups and nitro groups.
Examples include the o-bromobenzyloxycarbonyl, m-bromobenzyloxycarbonyl, p-bromobenzyloxycarbonyl, o-chlorobenzyloxycarbonyl, m-chlorobenz yloxycarbonyl, p-chlorobenzyloxycarbonyl, 2,4-dlchlorobenzyloxy-carbonyl, 2,5-dichlorobenzyloxycarbonyl, 3,4-dichlorobenzyloxy-carbonyl, p-methylbenzyloxycarbonyl, o-methoxybenzyloxycarbonyl, m-methoxybenzyloxycarbonyl, p-methoxybenzyloxycarbonyl, 2,3-di-methoxybenzyloxycarbonyl, 2,4-dimethoxybenzyloxycarbonyl, 3,4-di-metlloxybenzyloxycarbonyl, o-nitrobenzyloxycarbonyl, m-nitrobenzyl-oxycarbonyl, or p-nitrobenzyloxycarbonyl groups.

Where R or Rl r~p esen~ a sabstit~ ~d al o~ u~nyl , ~ ~

group, the alkoxy moiety may be straight or branched chain and preferably has from 2 to 6 carbon atoms. There are preferably from 1 to 3 substituents and these are preferably selected from halo~en atoms, lower alkoxy groups or chloroethoxy groups.
Examples include 2-bromoethoYycarbonyl, 2-chloroethcxycarbonyl, 2-iodoethoxycarbonyl, 2-fluoroethoxycarbonyl, 2,2-dichloroethoxy-carbonyl, 2,2,2-trichloroethoxycarbonyl, 2,2,2-trifluoroethoxy-carbonyl, 3-chloropropoxycarbonyl, 3-bromopropoxycarbonyl, 1-bromo-2-propoxycarbonyl, 1-chloro-2-propoxycarbonyl, 2,3-dibro~opropoxy-carbonyl, 2,3-dichloropropoxycarbonyl, 1,3-dibromo-2-propoxycarbonyl, 4-chlorobutoxycarbonyl, 6-chlorohexyloxycarbonyl, 2-methoxyethoxy-carbonyl, 2-ethoxyethoxycarbonyl, 2-(2-chloroethoxy)ethoxycarbonyl or 2-butoxyethoxycarbonyl groups.

Where R or R1 represents d cycloalkoxycarbonyl group, which may be substituted or unsubstitut~d, the substituents (if any) are preferably lower alkyl groups. Examples include cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, 2-methylcyclohexyloxy-carbonyl and cycloheptyloxycarbonyl groups.
:
Where R or R1 represents a heterocyclic methoxycarbonyl group, the heterocyclic moiety is preferably a furyl, pyridyl or thiophene group and examples include 2-furFuryloxycarbonyl, ; 2-pyridylmethoxycarbonyl, 3-pyridylmethoxycarbonyl, 4-pyridylmethoxy-carbonyl and 2-thiophenenlethoxycarbonyl groups.

~La1662Z
Where R or Rl represents a 3-pyridyloxycarbonyl group, the pyridyl moiety is optionally substituted by one or more halogen atoms and examples of such groups include 3-pyridyl-oxycarbonyl, 2-bromo-3-pyridyloxycarbonyl and 2-chloro-3-pyridyl-oxycarbonyl groups.
Where R or Rl represents an alkenyloxycarbonyl group, the alkenyl moiety preferably has 3 or 4 carbon atoms and examples of such groups are allyloxycarbonyl and 3-butenyl-1-oxycarbonyl groups.
Other preferred groups which may be represented by R
or Rl are the cyanoacetyl, phenoxycarbonyl and benzyloxycarbonyl groups- . 1 In the above formulae, R and R most preferably C2 C6 (C3 - C6 in the case of R) alkanoyl group a C2 - C4 haloalkanoyl group, a C3 - C6 alkenoyl group, a benzoyl group (Rl only), a benzoyl group having 1 or 2 substituents (the substituents being selected from Cl - C4 alkyl, Cl - C4 alkoxy, halogen, cyano and nitro groups), a phenylalkenoyl group in which the alkanoyl moiety has 2 or 3 carbon atoms, a C2 - C10 alkoxy-carbonyl group, a C3 - C7 halo - substituted alkoxycarbonyl group having 1 or 2 halo substituents, a C5 or C6 cycloalkanoyl group, a phenoxycarbonyl group, a phenoxycarbonyl group having 1 or 2substituents (thesubstituentsbeingselectedfromCl-C4 alkyl, Cl-C4 alkoxy-, halogen andacetyl groups),abenzyloxycarbonylgroup, a benzyloxycarbonyl group having 1 or 2 substituents (the sub-stituents being selected from Cl - C4 alkyl, Cl - C4 alkoxy and halogen groups), a 5 or 6 membered heterocyclic - carbonyl group in which the heteroatom is N, O or S, a nephthyloxycarbonyl group, an iodopropargyloxycarbonyl group or a furfuryloxycarbonyl group.
More preferably R or R represents a benzoyl group having 1 or 2 substituents (the substituents being selected from methyl, chlorine, bromine and methoxy groups), a sorboyl group or a benzyloxycarbonyl group.

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14.
Examples of iodopropargyl derivatives according to the present invention and falling within the scope of formula (I) or formula (Ia) are listed below. The compounds are hereafter referred to by the numbers assigned to them in this list.

1. 3-Asetoxy-1-iodo-1-propyne 2. 3-Propionyloxy-1-iodo-1-propyne 3. 3-Butyryloxy-1-iodo-1-propyne 4. 3-Isobutyryloxy-1-iodo-1-propyne S. 3-Pivaloyloxy-1-iodo-1-propyne 10 6. 3-Valeryloxy-1-iodo-1-propyne 7. 3-Isovaleryloxy-1-iodo-1-propyne . 3-(2-Methylbutyryloxy)-1-iodo-1-propyne 9. 3-Hexanoyloxy-1-iodo-1-propyne 10. 3-(2-Methylvaleryloxy)-1-iodo-1-propyne 11. 3-(2-Ethylbutyryloxy)-1-iodo-1-propyne .~.

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12. 3-Heptanoyloxy-1-iodo-1-pro?yne 13. 3-Octanoyloxy-1-iodo-1-propyne 14. 3-(2-Ethylhexanoyloxy)-1-iodo-1-propyne 15. 3-Nonanoyloxy-1-iodo-1-propyne 16. 3-Decanoyloxy-1-iodo-1-propyne 17. 3-Undecanoyloxy-1-iodo-1-propyne 18. 3-Lauroyloxy-1-iodo-1-propyne 19. 3-Myristoyloxy-1-iodo-1-propyne 20. 3-Palmitoyloxy-1-iodo-1-propyne 10 21. 3-Stearoyloxy-1-iodo-1-propyne 22. 3-Isostearoyloxy-1-iodo-1-propyne 2.3. 3-Acryloyloxy-1-iodo-1-propyne 24. 3-Methacryloyloxy-1-iodo-1-propyne 25. 3-Crotonoyloxy-1-iodo-1-propyne .

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26. 3-(3~Butenoyloxy)-1-iodo-1-propyne 27. 3-Sorboyloxy-l-iodo-1-propyne 28. 3-Oleoyloxy-l-iodo-l-propyne 29. 3-(10-Undecenoyloxy)-l-iodo-l-propyne 30. 3-Linolyloxy-1-iodo-1-propyne 31. 3-Bromoacetoxy-l-iodo-l-propyne 32. 3-Chloroacetoxy-l-iodo-l-propyne 33. 3-Dichloroacetoxy-1-iodo-1-propyne 34. 3-Trichloroacetoxy-l-iodo-l-propyne 10 35. 3-(2-Bromopropionyloxy)-1-iodo-1-propyne 36. 3-(3-Bro~opropionyloxy)-l-iodo-l-propyne 37. 3-(2-Chloropropionyloxy)-1-iodo-1~propyne 38. 3-(3-Chloropropionyloxy)-l-iodo-l-propyne 39. 3-(2-Bro~obutyryloxy)-1-iodo-1-propyne ~ . , .
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40. 3-(4-Chlorobutyryloxy)-1-iodo-1-propyne 41. 3-(2-Chlorobutyryloxy)-1-iodo-1-propyne 42. 3-(3-Chlorobutyryloxy)-1-iodo-1-propyne 43. 3-(2-Bromoisobutyryloxy)-l-iodo-1-propyne 44. 3-(2-Bromoisovaleryloxy)-1-iodo-1-propyne . .
- 45. 3-(2-Bromovaleryloxy)-1-iodo-1-propyne 46. 3-(2-Bromohexanoyloxy)-1-iodo-1-propyne 47. 3-(2-Bromooctanoyloxy)-1-iodo-1-propyne .

48. 3-(11-Bromoundecanoyloxy)-1-iodo-1-propyne 10 49 3-Cyanoacetoxy-1-iodo-1-propyne 50. 3-Cyclohexanecarbonyloxy-1-iodo-1-propyne 51. 3-Cyclopentanecarbonyloxy-1-iodo-1-propyne 52. 3-Cyclobutanecarbonyloxy-1-iodo-1-propyne 53. 3-Phenoxyacetoxy-1-iGdo-1-propyne .
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54. 3-p-Chlorophenoxyacetoxy-1-iodo-1-propyne 55. 3-(2,4-Dichlorophenoxyace~oxy)-1-iodo-1-propyne 56. 3-o-Chlorophenoxyacetoxy-l-iodo-l-propyne 57. 3-p-Bromophenoxyacetoxy~1-iodo-1-propyne 58. 3-(2-Phenoxypropionyloxy)-1-iodo-1-propyne 59. 3-(2-Phenoxybutyryloxy)-1-iodo-1-propyne 60~ 3-Phenylacetoxy-l-iodo-l-propyne 61. 3-Cinnamoyloxy-l-iodo-1-propyne 62. 3-(3-Phenylpropionyloxy)-1-iodo-1-propyne 63. 3-Benzoyloxy-1-iodo-1-propyne 64. 3-o-Chlorobenzoyloxy-1-iodo-1-propyne .

65. 3-m-Chlorobenzoyloxy-1-iodo-1-propyne 6fi. 3-p-Chlorobenzoyloxy-1-iodo-1-propyne 67. 3-o-Bromobenzoyloxy-1-iodo-1-propyne ,.

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68. 3-m-Bromobenzoyloxy-1-iodo-1~propyne 69. 3-p-Bromobenzoyloxy-1-iodo-1-propyne 70. 3-m-Fluorobenzoyloxy-l-iodo-1-propyne 71. 3-p-Fluorobenzoyloxy-1-iodo-1~propyne 72. 3-(2,4-Dichlorobenzoyloxy)-1-iodo-1-propyne 73. 3-(3,4-Dichlorobenzoyloxy)-1-iodo-1-propyne 74. 3-(3,5-Dichlorobenzoyloxy)-1-iodo-1-propyne 75. 3-o-Iodobenzoyloxy-1-iodo-1-propyne 76. 3-p-Iodobenzoyloxy-1-iodo-1-propyne 10 77. 3-m-Cyanobenzoyloxy-1-iodo-1-propyne 78. 3.-p-Cyanobenzoyloxy-1-iodo-1-propyne 79. 3-o-Methylbenzoyloxy-1-iodo-1-propyne 80. 3-m-Methylbenzoyloxy-1-iodo-1-propyne 81. 3-p-Methylbenzoyloxy-1~lodo-1-Dropyne ..

~1166Z2 ' ~i 20.

82. 3-m-Nitrobenzoy~oxy-l-iodo-1 propyne 83. 3-p-Nitrobenzoyloxy-l-iodo-l propyne 84. 3-o-Methoxybenzoyloxy-1-iodo-1-propyne 85. 3-m-Methoxybenzoyloxy-1-iodo-1-propyne 86. 3-~-Methoxybenzoyloxy-1-iodo-1-propyne 87. 3-(2,4-Dimethoxybenzoyloxy)-1-iodo-1-propyne .
88. 3-(3,4-Dimethoxybenzoyloxy)-l-iodo-1-propyne 89. 3-(3,4-Dimethylbenzoyloxy)-l-iodo-1-propyne 90. 3-t2-Methyl-3-nitrobenzoyloxy)-1-iodo-1-propyne 91. 3-(2-Methyl-6-nitrobenzoyloxy)-1-iodo-1-propyne 92. 3-(3-Methyl-~-nitrobenzoyloxy)-l-iodo-l-propyne 93. 3-(4-Methyl-3-nitrobenzoyloxy)-1-iodo-1-propyne ;
94. 3-Methoxycarbonyloxy-l-iodo-1-propyne ., .

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:: , , ~ ., .~ ~ ` ... : -:11166ZZ
21 .
95. 3-Ethoxycarbonyloxy-1-iodo-1-propyne 96. 3-Propoxycarbonyloxy-1-iodo-1-propyne 97. 3-lsopropoxycarbonyloxy-1-iodo-1-propyne 98. 3-Butoxycarbonyloxy-1-iodo-1-propyne 99. 3-Isobutoxycarbonyloxy-1-iodo-1-propyne 100. 3-sec-Butoxycarbonyloxy-1-iodo-1-propyne 101. 3-Pentyloxycarbonyloxy-1-iodo-1-propyne 102. 3-1sopentyloxycarbonyloxy-1-iodo-1-propyne 103~ 3-Hexyloxycarbonyloxy-1-iodo-1-propyne 104. 3-sec-Hexyloxycarbonyloxy-1-iodo-1-propyne .. :
105. 3-(2-Methylpentyloxycarbonyloxy)-1-iodo-propyne 106. 3-(4-~ethyl-2-pentyloxycarbonyloxy)-1-iodo-1-propyne 107. 3-Heptyloxycarbonyloxy-1-iodo-1-propyne :
108. 3-Octyloxycarbonyloxy-l-iodo-1-propyne .

22.
109. 3-(2-Ethylhexyloxycarbonyloxy)-1-iodo-1-propyne 110. 3-Nonyloxycarbonyloxy-1-iodo-1-propyne 111. 3-(3,5,5-Trimethylhexyloxycarbonyloxy)-1-iodo-1-propyne 112. 3-Decyloxycarbonyloxy-1-iodo-1-propyne 113. 3-Dodecyloxycarbonyloxy-1-iodo-1-propyne 114. 3-Benzyloxycarbonyloxy-1-iodo-1-propyne 115. 3-Phenoxycarbonyloxy-1-iodo-1-propyne 116. 3-Nicotinoyloxy-l-iodo-l-propyne 10 117. 3-lsonicotinoyloxy-1-iodo-1-propyne 118. 3-(2-Pyridinecarbonyloxy)-1-iodo-1-propyne 119. 3-(2-Thenoyloxy)-1-iodo-1-propyne 120. 3-(2-Furoyloxy)-1-iodo-1-propyne 121. 3-Benzenesulphonyloxy-1-iodo-1-propyne :, .

,., ,"

23.
122. 3-p-Chlorobenzenesulphollyloxy-1-iodo-1-propyne 123. 3-p-Bromobenzenesulphonyloxy-1-iodo-1-propyne 5124. 3-p-Fluorobenzenesulphonyloxy-1-iodo-1-propyne 125. 3-(2,5-Dichlorobenzenesulphonyloxy)-1-; - iodo-1-propyne 126. 3-p-Toluenesulphonyloxy-1-iodo-1-propyne 127. 3-p-Methoxybenzenesulphonyloxy-1-iodo-1-propyne 10128- 3-Propanesulphonyloxy-l-iodo_1_propyne 129. 3-Butanesulphonyloxy-1-iodo-1-propyne 130. 3-Octanesulphonyloxy-1-iodo-1-propyne 131. 3-m-Bromocinnamoyloxy-1-iodo-1-propyne ''' .

132. 3-p-Chlorocinnamoyloxy-1-iodo-1-propyne . ., 15 133. 3-p-Methoxycinnamoyloxy-1-iodo-1-propyne ` ' , , ' ' . , -: : , .
- .
.

134. 3-p-Methylc1nnamoyloxy-1-iodo-1-propyne 135. 3-o-Nitrocinnamoyloxy-1-iodo-l-propyne 136. 3-o-Bromophenoxycarbonyloxy-1-iodo-1-propyne 137. 3-m-Bromophenoxycarbonyloxy-1-iodo-1-propyne 138. 3-p-eromophenoxycarbonyloxy-1-iodo-1-propyne 139. 3-o-Chlorophenoxycarbonyloxy-l-iodo-1-propyne 140. 3-m-Chlorophenoxycarbonyloxy-1-iodo-1-propyne 141. 3-p-Chlorophenoxycarbonyloxy-1-iodo-1-propyne 142. 3-o-Fluorophenoxycarbonyloxy-1-iodo-1-propyne 143. 3 m Fluorophenoxycarbonyloxy-1-iodo-1-propyne 144. 3-p-Fluorophenoxycarbonyloxy-1-iodo-1-propyne 145. 3-(2,3-Dichlorophenox~carbonyloxy)-1-ioco-1-propyne 146. 3-(2,4-Dichlorophenoxycarbonyloxy)-l-iodo-l-propyne :

,: . , .
.. .

25.
147. 3-(2,5-Dich10rophenoxycarbonyloxy)-l-iodo-l-propyne 148. 3-(2,6-Dichlorophenoxycarbonyloxy)~ odo-1-propyne 149. 3-(3,4-Dichlorophenoxycarbonyloxy)-1-iodo-1-propyne 150. 3-(3,5-Dichloropnenoxycarbonyloxy)-1-iodo-1-propyne 151. 3-(2,3,5-Trichlorophenoxycarbonyloxy)-1-iodo-1-propyne 152. 3-(2,4,5-Trichlorophenoxycarbonyloxy)-1-iodo-l-propyne 153. 3-(2,4,6-Trichlorophenoxycarbonyloxy)-l-iodo-l-propyne 154. 3-(4-sec-Butylphenoxycarbonyloxy)-1-iodo-1-propyne 15 155. 3-(4-t-Butylphenoxycarbonyloxy)-l-iodo-l-propyne 156. 3-(4-Chloro-2-methylphenoxycarbonyloxy)-1-iodo-1-propyne " ' ,.

.

, . .

26.
157. 3-(4-Chloro-3-methylphenoxycarbonyloxy~-1-iodo-1-propyne 158. 3-o-Methylphenoxycarbonyloxy-1-iodo-1-propyne 159. 3-m-Methylphenoxycarbonyloxy-1-iodo-1-propyne .
160. 3-p-Methylphenoxycarbonyloxy-1-iodo-1-propyne 161. 3-(2,3-Dimethylphenoxycarbonyloxy)-1-iodo-1-propyne 162. 3-(2,4-Dimethylphenoxycarbonyloxy)-1-iodo-1-propyne ~ 10 163. 3-(2,5-Dimethylphenoxycarbonyloxy)-l-iodo-; 1-propyne `' .
164. 3-(2,6-Dimethylphenoxycarbonyloxy)-1-iodo-1-propyne .
165. 3-(3,4-Dimethylphenoxycarbonyloxy)-1-iodo-1-propyne `:
,; 166. 3-(2,3,5-Trimethylphenoxycarbonyloxy)-1-iodo-1-propyne ,:, ,' .

. ~ . , .
, ' , !: . ~ ':

. :' ' , ~. , ' : " ~.:

~3L6622 167. 3-o-Ethylphenoxycarbonyloxy-1-iodo-1-propyne 168. 3-m-Ethylphenoxycarbonyloxy-1-iodo-1-propyne 169. 3-p-Ethylphenoxycarbonyloxy-1-iodo-1-propyne 170. 3-o-Propylphenoxycarbonyloxy l iodo-l-propyne 171. 3-p-Propylphenoxycarbonyloxy-l-iodo-1-propyne 172. 3-o-Methoxyphenoxycarbonyloxy-l-iodo-1-propyne 173. 3-m-Methoxyphenoxycarbonyloxy-l iodo-l-propyne 174 3-~-Methoxyphenoxycarbonyloxy-l-iodo-1-propyne ' 10 175- 3-o-Nitrophenoxycarbonyloxy-1-iodo-1-propyne ; 176. 3-m-Nitrophenoxycarbonyloxy-1-iodo-1-propyne 1-77. 3-p-Nitrophenoxycarbonyloxy-l-iodo-1-propyne 178. 3-(2,4-Dinitrophenoxycarbonyloxy)-1-iodo-1-propyne ' , ~ .
' :, 28.
179. 3-o-Acetylphenoxycarbonyloxy-l-iodo~l-propyne 180. 3-m-Acetylphenoxycarbonyloxy-1-iodo-1-propyne 181. 3-p-Acetylphenoxycarbo,lyloxy-1-iodo-1-propyne 182. 3-(3-Methyl-4-nitrophenoxycarbonyloxy~-- 1-iodo-1-propyne --183. 3-(4-Methyl-2-nitrophenoxycarbonyloxy)-1-iodo-1-propyne 184. 3-(1-Naphthyloxycarbonyloxy)-l-iodo-1-propyne ~
; 185. 3-(2-Naphthyloxycarbonyloxy)-1-iodo-1-,.:
propyne .
'~ 186. 3-o-Bromobenzyloxycarbonyloxy-1-iodo-1-propyne 187. 3-m-Bromobenzyloxycarbonyloxy-1 iodo-1-propyne `; .
; 188. 3-p-Bromobenzyloxycarbonyloxy-l-iodo-1-propyne 189. 3-o-Chlorobenzyloxycarbonyloxy-1-iodo-1-propyne : - . -.. - - , - : .
~ : : i ., :.. .. : ....
., i ,. .

. - . .

: : ; ' , -1~66Z2 29.
190. 3-m-Chlorobenzyloxycarbonyloxy-l-iodo-1-propyne 191. 3-p-Chlorobenzyloxycarbonyloxy-l-iodo-l-propyne 192. 3-(2,4-Dichlorobenzyloxycarbonyloxy)-1-iodo-1-propyne 193. 3-(2,5-Dichlorobenzyloxycarbonyloxy)-1-iodo-1-propyne 194. 3-(3,4-Dichlorobenzyloxycarbonyloxy)-1-iodo-1-propyne 195. 3-o-Methoxybenzyloxycarbonyloxy-1-iodo-1-propyne :
196. 3-m-Methoxybenzyloxycarbonyloxy-1-iodo-1 propyne 197. 3-p-Methoxybenzyloxycarbonyloxy-1-iodo-1-propyne 198. 3-o-Ritrobenzyloxycarbonyloxy-1-iodo-1-propyne l99. 3-m-Nitrobenzyloxycarbonyloxy-1-iodo-1-propyne 200. 3-p-Nitrobenzyloxycarbonyloxy-1-iodo-1-propyne 201. 3-p-Methylbenzyloxycarbonyloxy-1-iodo-1-propyne 202. 3-(2,3-Dimethoxybellzyloxycarbonyloxy)-1-iodo-1-propyne 203. 3-(2,4-DimethoxybenzylnxycarDonyloxy)-1-iodo-1-propyne ' -~6ZZ
30.
204. 3-(3,4-Dimethoxxbenzyloxycarbonyloxy)-1-iodo-1-propyne 205. 3-(2-Bromoethoxycarbonyloxy)-1-iodo-1-propyne 206. 3-(2-Chloroethoxycarbonyloxy)-]-iodo-1-propyne 207. 3-(2-Iodoethoxycarbonyloxy)-1-iodo-1-propyne 208. 3-(2-Fluoroethoxycarbonyloxy)-1-iodo-1-propyne 209. 3-(2,2-Dichloroethoxycarbonyloxy)-1-iodo-1-propyne 210. 3-(2,2,2-Trichloroethoxycarbonyloxy)-1-iodo-1-propyne .
211. 3-(2,2,2-Trifluoroethoxycarbonyloxy)-1-iodo-1-propyne 212. 3-(3-Chloropropoxycarbonyloxy)-1-iodo-1-propyne ,, .

~ 10 213. 3-(3-Bromopropoxycarbonyloxy)-1-iodo-1-propyne ., 214. 3-(1-Bromo-2-propoxycarbonyloxy)-1-iodo-1-propyne .~, 215. 3-(1-Chloro-2-propoxycarbonyloxy)-1-iodo-1-propyne . :
216. 3-(2,3-Dibromopropoxycarbonyloxy)-1-iodo-1-propyne 217. 3-(2,3-Dichloropropoxycarbonyloxy)-1-iodo-1-propyne - .: . .
: ~ .

. , .
': ', ' ~ ~ ' ` ,. ` `.,, ' .: ,` ', -- , ::;" ~.;
: .
.

31.
218. 3-(1,3-Dibromo-2-propoxycarbonyloxy)-1-iodo-1-propyne 219. 3-(4-Chlorobutoxycarbonyloxy)-1-iodo-1-propyne 220. 3-(6-Chlorohexyloxycarbonyloxy)-1-iodo-1-propyne 221. 3 (2-Methoxyethoxycarbonyloxy)-1-iodo-1-propyne 222. 3-(2-Ethoxyethoxycarbonyloxy)-1-iodo-1-propyne 223. 3-[2-(2-Chloroethoxy)ethoxycarbonyloxy]-1-iodo-1-propyne 224. 3-(2-Butoxyethoxycarbonyloxy)-1-iodo-1-propyne 225. 3-(3-Iodopropargyloxycarbonyloxy)-1-iodo-1-propyne 226. 3-Cyclopentyloxycarbonyloxy-1-iodo-1-propyne 227. 3-Cyclohexyloxycarbonyloxy-1-iodo-1-propyne 228. 3-(2-Methylcyclohexyloxycarbonyloxy)-1-iodo-1-propyne 229. 3-Cycloheptyloxycarbonyloxy-1-iodo-1-propyne 230. 3-Furfuryloxycarbonyloxy-1-iodo-1-propyne 231. 3-(2-Pyridylmethyloxycarbonyloxy)-1-iodo-1 propynQ

. ' ~.~.~6ZZ
32.
232. 3-(2-Thiophenemethyloxycarbonyloxy)-l-iodo-1-propyne 233. 3-(3-Pyridylmethyloxycarbonyloxy)-1-iodo-1-propyne 234. 3-(4-Pyridylmethyloxycarbonyloxy)-1-iodo-1-propyne 235. 3-(3-Pyridyloxycarbonyloxy)-1-iodo-1-propyne 236. 3-(2-Bromo-3-pyridyloxycarbonyloxy)-1-iodo-1-propyne 237. 3-(2-Chloro-3-pyridyloxycarbonyloxy)-1-iodo-1-propyne : ' , 238. 3-Allyloxycarbonyloxy-l-iodo-1-propyne s ~i .

; _ :

: ~ .~ : .

Of the compounds listed above, all are new, except for Compounds 1 and 63, which have been disclosed as already described.

The compounds of the invention may be prepared by reacting 3-hydroxy-1-iodo-1-propyne with an acld halide, chlorocarbonic ; 5 acid ester or sulphonic acid halide of formula R1X:

IC _ C - CH2 - OH RlX(III) ~C~Y~ C - CH2 OR1 (II) (I) 3-Hydroxy-1-iodo-1-propyne is disclosed in US Patent ; Specification No. 3,075,938 and may be prepared as described in that US Specification. In the above equation, R1 is as defined above and X represents a halogen atom. The reaction ; is preferably carried out in the presence of an inert solvent.There is no particular limitation upon the nature of the solvent employed, provided that it does not adversely affect the reaction.
Examples of suitable solvents include: aromatic hydrocarbons, `~ for example benzene, toluene or xylene; aliphatic hydrocarbons, for example hexane or heptane; and cyclic amines, for example pyridine. There is also no particular limitation upon the reaction temperature and, in general, the temperature will be chosen so as to allow the reaction to proceed at a suitable speed; we prefer to employ a reaction temperature between 0C
and the reflux temperature of the solvent ~if any) used.
However, for convenience, the reaction is preferably carried out either at room temperature or under ice-cooling.

, ~ :
,~ ' ' 11~6622 34.
At the end of the reaction, the desired compound may be separated from the reaction mixture by conventional means. One suitable separation procedure comprises: extracting the desired compound with an organic solvent (for example ethyl acetate); washing the extract with water and then drying it; and finally distilling off the solvent under reduced pressure. If desired, further purification may be carried out by standard techniques, e.g recrystallization or chro~atography.

An alternative method of preparing certain of the desired 10 compounds is available where the group R1 contains a terminal oxycarbonyl moiety, that is to say where R1 represents a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted phenoxycarbonyl group, a substituted or unsubstituted benzyloxy-carbonyl group, a naphthyloxycarbonyl group, a cycloalkoxycarbonyl 15 group, a heterocyclic methoxycarbonyl group, a substituted or unsubstituted 3-pyridyloxycarbonyl group or an alkenyloxycarbonyl group. In this procedure, 3-hydroxy-1-iodo-1-propyne is reacted with phosgene to produce 3-chlorocarbonyloxy-1-iodo-1-propyne and this is then reacted with a suitable hydroxy group-containing 20 compound to produce the desired compound of formula (I) or (Ia), according to the following reaction scheme:

IC -~ C ~ CH2 ~ OH + CC12 ~ IC__~C -CH2 ~ OCOCl (II) (IV) oc~O~ Z
+~IC ~. C - CH2 - 4 (V) ~:
"' ' ; ~''~' ' , in which R represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a substituted or un-substituted benzyl group, a naphthyl group, an iodopropargyl group, a substituted or unsubstituted cycloalkyl group, a hetero-cyclic-methyl group, a 3-pyridyl group (optionally halo-substituted) or an alkenyl group.
Each of the two stages of this reaction scheme is pre-ferably carried out in the presence of a suitable inert solvent and preferably also of a base, particularly a cyclic amine, such as pyridine. There i6 no particular restriction upon the nature of the solvent, provided that it does not adversely affect the reac-tion. Suitable solvents which may be employed include: aliphatic hydrocarbons, such as hexane, heptane or octane; and aromatic hydrocarbons, such as benzene, toluene or xylene. The solvent in the two stages may be the same or different. We prefer to isolate the compound of formula (IV) produced in the first stage before reacting it, in the second stage, with the compound of formula (V), but this is not necessary.
There is no particular restriction upon the temperature employed for the reaction in both stages of this reaction scheme, although, if the reaction temperature is too low, the reaction time may be unnecessarily prolonged and, if the reaction temperature is too high, production of by-products may increase and low boiling reactants may start to boil off. Accordingly, we 1~6~Z~:
36.
prefer that each stage of the reaction should be carried out at a temperature between 0C and the reflux temperature of the lowest boiling component of the reaction mixture. For convenience, a temperature of about room temperature is most preferably used.

At the end of the reaction, the desired product may be isolated and purified as described above.

As already explained, the compounds of formula (Ia) i are valuable preservative, anti-fungal and ~ ~ drl ,f~C

10 The invention thus also provides a process for protecting an organic material against deterioration, fungal attack and termite attack, which comprises applying to or into said material a compound of formula (Ia), as defined above~

The invention also provides a preservative, anti-fungal 15 and termiticidal composition comprising, as active ingredient, a compound of formula (Ia) (as defined above) and a suitable carrier.

The compounds of the invention have been found to be effective against a wide range of fungi, particularly those 20 of the genera Penicill_um, Aspergillus, Rhizopus, Chaetomium, Cladosporium, Fusarium, and ~ , abs~w'ell as a wide variety of other fungi, including those belonging to the genus .... . .

- : :

, ~66Z~2 37.

Trichoderma and wood~staining fungi. However, the use of the compounds of the invention is not restricted to these particular genera of fungi. The compounds of the invention are particularly useful to preserve materials from damage by wood~de~troy~ng and wood soft rotting fungi.

The compounds of the invention also exhibit a po~erful activity against termites, which are parasitic on and injurious to wooden buildings (particularly houses) and general industrial ant/~er~ I `t ,` c organic materials. The compounds are thus useful as-tcrmi~id~-10 agents.

- Materials which may be preserved and protected from the harmful effects of fungi or termites by means of the compounds of the invention include, particularly, wood, as well as a variety of industrial materials such as wet pulp, paper, mats, fibres, 15 leather, adhesives, paints and synthetic resins; however, in general, any organic materials susceptible to deterioration by fungal or termite attack may be protected by the compounds of the invention.

The amount of compound of the invention to be applied 20 to the material to be protected may vary over a wide range, depending upon the method of application and on the material to which the compound is applied. In its brGadest aspect, the invention envisages Pmploying from 3.1 g to 20 kg of compound per cubic metre of material to be treated. Preferably, ~ . . ~- - - . ;

38.

where the compound is applied by coating or dipping, the amount A employed ranges from 0~1 to 40 g per~e~bt~ metre and, ~here the compound is applied by impregnation, the amount ranges from 20 g to 20 kg per cubic metre. Where the compound of the invention is to be applied principally to the surface of the material to be treated, the amount employed is more conveniently measured in terms of grams per sq. metre of surface area. In these terms, a preferred range is from 0.1 to 40 g per sq. metre, the precise amount depending upon the nature of the material 10 to be treated. Thus, for wood, a preferred amount is from 0.1 to 4 9 per sq. metre, for leather 0.1 to 10 g per sq. metre, for paper 0.1 to 2 9 per sq. metre and for paint 0.5 to 40 g per sq. metre.

Where the compound of the invention is employed in the 15 form of a composition in admixture with a carrier or adjuvant, the proportion of the compound may vary over a wide range, depending upon the nature of the composition and the material to be treated.
In general, the compound of the invention preferably forms from 0.005 to 95% by weight of the composition, this being more preferably 20 from 10 to 75% by weight for emulsifiable concentrates, from 0.005 to 5% by weight for oil-based compositions, from 1 to 957, by weight for dusts and from 2 to 50% by weight for wettable powders.

, : ' :

.

~662Z
39.

In yeneral, the composition of the invention may be in the form of oil-soluble preparations, emulsifiable concentrates, pastes, powders, wettable powders, aerosols and paints, as well as rnany other forms well-known to those skilled in the art.

Suitable carriers include: inert solid carriers, such as clay, talc, bentonite, kaolin, silicic anhydride, calcium carbonate and wood meal; liquid carriers, such as kerosine, ligroin, the xylenes, methylnaphthalene, dimethylformamide and dimethylsulphoxide; and vapour carriers, such as nitrogen gas, dimethyl ether, the vaporizable fluorocarbons and chlorofluor-carbons (such as those sold under the Trade Mark "Freon") and monomeric vinyl chloride. In order to improve the properties of the preparation and/or to enhance the anti-fungal and preservative effects of the composition, any suitable auxiliary agent may be employed in addition to these carriers. Examples include anionic, cationic and non-ionic surface active agents and various high molecular weight compounds, e.g. methylcellulose, vinyl acetate resins and sodium alginate. It is, of course, also possible to enhance the anti-fungal or preservative effect by using the compounds of the invention in admixture with other anti-fungal or preservative agents, such as 2-(4-thiazolyl)benz-rl imida701e (Thiabendazole), N,N-dim~thyl-N' ~ichlorofluoromethyl-A ~ ~,c hl l~ ~ni J
thio-N'-phenylsulphamide-T~ichlol-orl~M~I~ or other benzanilides 25 or other wood termiticidal agents, such as Chlordane.

- , . . .
', ' ~' ':

' .

~o.

The invention i`s further illustrated by the following Examples, of which Examples 1 to 5 illustrate the preparation of compounds according to the invention, Examples 6 to 11 illustrate c~n~ c the anti-fungal and t~ dal effect of the compounds ând the remaining Examples illustrate preservative, anti-fungal ar. ~ r f'7~' ~ L
and tcrmitici~al compositions containing the compounds of the invention.

EXAMPLE
Preparation of 3-myristoyloxy-1-iodo-1-propyne 10 ( COmpound_ 19 ) 1.4 9 of myristoyl chloride were added, with cooling, to a solution of 1.0 9 of 3-hydroxy-1-iodo-1-propyne (iodoprop-argyl alcohol) in 2 ml of pyridine, and the reaction mixture was left overnight. The mixture was then poured into ice-water and extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulphate, and then the solvent was distilled off under reduced pressure. The resulting oily substance was fractionated and purified by silica gel column chromatography eluted with a 3 : 1 by volume mixture of n-hexane 20 and ethyl acetate. 1.8 9 of the desired Compound 19 were obtained, melting point 39-40C.

. : ..
.. . , ~ :
~ ' ~
'''~ - ~ ~ - .

~1 .

Elemental Analysis - Calculated for C17H2902I:
C, 52.05%, H, 7.45%; I, 32.35%.
Found: C, 52.06%; H, 7.55%; I, 32.50%.

Preparation of 3-ethoxycarbonyloxy-iodo-1-propyne (Compound 95) 1.1 9 of ethyl chloroformate were added dropwise to a solution of 2.0 9 of 3-hydroxy-1-iodo-1-propyne in 3.5 ml of pyridine and the mixture was stirred at room temperature for 1 hour. The reaction mixture was then poured into ice-water ~ and subsequently treated as descrlbed in Example 1 to give 2~5 9 j of the desired Compound 95 as an oily product.
Infra-red absorption spectrum (Liquid film) v cm 1 2210, 1755.

Elemental Analysis Calculated for C6H703I:
-C, 28.36%; H, 2.77%; I, 49.95%.
Found: C, 28.51%; H, 2.86%, I, 4g.93%.

'' , . ~: ;"

1~662~ , 42.

~ EXAMPLE 3 Preparation of 3-p-toluenesulphonyloxy-1-iodo-1-propyne (Compound 126) A solution of 0.2 9 of sodium hydroxide in 1 ml of water was added, with stirring, at room temperature to a solution of 1.0 g of i-hydroxy-1-iodo-1-propyne and 1.0 9 of p-toluene-sulphonyl chloride in dioxan. After stirring the mixture for 30 minutes, it was poured into ice-water and the mixture was extracted with diethyl ether. The extract was washed with water and dried over anhydrous sodium sulphate, and then the solvent was distilled off under reduced pressure. The oily substance thus obtained was fractionated and purified by silica gel column chromatography eluted with a 3 : 1 by volume mixture of n-hexane and ethyl acetate. 1.47 g of the desired Compound 126 were obtained in the form of a semi-solid.
Infra-red absorption spectrum (liquid film) v cm 1 2200.
.
Elemental Analysis: , Calculated for C1oH903SI:
C, 35.73%; H, 2.70%; S, 9.54% I, 37.75%.
Found: C, 35.68%; H, 2.74X; S, 9.3I~; I, 33.05X.

, ~ . :

. . .

ti2 2 43.
~ EXAMPLE 4 Preparation of 3-p-bromophenoxycarbonyloxy-1-iodo-1-propyne (Compound 13~1 _ 20 ml of a 10% w/v ben~ene solution of phosgene were added to a solution of 1.8 g of 3-hydroxy-1-iodo-1-propyne in 3 c~ rc~ pS
20 ml of benzene, and then4~ of pyridine were added dropwise thereto. The resulting mixture was stirred at room temperature for 3 hours and then left overnight. At the end of this time, the solvent was distilled off under reduced pressure, leaving 2.4 9 of an oily substance, which was disolved in 5 ml of cooled pyridine. 1.7 9 of p-bromophenol were added thereto and the mixture thus obtained was stirred at room temperature for 3 hours. The reaction mixture was then poured into cold water and extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulphate, and then the solvent was distilled off under reduced pressure, giving an oily substance. This substance was then fractionated and purified by silica gel column chromatography eluted with a 3 : 1 by volume mixture of n-hexane and ethyl acetate, giving 1.8 g of the desired Compound 138, melting point 110 - 111C.
Elemental Analysis:
Calculated for C1OH603BrI:
C, 31.53%; H, 1.59%; Br, 20.97%; I, 33.31~.
Found: C, 31.46%; H, 1.45P; Br, 20.69%; I, 33.09%.

. . ...

~ ~.-..

~1~66ZZ
44 .

Preparation of 3-p-bromophenoxycarbonyloxy-1-iodo-1-propyne - (Compound 1381 2.4 9 of p-bromophenoxychloroformate [J. Org. Chem. 32, 300 - 307 (1967)] were added dropwise to a solution of 1.8 9 of 3-hydroxy-1-iodo-1-propyne in 4 ml of pyridine and the resulting mixture was stirred at room temperature for 1 hour. The mixture was then poured into ice-water and subsequently treated and purified as described in Example 4, giving 2.3 9 of the desired Compound 138, melting point 110 -111C.
Elemental Analysis:
Calculated for C1OH603BrI:
C, 31.53%; H, 1.59%; Br, 20.97%; I, 33.31%.
Found: C, 31.48%; H, 1.60%; 8r, 20.95%; I, 33.30.

Following the procedures described in the above Examples, the following compounds were also prepared; their properties are briefly summarized in the following Table and the compounds are identified by the numbers previously assigned to them.
.

, .

. .
.

11166~2 ¦ Compound ~iel ti ng O In~ra-re~ Analysis ( % ) No. or-: spnctrum Upper column: calculated . P'n~Jsical (c~ ). Lower column: Found I_ _ _- .
¦ 1 53 -.4 2200 C,26.81; H,2.25; I,56.65 ¦ 17ZS C,27.11; El,2.29; I,56.81 ¦ 2 Oily 2200 C,30.27; H,2.97; I,53.31 ¦ 1740 C,30.1S; H,3.03; I;53.47 I _ ¦ 3 Oily 2200 C,33.36; H,3.60; I,50.35 l 1740 C,33.08; H,3.61; I,50.50 . I .
¦ 4 Oily 1 2200 C,33.36; E;,3.60; I,50.35 l ¦ 1740 C,33.53; H,3.71; I,50.22 I . I
Oily 1 2200 C,36.11; H,4.17; I,47.69 ¦ 1730 ~ C,36.25; E1,4.30; I,47.87 . _ ¦ 7 Oily 2200 C,36.11; H,4.17; I,47.69 l 1740 C,36.34; El,4.21; I,47.63 ¦ 9 Oily 2200 C,38.59; H,4.68; I,45.31 1750 C,38.38; H,4.71; I~45.22 16 oily 2200 C,46.44; E~,6.30; I,37.74 1750 C,46.42; k,6.09; I,37.~56 18 32 - 3 ¦ 2210 1 C,49.46; H,6.92; I,34.84 ¦ 1750 C,49.39; H,7.03 I,34.92 42 - 3 2180 C,54.2g; H,7.91; I,30.19 1720 C,54.58; H,8.07; I,29.92 =~_ ~

~ .~

'~ ~ ' ': ~ .. ..

': . ;:' 11~66Z2 46.
. __.___ 21 57 9 2200 C,56.25; H,8.32; I,28.30 ~ `1730 C,56.44; H,8.26; I,28.46 . ____ __ . _ 23 Oily 2200 C,30.53; H,2.14; I,53`.37 1730 C,30.45; H,2.24; I,53.57 _ . .
52 - 3 2200 C,33.62; H,2.82; I,50.75 1710 C,33.42, H,2.78; I,50~98 _ 27 65 - 6 2200 C,39.15; H,3.29; I,45.97 1700 C,38.95; H,3.09; I,45.86 . _ .
28 Oily 2200 C,56.50; H,7.90; I,28.43 1750 C,56.71; H,7.76; I,28.42 _ 31 oily 2200 C,19.83; H,1.33; I,41.90 1740 C,19.76; H,1.31; I,41.82 . ~ .
32 Oily 2200 C,23.24; H,1.56; I,49.10 1740 C,23.06; H,1.62; I,49.00 .
Oily 2200 C,22.74; H,1.91; I,40.04 1740 C,22.89; H,1.97; I,40.25 __ ..
39 oily 2200 C,25.40; H,2.44; I,38.35 1740 C,25.54; H,2.49; I,38.50 '. I
oily 2180 C,29.35; H,2.81; I,44.30 1740 C,29.44; H,2.83; I,44.19 . _ 43 oily 2200 C,25.40; H,2.44; I,38.35 1740 C,25.53; H,2.55; I,38.47 . _ 49 80 - 12200 C,28.94; H,1.62; I,50.96 1740 C,29.01, H,1.63; I,51.01 .~ . ____ ~

~G622 I
Oily 2170 C,41.12; H,4.48; I,43.44 1730 C,41.13; H,4.42; I,43.31 ___ _ . _ I
53 Oily 2225 C,41.80; H,2.87; I,40.15 _ 1770 C,41.75; H,2 85; I,40.16 54 49 - 51 2200 C,37.69; Il,2.30; I,36.20 I 1765 C,37.86; ~,2.36; I,36.13 __ _ il 56 Oily 2200 C,37.69; H,2.30; I,36.20 1760 C,37.59; H,2.23; I,36.15 .
58 Oily 2200 C,43.66; H,3.36; I,38.44 1760 C,43.52; H,3.16; I,38.28 Oily 2180 C,44.03; H,3.02; I,42.29 1740 C,44.12; H,3.12; I,42.10 : . ~
61 56 - 7 2200 C,46.18, H,2.91; I,40.66 1700 C,46.10; H,2.78; I,40.63 62 Oily 2150 C,45.88; H,3.53; I,40.40 1740 C,45.g0; H,~3.69; I,40.51 63 54 - 6 2200 C,41.99; ~;,2.47; I,44.36 _____ 1725 C,42.18; EI,2.501 I,44.32 64 46 - 8 2210 C,37.47; H,1.89; I,39.59 _ 1730 C,37.69; H,1.97; I,39.39 51 - 2 2200 C,37.47; H,1.89; I,39.59 1720 C,37.~6; H,1.86; I,39.4g 66 63 - 4 2200 C,37.~7; H,1.89; I,39.59 1715 C,37.26; H,2.02; I,39.47 . _~_ _. _. . ~

.. . ' :
; - , - . ~ .. , - . -.. , ~ ~ .
: ~, ~1~166ZZ

__ ~_ . 68 41 - 2 2220 C,32.91; H,1.66; I,34.77 ` 1720 C,33.13; H,1.67; I,35.02 _ 69 82 - 4 2200 C,32.91; H,1.66; I,34:77 . 1730 C,32.98; H,1.73; I,34.67 .
72 oily 2 ~20 C,33. R4; H,1.42; I,35.75 1740 C,34.07, H,].51; I,35.69 .
73 69 - 71 2220 C,33.84; H,1.42; I,35.75 1735 C,33.69; H,1.36; I,35.50 7;1 85 - 8 2180 C,33.84; H,1.42; I,35.75 ':730 C,34.14; 11,1.~5; 1,35.50 . _ -. . .
78 119 - 121 22~0 C,42.47; H,1;94; I,40.79 1730 C,42.50; H,1.95; I,40.73 , . ..
79 49 - 50 2200 C,44.03; H,3.02; I,42.29 1710 C,44.15; H,3.11; I,42.2Q
I
39 - ~0 2180 C,44.03; H,3.02; I,42.2 1715 C,43.80; H,3.10; I,42.34 l 81 97 - 8 2200 C,44.03; H,3.02; I,42.29 ¦
1710 C,43.97; H,2.85; I,42.03 i ' ~ ` .. ~ . ~
82 86 - 8 2200 C,36.28; H,1.83; I,38.33 ¦
1740 C,36.30; H,1.96; I,38.31 I
83 145 - 7 2200 C,36.28; H,1.83; I,38.33 1730 C,36.32; H,1.72; I,38.28 I
84 91 - 2 2200 C,41.80; H,2.87; I,40.15 1720 C,41,66; ~l,2.80; :[,39.91 ___ , _ ~

, '~ .

. , ~ __ 86 10~ - 52200 C,41.80; H,2.87; I,40.15 1710 C,41.99~ H,2.75; I,40.13 _ _ .
94 40 - 12200 C,25.02; H,2.10; I,52 88 . 1750 C,25.01, H,2.14; I,52.96 98 Oily 2180 C,34.06; H,3.93; I,44.99 - 1750 C,34.29, H,4.13; I,44.72 .
99 Oily 2180 C,34.06; H,3. g3; I,44.99 1750 C,34.34; H,4.06; I,44.88 _ _.
103 Oily 2200 C,38.73; H,4.88; I,40.92 1750 C,39.01; H,4.99; I,40.78 _ .
110 Oily 2200 C,44.33; H,6.01; I,36.03 i750 C,44.47; H,6.10; I,35.93 , 114 oily 2180 C,41.80; H,2.87; I,40.15 1750 C,42.00; H,2.98; I,39.96 .
115 50 - 22210 C,39.76; H,2.34; I,42.01 1710 C,40.00; H,2.40; I,42.05 116 156 - 82200 C,37.66; H,2.11; I,44.21 1720 C,37.56; H,2.07; I,44.12 117 143 - 52180 C,37.66; H,2.11; I,44.21 1730 C,37.62; H,2.02; I,44.50 118 139 - 140 2200 C,37.66; H,2.11; I,44.21 1740 C,37.85; H,2.03; I,44.03 I _ _ ¦ 119 55 - 62200 C,32.90; H,1.73; I,43.45 ¦ 1710 C,32.80; H,1.72; I,43 32 i _._ .
_ ' ~ ; : -- ; :' ~

: ~ :
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1~66ZZ

50 .
. . ~ " ~
120 55 ~ 6 2200 , C~34.81; H!1.83; I~45.97 1690 C~34.44; 1]~1.70; I~46.06 _ ~
121 Oily 2200 C~33.56; H~2.19; I~39.40 . Ct33;67; H~2.37; I~39.48 l _ ~--r--122 58 - 9 2190 C'/30~32; H,1. 70; I, 35.59 . _ C/30.45; H~1;92; I,35.40 129 oily 2200 C / 27.83; H, 3.67; I, 42 ~ 00 l C~27.63; H~3~78; I~42.11 _ _ ,~ ~
136 Oily 2200 C~31.53; H~1.59; Br~20.98; I,33.31 1765 C~31.-26; H~1~62; Br~20.97; I~33.48 I . ~ .
139 71 ~ 2175 C~35.69; H~1~80; Cl~10.53; I~37.71 72 1750 C~35~52; H~1.66; C1,10.53; I~37.93 146 121 ~ ~ 2200 C~32~38; H~1~36; Cl ~19.11; I~34.21 122 1740 C~32.26; H,1.22; Ci;19.18; I~34~49 l .
152 100 ~ 2180 C~29.70; H~0~99; Ci ~26.29; I~31~38 101 1735 C~29~56; H~0.98; cl 26.26; I~31.12 _ 155 oily 2200 C,46.95; H~4~22; I~35~43 1770 C ~ 46.72 ; H ~ 4 ~ 13 ; I , 35 ~ 51 __ ~ .
160 106 - 2160 C~41.80; H~2.87; I~40.15 107 1745 C~41.90; H~2.70; I/39.94 . _ ~

~ ~
1~662Z
_ 51.
172 Oily 2200C,39.78; H,2.73; I,38.21 1765C,39.87; H,2.85; I,38.11 ,_ .
¦ 173 ¦ 74 - ¦ 2200 C,39.78; H,2.73; I,38.21 l ¦ 75 ¦ 1760 C,39.89; H,2.70; I,38.46 ~ ' i .,¦ 174 19~ - I 2200 C,39.78; H,2.73; I,38.2~
¦ j 99 ¦ 1780 C,39.80; H,2.62; I,38.09 I ' ' i . ~ I
¦ 177 125 - ! 2200 ¦ C,34.61; H,1.74; N,4.0~; I,36.56 126 1 1760 ¦ C,34.56i H,1 85i N,4.12; I,36.26 ¦ 178 131 - ¦ 2180 ¦ C,30.64; H,1.29; N,7.~a; I,32.37 ¦ i 132 ¦ 1780 ¦ C,30.77; H,1.24; N,6.93; I,32.37 I
¦181 134 - 2180 C,41.89; H,2.64; I j36.88 ¦ 136 1765 C,41.91; H,2.67; I,36.61 ~ .
I ~ 1 ~1670 . . , , ' ,, .' ~ .
184 ¦ 106 - I 2180 C,47.75; H,2.58; I,36.04 ` ¦ 107 ¦ 1745 C,47.46; H,2.56; I,36.29 l l . .
1~5 184 - 2200 C,47.75; H,2.58; I,36.04 ¦ 85 1750 C,47.48; H,2 75; I,36.25 I ~ . - i 186 Oily 2200 C,33.45; H,2.04; Br,20.23;-I,32.13 !
1750 C,33.59; H,2.13; Br,20.21; I,32.25 I
189 oily 2200 C,37.69; h,2.30; ~ll10.11; I,36.20 _ 1750 C,37 78 H,2 33; Gl,10.33; I,36.18 1116~2Z

._ __ ~ _ 190 Oily 2200 C,37.69; H,2.30; Cl ,10.11; I,36.20 1750 C,37.46; H,2.31; Cl,10.17; I,36.42 _ _ _ _ 191 128 _ 2200 C,37.69; H,2.30; C1,10.11; I,36.20 129 1760 C~37.45; H,2.34; C1,10.32; I,36 50 _ __ ' . . . I
192 Oily 2200 C,34.32; H,1;83; Cl ,18.42; I,32.96 . 1750 C,34.60; H,2.05; Cl ,18.55; I,33.23 !
195 ¦ Oily ¦ 2180 C,41.64; H,3.20; I,36.67 ¦ 1750 C,41.94; H,3.22; I,36.97 ~ I _ 196 ¦ Oily ! 2180 C,41.64; H,3.20; I,36.67 .
¦ 1750 C,41.47; H,3.03; I,36.46 I i ' 197 i 124 - I 2200 C,41.64; H,3.20; I,36.67 ¦ 125 ¦ 1740 C,41.54; H,3.15; I,36.57 ' ~
200 74 - ¦ 2180 C,36.58; H,2.23; N,3.87; I,35.43 : 75: ~ 1745. C,36.76; H,2.19; N,3~67; I,35.20 201 Oily ¦ 2170 C,43.66; H,3.36; I,38.44 ¦ 1750 C,43.73; H,3.23; I,38.6A
. ! , I .
204 98 - ¦ 2180 C,41.51; H,3.48; I,33.73 99 1 1735 C,41.48; H,3.37; I,33.71 2n5 Oily 2200 C,21.64; H,1.82; Br,24.00; I,38.12 _ ~750 C,2~.75; H,1.91; Br,24.23; I,38.25 ` ~1662Z
53 .
!_ ~ .~.. -¦2~ Oily 2200 I C,24.98, l-I,2.10; C1,12.23; I,43.99 1760 I C,24.76; H,2.15; Cl ,12.10; I,43.81 . . .....
210 oily 2180 C,20.16; H,1.12; Cl ,29.. 76; I,35.51 1760 C,19.99; El,1.17; Cl`,29.59; r, 35.47 212 ¦ Oily ¦ 2175 C,27.80; H,2.66; Cl ,11.72; I,41.95 I ¦ 1740 C,27.60; H,2.65; Cl ,11.52; I,41.85 ~ l .I
¦214 ~ ¦ Oily 2200 C,24.23; H,2~32; Br,23.03; I,36.58 ! 1760 C,24.50; H,2.15; Br,23.31; I,36.50 218 1 Oily 2200 C,19.72; H,1.64; Br,37.52; I,29.80 ¦ 1750 C,19.~80; H,1.64; Br,37.29; I,29.54 219- ¦ Oily 1 22`00 C,30.36; H,3.18; Cl ,11.20; I,40.09 ~ ¦ 1750 C,30.28; H,3.08; cl ,11.26; I,40.28 22C ¦ -Oily 2200 C,3~.83; H,4.06; Cl ,10.30; I,36.87 ¦ .: 1750 C,34.65; H,3.76; C1,10.30, I;36.91 221 Oily 2180 C,29.59; Ei,3.19; I,44.68 - 1750 C,29.33; H,3.18; I,44.49 222 Oily 2200 C,32.23; E,,3.72; I,42.57 ~ 1760 C,32.44; El,3.85; I,42.77 223 Oily 2200 C,28.90; H,3.03; Cl ,10.66; I,38.16 1750 C,28.75; H,3.10; Cl ,10.50; I,38.01 __ _ ~--~ ___ ____ . . ~

~, .
;:

~1~66Z2 224 oily 2200 C,36.83; H,4.64; I,38.91 .1750 C,36.76; H,4.75; I,38.85 , . . :
225 128 - 2200 C,21.56; H,1.03; I,65.09 129 1750 C,21.81; H,l;ll; I,65.34 _ 226 Oily 2180 C,36.75; H,3.77; I,43.15 1750 C,36.46; H,3.77; I,4i.37 __ . .
2?7 oily 2170 C,38.98; H,4.25; I,41.18 1740 C,38.72; H,4.02; I,41.02 _ 228 oily 2180 C,41.02; H,4.69; I,39.39 1750 C,40 79; H,4.50; I,39.60 . . ~ . .
230 Oily 2180 C,35.23; H,2.30; I,41.46 1750 C,35.54; H,2.17; I,41.44 .
231 125 2175 C,37.88; H,2.54; N,4.42; I,40.02 1750 C,37.93; H,2.50; N,4.33; I,40.27 233 129 - 2200 C,37.88; H,2.54; N,4.42; I,40.02 130 1760 C,37.69; H,2.45; N,4.26; I,40.32 _ .
234 127 - 2175 C,37.188; H,2.54; N,4.42; I,40.02 128 1750 C,37.69; H,2.49; N,4.67; I,40.05 _ I
236 148 - 2180 C,28.30; H,1.31; N,3.67; I,33.22 _____~ 150 1765 ~6~

55 .
_ ~___ Y.__ ~
238 Oily 2200 C,31.60; H,2.65; I,~7.70 _ ~ 1750 C, 31. 53; H, 2 . 67; I, 47 . 50 :
"~ ' ' .: :: ' . ~, ,.
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.

1~6622 Example 6 Test for anti-funaal activity _ _ _ In this test, the anti-fungal activities of compounds according to the present invention are evaluated and compared with the anti-fungal activity of a known anti-fungal agent, pentachloro-phenol laurate (PCP laurate). The test samples were pieces of sapwood (each 2 x 2 x 0.2 cm) from bamboo (Phyllostachys eduls Riv) and beech (Fagus crenata Blune). Each wooden test sample was dipped into a 0~5~ w/v dimethylformamide solution containing one of the test compounds shown in the following Table 1 for 5 seconds, air-dried, leached with water (at a rate of supply about 2 litres/
minute) for 1 hour, air-dried for 24 hours and then heated at 60C
for 24 hours and sterilized with hot air.
Each test sample was then tested for its resistanee to fungal attack by the procedure prescribed by Japanese Industrial Standard Z2911 ("Anti-fungal Tests"). Specifically, each wooden test sample was subjected to one of the following test fungi:
Aspergillus flavus (Test fungus No. 1) Penieillium luteum (Test fungus No. 2) 20 _izopus nigrieans (Test fungus No. 3) ?

Fusarium moniliforme (Test fungus No. 4) Pullularia ~ llulans (Test fungus l~o. 5) Chaetomium _ obosum (Test fungus No. 6) _ladosporium herbarum (Test fungus No. 7)__ A suspension of each test fungus was inoculated onto the wooden test sample and then incubated at 25C for 3 weeks in a sterile Petri dish containing wet filter papers. The growth of the myce-lium was evaluated and the results are shown in Table 1 using the following ratings:
+: No growth of fungus on test sample observed;
+: Only slight growth of fungus observed on test sample, -: Growth of fungus on test sample observed.
Untreated control specimens were also inoculated with fungus and the growth of each fungus under the same conditions was observed and is also reported in Table 1.

~1 - 57 -s8 .
~ab]e 1 Antifungal effect , ~ .
Com-pound ~o B~mboo Becch . -T~st fungus No. Test ~ungus No.

_ .
1 + + + ~ ~ ~ + -~ t + + + + +
2 - + -~ + + -~ + + + + + + ~ ~ +
. 3 ~ + + + + + + + ~ -~ + + + +
4 + + + + + + + + + ~ + + ~ +
+ + + + + + + . + + -~ + + + +
7 + + + + ~ ~ +. .+ + + + + -~
9 +++++++ ++'++++-~
16 + ~ + + + + +. + + + + + ~~ +
lB + + + + + +~ + + + + -~ + + +
. '19 ++++++-+ +++++++
+ + + + + + + + ~ + + + + +
21 ~ + + + + + + + + + + + + +
23 + + + + + ~ -~ + + + + + + +
+ + + + + + + ~ + + + + ~ -~
27 + + + + + + + + -~ + + + + t 28 + ~ + + + .~ + , + + + + + ~ +
31 .~ + + + + -~ + ~ + + + + + . +
32 + -~ + + + + + + + + + + + -~
+ + + + + ~ + + -~ + + + + +
39 + + + ~- + + + + + -~ + + + +
~0 + + + + + -~ + + + + + -~ -~ +
43 ~ + + ~ ~ + + + ~ ~ + + + ~
49 ~ + + -~ + + + + + + ~ + + +
~ ~-~ . ~ .

:

1~.166 59 .
Table ]. (coni.d) 50 + -~ + ~ + + ~ + -~ + + + + +
53 + + + + -~ + + + + ~ + + + +
54 ++++++-~ ++-~++++
56 . + + -t + + + + + + ~ ~. + + ~
58 ~ .~ + ~ ~ + + ~ + + -~ + -~ + +
~ + + + + + ~ + + + + + ~ +
61 + + ~ -~ + + + + + + + + -~ +
62 +++++++. +-~+++'++
63 ++++_+_ +++++,-~_ 64 +i++++i +++++++
65 . +++++++ +++++++
66 +++++++ ++++++-~
68 +++++++ +++++-~+
69 + + + + + + + + + + + + + +
72 ~ + _ _ + i`~t _ + :~: + + +
73 ~ + :: + + -~ + + + + + + + +
74 i + + :t + i + + + i + + + ~
78 + + ~ + + + ~. + ~ + + + + +
79 + + - + _ :~: :~: + + - + + t 80 +++++++ +++++~+
81 + + -~ + -~ + + + + :: + + + +
82- + + + _ + + i' + + _ + + + +
83 + + + + + + + + + + + ~ + +
84 + + ~ + + :t + +,;~+ + + i 86 + + + + + + -~ + ~ + + .I.
94 ~ ~ + + + + + +
_ - , .
' `'.
' ' ~:
~, 1~66Z2 60 .
Table 1 (contd) 95 _ ___ t ~ t ~ ~ ~
98 +++++++ +++-~+~+

~ _ _. . . + + i + + . +,. . ._. .
10-~ ~ + -~ + + + + ~ + + T ~ +, 110 ~ + - * + + + + + - ~ + + +
114. +++++++ +++++++
115 .+++.~+++ ++++++`+
116 - + -~ + + + + + + + + + + + +
117 + -~ + + + + + + + + + + + ~
118 + + + -~ + + -~ + + ~ + + + +
119 +++++++ ++++++,+
120 + _ + ~.+ + :t + - + + +.+ +
121 + + i + + + + + ~ + + + + +
122 +++++++ .+++++++
126 + + + + + + ~ + + + ~ + + + .
129 ~ t~t __ __ _ _ .

' ` , ;6Z2 61 ~
r_ abl~ 1 (coni) . . ~
136 1 + -t + + + + + r + + + -t + +. +
38 ~ + + + + + + + + + + + + - +
39 + + + + + -t + + + + + +; ~ +
46 ¦ + + + + ~ ~ . + + + + + +

152 1 + + + + + + + + + + + + + + .
155 . + + ~ + + -+ + + + + . + + + +
60, + -t + + + + ~+ ~ + + + + + +
72 1 + + _ + + + + + + _ + + -t ,+
173 1 + + $ + + + ~ + + + + + ~ +
174 1 + + + + + + + . + + + + +
77 i + + + ~ ~ + + +` + + + + + +
78 !' + + - + -+ -+ + + + -+ + + ~- +.
81` + + + + + + + + -~ + -~ + + +
84 + + + + + + + + -t + + + + +`
185 + + + + + + + + + + + + + +
+ + + + + + + + + + + + -t +
192 + + + + + + * + + + + ~ ~ +
+ + + + -~ + + + + + + + + +
96 + + - + + + + + + + + + + +
97 + + + + + + + + + + + + + +

__ ~ ~, ~ t ~ .

} ~ :, , b~-~l662Z
l~a~le 1 (contd) ~ ~_ ~

201 ~-t 204 ,+ + + -t -t + + j + + + + -t + +
205 ~ t + + t + + + .
206 + + + + + + ~ + + + + f 210 -t '+ + + + + + + + + + + -~ +
212 + + + + + + + + + + + -~ + -~
+ + + + + + ~ + + + + f + +
2~ , + + + + + + + + -~ + + + + +
219 ~ + + + + + + + + + -~ ~ + .+ +
221 ¦ + + + + + + + + + + ~ + + ~+
222 + + _ + + -t + .~ + _ + + + +
223 + + + + + + + + + + + + + + .
22L~ + + _ + -- + + + + + + + + +
225 + + - + + + ;~ + + + + -~ + +
226 + + - + + + + + + - + + -~ ~
230 ~ + + +~. + + + ~. + + + + + ~ '+
231 + + + + + + . + + ~ + + +
233 +++++++ +,++++.++
PCP 236 + + + + + + + + + + + + + +
laurate _ _ _ _ _ _ _ _ _ _ _ _ _ _ . . tr~ ~t~d _ ~ _ _ :~1662Z

Example 7 Test for wood preservative activity In this test, the ability of various of the compounds of the invention to preserve from attack by certain fungi test sam-ples of sapwood (each 2 x 2 x l cm) of Japanese cedar (Cryptomeria japonica) was evaluated and compared with the known preservative pentachlorophenol (PCP). The procedure adopted in this test is based on that prescribed by Japanese Industrial Standard A9302.
Into each wooden test sample was injected under pres-sure a 0.05% w/v methanolic solution of one of the test compoundslisted in following Table 2. The test samples were then air-dried, leached with water (at a rate of supply of about 2 litres/minute) for 5 hours, air dried for 24 hours and then heated at 60C for 24 hours. This procedure was then repeated. The test pieces were then subjected to hot air sterilization and each was then placed upon a colony of a wood-rotting fungus which had been grown on an agar medium (malt extract 2%, glucose 1%, peptone 0.5%) in a sterile Petri dish. The samples were then subjected to decay by the fungi at 25C for 3 weeks. The growth of mycelia on the test samples and the reduction in compressive strength of the samples were then evaluated and the results are shown in Table 2. The results are reported according to the following ratings:

.~ `, . .

~166Z2 +: No growth of~ mycelium on test piece observed and compressive strength the same as an unaffected sample of wood;
+: slight growth of mycelium observed on test piece or compressive strength reduced slightly;
-: growth of mycelium observed on test piece or ~ignificant reduction in compressive strength.
The fungi employed were _riolus versicolor , a white rot fungus, and Coriolellus palustris, a brown rot fungus.
Untreated control samples of wood were also exposed to the fungi under the same conditions and the resuts are also reported in Table 2.

~16~
Table 2 Compd. , Preservative effect ~ Compd. I Preservat ve effect C. Versi- C. Palus-i No. ~ C. Versi- C. Palus-¦ color tris ' l' color trls 3 I t + ' 73 , ~+ +
7 I + + 74 + +
'I + + 79 +
1 + + 80 ' + +
27 j + + 81 1 + +
39 1 + + 82 1 + +

j + + 83 ~ + +
43 ll + + 84 1 + +
1 + + ~86 1 + +
53 11 +, + ,95 1 + +
58 + + 98 1 + +
+ + 99 I + +
61 ~ + + '103 1 + +
62 1 + + '110 1 + +

63 + + 114 1 + +

~ + + 1116 1 + -+
66 1 + + 1117 1 + +
68 1 + + 119 + +
0~ ~ + + 120 ~ + +
.

~ - 65 -illG6ZZ
Table 2 (contd) __ .
Compd. ¦ C. Versi- ¦ C, Palus Compd. ¦C Versi- I C. Palus-No. color tris No. color tris _ 13~ 1 + + 212 + +
155 1 + + 214 + +
160 ~ + j + 218 + +
178 ~ + + 219 + +
184 ~ + + 220 + +
101 185 ~ + + 221 + +
186 j + I + 223 + +
189 ~~ + I + 224 + +
190 ' + , + 225 + +
191 1 + 'I -+ 226 + +
192 1 + , + 227 + +
195 I + , + 228 + +
196 ~ + + 230 + +
200 1 + + 231 + +
j 201 I + ~ 233 + +
201204 1 + + 234 + +
, 205 1 + . + 236 + +
il 206 1 + I + 238 + +
1210 + + PCP _ +
~ _ i _ ~ - 66 -1116~ Z
EXA~PIE 8 Tests for antitermitic activity In thls experiment, the ability of the compounds of the invention to preserve test samples of hemlock sapwood tdiameter 6.5 mm, thickness 0.2 mm) from attack by termites (Coptotermes formosanus Shiraki) was examined. Each test sample was dipped for 5 seconds into a 2~ w/v acetone solution containing one of the two compounds identified in Table 3. After this treatment, excess solvent was removed from the sample with a filter paper and the sample was then air-dried for 24 hours. Each test sample was then placed into a small glass bottle having an inner dia-meter of 1.6 cm and a height of 2.6 cm. 10 termite workers were then placed into each bottle and the bottle was set in a dark place at 27~C and a relative humidity above 95~ for 1 week, so that the workers could freely gnaw at the wooden test samples.
The extent of the damage from gnawing was observed and the re-sults are shown in Table 3. The results are reported in the Table according to the following ratings:
+: No damage from gnawing;
+: trace of damage by gnawing;
-: substantial damage from gnawing over whole test sample.

, r-:

~ 2`2 68 .

In addition, the same experiment was carried out, but the test sample was noc treated with any anti-termite agent.
~ or~e~5 Four-fifths or more of the sample was eaten away by the ~nrts.

.

. ~ ~
: ~ :

iGZ2 69.
ble ~

Compd. Antiter- Compd. Antiter- ¦ Compd. Antiter-No. mitic No. mitic No. mitic effect . . effect effect , __ _ _ , .
1 . + - 54 . . + 8~
2 + 56 ~86 +
3 + 58 +94 ~ -~
4 + 60 +98- .+ .
+ 61 +99 + .
7 + 62 +103 +
.9 + 63 +.110 +
16 + 64 +114 +
18 + 65 .~115 +
19 + 66 +116. +
20 . + 68 . +117 .+
23 + 1 69 +118 .+ .
28 + 72 +119 +
31 + 73 +120 +
32 + 74 ~- 121 +.
+ 78 + .122 . + .
~ 79 ~,126 +
43 + 81 +129 .. +

+ 82 + -.
53 + 83 +
_____:--v~ ~ , _ ~ .

, ~. , . , ~ -; :
:. :

ll~fi62Z
70.
~ _ e ~

.~_ ~_ __ Compd. ~ntitermitic Compd. Antitermitic No. efect . . . effect 136 . * . 20D .
138 . . 201 .
139 + 205 - . i - ' .
146 * ! 20~. ~ .
152 .~ . 210 + .
155 + 212 160 * 214 - .
172 . 218 . - ~ .
173 . ~ . . 219 ~ - .
- 17LI- + ,, 221 .
177 + - ~: 222 ~ .
178 ~ ., 223 . +
181 ~ , 2~4 184 . 225 , .
18~ . . 226 . . +
186 . + . 228 189 .. * 230 ~ .
190 231 .
~91 * 233 192 + 234 . -~
195 .~ 238 +
196 ~ Unt~eated _ _ ______~___ " ~

1~1662Z

71.

Emuls fiahle _ncentrate To a solution of 10 parts by weight of Compound No.
60 in 40 parts by weight of dimethylformamide were added 50 parts by weight of xylene and 10 parts by weight of polyoxyethylene nonyl phenyl ether. The mixture was then thoroughly blended to give an emulsifiable concentrate. This concentrate can be diluted with water for use and applied by various techniques, such as painting, dipping or spraying, to wooden materials and can also be used, together with an adhesive, for the treatment of plywood for ~uilding or particle boards.

Oil soluble preparation .' ' ,; .
In 2 parts by welght of dimethylformamide were dissolved 2 parts by weight of Compound 114; 96 parts by weight of solvent naphtha were then added to the solution to give an oil-soluble preparation. This preparation can be applied to wooden materials by various methods, such as spraying, painting~
9~a~
dipping or i-J~ett~g.

- , .

72 .

Powders 2 parts by we-ight of Cornpound No. 110 were dissolved in 10 parts by weight of acetone; 68 parts by weight of clay and 30 parts by weight of talc were then added to the solution and the mixture was hornogeneously blended. The acetone was then evaporated off to give a powder.

Wettable powder .

40 parts by weight of Compound No. 40, 56 parts by weight of clay, 3 parts by weight of sodium lauryl sulphonate and 1 part by weight of polyvinyl alcohol were homogeneously blended in a mixer and then pulverized by a hammer mill to give a wettable powder.

Paint lO parts by weight of Compound 115, 20 parts by weight of barytes powder, 10 parts by weight of a vinyl resin, 25 parts by weight of rosin and 35 parts by weight of xylene _ _ ~ .
~ ~ ' ,. .: .

~L1166ZZ
73 .

were homogeneously blended to give a paint.

Aerosol ~ parts by weight of Compound No. 3 and 0.5 parts by weight of a perfume were dissolved in 40 parts by weight of deodorized kerosene and the resulting solution was charged into an aerosol vessel. After fitting a valve to the vessel, 58 parts by weight of liquefied petroleum gas were charged into it under pressure to give an aerosol.

Emulsifiable concentrate To a solution of 10 parts by weight of Compound 160 in 40 parts by weight of dimethylformamide were added 50 parts by weight of xylene and 10 parts by weight of polyoxye-thylene nonyl phenyl ether. The mixture was then thoroughly blended t~ give an emulsifiable concentrate.

-: ~ - - . , , , .
.

1~66ZZ
74.

0il-soluble preparation In 2 parts by weight of dimethylformamide were dissolved 2 parts by weight of Compound 201; 96 parts by weight of solvent naptha were then added to give an oil-soluble preparation.

Powder 2 parts by weight of Compound 195 were dissolved in 10 parts by weight of acetone; 68 parts by weight of clay and 30 parts by weight of talc were added to the solution and then the mixture was homogeneously blended. The acetone was then evaporated off to give a powder.

.

Wettable powder 40 parts by weight of Compound 212, 56 parts by weight of clay, 3 parts by weight of sodium lauryl sulphonate and 1 part by weight of polyvinyl alcohol were homogeneously blended in a mixer and then pulverized by a ham~er mill to give a wettable pOWder.

, .. : . . . .

1~6622 75.

Paint 10 parts by weight of Compound 219, 20 parts by weight of barytes powder, 10 parts by weight of a vinyl resin, 25 parts by weight of rosin and 35 parts by weight of xylene were homo-geneously blended to give a paint.

Aerosol .

2 parts by weight of Compound 185 and 0.5 part by weight of a perfume were dissolved in 40 parts by weight of deodorized kerosene; the resulting solution was charged into an aerosol vessel. After attaching a valve to the vessel, 58 parts by weight of liquefied petroleum gas were charged into it under pressure to give an aerosol.

. ' ~ ~ . ' , ~. ' .

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Compounds of the general formula (I):
IC===C.CH2.OR (I) wherein R represents an alkanoyl group having at least 3 carbon atoms, a alkenoyl group, a halogenated alkanoyl group, a cyano-acetyl group, an .alpha.-pilenoxyalkanoyl group, a subsituted .alpha.-phenoxy-alkanoyl group, a phenylalkanoyl group, a cinnamoyl group, a sub-stituted cinnamoyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a cycloalkanoyl group, a substituted ben-zoyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a benzyloxycarbonyl group, a substituted benzyloxycarbonyl group, a heterocyclic carbonyl group in which the heterocyclic ring has 5 or 6 ring atoms and has in the ring at least one heterocyclic oxygen, nitrogen or sulphur atom, an alkylsulphonyl group, a benzenesulphonyl group, a substituted benzenesulphonyl group, a naphthyloxycarbonyl group, an iodopropargyloxycarbonyl group, a cycloalkoxycarbonyl group, a substituted cycloalkoxy-carbonyl group, a heterocyclic methoxycarbonyl group in which the heterocyclic ring has 5 or 6 ring atoms and has in the ring at least one heterocyclic oxygen, nitrogen or sulphur atom, a 3-pyridyloxycarbonyl group, a halo-substituted 3-pyridyloxycarbonyl group or an alkenyloxycarbonyl group.

2. Compounds as claimed in Claim 1, wherein R represents a C3-C6 alkanoyl group, a C2-C4 haloalkanoyl group, a C3-C6 alkenoyl group, a benzoyl group having 1 or 2 substituents (the substi-tuents being selected from C1-C4 alkyl, C1-C4 alkoxy, halogen, cyano and nitro groups), a phenylalkanoyl group in which the alkanoyl moiety has 2 or 3 carbon atoms, a C2-C10 alkoxy-carbonyl group, a C3-C7 halo-substituted alkoxycarbonyl group having 1 or 2 halo substituents, a C5 or C6 cycloalkanoyl group, a phenoxy-carbonyl group, a phenoxycarbonyl group having 1 or 2 substituents (the substituents being selected from C1 - C4 alkyl, C1 - C4 alkoxy, halogen and acetyl groups), a benzyloxy-carbonyl group, a benzylocarbonyl group having 1 or 2 substituents (the substituents being selected from C1 - C4 alkyl, C1 - C4 alkoxy and halogen groups), a 5 or 6 membered heterocyclic -carbonyl group in which the heteroatom is N, O or S, a naphthyl-oxycarbonyl group, an iodopropargyloxycarbonyl group or a furfuryloxycarbonyl group.

3. Compounds as claimed in Claim 1, wherein R represents a benzoyl group having 1 or 2 substituents (the substituents being selected from methyl, chlorine, bromine and methoxy groups), a sorboyl group or a benzyloxycarbonyl group.

4. 3-m-Methylbenzoyloxy-1-iodo-1-propyne.

5. 3-p-Methylbenzoyloxy-1-iodo-1-propyne.

6. 3-Myristoyloxy-1-iodo-1-propyne.

7. 3-Ethoxycarbonyloxy-1-iodo-1-propyne.

8. 3-p-Toluenesulphonyloxy-1-iodo-1-propyne.

9. 3-p-Bromophenoxycarbonyloxy-1-iodo-1-propyne.

10. A method of protecting a degradable organic material from fungal or termite attack, which comprises applying to or admixing with said material an iodopropargyl derivative of general formula (Ia):

IC?=C.CH2.OR1 (Ia) wherein R1 represents an alkanoyl group, an alkenoyl group, a halogenated alkanoyl group, a cyanoacetyl group, an .alpha.-phenoxy-alkanoyl group, a substituted .alpha.-phenoxyalkanoyl group, a phenyl-alkanoyl group, a cinnamoyl group, a substituted cinnamoyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a cycloalkanoyl group, a benzoyl group, a substituted benzoyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a benzyloxycarbonyl group, a substituted benzyloxycarbonyl group, a heterocyclic carbonyl group in which the heterocyclic ring has 5 or 6 ring atoms and has in the ring at least one he-terocyclic oxygen, nitrogen or sulphur atom, an alkylsulphonyl group, a benzenesulphonyl group, a substituted benzenesulphonyl group, a naphthyloxycarbonyl group, an iodopropargyloxycarbonyl group, a cycloalkoxycarbonyl group, a substituted cycloalkoxy-carbonyl group, a heterocyclic methoxycarbonyl group in which the heterocyclic ring has 5 or 6 ring atoms and has in the ring at least one heterocyclic oxygen, nitrogen or sulphur atom, a 3-pyridyl-oxycarbonyl group, a halo-substituted 3-pyridyloxycarbonyl group or an alkenyloxycarbonyl group.

11. A method as claimed in Claim 10, wherein R1 in said derivative represents a C2-C6 alkanoyl group, a C2-C4 haloalkanoyl group, a C3-C6 alkenoyl group, a benzoyl group, a benzoyl group having 1 or 2 substituents (the substituents being selected from C1-C4 alkyl, C1-C4 alkoxy, halogen, cyano and nitro groups), a phenyl-alkanoyl group in which the alkanoyl moiety has 2 or 3 carbon atoms, a C2-C10 alkoxycarbonyl group, a C3-C7 halo-substituted alkoxycarbonyl group having 1 or 2 halo substituents, a C5-C6 cycloalkanoyl group, a phenoxycarbonyl group, a phenoxycarbonyl group having 1 or 2 substituents (the substituents being selected from C1-C4 alkyl, C1-C4 alkoxy, halogen and acetyl groups), a benzyloxycarbonyl group, a benzyloxycarbonyl group having 1 or 2 substituents (the substituents being selected from C1-C4 alkyl, C1-C4 alkoxy and halogen groups), a 5 or 6 membered heterocyclic -carbonyl group in which the heteroatom is N, O or S, a naphthyloxy-carbonyl group, an iodopropargyloxycarbonyl group or a furfuryl-oxycarbonyl group.

12. A method as claimed in Claim 10, wherein R1 is said compound (IA) represents a benzoyl group having 1 or 2 sub-stituents (the substituents being selected from methyl, chlorine, bromine andmethoxy groups),a sorboyl group or a benzyoxycarbonyl group.

13. A method as claimed in Claim 10, wherein said derivative is 3-m-methylbenzoyloxy-1-iodo-1-propyne.

14. A method as claimed in Claim 10, wherein said derivative is 3-p-methylbenzoyloxy-1-iodo-1-propyne.

15. A method as claimed in Claim 10, wherein said derivative is 3-myristoyloxy-1-iodo-1-propyne.

16. A method as claimed in Claim 10, wherein said derivative is 3-ethoxycarbonyloxy-1-iodo-1-propyne.

17. A method as claimed in Claim 10, wherein said derivative is 3-p-toluenesulphonyloxy-1-iodo-1-propyne.

18. A method as claimed in Claim 10, wherein said derivative is 3-p-bromophenoxycarbonyloxy-1-iodo-1-propyne.

19. A method as claimed in Claim 10 or 11, wherein said organic material is wood.

20. A method as claimed in Claim 10 or 11, wherein said organic material is wood and said compound is applied by dipping, coating or impregnation.

21. A method as claimed in Claim 10 or 11, wherein said organic material is selected from the group consisting of wood, wet pulp, paper, mats, fibres, leathers, adhesives, paints and synthetic resins.