Method of manufacture of novel oxazolydinylacetamides and fungicide

<td>POLAND REPUBLIC CHINA</td><td>PATENT DESCRIPTION</td><td> 126 290</td>

<td></td><td>Additional patent patent -</td><td></td>

<td>in</td><td>Reported: 80.08.15 (P. 226259)</td><td>Int. Cl.³</td>

<td>ORZAD</td><td>Priority: 79.08.16 United Kingdom</td><td>C07D 263/26 A01N 43/76</td>

<td>PATENT</td><td>The application was announced: 81.04.24</td><td></td>

<td>PRL</td><td>Patent description published: 1985 10 31</td><td></td>

Author of the invention: Patent holder: Sandoz Aktiengesellschaft, Basel (Switzerland)

Production method for new oxazolidinylacetamides and fungicide

The present invention relates to a process for the production of new oxazolidinylacetamides and a fungicide containing these compounds as the active substance.

The compounds of the invention have general formula 1, wherein R1 is a group of formula 8, in which R₇ and R₈, independently of each other, represent an alkyl radical with 1-4 carbon atoms, a halogen atom or an alkoxy group with 1-4 carbon atoms, and R₉ is a hydrogen atom, an alkyl radical with 1 to 4 carbon atoms or a halogen atom; R₂ is a group of the formula CO-Ri ₀in which Rj ₀ is an alkoxyalkyl radical in which the alkoxy and alkyl moieties each contain 1-4 carbon atoms, an alkylfthioalkyl radical in which both alkyl moieties each contain 1-4 carbon atoms, a 2-furyl, 2-tetrahydrofuryl radical, halogenated 2-furyl, halogenated 2 - tetrahydrofuryl, 1-imidazolylmethyl, 1-pyrazolylmethyl, 2-tetrahydrofuryloxymethyl, 2-tetrahydropyranyloxymethyl or haloalkyl with 1 to 4 carbon atoms; R₃, R4, R₅ and R_about are independently of each other a hydrogen atom or an alkyl radical with 1-4 carbon atoms.

When any of the substituents R₃, R4, R₅, R_e, R₇, R₈ or R₉ is an alkyl radical or a group containing an alkyl radical (e.g. alkoxy), the alkyl radical preferably contains 1-3 carbon atoms, e.g. methyl, ethyl, n-propyl or i-propyl.

When R₇ or R₈ is halogen, i.e., F, Cl, Br or J, preferably F, Cl or Br, more preferably Cl or Br, especially Cl.

When R₉ or R₁₀ is or contains halogen, i.e., F, Cl, Br or J, preferably F, Cl or Br, especially Cl or Br.

Preferred halogenated 2-furyl radicals for the R substituent₁₀ are monohalogen-2-furyl radicals, e.g. 5-chloro-2-furyl or 5-bromo-2-furyl. Preferred haloalkyl radicals with 1 to 4 carbon atoms for the R1 substituent₀ are chloroalkyl or bromoalkyl radicals with 1 to 4 carbon atoms, e.g. chloromethyl, bromomethyl or C₂H₅CHBr-.

Preferred halogenated 2-tetrahydrofuryl radicals for the R substituent₁₀ are monohalogen, in particular mono- or monobromo-2-tetrahydrofuryl, e.g. 5-chloro-2-tetrahydrofuryl.

126 290

Preferred alkoxyalkyl radicals with 1-4 carbon atoms in the alkoxy and alkyl part for the R substituent₁₀ alkoxymethyl radicals are ol - 3 carbon atoms in the alkoxy part. especially CH₃ OCH₂ - or C.₂ H_s OCH₂

Preferred alkylthioalkyl radicals with 1-4 carbon atoms in each alkyl part for the R1 o substituent are alkylthiomethyl radicals with 1-3 carbon atoms in the alkyl part, e.g. CH₃ SCH₂

ri ₀ preferably it is an alkoxy alkyl, 2-furyl or 5-halogen-2-furyl radical.

When one of the substituents R₃ and R a represents an alkyl radical with 1 to 4 carbon atoms, the latter preferably being a hydrogen atom.

When one of the substituents R5 and R_e is an alkyl radical with 1 to 4 carbon atoms, the other preferably is hydrogen.

A preferred group of compounds of the present invention are those compounds of formula la, in which R₂'means -COCH2OCH₃, -COCH₂OC₂H_S, -CO- / 2-furyl / or -CO- / 5-halogen-2-furyl /, R₇'and R₈ 'independently mean CH₃, Cl or Br, and R₉ 'is H, Cl, Br or methyl, wherein R₇ 'and R₈ 'are preferably uniform.

The process according to the invention for the preparation of compounds of formula 1 consists in that the compound of formula 2, wherein Rj, R₃, R₄, R₅, R₆ and Rx ₀ have the above meanings and Y is a halogen atom, subjected to intramolecular condensation.

Y is preferably chlorine or bromine, especially chlorine.

The intramolecular condensation reaction is carried out in a known manner. The reaction is exothermic. It can, for example, be carried out in an anhydrous medium, using as solvent an ether such as dimethoxyethane, a hydrocarbon such as toluene or another solvent inert under the reaction conditions. The reaction temperature is not critical and may be 0 - 100 ° C. Since the reaction is exothermic, it usually starts at room temperature, followed by a gradual increase in temperature.

The reaction is usually carried out in the presence of an acid binding agent, such as sodium hydride, sodium amide or sodium alkoxide, e.g. sodium ethoxide.

The intramolecular condensation reaction can also be carried out in a two-phase water-organic system in the presence of an inorganic base, e.g. sodium hydroxide, and optionally a catalytic amount of a layer transfer catalyst. The organic layer can be any inert, water-immiscible solvent such as hydrocarbons or halogenated hydrocarbons, e.g. xylene, toluene, o-dichlorobenzene or dichloromethane. Suitable layer transfer catalysts are quaternary ammonium compounds, such as benzyltrimethylammonium bromide, quaternary phosphonium compounds, such as benzyltriphenylphosphonium chloride, or crown ethers, such as 18-crown-6.

The starting compounds of formula 2 are new compounds. They can be obtained by acylation of compounds of formula 3 in which Ri, R₃, R4, R_s, Re and Y are as defined above, by the compound of formula 4 in which Rx is as defined above and Z is halogen, preferably chlorine or a group of formula O-COR! ₀in which Ri ₀ has the above meaning.

Solvents used for the acylation reaction are hydrocarbons such as toluene or halogenated hydrocarbons such as chlorobenzene. The reaction is conveniently carried out at a temperature of about 50-120 ° C, e.g. 80 ° C.

Compounds of formula 3 can be obtained by converting compounds of formula 5 in which R1 is as defined above with compounds of formula 6 in which R₃, R4, R_s, R_e and Y are as defined above and X is halogen, preferably Cl.

The conversion can be carried out at a temperature from about 0 ° C to about 10 ° C, in water or in an organic solvent inert under the reaction conditions, preferably in the presence of a base, e.g. an organic amine or a bicarbonate.

The starting materials and reagents used in the processes described above are either known or, if they are not known, can be prepared in a manner analogous to the processes described above or known.

The compounds of formula I exhibit fungicidal activity, in particular against phytopathogenic fungi, especially fungi of the order Oomycetas, as shown in the following studies.

Test A. Fungicidal activity against Phytophtora infestans.

Young potted potato plants (3-5 leaf stage) were sprayed with an aqueous suspension containing 0.003% (weight / volume) of the compound of formula 1, e.g. 2-methoxy-N- / 2,6-dimethylphenyl / -N- / 2-keto -3-oxazolidinyl / acetamide (Preparation 1). Two hours later, the treated plants were inoculated with a spore suspension of Phytophtora infestans and transferred to a tent in which 100% relative humidity was maintained at an ambient temperature of 16 ° C and a day length of 16 hours. Inhibition of the disease was determined 4-5 days later

126290 3 by comparing treated and untreated plants vaccinated similarly. It was found that the tested compound causes significant inhibition of fungal infection, without signs of phytotoxicity towards host plants.

Test B. Fungicidal activity against Plasmopara viticola. .

Young potted vine plants (leaf stage 3-6) were sprayed with an aqueous suspension containing 0.0008% (density / volume) of the compound of formula 1, e.g. 2-methoxy-N- / 2,6-dimethylphenyl / -N- (2-keto-3-oxazazinyl) acetamide (Preparation 1) two hours later the treated plants were inoculated with a spore suspension of Plasmopara viticola and transferred to a tent in which 100% relative humidity was maintained at an ambient temperature of 15-22 ° C (changing over a 24-hour period) and day length 16 hours. Disease inhibition was evaluated 6 days later by comparing treated plants with untreated plants similarly vaccinated. Significant inhibition of fungal infection was found for the test compound, with no signs of phytotoxicity in relation to host plants.

Test C. Therapeutic fungicidal activity against Plasmopara viticola.

Young potted vine plants (stage 3-6 leaves) were inoculated as in test B, whereas treatment with a compound, e.g. 2-methoxy-N- / 2,6-dimethylphenyl / - N- / 2-keto-3-oxazolidinyl / acetamide (Preparation 1) occurred 3 days after vaccination. Incubation conditions were as described in test B. Disease inhibition was assessed as in test B. Significant control of fungal infection by the test compound was found.

Test D. Fungicidal activity leading to complete eradication of Plasmopara viticola.

The procedure for determining this type of action of the compounds was the same as that described in test C, with the difference that the treatment was carried out 6 days after inoculation, when sporulation on the lower leaf surface was already detected. 7 days after administration of e.g. 0.012% 2-methoxy-N- / 2,6-dimethylphenyl - N- (2-keto-3-oxazolidinyl) acetamide (Preparation 1), disease control was determined. The effect of inhibiting the growth of already sporulating zones and complete stopping of sporulation was found.

Test E. Transfer on treated vine leaves.

The cut vine leaves were treated by spraying with an aqueous suspension containing 0.012% of the compound of formula 1, e.g. 2-methoxy-N- (2,6-dimethylphenyl) - N- (2-keto-3-oxazolidinyl) acetamide (Preparation 1), in such a way that only the lower half of the leaf was treated. Two hours after treatment, the entire leaf was inoculated with a spore suspension of Plasmopara viticola, after which the leaves were placed in a tent in which 100% relative humidity was maintained under the conditions described in test B. Although only the lower half of the leaf was treated, it was found that the test compound inhibited the entire leaf. The experiment thus showed that 2-methoxy-N- (2,6-dimethylphenyl) - N- (2-keto-3-oxazolidinyl) acetamide (Preparation 1) was separated on the leaf on both sides thereof.

Test F. Soil treatment

In vivo study for Pythium aphanidermatum

The fungus was grown in a sterile mixture of sand and cornstarch in a 97: 3 volume ratio, to which water was added in a 1: 4 volume ratio. Cultivation lasted 4 days at 25 ° C. The fungus was then mixed with a semi-sterile mixture of peat and sand and treated with a suspension containing the active substance preparation so as to obtain a concentration of 10 - 160 ppm (e.g. 10, 40 and 160 ppm), calculated relative to the volume of the substrate. The medium was transferred to 5 cm pots and seeded with cucumber seeds. Pots were incubated at 24 ° C and 60-70% relative humidity in a greenhouse for 7 days, after which disease attack was determined by comparing the number of diseased plants with untreated, similarly infected control pots. Compound with code number 1 (Example 1), when used as a wettable powder formulation, completely eradicates the disease.

Tests analogous to those in test F, carried out for peas and sugar cane, gave similar results. Each of the compounds listed in the examples below has been found to exhibit fungicidal properties and may be useful as a fungicide.

Particularly beneficial fungicidal activity has been found in the above tests for compounds' of formula la, in which R₂'means COCH₂OC₂H₅, R₇'and R₈'means CH₃, R₉'means Halbo R₂'means CO- (2-furyl), R₇'and R₈'means CH₃, R / is H or R₂'means CO- (5-bromo-2-furyl), R₇'and R₈'means CH₃ , R₉'means H or R₂'means COCH₂OCH₃, R₇'and Re' are Cl, R / is H or R₂'means COCH₂OCH₃, R₇'and R₈'means CH₃, R &amp; apos; is 3-Br, especially for a compound of formula la. in which R₂'means COCH₂OCH₃, R₇'and R₈'means CH₃ and R₉'means H.

The agent according to the invention serves to control phytopathogenic fungi, especially of the order of Oomycetes. The agent contains a fungicidal amount of the compound of formula 1 and is treated with plants, seeds or soil.

Mushrooms of the order Oomycetes, against which the agent of the invention has a particularly beneficial effect, belong to the genus Phytophtora and are found on plants such as potatoes, tomatoes, tobacco, citrus trees, cocoa, rubber, apples, strawberries, vegetables, decorative plants, e.g. Phytophtora infestans on potatoes and tomatoes; mushrooms of the genus Plasmopara viticola on the vine; Peronospora on plants such as tobacco, e.g. Peronospora tabacina on tobacco; Pseudoperonospora species on plants such as hop cones and cucumber, e.g., Pseudoperonospora humuli on hops; of the genus Bremia on plants such as lettuce, e.g. Bremia lactucae on lettuce, of the genus Pythium, causing black leg and root ingrowth in many plants, such as vegetables, sugar cane, ornamental plants and conifers, e.g. Pythium aphanidermatum on sugar cane; Sclerospora on plants such as sorghum and corn, e.g. Sclerospora sorghis on sorghum.

The amount of preparation used depends on such factors as the species of fungus to be controlled, the time and type of administration as well as the amount and type of the compound of formula I used.

However, generally, satisfactory results are obtained with topical application, e.g. to crops or soil, doses in the range of about 0.05-5 kg, preferably 0.1-3 kg, of the compound of formula 1 per hectare of treatment site, the treatment being repeated if needed. When the agent is used as a seed treatment, satisfactory results are obtained with dosages of about 0.05-0.5, preferably about 0.1-03 g of the compound of formula 1 per kilogram of seeds.

The compounds of the formula I are preferably used in combination with fungicides which act against phytopathogenic fungi against which the compounds of the formula I are less or not active at all, which allows a larger range of fungi to be controlled than the compounds of the formula I.

The fungicide according to the invention contains compounds of formula 1 in combination with an agriculturally acceptable carrier or diluent. In addition, the agent may contain other active substances such as fungicides in addition to the compound of formula 1 as the active substance. The agent can be both liquid and solid, e.g. wettable powder, emulsion concentrate, suspension dispersible in water concentrate, dusting powder, granulate, delayed release formulation, these preparations containing conventional carriers, diluents and / or additives. Such preparations are prepared by known methods.

Spray preparations, such as water-dispersible concentrates or wettable powders, may contain surfactants, such as wetting or dispersing agents, e.g., the condensation product of formaldehyde with naphthalenesulfonate, alkylarylsulfonate, lignosulfonate, fatty alkyl sulfates, ethoxylated alkylphenol or ethoxylated alcohol fatty.

• The formulations generally contain 0.01 - 90% by weight of the active substance, which is at least one compound of formula 1 or mixtures thereof with other active substances.

Concentrated forms of the formulation usually contain 2-80%, preferably 5-70% by weight of the active ingredient. Liquid preparations may contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight, of the active ingredient.

The invention is illustrated by the following examples in which parts and percentages are given by weight and temperature in ° C.

Formulation 1. Wettable powder · parts of 2-methoxy-N- / 2,6-dimethylphenyl / -N- / 2-keto-3-oxazolidinyl / acetamide is mixed with 2 parts lauryl sulfate, 3 parts sodium lignosulfonate and 45 parts finely ground kaolinite with an average particle size below 5 microns. The wettable powder thus obtained is diluted with water to a concentration of 0.01-5% of the active substance before use. The resulting liquid can be used for spraying leaves or for sprinkling roots.

Preparation 2. Granules

To the 94.5 parts of quartz sand in a drum mixer, 0.5 parts of a binder (non-ionic tenside) are injected and the whole is thoroughly mixed. Then 5 parts of 2-methoxy-N / 2,6-dimethylphenyl / -N- / 2-keto-3-oxazolidinyl / acetamide powder are added and mixing is continued until granules having a particle size in the range of 0.3-0.7 mm . Granules can be used for introduction into the soil near plants whose leaves are to be treated with the drug.

Example 1. Preparation of 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-keto-3-oxazolidinyl) acetamide (code number 1).

11.8 g (0.0375 mol) of 2-chloroethyl 2- (methoxyacetyl) -2- (2,6-dimethylphenyl) hydrazinecarboxylate is added in portions to a suspension of 2 g of sodium hydride (in the form of about 55% by weight in mineral oil) , in 100 ml absolute toluene, at room temperature, under nitrogen. The reaction temperature is gradually increased during the addition to 40 °. After the addition is complete, the mixture is stirred for 30 minutes without cooling, then cooled to 10 °. Unreacted sodium hydride is decomposed with ethanol and the resulting solution is washed with water, dried over MgSO₄ and stripping the solvent under reduced pressure 126290. The product obtained is recrystallized from ethanol to give colorless crystals of the title compound, m.p. 103-104 °.

The starting 2-methoxyacetyl (-2 / 2,6-dimethylphenyl) 2-chloroethyl hydrazinecarboxylate starting material used in Example 1 is obtained as follows:

A mixture of 14.7 g (0.06 mol) of 2-chloroethyl 2- / 2,6-dimethylphenyl / hydrazinecarboxylate and 16.2g (0.1 mol) of methoxyacetic anhydride [/ CH₃OCH₂WHAT/₂O] is stirred in 100 ml dry toluene for 1 hour at 80 °. After cooling, the mixture is washed with water, then with 5% aqueous NaHCO₃ and again with water. The solution is dried with MgSO₄ and stripping the solvent under reduced pressure to give the desired product.

The 2-chloroethyl 2- (2,6-dimethylphenyl) -hydrazinecarboxylate used for the above synthesis is obtained as follows:

To a mixture of 127 g (0.935 mol) 2,6-dimethylphenylhydrazine, 102.5 g (1.3 mol) pyridine and 400 ml water are added, at 0-5 °, 133.5 g (0.935 mol) ester 0- chloroethyl chloroformic acid. After the addition, the mixture is stirred for 2 hours at room temperature, the precipitate is filtered off, washed with water and dried. The desired product obtained is recrystallized from toluene to obtain colorless crystals, mp 74 ° -75 °.

Example II Preparation of 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-keto-3-oxazolidinyl) acetamide (code number 2).

236.1 g (0.75 mol) 2-chloroethyl 2- (methoxyacetyl) -2- (2,6-dimethylphenyl) -hydrazinecarboxylate, 375 ml xylene and 187 ml water are mixed and 82.5 ml are added with external cooling (0.82 mol) aqueous sodium hydroxide solution (containing about 0.4 g NaOH per ml) at such times to maintain a mixture temperature of about 20 °. After the addition is complete, the mixture is stirred for 1 hour at 20 ° C and 2 hours at 0 °. The precipitate is filtered off, washed with 150 [mu] m and dried. The desired compound is obtained in the form of a lightly colored solid with an incense temperature of 102-103.

The starting 2- (methoxyacetyl) -2- (2,6-dimethylphenyl) -hydrazinecarbolic acid * if &amp; 2-chloroethyl is obtained as follows:

20Gg (0.825 mol) 2- (2,6-dimethylphenyl) -hydrazo-2-chloroethyl silylate in 500 ml xylene is heated to 80 ° and added to hot iS ^^ solution of 2-methoxyacetyhi chloride in 250 ml xylene, prepared in situ by treatment of 73 ^ 5 ^ (5 ^ 826 mol) 2-methoxyacetic acid in 250 ml xylene, 107.1 g (0.9 mol) thionyl chloride at 80 ° C for 2 hours. The mixture is heated at 80 ° for 30 minutes and then proceeded as described in Example 1.

The 2-chloroethyl 2-, 2,8-dimethylphenyl dihydrazine carboxylate used in the above synthesis as the starting compound is prepared as follows:

Mixture, 7 g (0.1 mol) 2,6-dimethylphenylhydrazine hydrochloride, 21.2 g (0.2 mol) sodium carbonate in 50 ml water and 50 mt xylene are stirred for 30 minutes at room temperature, and then cooled to 5 °. Then, maintaining the temperature at 5 °, 14.3 g (0.1 mol) of 2-chloroethyl ester of chloroformic acid are added within one hour. The mixture is stirred for another hour at 5 and finally 100 ml of water are added. The precipitate is filtered off, washed with water and dried. Then proceed as described in example I.

The following compounds of formula 1 are prepared in an analogous manner to those described in examples I and II.

<td>Relationship Code No.</td><td>r₃</td><td>R</td><td>rs</td><td>R "</td><td>r₇</td><td>Re</td><td>r₉</td><td>rio</td><td>Temperature m.p. (° C)</td>

<td> 3</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>CH₂OC₂H₅</td><td> 62-4</td>

<td> 4</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>cl</td><td>H</td><td>CH₂OCH₃</td><td> 99-100</td>

<td> 5</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>formula 9</td><td> 190 — 1</td>

<td> 6</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>4-Cl</td><td>ch₂oh₃</td><td> 107-9</td>

<td> 7</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>ch₂oh₃</td><td></td>

<td> 8</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>ch₂sch₃</td><td> 113-5</td>

<td> 9</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>CHjCI</td><td> 134-6</td>

126 290

<td>Relationship Code No.</td><td>r₃</td><td>R4</td><td>rs</td><td>R "</td><td>r₇</td><td>rs</td><td>r₉</td><td>Ri 0</td><td>Temperature m.p. (° C)</td>

<td> 10</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>cl</td><td>H</td><td>CH₂C1</td><td> 135-6</td>

<td> 11</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>CH₂OH / CH₃/₂</td><td></td>

<td> 12</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>cl</td><td>H</td><td>ch₂oh / ch₃/₂</td><td></td>

<td> 13</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>cl</td><td>H</td><td>formula 9</td><td> 166-7</td>

<td> 14</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>CH₂SC₄H9 / n /</td><td>Oil</td>

<td> 15</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>cl</td><td>H</td><td>CH₂SC₄H₉/ N /</td><td>Oil</td>

<td> 16</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>formula 14</td><td> 123-4</td>

<td> 17</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>formula 15</td><td> 147-8</td>

<td> 18</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>formula 10</td><td> 143-4</td>

<td> 19</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td></td><td> 119-20</td>

<td> 20</td><td>H</td><td>H</td><td>H</td><td>H</td><td>cl</td><td>cl</td><td>H</td><td>ch₂oh₃</td><td> 107-9</td>

<td> 21</td><td>H</td><td>H</td><td>H</td><td>H</td><td>cl</td><td>cl</td><td>H</td><td>ch₂these</td><td> 142-4</td>

<td> 22</td><td>H</td><td>H</td><td>H</td><td>H</td><td>cl</td><td>cl</td><td>H</td><td>formula 9</td><td> 173-4</td>

<td> 23</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>model 11,</td><td> 139 - 41</td>

<td> 24</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>4-CH₃</td><td>ch₂oh₃</td><td>Oil</td>

<td> 25</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>C₂H_s</td><td>H</td><td>CH₂C1</td><td>Oil</td>

<td> 26</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>3-Cl</td><td>CH₂OCH₃</td><td> 90-2</td>

<td> 27</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>3-Br</td><td>ch₂oh₃</td><td> 96-7</td>

<td> 28</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>3-Br</td><td>CH₂C1</td><td> 182-3</td>

<td> 29</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>3-Br</td><td>formula 9</td><td> 145-8</td>

<td> 30</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>br</td><td>4-CH₃</td><td>ch₂oh₃</td><td> 125-6</td>

<td> 31</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>br</td><td>4-CH₃</td><td>ch₂these</td><td> 124-6</td>

<td> 32</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>br</td><td>4-CH₃</td><td>formula 9</td><td> 193-4</td>

<td> 33</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>formula 16</td><td> 90-4</td>

<td> 34</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>formula 12</td><td> 149 - 52</td>

<td> 35</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>4-C1</td><td>CH₂C1</td><td>gum</td>

<td> 36</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>4-Cl</td><td>formula 9</td><td> 164-5</td>

<td> 37</td><td>H</td><td>H</td><td>H</td><td>H</td><td>C₂H_s</td><td>c₂h₅</td><td>H</td><td>ch₂oh₃</td><td> 109 - 12</td>

<td> 38</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>CH₂OC₃H₇/ N /</td><td>Oil</td>

<td> 39</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>CH₂OC₄H₉/ N /</td><td></td>

<td> 40</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>formula 7</td><td></td>

<td> 41</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>CH₂OCH₂CH = C1</td><td> [₂ 98 - 100</td>

<td> 42</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>ch₂oh₂C = CH</td><td> 91 -93</td>

<td> 43</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>formula 13</td><td> 107-8</td>

<td> 44</td><td>H</td><td>H</td><td>ch₃</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>ch₂oh₃</td><td> 79-80</td>

<td> 45</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>formula 11</td><td> 56</td>

<td> 46</td><td>H</td><td>H</td><td>H</td><td>H</td><td>c₂h₅</td><td>c₂h₅</td><td>H</td><td>formula 9</td><td> 142-4</td>

<td> 47</td><td>H</td><td>H</td><td>H</td><td>H</td><td>C₂H_s</td><td>C₂H_s</td><td>H</td><td>CH₂C1</td><td> 88-9</td>

<td>Relationship Code No.</td><td>ra</td><td>R4</td><td>rs</td><td>R "</td><td>r₇</td><td>r₈</td><td>R</td><td>rio</td><td>Temperature m.p. (° C)</td>

<td> 48</td><td>H</td><td>H</td><td>H</td><td>H</td><td>br</td><td>br</td><td>H</td><td>ch₂oh₃</td><td> 150-2</td>

<td> 49</td><td>H</td><td>H</td><td>H</td><td>H</td><td>cl</td><td>cl</td><td>4-Cl</td><td>ch₂oh₃</td><td> 128-9</td>

<td> 50</td><td>H</td><td>H</td><td>H</td><td>H</td><td>c₃h₅</td><td>c₂h₅</td><td>4-Cl</td><td>ch₂oh₃</td><td> 114-6</td>

<td> 51</td><td>H</td><td>H</td><td>H</td><td>H</td><td>br</td><td>cl</td><td>4-CH₃</td><td>ch₂oh₃</td><td> 131 -4</td>

<td> 52</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>c₂h₅</td><td>H</td><td>ch₂oh₃</td><td> 96-8</td>

<td> 53</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>4-Br</td><td>ch₂oh₃</td><td> 137-8</td>