ORGANOMETALLIC COMPOUNDS

Abstract

The invention relates to a one-pot method for preparing oxido (tetraalkoxido) tungsten compounds according to the general formula [W(O)(OR).sub.4] (I), originating from WCl.sub.6, hexamethyldisiloxane, an alcohol ROH and an amine or NH.sub.3 gas. The invention further relates to the use of a compounds [W(O)(OR).sub.4] (I) and to a substrate which has on one surface a tungsten layer or a layer containing tungsten which are suitable for producing photovoltaic elements, semiconductor elements or car exhaust catalytic converters. The method permits the preparation of defined products in a simple, cost-effective and reproducible manner in high purity and good to very good yields.

Claims

1. A method for the preparation of oxido (tetraalkoxido) tungsten compounds according to the general formula
[W(O)(OR).sub.4]  (I) by means of a one-pot synthesis without isolation of the intermediate, wherein R is selected from the group consisting of straight-chain, branched or cyclic (C5-C10) alkyl groups, a straight-chain, branched or cyclic partially or fully halogenated (C5-C10) alkyl group, an alkylene alkyl ether group (R.sup.E—O)n—R.sup.F, a benzyl group, a partially or fully substituted benzyl group, a mononuclear or polynuclear aryl, a partially or fully substituted mononuclear or polynuclear aryl, a mononuclear or polynuclear heteroaryl and a partially or fully substituted mononuclear or polynuclear heteroaryl, wherein R.sup.E are selected independently of one another from the group consisting of a straight-chain, branched or cyclic (C1-C6) alkylene group and a straight-chain, branched or cyclic partially or fully halogenated (C1-C6) alkylene group, R.sup.F are selected independently of one another from the group consisting of a straight-chain, branched or cyclic (C1-C10) alkyl group, a straight-chain, branched or cyclic partially or fully halogenated (C1-C10) alkyl group, and n=1 to 5 or 1, 2 or 3, comprising the following steps: a) reacting WCl.sub.6 with hexamethyldisiloxane in an aprotic solvent in a reaction vessel, b) removing by-products and solvents from the reaction mixture by distillation, c) adding an alcohol ROH, wherein R is as defined above; and a molar ratio of WCl.sub.6:ROH is at least 1:4, and d) supplying at least one amine or ammonia (NH.sub.3); e) separating out precipitated by-products.

2. The method according to claim 1, wherein the alcohol ROH is selected from the group consisting of, sBuCH.sub.2OH, iBuCH.sub.2OH, (iPr)(Me)CHOH, (nPr)(Me)CHOH, (Et).sub.2CHOH, (Et)(Me).sub.2COH, C.sub.6H.sub.11OH, C.sub.6H.sub.5CH.sub.2OH and C.sub.6H.sub.5OH or the alcohol ROH is a glycol ether.

3. The method according to claim 1, wherein the by-products removed by distillation contain at least in part silicon, in particular at least in part (CH.sub.3).sub.3SiCl.

4. The method according to claim 1, wherein the removal of solvent and by-products by distillation can take place completely or partially.

5. The method according to claim 2, wherein the glycol ether is selected from the group consisting of a monoethylene glycol monoalkyl ether, a diethylene glycol monoalkyl ether, a triethylene glycol monoalkyl ether, a monopropylene glycol monoalkyl ether, a dipropylene glycol monoalkyl ether, a tripropylene glycol monoalkyl ether, a monooxomethylene monoalkyl ether, a dioxomethylene monoalkyl ether and a trioxomethylene monoalkyl ether.

6. The method according to claim 2, wherein the glycol ether is selected from the group consisting of selected from the group consisting of methyl glycol CH.sub.3—O—CH.sub.2CH.sub.2—OH, ethoxyethanol CH.sub.3CH.sub.2—O—CH.sub.2CH.sub.2—OH, ethylene glycol monopropyl ether CH.sub.3CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, ethylene glycol monoisopropyl ether (CH.sub.3).sub.2CH—O—CH.sub.2CH.sub.2—OH, ethylene glycol monobutyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, ethylene glycol monopentyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, ethylene glycol monohexyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, ethylene glycol monophenyl ether C.sub.6H.sub.5—O—CH.sub.2CH.sub.2—OH, ethylene glycol monobenzyl ether C.sub.6H.sub.5CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monomethyl ether CH.sub.3—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monoethyl ether CH.sub.3CH.sub.2—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monopropyl ether CH.sub.3CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monoisopropyl ether (CH.sub.3).sub.2CH—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monobutyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monopentyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monohexyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monophenyl ether C.sub.6H.sub.5—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, diethylene glycol monobenzyl ether C.sub.6H.sub.5CH.sub.2—O—CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2—OH, propylene glycol monomethyl ether CH.sub.3—O—CH.sub.2CH.sub.2CH.sub.2—OH, propylene glycol monoethyl ether CH.sub.3CH.sub.2—O—CH.sub.2CH.sub.2CH.sub.2—OH, propylene glycol monopropyl ether CH.sub.3CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2CH.sub.2—OH, propylene glycol monoisopropyl ether (CH.sub.3).sub.2CH—O—CH.sub.2—C(CH.sub.3)—OH, propylene glycol monobutyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2CH.sub.2—OH, propylene glycol monopentyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2CH.sub.2—OH, propylene glycol monohexyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2CH.sub.2CH.sub.2—OH, propylene glycol monophenyl ether C.sub.6H.sub.5—O—CH.sub.2CH.sub.2CH.sub.2—OH, propylene glycol monobenzyl ether C.sub.6H.sub.5CH.sub.2—O—CH.sub.2CH.sub.2CH.sub.2—OH, iso-propylene glycol monomethyl ether CH.sub.3—O—CH.sub.2—C(CH.sub.3)—OH, iso-propylene glycol monoethyl ether CH.sub.3CH.sub.2—O—CH.sub.2—C(CH.sub.3)—OH, iso-propylene glycol monopropyl ether CH.sub.3CH.sub.2CH.sub.2—O—CH.sub.2—C(CH.sub.3)—OH, iso-propylene glycol monoisopropyl ether (CH.sub.3).sub.2CH—O—CH.sub.2—C(CH.sub.3)—OH, iso-propylene glycol monobutyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2—C(CH.sub.3)—OH, iso-propylene glycol monopentyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2—C(CH.sub.3)—OH, iso-propylene glycol monohexyl ether CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2—O—CH.sub.2—C(CH.sub.3)—OH, iso-propylene glycol monophenyl ether C.sub.6H.sub.5—O—CH.sub.2—C(CH.sub.3)—OH, dipropylene glycol monopropyl ether CH.sub.3CH.sub.2CH.sub.2—O—CH.sub.2CH(CH.sub.3)OCH.sub.2CH(CH.sub.3)OH and iso-propylene glycol monobenzyl ether C.sub.6H.sub.5CH.sub.2—O—CH.sub.2—C(CH.sub.3)—OH, dipropylene glycol monomethyl ether CH.sub.3OCH.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2OH or the isomer mixtures thereof, 1-methoxy-2-propanol CH.sub.3OCH.sub.2CH.sub.2CH.sub.2OH or the isomer mixtures thereof, tripropylene glycol monomethyl ether CH.sub.3OCH.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2OH or the isomer mixtures thereof, dipropylene glycol monobutyl ether C.sub.4H.sub.9OCH.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2OH or the isomer mixtures thereof, 1-butoxy-2-propanol C.sub.4H.sub.9OCH.sub.2CH.sub.2CH.sub.2OH or the isomer mixtures thereof, tripropylene glycol monobutyl ether C.sub.4H.sub.9OCH.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2OH or the isomer mixtures thereof, 1-propoxy-2-propanol C.sub.3H.sub.7OCH.sub.2CH.sub.2CH.sub.2OH or the isomer mixtures thereof, the isomer mixtures thereof and the mixtures thereof.

7. The method according to claim 1, wherein the aprotic solvent is selected from the group consisting of aliphatic hydrocarbons, benzene derivatives and halogenated hydrocarbons.

8. The method according to claim 1, wherein in step a) the reaction of WCl.sub.6 with hexamethyldisiloxane in the aprotic solvent in the reaction vessel comprises the following steps: i) providing a solution or suspension of WCl.sub.6 in the aprotic solvent, ii) adding hexamethyldisiloxane, wherein during the addition and/or after the addition of hexamethyldisiloxane, a reaction of WCl.sub.6 with hexamethyldisiloxane takes place.

9. The method according to claim 1, wherein the reaction of WCl.sub.6 with hexamethyldisiloxane in the aprotic solvent is carried out at an internal temperature T.sub.U of the reaction vessel, the internal temperature T.sub.U being between 0° C. and 150° C., in particular 10° C. to 140° C.

10. The method according to claim 1, wherein the molar ratio of WCl.sub.6:ROH is between 1:4 and 1:40.

11. The method according to claim 1, wherein an internal temperature T.sub.C of the reaction vessel during the addition and/or after the addition of the alcohol ROH is between −30° C. and 50° C.

12. The method according to claim 1, wherein an internal temperature T.sub.N of the reaction vessel during the introduction and/or after the introduction of NH.sub.3 gas is between −30° C. and 100° C.

13. The method according to claim 12, wherein an internal temperature T.sub.N1 of the reaction vessel during a first phase of the introduction of NH.sub.3 gas is between −30° C. and 20° C. and internal temperature T.sub.N2 of the reaction vessel during a second phase and/or after the second phase of the introduction of NH.sub.3 gas is between 21° C. and 100° C.

14. The method according to claim 1, wherein, after step e), a step f) is carried out, which comprises isolating [W(O)(OR).sub.4].

Description

EXAMPLES

Comparative Example 1-3: General Procedure

[0082] Reaction of WCl.sub.6 with (TMS).sub.2O, ROH and NH.sub.3(g) in heptane without reaction step b)

[0083] WCl.sub.6 (50.832 g; 128.17 mmol) is weighed into flasks and dissolved/suspended in 300 mL heptane (abs. or EMSURE). In a separate dropping funnel, 20.875 g (128.17 mmol, stoichiometric) of hexamethyldisiloxane are weighed in and diluted with heptane to give a 50 vol % solution. The hexamethyldisiloxane solution is metered in slowly over 30 min with stirring at an internal temperature of 19-30° C. After metering is complete, the reaction mixture is subsequently stirred for 3 hours. The color of the reaction solution changes from dark red-violet to orange-yellow.

[0084] To the reaction suspension are added 512.67 mmol of the corresponding alcohol or glycol ether (4.0 equivalents) dropwise at 0° C., with stirring, over a period of 30 min. The reaction mixture slowly changes color to a clear colorless or yellow solution.

[0085] After the end of the metering, the reaction solution is cooled to 15° C., and the feed temperature is set to 0° C. A gas introduction pipe is placed onto the apparatus, and the gas path is initially flushed with argon or nitrogen. Inert gas is then passed through the reaction solution for 10 min to displace excess HCl. After 10 min, ammonia is slowly introduced at a temperature of 10-15° C. The gas flow is initially so strong that the ammonia introduced is completely absorbed by the reaction solution. The temperature should be within a range of 0-40° C. during the introduction. The gas introduction is terminated as soon as the temperature of the reaction mixture falls and gas is blown off through the pressure relief valve. Inert gas is then passed through the reaction mixture again for 10 min. After 10 min, ammonia is again passed through the reaction mixture in order to ensure complete reaction. The excess ammonia is then flushed from the solution by inert gas, and the colorless reaction mixture is stirred for 16 h.

[0086] Following stirring, the reaction mixture is discharged onto a filter frit and filtered. After filtration is complete, the filter cake is washed with 3×200 mL of heptane. All volatile constituents are distilled off from the obtained filtrate in vacuo (10.sup.−3 mbar-1 mbar) at 40-60° C. The product obtained is then dried again for 4 h at 50-60° C. and 1×10.sup.−3 mbar from.

Exemplary Embodiment 1-3: Analytical Data

[0087] Exemplary Embodiment 1: WO(OR).sub.4 where R=iPr; 4.0 eq. iPrOH; colorless solid, 81% yield

[0088] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K)δ(ppm)=1.30 (d, 6 H), 4.79-4.95 (m, 1 H); trace metals analysis (ICP-OES): all trace metals<10 ppm; silicon content (ICP-OES): 120 ppm.

[0089] Exemplary Embodiment 2: WO(OR).sub.4 where R=C.sub.3H.sub.6OCH.sub.3; 4.0 eq. CH.sub.3OC.sub.3H.sub.6OH; yellow oil, 81% yield

[0090] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K)δ(ppm)=1.23-1.27 (m, 12 H, CHCH3) 3.38-3.43 (m, 20 H, OCH2+OCH3), 4.74-4.83 (m, 4 H, CH); trace metals analysis (ICP-OES): all trace metals<10 ppm; silicon content (ICP-OES): 860 ppm.

[0091] Exemplary Embodiment 3: WO(OR).sub.4 where R=C.sub.3H.sub.6OC.sub.3H.sub.6OC.sub.3H.sub.7; 4.0 eq. C.sub.3H.sub.7OC.sub.3H.sub.6OC.sub.3H.sub.6OH; orange-colored oil, 87% yield

[0092] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K)δ(ppm)=0.85-0.97 (m, 3 H) 1.08-1.40 (m, 7 H), 1.58 (t, J=7.08 Hz, 2 H), 3.30-4.05 (m, 7 H), 4.24-4.61 (m, 1 H), 4.67-4.93 (m, 1 H); trace metals analysis (ICP-OES): all trace metals <10 ppm, silicon content (ICP-OES): 3500 ppm.

Exemplary Embodiment 4-7: General Procedure

[0093] Reaction of WCl.sub.6 with (TMS).sub.2O, ROH and NH.sub.3(g) or Et.sub.2NH in heptane with reaction step b)

[0094] WCl.sub.6 (50.832 g; 128.17 mmol) is weighed into flasks and dissolved/suspended in 300 mL heptane (abs. or EMSURE). In a separate dropping funnel, 20.875 g (128.17 mmol, stoichiometric) of hexamethyldisiloxane are weighed in and diluted with heptane to give a 50 vol % solution. The hexamethyldisiloxane solution is metered in slowly over 30 min with stirring at an internal temperature of 19-30° C. After metering is complete, the reaction mixture is subsequently stirred for 3 hours. The color of the reaction solution changes from dark red-violet to orange-yellow.

[0095] After the end of the stirring time, a distillation bridge with a scaled 250 mL Schlenk tube is attached. The pressure is carefully reduced to 170 mbar, and the temperature of the reaction mixture is slowly increased to 40° C. First distillate is obtained starting from a top temperature of 34-36° C. The distillation is continued at 170 mbar/40° C. until no more distillate is collected in the Schlenk flask and the top temperature of the distillation apparatus decreases from 38° C. to below 34° C. The pressure is then lowered slowly in 10 mbar-steps to 160 mbar, 150 mbar and 140 mbar, and in each case distillation is carried out until no more distillate is collected and the top temperature falls below 34° C. Finally, the pressure is reduced to 120 mbar (boiling point of heptane at 40° C.) and a drag distillation is carried out. In the method, a volume of heptane twice that of the previously collected distillate is additionally distilled off. After the distillation has ended, the distillation apparatus is removed again and exchanged for a dropping funnel. The distillate is discarded.

[0096] To the reaction suspension are added 512.67 mmol of the corresponding alcohol or glycol ether (4.0 equivalents) dropwise at 0° C., with stirring, over a period of 30 min. The reaction mixture slowly changes color to a clear colorless or yellow solution.

[0097] After the end of the metering, the reaction solution is cooled to 15° C., and the feed temperature is set to 0° C. (with base=Et.sub.2NH to 5° C.). The base is added in accordance with procedure a) or b):

a) A gas introduction pipe is placed on the apparatus, and the gas path is initially flushed with argon or nitrogen. Inert gas is then passed through the reaction solution for 10 min to displace excess HCl. After 10 min, ammonia is slowly introduced at a temperature of 10-15° C. The gas flow is initially so strong that the ammonia introduced is completely absorbed by the reaction solution. The temperature should be within a range of 0-40° C. during the introduction. The gas introduction is terminated as soon as the temperature of the reaction mixture falls and gas is blown off through the pressure relief valve. Inert gas is then passed through the reaction mixture again for 10 min. After 10 min, ammonia is again passed through the reaction mixture in order to ensure complete reaction. The excess ammonia is then flushed from the solution by inert gas, and the colorless reaction mixture is stirred for 16 h. b) 38.02 g of diethylamine (517.80 mmol, 4.04 equivalents) are metered in slowly in the course of 1 h at 25-35° C. After metering is complete, the receiver is subsequently flushed with 20 mL of heptane, and the reaction mixture is stirred for a further 16 h at RT.

[0098] Following stirring, the reaction mixture is discharged onto a filter frit and filtered. After filtration is complete, the filter cake is washed with 3×200 mL of heptane. All volatile constituents are distilled off from the obtained filtrate in vacuo (10.sup.−3 mbar-1 mbar) at 40-60° C. The product obtained is then dried again for 4 h at 50-60° C. and 1×10.sup.−3 mbar from.

Exemplary Embodiment 4-7: Analytical Data

[0099] Exemplary Embodiment 4: WO(OR).sub.4 where R=iPr; 4.0 eq. iPrOH; base=NH.sub.3; colorless solid, 77% yield

[0100] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K)δ(ppm)=1.30 (d, 6 H), 4.79-4.95 (m, 1 H); trace metals analysis (ICP-OES): all trace metals<10 ppm; silicon content (ICP-OES): 150 ppm.

[0101] Exemplary Embodiment 5: WO(OR).sub.4 where R=C.sub.3H.sub.6OCH.sub.3; 4.0 eq. CH.sub.3OC.sub.3H.sub.6OH; base=NH.sub.3; yellow oil, 84% yield

[0102] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K)δ(ppm)=1.23-1.27 (m, 12 H, CHCH3) 3.38-3.43 (m, 20 H, OCH2+OCH3), 4.74-4.83 (m, 4 H, CH); trace metals analysis (ICP-OES): all trace metals<10 ppm; silicon content (ICP-OES): 230 ppm.

[0103] Exemplary Embodiment 6: WO(OR).sub.4 where R=C.sub.3H.sub.6OC.sub.3H.sub.6OC.sub.3H.sub.7; 4.0 eq. C.sub.3H.sub.7OC.sub.3H.sub.6OC.sub.3H.sub.6OH; base=NH.sub.3; orange-colored oil, 90% yield

[0104] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K)δ(ppm)=0.85-0.97 (m, 3 H) 1.08-1.40 (m, 7 H), 1.58 (t, J=7.08 Hz, 2 H), 3.30-4.05 (m, 7 H), 4.24-4.61 (m, 1 H), 4.67-4.93 (m, 1 H); trace metals analysis (ICP-OES): all trace metals <10 ppm, silicon content (ICP-OES): 190 ppm.

[0105] Exemplary Embodiment 7: WO(OR).sub.4 where R=C.sub.3H.sub.6OC.sub.3H.sub.6OC.sub.3H.sub.7; 4.0 eq. C.sub.3H.sub.7OC.sub.3H.sub.6OC.sub.3H.sub.6OH; base=Et.sub.2NH; orange-colored oil, 86% yield

[0106] .sup.1H-NMR (CDCl.sub.3, 600 MHz, 300 K)δ(ppm)=0.85-0.97 (m, 3 H) 1.08-1.40 (m, 7 H), 1.58 (t, J=7.08 Hz, 2 H), 3.30-4.05 (m, 7 H), 4.24-4.61 (m, 1 H), 4.67-4.93 (m, 1 H); trace metals analysis (ICP-OES): all trace metals <10 ppm, silicon content (ICP-OES): 270 ppm.

Exemplary Embodiments 8

[0107] Based on examples 1 to 7, the results of the following examples can be obtained by varying the alcohol and the base.

Abbreviations: NH3: ammonia, DA: diethylamine, No.: number of example
The silicon contents were always within the range of 180 to 280 ppm. Without a distillation step, the silicon contents were between 800 and 5000 ppm with comparable yields.

TABLE-US-00001 Base Base Yield No. Alcohol NH3 DA [%] 1 2-Methylbutane-1-ol X 91 2 X 94 3 3-Methylbutane-1-ol X 92 4 X 90 5 2-Methylbutane-2-ol X 93 6 X 97 7 3-Methylbutane-2-ol X 96 8 X 97 9 Pentane-1-ol X 96 10 X 95 11 Pentane-2-ol X 83 12 X 89 13 Pentane-3-ol X 92 14 X 90 15 2,2-Dimethylpropane-1-ol X 96 16 X 91 17 Hexane-1-ol X 88 18 X 97 19 Hexane-2-ol X 77 20 X 91 21 Hexane-3-ol X 88 22 X 94 23 2-Methylpentane-1-ol X 88 24 X 93 25 3-Methylpentane-1-ol X 80 26 X 93 27 4-Methylpentane-1-ol X 84 28 X 89 29 X 84 30 2-Methylpentane-2-ol X 96 31 3-Methylpentane-2-ol X 81 32 X 93 33 4-Methylpentane-2-ol X 87 34 X 95 35 2-Methylpentane-3-ol X 82 36 X 94 37 3-Methylpentane-3-ol X 85 38 X 93 39 2,2-Dimethylbutane-1-ol X 85 40 X 87 41 2,3-Dimethylbutane-1-ol X 83 42 X 92 43 1-Methoxyethanol X 86 44 X 92 45 1-Ethoxyethanol X 87 46 X 95 47 1-Methoxy-2-propanol X 86 48 X 84 49 1-Ethoxy-2-propanol X 87 50 X 96 51 1-Propoxy-2-propanol X 86 52 X 94 53 1-Butoxy-2-propanol X 83 54 X 93 55 Heptane-1-ol X 83 56 X 95 57 Heptane-2-ol X 88 58 X 95 59 Heptane-3-ol X 78 60 X 96 61 1-Decanol X 89 62 X 93 63 Ethylene glycol monopropyl ether X 92 64 X 85 65 Ethylene glycol monoisopropyl ether X 91 66 X 94 67 Ethylene glycol monobutyl ether X 84 68 X 89 69 Ethylene glycol monopentyl ether X 88 70 X 94 71 Ethylene glycol monohexyl ether X 83 72 X 94 73 Ethylene glycol monophenyl ether X 88 74 X 93 75 Diethylene glycol monomethyl ether X 82 76 X 97 77 Diethylene glycol monoethyl ether X 84 78 X 94 79 Diethylene glycol monopropyl ether X 81 80 X 93 81 Diethylene glycol monoisopropyl ether X 86 82 X 93 83 Diethylene glycol monobutyl ether X 83 84 X 95 85 Diethylene glycol monopentyl ether X 88 86 X 92 87 Diethylene glycol monohexyl ether X 83 88 X 91 89 Diethylene glycol monophenyl ether X 84 90 X 89 91 X 88 92 Diethylene glycol monobenzyl ether X 93 93 Propylene glycol monoethyl ether X 81 94 X 93 95 Propylene glycol monopropyl ether X 84 96 X 94 97 Propylene glycol monoisopropyl ether X 87 98 X 91 99 Propylene glycol monobutyl ether X 87 100 X 92 101 Propylene glycol monopentyl ether X 87 102 X 93 103 Propylene glycol monohexyl ether X 81 104 X 97 105 Propylene glycol monophenyl ether X 84 106 X 94 107 Propylene glycol monobenzyl ether X 81 108 X 93 109 Isopropylene glycol monomethyl ether X 82 110 X 96 111 Isopropylene glycol monoethyl ether X 86 112 X 96 113 Isopropylene glycol monopropyl ether X 88 114 X 92 115 Isopropylene glycol monoisopropyl ether X 82 116 X 94 117 Isopropylene glycol monobutyl ether X 87 118 X 94 119 Isopropylene glycol monopentyl ether X 83 120 X 94 121 Isopropylene glycol monohexyl ether X 87 122 X 93 123 Isopropylene glycol monophenyl ether X 84 124 X 95 125 Dipropylene glycol monopropyl ether X 86 126 X 90 127 Isopropylene glycol monobenzyl ether X 87 128 X 95 129 Dipropylene glycol monomethyl ether X 89 130 X 92 131 Ethylene glycol monobenzyl ether X 82 132 X 91 133 Tripropylene glycol monomethyl ether X 85 134 X 97 135 Dipropylene glycol monobutyl ether X 84 136 X 93 137 Tripropylene glycol monobutyl ether X 86 138 X 95